A high-toughness impact-resistant PPR pipe and preparation method thereof

Abstract

The present invention discloses a high-toughness impact-resistant PPR pipe, comprising the following raw materials in mass percentage: 25-40% of cardanol grafted PPR, 12-16% of glycidyl methacrylate grafted POE, 0.1-0.3% of quaternary ammonium salt catalyst, 0.5-2% of coupling agent, 1-3% of antioxidant, and the balance is PPR. The present invention also discloses a preparation method of the above-mentioned high-toughness impact-resistant PPR pipe. The PPR pipe prepared by the present invention not only has the characteristics of high toughness and excellent low-temperature impact resistance, but also has high tensile strength and excellent mechanical properties, which can better meet the needs of practical applications and improve the durability of the pipe.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a high-toughness impact-resistant PPR pipe and a preparation method thereof. Background Art

[0002] Random copolymer polypropylene (PPR) is obtained by copolymerizing propylene and a small amount of ethylene under certain temperature, pressure and catalyst, and is a commonly used plastic pipe material. Compared with traditional cast iron pipes and galvanized steel pipes, PPR pipes have the advantages of light weight, pressure resistance, corrosion resistance, no scaling, simple construction, energy saving and environmental protection, and moderate price. They are widely used in the fields of building hot and cold water, industrial fluid transportation, and agricultural irrigation. However, PPR has poor impact toughness, especially in low temperature environments in winter, its impact resistance will be significantly deteriorated, resulting in pipeline embrittlement and damage, and poor adaptability to the climate, which limits its promotion and application. At present, the methods to improve the low-temperature impact resistance of PPR mainly include elastomer toughening, β-nucleating agent toughening, nanoparticle toughening, etc. POE is a widely used toughening agent with good comprehensive performance. However, due to the large amount of addition and the introduction of elastomer toughening will significantly reduce the tensile strength, the strength of PPR pipes toughened by POE is often not ideal. Summary of the invention

[0003] The purpose of the present invention is to make up for the defects of the existing technology and provide a high-toughness impact-resistant PPR pipe and a preparation method thereof. The prepared PPR pipe has the characteristics of high toughness, excellent low-temperature impact resistance, and high tensile strength, which can meet the actual application needs.

[0004] The present invention is achieved through the following technical solutions:

[0005] A high-toughness impact-resistant PPR pipe comprises the following raw materials in percentage by mass: 25-40% of cardanol grafted PPR, 12-16% of glycidyl methacrylate grafted POE, 0.1-0.3% of quaternary ammonium salt catalyst, 0.5-2% of coupling agent, 1-3% of antioxidant, and the balance of PPR.

[0006] Preferably, the preparation method of the cardanol-grafted PPR is: after mixing PPR, cardanol and an initiator, adding them into an extruder for melt extrusion, cooling and granulating to obtain the product.

[0007] Preferably, the mass ratio of the PPR, cardanol and initiator is 100:(3-4):(0.15-0.5).

[0008] Among them, cardanol is the main component of cashew nut shell oil. It is a natural biomass phenol with unique long-chain alkanes. Its benzene ring contains unsaturated long side carbon chains and phenolic hydroxyl groups. One of the structures of cardanol is as follows (CAS NO: 37330-39-5):

[0009]

[0010] Preferably, the initiator is one of dicumyl peroxide, benzoyl peroxide, di-tert-butyl peroxide, or a mixture of several thereof.

[0011] Preferably, the temperature of the melt extrusion is 170-180°C.

[0012] Preferably, the grafting rate of the glycidyl methacrylate grafted POE is 1-2%, and the melt flow rate at 190° C. and 2.16 kg is 2-5 g / 10 min.

[0013] Among them, the structural formula of POE-g-GMA (glycidyl methacrylate grafted POE) is as follows:

[0014]

[0015] Preferably, the quaternary ammonium salt catalyst is one of tetramethylammonium bromide, tetraethylammonium bromide, tetramethylammonium chloride, and tetraethylammonium chloride, or a mixture of several of them.

[0016] Preferably, the coupling agent is a silane coupling agent, a titanate coupling agent or a mixture thereof.

[0017] Preferably, the antioxidant is one of antioxidant 1010, antioxidant 1076, and antioxidant 168, or a mixture of several of them.

[0018] A method for preparing the high-toughness impact-resistant PPR pipe comprises the following steps: weighing PPR, cardanol grafted PPR, glycidyl methacrylate grafted POE, quaternary ammonium salt catalyst, coupling agent, and antioxidant by mass percentage, mixing them evenly, adding them into an extruder for melt extrusion, cooling and granulating to obtain the pipe.

[0019] Preferably, the temperature of the melt extrusion is 180-220°C.

[0020] The advantages of the present invention are:

[0021] The invention uses PPR, cardanol grafted PPR, glycidyl methacrylate grafted POE, a coupling agent and an antioxidant as raw materials, and prepares the PPR pipe by melt extrusion granulation. Among them, POE grafted with glycidyl methacrylate contains epoxy groups, which have better adhesion and compatibility with the polymer matrix, and cardanol and PPR are melt-extruded and grafted under the action of an initiator to obtain cardanol grafted PPR, in which benzene rings, phenolic hydroxyl groups and flexible long side carbon chains are introduced into PPR, and the residual ungrafted cardanol can play a certain plasticizing role to improve the flexibility of the material; when PPR, cardanol grafted PPR and glycidyl methacrylate grafted POE and other raw materials are mixed and melt-extruded at high temperature, the phenolic hydroxyl groups can react with the epoxy groups under high temperature to form a new cross-linking structure outside the main chain of POE elastomer and PPR, and the formed cross-linking system can greatly improve the toughness and tensile properties of the PPR material, combined with the plasticizing effect of the residual cardanol and the strengthening effect of the phenyl group, so that the obtained PPR pipe not only has the characteristics of high toughness and excellent low-temperature impact resistance, but also has high tensile strength and excellent mechanical properties, which can better meet the needs of practical applications and improve the durability of the pipe. DETAILED DESCRIPTION

[0022] Example 1

[0023] A high-toughness impact-resistant PPR pipe, comprising the following raw materials in percentage by mass: 30% of cardanol grafted PPR, 15% of glycidyl methacrylate grafted POE, 0.2% of tetraethylammonium bromide, 1% of silane coupling agent KH-560, 1% of antioxidant 10101%, 0.5% of antioxidant 168, and 52.3% of PPR;

[0024] Among them, the grafting rate of glycidyl methacrylate grafted POE is 1%, and the melt flow rate at 190°C and 2.16kg is 4g / 10min; the preparation method of cardanol grafted PPR is: after mixing PPR, cardanol, and diisopropylbenzene peroxide in a mass ratio of 100:4:0.5, adding them into a twin-screw extruder, melt-extrude at 170-180°C, cool and granulate to obtain.

[0025] Preparation of the above-mentioned high-toughness and impact-resistant PPR pipe: PPR, cardanol grafted PPR, glycidyl methacrylate grafted POE, tetraethylammonium bromide, silane coupling agent kh-560, antioxidant 1010, and antioxidant 168 are weighed by mass percentage and mixed evenly, added to a twin-screw extruder, melt-extruded at 180-220°C, cooled and granulated to obtain the obtained product.

[0026] Example 2

[0027] A high-toughness impact-resistant PPR pipe, comprising the following raw materials in percentage by mass: 25% of cardanol grafted PPR, 12% of glycidyl methacrylate grafted POE, 0.1% of tetramethylammonium bromide, 0.5% of silane coupling agent kh-570, 2% of antioxidant 10102%, 1681% of antioxidant, and 59.4% of PPR;

[0028] Among them, the grafting rate of glycidyl methacrylate grafted POE is 1%, and the melt flow rate at 190°C and 2.16kg is 4g / 10min; the preparation method of cardanol grafted PPR is: after mixing PPR, cardanol and di-tert-butyl peroxide in a mass ratio of 100:3.5:0.15, adding them into a twin-screw extruder, melt-extrude at 170-180°C, cool and granulate to obtain.

[0029] Preparation of the above-mentioned high-toughness and impact-resistant PPR pipe: weigh PPR, cardanol grafted PPR, glycidyl methacrylate grafted POE, tetramethylammonium bromide, silane coupling agent kh-570, antioxidant 1010, and antioxidant 168 by mass percentage, mix them evenly, add them to a twin-screw extruder, melt-extrude at 180-220°C, cool and granulate to obtain the product.

[0030] Example 3

[0031] A high-toughness impact-resistant PPR pipe, comprising the following raw materials in percentage by mass: 40% of cardanol grafted PPR, 16% of glycidyl methacrylate grafted POE, 0.3% of tetraethylammonium bromide, 2% of titanate coupling agent TMC-20, 0.5% of antioxidant 1010, 0.5% of antioxidant 168, and 40.7% of PPR;

[0032] Among them, the grafting rate of glycidyl methacrylate grafted POE is 1%, and the melt flow rate at 190°C and 2.16kg is 4g / 10min; the preparation method of cardanol grafted PPR is: after mixing PPR, cardanol and benzoyl peroxide in a mass ratio of 100:3:0.3, adding them into a twin-screw extruder, melt-extrude at 170-180°C, cool and granulate to obtain.

[0033] Preparation of the above-mentioned high-toughness and impact-resistant PPR pipe: PPR, cardanol grafted PPR, glycidyl methacrylate grafted POE, tetraethylammonium bromide, titanate coupling agent TMC-201, antioxidant 1010, and antioxidant 168 are weighed by mass percentage, mixed evenly, added into a twin-screw extruder, melt-extruded at 180-220°C, cooled and granulated to obtain the obtained product.

[0034] Comparative Example 1

[0035] A PPR pipe comprises the following raw materials in percentage by mass: 15% of glycidyl methacrylate grafted POE, 0.2% of tetraethylammonium bromide, 1% of silane coupling agent KH-560, 1% of antioxidant 10101%, 0.5% of antioxidant 168, and 82.3% of PPR;

[0036] The grafting rate of glycidyl methacrylate grafted POE is 1%, and the melt flow rate at 190° C. and 2.16 kg is 4 g / 10 min.

[0037] Preparation of the above-mentioned PPR pipe: PPR, glycidyl methacrylate grafted POE, tetraethylammonium bromide, silane coupling agent KH-560, antioxidant 1010, and antioxidant 168 are weighed by mass percentage, mixed evenly, added into a twin-screw extruder, melt-extruded at 180-220°C, cooled and granulated to obtain the obtained pipe.

[0038] Comparative Example 2

[0039] A PPR pipe comprises the following raw materials in percentage by mass: 30% of cardanol grafted PPR, 15% of POE, 0.2% of tetraethylammonium bromide, 1% of silane coupling agent KH-560, 1% of antioxidant 10101%, 0.5% of antioxidant 168, and 52.3% of PPR;

[0040] The preparation method of cardanol grafted PPR is as follows: PPR, cardanol and dicumyl peroxide are mixed in a mass ratio of 100:4:0.5, added into a twin-screw extruder, melt-extruded at 170-180° C., cooled and granulated to obtain the product.

[0041] Preparation of the above-mentioned PPR pipe: PPR, cardanol grafted PPR, POE, tetraethylammonium bromide, silane coupling agent kh-560, antioxidant 1010, and antioxidant 168 are weighed by mass percentage, mixed evenly, added into a twin-screw extruder, melt-extruded at 180-220°C, cooled and granulated to obtain the obtained product.

[0042] Comparative Example 3

[0043] A PPR pipe comprises the following raw materials in percentage by mass: POE 15%, silane coupling agent kh-5601%, antioxidant 10101%, antioxidant 1680.5%, PPR 82.5%;

[0044] Preparation of the above-mentioned PPR pipe: PPR, POE, silane coupling agent kh-560, antioxidant 1010, and antioxidant 168 are weighed and mixed evenly according to mass percentage, added into a twin-screw extruder, melt-extruded at 180-220°C, cooled and granulated to obtain the obtained product.

[0045] The PPR pipes prepared in Example 1 and Comparative Examples 1-3 were subjected to performance tests, wherein the impact performance test was conducted in accordance with GB / T 1043.1-2008, and the tensile performance test was conducted in accordance with GB / T 1040-2006; the test results are shown in Table 1:

[0046] Table 1 PPR pipe performance test results

[0047]

[0048] It can be seen from Table 1 that the tensile strength and low-temperature impact resistance of the PPR pipe of the present invention are greatly improved.

Claims

1. A high-toughness impact-resistant PPR pipe, characterized in that: The invention comprises the following raw materials in percentage by weight: 25-40% of cardanol grafted PPR, 12-16% of glycidyl methacrylate grafted POE, 0.1-0.3% of quaternary ammonium salt catalyst, 0.5-2% of coupling agent, 1-3% of antioxidant and the balance of PPR.

2. The high-toughness impact-resistant PPR pipe according to claim 1 is characterized in that: The preparation method of the cardanol-grafted PPR is as follows: PPR, cardanol and an initiator are mixed, added into an extruder for melt extrusion, and cooled for granulation to obtain the product.

3. The high-toughness impact-resistant PPR pipe according to claim 2 is characterized in that: The mass ratio of the PPR, cardanol and initiator is 100:(3-4):(0.15-0.5).

4. The high-toughness impact-resistant PPR pipe according to claim 2, characterized in that: The initiator is one of dicumyl peroxide, benzoyl peroxide and di-tert-butyl peroxide or a mixture of several of them.

5. The high-toughness impact-resistant PPR pipe according to claim 2, characterized in that: The temperature of the melt extrusion is 170-180°C.

6. The high-toughness impact-resistant PPR pipe according to claim 1, characterized in that: The grafting rate of the glycidyl methacrylate grafted POE is 1-2%, and the melt flow rate at 190° C. and 2.16 kg is 2-5 g / 10 min.

7. The high-toughness impact-resistant PPR pipe according to claim 1, characterized in that: The quaternary ammonium salt catalyst is one of tetramethylammonium bromide, tetraethylammonium bromide, tetramethylammonium chloride and tetraethylammonium chloride, or a mixture of several of them.

8. The high-toughness impact-resistant PPR pipe according to claim 1, characterized in that: The coupling agent is a silane coupling agent, a titanate coupling agent or a mixture thereof; the antioxidant is one of antioxidant 1010, antioxidant 1076, and antioxidant 168, or a mixture of several thereof.

9. A method for preparing a high-toughness impact-resistant PPR pipe according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: weighing PPR, cardanol grafted PPR, glycidyl methacrylate grafted POE, quaternary ammonium salt catalyst, coupling agent and antioxidant by mass percentage, mixing them evenly, adding them into an extruder for melt extrusion, cooling and granulating to obtain the product.

10. The method for preparing high-toughness impact-resistant PPR pipe according to claim 9, characterized in that: The temperature of the melt extrusion is 180-220°C.

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