PVC / PU modified material and preparation method thereof

Abstract

The application discloses PVC / PU modified material and a preparation method thereof, and belongs to the technical field of high polymer materials. The PVC / PU modified material comprises the following raw materials in parts by weight: PVC: 80-100 parts, PU: 30-40 parts, plasticizer: 10-20 parts, modified flame-retardant antioxidant: 4-8 parts, stabilizer: 2-4 parts, and lubricant: 3-5 parts. The application prepares an intermediate 1 by the reaction of cyanuric chloride and N-phenyl-p-phenylenediamine, then prepares an intermediate 2 by the reaction of the intermediate 1 and 1-amino-10-undecene, then prepares an intermediate 3 by the reaction of diphenylphosphinic chloride and 1-amino-10-undecene, and finally prepares the modified flame-retardant antioxidant by the reaction of the intermediate 2 and the intermediate 3. The PVC / PU modified material prepared by the application has excellent anti-aging performance and flame-retardant performance.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to a PVC / PU modified material and its preparation method. Background Technology

[0002] Polyvinyl chloride (PVC) is a high-molecular polymer, a white amorphous powder at room temperature, synthesized from vinyl chloride monomer through polymerization. Due to its excellent performance, low price, and simple processing, PVC is widely used in many fields such as automobiles (vehicle interior seals, floor mats, etc.), construction, packaging, synthetic leather, and medical supplies. Polyurethane (PU) is a new type of polymer material with high flexibility and excellent wear resistance. When combined with PVC, it can enhance the flexibility and durability of PVC and is widely used in coatings, adhesives, printing, leather, textiles, and the construction industry. However, PVC itself also has many weaknesses, such as residual initiators, end-group metal impurities, and oxygen-containing structures. These unstable factors can oxidize under external factors such as light, heat, and oxygen, causing its physical and mechanical properties to deteriorate and rendering it unusable. Therefore, improving the service life of PVC / PU materials and enhancing their anti-aging and flame-retardant properties is of great significance.

[0003] Chinese invention patent CN110511506A discloses a low-volatile PVC modified material and its preparation method. This PVC modified material comprises the following components: PVC resin powder, butadiene-type thermoplastic polyurethane, styrene-ethylene / butene-styrene block copolymer, cycloalkyl oil, SEBS maleic anhydride graft, calcium-zinc stabilizer, lubricant, and antioxidant. This PVC modified material releases very little volatile odor gas under long-term use or heating conditions, but its anti-aging and flame-retardant properties are poor. Summary of the Invention

[0004] In view of the shortcomings of the existing technology, the purpose of this invention is to provide a PVC / PU modified material and its preparation method.

[0005] To achieve the above objectives, the present invention provides the following technical solution:

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

[0007] PVC: 80-100 parts

[0008] PU: 30-40 parts

[0009] Plasticizer: 10-20 parts

[0010] Modified flame retardant and antioxidant: 4-8 parts

[0011] Stabilizer: 2-4 parts

[0012] Lubricant: 3-5 parts;

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

[0014] S1: Toluene and cyanuric chloride are added sequentially to the reactor and stirred until homogeneous at 0-5°C. Then, N-phenyl-p-phenylenediamine is added, followed by dropwise addition of Na2CO3 aqueous solution. The reaction is allowed to proceed for 3-5 hours, followed by the addition of N-phenyl-p-phenylenediamine. The reaction is then brought to room temperature and allowed to proceed for 44-48 hours to obtain intermediate 1. The reaction equation is shown below:

[0015] ;

[0016] S2: Toluene and intermediate 1 are added sequentially to the reactor and stirred at 90-95℃ until homogeneous. Then, 1-amino-10-undecene is added, followed by dropwise addition of Na2CO3 aqueous solution. The reaction is carried out for 12-18 hours to obtain intermediate 2. The reaction equation is shown below:

[0017] ;

[0018] S3: Under nitrogen protection, chloroform and 1-amino-10-undecene were added sequentially to the reactor and stirred at room temperature until homogeneous. Then, Na2CO3 aqueous solution was added dropwise, and the reaction was allowed to proceed for 1-2 hours. Next, diphenylphosphine chloride was added, and the reaction was allowed to proceed for 2-4 hours at room temperature to obtain intermediate 3. The reaction equation is shown below:

[0019] ;

[0020] S4: Under nitrogen protection, tetrahydrofuran, intermediate 2, intermediate 3, and azobisisobutyronitrile were added sequentially to the reaction vessel, stirred and mixed, and the temperature was raised to 60-80℃. The reaction was carried out for 14-18 hours to obtain the modified flame retardant and antioxidant. The reaction equation is shown below:

[0021]

[0022] Where m and n are natural numbers.

[0023] The number average molecular weight of the modified flame retardant and antioxidant is 20,000-35,000.

[0024] In step S1, the mass ratio of toluene, cyanuric chloride, the first addition of N-phenyl-p-phenylenediamine, the second addition of N-phenyl-p-phenylenediamine, and the Na2CO3 aqueous solution is 300:(18-22):(18-20):(18-20):(100-120).

[0025] In step S2, the mass ratio of toluene, intermediate 1, 1-amino-10-undecene, and Na2CO3 aqueous solution is 350:(46-50):(18-20):(50-60).

[0026] In step S3, the mass ratio of chloroform, 1-amino-10-undecene, diphenylphosphine chloride, and Na2CO3 aqueous solution is 150:(15-19):(22-26):(50-70).

[0027] In step S4, the mass ratio of tetrahydrofuran, intermediate 2, intermediate 3, and azobisisobutyronitrile is 120:(28-32):(18-20):(0.14-0.18).

[0028] The plasticizer is one of diisononyl phthalate, tributyl citrate, and dioctyl adipate.

[0029] The stabilizer is one of calcium stearate, zinc stearate, and barium stearate.

[0030] The lubricant is one of microcrystalline wax, oxidized paraffin, or polyethylene wax.

[0031] A method for preparing a PVC / PU modified material includes the following steps:

[0032] S1: Weigh out the following by weight: PVC: 80-100 parts, PU: 30-40 parts, plasticizer: 10-20 parts.

[0033] Modified flame retardant and anti-aging agent: 4-8 parts, stabilizer: 2-4 parts, lubricant: 3-5 parts;

[0034] S2: Add PVC, PU, ​​plasticizer, modified flame retardant and anti-aging agent, stabilizer and lubricant to a high-speed mixer, stir at 100-140℃ for 20-30 minutes, and then extrude and granulate through a twin-screw extruder to obtain PVC / PU modified material; the zone temperatures of the twin-screw extruder are: feeding section 175-185℃, compression section 165-175℃, melting section 165-175℃, metering section 160-170℃, extrusion die body section 170-180℃, and die section 180-200℃.

[0035] Due to the adoption of the above technical solutions, the beneficial effects of the present invention include:

[0036] (1) In this invention, intermediate 1 was prepared by reacting cyanuric chloride and N-phenyl-p-phenylenediamine. Then, intermediate 1 was reacted with 1-amino-10-undecene to prepare intermediate 2. After that, diphenylphosphine chloride was reacted with 1-amino-10-undecene to prepare intermediate 3. Finally, intermediate 2 and intermediate 3 were reacted to prepare the modified flame retardant and antioxidant.

[0037] (2) The modified flame retardant and antioxidant prepared in this invention is an amine antioxidant. It can effectively capture the active free radicals generated by PVC during the aging process. By releasing its own active hydrogen atoms, it makes these free radicals lose their activity, thereby preventing them from continuing to damage other molecular chains and achieving the purpose of delaying or terminating the oxidation reaction. Furthermore, through the grafting reaction, its molecular weight is increased, which improves the problem of low molecular weight antioxidants being unable to migrate and easily volatilizing, thereby improving the anti-aging ability of PVC / PU modified materials.

[0038] (3) The flame-retardant group introduced in the modified flame retardant and anti-aging agent prepared in this invention is a phosphorus-containing group. The phosphorus element in this group can promote the carbonization of combustion molecules through the change of its own oxidation state. The generated carbon can physically hinder the smoke and heat generated by combustion and hinder the transfer of combustion molecule fragments between the burned and unburned components, thereby achieving a good flame-retardant effect and improving the flame-retardant performance of PVC / PU modified materials. Attached Figure Description

[0039] Figure 1 The 1H NMR spectrum of intermediate 2 prepared in Example 2;

[0040] Figure 2 The 1H NMR spectrum of intermediate 3 prepared in Example 2. Detailed Implementation

[0041] The following description, in conjunction with specific embodiments, provides further details, but the present invention is not limited to these embodiments.

[0042] Example 1: Preparation of modified flame retardant and antioxidant:

[0043] S1: 300g toluene and 18g cyanuric chloride were added sequentially to the reactor and stirred at 0-5℃ until homogeneous. Then, 18g N-phenyl-p-phenylenediamine was added, followed by 100g Na2CO3 (20wt%) aqueous solution. The addition was carried out dropwise for 15min, and the reaction was allowed to proceed for 3h. Then, 18g N-phenyl-p-phenylenediamine was added again, and the reaction was allowed to proceed to room temperature for 44h. After the reaction was complete, deionized water and ethyl acetate were added for extraction three times (each time using 500mL deionized water and 300mL ethyl acetate). The mixture was then dried with 200g anhydrous sodium sulfate for 2h, distilled under reduced pressure at 50℃ for 2h, and dried under vacuum at 50℃ for 6h to obtain intermediate 1.

[0044] S2: 350g toluene and 46g intermediate 1 were added sequentially to the reactor and stirred at 90-95℃ until homogeneous. Then, 18g of 1-amino-10-undecene was added, followed by dropwise addition of 50g of Na2CO3 (20wt%) aqueous solution over 5 min. After reacting for 12 h, the insoluble matter in the system was removed by filtration. The filtrate was transferred to a separatory funnel and allowed to stand to separate into layers. After removing the aqueous layer, the toluene solution was washed with 40g of dilute hydrochloric acid (10wt%), then washed with 300g of saturated Na2CO3 solution, and then washed with 500g of deionized water until neutral. The washed toluene layer was dried with 200g of anhydrous sodium sulfate for 2 h, distilled under reduced pressure at 60℃ for 1 h to remove the solvent, and then dried under vacuum at 50℃ for 6 h to obtain intermediate 2.

[0045] S3: Under nitrogen protection, 150g of chloroform and 15g of 1-amino-10-undecene were added sequentially to the reactor and stirred at room temperature. Then, 50g of Na2CO3 (20wt%) aqueous solution was added dropwise over 10 minutes, and the reaction was allowed to proceed for 1 hour. Next, 22g of diphenylphosphine chloride was added, and the reaction was allowed to proceed for 2 hours at room temperature. The insoluble matter in the system was removed by filtration. The filtrate was transferred to a separatory funnel, allowed to stand for separation, and the aqueous layer was removed. The chloroform layer was then washed with 500g of deionized water until neutral. The washed chloroform layer was dried with 200g of anhydrous sodium sulfate for 2 hours, distilled under reduced pressure at 65℃ for 2 hours to remove the solvent, and dried under vacuum at 50℃ for 6 hours to obtain intermediate 3.

[0046] S4: Under nitrogen protection, 120g tetrahydrofuran, 28g intermediate 2, 18g intermediate 3, and 0.14g azobisisobutyronitrile were added sequentially to a reaction vessel, stirred and mixed, heated to 60℃, and reacted for 18h. After the reaction was completed, the solvent was removed by vacuum distillation at 65℃ for 2h, 100g methanol was added, filtered, washed with 50g methanol, and dried under vacuum at 70℃ for 5h to obtain a modified flame retardant and antioxidant with a number average molecular weight of 20580.

[0047] Example 2: Preparation of modified flame retardant and antioxidant:

[0048] S1: 300g toluene and 20g cyanuric chloride were added sequentially to the reactor and stirred at 0-5℃ until homogeneous. Then, 19g N-phenyl-p-phenylenediamine was added, followed by dropwise addition of 110g Na2CO3 (20wt%) aqueous solution for 20min. The reaction was allowed to proceed for 4h, and then another 19g N-phenyl-p-phenylenediamine was added. The reaction was allowed to proceed to room temperature for 46h. After the reaction was complete, deionized water and ethyl acetate were added for extraction three times (500mL deionized water and 300mL ethyl acetate were used each time). The mixture was then dried with 200g anhydrous sodium sulfate for 2h, distilled under reduced pressure at 50℃ for 2.5h, and dried under vacuum at 60℃ for 5h to obtain intermediate 1.

[0049] S2: 350g toluene and 48g intermediate 1 were added sequentially to the reactor and stirred at 90-95℃ until homogeneous. Then, 19g of 1-amino-10-undecene was added, followed by dropwise addition of 55g of Na2CO3 (20wt%) aqueous solution over 10 min. After reacting for 16 h, the insoluble matter in the system was removed by filtration. The filtrate was transferred to a separatory funnel and allowed to stand to separate into layers. After removing the aqueous layer, the toluene solution was washed with 50g of dilute hydrochloric acid (10wt%), then with 300g of saturated Na2CO3 solution, and finally with 500g of deionized water until neutral. The washed toluene layer was dried with 200g of anhydrous sodium sulfate for 2 h, distilled under reduced pressure at 60℃ for 1.5 h to remove the solvent, and then dried under vacuum at 60℃ for 5 h to obtain intermediate 2. Its 1H NMR spectrum (see [reference needed]). Figure 1 The data is as follows: 1 H NMR (500 MHz, Chloroform-d) δ 8.63 (s,2H), 7.70 – 7.51 (m, 4H), 7.18 (s, 4H), 7.09 – 7.03 (m, 4H), 6.98 – 6.92 (m,4H), 6.83 (tt, J = 6.8, 1.1 Hz, 2H), 6.14 (s, 2H), 6.08 (t, J = 4.6 Hz, 1H), 5.86 – 5.73 (m, 1H), 5.10 (ddt, J = 10.2, 2.3, 1.5 Hz, 1H), 4.96 (ddt, J =17.0, 2.4, 1.3 Hz, 1H), 3.20 (td, J = 7.2, 4.6 Hz, 2H), 2.03 (tdt, J = 8.0,6.7, 1.4 Hz, 2H), 1.72 (s, 2H), 1.39 – 1.27 (m, 6H), 1.27 – 1.19 (m, 6H).

[0050] S3: Under nitrogen protection, 150g of chloroform and 17g of 1-amino-10-undecene were added sequentially to the reactor and stirred at room temperature. Then, 60g of 20wt% Na₂CO₃ aqueous solution was added dropwise over 15 minutes, and the reaction was allowed to proceed for 1.5 hours. Next, 24g of diphenylphosphine chloride was added, and the reaction was allowed to proceed for 3 hours at room temperature. The insoluble matter was removed by filtration. The filtrate was transferred to a separatory funnel and allowed to stand for separation. After removing the aqueous layer, the chloroform layer was washed with 500g of deionized water until neutral. The washed chloroform layer was dried with 200g of anhydrous sodium sulfate for 2 hours, distilled under reduced pressure at 65℃ for 2.5 hours to remove the solvent, and dried under vacuum at 60℃ for 5 hours to obtain intermediate 3. Its 1H NMR spectrum (see...) Figure 2 The data is as follows: 1H NMR (500 MHz, Chloroform-d) δ 7.83 – 7.75 (m, 4H), 7.58 – 7.48 (m, 6H), 5.86 – 5.73 (m, 1H), 5.13 – 5.06 (m, 2H), 4.96 (ddt, J = 17.2, 2.4, 1.3 Hz, 1H), 2.86 (dt, J = 5.7, 4.7 Hz, 2H), 2.03 (tdt, J = 8.2, 6.8, 1.4 Hz, 2H), 1.54 (s, 2H), 1.37 – 1.22 (m, 12H).

[0051] S4: Under nitrogen protection, 120g tetrahydrofuran, 30g intermediate 2, 19g intermediate 3, and 0.16g azobisisobutyronitrile were added sequentially to a reaction vessel, stirred and mixed, heated to 70℃, and reacted for 16h. After the reaction was completed, the solvent was removed by vacuum distillation at 65℃ for 2.5h. 100g methanol was added, filtered, washed with 50g methanol, and dried under vacuum at 80℃ for 4h to obtain a modified flame retardant and antioxidant with a number average molecular weight of 27440.

[0052] Example 3: Preparation of modified flame retardant and antioxidant:

[0053] S1: 300g toluene and 22g cyanuric chloride were added sequentially to the reactor and stirred at 0-5℃ until homogeneous. Then 20g N-phenyl-p-phenylenediamine was added, followed by dropwise addition of 120g Na2CO3 (20wt%) aqueous solution for 15min. The reaction was allowed to proceed for 5h. Then another 20g N-phenyl-p-phenylenediamine was added, and the reaction was allowed to proceed to room temperature for 48h. After the reaction was complete, deionized water and ethyl acetate were added for extraction three times (500mL deionized water and 300mL ethyl acetate were used each time). The mixture was then dried with 200g anhydrous sodium sulfate for 2h, distilled under reduced pressure at 50℃ for 3h, and dried under vacuum at 70℃ for 4h to obtain intermediate 1.

[0054] S2: 350g toluene and 50g intermediate 1 were added sequentially to the reactor and stirred at 90-95℃ until homogeneous. Then, 20g of 1-amino-10-undecene was added, followed by dropwise addition of 60g of Na2CO3 (20wt%) aqueous solution over 5 min. After reacting for 18 h, the insoluble matter in the system was removed by filtration. The filtrate was transferred to a separatory funnel and allowed to stand to separate into layers. After removing the aqueous layer, the toluene solution was washed with 60g of dilute hydrochloric acid (10wt%), then with 300g of saturated Na2CO3 solution, and finally with 500g of deionized water until neutral. The washed toluene layer was dried with 200g of anhydrous sodium sulfate for 2 h, distilled under reduced pressure at 60℃ for 2 h to remove the solvent, and then dried under vacuum at 70℃ for 4 h to obtain intermediate 2.

[0055] S3: Under nitrogen protection, 150g of chloroform and 19g of 1-amino-10-undecene were added sequentially to the reactor and stirred at room temperature. Then, 70g of Na2CO3 (20wt%) aqueous solution was added dropwise over 10 minutes, and the reaction was allowed to proceed for 2 hours. Next, 26g of diphenylphosphine chloride was added, and the reaction was allowed to proceed for 4 hours at room temperature. The insoluble matter in the system was removed by filtration. The filtrate was transferred to a separatory funnel, allowed to stand for separation, and the aqueous layer was removed. The chloroform layer was then washed with 500g of deionized water until neutral. The washed chloroform layer was dried with 200g of anhydrous sodium sulfate for 2 hours, distilled under reduced pressure at 65℃ for 3 hours to remove the solvent, and dried under vacuum at 70℃ for 4 hours to obtain intermediate 3.

[0056] S4: Under nitrogen protection, 120g tetrahydrofuran, 32g intermediate 2, 20g intermediate 3, and 0.18g azobisisobutyronitrile were added sequentially to a reaction vessel, stirred and mixed, heated to 80℃, and reacted for 14h. After the reaction was completed, the solvent was removed by vacuum distillation at 65℃ for 3h. 100g methanol was added, filtered, washed with 50g methanol, and dried under vacuum at 90℃ for 3h to obtain a modified flame retardant and antioxidant with a number average molecular weight of 34870.

[0057] Example 4: Preparation of PVC / PU modified materials:

[0058] S1: Weigh out the following by weight: PVC: 800g, PU: 300g, plasticizer: 100g (diisononyl phthalate), modified flame retardant and antioxidant: 40g (prepared in Example 1), stabilizer: 20g (calcium stearate), lubricant: 30g (microcrystalline wax).

[0059] S2: Add PVC, PU, ​​plasticizer, modified flame retardant and anti-aging agent, stabilizer and lubricant to a high-speed mixer, stir at 100℃ for 20 minutes, and then extrude and granulate through a twin-screw extruder to obtain PVC / PU modified material; the zone temperatures of the twin-screw extruder are: feeding section 175℃, compression section 165℃, melting section 165℃, metering section 160℃, extrusion die body section 170℃, and die section 180℃.

[0060] Example 5: Preparation of PVC / PU modified materials:

[0061] S1: Weigh out the following by weight: PVC: 900g, PU: 350g, plasticizer: 150g (tributyl citrate), modified flame retardant and anti-aging agent: 60g (prepared in Example 2), stabilizer: 30g (zinc stearate), lubricant: 40g (paraffin oxide).

[0062] S2: Add PVC, PU, ​​plasticizer, modified flame retardant and anti-aging agent, stabilizer and lubricant to a high-speed mixer, stir at 125℃ for 15 minutes, and then extrude and granulate through a twin-screw extruder to obtain PVC / PU modified material; the zone temperature of the twin-screw extruder is: feeding section 190℃, compression section 180℃, melting section 180℃, metering section 175℃, extrusion die body section 185℃, and die section 200℃.

[0063] Example 6: Preparation of PVC / PU modified materials:

[0064] S1: Weigh out the following by weight: PVC: 1000g, PU: 400g, plasticizer: 200g (dioctyl adipate), modified flame retardant and anti-aging agent: 80g (prepared in Example 3), stabilizer: 20-40g (barium stearate), lubricant: 50g (polyethylene wax).

[0065] S2: Add PVC, PU, ​​plasticizer, modified flame retardant and anti-aging agent, stabilizer and lubricant to a high-speed mixer, stir at 140℃ for 30 minutes, and then extrude and granulate through a twin-screw extruder to obtain PVC / PU modified material; the zone temperature of the twin-screw extruder is: feeding section 185℃, compression section 175℃, melting section 175℃, metering section 170℃, extrusion die body section 180℃, and die section 200℃.

[0066] Comparative Example 1

[0067] A modified PVC / PU material has the same raw material composition and process as in Example 5, except that no modified flame retardant or anti-aging agent is added to the components.

[0068] Comparative Example 2

[0069] A modified PVC / PU material, with the same raw material composition and process as in Example 5, except that the modified flame retardant and anti-aging agent is replaced with an equal weight of intermediate 1 prepared in step S1 of Example 2.

[0070] Comparative Example 3

[0071] A modified PVC / PU material, with the same raw material composition and process as in Example 5, except that the modified flame retardant and anti-aging agent is replaced with an equal weight of intermediate 2 prepared in step S2 of Example 2.

[0072] Comparative Example 4

[0073] A modified PVC / PU material, with the same raw material composition and process as Example 5, except that the modified flame retardant and anti-aging agent is replaced with an equal weight of intermediate 3 prepared in step S3 of Example 2.

[0074] Comparative Example 5

[0075] A modified PVC / PU material has the same raw material composition and process as in Example 5, except that the modified flame retardant and antioxidant is replaced with 36.73g of intermediate 2 (prepared in step S2 of Example 2) and 23.27g of intermediate 3 (prepared in step S3 of Example 2).

[0076] Comparative Example 6

[0077] A modified PVC / PU material, with the same raw material composition and process as in Example 5, except that the modified flame retardant and antioxidant is replaced with an equal weight of a modified flame retardant and antioxidant with a number average molecular weight of 15680 prepared by the following method.

[0078] The modified flame retardant and antioxidant in this comparative example was prepared by the following method:

[0079] S4: Under nitrogen protection, 120g tetrahydrofuran, 25g intermediate 2 (prepared in Example 2), 15g intermediate 3 (prepared in Example 2), and 0.12g azobisisobutyronitrile were added sequentially to a reaction vessel, stirred and mixed, heated to 60℃, and reacted for 14h. After the reaction was completed, the solvent was removed by vacuum distillation at 65℃ for 2.5h. 100g methanol was added, filtered, washed with 50g methanol, and dried under vacuum at 70℃ for 4h to obtain a modified flame retardant and antioxidant with a number average molecular weight of 15680.

[0080] Comparative Example 7

[0081] A modified PVC / PU material, with the same raw material composition and process as in Example 5, except that the modified flame retardant and antioxidant is replaced with an equal weight of a modified flame retardant and antioxidant with a number average molecular weight of 40180 prepared by the following method.

[0082] The modified flame retardant and antioxidant in this comparative example was prepared by the following method:

[0083] S4: Under nitrogen protection, 180g of tetrahydrofuran, 50g of intermediate 2 (prepared in Example 2), 30g of intermediate 3 (prepared in Example 2), and 0.22g of azobisisobutyronitrile were added sequentially to a reaction vessel, stirred and mixed, heated to 70℃, and reacted for 20h. After the reaction was completed, the solvent was removed by vacuum distillation at 65℃ for 3h, 100g of methanol was added, filtered, washed with 50g of methanol, and dried under vacuum at 80℃ for 4h to obtain a modified flame retardant and antioxidant with a number average molecular weight of 40180.

[0084] Comparative Example 8

[0085] PVC / PU material prepared using the raw materials and method described in Example 5 of Chinese Invention Patent Publication No. CN110511506A.

[0086] Comparative Example 9

[0087] A modified PVC / PU material has the same raw material composition and process as in Example 5, except that the modified flame retardant and antioxidant is replaced with an equal weight of the modified flame retardant and antioxidant prepared by the following method.

[0088] The modified flame retardant and antioxidant in this comparative example was prepared by the following method:

[0089] Under nitrogen protection, 120g of tetrahydrofuran, 30g of N-(4-anilinephenyl)-methacrylamide, 19g of intermediate 3 (prepared in Example 2), and 0.16g of azobisisobutyronitrile were added sequentially to a reaction vessel, stirred and mixed, heated to 70°C, and reacted for 16h. After the reaction was completed, the solvent was removed by vacuum distillation at 65°C for 2.5h. 100g of methanol was added, filtered, washed with 50g of methanol, and dried under vacuum at 80°C for 4h to obtain the modified flame retardant and antioxidant.

[0090] The PVC used in Examples 4-6 and Comparative Examples 1-9 of this application is of grade WH1000F, produced by Yantai Wanhua Group Co., Ltd.; the microcrystalline wax is of grade 70A, produced by Jingmen Branch of China Petroleum & Chemical Corporation; the oxidized paraffin is of type 733, produced by Wuhan Kanos Technology Co., Ltd.; and the polyethylene wax is of type NV-438P, produced by Comino New Materials Technology (Zhejiang) Co., Ltd. The PU used in Examples 4-5 and Comparative Examples 1-8 of this application is of grade PU850, produced by Ningbo Di Specialty Chemicals (Shanghai) Co., Ltd.; and the PU used in Example 6 is of grade T-100, produced by Zibo Hengjiu Polyurethane Technology Co., Ltd.

[0091] The PVC / PU modified materials prepared in Examples 4-6 and Comparative Examples 1-9 were subjected to tensile strength and elongation at break tests. The test methods were carried out in accordance with GB / T528-2009 standard. The dumbbell-shaped sample was selected as the test condition, and the tensile speed was 100 mm / min. The test results are shown in Table 1.

[0092] The PVC / PU modified materials prepared in Examples 4-6 and Comparative Examples 1-9 were subjected to hot air aging performance tests. The test methods were carried out in accordance with GB / T3512-2001 standard. The test results are shown in Table 1.

[0093] Flame retardancy tests were conducted on the PVC / PU modified materials prepared in Examples 4-6 and Comparative Examples 1-9, as well as the aged materials. The test methods were performed according to the UL-94 standard, and the test results are shown in Table 1.

[0094] Table 1

[0095]

[0096] As can be seen from Examples 4, 5 and 6 in Table 1, the PVC / PU modified materials prepared by the present invention have tensile strength greater than 31 MPa and elongation at break greater than 390%. After aging, the tensile strength is greater than 27 MPa and the elongation at break is greater than 360%, which shows excellent tensile properties and elongation at break. Moreover, the flame retardant rating remains at V-0 after aging.

[0097] Comparative Example 1 is a comparative example without modified flame retardant and antioxidant. As can be seen from the data in Table 1, its tensile strength after aging is 18.3 MPa, its elongation at break is 303%, and its flammability rating (UL-94) is V-2.

[0098] Comparative Example 2 is a comparative example different from Example 5. The difference is that the modified flame retardant and antioxidant is replaced with an equal weight of intermediate 1 prepared in step S1 of Example 2. As can be seen from the data in Table 1, its tensile strength after aging is 23.1 MPa, its elongation at break is 331%, and its flammability rating (UL-94) is V-2.

[0099] Comparative Example 3 is a comparative example different from Example 5. The difference is that the modified flame retardant and antioxidant is replaced with an equal weight of intermediate 2 prepared in step S2 of Example 2. As can be seen from the data in Table 1, its tensile strength after aging is 24.5 MPa, its elongation at break is 342%, and its flammability rating (UL-94) is V-2.

[0100] Comparative Example 4 is a comparative example different from Example 5. The difference is that the modified flame retardant and antioxidant is replaced with an equal weight of intermediate 3 prepared in step S3 of Example 2. As can be seen from the data in Table 1, its tensile strength after aging is 18.7 MPa, its elongation at break is 310%, and its flammability rating (UL-94) is V-0.

[0101] Comparative Example 5 is a comparative example different from Example 5. The difference is that the modified flame retardant and antioxidant was replaced with 36.73g of intermediate 2 (prepared in step S2 of Example 2) and 23.27g of intermediate 3 (prepared in step S3 of Example 2). As can be seen from the data in Table 1, its tensile strength after aging is 23.8MPa, its elongation at break is 337%, and its flammability rating (UL-94) is V-1.

[0102] The modified flame retardant and antioxidant added in Comparative Example 6 has a number-average molecular weight of 15680. As can be seen from the data in Table 1, its tensile strength after aging is 26.0 MPa, its elongation at break is 351%, and its flammability rating (UL-94) is V-0.

[0103] The modified flame retardant and antioxidant added in Comparative Example 7 has a number-average molecular weight of 40,180. As can be seen from the data in Table 1, its tensile strength after aging is 25.8 MPa, its elongation at break is 349%, and its flammability rating (UL-94) is V-0.

[0104] Comparative Example 8 is a PVC / PU material prepared using the raw materials of Example 5 of Chinese Invention Patent Publication No. CN110511506A and the process of this application. As can be seen from the data in Table 1, its tensile strength after aging is 23.2 MPa, its elongation at break is 335%, and its flammability rating (UL-94) is V-2.

[0105] Comparative Example 9 used N-(4-anilinephenyl)-methacrylamide and intermediate 3 prepared in Example 2 to obtain a modified flame retardant and anti-aging agent. As can be seen from the data in Table 1, the tensile strength and elongation at break of the PVC / PU material after aging are not as good as those in Examples 4-6.

[0106] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. However, any modifications, alterations, and variations made by those skilled in the art without departing from the scope of the present invention based on the disclosed technical content are equivalent embodiments of the present invention. Furthermore, any modifications, alterations, and variations made to the above embodiments based on the essential technology of the present invention are still within the protection scope of the present invention.

Claims

1. A PVC / PU modified material, characterized in that, The raw materials include the following weight parts: PVC: 80-100 parts, PU: 30-40 parts, Plasticizer: 10-20 parts, Modified flame-retardant antioxidant: 4-8 parts, Stabilizer: 2-4 parts, Lubricant: 3-5 parts. The modified flame-retardant antioxidant is prepared by the following method: S1: Toluene, trichloro cyanuric acid are sequentially added to the reactor, stirred and mixed at 0-5℃, then N-phenyl-p-phenylenediamine is added, Na2CO3 aqueous solution is added dropwise, reacted for 3-5h, N-phenyl-p-phenylenediamine is added again, and reacted for 44-48h at room temperature to obtain intermediate 1; S2: Toluene, intermediate 1 are sequentially added to the reactor, stirred and mixed at 90-95℃, then 1-amino-10-undecene is added, Na2CO3 aqueous solution is added dropwise, and reacted for 12-18h to obtain intermediate 2; S3: Chloroform, 1-amino-10-undecene are sequentially added to the reactor under nitrogen protection, stirred and mixed at room temperature, Na2CO3 aqueous solution is added dropwise, reacted for 1-2h, then diphenylphosphinic chloride is added, and reacted for 2-4h at room temperature to obtain intermediate 3; S4: Tetrahydrofuran, intermediate 2, intermediate 3, and azobisisobutyronitrile are sequentially added to the reaction container under nitrogen protection, stirred and mixed, heated to 60-80℃, and reacted for 14-18h to obtain the modified flame-retardant antioxidant; In step S1, the mass ratio of the toluene, trichloro cyanuric acid, the first added N-phenyl-p-phenylenediamine, the second added N-phenyl-p-phenylenediamine, and Na2CO3 aqueous solution is 300:(18-22):(18-20):(18-20):(100-120); In step S4, the mass ratio of the tetrahydrofuran, intermediate 2, intermediate 3, and azobisisobutyronitrile is 120:(28-32):(18-20):(0.14-0.18).

2. The PVC / PU modified material according to claim 1, characterized in that, The number average molecular weight of the modified flame-retardant antioxidant is 20000-35000.

3. The PVC / PU modified material according to claim 1, characterized in that, In step S2, the mass ratio of the toluene, intermediate 1, 1-amino-10-undecene, and Na2CO3 aqueous solution is 350:(46-50):(18-20):(50-60).

4. The PVC / PU modified material according to claim 1, characterized in that, In step S3, the mass ratio of the chloroform, 1-amino-10-undecene, diphenylphosphinic chloride, and Na2CO3 aqueous solution is 150:(15-19):(22-26):(50-70).

5. The PVC / PU modified material according to claim 1, characterized in that, The plasticizer is one of diisononyl phthalate, tri-n-butyl citrate, and dioctyl adipate.

6. The PVC / PU modified material according to claim 1, characterized in that, The stabilizer is one of calcium stearate, zinc stearate, and barium stearate.

7. The PVC / PU modified material according to claim 1, characterized in that, The lubricant is one of microcrystalline wax, oxidized paraffin wax, and polyethylene wax.

8. A process for the preparation of the PVC / PU-modified material according to any one of claims 1 to 7, characterized in that The method includes the following steps: S1: The following are weighed by weight parts: PVC: 80-100 parts, PU: 30-40 parts, plasticizer: 10-20 parts, Modified flame-retardant antioxidant: 4-8 parts, stabilizer: 2-4 parts, lubricant: 3-5 parts; S2: adding PVC, PU, plasticizer, modified flame-retardant antioxidant, stabilizer and lubricant into a high-speed blender, stirring at 100-140 DEG C for 20-30 min, and then extruding and granulating through a double-screw extruder, to obtain the PVC / PU modified material; the partition temperature of the double-screw extruder is: 175-185 DEG C for feeding section, 165-175 DEG C for compression section, 165-175 DEG C for melting section, 160-170 DEG C for metering section, 170-180 DEG C for extrusion die body section, and 180-200 DEG C for die section.

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