CN111423466B - Preparation method of ionic rubber cross-linking agent - Google Patents
Preparation method of ionic rubber cross-linking agent Download PDFInfo
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- CN111423466B CN111423466B CN202010187185.7A CN202010187185A CN111423466B CN 111423466 B CN111423466 B CN 111423466B CN 202010187185 A CN202010187185 A CN 202010187185A CN 111423466 B CN111423466 B CN 111423466B
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- ionic
- linking agent
- crosslinking agent
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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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
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
Abstract
A preparation method of an ionic rubber crosslinking agent comprises the following steps: 1) mixing ZDMA with N-methyl-2-pyrrolidone (NMP), and dissolving uniformly with the aid of an ultrasonic cleaner to obtain a solution; 2) adding formic acid, hydrogen peroxide with the concentration of 35% and Si-69 into the solution obtained in the step 1) respectively, and reacting to obtain a reaction solution; 3) centrifugally separating the reaction liquid obtained in the step 2), repeatedly washing the precipitate with ethanol, and drying in an oven to obtain the ionic cross-linking agent; has the characteristics of simple process, low cost, convenient recovery and biodegradability.
Description
Technical Field
The invention discloses a preparation method of an ionic rubber cross-linking agent, and particularly relates to a cross-linking network capable of constructing ionic bonds in a rubber cross-linking process.
Background
Rubber is a common thermoset material, and has reached a global production of 1.6 million tons in 2017. The rubber material and a vulcanizing agent are subjected to a crosslinking reaction at a high temperature, linear rubber molecules are crosslinked into a three-dimensional network structure, and excellent physical properties are endowed to the material. In the daily life of people, rubber products are seen everywhere, such as: rubber tires, sealing rings, gloves and the like, which make contributions to the life of people and have the problems of difficult recycling and biodegradation, cause huge environmental problems and resource wasteAnd (4) charging. According to the statistics of the world health organization, the global waste tire reserves reach 30 hundred million, and the number is increased by 10 hundred million every year. The reason for this is because the conventional rubber crosslinking agents generate a covalent, irreversible three-dimensional network structure during the crosslinking process. Conventional rubber crosslinking agents include: sulfur, peroxides, metal oxides, etc., the rubber being irreversibly covalently crosslinked by the action of such crosslinking agents, e.g. C-S-C, C-SX-C, C-C, C-O and the like. Due to the irreversibility, the rubber product is difficult to recover and reduce after being discarded, thereby causing environmental pollution and resource waste. Therefore, the development of an ionic crosslinking agent has important practical significance.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of an ionic type rubber crosslinking agent, which introduces ionic bonds into a crosslinking network of rubber, and the prepared ionic type crosslinking agent can crosslink all unsaturated rubbers under the existing rubber process; has the characteristics of simple process, low cost, convenient recovery and biodegradability.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of an ionic rubber cross-linking agent is characterized in that zinc methacrylate (ZDMA) and bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide (Si-69) are adopted to prepare the ionic cross-linking agent, and specifically comprises the following steps:
1) mixing 0.25-20g of ZDMA with 7.5-600mL of N-methyl-2-pyrrolidone (NMP), and uniformly dissolving with the aid of an ultrasonic cleaner to obtain a solution;
2) respectively adding 0.5-5g of formic acid, 0.25-20g of 35% hydrogen peroxide and 0.25-20 mL of Si-69 into the solution obtained in the step 1), and reacting at 90 ℃ for 12h to obtain a reaction solution;
3) centrifuging the reaction solution obtained in the step 2) at 3500rpm, repeatedly washing the precipitate with 95% ethanol for 5 times, and drying in an oven at 85 ℃ for 12h to obtain the ionic crosslinking agent.
In step 1), the zinc methacrylate can be replaced by unsaturated carboxylic acid metal salt magnesium methacrylate or aluminum methacrylate.
In the step 2), the mass ratio of formic acid, zinc methacrylate and hydrogen peroxide is 1:0.5:2-1:4: 6.
The invention has the following beneficial effects:
the invention dissolves ZDMA in NMP; and then formic acid, hydrogen peroxide and Si-69 are respectively added into the ZDMA/NMP solution, and the ionic rubber cross-linking agent is prepared by a one-pot method.
The invention has simple process and low cost. The prepared cross-linking agent can cross-link most unsaturated rubber to generate an ionic cross-linked network, so that the cross-linked rubber can be dissolved in a solvent to realize recovery, the ionic cross-linked network can be reconstructed in the recovered rubber to realize reprocessing of materials, and the ionic cross-linked network can be degraded by microorganisms.
The ionic rubber crosslinking agent is prepared by combining an ionic compound zinc methacrylate and a crosslinking agent Si-69 through chemical reaction. Compared with the traditional rubber crosslinking agent, the ionic crosslinking agent can construct a three-dimensional ionic crosslinking network in rubber, and provides possibility for convenient recovery and biodegradation of crosslinked rubber.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
A method for preparing ionic cross-linking agent for rubber adopts zinc methacrylate (ZDMA) and bis- [ gamma- (triethoxy silicon) propyl ] tetrasulfide (Si-69) to prepare ionic cross-linking agent, which comprises the following steps:
1) mixing 0.25-20g of ZDMA with 7.5-600mL of N-methyl-2-pyrrolidone (NMP), and uniformly dissolving with the aid of an ultrasonic cleaner to obtain a solution;
2) respectively adding 0.5-5g of formic acid, 0.25-20g of 35% hydrogen peroxide and 0.25-20 mL of Si-69 into the solution obtained in the step 1), and reacting at 90 ℃ for 12h to obtain a reaction solution;
3) centrifuging the reaction liquid obtained in the step 2) at 3500rpm, repeatedly washing the precipitate with 95% ethanol for 5 times, and drying in an oven at 85 ℃ for 12h to obtain the ionic crosslinking agent.
Example one
1) Mixing 8g of ZDMA with 300mL of N-methyl-2-pyrrolidone (NMP), and dissolving uniformly with the aid of an ultrasonic cleaner;
2) then 1.97g of formic acid, 14.48g of hydrogen peroxide (35%) and 8mL of Si-69 are respectively added into the solution obtained in the step 1) and reacted for 12 hours at 90 ℃;
3) centrifuging the reaction solution obtained in the step 2) at 3500rpm, repeatedly washing the lower-layer precipitate with ethanol (95%) for 5 times, and drying in an oven at 85 ℃ for 12h to obtain the ionic cross-linking agent.
The ionic crosslinker prepared from example one had a mass of 4.2g and a yield of 52.5%.
Example two
(1) Mixing 10g of ZDMA with 300mL of N-methyl-2-pyrrolidone (NMP), and dissolving uniformly with the aid of an ultrasonic cleaner;
(2) then adding 1.97g of formic acid, 14.48g of hydrogen peroxide (35%) and 10 mL of Si-69 into the solution obtained in the step (1) respectively, and reacting for 12h at 90 ℃;
(3) and (3) centrifuging the reaction solution obtained in the step (2) at 3500rpm, repeatedly washing the lower-layer precipitate with ethanol (95%) for 5 times, and drying in an oven at 85 ℃ for 12 hours to obtain the ionic cross-linking agent.
The mass of ionic crosslinker prepared in example two was 5.2 g, the yield was 52.0%
Example three:
1) mixing 10g of ZDMA with 350 mL of N-methyl-2-pyrrolidone (NMP), and uniformly dissolving with the aid of an ultrasonic cleaner;
2) then adding 1.97g of formic acid, 14.48g of hydrogen peroxide (35%) and 12 mL of Si-69 into the solution obtained in the step 1) respectively, and reacting for 12 hours at 90 ℃;
3) centrifuging the reaction solution obtained in the step 2) at 3500rpm, repeatedly washing the lower-layer precipitate with ethanol (95%) for 5 times, and drying in an oven at 85 ℃ for 12h to obtain the ionic crosslinking agent.
The ionic crosslinking agent prepared in example two had a mass of 5.06 g and a yield of 50.6%.
Example four
A method for preparing ionic rubber cross-linking agent, which adopts zinc methacrylate (ZDMA) and bis- [ gamma- (triethoxy silicon) propyl ] tetrasulfide (Si-69) to prepare ionic cross-linking agent, comprises the following steps:
1) mixing 0.25g of ZDMA with 7.5mL of N-methyl-2-pyrrolidone (NMP), and uniformly dissolving with the aid of an ultrasonic cleaner to obtain a solution;
2) then adding 0.5g of formic acid, 0.25g of 35% hydrogen peroxide and 0.25mL of Si-69 into the solution obtained in the step 1) respectively, and reacting for 12 hours at 90 ℃ to obtain a reaction solution;
3) centrifuging the reaction solution obtained in the step 2) at 3500rpm, repeatedly washing the precipitate with 95% ethanol for 5 times, and drying in an oven at 85 ℃ for 12h to obtain the ionic crosslinking agent.
The ionic crosslinking agent prepared in example four had a mass of 0.12g and a yield of 48%.
EXAMPLE five
A method for preparing ionic cross-linking agent for rubber adopts zinc methacrylate (ZDMA) and bis- [ gamma- (triethoxy silicon) propyl ] tetrasulfide (Si-69) to prepare ionic cross-linking agent, which comprises the following steps:
1) mixing 20g of ZDMA with 600mL of N-methyl-2-pyrrolidone (NMP), and uniformly dissolving with the aid of an ultrasonic cleaner to obtain a solution;
2) respectively adding 5g of formic acid, 20g of 35% hydrogen peroxide and 20mL of Si-69 into the solution obtained in the step 1), and reacting at 90 ℃ for 12 hours to obtain a reaction solution;
3) centrifuging the reaction solution obtained in the step 2) at 3500rpm, repeatedly washing the precipitate with 95% ethanol for 5 times, and drying in an oven at 85 ℃ for 12h to obtain the ionic crosslinking agent.
The ionic crosslinking agent prepared in example five had a mass of 12g and a yield of 60%.
EXAMPLE six
A method for preparing ionic cross-linking agent for rubber adopts zinc methacrylate (ZDMA) and bis- [ gamma- (triethoxy silicon) propyl ] tetrasulfide (Si-69) to prepare ionic cross-linking agent, which comprises the following steps:
1) mixing 10.13g of ZDMA with 303.7mL of N-methyl-2-pyrrolidone (NMP), and uniformly dissolving with the aid of an ultrasonic cleaner to obtain a solution;
2) respectively adding 2.3g of formic acid, 10.13g of 35% hydrogen peroxide and 10.13g of mL of Si-69 into the solution obtained in the step 1), and reacting at 90 ℃ for 12 hours to obtain a reaction solution;
3) centrifuging the reaction solution obtained in the step 2) at 3500rpm, repeatedly washing the precipitate with 95% ethanol for 5 times, and drying in an oven at 85 ℃ for 12h to obtain the ionic crosslinking agent.
The ionic crosslinking agent prepared in example six had a mass of 5.5g and a yield of 54%.
The invention is not limited to the examples, and any equivalent changes to the technical solution of the invention by a person skilled in the art after reading the description of the invention are covered by the claims of the invention.
Claims (3)
1. A method for preparing ionic cross-linking agent for rubber is characterized in that zinc methacrylate and bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide are used for preparing the ionic cross-linking agent, and the ionic cross-linking agent and the bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide are combined together through chemical reaction, and the method specifically comprises the following steps:
1) mixing 0.25-20g of zinc methacrylate and 7.5-600ml of LN-methyl-2-pyrrolidone, and uniformly dissolving with the aid of an ultrasonic cleaner to obtain a solution;
2) respectively adding 0.5-5g of formic acid, 0.25-20g of 35% hydrogen peroxide and 0.25-20 mL of bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide into the solution obtained in the step 1), and reacting at 90 ℃ for 12h to obtain a reaction solution;
3) centrifuging the reaction liquid obtained in the step 2) at 3500rpm, repeatedly washing the precipitate with 95% ethanol for 5 times, and drying in an oven at 85 ℃ for 12h to obtain the ionic crosslinking agent.
2. The method of claim 1, wherein the crosslinking agent is selected from the group consisting of a crosslinking agent,
in the step 1), the zinc methacrylate is replaced by unsaturated carboxylic acid metal salt magnesium methacrylate or aluminum methacrylate.
3. The method for preparing an ionic rubber crosslinking agent according to claim 1, wherein:
in the step 2), the mass ratio of formic acid, zinc methacrylate and hydrogen peroxide is 1:0.5:2-1:4: 6.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008150546A (en) * | 2006-12-20 | 2008-07-03 | Shin Etsu Chem Co Ltd | Compounding agent for rubber |
| JP2012102176A (en) * | 2010-11-08 | 2012-05-31 | Yokohama Rubber Co Ltd:The | Silane coupling agent, and rubber composition for tire using the same |
| CN104710449A (en) * | 2013-12-13 | 2015-06-17 | 信越化学工业株式会社 | Sulfur-containing organosilicon compound, making method, rubber compounding ingredient, and rubber composition |
| CN105001252A (en) * | 2014-04-22 | 2015-10-28 | 赢创工业集团股份有限公司 | Azocarbonyl-functionalized silanes |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008150546A (en) * | 2006-12-20 | 2008-07-03 | Shin Etsu Chem Co Ltd | Compounding agent for rubber |
| JP2012102176A (en) * | 2010-11-08 | 2012-05-31 | Yokohama Rubber Co Ltd:The | Silane coupling agent, and rubber composition for tire using the same |
| CN104710449A (en) * | 2013-12-13 | 2015-06-17 | 信越化学工业株式会社 | Sulfur-containing organosilicon compound, making method, rubber compounding ingredient, and rubber composition |
| CN105001252A (en) * | 2014-04-22 | 2015-10-28 | 赢创工业集团股份有限公司 | Azocarbonyl-functionalized silanes |
Non-Patent Citations (1)
| Title |
|---|
| Three-Dimensional Graphene Foam-Filled Elastomer Composites with High Thermal and Mechanical Properties;Haoming Fang等;《ACS Appl. Mater. Interfaces》;20170721;第9卷;26447-26459 * |
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