CN104629195B - A kind of hot water pipe polybutene alloy PP Pipe Compound and preparation method thereof - Google Patents

Abstract

The invention relates to a special polybutene alloy pipe material for hot and cold water pipes and a preparation method thereof, belonging to the field of polymer materials. Its components include polybutene alloy, antioxidant, halogen absorbing agent, light stabilizer, color masterbatch, and nucleating agent; the preparation method is to mix polybutene alloy, antioxidant, halogen absorbing agent, light stabilizer, The nucleating agent and color masterbatch are uniformly mixed with a high-speed mixing mixer, extruded and granulated to obtain the special material for polybutene alloy pipes for hot and cold water pipes. On the basis of maintaining the impact resistance of polybutene, excellent environmental stress crack resistance and heat creep resistance, the special material for polybutene alloy pipes has greatly improved tensile strength and flexural modulus, and can be used as cold and hot Water pipes and fittings materials used.

Description

A special polybutene alloy material for hot and cold water pipes and its preparation method

technical field

The invention relates to a special polybutene alloy pipe material for hot and cold water pipes, a preparation method and application thereof, and belongs to the field of polymer materials, especially the processing and application of polymer materials.

Background technique

Because polypropylene PP is light in weight, high in strength, insoluble in common solvents at room temperature, resistant to chemical corrosion, non-toxic, recyclable, and environmentally friendly, it can be used as a piping material for construction piping and industrial piping. However, polypropylene is a quasi-tough material with high notch sensitivity, poor impact performance at room temperature or low temperature, and low temperature resistance. Especially, the working temperature and working pressure are directly related to its service life, which greatly limits its application in the field of pipes. application.

In the traditional polypropylene modification technology, the blending of rubber or elastomer with PP can improve its impact resistance, but at the same time greatly reduce the tensile strength and bending strength, making it difficult to achieve a comprehensive balance of strength and toughness. In the crystal structure of PP, the β crystal form PP has excellent impact properties, and other mechanical properties are not significantly lower than those of the α crystal form. It can be used as a toughening application and has become an important development in the field of polypropylene pipes. direction.

CN 103171068 discloses improving the impact resistance of polypropylene pipes by controlling the cooling box. CN103930481 discloses that a polypropylene blend and a propylene copolymer with β-nucleation effect are prepared by staged polymerization using a single-site catalyst and a Z-N catalyst system, and improved impact resistance is obtained. Chinese invention patents CN201210104449.3 and CN201310496215 disclose the use of block polypropylene and copolymerized polypropylene as the resin matrix to prepare cold water pipe materials, and clarify the ingredient system and processing methods such as fillers. Chinese invention patents CN201110368990, CN201310112454, CN201019026051, CN200510017644, etc. disclose methods of using whiskers such as β crystal nucleating agents, silicates, aluminates, magnesium salts, etc., so that the processed polypropylene has more β crystal forms PP, which improves its impact resistance and can be used in pipes. However, the dispersion and phase interface of the β crystal nucleating agent in melt blending with polypropylene are the main problems affecting the final properties of homopolypropylene. Polybutene resin has excellent creep resistance and environmental stress crack resistance, and can be used as hot and cold water pipes or pipe fittings. However, due to the crystallization of polybutene in the melt, there will be a transformation from crystal form II to crystal form I, which takes a long time, thereby limiting its processing and application. There are many ways to shorten the curing time. Japanese Patent No. 2618469 discloses the method of adding propylene homopolymer and HDPE to shorten the transition period, but its performance becomes worse. Chinese invention patent ZL 200410032739.7 discloses a composition that uses acetylene black as a nucleating agent to promote the inherent crystal transformation phenomenon of 1-butene homopolymer or 1-butene copolymer, while improving its resistance to chlorine water.

Chinese invention patent 01142929.1 discloses a butene and a copolymer of butene and higher α-olefins and polypropylene resin to prepare a polybutene resin composition through melt kneading and physical blending, and produce a polybutene resin composition that can be used for hot and cold water The field of pipes and pipe fittings.

Chinese invention patent CN2013106486926 uses copolymerized polypropylene as the matrix material to prepare a pipe with impact resistance, and adds melamine resin to improve its water resistance. Chinese invention patent CN201210398867 discloses that polypropylene is physically blended with a certain amount of polyethylene and high-cis-butadiene rubber to prepare a high-impact polypropylene pipe material. However, due to the addition of melamine resin or butadiene rubber, it is very difficult to recycle the pipe material. At the same time, when two or more polymers are physically blended, the mixing and dispersing effect has a great correlation with the bulk properties, surface and interface properties, compatibility and phase morphology of the polymers. Under the premise, the performance of the final product cannot be effectively improved.

Chinese invention patent ZL 201010198121.3 discloses a new type of polybutene alloy material, which consists of homopolypropylene, homopolybutene and butene-propylene copolymer. The polybutene alloy shortens the molding cycle as much as possible and improves its strength and modulus without affecting the high temperature creep resistance and flexibility of the polybutene resin. At the same time, the preparation of polybutene alloy by in-situ polymerization in the kettle can not only effectively improve the two-phase dispersion and phase interface morphology existing in the physical blending of polybutene and polypropylene, but also affect the performance of polybutene alloy products. , at the same time, the in-situ synthesis of a small amount of copolymer can significantly improve the phase interface problem of the alloy, and at the same time, parameters such as the component content, molecular weight and distribution of the alloy can be adjusted by adjusting the polymerization process parameters. The patent mentions that polybutene alloys can be used in the field of water pipes or polypropylene toughening materials, but does not involve the formulation and processing of specific pipe materials.

Contents of the invention

The object of the present invention is to provide a special polybutene pipe material for cold and hot water pipes with polybutene alloy as the main component, its preparation method and application, the special polybutene alloy pipe material maintains the impact resistance of polybutene , Excellent resistance to environmental stress cracking and thermal creep resistance, while the tensile strength and flexural modulus are greatly improved, it can be used as hot and cold water pipes and pipe fittings.

The present invention has improved impact resistance, environmental stress cracking resistance and thermal creep resistance, and a formula of special polybutene alloy pipe material for hot and cold water pipes with higher tensile strength and flexural modulus. Parts by weight:

Polybutene alloy resin 100 parts

Antioxidant 0.2～9 parts

Halogen absorbing agent 0.01～0.2 parts

Light stabilizer 0.01～2 parts

Color masterbatch 0.1～5 parts

Nucleating agent 0.01～6 parts

The polybutene alloy resin is a heterogeneous and multi-component in-kettle alloy resin, wherein the weight percentage of high isotactic polybutene (iPB) is 66% to 98.98%, and the weight percentage of high isotactic polypropylene (iPP) is The weight percentage of polybutene-polypropylene block copolymer is 0.01-5%, and the weight percentage of random polybutene and random polypropylene is 0.01-4%. A small amount of block copolymer, random polybutene and random polypropylene can play the role of auxiliary nucleating agent.

The melt mass flow rate of the polybutene alloy resin is 0.5-2 g/10 min under the condition of 190° C. and a weight of 2.16 kg.

Described antioxidant is made up of main antioxidant and auxiliary antioxidant; One or more compound in main antioxidant BHT, Hostanox3, 2246, 1010, 1076; Auxiliary antioxidant is 168, 626, One or more compounds of 9228, DLTDP, DSTDP, DMTDP, DTDTP; the weight ratio of primary antioxidant to secondary antioxidant is 1:1-4. The total parts of the antioxidant is calculated based on 100 parts by weight of the polybutene alloy resin, and is 0.1 to 9 parts by weight, preferably 0.3 to 5 parts by weight.

The nucleating agent is dibenzylidene sorbitol, bis(p-methylbenzylidene) sorbitol, 2,2'-methylenebis(4,6-tert-butylphenol) aluminum phosphonate, 2,2 Sodium '-methylenebis(4,6-tert-butylphenol) phosphonate, potassium 2,2'-methylenebis(4,6-tert-butylphenol)phosphonate, diamide compounds and their derivatives One or a mixture of two or more of them. The nucleating agent is used in an amount of 0.01-6 parts by weight based on 100 parts by weight of the resin, preferably 0.3-1 part by weight.

The halogen-absorbing agent is one or more of calcium stearate, sodium stearate or zinc stearate. The amount of the halogen-absorbing agent is 0.01-0.2 parts by weight (calculated on the basis of 100 parts by weight of polybutene alloy resin).

The light stabilizer is one or more of benzophenones or hindered amines. The dosage thereof is 0.01-2 parts by weight (calculated on the basis of 100 parts by weight of polybutene alloy resin).

The color masterbatch comprises the following composition: 40-95 parts by weight of high isotactic polybutene as a matrix resin, 0.1-8 parts by weight of dispersant, 0.1-5 parts by weight of titanium dioxide, 0.001-5 parts by weight of pigment and 0.01-4 parts by weight of anti-aging agent. The dispersing agent is one or two kinds of polyethylene wax and polyethylene glycol.

The special material for polybutene alloy pipe material of the present invention, its preparation method comprises the following steps:

(1) Take each raw material according to the above-mentioned parts by mass, polybutene alloy, antioxidant, halogen absorbing agent, light stabilizer, color masterbatch, nucleating agent batching;

(2) Mix the above-mentioned components in a high-speed mixer for 5 minutes, so that the components are mixed evenly;

(3) Add the homogeneously mixed material in the second step into a twin-screw extruder with an aspect ratio of 30-50:1 to melt and disperse, and extrude to granulate.

The aspect ratio of the twin-screw extruder is 30-50:1.

The extrusion granulation process is as follows: first zone 140-160°C, second zone 160-170°C, third zone 175-185°C, fourth zone 180-200°C, fifth zone 190-230°C, head 190-230°C ℃, rotating speed 10~30r/min, melt pressure 12~20MPa.

The special polybutene alloy pipe material for hot and cold water pipes prepared by the present invention can provide and maintain polybutene impact resistance, excellent environmental stress crack resistance and thermal creep resistance, and at the same time The tensile strength and flexural modulus have been greatly improved, and it can be used as hot and cold water pipes and pipe fittings.

detailed description

The following examples are for better explaining the present invention, but do not limit the claims of the present invention.

Example 1

Components and formulations provided by Table 1 (according to weight percent, the following examples are all the same) weigh the material, after mixing in a high-speed mixer for 5 minutes, in a twin-screw extruder with an aspect ratio of 45 and a diameter of 50 Extrusion granulation to obtain the special material for polybutene alloy resin pipes. The mass content of iPB in the polybutene alloy resin used is 66%, and its melt flow rate (190° C., load 2.16 kg) is 0.5 g/10 min. The temperature of each section of the extruder is: 150°C in zone 1, 165°C in zone 2, 180°C in zone 3, 190°C in zone 4, 210°C in zone 5, 230°C at the head, 20 rpm of extruder, and melt pressure 15MPa.

The performance test results are shown in Table 2.

Comparative example 1

Components and formulations provided by Table 1 (according to weight percent, the following examples are all the same) weigh the material, after mixing in a high-speed mixer for 5 minutes, in a twin-screw extruder with an aspect ratio of 45 and a diameter of 50 Extrusion granulation to obtain polypropylene pipe material. The polypropylene used is a polypropylene resin with an isotacticity greater than 98%, and its melt flow rate (230° C., load 2.16 kg) is 1.2 g/10 min. The temperature of each section of the extruder is: 150°C in zone 1, 165°C in zone 2, 180°C in zone 3, 190°C in zone 4, 210°C in zone 5, 230°C at the head, 20 rpm of extruder, and melt pressure 15MPa.

The performance test results are shown in Table 2.

The difference between Example 1 and Comparative Example 1 is only that the base resin used is different, and all other components, materials and production processes are completely the same. From the results of Example 1 and Comparative Example 1, it can be seen that compared with the special material for polypropylene pipes, the special material for pipes made of polybutene alloy resin has a lower notched impact on the premise that the bending performance and heat distortion temperature are not greatly reduced. Strength and shrinkage are greatly improved.

Component and formula of table 1 embodiment 1 and comparative example 1

components Example 1 Comparative example 1 Polybutene alloy resin/part 100 0 Polypropylene/part 0 100 Nucleating agent TMB/part 1.5 1.5 Antioxidant 1010/part 0.1 0.1 Antioxidant 168/part 0.2 0.2 Halogen absorbing agent/part 0.1 0.1 Light stabilizer/part 0.8 0.8 masterbatch/part 2 2

The performance of the produced material of table 2 embodiment 1 and comparative example 1

Test items unit Example 1 Comparative example 1 The melt flow rate g/10min 0.6 1.5 tensile yield strength MPa 40 39 Shrinkage % 0.2 3 Izod notched impact strength at room temperature KJ/ ^M2 58 3.6 Bending strength MPa 46 50 Flexural modulus MPa 1100 1240 Heat distortion temperature ℃ 103.4 104

Embodiment 2-4

Components and formulations provided by Table 3 (according to weight percent, the following examples are the same) weigh the material, after mixing in a high-speed mixer for 5 minutes, in a twin-screw extruder with an aspect ratio of 45 and a diameter of 50 Extrusion granulation to obtain special materials for polybutene alloy pipes. The temperature of each section of the extruder is: 140-160°C for the first zone, 160-170°C for the second zone, 175-185°C for the third zone, 180-200°C for the fourth zone, 190-230°C for the fifth zone, 190-230°C for the head, The speed is 10~30r/min, and the melt pressure is 12~20MPa.

The performance test results are shown in Table 4.

From the test results in Table 4, it can be seen that through proper proportioning and optimized processing conditions, special polybutene alloy pipe materials that meet the requirements for the use of pipe materials for cold and hot water pipes can be prepared.

Components, formula and process of table 3 embodiment 2～4

The performance of the produced material of table 4 embodiment 2～4

Test items unit Example 2 Example 3 Example 4 tensile yield strength MPa 38 41 43 Shrinkage % 0.4 0.4 0.4 Izod notched impact strength at room temperature J/M 67 60 60 Flexural modulus MPa 430 480 560 Heat distortion temperature ℃ 87 85 88

Comparative example 2～4

Components and formulations provided by Table 5 (according to weight percent, the following examples are the same) weigh the material, after mixing in a high-speed mixer for 5 minutes, in a twin-screw extruder with an aspect ratio of 45 and a diameter of 50 Extrusion granulation to obtain special material for polybutene/polypropylene blended composite pipe. The polybutene used is homopolybutene with an isotacticity of 98%, and its melt flow rate is 0.8g/10min; the polypropylene polypropylene used is impact polypropylene 30R, with an isotacticity of 95%, and its melt flow rate (230°C, load 2.16kg) is 13g/10min. The temperature of each section of the extruder is: 140-160°C for the first zone, 160-170°C for the second zone, 175-185°C for the third zone, 180-200°C for the fourth zone, 190-230°C for the fifth zone, 190-230°C for the head, The speed is 10~30r/min, and the melt pressure is 12-20MPa.

The performance test results are shown in Table 6.

From the comparison of Examples 2-4 with Examples 2-4, it can be seen that the notched impact strength and flexural modulus ratio of the special material for cold and hot water pipes prepared by polybutene alloy, the ratio of physical blending of polybutene/polyethylene The propylene pipe material is much larger, and as the proportion of polypropylene increases, the impact strength decreases significantly. At the same time, as cold and hot water pipes, the Vicat softening temperature of the polybutene/polypropylene blend pipe material prepared by physical blending is low, and its application occasions are limited and its service life is reduced.

Components, formulations and processes of Table 5 Comparative Examples 2 to 4

The performance of the produced material of table 6 comparative examples 2～4

Test items unit Comparative example 2 Comparative example 3 Comparative example 4 tensile yield strength MPa 37 40 38 Shrinkage % 0.6 0.65 0.7 Izod notched impact strength at room temperature J/M 65 53 40 Flexural modulus MPa 358 486 487 Heat distortion temperature ℃ 80 79 78

Claims (9)

1. A special material for polybutene alloy pipes for hot and cold water pipes, characterized in that, it is composed of the following components by weight fraction: Polybutene alloy resin 100 parts Antioxidant 0.2~9 parts Halogen absorbing agent 0.01~0.2 parts Light stabilizer 0.01~2 parts Color masterbatch 0.1~5 parts Nucleating agent 0.01~6 parts; The weight percentage of high isotactic polybutene in the polybutene alloy resin is 66~98.98%, the weight percentage of high isotactic polypropylene is 1~25%, and the polybutene-polypropylene block copolymer The weight percentage is 0.01-5%, and the weight percentage of random polybutene and random polypropylene is 0.01-4%. 2. The special polybutene alloy pipe material for hot and cold water pipes according to claim 1, characterized in that, the polybutene alloy resin has a melt mass flow rate of 0.5~2g/10min. 3. The special polybutene alloy pipe material for hot and cold water pipes according to claim 1, wherein the antioxidant is compounded by one or more of the main antioxidants BHT, 2246, 1010, 1076 The blended and auxiliary antioxidant is composed of one or more of 168, 626, 9228, DLTDP, DSTDP, DMTDP, and DTDTP; the weight ratio of the main antioxidant to the auxiliary antioxidant is 1:1~4. 4. The special material for polybutene alloy pipes for hot and cold water pipes according to claim 1, wherein the halogen absorbing agent is one of calcium stearate, sodium stearate or zinc stearate or Several kinds. 5. The special material for polybutene alloy pipes for hot and cold water pipes according to claim 1, wherein the light stabilizer is one or more of benzophenones or hindered amines. 6. The special material for polybutene alloy pipes for hot and cold water pipes according to claim 1, wherein the nucleating agent is dibenzylidene sorbitol, di(p-methylbenzylidene) sorbitol, 2 ,2'-Methylenebis(4,6-tert-butylphenol)aluminum phosphonate, 2,2'-Methylenebis(4,6-tert-butylphenol)sodium phosphonate, 2,2'- One or two or more kinds of potassium methylene bis(4,6-tert-butylphenol)phosphonate, diamide compounds and their derivatives. 7. The special polybutene alloy pipe material for hot and cold water pipes according to claim 1, wherein the color masterbatch comprises the following components by weight: 40-95 parts of high isotactic polybutene; 0.1-8 parts of polyethylene wax or polyethylene glycol as dispersant; 0.1-5 parts of titanium dioxide; 0.001-5 parts of pigment; 0.01-4 parts of anti-aging agent. 8. A method for preparing the special polybutene alloy pipe material for hot and cold water pipes according to any one of claims 1 to 7, characterized in that, the specific steps are: The first step is to weigh each raw material in proportion: polybutene alloy, antioxidant, halogen absorbing agent, light stabilizer, color masterbatch, and nucleating agent ingredients; In the second step, the above-mentioned components are mixed uniformly in a mixer; The third step is to add the homogeneously mixed material in the second step into a twin-screw extruder with a length-to-diameter ratio of 30~50:1 to melt and disperse, extrude and granulate. The process is: first zone 140~160°C, second zone 160~170℃, 175~185℃ in the third zone, 180~200℃ in the fourth zone, 190~230℃ in the fifth zone, 190~230℃ in the head, 10-30r/min rotating speed, 12-20MPa melt pressure. 9. An application of the special polybutene alloy pipe material for hot and cold water pipes according to any one of claims 1 to 7, characterized in that it is used in the manufacture of hot and cold water pipes.