Flame-retardant high-toughness modified PP material, preparation method and application thereof

Abstract

The present application relates to the technical field of polypropylene, and discloses a kind of flame-retardant high toughness modified PP material and preparation method and application thereof, the present application is fused extrusion to melamine graft POE elastomer, phosphated polyvinyl alcohol, polypropylene resin etc., granulation, obtains flame-retardant high toughness modified PP material.POE elastomer has good toughening effect to polypropylene, simultaneously POE elastomer grafts melamine structure, and its amino group and the phosphoric acid group of phosphated polyvinyl alcohol form ammonium phosphate structure, improves the compatibility between polyvinyl alcohol and polypropylene, reduces the adverse effect of polyvinyl alcohol on the toughness and mechanical property of polypropylene.POE elastomer grafts melamine structure as gas source, phosphated polyvinyl alcohol as acid source and carbon source, forms intumescent flame retardant, improves the flame-retardant property of polypropylene material, has higher limiting oxygen index, and the prepared PP material has very good practical application in six kinds of network line cross skeleton, wire sheath material etc.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of polypropylene, in particular to a kind of flame-retardant high toughness modified PP material and preparation method and application thereof. BACKGROUND

[0002] Polypropylene is a common thermoplastic polymer resin, with low density, light weight, and high mechanical strength, good chemical stability and heat resistance, and has important applications in wire and cable, furniture and household appliances, medical devices, etc. The toughness of ordinary polypropylene resin is poor, and the flame retardant performance is poor, which is not conducive to the practical application of polypropylene in network cable, wire sheath material, cross skeleton of six types of network cable, etc.

[0003] Polyvinyl alcohol will undergo intramolecular dehydration and aromatic ring structure at high temperature, which can be used as a carbon source, and can be compounded with nitrogen-based and phosphorus-based flame retardants, etc. It has broad application prospects in high polymer materials. Patent CN112390992B discloses a kind of corrosion-resistant flame-retardant cable sheath material, which is prepared from chlorinated polypropylene, nitrile rubber, polyvinyl alcohol, melamine phosphate, polyolefin elastomer, etc. The cable sheath material prepared has good mechanical properties, flame retardance and other properties, but the compatibility of polyvinyl alcohol and polypropylene is poor, which will affect the mechanical properties of the material. SUMMARY

[0004] (I) The technical problem to be solved: In view of the shortcomings of the prior art, the present application provides a kind of flame-retardant high toughness modified PP material and preparation method and application thereof, which solves the problem of poor flame retardance and toughness of polypropylene.

[0005] (II) Technical scheme: A preparation method of a kind of flame-retardant high toughness modified PP material:

[0006] (1) The preparation method of phosphonated polyvinyl alcohol is as follows: polyvinyl alcohol, phosphoric acid and urea are added to water, heated to 50-60℃, stirred for 7-10h, then heated to 90-100℃, stirred for 3-5h, ethanol is added, filtered and washed with ethanol for purification, dried to obtain phosphonated polyvinyl alcohol.

[0007] (2) Mix ethylene-octene copolymer elastomer, 2,4-diamino-6-allylamine-1,3,5-triazine and dicumyl peroxide, and graft reaction in a twin-screw extruder. Add the product to dimethylbenzene, heat to reflux, stir, add acetone for precipitation, filter and wash with acetone for purification, and then dry to obtain melamine grafted POE elastomer.

[0008] (3) Add melamine grafted POE elastomer and phosphonated polyvinyl alcohol to water, stir and dry, then add polypropylene resin and antioxidant to a mixer and mix, then melt extrude in a twin-screw extruder, cut into particles to obtain a flame-retardant high toughness modified PP material.

[0009] Further, the amount of polyvinyl alcohol in (1) is 100 parts by weight, the amount of phosphoric acid is 160-240 parts by weight, and the amount of urea is 5-11 parts by weight.

[0010] Further, the amount of ethylene-octene copolymer elastomer in (2) is 100 parts by weight, the amount of 2,4-diamino-6-allylamine-1,3,5-triazine is 4-12 parts by weight, and the amount of dicumyl peroxide is 0.3-0.8 parts by weight.

[0011] Further, the temperature of the 1-6 segments of the screw extruder in (2) is 160-180°C, and the screw rotation speed is 50-80 r / min.

[0012] Further, the amount of polypropylene resin in (3) is 100 parts by weight, the amount of melamine grafted POE elastomer is 10-30 parts by weight, and the amount of phosphonated polyvinyl alcohol is 8-20 parts by weight.

[0013] Further, the temperature during stirring in (3) is 70-95°C, and the time is 2-4 h.

[0014] Further, the temperature of the 1-6 segments of the twin-screw extruder in (3) is 160-200°C, and the screw rotation speed is 50-100 r / min.

[0015] Further, the flame-retardant high-toughness modified PP material is applied to network cable and wire sheath material.

[0016] (Three) Beneficial technical effects: The present application melts and grafts 2,4-diamino-6-allylamine-1,3,5-triazine onto ethylene-octene copolymer elastomer to obtain melamine grafted POE elastomer, which is then melt blended and granulated with polypropylene resin and phosphonated polyvinyl alcohol to obtain flame-retardant high-toughness modified PP material. The toughness of the POE elastomer is high, the mechanical properties are good, and the POE elastomer has a good toughening effect on polypropylene, which is beneficial to improving the impact strength and elongation at break of the material.

[0017] The POE elastomer of the present application is grafted with a melamine structure, and the amino group and the phosphoric acid group of the phosphonated polyvinyl alcohol form an ammonium phosphate salt structure, so that the POE elastomer and the polyvinyl alcohol form a chemical bond interaction, and the compatibility of the POE elastomer and the polypropylene is good, thereby improving the compatibility between the polyvinyl alcohol and the polypropylene and reducing the adverse effect of the polyvinyl alcohol on the toughness and mechanical properties of the polypropylene.

[0018] The POE elastomer of the present application is grafted with melamine structure as gas source, phosphonated polyvinyl alcohol as acid source and carbon source to form intumescent flame retardant, improve the flame retardant property of polypropylene material, and has higher limiting oxygen index, and the prepared PP material has good practical application in six kinds of network cross skeleton, wire sheath material and the like. DETAILED DESCRIPTION

[0019] The concept and the technical effects of the present application will be described clearly and completely in combination with the embodiments, so as to fully understand the purpose, features and effects of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, but not all the embodiments. Based on the embodiments of the present application, other embodiments obtained by those skilled in the art without creative labor are within the protection scope of the present application.

[0020] Into 350 mL of ethanol, 350 mL of water, 2.8 g of allylamine, 3.4 g of sodium bicarbonate, 6 g of 2-chloro-4,6-diamino-1,3,5-triazine are added, heated to 80℃, and condensed reflux reaction is carried out for 24 h. After filtration, the filtrate is heated and evaporated, and the precipitate is separated out in an ice bath to obtain 2,4-diamino-6-allylamine-1,3,5-triazine. The structural formula is

[0021]

[0022] (1) Into 150 mL of water, 40 g of polyvinyl alcohol, 64 g of phosphoric acid, and 2 g of urea are added, heated to 50℃, and stirred for 8 h. Then, it is heated to 100℃, and stirred for 3 h. Ethanol is added, and after filtration, ethanol washing purification is carried out, and dried to obtain phosphonated polyvinyl alcohol.

[0023] (2) 200 g of ethylene-octene copolymer elastomer, 8 g of 2,4-diamino-6-allylamine-1,3,5-triazine, and 0.6 g of dicumyl peroxide are mixed, and placed in a twin-screw extruder for grafting reaction. The temperature of 1-6 sections is 160℃, 170℃, 175℃, 180℃, 180℃, and 180℃, and the screw rotation speed is 80 r / min. The product is added to 6 L of xylene, heated to reflux, stirred, and then acetone is added for precipitation. After filtration, acetone washing purification is carried out, and then dried to obtain melamine grafted POE elastomer.

[0024] (3) Into 4 L of water, 0.5 kg of melamine grafted POE elastomer and 0.4 kg of phosphonated polyvinyl alcohol are added, heated to 90℃, and stirred for 2 h. After drying to remove water, 5 kg of polypropylene resin and 13 g of antioxidant 1010 are added to a mixer for mixing, and then placed in a twin-screw extruder for melt extrusion. The temperature of 1-6 sections is 160℃, 180℃, 195℃, 200℃, 200℃, and 195℃, and the screw rotation speed is 100 r / min. After granulation, a flame-retardant high-toughness modified PP material is obtained.

[0025] Example 2:

[0026] (1) To 180 mL of water, add 40 g of polyvinyl alcohol, 96 g of phosphoric acid, 4.4 g of urea, heat to 50°C, stir for 10 h, then heat to 90°C, stir for 5 h, add ethanol, filter and purify with ethanol washing, and dry to obtain phosphonated polyvinyl alcohol.

[0027] (2) Mix 200 g of ethylene-octene copolymer elastomer, 15 g of 2,4-diamino-6-allylamine-1,3,5-triazine, and 1 g of dicumyl peroxide, and place in a twin-screw extruder for grafting reaction, with the temperature of 1-6 segments being 160°C, 170°C, 175°C, 180°C, 180°C, and 180°C, and the screw rotation speed being 50 r / min. Add the product to 8 L of xylene, heat to reflux, stir, add acetone for precipitation, filter and purify with acetone washing, and then dry to obtain melamine-grafted POE elastomer.

[0028] (3) To 5 L of water, add 1 kg of melamine-grafted POE elastomer and 0.7 kg of phosphonated polyvinyl alcohol, heat to 70°C, stir for 4 h, dry to remove water, then mix with 5 kg of polypropylene resin and 10 g of antioxidant 1010 in a mixer, melt and extrude in a twin-screw extruder, with the temperature of 1-6 segments being 160°C, 180°C, 195°C, 200°C, 200°C, and 195°C, and the screw rotation speed being 50 r / min, and cut into granules to obtain flame-retardant high-toughness modified PP material.

[0029] Example 3:

[0030] (1) To 180 mL of water, add 40 g of polyvinyl alcohol, 82 g of phosphoric acid, and 3.5 g of urea, heat to 60°C, stir for 7 h, then heat to 95°C, stir for 5 h, add ethanol, filter and purify with ethanol washing, and dry to obtain phosphonated polyvinyl alcohol.

[0031] (2) Mix 200 g of ethylene-octene copolymer elastomer, 24 g of 2,4-diamino-6-allylamine-1,3,5-triazine, and 1.6 g of dicumyl peroxide, and place in a twin-screw extruder for grafting reaction, with the temperature of 1-6 segments being 160°C, 170°C, 175°C, 180°C, 180°C, and 180°C, and the screw rotation speed being 50 r / min. Add the product to 8 L of xylene, heat to reflux, stir, add acetone for precipitation, filter and purify with acetone washing, and then dry to obtain melamine-grafted POE elastomer.

[0032] (3) To 6L water, add 1.5kg melamine grafted POE elastomer, 1kg phosphated polyvinyl alcohol, heat to 95℃, stir for 3h, dry to remove water, then add 5kg polypropylene resin, 15g antioxidant 1010 into a mixer, melt extrude in a twin-screw extruder, temperature of 1-6 section is 160℃, 180℃, 195℃, 200℃, 200℃, 195℃, screw rotation speed is 80r / min, cut into particles, to obtain flame-retardant high-toughness modified PP material.

[0033] Comparative Example 1, the difference between this comparative example and Example 1 is that 0.4kg phosphated polyvinyl alcohol is not added.

[0034] (1) To 4L water, add 0.5kg melamine grafted POE elastomer, heat to 90℃, stir for 2h, dry to remove water, then add 5kg polypropylene resin, 13g antioxidant 1010 into a mixer, melt extrude in a twin-screw extruder, temperature of 1-6 section is 160℃, 180℃, 195℃, 200℃, 200℃, 195℃, screw rotation speed is 100r / min, cut into particles, to obtain modified PP material.

[0035] Comparative Example 2, the difference between this comparative example and Example 1 is that polyvinyl alcohol is used instead of phosphated polyvinyl alcohol.

[0036] (1) To 4L water, add 0.5kg melamine grafted POE elastomer, 0.4kg polyvinyl alcohol, heat to 90℃, stir for 2h, dry to remove water, then add 5kg polypropylene resin, 13g antioxidant 1010 into a mixer, melt extrude in a twin-screw extruder, temperature of 1-6 section is 160℃, 180℃, 195℃, 200℃, 200℃, 195℃, screw rotation speed is 100r / min, cut into particles, to obtain modified PP material.

[0037] Comparative Example 3, the difference between this comparative example and Example 1 is that ethylene-octene copolymer elastomer is used instead of melamine grafted POE elastomer.

[0038] (1) To 4L water, add 0.5kg ethylene-octene copolymer elastomer, 0.4kg phosphated polyvinyl alcohol, heat to 90℃, stir for 2h, dry to remove water, then add 5kg polypropylene resin, 13g antioxidant 1010 into a mixer, melt extrude in a twin-screw extruder, temperature of 1-6 section is 160℃, 180℃, 195℃, 200℃, 200℃, 195℃, screw rotation speed is 100r / min, cut into particles, to obtain modified PP material.

[0039] Comparative Example 4, the difference between this comparative example and Example 1 is that N-allyl imidazole is used instead of 2,4-diamino-6-allylamine-1,3,5-triazine.

[0040] (1) 200 g of ethylene-octene copolymer elastomer, 8 g of N-allyl imidazole, and 0.6 g of dicumyl peroxide were mixed and subjected to a graft reaction in a twin-screw extruder, with the temperature of 1-6 segments being 160°C, 170°C, 175°C, 180°C, 180°C, and 180°C, and the screw rotation speed being 80 r / min. The product was added to 6 L of xylene, heated to reflux, and after stirring, acetone was added for precipitation. The product was purified by filtration and acetone washing, and then dried to obtain an imidazole-grafted POE elastomer.

[0041] (2) 0.5 kg of the imidazole-grafted POE elastomer and 0.4 kg of phosphonated polyvinyl alcohol were added to 4 L of water, heated to 90°C, stirred for 2 h, and then dried to remove water. Then, 5 kg of polypropylene resin and 13 g of antioxidant 1010 were added to a mixer and mixed, and then subjected to melt extrusion in a twin-screw extruder, with the temperature of 1-6 segments being 160°C, 180°C, 195°C, 200°C, 200°C, and 195°C, and the screw rotation speed being 100 r / min. The product was pelletized to obtain a modified PP material.

[0042] The PP plastic was subjected to injection molding using an injection molding machine, with the temperature of three segments being 195°C, 210°C, and 210°C, and the pressure being 50 MPa, to produce a sample. The impact strength was tested according to the GB / T 1043.1-2008 standard. The elongation at break was tested according to the GB / T 1040.1-2018 standard. The combustion performance was tested according to the GB / T 2406.1-2008 standard.

[0043] Table 1 Properties of PP materials

[0044]

[0045]

[0046] The impact strength and elongation at break of the PP materials of Examples 1 to 3 are high, the toughness is good, and the limiting oxygen index is large, and the flame retardant performance is excellent, mainly because the melamine grafted POE elastomer is added, the POE elastomer has a good toughening effect on the polypropylene, which is beneficial to improve the impact strength and elongation at break of the material, the POE elastomer is grafted with a melamine structure, and the amino group and the phosphoric acid group of the phosphonated polyvinyl alcohol form an ammonium phosphate salt structure, so that the POE elastomer and the polyvinyl alcohol form a chemical bond interaction, and the compatibility of the POE elastomer and the polypropylene is good, thereby improving the compatibility between the polyvinyl alcohol and the polypropylene, reducing the adverse effect of the polyvinyl alcohol on the toughness and mechanical properties of the polypropylene, and keeping the polypropylene with good impact strength and elongation at break. At the same time, the POE elastomer grafted with the melamine structure as a gas source and the phosphonated polyvinyl alcohol as an acid source and a carbon source form an intumescent flame retardant, which improves the flame retardant performance of the polypropylene and has a higher limiting oxygen index.

[0047] Comparative Example 1 does not add phosphonated polyvinyl alcohol, and the limiting oxygen index of the PP material is very low, and the flame retardant performance is poor.

[0048] Comparative Example 2 uses polyvinyl alcohol instead of phosphonated polyvinyl alcohol, the melamine grafted POE elastomer cannot form an ammonium phosphate salt chemical bond interaction with the polyvinyl alcohol, and the compatibility between the polyvinyl alcohol and the polypropylene is not improved, the polyvinyl alcohol has a great influence on the toughness and mechanical properties of the polypropylene, resulting in a decrease in the impact strength and elongation at break, and the polyvinyl alcohol does not contain a phosphoric acid group, and cannot form an intumescent flame retardant, so the limiting oxygen index of the material is low, and the flame retardant performance is poor.

[0049] Comparative Example 3 uses ethylene-octene copolymer elastomer instead of melamine grafted POE elastomer, which does not contain amino groups and cannot form an ammonium phosphate salt chemical bond interaction with the phosphonated polyvinyl alcohol, and the compatibility between the polyvinyl alcohol and the polypropylene is not improved, the polyvinyl alcohol has a great influence on the toughness and mechanical properties of the polypropylene, resulting in a decrease in the impact strength and elongation at break, and the POE elastomer does not contain a melamine structure, and cannot form an intumescent flame retardant, so the limiting oxygen index of the material is low, and the flame retardant performance is poor.

[0050] Comparative Example 4 uses N-allyl imidazole to melt graft ethylene-octene copolymer elastomer, and the obtained imidazole grafted POE elastomer does not contain amino groups and cannot form an ammonium phosphate salt chemical bond interaction with the phosphonated polyvinyl alcohol, and the compatibility between the polyvinyl alcohol and the polypropylene is not improved, the polyvinyl alcohol has a great influence on the toughness and mechanical properties of the polypropylene, resulting in a decrease in the impact strength and elongation at break, and the nitrogen content of the N-imidazole structure is lower than that of melamine, resulting in a lower nitrogen element content in the intumescent flame retardant, and the limiting oxygen index of the material is lower than that of Example 1.

[0051] The application is described in detail above in combination with the embodiments, but the application is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the purpose of the application. In addition, the embodiments of the application and the features in the embodiments can be combined with each other without conflict.

Claims

1. A method for preparing a flame-retardant, high-toughness modified PP material, characterized in that, The preparation method includes: (1) Ethylene-octene copolymer elastomer, 2,4-diamino-6-allylamino-1,3,5-triazine and dicumyl peroxide were mixed and placed in a twin-screw extruder for grafting reaction. After purification, melamine-grafted POE elastomer was obtained. (2) Add melamine-grafted POE elastomer and phosphorylated polyvinyl alcohol to water, stir and dry to remove water, then add polypropylene resin and antioxidant to a mixer and mix, then place in a twin-screw extruder for melt extrusion, and pelletize to obtain flame-retardant high-toughness modified PP material. The amount of ethylene-octene copolymer elastomer in (1) is 100 parts by weight, 2,4-diamino-6-allylamino-1,3,5-triazine is 4-12 parts by weight, and dicumyl peroxide is 0.3-0.8 parts by weight; In (2), the amount of polypropylene resin is 100 parts by weight, the amount of melamine-grafted POE elastomer is 20-30 parts by weight, and the amount of phosphorylated polyvinyl alcohol is 8-20 parts by weight. The preparation method of phosphorylated polyvinyl alcohol in (2) is as follows: add 100 parts by weight of polyvinyl alcohol, 160-240 parts by weight of phosphoric acid and 5-11 parts by weight of urea to water, heat to 50-60℃, stir for 7-10h, then heat to 90-100℃, stir for 3-5h, and obtain phosphorylated polyvinyl alcohol after purification.

2. The preparation method of the flame-retardant high-toughness modified PP material according to claim 1, characterized in that, The temperature of sections 1-6 of the twin-screw extruder in (1) is 160-180℃, and the screw speed is 50-80r / min.

3. The method for preparing the flame-retardant, high-toughness modified PP material according to claim 1, characterized in that, The temperature during stirring in (2) is 70-95℃ and the time is 2-4h.

4. The preparation method of the flame-retardant high-toughness modified PP material according to claim 1, characterized in that, The temperature of sections 1-6 of the twin-screw extruder in (2) is 160-200℃, and the screw speed is 50-100r / min.

5. A flame-retardant, high-toughness modified PP material obtained by the preparation method according to any one of claims 1-4.

6. The application of the flame-retardant, high-toughness modified PP material as described in claim 5 in network cables.

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