A fire-retardant temperature-resistant reinforced and toughened alloy pipe and a preparation method thereof

Abstract

The application discloses a kind of fire-retardant temperature-resistant reinforced toughened alloy pipes and preparation method thereof, belong to alloy pipe technical field.Alloy pipe includes inner layer pipe and outer layer pipe, inner layer pipe component includes the following weight parts: polypropylene 70-80 parts, nylon 10-15 parts, ABS 7-10 parts, compatible agent 0.5-2 parts, toughening agent 0.5-4 parts, antioxidant 0.05-0.1 part, flame retardant 5-30 parts;Outer layer pipe component includes the following weight parts: polypropylene 70-80 parts, nylon 10-15 parts, ABS 7-10 parts, compatible agent 0.5-2 parts, toughening agent 0.5-4 parts, antioxidant 0.05-0.1 part.Wherein compatible agent is modified hollow glass microsphere, greatly improve the compatibility of system, strengthen the mechanical strength and mechanical properties of alloy pipe.The alloy pipe of the application has excellent toughness and rigidity and aging resistance, heat resistance and flame resistance, greatly widen the use of product.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of alloy pipes, and particularly relates to a flame-retardant temperature-resistant reinforced and toughened alloy pipe and a preparation method thereof. BACKGROUND

[0002] Alloy corrugated pipes are commonly seen in daily life and are mainly used in the fields of power supply, drainage, sewage discharge, chemical delivery, hot air discharge and the like. The corrugated pipes on the market are mainly extruded from high polymer materials such as PE, PP and PA and are widely used as sleeve pipes for wire harnesses in automobiles, household appliances and mechanical equipment. Different base materials are selected to produce corrugated pipes as sleeve pipes for wire harnesses according to the environment and conditions.

[0003] However, with the increasing personalized needs of consumers, people have higher and higher requirements for alloy corrugated pipes. The existing alloy corrugated pipes generally have the defect of poor flame retardancy. Once a fire occurs, the alloy corrugated pipes are very easy to burn, which brings great safety hazards and also causes great economic losses. Meanwhile, the strength of the polypropylene alloy pipe is not high in the use environment at a higher temperature, and the strength, temperature resistance and friction resistance are not good compared with metal pipes, thereby limiting the application of the polypropylene alloy pipe in some special fields. Therefore, it is necessary to develop an alloy pipe with good flame-retardant effect, strength and toughness, so as to greatly broaden the application field of the alloy pipe. SUMMARY

[0004] The application aims to provide a flame-retardant temperature-resistant reinforced and toughened alloy pipe and a preparation method thereof, so as to solve the problem of low strength of the alloy pipe.

[0005] The object of the application can be achieved by the following technical scheme.

[0006] A flame-retardant temperature-resistant reinforced and toughened alloy pipe, which comprises an inner layer pipe and an outer layer pipe.

[0007] The inner layer pipe comprises the following components in parts by weight: 70-80 parts of polypropylene, 10-15 parts of nylon, 7-10 parts of ABS, 0.5-2 parts of a compatibilizer, 0.5-4 parts of a toughening agent, 0.05-0.1 parts of an antioxidant and 5-30 parts of a flame retardant.

[0008] The outer layer pipe comprises the following components in parts by weight: 70-80 parts of polypropylene, 10-15 parts of nylon, 7-10 parts of ABS, 0.5-2 parts of a compatibilizer and 0.5-4 parts of a toughening agent.

[0009] The compatibilizer is modified hollow glass microbeads and is prepared by the following steps.

[0010] The hydroxylated hollow glass microspheres, ethyl acrylate and dibenzoyl peroxide are added into ethyl acetate, and then heated and stirred under nitrogen protection to react, centrifuged, washed, and vacuum dried to obtain pretreated hollow glass microspheres; glycidyl methacrylate is added into ethyl acetate, and then heated and stirred, and the pretreated hollow glass microspheres and an initiator are added and continuously stirred, and then centrifuged and vacuum dried to obtain modified hollow glass microspheres.

[0011] Further, the use amount ratio of the hydroxylated hollow glass microspheres, ethyl acrylate, dibenzoyl peroxide and ethyl acetate is 1g:0.6:0.25g:50mL; the use amount ratio of glycidyl methacrylate, ethyl acetate, pretreated hollow glass microspheres and an initiator is 0.15-0.25g:50mL:0.5g:0.24g.

[0012] Further, the initiator is one of potassium persulfate and ammonium persulfate.

[0013] Further, the hydroxylated hollow glass microspheres are prepared by the following steps:

[0014] The hollow glass microspheres are added into a NaOH solution, heated and stirred, washed, filtered under reduced pressure, and dried to obtain the hydroxylated hollow glass microspheres.

[0015] Further, the use amount ratio of the hollow glass microspheres and the NaOH solution is 1.5g:25mL; and the particle size of the hollow glass microspheres is 20-200μm.

[0016] Further, the toughening agent is one of ethylene-propylene block copolymer and styrene-butadiene thermoplastic elastomer.

[0017] Further, the antioxidant is one or both of antioxidant 1010 and antioxidant 168 mixed in any ratio.

[0018] Further, the flame retardant is one or more of aluminum hydroxide, magnesium hydroxide and ammonium polyphosphate.

[0019] The application also provides a preparation method of the flame-retardant temperature-resistant reinforced and toughened alloy pipe, which comprises the following steps:

[0020] A1, an inner layer material for an inner layer pipe is prepared by weighing polypropylene, nylon, ABS, a compatilizer, a toughening agent, an antioxidant and a flame retardant according to weight parts, and then stirring and mixing at 110-120℃ for 0.5-1h at a stirring rate of 3200-3500r / min to obtain the inner layer material for the inner layer pipe;

[0021] Preparation of the outer layer material for the outer layer pipe: the polypropylene, nylon, ABS, compatibilizer, toughening agent and antioxidant are weighed in parts by weight, mixed under stirring at a temperature of 110-120 DEG C, the stirring time is 0.5-1h, and the stirring rate is 3200-3500r / min, to obtain the outer layer material for the outer layer pipe;

[0022] A2, preparation of the inner layer pipe: the inner layer material in A1 is introduced into an extruder, and is extrusion molded to obtain the inner layer pipe;

[0023] A3, preparation of the pipe material: the obtained inner layer pipe is arranged in a mold, and the outer layer material is introduced into an extruder, melt compounded and extrusion molded to obtain the flame-retardant temperature-resistant reinforced toughened alloy pipe material.

[0024] Further, in A2 and A3, the barrel temperature of the extruder is: the first zone is 120-130 DEG C, the second zone is 130-140 DEG C, the third zone is 145-155 DEG C, the fourth zone is 165-185 DEG C, the fifth zone is 195-210 DEG C, the sixth zone temperature is 210-225 DEG C, and the screw rotation speed is 15-35r / min.

[0025] In the above technical solution, the nylon resin has the advantages of high strength, flame retardation, easy processing and the like, and after being blended with the polypropylene resin, the performance defects of the polypropylene, such as poor aging resistance, large low-temperature brittleness and large linear expansion coefficient, can be effectively improved, and a high-strength and high-toughness composite material is obtained.

[0026] In the above technical solution, the added ABS can compatibilize the blend and improve the mechanical properties of the blend, in addition, can promote the combination of the two phases, play a compatibilization role, and further increase the compatibility.

[0027] In the above technical solution, the aluminum hydroxide and magnesium hydroxide as the flame retardant have the characteristics of low smoke, non-toxicity and green environmental protection; the ammonium polyphosphate as the phosphorus-based halogen-free flame retardant has the advantages of low smoke, low toxicity, low price and less harm to the environment, and can achieve excellent flame retardation effect.

[0028] The beneficial effects of the present application are:

[0029] 1. The hollow glass microbeads are modified in the present application, the dispersibility is improved, and the compatibility with the matrix is improved. As a compatibilizer, the interface interaction occurs by the reaction of the surface containing epoxy functional groups with the amide groups in the nylon, the interfacial tension between the polymers is obviously reduced, the interfacial bonding force between the polymers is improved, and the dispersion of the hollow glass microbeads in the matrix is more uniform; the compatibilization and reinforcement of the microbeads improve the thermal stability, tensile strength and elastic modulus of the blend, and further improve the toughness and strength of the alloy pipe material.

[0030] 2. Modified microspheres can also be used as inorganic lightweight fillers to fill the matrix. After blending with the matrix, they can achieve the effects of toughening, improving temperature resistance, and mechanical reinforcement. Furthermore, the addition of microspheres gives the material a certain sound absorption effect, providing noise reduction in drainage and other engineering projects, thus expanding its application range. The flame-retardant, temperature-resistant, reinforced, and toughened alloy pipe prepared in this invention is simple, environmentally friendly, low-cost, has significant modification effects, and is widely applicable. Detailed Implementation

[0031] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0032] Example 1

[0033] This embodiment provides a modified hollow glass microsphere, the steps of which are as follows:

[0034] 1.5 g of hollow glass microspheres (100 μm) were dried at 100 °C. The dried microspheres were then placed in 25 mL of 0.3 mol / L NaOH solution and stirred at 60 °C for 4 h. The microspheres were washed three times alternately with deionized water and anhydrous ethanol. The microspheres were then filtered under reduced pressure to remove excess water and dried in an oven at 100 °C for 12 h to obtain hydroxylated hollow glass microspheres.

[0035] 1 g of hydroxylated hollow glass microspheres, 0.6 g of ethyl acrylate and 0.25 g of benzoyl peroxide were added to 50 mL of ethyl acetate. Under nitrogen protection, the mixture was heated to 70 °C and stirred. The mixture was refluxed and condensed for 12 h. After centrifugation and filtration, the filtrate was added to methanol for precipitation. After centrifugation and filtration, the precipitate was washed with methanol until no precipitate was formed in methanol. The resulting product was dried in a vacuum drying oven at 50 °C for 24 h to obtain pretreated hollow glass microspheres.

[0036] 0.15 g glycidyl methacrylate was added to 50 mL of ethyl acetate, heated to 65 °C, refluxed and stirred for 0.5 h, 0.5 g of pretreated hollow glass microspheres and 0.24 g of potassium persulfate were added, and stirring was continued for 12 h. After centrifugation, the mixture was dried under vacuum at 50 °C for 20 h to obtain modified hollow glass microspheres.

[0037] Example 2

[0038] The only difference from Example 1 is that 0.15g of glycidyl methacrylate is replaced with 0.2g of glycidyl methacrylate. All other raw materials and steps are the same as in Example 1.

[0039] Example 3

[0040] The difference between this example and example 1 is that 0.15 g of glycidyl methacrylate is replaced by 0.25 g of glycidyl methacrylate. The remaining raw materials and steps are the same as example 1.

[0041] Example 4

[0042] A method for preparing a flame-retardant temperature-resistant reinforced and toughened alloy pipe, comprising the following steps:

[0043] A1, preparing an inner layer material for an inner layer pipe: 75 parts by weight of polypropylene, 12 parts by weight of nylon, 8 parts by weight of ABS, 0.8 parts by weight of modified hollow glass microspheres in example 1, 1.2 parts by weight of ethylene-propylene block copolymer, 0.05 parts by weight of antioxidant 1010 and 8 parts by weight of aluminum hydroxide are weighed, stirred and mixed at 110℃, the stirring time is 1h, and the stirring rate is 3200r / min, to obtain an inner layer material for an inner layer pipe;

[0044] Preparation of outer layer material for outer layer pipe: 78 parts by weight of polypropylene, 10 parts by weight of nylon, 8 parts by weight of ABS, 0.8 parts by weight of modified hollow glass microspheres in example 1, 1.2 parts by weight of ethylene-propylene block copolymer and 0.05 parts by weight of antioxidant 1010 are weighed, stirred and mixed at 112℃, the stirring time is 1h, and the stirring rate is 3200r / min, to obtain an outer layer material for an outer layer pipe;

[0045] A2, preparing an inner layer pipe: the inner layer material in A1 is introduced into an extruder, the barrel temperature is: the first zone is 120℃, the second zone is 130℃, the third zone is 145℃, the fourth zone is 165℃, the fifth zone is 195℃, and the sixth zone temperature is 210℃, the screw rotation speed is 20r / min, and the extrusion molding is obtained, to obtain an inner layer pipe;

[0046] A3, preparing a pipe: the obtained inner layer pipe is arranged in a mold, the outer layer material is introduced into an extruder, and the melt is compounded, the barrel temperature is: the first zone is 125℃, the second zone is 135℃, the third zone is 150℃, the fourth zone is 165℃, the fifth zone is 195℃, and the sixth zone temperature is 215℃, the screw rotation speed is 25r / min, and the extrusion molding is obtained, to obtain a flame-retardant temperature-resistant reinforced and toughened alloy pipe.

[0047] The flame-retardant temperature-resistant reinforced and toughened alloy pipe is prepared by the above steps.

[0048] Example 5

[0049] The difference between this example and example 4 is that 0.8 parts by weight of modified hollow glass microspheres in example 1 is replaced by 0.8 parts by weight of modified hollow glass microspheres in example 2. The remaining raw materials and steps are the same as example 4.

[0050] Example 6

[0051] The only difference between Example 4 and this example is that 0.8 parts of the modified hollow glass microspheres in Example 1 is replaced by 1.8 parts of the modified hollow glass microspheres in Example 1. The remaining raw materials and steps are the same as in Example 4.

[0052] Example 7

[0053] The only difference between Example 4 and this example is that 0.8 parts of the modified hollow glass microspheres in Example 1 is replaced by 1.8 parts of the modified hollow glass microspheres in Example 1. The remaining raw materials and steps are the same as in Example 4.

[0054] Example 8

[0055] The only difference between Example 4 and this example is that 8 parts of aluminum hydroxide is replaced by 8 parts of ammonium polyphosphate. The remaining raw materials and steps are the same as in Example 4.

[0056] Example 9

[0057] The only difference between Example 4 and this example is that 8 parts of aluminum hydroxide is replaced by a mixture of 8 parts of ammonium polyphosphate and aluminum hydroxide (weight ratio of 1:1). The remaining raw materials and steps are the same as in Example 4.

[0058] Example 10

[0059] The only difference between Example 4 and this example is that:

[0060] A2, preparation of the inner layer tube: the inner layer material in A1 is introduced into the extruder, the barrel temperature is: zone 1 is 125℃, zone 2 is 135℃, zone 3 is 150℃, zone 4 is 180℃, zone 5 is 210℃, zone 6 temperature is 225℃, the screw speed is 20r / min, and the extrusion molding is obtained. The remaining raw materials and steps are the same as in Example 4.

[0061] Comparative Example 1

[0062] The only difference between Example 4 and this example is that 0.8 parts of the modified hollow glass microspheres in Example 1 is replaced by 0.8 parts of the hydroxylated hollow glass microspheres in Example 1. The remaining raw materials and steps are the same as in Example 4.

[0063] Comparative Example 2

[0064] The only difference between Example 5 and this example is that 0.8 parts of the modified glass microspheres in Example 2 is replaced by 0.4 parts of the modified glass microspheres in Example 2. The remaining raw materials and steps are the same as in Example 5.

[0065] Comparative Example 3

[0066] The only difference between Example 6 and this example is that 0.8 parts of the modified glass microspheres in Example 3 is replaced by 2.1 parts of the modified glass microspheres in Example 6.

[0067] Comparative Example 4

[0068] Compared with Example 4, 8 parts of aluminum hydroxide is replaced by 3 parts of aluminum hydroxide; the remaining raw materials and steps are the same as those in Example 4.

[0069] Comparative Example 5

[0070] Compared with Example 4,

[0071] A2, preparation of the inner layer tube: the inner layer material in A1 is introduced into an extruder, the barrel temperature is: 110℃ for the first zone, 125℃ for the second zone, 140℃ for the third zone, 160℃ for the fourth zone, 190℃ for the fifth zone, and 205℃ for the sixth zone, and the screw rotation speed is 10r / min, and the extrusion molding is carried out to obtain the inner layer tube;

[0072] The remaining raw materials and steps are the same as those in Example 4.

[0073] Performance tests are carried out on Examples 4-10 and Comparative Examples 1-5:

[0074] (1) Tensile strength and elongation at break: the obtained alloy pipe is tested according to the standard GB / T 1040.1-2018 to test the tensile strength and elongation at break at 23℃.

[0075] (2) Bending modulus: the obtained alloy pipe is tested according to the standard GB / T 9341-2008;

[0076] (3) Vicat softening temperature: the obtained alloy pipe is tested according to the standard GB / T 1633-2000 for the determination of the Vicat softening temperature (VST) of thermoplastic plastics;

[0077] (4) Impact performance test: the obtained alloy pipe is tested for impact performance according to the requirements of the needle rotation method in GB / T 14152-2001 Test method for resistance to external impact of thermoplastics pipes;

[0078] (5) Oxygen index test: the obtained alloy pipe is tested according to the standard GB / T 2406.1-2008.

[0079] The test results are shown in Table 1:

[0080] Table 1

[0081]

[0082]

[0083] According to the ring flexibility test, the alloy pipe prepared in the present application has no reverse bending, no rupture, and no separation of the two walls, and has excellent ring flexibility, excellent toughness and rigidity.

[0084] As can be seen from Table 1, compared with Comparative Example 1, the toughening effect of the modified hollow glass microspheres added in Examples 4-6 on the alloy pipe is better, and the strength is higher. According to Comparative Examples 1-5 and Examples 4-10, it can be seen that the type and amount of the compatilizer and the flame retardant and the temperature of the extruder will affect the comprehensive performance of the alloy pipe. Therefore, the flame-retardant temperature-resistant reinforced and toughened alloy pipe prepared in the present application has excellent comprehensive performance, can maintain good impact resistance while having a high ring stiffness grade, and has a good application prospect.

[0085] It should be noted that, in this document, relational terms such as first and second and the like can be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises", "comprising", or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but can include other elements not expressly listed or inherent to such process, method, article, or apparatus.

[0086] Although embodiments of the present application have been shown and described, it is to be understood that various modifications, substitutions, alternatives, and variations can be made in the embodiments without departing from the spirit and scope of the present application as defined by the appended claims and their equivalents.

Claims

1. A fire resistant, heat resistant, reinforced, toughened alloy pipe, characterized in that, The alloy pipe comprises an inner layer pipe and an outer layer pipe; The inner layer pipe comprises the following components by weight: polypropylene 70-80 parts, nylon 10-15 parts, ABS 7-10 parts, a compatibilizer 0.5-2 parts, a toughening agent 0.5-4 parts, an antioxidant 0.05-0.1 parts, and a flame retardant 5-30 parts; The outer layer pipe comprises the following components by weight: polypropylene 70-80 parts, nylon 10-15 parts, ABS 7-10 parts, a compatibilizer 0.5-2 parts, a toughening agent 0.5-4 parts, an antioxidant 0.05-0.1 parts; The compatibilizer is modified hollow glass microbeads, which are prepared by the following steps: The hydroxylated hollow glass microbeads, ethyl acrylate and dibenzoyl peroxide are added into ethyl acetate, and heated and stirred under nitrogen protection, centrifugal filtration, washing, vacuum drying, to obtain pretreated hollow glass microbeads; glycidyl methacrylate is added into ethyl acetate, and heated and stirred, and the pretreated hollow glass microbeads and an initiator are added, and continue to stir, centrifugal separation, vacuum drying, to obtain modified hollow glass microbeads. The preparation method of the flame-retardant temperature-resistant reinforced and toughened alloy pipe comprises the following steps: A1, preparing an inner layer material for the inner layer pipe: polypropylene, nylon, ABS, a compatibilizer, a toughening agent, an antioxidant and a flame retardant are weighed by weight parts, and are stirred and mixed at 110-120 DEG C, the stirring time is 0.5-1h, and the stirring rate is 3200-3500r / min, to obtain the inner layer material for the inner layer pipe; preparing an outer layer material for the outer layer pipe: polypropylene, nylon, ABS, a compatibilizer, a toughening agent and an antioxidant are weighed by weight parts, and are stirred and mixed at a temperature of 110-120 DEG C, the stirring time is 0.5-1h, and the stirring rate is 3200-3500r / min, to obtain the outer layer material for the outer layer pipe; A2, preparing the inner layer pipe: the inner layer material in A1 is introduced into an extruder, and is extruded and molded to obtain the inner layer pipe; A3, preparing the pipe: the obtained inner layer pipe is arranged in a mold, and the outer layer material is introduced into an extruder, and is melt compounded and extruded and molded to obtain the flame-retardant temperature-resistant reinforced and toughened alloy pipe. In steps A2 and A3, the temperature of the extruder barrel is: zone 1 is 120-130 DEG C, zone 2 is 130-140 DEG C, zone 3 is 145-155 DEG C, zone 4 is 165-185 DEG C, zone 5 is 195-210 DEG C, and zone 6 is 210-225 DEG C, and the screw rotation speed is 15-35r / min.

2. A fire resistant, heat resistant, reinforced, toughened alloy pipe according to claim 1, characterized in that, The amount ratio of the hydroxylated hollow glass microbeads, ethyl acrylate, dibenzoyl peroxide and ethyl acetate is 1g:0.6:0.25g:50mL; the amount ratio of glycidyl methacrylate, ethyl acetate, pretreated hollow glass microbeads and initiator is 0.15-0.25g:50mL:0.5g:0.24g.

3. A fire resistant, heat resistant, reinforced, toughened alloy pipe according to claim 1, characterized in that, The initiator is one of potassium persulfate and ammonium persulfate.

4. The fire resistant, heat resistant, reinforced, toughened alloy pipe of claim 1, wherein, The hydroxylated hollow glass microbeads are prepared by the following steps: The hollow glass microbeads are added into NaOH solution, heated and stirred, washed, reduced pressure suction filtration, and dried to obtain the hydroxylated hollow glass microbeads.

5. A fire resistant, heat resistant, reinforced, toughened alloy pipe according to claim 4, characterized in that, The hollow glass microbeads and the NaOH solution are used in a ratio of 1.5g:25mL; the particle size of the hollow glass microbeads is 20-200μm.

6. The fire resistant, heat resistant, reinforced, toughened alloy pipe of claim 1, wherein, The toughening agent is one of ethylene-propylene block copolymer and styrene-butadiene thermoplastic elastomer.

7. The fire resistant, heat resistant, reinforced, toughened alloy pipe of claim 1, wherein, The antioxidant is one or both of antioxidant 1010 and antioxidant 168 in any ratio.

8. The fire resistant, heat resistant, reinforced, toughened alloy pipe of claim 1, wherein, The flame retardant is one or more of aluminum hydroxide, magnesium hydroxide, and ammonium polyphosphate.

9. A process for producing a fire resistant, heat resistant, reinforced and toughened alloy pipe as claimed in claim 1, wherein, The method comprises the following steps: A1, preparing an inner layer material for an inner layer tube: weighing polypropylene, nylon, ABS, a compatibilizer, a toughening agent, an antioxidant, and a flame retardant in parts by weight, stirring and mixing at 110-120℃, stirring for 0.5-1h, and stirring at a rate of 3200-3500r / min to obtain the inner layer material for the inner layer tube; A2, preparing an inner layer tube: introducing the inner layer material in A1 into an extruder and extruding to form the inner layer tube; A3, preparing a tube material: placing the inner layer tube obtained into a mold, introducing the outer layer material into an extruder, melt-combining, and extruding to form the flame-retardant, temperature-resistant, reinforced, and toughened alloy tube material. ​

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