A PVC / CPE modified material and preparation method thereof

Abstract

The invention discloses a PVC / CPE modified material and a preparation method thereof, and belongs to the technical field of polymer materials. The PVC / CPE modified material comprises the following raw materials in parts by weight: 80-100 parts of PVC, 20-40 parts of CPE, 3-30 parts of plasticizer, 2-4 parts of modified flame retardant antioxidant, 2-3 parts of stabilizer, and 3-5 parts of lubricant; the present invention prepares intermediate 1 by silicone resin and 4-((4-(hydroxymethyl)phenyl)(phenyl)amino)benzaldehyde, and then intermediate 1 and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide prepare intermediate 2, and then cyanuric chloride and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine prepare intermediate 3, and finally intermediate 2 and intermediate 3 prepare modified flame retardant antioxidant. The PVC / CPE modified material prepared by the present invention has excellent anti-aging performance and flame retardant performance.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a PVC / CPE modified material and a preparation method thereof. Background Art

[0002] Polyvinyl chloride (PVC) is a high molecular polymer, which is a white amorphous powder at room temperature and is synthesized from vinyl chloride monomers through polymerization. PVC is widely used in building materials, films, pipes, and coatings. Chlorinated polyethylene is a product formed by replacing hydrogen atoms on the polyethylene main chain with chlorine atoms. It has no unsaturated bonds, does not crystallize, and is a saturated polymer material. Chlorinated polyethylene is divided into resin-type chlorinated polyethylene (CPE) and elastomer-type chlorinated polyethylene (CM) according to its different structures and different application methods. CPE is widely used in wires and cables, tapes, hoses, and waterproof membranes. However, polyvinyl chloride has poor stability to light and heat. It will decompose at temperatures above 100°C or after long-term exposure to sunlight to produce hydrogen chloride, and further autocatalytic decomposition will cause discoloration, and the physical and mechanical properties will also decline rapidly. Therefore, more requirements are put forward for PP / CPE modified materials, such as higher flame retardancy and anti-aging properties.

[0003] The Chinese invention patent with publication number CN106188908A discloses a CPE-PVC radiation cross-linked sheath rubber compound and a preparation method thereof. The sheath rubber compound comprises the following raw materials in parts by weight: 100 parts of CPE, 40-60 parts of PVC particles, 50-80 parts of talc, 10-30 parts of magnesium hydroxide, 1-3 parts of antimony trioxide, 15-35 parts of carbon black, 20-40 parts of plasticizer, and 3-15 parts of sensitizer. The sheath rubber compound has excellent mechanical properties, but poor anti-aging and flame retardant properties. Summary of the invention

[0004] In view of the shortcomings of the prior art, the object of the present invention is to provide a PVC / CPE modified material and a preparation method thereof.

[0005] To achieve the above object, the present invention is implemented through the following technical solutions:

[0006] A PVC / CPE modified material comprises the following raw materials in parts by weight:

[0007] PVC: 80-100 parts,

[0008] CPE: 20-40 copies,

[0009] Plasticizer: 3-30 parts,

[0010] Modified flame retardant antioxidant: 2-4 parts,

[0011] Stabilizer: 2-3 parts,

[0012] Lubricant: 3-5 parts;

[0013] The modified flame retardant antioxidant is prepared by the following method:

[0014] S1: Under nitrogen protection, toluene, silicone resin, and 4-((4-(hydroxymethyl)phenyl)(phenyl)amino)benzaldehyde are added to the reactor in sequence, ultrasonically mixed, and then glacial acetic acid is added. The temperature is raised and refluxed for reaction for 5-7 hours. After post-treatment, intermediate 1 is obtained. The reaction equation is shown as follows:

[0015]

[0016] S2: Under nitrogen protection, DMF and intermediate 1 are added to the reactor, stirred and mixed, and the temperature is raised to 80-100°C, and then 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is added, and the reaction is carried out for 8-10 hours. After post-treatment, intermediate 2 is obtained. The reaction equation is shown as follows:

[0017]

[0018] S3: Toluene and cyanuric chloride are added to the reactor, stirred in an ice bath to mix well, and then N-butyl-2,2,6,6-tetramethyl-4-piperidinamine is slowly added to react for 2-4 hours; sodium hydroxide solution is then added dropwise, the temperature is raised to 70-90°C, and the reaction is continued for 14-16 hours. Intermediate 3 is obtained by post-treatment, and the reaction equation is shown as follows:

[0019]

[0020] S4: Add DMSO, intermediate 3 and potassium hydroxide into the reactor, stir and mix, replace the air with nitrogen, pressurize to 0.5MPa, heat to 150-170℃ and then increase the pressure to 1.0MPa, then slowly add intermediate 2, react for 16-20h, and post-treat to obtain the modified flame retardant antioxidant. The reaction equation is as follows:

[0021]

[0022] Among them, m and n are natural numbers.

[0023] In step S1, the mass ratio of toluene, silicone resin and 4-((4-(hydroxymethyl)phenyl)(phenyl)amino)benzaldehyde is 50:(10-15):(10-12).

[0024] In step S2, the mass ratio of DMF, intermediate 1, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 100:(15-25):(10-20).

[0025] In step S3, the mass ratio of toluene, cyanuric chloride and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine is 100:(6-8):(12-15).

[0026] In step S4, the mass ratio of DMSO, intermediate 3, potassium hydroxide and intermediate 2 is 50:(5-10):(0.5-1):(10-14).

[0027] The plasticizer is one of dioctyl phthalate, dibutyl phthalate and diisononyl phthalate.

[0028] The stabilizer is a combination of one or more of JX-181 organic tin heat stabilizer, JX-107 reverse ester tin heat stabilizer, and JT-101 antimony mercaptan heat stabilizer.

[0029] The lubricant is one or a combination of paraffin wax, stearic acid and polyethylene wax.

[0030] A method for preparing a PVC / CPE modified material comprises the following steps:

[0031] S1: Weigh by weight: PVC: 80-100 parts, CPE: 20-40 parts, plasticizer: 3-30 parts,

[0032] Modified flame retardant antioxidant: 2-4 parts, stabilizer: 2-3 parts, lubricant: 3-5 parts;

[0033] S2: Add PVC, CPE and plasticizer into a high-speed mixer, mix at 100-120°C for 20-30 minutes, heat to 120-140°C, add modified flame retardant, stabilizer and lubricant, mix, pre-plasticize for 20-40 minutes, convey to a twin-screw extruder for extrusion, mixing and plasticizing, air-cooling and sieving, and obtain PVC / CPE modified material.

[0034] Due to the adoption of the above technical solution, the beneficial effects of the present invention include:

[0035] (1) The present invention uses silicone resin and 4-((4-(hydroxymethyl)phenyl)(phenyl)amino)benzaldehyde to react to prepare intermediate 1, then react intermediate 1 with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to prepare intermediate 2, then react cyanuric chloride with N-butyl-2,2,6,6-tetramethyl-4-piperidinamine to prepare intermediate 3, and finally react intermediate 2 with intermediate 3 to prepare a modified flame retardant antioxidant.

[0036] (2) The silicone resin used in the modified flame retardant and anti-aging agent prepared by the present invention has a lower heat release rate due to the Si-O bond energy of the molecular chain in the silicon-based polymer being much greater than the CC bond energy. Generally, silicon-based flame retardants migrate and gather on the polymer surface during combustion to form a stable and dense heat-insulating polysiloxane cross-linked carbon layer. The structure of the residual carbon includes Si-O-Si and -Si-C- bonds, which can effectively improve the oxidation resistance and barrier effect of the carbon layer, making its flame retardant and heat-insulating effects better than those of ordinary carbon layers, thereby improving the flame retardant properties of PVC / CPE modified materials.

[0037] (3) The intermediate 3 prepared by the modified flame retardant and antioxidant prepared by the present invention contains a piperidine group, but due to its small molecular weight, it is not resistant to migration. Through the grafting reaction, its molecular weight is increased, the migration and extraction resistance of the modified flame retardant and antioxidant are reduced, and the anti-aging ability of the PVC / CPE modified material is improved. DETAILED DESCRIPTION

[0038] The invention will be further described below with reference to the embodiments, but the invention is not limited to these embodiments.

[0039] Example 1 Preparation of silicone resin:

[0040] Add 43.26g of phenyltriethoxysilane to the reactor, then add 20mL of 15wt% hydrochloric acid solution as a catalyst, slowly add 4.12g of N-(β-aminoethyl-)-γ-aminopropylmethyl-dimethoxysilane, add for 30s, stir to mix, reflux for 4h, add 11.34g of hexamethyldisiloxane to cap, react for another 1h, then slowly add 25%wt ammonia water to adjust the pH to 8-9, produce a precipitate, filter, wash with deionized water 3 times (50g of deionized water each time), and dry in vacuo at 80°C for 5h to obtain a silicone resin.

[0041] Example 2 Preparation of modified flame retardant antioxidant:

[0042] S1: Under nitrogen protection, 500 g of toluene, 100 g of silicone resin (prepared in Example 1), and 100 g of 4-((4-(hydroxymethyl)phenyl)(phenyl)amino)benzaldehyde were added to the reactor in sequence, and mixed evenly by ultrasonication for 10 min. Then, 2 ml of glacial acetic acid was added dropwise, and the temperature was raised to reflux for reaction for 7 h. The mixture was cooled to room temperature, 1.5 kg of anhydrous ethanol was added for precipitation, filtered, and dried in vacuo at 60 ° C for 10 h to obtain intermediate 1.

[0043] S2: Under nitrogen protection, 1 kg DMF and 150 g intermediate 1 were added into the reactor, stirred and mixed, and the temperature was raised to 80°C. Then, 100 g 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was added. The mixture was reacted for 10 h, rotary evaporated at 60°C for 3 h, and vacuum dried at 80°C for 4 h to obtain intermediate 2.

[0044] S3: 1 kg of toluene and 60 g of cyanuric chloride were added to the reactor, stirred in an ice bath to mix, and then 120 g of N-butyl-2,2,6,6-tetramethyl-4-piperidinamine was slowly added and reacted for 2 h; then 10 ml of 40 wt% sodium hydroxide solution was added dropwise for 2 min, the temperature was raised to 70 ° C and the reaction was continued for 16 h. After the reaction was completed, deionized water and ethyl acetate were added for extraction 3 times (1000 mL of deionized water and 400 mL of ethyl acetate were used each time), and then dried with 300 g of anhydrous sodium sulfate for 2 h, rotary evaporated at 50 ° C for 3 h, and vacuum dried at 70 ° C for 5 h to obtain intermediate 3.

[0045] S4: Add 500g DMSO, 50g intermediate 3 and 5g potassium hydroxide into the reactor, stir and mix, replace the air with nitrogen, pressurize at 0.5MPa, heat to 150℃ and then increase the pressure to 1.0MPa, then slowly add 100g intermediate 2, react for 20h, distill at 60℃ under reduced pressure for 5h, and vacuum dry at 80℃ for 4h to obtain a modified flame retardant antioxidant with a number average molecular weight of 10280.

[0046] Example 3 Preparation of modified flame retardant antioxidant:

[0047] S1: Under nitrogen protection, 500 g of toluene, 125 g of silicone resin (prepared in Example 1), and 110 g of 4-((4-(hydroxymethyl)phenyl)(phenyl)amino)benzaldehyde were added to a reactor in sequence, and mixed by ultrasonication for 12 min. Then, 2 ml of glacial acetic acid was added dropwise, and the temperature was raised to reflux for reaction for 6 h. The mixture was cooled to room temperature, 1.5 kg of anhydrous ethanol was added for precipitation, filtered, and dried in vacuo at 70 ° C for 9 h to obtain intermediate 1.

[0048] S2: Under nitrogen protection, 1 kg DMF and 200 g intermediate 1 were added into the reactor, stirred and mixed, and the temperature was raised to 90°C. Then, 150 g 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was added. The reaction was continued for 9 h, rotary evaporated at 70°C for 3 h, and vacuum dried at 90°C for 3 h to obtain intermediate 2.

[0049] S3: 1 kg of toluene and 70 g of cyanuric chloride were added to the reactor, stirred in an ice bath to mix, and then 135 g of N-butyl-2,2,6,6-tetramethyl-4-piperidinamine was slowly added and reacted for 3 h; then 12 ml of 40 wt% sodium hydroxide solution was added dropwise for 3 min, the temperature was raised to 80 ° C and the reaction was continued for 15 h. After the reaction was completed, deionized water and ethyl acetate were added for extraction 3 times (1000 mL of deionized water and 400 mL of ethyl acetate were used each time), and then dried with 300 g of anhydrous sodium sulfate for 2 h, rotary evaporated at 60 ° C for 2 h, and vacuum dried at 80 ° C for 4 h to obtain intermediate 3.

[0050] S4: Add 500g DMSO, 75g intermediate 3 and 8g potassium hydroxide into the reactor, stir and mix, replace the air with nitrogen, pressurize at 0.5MPa, heat to 160℃ and then increase the pressure to 1.0MPa, then slowly add 120g intermediate 2, react for 18h, distill at 70℃ under reduced pressure for 4h, and vacuum dry at 90℃ for 3h to obtain a modified flame retardant antioxidant with a number average molecular weight of 11800.

[0051] Example 4 Preparation of modified flame retardant antioxidant:

[0052] S1: Under nitrogen protection, 500 g of toluene, 150 g of silicone resin (prepared in Example 1), and 120 g of 4-((4-(hydroxymethyl)phenyl)(phenyl)amino)benzaldehyde were added to the reactor in sequence, and mixed by ultrasonication for 15 min. Then, 2.5 ml of glacial acetic acid was added dropwise, and the temperature was raised to reflux for reaction for 5 h. The mixture was cooled to room temperature, 1.5 kg of anhydrous ethanol was added for precipitation, filtered, and dried in vacuo at 80 ° C for 8 h to obtain intermediate 1.

[0053] S2: Under nitrogen protection, 1 kg DMF and 250 g intermediate 1 were added into the reactor, stirred and mixed, and the temperature was raised to 100°C. Then, 200 g 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was added, and the reaction was continued for 8 h. The mixture was rotary evaporated at 70°C for 3 h, and vacuum dried at 100°C for 2 h to obtain intermediate 2.

[0054] S3: 1 kg of toluene and 80 g of cyanuric chloride were added into the reactor, stirred in an ice bath to mix, and then 150 g of N-butyl-2,2,6,6-tetramethyl-4-piperidinamine was slowly added and reacted for 4 h; then 15 ml of 40 wt% sodium hydroxide solution was added dropwise for 4 min, the temperature was raised to 90 °C and the reaction was continued for 14 h. After the reaction was completed, deionized water and ethyl acetate were added for extraction 3 times (1000 mL of deionized water and 400 mL of ethyl acetate were used each time), and then dried with 300 g of anhydrous sodium sulfate for 2 h, rotary evaporated at 70 °C for 1 h, and vacuum dried at 90 °C for 3 h to obtain intermediate 3.

[0055] S4: Add 500g DMSO, 100g intermediate 3 and 10g potassium hydroxide into the reactor, stir and mix, replace the air with nitrogen, pressurize at 0.5MPa, heat to 170℃ and then increase the pressure to 1.0MPa, then slowly add 140g intermediate 2, react for 16h, distill at 80℃ under reduced pressure for 3h, and vacuum dry at 100℃ for 2h to obtain a modified flame retardant antioxidant with a number average molecular weight of 13400.

[0056] Example 5 Preparation of PVC / CPE modified material:

[0057] S1: weigh PVC: 800g, CPE: 200g, plasticizer (dioctyl phthalate): 30g, modified flame retardant antioxidant (prepared in Example 1): 20g, stabilizer (JX-181 organic tin heat stabilizer): 20g, lubricant (paraffin): 30g;

[0058] S2: Add PVC, CPE and plasticizer into a high-speed mixer, mix at 100°C for 20 minutes, heat to 120°C, add modified flame retardant and antioxidant, stabilizer and lubricant, mix, pre-plasticize for 20 minutes, and transport to a twin-screw extruder for extrusion, mixing and plasticization. The screw speed of the twin-screw extruder is 20r / s, the temperature of the conveying section of the twin-screw extruder is 100°C, the temperature of the melting section is 120°C, the temperature of the mixing rubber section is 130°C, and the temperature of the homogenizing section is 125°C. Air-cooled and sieved, PVC / CPE modified material is obtained.

[0059] Example 6 Preparation of PVC / CPE modified material:

[0060] S1: weigh PVC: 900g, CPE: 300g, plasticizer (dibutyl phthalate): 175g, modified flame retardant antioxidant (prepared in Example 2): 30g, stabilizer (JX-107 reverse ester tin heat stabilizer): 25g, lubricant (stearic acid): 40g;

[0061] S2: Add PVC, CPE and plasticizer into a high-speed mixer, mix at 110°C for 25 minutes, heat to 130°C, add modified flame retardant and antioxidant, stabilizer and lubricant, mix, pre-plasticize for 30 minutes, and transport to a twin-screw extruder for extrusion, mixing and plasticizing. The screw speed of the twin-screw extruder is 30r / s, the temperature of the conveying section of the twin-screw extruder is 110°C, the temperature of the melting section is 130°C, the temperature of the mixing rubber section is 140°C, and the temperature of the homogenizing section is 130°C. Air-cooled and sieved, PVC / CPE modified material is obtained.

[0062] Example 7 Preparation of PVC / CPE modified material:

[0063] S1: weigh PVC: 1 kg, CPE: 400 g, plasticizer (diisononyl phthalate): 300 g, modified flame retardant antioxidant (prepared in Example 3): 40 g, stabilizer (JT-101 antimony mercaptan heat stabilizer): 30 g, lubricant (polyethylene wax): 50 g;

[0064] S2: Add PVC, CPE and plasticizer into a high-speed mixer, mix at 120°C for 30 minutes, heat to 140°C, add modified flame retardant antioxidant, stabilizer and lubricant, mix, pre-plasticize for 40 minutes, and transport to a twin-screw extruder for extrusion, mixing and plasticization. The screw speed of the twin-screw extruder is 40r / s, the temperature of the conveying section of the twin-screw extruder is 120°C, the temperature of the melting section is 140°C, the temperature of the mixing rubber section is 150°C, and the temperature of the homogenizing section is 135°C. Air-cooled and sieved, PVC / CPE modified material is obtained.

[0065] Comparative Example 1

[0066] A PVC / CPE modified material, the raw material composition and process are basically the same as those of Example 6, the difference being that no modified flame retardant antioxidant is added to the component.

[0067] Comparative Example 2

[0068] A PVC / CPE modified material, the raw material composition and process are basically the same as those of Example 6, the difference being that the modified flame retardant and antioxidant is replaced by an equal weight of the intermediate 3 prepared in step S3 of Example 3.

[0069] Comparative Example 3

[0070] A PVC / CPE modified material, the raw material composition and process are basically the same as those of Example 6, the difference being that the modified flame retardant and antioxidant is replaced by an equal weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

[0071] Comparative Example 4

[0072] A PVC / CPE modified material, the raw material composition and process are basically the same as those of Example 6, except that the modified flame retardant and antioxidant are replaced by 12g of intermediate 3 (prepared in step S3 of Example 3) and 18g of intermediate 2 (prepared in step S2 of Example 3).

[0073] Comparative Example 5

[0074] A PVC / CPE modified material is prepared by the following raw materials and processes:

[0075] S1: weigh PVC: 900g, CPE: 300g, plasticizer (dibutyl phthalate): 175g, modified flame retardant antioxidant: 30g, stabilizer (JX-107 reverse ester tin heat stabilizer): 25g, lubricant (stearic acid): 40g;

[0076] S2: Add PVC, CPE and plasticizer into a high-speed mixer, mix at 110°C for 25 minutes, heat to 130°C, add modified flame retardant and antioxidant, stabilizer and lubricant, mix, pre-plasticize for 30 minutes, and transport to a twin-screw extruder for extrusion, mixing and plasticizing. The screw speed of the twin-screw extruder is 30r / s, the temperature of the conveying section of the twin-screw extruder is 110°C, the temperature of the melting section is 130°C, the temperature of the mixing rubber section is 140°C, and the temperature of the homogenizing section is 130°C. Air-cooled and sieved, PVC / CPE modified material is obtained.

[0077] The modified flame retardant antioxidant in this comparative example is prepared by the following method:

[0078] S1: Under nitrogen protection, 500 g of toluene, 100 g of silicone resin, and 100 g of 4-((4-(hydroxymethyl)phenyl)(phenyl)amino)benzaldehyde were added to the reactor in sequence, and mixed by ultrasonication for 10 min. Then, 2 ml of glacial acetic acid was added dropwise, and the temperature was raised to reflux for reaction for 7 h. After cooling to room temperature, 1.5 kg of anhydrous ethanol was added for precipitation, filtered, and dried in vacuo at 60 ° C for 10 h to obtain intermediate 1.

[0079] S2: Under nitrogen protection, 1 kg DMF and 150 g intermediate 1 were added into the reactor, stirred and mixed, and the temperature was raised to 80°C. Then, 100 g 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was added. The mixture was reacted for 10 h, rotary evaporated at 60°C for 3 h, and vacuum dried at 80°C for 4 h to obtain intermediate 2.

[0080] S3: 1 kg of toluene and 60 g of cyanuric chloride were added into the reactor, stirred in an ice bath to mix, and then 120 g of N-butyl-2,2,6,6-tetramethyl-4-piperidinamine was slowly added and reacted for 2 h; then 10 ml of 40 wt% sodium hydroxide solution was added dropwise for 2 min, the temperature was raised to 70 °C and the reaction was continued for 16 h. After the reaction was completed, deionized water and ethyl acetate were added for extraction 3 times (200 mL of deionized water and 100 mL of ethyl acetate were used each time), and then dried with 300 g of anhydrous sodium sulfate for 2 h, rotary evaporated at 50 °C for 3 h, and vacuum dried at 70 °C for 5 h to obtain intermediate 3.

[0081] S4: Add 500g DMSO, 35g intermediate 3 and 2g potassium hydroxide into the reactor, stir and mix, replace the air with nitrogen, pressurize to 0.5MPa, heat to 150℃ and then increase the pressure to 1.0MPa, then slowly add 80g intermediate 2, react for 15h, distill at 60℃ under reduced pressure for 5h, and vacuum dry at 80℃ for 4h to obtain a modified flame retardant antioxidant with a number average molecular weight of 8680.

[0082] Comparative Example 6

[0083] The PVC / CPE material is prepared by using the raw material composition and proportion of Example 4 of the Chinese invention patent with publication number CN106188908A and the following method.

[0084] PVC, CPE and plasticizer were added to a high-speed mixer, mixed at 110°C for 25 minutes, heated to 130°C, and then other additives (refer to the raw materials of Example 4 of Chinese invention patent with publication number CN106188908A) were added and mixed, pre-plasticized for 30 minutes, and transported to a twin-screw extruder for extrusion, mixing and plasticization. The screw speed of the twin-screw extruder was 30r / s, the conveying section temperature of the twin-screw extruder was 110°C, the melting section temperature was 130°C, the mixing rubber section temperature was 140°C, and the homogenizing section temperature was 130°C. The mixture was air-cooled and sieved to obtain PVC / CPE material.

[0085] The polyvinyl chloride used in Examples 5-7 and Comparative Examples 1-5 of the present application: brand SG-5, purchased from Chengdu Jinlu Resin Co., Ltd.; chlorinated polyethylene: brand 135A, chlorine content of 35%, purchased from Weifang Yaxing Chemical Co., Ltd.

[0086] The PVC / CPE modified materials prepared in Examples 5-7 and Comparative Examples 1-6 were subjected to tensile strength and elongation at break tests. The test method was based on GB / T1040.2-2006, with a temperature of 23°C, a type 1B specimen, and a tensile speed of 100 mm / min; test instrument: electronic tensile testing machine AI-7000, China High Speed ​​Railway Technology Co., Ltd.; hot air aging performance was performed in accordance with GB / T3512-2001, and the test results are shown in Table 1.

[0087] The PVC / CPE modified materials prepared in Examples 5-7 and Comparative Examples 1-6 and the aged materials were subjected to a vertical combustion (UL-94) test according to GB / T 2408 standard. The test results are shown in Table 1.

[0088] Table 1

[0089]

[0090] It can be seen from Examples 5, 6 and 7 in Table 1 that the PVC / CPE modified materials prepared by the present invention have a tensile strength greater than 25 MPa, a tensile strength greater than 21 MPa after aging, excellent tensile properties and elongation at break, and the flame retardant grade remains at V-0 after aging.

[0091] Comparative Example 1 is a comparative example without adding modified flame retardant antioxidant. It can be seen from the data in Table 1 that its tensile strength after aging is 14.7 MPa, the elongation at break is 310.4%, and the combustion grade (UL-94) is V-2.

[0092] Comparative Example 2 is different from Example 6, and the difference is that the modified flame retardant and antioxidant is replaced by the intermediate 3 prepared in step S3 of Example 2. It can be seen from the data in Table 1 that the tensile strength after aging is 18.2 MPa, the elongation at break is 334.7%, and the flammability grade (UL-94) is V-2.

[0093] Comparative Example 3 is different from Example 6, and the difference is that the modified flame retardant and antioxidant is replaced by 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. It can be seen from the data in Table 1 that the tensile strength after aging is 15.0 MPa, the elongation at break is 314.6%, and the combustion grade (UL-94) is V-1.

[0094] Comparative Example 4 is different from Example 6, in that the modified flame retardant and antioxidant are replaced with 12g of intermediate 3 and 18g of intermediate 2. It can be seen from the data in Table 1 that the tensile strength after aging is 17.4MPa, the elongation at break is 325.9%, and the flammability grade (UL-94) is V-1.

[0095] The number average molecular weight of the modified flame retardant antioxidant added in Comparative Example 5 is 8680. From the data in Table 1, it can be seen that the tensile strength after aging is 20.1 MPa, the elongation at break is 340.8%, and the combustion grade (UL-94) is V-0.

[0096] Comparative Example 6 is a PVC / CPE material prepared using the raw materials of Example 4 of Chinese invention patent publication number CN106188908A and the process of the present application. It can be seen from the data in Table 1 that its tensile strength after aging is 14.4 MPa, the elongation at break is 320.1%, and the flammability rating (UL-94) is V-1.

[0097] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. However, any equivalent changes, modifications and evolutions made by ordinary technicians in the field without departing from the scope of the technical solution of the present invention by using the technical content disclosed above are all equivalent embodiments of the present invention. At the same time, any equivalent changes, modifications and evolutions made to the above embodiments based on the essential technology of the present invention are still within the protection scope of the technical solution of the present invention.

Claims

1. A PVC / CPE modified material, characterized in that: The invention comprises the following raw materials in parts by weight: PVC: 80-100 parts, CPE: 20-40 copies, Plasticizer: 3-30 parts, Modified flame retardant antioxidant: 2-4 parts, Stabilizer: 2-3 parts, Lubricant: 3-5 parts; The modified flame retardant antioxidant is prepared by the following method: S1: Under nitrogen protection, toluene, silicone resin, and 4-((4-(hydroxymethyl)phenyl)(phenyl)amino)benzaldehyde are added to a reactor in sequence, ultrasonically mixed, and then glacial acetic acid is added. The temperature is raised and refluxed for reaction for 5-7 hours, and intermediate 1 is obtained after post-treatment; S2: Under nitrogen protection, DMF and intermediate 1 are added into a reactor, stirred and mixed, and the temperature is raised to 80-100° C., and then 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is added, and the reaction is carried out for 8-10 hours. Intermediate 2 is obtained after post-treatment; S3: Add toluene and cyanuric chloride into the reactor, stir and mix in an ice bath, then slowly add N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, and react for 2-4 hours; then dropwise add sodium hydroxide solution, raise the temperature to 70-90°C, and continue to react for 14-16 hours, and post-treat to obtain intermediate 3; S4: Add DMSO, intermediate 3 and potassium hydroxide into the reactor, stir and mix, replace the air with nitrogen, pressurize to 0.5MPa, heat to 150-170℃ and then increase the pressure to 1.0MPa, then slowly add intermediate 2, react for 16-20h, and obtain the modified flame retardant antioxidant after post-treatment.

2. A PVC / CPE modified material according to claim 1, characterized in that: In step S1, the mass ratio of toluene, silicone resin and 4-((4-(hydroxymethyl)phenyl)(phenyl)amino)benzaldehyde is 50:(10-15):(10-12).

3. A PVC / CPE modified material according to claim 1, characterized in that: In step S2, the mass ratio of DMF, intermediate 1, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 100:(15-25):(10-20).

4. A PVC / CPE modified material according to claim 1, characterized in that: In step S3, the mass ratio of toluene, cyanuric chloride and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine is 100:(6-8):(12-15).

5. A PVC / CPE modified material according to claim 1, characterized in that: In step S4, the mass ratio of DMSO, intermediate 3, potassium hydroxide and intermediate 2 is 50:(5-10):(0.5-1):(10-14).

6. A PVC / CPE modified material according to claim 1, characterized in that: The plasticizer is one of dioctyl phthalate, dibutyl phthalate and diisononyl phthalate.

7. A PVC / CPE modified material according to claim 1, characterized in that: The stabilizer is a combination of one or more of JX-181 organic tin heat stabilizer, JX-107 reverse ester tin heat stabilizer, and JT-101 antimony mercaptan heat stabilizer.

8. A PVC / CPE modified material according to claim 1, characterized in that: The lubricant is one or a combination of paraffin wax, stearic acid and polyethylene wax.

9. A method for preparing the PVC / CPE modified material according to any one of claims 1 to 8, characterized in that: The following steps are involved: S1: Weigh by weight: PVC: 80-100 parts, CPE: 20-40 parts, plasticizer: 3-30 parts, Modified flame retardant antioxidant: 2-4 parts, stabilizer: 2-3 parts, lubricant: 3-5 parts; S2: Add PVC, CPE and plasticizer into a high-speed mixer, mix at 100-120°C for 20-30 minutes, heat to 120-140°C, add modified flame retardant, stabilizer and lubricant, mix, pre-plasticize for 20-40 minutes, convey to a twin-screw extruder for extrusion, mixing and plasticizing, air-cooling and sieving, and obtain PVC / CPE modified material.

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