CN114933765A - Acid-etching-resistant antistatic PVC composition, and preparation method and application thereof - Google Patents
Acid-etching-resistant antistatic PVC composition, and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/017—Additives being an antistatic agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/00—Properties
- C08L2201/04—Antistatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The invention discloses an acid-corrosion-resistant antistatic PVC composition, and a preparation method and application thereof. The PVC composition comprises the following components in parts by weight: 100 parts of polyvinyl chloride, 10-50 parts of anhydrous calcium sulfate, 5-15 parts of an antistatic agent, 5-10 parts of a plasticizer, 5-10 parts of a stabilizer, 1-3 parts of a processing aid and 1-3 parts of a lubricant; the antistatic agent is lignin and/or sodium lignosulfonate. Through the mutual matching and synergistic interaction of the specific antistatic agent and the anhydrous calcium sulfate, the PVC composition disclosed by the invention is excellent in antistatic performance and acid corrosion resistance, good in material stability, and still keeps good antistatic performance in a high-humidity high-acid environment.
Description
Technical Field
The invention relates to the technical field of polyvinyl chloride materials, in particular to an acid-corrosion-resistant antistatic PVC composition, and a preparation method and application thereof.
Background
Polyvinyl chloride (PVC) is a general polymer material and has wide application in industrial and agricultural production, transportation, building engineering and daily life of people. In different fields of application, different requirements are placed on the properties of polyvinyl chloride materials, where acid etch resistance and antistatic properties are important properties.
Because the general PVC material has high filling property, a large amount of calcium carbonate is usually added to increase the strength of the material, and meanwhile, the filler can effectively reduce the formula cost. However, calcium carbonate is easy to react with acid, and when PVC products containing calcium carbonate are in an acid environment, such as in the transportation of acid liquor or domestic wastewater, the material is easy to corrode and age, and the acid corrosion resistance of the PVC material is poor. In addition, because the surface resistance of the PVC material is too high, static accumulation is easily caused in the using process, and when the PVC material is used in buildings or underground coal mine materials, the explosion phenomenon caused by the static accumulation is easily caused, so that great potential safety hazards exist.
In the prior art, the antistatic performance of PVC materials is improved mainly by adding an antistatic agent. But the acid etching resistance of the prepared PVC material is still poor. The prior Chinese patent reports a corrosion-resistant antistatic enhanced plastic floor, which comprises a surface film layer and a bottom film layer, wherein the material matrixes of the surface film layer and the bottom film layer are PVC resin powder, and the plastic floor also contains a liquid antistatic agent, so that the antistatic property of the floor is improved; the surfaces of the surface film layer and the bottom film layer are respectively coated with PVDF layers, so that the floor has good corrosion resistance. The plastic flooring, although having improved antistatic properties and corrosion resistance, is not directly mixed with the extruded PVC composition, but is a multi-layered material.
Therefore, it is required to develop a PVC composition having both antistatic and acid etching resistance.
Disclosure of Invention
The invention provides an acid-corrosion-resistant and antistatic PVC composition for overcoming the defects of poor antistatic performance and acid-corrosion-resistant performance in the prior art. Sulfate ions in the anhydrous calcium sulfate are strong acid ions and are not easy to react with acid, so that the acid resistance of the PVC composition is excellent; the antistatic agent is lignin and/or sodium lignosulfonate, has good compatibility with PVC and anhydrous calcium sulfate, and plays a good antistatic improvement effect by adsorbing water molecules in the air; the anhydrous calcium sulfate can also be combined with water, so that the antistatic property of the material is improved to a certain extent. Under the synergistic effect of anhydrous calcium sulfate, lignin and/or sodium lignosulfonate with small dosage can be matched, so that excellent antistatic performance can be realized.
Another object of the present invention is to provide a process for the preparation of the above PVC composition.
Another object of the present invention is to provide the use of the above PVC composition.
In order to solve the technical problems, the invention adopts the technical scheme that:
an acid-etching-resistant antistatic PVC composition comprises the following components in parts by weight:
100 parts of polyvinyl chloride (PVC),
10-50 parts of anhydrous calcium sulfate,
5-15 parts of an antistatic agent,
5-10 parts of a plasticizer,
5-10 parts of a stabilizer,
1-3 parts of a processing aid,
1-3 parts of a lubricant;
the antistatic agent is lignin and/or sodium lignosulfonate.
Compared with calcium carbonate which is a common filler in PVC materials, the anhydrous calcium sulfate which is also called anhydrous gypsum has better acid resistance. Sulfate ions are strong acid ions, and according to the double decomposition reaction generation conditions: weak acid is prepared by strong acid, common acid such as hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, dicarboxylic acid, benzoic acid, citric acid and the like can not dissolve calcium sulfate, and displacement reaction can not occur.
The antistatic agent is lignin and/or sodium lignosulfonate, which forms a layer of conductive solution on the surface of the material by adsorbing water molecules in the air, thereby achieving a good antistatic improvement effect.
The basic structural units of lignin are mainly classified into three types: the G type (guaiacyl phenyl propane unit), the H type (p-hydroxy phenyl propane unit), the S type (lilac type phenyl propane unit), the molecular structure is respectively:
the lignosulfonate is from sulfite pulping in an acid pulping process, and has a molecular structure as follows:
the two lignin antistatic agents have a large amount of active hydroxyl groups, have good compatibility with PVC and anhydrous calcium sulfate, and can be uniformly dispersed in the PVC system, so that conductive solutions at different parts of the surface of the PVC material are more uniformly distributed, and the antistatic performance of the PVC composition is further improved. The lignosulfonate has good water solubility due to the introduction of sulfonic acid groups in molecules, so that the reaction capacity of the lignosulfonate is greatly improved, and the lignosulfonate can be used as an antistatic agent added into PVC resin, can adsorb water molecules on the surface and improve the antistatic property of the material.
Meanwhile, the anhydrous calcium sulfate can be combined with water, so that the antistatic property of the material is improved to a certain extent. Under the synergistic effect of anhydrous calcium sulfate, lignin and/or sodium lignosulfonate with small dosage can be matched, so that excellent antistatic performance can be realized.
Under the mutual matching and synergistic effect of the antistatic agent and the anhydrous calcium sulfate, the PVC composition disclosed by the invention is excellent in antistatic property and acid corrosion resistance, good in material stability, and still keeps good antistatic property in a high-humidity and high-acid environment.
Preferably, the antistatic agent is a mixture of lignin and sodium lignosulfonate.
More preferably, the antistatic agent is lignin and sodium lignosulfonate in a mass ratio of 1: (1.2-1.5).
The sodium lignosulfonate is independently added into the PVC material, so that the antistatic property of the material can be effectively improved, but the mechanical property of part of the material can be reduced. After the sodium lignosulfonate and the lignin are compounded for use, the material still has an antistatic effect under the condition that the mechanical property of the PVC composition is improved.
The plasticizer may be a plasticizer commonly used in PVC materials.
Optionally, the plasticizer is one or more of dioctyl phthalate (DOP), diisooctyl phthalate, diisononyl phthalate, diisooctyl terephthalate, dioctyl adipate or octyl sebacate.
Preferably, the plasticizer is dioctyl phthalate. The speed increasing effect of the dioctyl phthalate serving as the plasticizer is better.
The stabilizer may be a stabilizer commonly used in PVC materials.
Optionally, the stabilizer is one or more of a calcium zinc stabilizer, a lead salt stabilizer or a barium zinc stabilizer.
Preferably, the stabilizer is a calcium zinc stabilizer.
Preferably, the processing aid is Chlorinated Polyethylene (CPE) or an acrylate-based impact modifier (ACR).
The lubricant may be a lubricant commonly used in PVC materials.
Optionally, the lubricant is one or more of stearic acid, paraffin wax, polyethylene wax, oxidized polyethylene wax or fatty acid ester.
Preferably, the lubricant is a mixture of stearic acid and paraffin wax.
Preferably, the D90 particle size of the anhydrous calcium sulfate is 8-15 μm.
Optionally, the PVC is one or more of SG5 type, SG6 type or SG7 type.
Preferably, the polymerization degree of the PVC is 1000-1150.
The polymerization degree of SG5 type PVC is 1000-1150, the polymerization degree is suitable, and the prepared PVC composition has better comprehensive performance.
The invention also provides a preparation method of the PVC composition, which comprises the following steps:
and mixing polyvinyl chloride, anhydrous calcium sulfate, an antistatic agent, a plasticizer, a stabilizer, a processing aid and a lubricant, adding the mixture into an extruder, and performing melt mixing and extrusion to obtain the PVC composition.
Preferably, the mixing is carried out at the temperature of 60-110 ℃.
Preferably, the extruder is a twin screw extruder.
Preferably, the barrel temperature of the twin-screw extruder in the material advancing direction is: 130 to 145 ℃, 140 to 155 ℃, 160 to 170 ℃, 170 to 175 ℃, 180 to 185 DEG C
Preferably, the screw rotating speed of the double-screw extruder is 130-180 rpm.
The invention also protects the application of the PVC composition in preparing PVC drainage pipes.
The PVC drainage pipe can be used for transportation of industrial and/or domestic wastewater and mine underground water.
Compared with the prior art, the invention has the beneficial effects that:
the invention develops an acid-corrosion-resistant antistatic PVC composition. The anhydrous calcium sulfate has excellent acid resistance and is better. The antistatic agent is lignin and/or sodium lignosulfonate, has good compatibility with PVC and anhydrous calcium sulfate, and forms a layer of uniform conductive solution on the surface of the material by adsorbing water molecules in the air, thereby having good antistatic improvement effect. Meanwhile, the anhydrous calcium sulfate can be combined with water, so that the antistatic property of the material is improved to a certain extent. Under the synergistic effect of calcium sulfate, lignin and/or sodium lignosulfonate with small dosage are/is matched, so that excellent antistatic performance can be realized.
Under the mutual matching and synergistic effect of the specific lignin antistatic agent and the anhydrous calcium sulfate, the PVC composition disclosed by the invention is excellent in antistatic performance and acid corrosion resistance, good in material stability, and still keeps good antistatic performance in a high-humidity high-acid environment.
Detailed Description
The present invention will be further described with reference to the following embodiments.
The starting materials in the examples and comparative examples are commercially available as follows:
PVC, purchased from China Tai chemical Co., Ltd, model SG5, with a degree of polymerization of 1000-1150;
anhydrous calcium sulfate, purchased from Jintu technologies, Hunan, D90 particle size 8.6 μm;
lignin, purchased from dongli new materials science co ltd;
sodium lignosulfonate, purchased from dongli new materials science and technology limited;
stearic acid, purchased from Hangzhou grease chemical Co., Ltd, SA 1840;
paraffin, purchased from ita chemical (shanghai) limited;
CPE, purchased from Hebei Xiongfa New Material science and technology Co., Ltd, CPE-136;
calcium zinc stabilizer, purchased from new materials science and technology Co., Ltd of Jinchang resin, Shandong, TCS-108A-B;
DOP, purchased from Wengjiang chemical reagents, Inc., Guangzhou;
diisononyl phthalate DINP purchased from a new best material;
calcium carbonate, purchased from Confucius non-metallic materials, Inc. of Jiangmen City, with a particle size of 6.9 μm of BT-2 and D90;
50 percent of acetylene black and an antistatic agent are purchased from Tianjin excellent union chemical technology Co.
Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Examples 1 to 12
Examples 1 to 12 respectively provide a PVC composition, the component contents of which are shown in table 1, and the preparation method is as follows:
mixing the components at 60-110 ℃ according to table 1, and adding the mixture into a double-screw extruder, wherein the temperature of a screw cylinder of the double-screw extruder in the advancing direction of the materials is as follows: 130-145 ℃, 140-155 ℃, 160-170 ℃, 170-155 ℃, 170-175 ℃, 180-185 ℃ and 180-185 ℃; the rotating speed of the screw is 130-180 rpm;
and carrying out melt mixing and extrusion granulation to obtain the PVC composition.
TABLE 1 component content (parts by weight) of PVC compositions of examples 1 to 12
Comparative examples 1 to 4
Comparative examples 1 to 4 respectively provide a PVC composition, the component contents of which are shown in Table 2, and the preparation method is as follows:
mixing the components at the temperature of 60-110 ℃ according to table 2, and adding the mixture into a double-screw extruder, wherein the temperature of a screw cylinder of the double-screw extruder in the advancing direction of the materials is as follows: 130-145 ℃, 140-155 ℃, 160-170 ℃, 170-155 ℃, 170-175 ℃, 180-185 ℃ and 180-185 ℃; the rotating speed of the screw is 130-180 rpm;
and carrying out melt mixing and extrusion granulation to obtain the PVC composition.
TABLE 2 component content (parts by weight) of PVC compositions of comparative examples 1 to 4
Performance test
The PVC compositions prepared in the above examples and comparative examples were tested for their properties by the following specific methods:
tensile strength: testing according to the GB/T1040-2006 standard method;
elongation at break: testing according to the GB/T1040-2006 standard method;
bending strength: testing according to GB/T9341-2000 standard method;
flexural modulus: testing according to the GB/T9341-2000 standard method;
impact strength of the simply supported beam notch: testing according to the GB/T9341-2000 standard method;
surface resistance: testing according to the GB/T1410-2006 standard method;
corrosion degree: according to the QB/T3801-1999 standard method, the surface of a PVC sample strip to be tested is wiped with petroleum ether, soaked with water, dried, measured for mass, immersed in 38% nitric acid solution, taken out after 6 hours, washed with distilled water, dried, weighed, and corrosion degree calculated in unit g/m 2 。
The test results are shown in Table 3.
TABLE 3 test results of examples and comparative examples
According to the test results in Table 3, the PVC composition prepared by the method has good mechanical properties, the tensile strength is more than or equal to 30MPa, and the elongation at break is more than or equal to 28%; has excellent antistatic performance and surface resistance not more than 5 × 10 11 Omega.m; and the acid etching resistance is excellent, and after the material is soaked in 38 percent nitric acid solution for 6 hours, the corrosion degree is less than or equal to 3.3g/m 2 。
According to the embodiments 1-7, it can be seen that when the antistatic agent is a mixture of lignin and sodium lignosulfonate, the PVC composition has excellent antistatic property and better mechanical property; the PVC composition of example 7 had a slightly lower tensile strength and elongation at break, and relatively poorer mechanical properties. In examples 1 to 6, the mechanical properties, antistatic properties and acid etching resistance of the PVC compositions of examples 1, 4 and 6 are superior in combination, and therefore, the antistatic agent is preferably lignin and sodium lignosulfonate in a mass ratio of 1: (1.2-1.5).
In comparative example 1, anhydrous calcium sulfate was replaced with calcium carbonate, the acid etching resistance of the PVC composition was very poor, and the degree of etching after 6 hours of immersion in 38% nitric acid solution was 9.47g/m 2 . In comparative example 2, the content of the antistatic agent was too large, and beyond the scope of the present technical solution, the mechanical properties of the PVC composition were seriously deteriorated. In comparative example 4, where the antistatic agent was 50% acetylene black, and not the lignin-based antistatic agent of the present application, the addition of carbon black resulted in a significant decrease in the tensile strength of the PVC composition.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The acid-corrosion-resistant antistatic PVC composition is characterized by comprising the following components in parts by weight:
100 parts of polyvinyl chloride (PVC), and mixing the components,
10-50 parts of anhydrous calcium sulfate,
5-15 parts of an antistatic agent,
5-10 parts of a plasticizer,
5-10 parts of a stabilizer,
1-3 parts of a processing aid,
1-3 parts of a lubricant;
the antistatic agent is lignin and/or sodium lignosulfonate.
2. Acid-etching resistant, antistatic PVC composition according to claim 1, characterized in that the antistatic agent is a mixture of lignin and sodium lignosulfonate.
3. The acid-etching-resistant antistatic PVC composition according to claim 1, wherein the antistatic agent is lignin and sodium lignosulfonate in a mass ratio of 1: (1.2-1.5).
4. The acid-etch resistant, antistatic PVC composition of claim 1 wherein the plasticizer is one or more of dioctyl phthalate, diisooctyl phthalate, diisononyl phthalate, diisooctyl terephthalate, dioctyl adipate or octyl sebacate.
5. Acid-etching-resistant, antistatic PVC composition according to claim 1, characterized in that the stabilizer is one or more of calcium zinc stabilizer, lead salt stabilizer or barium zinc stabilizer.
6. The acid-etch resistant, antistatic PVC composition of claim 1 wherein the processing aid is chlorinated polyethylene or an acrylate impact modifier.
7. The acid-etch resistant, antistatic PVC composition of claim 1 wherein the lubricant is one or more of stearic acid, paraffin wax, polyethylene wax, oxidized polyethylene wax or fatty acid ester.
8. The acid-etching-resistant and antistatic PVC composition of claim 1, wherein the anhydrous calcium sulfate has a D90 particle size of 8-15 μm.
9. A process for the preparation of a PVC composition according to any of claims 1 to 8, comprising the steps of:
and mixing polyvinyl chloride, anhydrous calcium sulfate, an antistatic agent, a plasticizer, a stabilizer, a processing aid and a lubricant, adding the mixture into an extruder, and performing melt mixing and extrusion to obtain the PVC composition.
10. Use of the PVC composition of any one of claims 1 to 8 in the preparation of PVC drainage pipe.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107778690A (en) * | 2016-08-29 | 2018-03-09 | 广西金滩管业科技有限公司 | Impact pvc pipe and its production method |
| WO2020233028A1 (en) * | 2019-05-22 | 2020-11-26 | 宁波先锋新材料股份有限公司 | Flame-retardant and smoke-suppressing soft polyvinyl chloride composite material having good mechanical performance and preparation method therefor |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107778690A (en) * | 2016-08-29 | 2018-03-09 | 广西金滩管业科技有限公司 | Impact pvc pipe and its production method |
| WO2020233028A1 (en) * | 2019-05-22 | 2020-11-26 | 宁波先锋新材料股份有限公司 | Flame-retardant and smoke-suppressing soft polyvinyl chloride composite material having good mechanical performance and preparation method therefor |
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| Title |
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| 钟雷等, 浙江科学技术出版社 * |
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