CN111286080B - Protective material special for polar rubber and preparation method thereof - Google Patents
Protective material special for polar rubber and preparation method thereof Download PDFInfo
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- CN111286080B CN111286080B CN202010330631.5A CN202010330631A CN111286080B CN 111286080 B CN111286080 B CN 111286080B CN 202010330631 A CN202010330631 A CN 202010330631A CN 111286080 B CN111286080 B CN 111286080B
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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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
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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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/32—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing phosphorus or sulfur
- C08L23/34—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing phosphorus or sulfur by chlorosulfonation
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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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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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
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Abstract
The invention discloses a special protective material for polar rubber and a preparation method thereof. The protective material comprises the following components in parts by weight: 40-50 parts of nickel dibutyl dithiocarbamate; 30-40 parts of nickel terephthalate; 10-30 parts of calcium terephthalate. The preparation method of the protective material comprises the following steps: (1) mixing and dissolving the alkali reduction wastewater, dibutylamine, carbon disulfide and caustic soda according to a certain proportion, and filtering by active carbon to obtain a clear solution; (2) reacting the solution obtained in the step (1) with a nickel chloride solution to obtain slurry A; (3) reacting alkali-reduced water filtered by activated carbon with a calcium chloride solution to obtain slurry B; (4) and (3) uniformly mixing the slurry A in the step (2) and the slurry B in the step (3), and then separating, washing and drying to obtain the target product. The protective material disclosed by the invention is moderate in price, good in dispersibility in rubber materials, excellent in protective performance and capable of overcoming the defect that the rubber materials are easy to adhere.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a special protective material for polar rubber and a preparation method thereof.
Background
Among the types of rubbers commonly used, polar rubbers are mainly chloroprene rubber, nitrile rubber, hydrogenated nitrile rubber, carboxylated nitrile rubber, fluororubber, urethane rubber, polyether rubber, polysulfide rubber, acrylate rubber, chlorinated polyvinyl chloride rubber, chlorosulfonated polyethylene rubber, and the like. The properties of such rubbers are shown as: the cable has good oil resistance, good heat resistance, high strength and low insulativity, and is commonly used in oil-resistant and high-temperature-resistant occasions.
During the processing, storage and use of the rubber and the products thereof, the aging symptoms such as cracking, stickiness, hardening, softening, powdering, discoloration, mold growth and the like can occur due to the combined action of internal and external factors, and finally the use value is lost. The rubber anti-aging agent is a product capable of preventing or delaying rubber aging.
The anti-aging agent NBC (nickel dibutyl dithiocarbamate) is a commonly used ozone aging resistant material for polar rubber, and can improve the heat resistance of the polar rubber; however, it has the disadvantages of high cost and easy migration of blooming. In addition, the rubber material needs to be added with an additional material to overcome the defect of easy adhesion during storage.
The invention aims to improve an anti-aging agent NBC and provide a special protective material for polar rubber, which has moderate price, is not easy to frost and can prevent adhesion.
Disclosure of Invention
The invention aims to provide a special protective material for polar rubber and a preparation method thereof. The protective material prepared by the method has the characteristics of moderate price, difficult frosting, polar adhesion prevention and excellent protective performance.
In order to achieve the purpose, the invention is realized by the following technical scheme: the special protective material for polar rubber comprises the following components: the nickel dibutyl dithiocarbamate, the nickel terephthalate and the calcium terephthalate comprise the following components in parts by weight: 40-50 parts of nickel dibutyl dithiocarbamate, 30-40 parts of nickel terephthalate and 10-30 parts of calcium terephthalate.
The preparation method of the special protective material for preparing polar rubber comprises the following steps:
(1) under the condition of continuous stirring, mixing the alkali-reduction wastewater, dibutylamine, carbon disulfide and caustic soda according to a certain proportion, after completely dissolving, adding active carbon accounting for 0.2 percent of the mass of the solution, stirring for 10-20min to uniformly disperse the active carbon in the solution, and then filtering to obtain a decolored clear sodium salt solution;
(2) under the condition of continuous stirring, mixing the sodium salt solution obtained in the step (1) with 35-60% of nickel chloride solution in percentage by mass, and continuously stirring and reacting for 20-60 min at the rotating speed of 150-500 rpm to obtain mixed slurry A;
(3) under the condition of continuous stirring, mixing alkali-reduced water filtered by activated carbon with a calcium chloride solution with the mass percentage of 30-40%, and continuously stirring and reacting for 20-60 min at the rotating speed of 150-500 rpm to obtain mixed slurry B;
(4) and (3) mixing the slurry A obtained in the step (2) and the slurry B obtained in the step (3) for 20-60 min at a stirring speed of 300-700 rpm, and then separating, washing and drying to obtain the target product.
Further, the main components of the alkali weight reduction wastewater in the preparation step are ethylene glycol, sodium hydroxide and sodium terephthalate, and the temperature of the wastewater is not lower than 30 ℃.
Has the advantages that:
(1) the invention utilizes alkali decrement waste water to prepare the special protective material for polar rubber, has low raw material price, and leads the price of a target product to be about 30 percent lower than that of nickel dibutyl dithiocarbamate;
(2) the ethylene glycol is contained in the alkali deweighting water, so that the surface tension of a reaction system is reduced, the obtained target product is not easy to agglomerate in the drying process, the dispersibility of the target product in the sizing material is improved, and the protective performance is exerted efficiently;
(3) the calcium terephthalate can relieve the adhesion among the polar rubber sheets and improve the process performance;
(4) stronger intermolecular force can be generated between the terephthalate and the polar rubber, so that the defect that the nickel dibutyl dithiocarbamate is easy to migrate and frost is overcome.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. The invention will be better understood from the following examples. The examples are not intended to limit the scope of the present invention.
Example 1
The special protective material for polar rubber comprises the following components in parts by weight: 40 parts of nickel dibutyl dithiocarbamate, 30 parts of nickel terephthalate and 30 parts of calcium terephthalate.
The preparation method of the special protective material for polar rubber comprises the following steps:
(1) under the condition of continuous stirring, mixing the alkali-reduction wastewater, dibutylamine, carbon disulfide and caustic soda according to a certain proportion, after completely dissolving, adding active carbon accounting for 0.2 percent of the mass of the solution, stirring for 10min to uniformly disperse the active carbon in the solution, and then filtering to obtain a decolored clear sodium salt solution;
(2) under the condition of continuous stirring, mixing the sodium salt solution obtained in the step (1) with a nickel chloride solution with the mass percentage of 35%, and continuously stirring and reacting for 60min at the rotating speed of 150rpm to obtain mixed slurry A;
(3) under the condition of continuous stirring, mixing alkali-reduced water filtered by active carbon with a calcium chloride solution with the mass percentage of 30%, and continuously stirring and reacting for 60min at the rotating speed of 150rpm to obtain mixed slurry B;
(4) and (3) mixing the slurry A obtained in the step (2) and the slurry B obtained in the step (3) for 60min at the stirring speed of 300rpm, and then separating, washing and drying to obtain the target product.
Further, the main components of the alkali weight reduction wastewater in the preparation step are ethylene glycol, sodium hydroxide and sodium terephthalate, and the temperature of the wastewater is not lower than 30 ℃.
Example 2
Example 2 differs from example 1 in that:
the special protective material for polar rubber comprises the following components in parts by weight: 50 parts of nickel dibutyl dithiocarbamate, 40 parts of nickel terephthalate and 10 parts of calcium terephthalate.
The preparation method of the special protective material for polar rubber comprises the following steps:
(1) under the condition of continuous stirring, mixing the alkali-reduction wastewater, dibutylamine, carbon disulfide and caustic soda according to a certain proportion, after completely dissolving, adding active carbon accounting for 0.2 percent of the mass of the solution, stirring for 20min to uniformly disperse the active carbon in the solution, and then filtering to obtain a decolored clear sodium salt solution;
(2) mixing the sodium salt solution obtained in the step (1) with a nickel chloride solution with the mass percentage of 60% under continuous stirring, and continuously stirring and reacting for 20min at the rotating speed of 500rpm to obtain mixed slurry A;
(3) under the condition of continuous stirring, mixing alkali-reduced water filtered by active carbon with a calcium chloride solution with the mass percentage of 40%, and continuously stirring and reacting for 20min at the rotating speed of 500rpm to obtain mixed slurry B;
(4) and (3) mixing the slurry A obtained in the step (2) and the slurry B obtained in the step (3) for 20min at the stirring speed of 700rpm, and then separating, washing and drying to obtain the target product.
Example 3
Example 3 differs from example 1 in that:
the special protective material for polar rubber comprises the following components in parts by weight: 45 parts of nickel dibutyl dithiocarbamate, 35 parts of nickel terephthalate and 20 parts of calcium terephthalate.
The preparation method of the special protective material for polar rubber comprises the following steps:
(1) under the condition of continuous stirring, mixing the alkali-reduction wastewater, dibutylamine, carbon disulfide and caustic soda according to a certain proportion, after completely dissolving, adding activated carbon accounting for 0.2 percent of the mass of the solution, stirring for 15min to uniformly disperse the activated carbon in the solution, and then filtering to obtain a decolored clear sodium salt solution;
(2) under the condition of continuous stirring, mixing the sodium salt solution obtained in the step (1) with a nickel chloride solution with the mass percentage of 45%, and continuously stirring and reacting for 45min at the rotating speed of 300rpm to obtain mixed slurry A;
(3) under the condition of continuous stirring, mixing alkali-reduced water filtered by active carbon with a calcium chloride solution with the mass percentage of 35%, and continuously stirring and reacting for 45min at the rotating speed of 300rpm to obtain mixed slurry B;
(4) and (3) mixing the slurry A obtained in the step (2) and the slurry B obtained in the step (3) for 40min at the stirring speed of 450rpm, and then separating, washing and drying to obtain the target product.
Comparative example 1
The special protective material for polar rubber comprises the following components in parts by weight: 100 parts of nickel dibutyl dithiocarbamate.
The preparation method of the special protective material for polar rubber comprises the following steps:
(1) under the condition of continuous stirring, mixing dibutylamine, carbon disulfide and caustic soda according to a certain proportion, and obtaining a clear sodium salt solution after complete dissolution;
(2) under the condition of continuous stirring, mixing the sodium salt solution obtained in the step (1) with a nickel chloride solution with the mass percentage of 35%, and continuously stirring and reacting for 60min at the rotating speed of 150rpm to obtain mixed slurry;
(3) and (3) separating, washing and drying the mixed slurry obtained in the step (2) to obtain the target product.
Test 1
Different types of antioxidants were applied to the rubber formulations, which are shown in table 1.
The rubber material is mixed on an open mill, and the mixing process comprises the following steps: adjusting the roll spacing of the open mill to 1 mm, respectively thinly passing the NBR and the CSM for 10 times, then blending, and thinly passing for 5 times; adjusting the roller spacing to 2 mm, adding plasticated raw rubber, sequentially adding zinc oxide, stearic acid and an anti-aging agent after the rollers are wrapped, adding a plasticizer and carbon black, and finally adding sulfur and a promoter; packaging with triangular bag, rolling for 5 times, and discharging. Standing the mixed rubber for 16 h, then remilling the mixed rubber on an open mill, and covering a roller and then discharging pieces. The vulcanization is carried out on a press vulcanizer. The test was carried out according to the national standard and the properties obtained are shown in Table 2.
Table 1 sizing formulations
| Formulation 1 | Formulation 2 | Formulation 3 | Formulation 4 | |
| NBR | 40 | 40 | 40 | 40 |
| CSM | 60 | 60 | 60 | 60 |
| N550 | 55 | 55 | 55 | 55 |
| Zinc oxide | 2.5 | 2.5 | 2.5 | 2.5 |
| Stearic acid | 1 | 1 | 1 | 1 |
| Chlorinated paraffin | 10 | 10 | 10 | 10 |
| Sulfur | 1 | 1 | 1 | 1 |
| Accelerator TMTD | 0.5 | 0.5 | 0.5 | 0.5 |
| Accelerant CZ | 0.9 | 0.9 | 0.9 | 0.9 |
| EXAMPLE 1 preparation of antioxidant | 2 | — | — | — |
| Comparative example 1 preparation of antioxidant | — | 2 | 0.8 | 1.4 |
| Nickel terephthalate | — | — | 0.6 | — |
| Terephthalic acid calcium salt | — | — | 0.6 | 0.6 |
TABLE 2 Properties of the rubber mixtures
Analysis of the data in table 2 shows that: (1) it can be seen from the situation of unvulcanized rubber tackiness that the easy-to-stick characteristic of the rubber compound is improved after the calcium terephthalate is added into the formula. (2) The comparison of the data of the formula 1 and the formula 2 shows that the anti-aging agent prepared by the invention has more efficient and more excellent protection effect than pure nickel dibutyl dithiocarbamate, which is closely related to good dispersibility in rubber material and long-acting effect of effective components. (3) The comparison of the data of the formula 1 and the formula 3 shows that the comprehensive use effect of the target product prepared by the in-situ method is more excellent than the effect of simply mixing the components.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the foregoing description only for the purpose of illustrating the principles of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims, specification, and equivalents thereof.
Claims (1)
1. The special protective material for polar rubber is characterized by comprising the following components in parts by weight:
40-50 parts of nickel dibutyl dithiocarbamate;
30-40 parts of nickel terephthalate;
10-30 parts of calcium terephthalate;
the preparation method of the special protective material for polar rubber is characterized by comprising the following steps:
(1) under the condition of continuous stirring, mixing the alkali-reduction wastewater, dibutylamine, carbon disulfide and caustic soda according to a certain proportion, after completely dissolving, adding active carbon accounting for 0.2 percent of the mass of the solution, stirring for 10-20min to uniformly disperse the active carbon in the solution, and then filtering to obtain a decolored clear sodium salt solution;
(2) under the condition of continuous stirring, mixing the sodium salt solution obtained in the step (1) with 35-60% of nickel chloride solution in percentage by mass, and continuously stirring and reacting for 20-60 min at the rotating speed of 150-500 rpm to obtain mixed slurry A;
(3) under the condition of continuous stirring, mixing alkali-reduced water filtered by activated carbon with a calcium chloride solution with the mass percentage of 30-40%, and continuously stirring and reacting for 20-60 min at the rotating speed of 150-500 rpm to obtain mixed slurry B;
(4) mixing the slurry A obtained in the step (2) and the slurry B obtained in the step (3) for 20-60 min at a stirring speed of 300-700 rpm, and then separating, washing and drying to obtain a target product;
the main components of the alkali weight reduction wastewater in the step (1) are ethylene glycol, sodium hydroxide and sodium terephthalate, and the temperature of the wastewater is not lower than 30 ℃.
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| WO2000050393A1 (en) * | 1999-02-22 | 2000-08-31 | Flexsys B.V. | Solvent-free process for preparing thiuram disulfides |
| CN101121683A (en) * | 2007-09-19 | 2008-02-13 | 濮阳蔚林化工股份有限公司 | Method for producing rubber vulcanization accelerant zinc dibutyl dithiocaarbamate |
| CN102583813B (en) * | 2012-01-12 | 2013-11-13 | 江苏爱特恩高分子材料有限公司 | Recovery method for terephthalic acid in alkali deweighting wastewater as well as production method and application of terephthalic acid metal salt whisker |
| CN105778155B (en) * | 2016-05-12 | 2019-04-19 | 上海橡瑞新材料科技有限公司 | A kind of antioxidant NBC and preparation method thereof coating nano material |
| CN107090099B (en) * | 2017-06-14 | 2019-03-19 | 常州市五洲环保科技有限公司 | A kind of preparation method of rubber protective materials |
| CN109111718A (en) * | 2018-07-11 | 2019-01-01 | 宁波艾克姆新材料有限公司 | Pre-dispersed masterbatch particles of nickel dibutyl dithiocarbamate and preparation method thereof |
| CN110922638A (en) * | 2019-12-23 | 2020-03-27 | 常州市五洲环保科技有限公司 | Method for preparing protective material for rubber by recycling textile white mud |
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