High-performance PVC material for joints and method for producing same

Abstract

The application relates to the technical field of materials, and discloses a high-performance PVC material for joints and a preparation method thereof. The PVC material is prepared through a mixing and melt extrusion process by taking PVC resin as a base material and taking chlorinated polyvinyl chloride, butyronitrile rubber and fiber modification substances as auxiliary materials. The fiber modification substance is prepared by grafting macromolecular polymers containing a large number of hindered amine antioxidant groups on the surface of glass fibers. The existence of the macromolecular polymers can intertwine with the polyvinyl chloride molecular chains, is beneficial to improving the compatibility between the glass fibers and the polyvinyl chloride base material, makes the glass fibers efficiently play the self-reinforcing advantages, and improves the mechanical strength of the polyvinyl chloride material. The existence of the hindered amine antioxidant groups can effectively play the antioxidant role and improve the antioxidant property of the polyvinyl chloride material.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of materials, in particular to a high-performance PVC material for joints and a preparation method thereof. BACKGROUND

[0002] The PVC plastic waterstop is a flexible waterstop extruded from polyvinyl chloride as a base material, which is generally used in construction joints and deformation joints during concrete pouring and is integrated with concrete. It is widely used in projects such as tunnels, culverts, water diversion aqueducts, water retaining dams, liquid storage structures, and underground facilities due to its high quality, low price, and easy construction. The plastic waterstop makes full use of the elastic deformation characteristics of polyvinyl chloride resin to prevent leakage and seepage in building joint structures and has the characteristics of corrosion resistance and good durability. However, when the PVC plastic waterstop encounters a multi-directional structure, the quality of the joint is difficult to guarantee. Therefore, developing a joint with excellent comprehensive performance is of great significance for the further application of the PVC plastic waterstop.

[0003] Since polyvinyl chloride can resist corrosion from acids, bases, oils, and solvents, has good electrical insulation, is easy to install, and has low cost, using polyvinyl chloride as the base material of the structural part has a positive effect on the seepage prevention of the PVC plastic waterstop.

[0004] However, since the PVC plastic waterstop is difficult to be constructed twice, higher requirements are placed on the long-term performance of the joint part. During long-term use, the plastic part will inevitably age, leading to a significant decrease in material performance and a significant reduction in the seepage prevention effect of the waterstop. Therefore, aging-resistant modification of polyvinyl chloride is the key to its use in the production of waterstop joint parts.

[0005] In the prior art, the aging resistance of polyvinyl chloride is generally improved by adding antioxidants such as antioxidant 1010 and antioxidant 1076. However, these small molecule substances can migrate and precipitate, and cannot guarantee the long-term oxidation resistance of polyvinyl chloride. SUMMARY

[0006] (I) Technical problems to be solved

[0007] In view of the deficiencies of the prior art, the present application provides a high-performance PVC material for joints and a preparation method thereof.

[0008] (II) Technical solutions

[0009] A preparation method of a high-performance PVC material for joints, wherein the PVC material is prepared from the following raw materials in the following proportions by weight:

[0010] 75-85 parts of PVC resin, 15-25 parts of chlorinated polyvinyl chloride, 6-15 parts of nitrile rubber material, 2-8 parts of fiber modification material, 5-10 parts of plasticizer, 1-3 parts of heat stabilizer, 1-2 parts of lubricant, 5-10 parts of color powder, 1-1.5 parts of processing aid ACR;

[0011] The preparation method comprises the following steps:

[0012] In the first step, the raw materials are weighed and added to a high-speed mixer, and then mixed uniformly at a stirring speed of 800-1000 r / min to obtain a premix;

[0013] In the second step, the premix is put into a double-screw extruder, and the temperature of each zone is controlled as follows: 170-180℃ for zone 1, 180-190℃ for zone 2, 190-200℃ for zone 3, 200-210℃ for zone 4, and 190-200℃ for zone 5, and the screw rotation speed is 50-60 rpm, and then the melting extrusion process is carried out to obtain the PVC material.

[0014] As a further scheme of the present application, the preparation method of the fiber modification material is as follows:

[0015] In the first step, the glass fiber is dispersed in an ethanol aqueous solution, and an amino silane coupling agent is used to modify the glass fiber to obtain organic glass fiber;

[0016] In the second step, the organic glass fiber is added to toluene and ultrasonically treated, and then an excess amount of polyglycidol ether is added to the formed dispersion, and stirred at 70-80℃ for 2-4h, and then the temperature is reduced to 40-50℃, and then a hindered amine chain extender and a phase transfer catalyst are added, and stirred and mixed uniformly, and then the temperature is increased to 90-100℃, and the stirring and heating are continued for 12-18h, and then the heating is stopped and the temperature is reduced to discharge the material, and the fiber modification material is obtained.

[0017] As a further scheme of the present application, the amino silane coupling agent is selected from any one of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane or N-(2-aminoethyl)-3-aminopropyltrimethoxysilane.

[0018] As a further scheme of the present application, the volume fraction of the ethanol aqueous solution is 60-70%.

[0019] As a further scheme of the present application, the polyglycidol ether is at least one of pentaerythritol tetraglycidyl ether, glycerol triglycidyl ether or ethylene glycol diglycidyl ether.

[0020] As a further scheme of the present application, the preparation method of the hindered amine chain extender is as follows:

[0021] N-(4-phenylamino phenyl) maleic imide and mercaptosuccinic acid are added into tetrahydrofuran, after being dissolved by stirring, nitrogen protection is conducted, heating is conducted to 60-65 DEG C, triethylamine is continuously added, under the condition of continuous stirring, 12-16h of heat preservation is conducted, the solvent is removed under reduced pressure, and the hindered amine chain extender can be obtained through a purification treatment process.

[0022] As a further scheme of the present application, the molar ratio of the N-(4-phenylamino phenyl) maleic imide and the mercaptosuccinic acid is 1:1.

[0023] As a further scheme of the present application, the phase transfer catalyst is any one of tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate or tetrabutylammonium chloride.

[0024] In the above technical scheme, first, the glass fiber is surface modified by using the amino silane coupling agent to obtain the amino-modified organic glass fiber, then, the polyglycidyl ether is used as a connecting agent, one end of the polyglycidyl ether is subjected to ring-opening reaction with the amino group of the organic glass fiber, and the other end is subjected to ring-opening esterification with the substituted carboxyl in the structure of the hindered amine chain extender under the action of the phase transfer catalyst, in the reaction process, the excessive polyglycidyl ether in the system continuously undergoes ring-opening esterification with the hindered amine chain extender, so that the polymer with a macromolecular structure is grafted on the surface of the glass fiber to obtain the fiber modification material.

[0025] The hindered amine chain extender is prepared from N-(4-phenylamino phenyl) maleic imide and mercaptosuccinic acid through a click reaction.

[0026] As a further scheme of the present application, the plasticizer is dioctyl phthalate or dibutyl phthalate, the heat stabilizer is calcium-zinc stabilizer or barium-zinc stabilizer, the lubricant is polyethylene wax or paraffin wax, and the toner is any one of calcium carbonate, carbon black or titanium dioxide.

[0027] A high-performance PVC material for a connector is prepared by using the above preparation method.

[0028] (III) Beneficial technical effects

[0029] The application prepares a fiber modification material by grafting a macromolecular polymer containing a large number of hindered amine antioxidant groups on the surface of glass fiber. Firstly, the presence of the macromolecular polymer can intertwine with the molecular chains of polyvinyl chloride during the melt extrusion process to form an interwoven molecular chain structure, which is beneficial to improving the compatibility between the glass fiber and the polyvinyl chloride base material and also beneficial to the glass fiber to effectively exert its own reinforcing advantage and improve the mechanical strength of the polyvinyl chloride material. The presence of the hindered amine antioxidant group can effectively play an antioxidant role to improve the antioxidant performance of the polyvinyl chloride material. Moreover, since the hindered amine antioxidant structure is limited on the surface of the glass fiber, it cannot migrate and precipitate, thereby ensuring the long-acting antioxidant performance of the polyvinyl chloride material. DETAILED DESCRIPTION

[0030] In order to facilitate the understanding of the present application, the present application will be described more fully below. The preferred embodiments of the present application are given below. However, the present application can be realized in many different forms and is not limited to the embodiments described herein. On the contrary, these embodiments are provided to make the disclosure of the present application more thorough and comprehensive.

[0031] Example 1

[0032] A high-performance PVC material for joints is prepared by using the following raw materials measured by weight fraction:

[0033] 75 parts of PVC resin, 15 parts of chlorinated polyvinyl chloride, 6 parts of nitrile rubber, 2 parts of fiber modification material, 5 parts of plasticizer dioctyl phthalate, 1 part of calcium-zinc stabilizer, 1 part of lubricant polyethylene wax, 5 parts of calcium carbonate, and 1 part of processing aid ACR;

[0034] The preparation method of the PVC material comprises the following steps:

[0035] First step, the raw materials measured by weight fraction are added to a high-speed mixer, and mechanically stirred at a stirring rate of 1000 r / min to obtain a premix;

[0036] Second step, the premix is put into a double-screw extruder, and the temperature of each zone is controlled in sequence as follows: 175℃ for zone one, 185℃ for zone two, 195℃ for zone three, 205℃ for zone four, and 195℃ for zone five. The screw rotation speed is 50 rpm. The melt extrusion process is carried out to obtain the PVC material.

[0037] Example 2

[0038] A high-performance PVC material for joints is prepared by using the following raw materials measured by weight fraction:

[0039] 80 parts of PVC resin, 20 parts of chlorinated polyvinyl chloride, 10 parts of nitrile rubber material, 7.5 parts of fiber modifying material, 6 parts of plasticizer dibutyl phthalate, 2 parts of barium-zinc stabilizer, 1.5 parts of lubricant paraffin wax, 6 parts of carbon black, 1.2 parts of processing aid ACR;

[0040] The preparation method of the PVC material comprises the following steps:

[0041] Firstly, the raw materials are weighed and added into a high-speed mixer, and then mechanically stirred at a stirring speed of 1000 r / min to obtain a premix;

[0042] Secondly, the premix is put into a double-screw extruder, and the temperature of each zone is controlled to be 175°C, 185°C, 195°C, 205°C and 195°C in sequence, and the screw rotation speed is 50 rpm, so that the melt extrusion process is carried out to obtain the PVC material.

[0043] Example 3

[0044] A high-performance PVC material for a joint is prepared by using the following raw materials in parts by weight:

[0045] 85 parts of PVC resin, 25 parts of chlorinated polyvinyl chloride, 15 parts of nitrile rubber material, 8 parts of fiber modifying material, 10 parts of plasticizer dibutyl phthalate, 3 parts of barium-zinc stabilizer, 2 parts of lubricant paraffin wax, 10 parts of titanium white, and 1.5 parts of processing aid ACR;

[0046] The preparation method of the PVC material comprises the following steps:

[0047] Firstly, the raw materials are weighed and added into a high-speed mixer, and then mechanically stirred at a stirring speed of 800-1000 r / min to obtain a premix;

[0048] Secondly, the premix is put into a double-screw extruder, and the temperature of each zone is controlled to be 175°C, 185°C, 195°C, 205°C and 195°C in sequence, and the screw rotation speed is 50 rpm, so that the melt extrusion process is carried out to obtain the PVC material.

[0049] The fiber modifying material in the above examples is prepared by the following method:

[0050] Step one, 3.5g of glass fiber is dispersed in an ethanol aqueous solution with a volume fraction of 60%, and then 1.6g of 3-aminopropyl triethoxysilane is added to the dispersion, and after the addition is completed, stirring is carried out at a temperature of 70°C for 6h, and the material is centrifuged, washed and vacuum dried to obtain organic glass fiber;

[0051] Step two, 2.6g organic glass fiber is added into toluene, ultrasonic treatment, then 10.5g pentaerythritol tetraglycidyl ether is added into the formed dispersion, after stirring at 75℃ for 3h, the temperature is reduced to 40℃, then 8g hindered amine chain extender and 0.2g tetrabutylammonium bromide are added, after mixing well, the temperature is increased to 95℃, and the mixture is stirred for 16h, then the heating is stopped, and the temperature is reduced to obtain the fiber modified material.

[0052] The preparation method of the hindered amine chain extender is as follows:

[0053] 0.8g N-(4-anilino phenyl) maleimide and 0.45g mercaptobutane dicarboxylic acid are added into tetrahydrofuran, after stirring and dissolving, nitrogen protection is performed, heating is performed to 65℃, 0.1g triethylamine is continuously added, and the mixture is stirred and heated for 15h, then the solvent is removed under reduced pressure, and the hindered amine chain extender is obtained through a purification process.

[0054] Comparative example 1

[0055] A high-performance PVC material for joints is prepared by using the following raw materials in the following proportions by weight:

[0056] 80 parts of PVC resin, 20 parts of chlorinated polyvinyl chloride, 10 parts of butyronitrile rubber, 7.5 parts of glass fiber, 6 parts of plasticizer dibutyl phthalate, 2 parts of barium-zinc stabilizer, 1.5 parts of lubricant paraffin, 6 parts of carbon black, and 1.2 parts of processing aid ACR;

[0057] The preparation method of the PVC material comprises the following steps:

[0058] Step one, the raw materials are weighed and added into a high-speed mixer, and the mixture is mechanically stirred at a stirring speed of 1000r / min to obtain a premix;

[0059] Step two, the premix is put into a double-screw extruder, the temperature of each zone is controlled to be 175℃, 185℃, 195℃, 205℃ and 195℃ in sequence, the screw rotation speed is 50rpm, and the melt extrusion process is performed to obtain the PVC material.

[0060] Comparative example 2

[0061] A high-performance PVC material for joints is prepared by using the following raw materials in the following proportions by weight:

[0062] 80 parts of PVC resin, 20 parts of chlorinated polyvinyl chloride, 10 parts of butyronitrile rubber, 6 parts of plasticizer dibutyl phthalate, 2 parts of barium-zinc stabilizer, 1.5 parts of lubricant paraffin, 6 parts of carbon black, and 1.2 parts of processing aid ACR;

[0063] The preparation method of the PVC material comprises the following steps:

[0064] Firstly, the raw materials are weighed and added into a high-speed mixer, and then mechanically stirred at a stirring speed of 1000 r / min to obtain a premix;

[0065] Secondly, the premix is put into a double-screw extruder, and the temperature of each zone is controlled in sequence as follows: 175℃ for the first zone, 185℃ for the second zone, 195℃ for the third zone, 205℃ for the fourth zone, and 195℃ for the fifth zone, and the screw rotation speed is 50 rpm, so that the melt extrusion process is carried out to obtain the PVC material.

[0066] Test example

[0067] a. The PVC materials in the examples and comparative examples are made into test samples meeting the specifications, the tensile strength of the test samples is tested according to the standard GB / T1040.1-2018, and the tensile rate is set to 100 mm / min;

[0068] b. The samples are placed in an oven at 120℃ for accelerated aging for 2 days, then taken out, and the sample phenomenon is observed to evaluate the antioxidant performance, and the test results are shown in the following table:

[0069] Tensile strength / MPa Phenomena Example 1 53.4 No significant phenomena Example 2 53.8 No significant phenomena Example 3 53.5 No significant phenomena Comparative Example 1 48.1 Yellowing, softening Comparative Example 2 41.9 Yellowing, softening with slight cracking

[0070] The principles and implementation modes of the present application are described by applying specific examples in this paper, and the above example description is only used to help understand the method and its core idea of the present application, including the best mode, and also enables any person skilled in the art to practice the present application, including manufacturing and using any device or system, and implementing any combined method. It should be noted that for ordinary skilled persons in the art, without departing from the principles of the present application, some improvements and modifications can be made to the present application, and these improvements and modifications also fall within the protection scope of the claims of the present application. The scope of the patent protection of the present application is defined by the claims, and can include other embodiments that can be thought of by those skilled in the art. If these other embodiments have structural elements similar to the wording of the claims, or if they include equivalent structural elements that are not substantially different from the wording of the claims, then these other embodiments should also be included in the scope of the claims.

[0071] According to the ideal embodiments of the present application, through the above description, relevant personnel can definitely make various changes and modifications without deviating from the technical idea of the present application. The technical scope of the present application is not limited to the contents in the specification, and must be determined according to the scope of the claims.

Claims

1. A method for preparing a high-performance PVC material for joints, characterized in that, The PVC material is made from the following raw materials measured in parts by weight: 75-85 parts PVC resin, 15-25 parts chlorinated polyvinyl chloride, 6-15 parts nitrile rubber, 2-8 parts fiber modifier, 5-10 parts plasticizer, 1-3 parts heat stabilizer, 1-2 parts lubricant, 5-10 parts color powder, 1-1.5 parts processing aid ACR; The preparation method includes the following steps: Step 1: Add the weighed ingredients to a high-speed mixer and mechanically mix them at a mixing speed of 800-1000 r / min to obtain a premix. The second step is to feed the premixed material into a twin-screw extruder and control the temperature of each zone as follows: Zone 1 170-180℃, Zone 2 180-190℃, Zone 3 190-200℃, Zone 4 200-210℃, Zone 5 190-200℃, and the screw speed is 50-60 rpm to carry out the melt extrusion process and obtain PVC material. The preparation method of the fiber-modified material is as follows: Step 1: Disperse glass fibers in an ethanol aqueous solution and modify the glass fibers with an aminosilane coupling agent to obtain organic glass fibers; Step 2: Add the organic glass fiber to toluene and sonicate it. Then add an excess of polyglycidyl ether to the resulting dispersion and stir at 70-80℃ for 2-4 hours. Then lower the temperature to 40-50℃ and add the hindered amine chain extender and phase transfer catalyst. After the addition is complete, stir and mix evenly. Then raise the temperature to 90-100℃ and continue stirring for 12-18 hours. Then stop heating, cool down and discharge the material to obtain the fiber-modified material. The hindered amine chain extender is prepared as follows: N-(4-phenylaminophenyl)maleimide and mercaptosuccinic acid are added to tetrahydrofuran, stirred thoroughly to dissolve, and then heated to 60-65°C under nitrogen protection. Triethylamine is then added, and the mixture is kept at this temperature for 12-16 hours with continuous stirring. The solvent is removed under reduced pressure, and the hindered amine chain extender is obtained through purification.

2. The method for preparing a high-performance PVC material for a connector according to claim 1, characterized in that, The aminosilane coupling agent is selected from any one of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, or N-(2-aminoethyl)-3-aminopropyltrimethoxysilane.

3. The method for preparing a high-performance PVC material for a joint according to claim 1, characterized in that, The volume fraction of the ethanol-water solution is 60-70%.

4. The method for preparing a high-performance PVC material for a joint according to claim 1, characterized in that, The polyglycidyl ether is at least one of pentaerythritol tetraglycidyl ether, glycerol triglycidyl ether, or ethylene glycol diglycidyl ether.

5. The method for preparing a high-performance PVC material for a connector according to claim 1, characterized in that, The molar ratio of N-(4-anilinephenyl)maleimide to mercaptosuccinic acid is 1:

1.

6. The method for preparing a high-performance PVC material for a connector according to claim 1, characterized in that, The phase transfer catalyst is any one of tetrabutylammonium bromide, tetrabutylammonium bisulfate, or tetrabutylammonium chloride.

7. The method for preparing a high-performance PVC material for a connector according to claim 1, characterized in that, The plasticizer is dioctyl phthalate or dibutyl phthalate; the heat stabilizer is calcium-zinc stabilizer or barium-zinc stabilizer; the lubricant is polyethylene wax or paraffin wax; and the colorant is any one of calcium carbonate, carbon black, or titanium dioxide.

8. A high-performance PVC material for connectors, characterized in that, It is prepared by the preparation method described in any one of claims 1-7.