CN108239357B - Preparation method of EVA modified calcium carbonate toughening system electrical casing - Google Patents
Preparation method of EVA modified calcium carbonate toughening system electrical casing Download PDFInfo
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- CN108239357B CN108239357B CN201810158498.2A CN201810158498A CN108239357B CN 108239357 B CN108239357 B CN 108239357B CN 201810158498 A CN201810158498 A CN 201810158498A CN 108239357 B CN108239357 B CN 108239357B
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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Abstract
A preparation method of an EVA modified calcium carbonate toughening system electrical casing comprises the following steps: (1) preparing EVA modified calcium carbonate; (2) putting the raw materials into a high-speed mixer according to the composition ratio, stirring until the temperature of the materials is more than or equal to 120 ℃, discharging the mixture into a cold mixing pot, stirring and cooling to form a mixture, and discharging for later use; (3) and extruding the mixture by using an extruder, and cooling and shaping to obtain the EVA modified calcium carbonate toughening system electrical casing. The preparation method has simple operation procedures and low manufacturing cost, is convenient for large-scale production, can effectively reduce the using amount of the stabilizer and reduce the manufacturing cost of the electrical casing by emulsifying the calcium carbonate; the electrical casing obtained by the preparation method has better rigidity, creep property, thermal shrinkage property and compression resistance; meanwhile, the toughness of the EVA can effectively improve the phenomena of whitening of PVC during bending and easy cracking at low temperature.
Description
Technical Field
The invention relates to the field of plastic pipes for cables, in particular to a preparation method of an EVA modified calcium carbonate toughening system electrical casing.
Background
At present, the rubber used for the cable material with the characteristics of high temperature resistance, cold resistance, oil resistance and high flame retardance is chloroprene rubber, chlorosulfonated polyethylene rubber and chlorinated polyethylene rubber. The chlorinated polyethylene rubber has better flame retardance and oil resistance due to the chlorine element contained in the main chain, and has the performances of high temperature resistance and low temperature resistance, the maximum use temperature can reach 105 ℃, the mixing and extrusion speeds are high, and the production benefit is high. Compared with steel pipes, the existing chlorinated Polyethylene (PVC) electrical casing pipe has the advantages of light weight, easy cutting, easy bending, flexible and convenient installation, quick construction and the like in construction, and is mainly applied to concrete of buildings, floor slabs or walls as a wire conduit (hidden pipe), and also as a general wiring conduit (exposed pipe), a conduit for post and telecommunications, a conduit for network wiring and the like.
CN 102702644a discloses a method for manufacturing cold-bending electrical protective sleeves. The PVC resin-modified polyvinyl chloride composite material is prepared from 75kg of PVC resin, 3.8 kg of composite stabilizer, 0.5kg of stearic acid, 0.5kg of chlorinated polyethylene, 3kg of Qinzhou white powder, 0.6 kg of paraffin, 30kg of light calcium carbonate and 1kg of 401 auxiliary agent. Although the Acrylate (ACR) 401 toughening system is adopted in the cold-bending electrical sheath tube, the phenomenon that the electrical sheath tube is whitened and even cracked when bent in winter is caused due to poor dispersion in processing, and the flexibility of the electrical sheath tube needs to be enhanced.
With the development of society, people put higher demands on the performance of cable materials, and further improvement on the processing technology of the cable materials is needed to improve the physical and chemical properties of the electrical casing.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the method for preparing the electric casing of the EVA modified calcium carbonate toughening system has the advantages of simple manufacturing process, low manufacturing cost and convenience for large-scale production, and the electric casing prepared by the method has good physical and chemical properties such as rigidity, load thermal deformation strength, creep property, thermal shrinkage property, expansion coefficient, toughness and the like.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of an EVA modified calcium carbonate toughening system electrical casing comprises the following steps:
(1) preparing EVA modified calcium carbonate;
(2) putting PVC resin, EVA modified calcium carbonate, a composite stabilizer, a lubricant, a processing aid and titanium dioxide into a high-speed mixer according to the composition ratio of raw materials, stirring until the temperature of the materials is more than or equal to 120 ℃, discharging the mixture into a cold mixing pot, stirring and cooling to form a mixture, and discharging for later use;
(3) and (3) extruding the mixture prepared in the step (2) by using an extruder, and cooling and shaping to obtain the EVA modified calcium carbonate toughening system electrical casing.
Further, in the step 1), in the step (1), the preparation of the EVA modified calcium carbonate specifically comprises the following operations: and calcining the marble at a high temperature of more than 800 ℃ to obtain calcium oxide, digesting the calcium oxide into calcium hydroxide by water, adding 2% (w/w) of EVA emulsion of a calcium hydroxide solution into the calcium hydroxide at a stage of introducing carbon dioxide into the calcium hydroxide, and drying and sieving the mixture to obtain the EVA modified calcium carbonate.
Further, the EVA emulsion is characterized in that the content of EVA in the emulsion is 35-50% (w/w).
According to the EVA modified calcium carbonate, the EVA emulsion is added during the preparation of the calcium carbonate, so that the surface of the calcium carbonate is well coated, the surface activity of the calcium carbonate is increased, and the calcium carbonate and PVC resin have stronger binding force under the action of a bridge frame of the EVA. And the EVA and the PVC are compatible systems, so that the calcium carbonate can be uniformly dispersed in the PVC system in the processing process. Because EVA itself possesses fine toughness, can effectively avoid PVC electrician's sleeve pipe crooked blushing, the phenomenon that low temperature is breakable.
Further, the raw materials comprise the following components in parts by weight: 50-100 parts of PVC resin, 20-40 parts of EVA modified calcium carbonate, 3-5 parts of composite stabilizer, 0.2-1 part of lubricant, 0.5-2 parts of processing aid and 1-2 parts of titanium dioxide.
Further, the PVC resin is SG-5 type PVC resin, and the titanium dioxide is rutile type titanium dioxide. In the invention, the composite stabilizer is a lead salt composite stabilizer, a calcium-zinc stabilizer or an organic tin stabilizer; the lubricant is PE wax and stearic acid; the processing aid is chlorinated polyethylene.
Further, in step 2), the mixture is stirred and then cooled to 50 ℃ or lower.
Further, in the step 3), the extruder is a tapered twin-screw extruder, the barrel temperature of the extruder is 180-.
Further, in the step 3), the cooling and shaping are completed in a vacuum environment.
The preparation method of the EVA modified calcium carbonate toughening system electrical casing has the beneficial effects that: the preparation method has the advantages of simple operation process, low manufacturing cost and convenience for large-scale production.
By emulsifying the calcium carbonate, the use amount of the stabilizer can be effectively reduced, and the raw material cost and the preparation and processing cost of the electrical casing can be effectively reduced; the EVA emulsion is added into the formula to treat calcium carbonate, so that the prepared electrical casing has better rigidity, creep property, thermal shrinkage property and compression resistance; meanwhile, the toughness of the EVA can effectively improve the phenomena of whitening of PVC during bending and easy cracking at low temperature.
Detailed Description
The present invention is further illustrated by the following examples.
Comparative example 1
A preparation method of an active calcium carbonate filling system electrical casing comprises the following steps: weighing raw materials of Ge according to a ratio, adding 100 parts of PVC resin SG-5, 25 parts of active light calcium carbonate, 5 parts of composite stabilizer, 0.8 part of lubricant, 1.5 parts of processing aid and 1.5 parts of rutile titanium dioxide into a high-speed mixer, stirring until the temperature of the materials is 120 ℃, discharging the mixture into a cold mixing pot, stirring and cooling to 50 ℃ to form a mixture, and discharging. Extruding the obtained mixture by adopting a conical double screw, wherein the barrel temperature of an extruder is 180-fold and 190-fold, the die head temperature is 190-fold and 200-fold, and carrying out vacuum cooling and shaping to obtain the EVA toughening system electrical casing.
The composite stabilizer is a lead salt composite stabilizer; the lubricant is PE wax and stearic acid; the processing aid is chlorinated polyethylene.
Example 1
The preparation method of the electric bushing of the EVA modified calcium carbonate toughening system of the embodiment comprises the following steps:
(1) preparing EVA modified calcium carbonate: calcining marble at high temperature of 800 ℃ to obtain calcium oxide, digesting the calcium oxide into calcium hydroxide by water, adding 2% (W/W) of EVA emulsion (the EVA content in the emulsion is 40% (W/W)) of the calcium hydroxide solution into the calcium hydroxide solution, introducing carbon dioxide while stirring, filtering precipitates, drying in a 120 ℃ drying oven, and sieving by a 500-mesh sieve to obtain EVA modified calcium carbonate;
(2) adding 100 parts of PVC resin SG-5, 25 parts of EVA modified calcium carbonate, 5 parts of composite stabilizer, 0.8 part of lubricant, 1.5 parts of processing aid and 1.5 parts of rutile titanium dioxide into a high-speed mixer, stirring until the temperature of the materials reaches 120 ℃, discharging the mixture into a cold mixing pot, stirring and cooling to 50 ℃ to form a mixture, and discharging for later use;
(3) and (3) extruding the mixture prepared in the step (2) by using an extruder, wherein the barrel temperature of the extruder is 180-.
The composite stabilizer is a lead salt composite stabilizer; the lubricant is PE wax and stearic acid; the processing aid is chlorinated polyethylene.
Example 2
The preparation method of the electric bushing of the EVA modified calcium carbonate toughening system of the embodiment comprises the following steps:
(1) preparing EVA modified calcium carbonate: calcining marble at high temperature of 800 ℃ to obtain calcium oxide, digesting the calcium oxide into calcium hydroxide by water, adding 2% (W/W) of EVA emulsion (the EVA content in the emulsion is 50% (W/W)) of the calcium hydroxide solution into the calcium hydroxide solution, introducing carbon dioxide while stirring, filtering precipitates, drying in a 120 ℃ drying oven, and sieving by a 500-mesh sieve to obtain EVA modified calcium carbonate;
(2) adding 100 parts of PVC resin SG-5, 20 parts of EVA modified calcium carbonate, 4 parts of composite stabilizer, 0.5 part of lubricant, 1.5 parts of processing aid and 1.5 parts of rutile titanium dioxide into a high-speed mixer, stirring until the temperature of the materials reaches 120 ℃, discharging the mixture into a cold mixing pot, stirring and cooling to 50 ℃ to form a mixture, and discharging for later use;
(3) and (3) extruding the mixture prepared in the step (2) by using an extruder, wherein the barrel temperature of the extruder is 180-.
The composite stabilizer is calcium zinc stabilizer, and the calcium zinc stabilizer is HKS698 of Han Fushan family.
Example 3
The preparation method of the electric bushing of the EVA modified calcium carbonate toughening system of the embodiment comprises the following steps:
(1) preparing EVA modified calcium carbonate: calcining marble at high temperature of 800 ℃ to obtain calcium oxide, digesting the calcium oxide into calcium hydroxide by water, adding 2% (W/W) of EVA emulsion (the EVA content in the emulsion is 38% (W/W)) of the calcium hydroxide solution into the calcium hydroxide solution, introducing carbon dioxide while stirring, filtering precipitates, drying in a 120 ℃ drying oven, and sieving by a 500-mesh sieve to obtain EVA modified calcium carbonate;
(2) adding 100 parts of PVC resin SG-5, 33 parts of EVA modified calcium carbonate, 4 parts of composite stabilizer, 1 part of lubricant, 1.5 parts of processing aid and 1.5 parts of rutile titanium dioxide into a high-speed mixer according to the composition ratio of the raw materials, stirring until the temperature of the materials reaches 120 ℃, discharging the mixture into a cold mixing pot, stirring and cooling to 50 ℃ to form a mixture, and discharging for later use;
(3) and (3) extruding the mixture prepared in the step (2) by using an extruder, wherein the barrel temperature of the extruder is 180-.
The composite stabilizer is an organic tin stabilizer, and the organic tin stabilizer is F-50 of Delong chemical Co., Ltd.
The performance test structures of the electrical sleeves obtained by the preparation methods of the comparative example and the examples 1 to 3 are shown in table 2.
TABLE 2 Performance parameters of Electrical bushings obtained in comparative examples and in the preparation methods of examples 1 to 3
Compared with the preparation method of the traditional active calcium carbonate filling system electrical casing, the calcium carbonate is subjected to EVA emulsification treatment, so that the surface of the calcium carbonate is well coated, the surface activity of the calcium carbonate is increased, and the calcium carbonate and PVC resin have stronger binding force under the bridge action of EVA. And the EVA and the PVC are compatible systems, so that the calcium carbonate can be uniformly dispersed in the PVC system in the processing process. Because EVA itself possesses fine toughness, can effectively avoid PVC electrician's sleeve pipe crooked blushing, the phenomenon that low temperature is breakable.
As can be seen from table 2, the electrical casing prepared by the preparation method has better compression resistance, especially low-temperature impact resistance and bending property than the electrical casing added with light activated calcium carbonate.
Claims (6)
1. A preparation method of an EVA modified calcium carbonate toughening system electrical casing comprises the following steps:
(1) preparing EVA modified calcium carbonate; the preparation method of the EVA modified calcium carbonate comprises the following specific operations: calcining marble at a high temperature of more than 800 ℃ to obtain calcium oxide, digesting the calcium oxide into calcium hydroxide by water, adding 2% (w/w) of EVA emulsion of a calcium hydroxide solution into the calcium hydroxide at a stage of introducing carbon dioxide into the calcium hydroxide, and drying and sieving the mixture to obtain EVA modified calcium carbonate;
(2) putting PVC resin, EVA modified calcium carbonate, a composite stabilizer, a lubricant, a processing aid and titanium dioxide into a high-speed mixer according to the composition ratio of raw materials, stirring until the temperature of the materials is more than or equal to 120 ℃, discharging the mixture into a cold mixing pot, stirring and cooling to form a mixture, and discharging for later use;
(3) and (3) extruding the mixture prepared in the step (2) by using an extruder, and cooling and shaping to obtain the EVA modified calcium carbonate toughening system electrical casing.
2. The method for preparing the EVA modified calcium carbonate toughening system electrical casing according to claim 1, wherein the EVA emulsion is an emulsion in which the EVA content is 35-50% (w/w).
3. The method for preparing the EVA modified calcium carbonate toughening system electrical casing according to claim 1, wherein the raw materials comprise the following components in percentage by weight: 50-100 parts of PVC resin, 20-40 parts of EVA modified calcium carbonate, 3-5 parts of composite stabilizer, 0.2-1 part of lubricant, 0.5-2 parts of processing aid and 1-2 parts of titanium dioxide.
4. The method for preparing the EVA modified calcium carbonate toughening system electrical casing according to any one of claims 1 to 3, wherein in the step 2), the mixture is stirred and then cooled to below 50 ℃.
5. The method for preparing the EVA modified calcium carbonate toughening system electrical casing according to any one of claims 1 to 3, wherein in the step 3), the extruder is a tapered twin-screw extruder, the barrel temperature of the extruder is 180-200 ℃, and the die head temperature is 200-210 ℃.
6. The method for preparing the EVA modified calcium carbonate toughening system electrical casing according to any one of claims 1 to 3, wherein in the step 3), the cooling and shaping are completed in a vacuum environment.
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| CN1204052C (en) * | 2003-06-07 | 2005-06-01 | 浙江大学 | Method for producing light active calcium carbonate |
| CN102702644B (en) * | 2012-06-02 | 2014-10-08 | 安徽玉发塑业有限公司 | Cold bending electrical protective casing and manufacturing method thereof |
| CN106317705B (en) * | 2016-08-31 | 2019-02-05 | 爱康企业集团(上海)有限公司 | A kind of hard PVC talc system electrical casing pipe |
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| "聚丙烯酸酯/纳米碳酸钙复合增韧剂的制备及其应用于PVC改性的研究";董源;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20131015(第10期);第B016-32页 * |
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