Method for producing mpp functional material for communication conduit

Abstract

The application relates to the technical field of materials, and discloses a production method of MPP functional material for communication pipelines, the MPP functional material is prepared by mixing polypropylene as a base material with multiple additives and then performing a melt extrusion process, modified additive one and modified additive two in the additives can react with a maleic anhydride grafted polypropylene compatibilizer in the melt extrusion process, can not only introduce rigid cyclobutane and carbazole alternate chain links into the polypropylene structure, effectively improve the impact toughness of the polypropylene, but also form a micro three-dimensional connection network between the aluminum silicate fiber and the polypropylene base material, enable the aluminum silicate fiber to undertake a chemical crosslinking core, realize efficient stress load transmission and transfer, enable the advantages of the aluminum silicate fiber to be efficiently utilized, thereby effectively enhancing the mechanical strength of the polypropylene, in addition, the natural rubber can play a toughening effect, and further improve the toughness of the material.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of materials, in particular to a production method of MPP functional material for communication pipelines. BACKGROUND

[0002] With the rapid development of information technology, the communication industry has become one of the indispensable infrastructures in modern society. As an important part of the communication system, the communication pipeline undertakes the important task of protecting the transmission medium such as optical fiber and cable. Among many communication pipeline materials, the modified polypropylene (MPP for short) functional material has good electrical insulation, can effectively isolate the contact between the transmission medium such as optical fiber and cable and the external environment, reduce the electrical failure caused by factors such as moisture and corrosion, and protect the safe and stable operation of the communication system. With its unique performance and wide application prospect, the modified polypropylene has gradually become one of the main materials for manufacturing communication pipeline sheath materials. However, the communication pipeline needs to bear a large external stress during laying, so the sheath material needs to exhibit high mechanical strength. However, the polypropylene has a straight chain structure, and its mechanical properties are not outstanding, which greatly limits the further application of polypropylene in communication pipelines.

[0003] By adding inorganic fillers and other ways during the manufacturing process of the polypropylene material, the mechanical properties of the polypropylene material can be improved to a certain extent. However, there is a large interface problem between the inorganic material and the high molecular material such as polypropylene, which leads to that the addition amount of the inorganic material cannot be too high, and too high will lead to the agglomeration of the inorganic material, which will have a negative impact on the performance of the polypropylene. At the same time, it also cannot be too low, and too low will not effectively play the advantages. Therefore, by adjusting the formula of the polypropylene, the mechanical properties of the polypropylene can be improved. Based on this, the application provides a MPP functional material which has good mechanical properties and can be directly used to manufacture the sheath material of the communication pipeline. SUMMARY

[0004] In order to solve the problems mentioned in the background, the purpose of the application is to provide a production method of MPP functional material for communication pipelines.

[0005] The purpose of the application can be realized by the following technical scheme:

[0006] A production method of MPP functional material for communication pipelines, the MPP functional material is made of raw materials including the following weight fractions:

[0007]

[0008] The production method comprises the following steps:

[0009] Firstly, the raw materials are weighed according to the weight fractions, and are ready for use.

[0010] The second step is to put the polypropylene resin, the maleic anhydride grafted polypropylene, the modified additive one, the modified additive two, the filler, the coupling agent, the lubricant and the antioxidant into a mixer, control the rotating speed to be 1000-2000r / min, and mechanically stir and mix for 20-40min to obtain a premix;

[0011] The third step is to feed the premix into a double-screw extruder through a feeding port, control the temperature to be 200-220℃, and control the screw rotating speed to be 40-60rpm, and the MPP functional material can be obtained through an extrusion process.

[0012] As a further scheme of the present application, the preparation method of the modified additive one is as follows:

[0013] 1,1-cyclobutane dimethyl alcohol and toluene are added into a reaction kettle filled with nitrogen, stirred to form a uniform mixture, then a sodium hydroxide solution is slowly added into the reaction kettle, after the addition is completed, stirring is carried out at a temperature of 40-50℃ for 1-3h, then 9-benzyl-3,6-dibromocarbazole is added, after the addition is completed, the temperature is increased to 70-80℃, and stirring is continuously carried out for 8-12h, then the solvent is evaporated, and the product is collected to obtain the modified additive one.

[0014] As a further scheme of the present application, the molar ratio of the 1,1-cyclobutane dimethyl alcohol and the 9-benzyl-3,6-dibromocarbazole is 1:0.8-1.

[0015] As a further scheme of the present application, the mass fraction of the sodium hydroxide solution is 10-25%.

[0016] In the above technical scheme, the hydroxyl in the structure of 1,1-cyclobutane dimethyl alcohol is activated by using sodium hydroxide, and then the halogen substituent in the structure of 9-benzyl-3,6-dibromocarbazole is continuously replaced under high temperature conditions to form an alternating polymerization type macromolecular substance connected by ether bonds, and by controlling the dosage ratio of the two, the modified additive one can be prepared by making the hydroxyl end-capped.

[0017] As a further scheme of the present application, the preparation method of the modified additive two comprises the following steps:

[0018] Step one, the aluminum silicate fiber is soaked in a hydrochloric acid solution, taken out after 6-12h, and then immersed in a sodium hydroxide solution, the temperature is set to be 70-80℃, and the heat preservation is carried out for 9-12h, the solid product is filtered out, and after the washing and vacuum drying treatment, the alkali treated aluminum silicate fiber is obtained.

[0019] Step 2: Disperse the alkali-treated aluminum silicate fiber in N,N-dimethylformamide to form a uniform dispersion, then add the epoxidized natural rubber to the dispersion, introduce nitrogen to remove oxygen, and then add a tin metal catalyst. After the addition is completed, control the temperature to 130-150°C, keep warm for 7-9 hours, and centrifuge the solid material to obtain the modified additive II.

[0020] As a further embodiment of the present invention, in step 1, the concentration of the hydrochloric acid solution is 0.1-0.5 mol / L; the concentration of the sodium hydroxide solution is 1-3 mol / L.

[0021] As a further embodiment of the present invention, in step 2, the mass ratio of the alkali-treated aluminum silicate fiber to the epoxidized natural rubber is 1:6-10.

[0022] As a further embodiment of the present invention, in step 2, the epoxidation degree of the epoxidized natural rubber is 25%.

[0023] As a further embodiment of the present invention, in step 2, the tin metal catalyst is stannous chloride.

[0024] In the above technical solution, the aluminum silicate fiber is first pretreated with hydrochloric acid to remove impurities on the fiber surface, and then the aluminum silicate fiber is alkali-treated to fully expose the hydroxyl groups on the surface of the aluminum silicate fiber to form alkali-treated aluminum silicate fiber. Then, under the action of a catalyst, the epoxy groups in the epoxidized natural rubber structure and the hydroxyl groups on the surface of the alkali-treated aluminum silicate fiber are ring-opened, thereby modifying the natural rubber macromolecules on the surface of the aluminum silicate fiber to obtain modified additive two.

[0025] As a further embodiment of the present invention, the filler is at least one of fumed silica, titanium dioxide or talc; the coupling agent is 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane; the lubricant is at least one of polyethylene wax, zinc stearate or calcium stearate; and the antioxidant is at least one of antioxidant 1010, antioxidant 1076 or antioxidant 168.

[0026] Beneficial effects of the present invention:

[0027] (1) The present invention first prepares a polymeric macromolecule having an alternating structure of cyclobutane and carbazole as a modifying additive. Since the polymeric macromolecule has a hydroxyl endcapping, it can react with the maleic anhydride grafted polypropylene compatibilizer during the melt extrusion process, thereby introducing rigid cyclobutane and carbazole alternating chain segments into the polypropylene structure. It can also act as a cross-linking agent to transform the polypropylene from a linear structure to a three-dimensional network structure, thereby effectively improving the impact toughness of the polypropylene.

[0028] (2) the present application, by preparing the aluminum silicate fiber modified with natural rubber macromolecules as a modified additive two, on the one hand, the substituted hydroxyl groups generated by ring opening in the structure can also interact with maleic anhydride grafted polypropylene in the melting process, thereby forming a micro three-dimensional connection network at the interface of the aluminum silicate fiber and the polypropylene, enabling the aluminum silicate fiber to bear the chemical crosslinking core, realizing efficient stress load transfer and transfer, enabling the advantages of the aluminum silicate fiber to be efficiently utilized, thereby effectively enhancing the mechanical strength of the polypropylene, in addition, the natural rubber can play a toughening effect, further improving the toughness of the material.

[0029] Of course, implementing any product of the present application does not necessarily require achieving all the advantages described above at the same time. BRIEF DESCRIPTION OF DRAWINGS

[0030] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for the description of the embodiments will be briefly introduced as follows. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0031] Figure 1 The infrared test diagram of the modified additive one;

[0032] Figure 2 The scanning electron microscope diagram of the aluminum silicate fiber and the modified additive two, wherein (A) is the aluminum silicate fiber and (B) is the modified additive two. DETAILED DESCRIPTION

[0033] The technical solutions in the embodiments of the present application will be described clearly and completely in combination with the drawings in the embodiments of the present application. Obviously, the described embodiments are only some embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0034] Preparation Example 1

[0035] Preparation of the modified additive one:

[0036] 0.2g of 1,1-cyclobutane dimethyl alcohol and toluene were added to a nitrogen-filled reaction kettle, stirred to form a uniform mixture, then 10mL of 15% mass fraction sodium hydroxide solution was slowly added to the reaction kettle, after addition, stirring at 45℃ for 2h, then 0.6g of 9-benzyl-3,6-dibromocarbazole was added, after addition, the temperature was increased to 75℃, and stirring was continued for 9h, then the solvent was evaporated, and the product was collected to obtain the modified additive one.

[0037] The infrared analysis test result of the modified additive one is shown in the following table: Figure 1 In which, the absorption peak at 3266cm-1 is the characteristic absorption peak of terminal hydroxyl group, the absorption peak at 3000-3100cm-1 is the benzene ring C-H absorption peak of carbazole skeleton, the absorption peak at 2919cm-1 and 2898cm-1 is the C-H characteristic absorption peak of methylene, the absorption peak at 1049cm-1 is the C-O-C characteristic absorption peak of ether bond. -1 -1 -1 -1 -1

[0038] Preparation example 2

[0039] Preparation of the modified additive two:

[0040] Step one, immerse 2.8g aluminum silicate fiber in hydrochloric acid solution with concentration of 0.2mol / L, take out after 8h, then immerse it in sodium hydroxide solution with concentration of 2mol / L, set the temperature to 75℃, keep for 9h, filter out the solid product, wash, vacuum dry to get the alkali treated aluminum silicate fiber;

[0041] Step two, disperse 2.4g alkali treated aluminum silicate fiber in N,N-dimethylformamide to form a uniform dispersion, then add 18g epoxidized natural rubber with epoxy degree of 25% into the dispersion, introduce nitrogen to remove oxygen, then add 0.02g stannous chloride, after adding, control the temperature to 140℃, keep for 8h, centrifuge the solid material to get the modified additive two.

[0042] Figure 2 The scanning electron microscope images of the aluminum silicate fiber and the modified additive two are shown in the following table, in which (A) is the aluminum silicate fiber, (B) is the modified additive two, it can be obviously observed that the surface of the aluminum silicate fiber is smooth, while the surface of the modified additive two obviously presents the concave-convex morphology, which is due to the covalent bonding of the aluminum silicate fiber and the rubber molecular chain, and the rubber molecular chain is coated on the surface of the aluminum silicate fiber, resulting in the special morphology of the surface of the aluminum silicate fiber.

[0043] Example 1

[0044] An MPP functional material for communication pipeline is made from the following raw materials by weight:

[0045]

[0046]

[0047] The production method of the MPP functional material includes the following steps:

[0048] ​​​​​First step, each raw material is weighed according to the weight fraction, standby;

[0049] Second step, polypropylene resin, maleic anhydride grafted polypropylene, modified additive one, modified additive two, fumed silica, 3-aminopropyl trimethoxysilane, polyethylene wax and antioxidant 1010 are put into the mixer, the rotating speed is controlled at 1000r / min, and mechanical stirring is mixed for 40min to obtain a premix;

[0050] Third step, the premix is fed into the double screw extruder through the feeding port, the temperature is controlled at 210℃, and the screw rotating speed is 50rpm, and the MPP functional material can be obtained through the extrusion process.

[0051] The preparation method of the modified additive one is shown in preparation example 1, and the preparation method of the modified additive two is shown in preparation example 2, and the following is the same.

[0052] Example 2

[0053] A kind of MPP functional material for communication pipeline, which is made of the following raw materials by weight fraction:

[0054]

[0055]

[0056] The production method of the MPP functional material includes the following steps:

[0057] First step, each raw material is weighed according to the weight fraction, standby;

[0058] Second step, polypropylene resin, maleic anhydride grafted polypropylene, modified additive one, modified additive two, titanium dioxide, 3-aminopropyl triethoxysilane, zinc stearate and antioxidant 1076 are put into the mixer, the rotating speed is controlled at 1500r / min, and mechanical stirring is mixed for 30min to obtain a premix;

[0059] Third step, the premix is fed into the double screw extruder through the feeding port, the temperature is controlled at 220℃, and the screw rotating speed is 50rpm, and the MPP functional material can be obtained through the extrusion process.

[0060] Example 3

[0061] A kind of MPP functional material for communication pipeline, which is made of the following raw materials by weight fraction:

[0062]

[0063]

[0064] The production method of the MPP functional material includes the following steps:

[0065] First step, each raw material is weighed according to the weight fraction, standby;

[0066] Second step, polypropylene resin, maleic anhydride grafted polypropylene, modified additive one, modified additive two, talc, 3-aminopropyl triethoxysilane, calcium stearate and antioxidant 168 are put into the mixer, the rotating speed is controlled at 2000r / min, and mechanical stirring is mixed for 20min to obtain a premix;

[0067] Third step, the premix is fed into the double screw extruder through the feeding port, the temperature is controlled at 220℃, and the screw rotating speed is 50rpm. After extrusion process, MPP functional material can be obtained.

[0068] Comparative example 1

[0069] A kind of MPP functional material for communication pipeline, which is made from the following raw materials by weight fraction:

[0070]

[0071]

[0072] The production method of the MPP functional material includes the following steps:

[0073] First step, each raw material is weighed according to the weight fraction, standby;

[0074] Second step, polypropylene resin, maleic anhydride grafted polypropylene, modified additive two, titanium dioxide, 3-aminopropyl triethoxysilane, zinc stearate and antioxidant 1076 are put into the mixer, the rotating speed is controlled at 1500r / min, and mechanical stirring is mixed for 30min to obtain a premix;

[0075] Third step, the premix is fed into the double screw extruder through the feeding port, the temperature is controlled at 220℃, and the screw rotating speed is 50rpm. After extrusion process, MPP functional material can be obtained.

[0076] Comparative example 2

[0077] A kind of MPP functional material for communication pipeline, which is made from the following raw materials by weight fraction:

[0078]

[0079] The production method of the MPP functional material includes the following steps:

[0080] First step, each raw material is weighed according to the weight fraction, standby;

[0081] In the second step, polypropylene resin, maleic anhydride grafted polypropylene, modified additive 1, aluminum silicate fiber, titanium dioxide, 3-aminopropyltriethoxysilane, zinc stearate and antioxidant 1076 were put into a mixer, the speed was controlled at 1500 r / min, and mechanical stirring was carried out for 30 minutes to obtain a premix;

[0082] The third step is to feed the premix into the twin-screw extruder through the feeding port, control the temperature to 220°C and the screw speed to 50 rpm, and obtain the MPP functional material through the extrusion process.

[0083] Comparative Example 3

[0084] An MPP functional material for communication pipes is made of the following raw materials in parts by weight:

[0085]

[0086] The production method of the MPP functional material comprises the following steps:

[0087] The first step is to weigh each raw material according to the weight and set aside;

[0088] Step 2: Put polypropylene resin, maleic anhydride grafted polypropylene, modified additive 1, titanium dioxide, 3-aminopropyltriethoxysilane, zinc stearate and antioxidant 1076 into a mixer, control the speed to 1500r / min, and mechanically stir and mix for 30min to obtain a premix;

[0089] The third step is to feed the premix into the twin-screw extruder through the feeding port, control the temperature to 220°C and the screw speed to 50 rpm, and obtain the MPP functional material through the extrusion process.

[0090] Test Case

[0091] According to various standards, the functional materials of Examples 1 to 3 and Comparative Examples 1 to 3 were made into test samples and various performance tests were performed. The results are shown in the following table:

[0092] Tensile strength Elongation at break Impact strength Flexural strength Example 1 75.7 MPa 215％ <![CDATA[58.1kJ / m 2 ]]> 107.3 MPa Example 2 76.1 MPa 220％ <![CDATA[58.4kJ / m 2 ]]> 108.1 MPa Example 3 76.0 MPa 216％ 58.2 kJ / m 2 ]] 107.8 MPa Comparative Example 1 68.4 MPa 201％ 41.8 kJ / m 2 ]] 103.9 MPa Comparative Example 2 62.9 MPa 198％ 54.5 kJ / m 2 ]]> 96.9 MPa Comparative Example 3 51.3 MPa 192％ <![CDATA[46.7kJ / m 2 ]]> 85.4 MPa

[0093] Note: For tensile properties test, refer to GB / T 10401.1-2006; for impact strength test, refer to GB / T14152-2001; for flexural strength test, refer to GB / T 9341-2008.

[0094] The test data show that the use of the modified additives 1 and 2 prepared by the present invention as functional additives can effectively enhance the mechanical strength and impact toughness of polypropylene functional materials.

[0095] After the modifying additives are directly removed, the polypropylene structure lacks rigid chain links, resulting in a decrease in mechanical strength and toughness.

[0096] After replacing the second modifying additive with aluminum silicate fiber, the mechanical properties of the material decreased due to interface problems with the polypropylene matrix. Furthermore, the toughness of the material also decreased due to the loss of the toughening effect of natural rubber. Directly removing the second modifying additive further reduced the mechanical strength.

[0097] Specific examples are used herein to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only used to help understand the method of the present invention and its core ideas, including the best mode, and also enable any technician in the field to practice the present invention, including making and using any device or system, and implementing any combined method. It should be pointed out that for ordinary technicians in this technical field, without departing from the principles of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the scope of protection of the claims of the present invention. The scope of patent protection of the present invention is defined by the claims and may include other embodiments that can be thought of by those skilled in the art. If these other embodiments have structural elements similar to the literal description of the claims, or if they include equivalent structural elements that are not substantially different from the literal description of the claims, then these other embodiments should also be included in the scope of the claims.

[0098] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A method for producing MPP functional materials for communication pipelines, characterized in that: The MPP functional material is made of the following raw materials in parts by weight: 80-90 parts of polypropylene resin; 5-12 parts of maleic anhydride grafted polypropylene; Modifying additives - 3-6.5 parts; 2-4 parts of modified additive II; 6-10 parts of filling material; 3-5 parts of coupling agent; 0.5-1.5 parts of lubricant; 0.5-1 part antioxidant; The production method comprises the following steps: The first step is to weigh each raw material according to the weight and set aside; Step 2: Put polypropylene resin, maleic anhydride grafted polypropylene, modification additive 1, modification additive 2, filler, coupling agent, lubricant and antioxidant into a mixer, control the speed to 1000-2000 r / min, and mechanically stir and mix for 20-40 minutes to obtain a premix; The third step is to feed the premix into the twin-screw extruder through the feeding port, control the temperature to 200-220°C, and the screw speed to 40-60rpm. After the extrusion process, the MPP functional material can be obtained; The preparation method of the modified additive 1 is as follows: 1,1-cyclobutane dimethanol and toluene are added to a reactor filled with nitrogen and stirred until a uniform mixture is formed. Then, sodium hydroxide solution is slowly added to the reactor. After the addition is complete, the mixture is stirred at 40-50° C. for 1-3 hours. Then, 9-benzyl-3,6-dibromocarbazole is added. After the addition is complete, the mixture is heated to 70-80° C. and stirred continuously for 8-12 hours. The solvent is evaporated and the product is collected to obtain a modified additive 1. The molar ratio of 1,1-cyclobutane dimethanol to 9-benzyl-3,6-dibromocarbazole is 1:0.8-1; The preparation method of the modified additive 2 comprises the following steps: Step 1: Soak the aluminum silicate fiber in a hydrochloric acid solution, take it out after 6-12 hours, and then immerse it in a sodium hydroxide solution, set the temperature to 70-80°C, keep it warm for 9-12 hours, filter out the solid product, wash it, and vacuum dry it to obtain alkali-treated aluminum silicate fiber; Step 2: Disperse the alkali-treated aluminum silicate fiber in N,N-dimethylformamide to form a uniform dispersion, then add the epoxidized natural rubber to the dispersion, introduce nitrogen to remove oxygen, and then add a tin metal catalyst. After the addition is completed, control the temperature to 130-150°C, keep warm for 7-9 hours, and centrifuge the solid material to obtain the modified additive II.

2. The method for producing MPP functional materials for communication pipes according to claim 1, characterized in that: The mass fraction of the sodium hydroxide solution is 10-25%.

3. The method for producing MPP functional materials for communication pipes according to claim 1, characterized in that: In step 1, the concentration of the hydrochloric acid solution is 0.1-0.5 mol / L; the concentration of the sodium hydroxide solution is 1-3 mol / L.

4. The method for producing MPP functional materials for communication pipes according to claim 1, characterized in that: In step 2, the mass ratio of the alkali-treated aluminum silicate fiber to the epoxidized natural rubber is 1:6-10.

5. The method for producing MPP functional materials for communication pipes according to claim 1, characterized in that: In step 2, the epoxidation degree of the epoxidized natural rubber is 25%.

6. The method for producing MPP functional materials for communication pipes according to claim 1, characterized in that: In step 2, the tin metal catalyst is stannous chloride.

7. The method for producing MPP functional materials for communication pipes according to claim 1, characterized in that: The filler is at least one of fumed silica, titanium dioxide or talc; the coupling agent is 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane; the lubricant is at least one of polyethylene wax, zinc stearate or calcium stearate; and the antioxidant is at least one of antioxidant 1010, antioxidant 1076 or antioxidant 168.

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