CN114437408A - Modified peroxide vulcanizing agent and preparation method and application thereof - Google Patents

Modified peroxide vulcanizing agent and preparation method and application thereof Download PDF

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CN114437408A
CN114437408A CN202011109543.9A CN202011109543A CN114437408A CN 114437408 A CN114437408 A CN 114437408A CN 202011109543 A CN202011109543 A CN 202011109543A CN 114437408 A CN114437408 A CN 114437408A
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silane coupling
curing agent
coupling agent
peroxide
peroxide curing
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CN114437408B (en
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唐瀚滢
解希铭
王丽静
谭晓村
刘苹
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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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
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K5/14—Peroxides
    • 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
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • 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
    • C08K9/02—Ingredients treated with inorganic substances

Abstract

The invention relates to the field of rubber vulcanizing agents, and particularly discloses a modified peroxide vulcanizing agent, a preparation method and application thereof. The modified peroxide curing agent has high grafting amount and excellent extraction resistance.

Description

Modified peroxide vulcanizing agent and preparation method and application thereof
Technical Field
The invention relates to the field of rubber vulcanizing agents, in particular to a modified peroxide vulcanizing agent, and a preparation method and application thereof.
Background
With the continuous development of the rubber industry and the enhancement of the environmental awareness of human beings, the preparation of novel, efficient, multifunctional, low-cost and environment-friendly rubber additives becomes a new direction for the development of the rubber industry. Vulcanization of rubber is a key factor that imparts value to rubber.
However, the small molecule vulcanizing agent commonly used in the industry at present has the defects of easy blooming, single function, environmental pollution and the like. In order to solve the problems, the preparation of a novel efficient, multifunctional and environment-friendly vulcanizing agent is a necessary trend in the development of the rubber auxiliary industry. The prepared load-type vulcanizing agent not only has the function of vulcanization crosslinking, but also can improve the dispersion of the filler in the rubber matrix and improve the volatilization resistance and the extraction resistance.
CN103360628A discloses a supported rubber vulcanization accelerator and a preparation method and application thereof, wherein the method comprises the following steps: firstly, preparing a solution with the mass concentration of 0.5-30% by using a silane coupling agent and an organic solvent, mixing the solution with an inorganic carrier to obtain a mixture with the solid content of 2-80%, and stirring and reacting for 6-30 hours at the temperature of 40-100 ℃. And then adding a rubber vulcanization accelerator with the mole number 1.0-1.8 times that of the coupling agent into the reaction product, and reacting for 10-20 hours under the protection of nitrogen and at the temperature of 50-80 ℃. And finally, filtering and drying the reaction product to obtain the supported rubber vulcanization accelerator.
CN106700160A discloses a preparation method and application of a supported rubber vulcanizing agent, wherein the preparation method comprises the following specific steps: adding an inorganic carrier into an organic solvent, uniformly stirring, adding sulfur-containing compounds with different dosages into the mixture, and reacting for 8-20 hours under the protection of nitrogen and at the temperature of 30-80 ℃. And finally, filtering, washing and drying the reaction product to obtain the supported rubber vulcanizing agent.
CN106496700A discloses a supported rubber vulcanization accelerator and a preparation method and application thereof. Firstly, preparing a coupling agent modified inorganic carrier by a solid phase method, namely dripping the coupling agent into the inorganic carrier, and stirring and reacting for 2-6 hours at 60-100 ℃; and adding a rubber vulcanization accelerator into the reaction product, and reacting for 1-5 hours at 50-80 ℃ under the protection of nitrogen. And finally, washing and vacuum drying to obtain the load type rubber vulcanization accelerator.
The above patent applications are all prepared by grafting the vulcanizing agent on the surface of silica to prepare the extraction-resistant nano vulcanizing agent, but the performance of the supported vulcanizing agent needs to be further improved.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a modified peroxide vulcanizing agent with high grafting amount and excellent extraction resistance, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides, in a first aspect, a modified peroxide curing agent obtained by modifying silica with a peroxide curing agent, the peroxide curing agent and the silica being coupled by a silane coupling agent to perform the modification, wherein the peroxide curing agent and the silane coupling agent, and the silane coupling agent and the silica are both chemically bonded, and the chemical bond between the silane coupling agent and the silica is formed by a condensation reaction;
wherein, based on the total weight of the modified peroxide curing agent, the content of the structure provided by the peroxide curing agent is 0.5-35 wt%, the content of the structure provided by the silane coupling agent is 1-60 wt%, and the balance is the content of the structure provided by the silica.
In a second aspect, the present invention provides a process for preparing a modified peroxide curative, the process comprising:
(1) in the presence of a first solvent, carrying out a first reaction on silicate ester and a silane coupling agent to obtain an intermediate product A, wherein the intermediate product A is co-condensed silicon dioxide;
(2) in the presence of a second solvent, carrying out a second reaction on a peroxide vulcanizing agent and the intermediate product A to obtain the modified peroxide vulcanizing agent;
wherein the conditions of the first reaction comprise: the reaction temperature is 20-70 ℃, and the reaction time is 30 min-24 h; the conditions of the second reaction include: the reaction temperature is 20-140 ℃, and the reaction time is 6-48 h;
the silicate, the peroxide curing agent and the silane coupling agent are used in amounts such that, in the obtained modified peroxide curing agent, the content of the structure provided by the peroxide curing agent is 0.5-35 wt%, the content of the structure provided by the silane coupling agent is 1-60 wt%, and the balance is the content of the structure provided by silica, based on the total weight of the modified peroxide curing agent.
In a third aspect, the present invention provides a process for preparing a modified peroxide curative, the process comprising:
(a) in the presence of a third solvent, carrying out first contact on a peroxide vulcanizing agent and a silane coupling agent to obtain an intermediate product B, wherein the intermediate product B is a functionalized silane coupling agent;
(b) in the presence of a fourth solvent, carrying out second contact on silicate and the intermediate product B to obtain the modified peroxide vulcanizing agent;
wherein the conditions of the first contacting include: the reaction temperature is 20-140 ℃, and the reaction time is 6-48 h; the conditions of the second contacting include: the reaction temperature is 20-70 ℃, and the reaction time is 30 min-24 h;
the silicate, the peroxide curing agent and the silane coupling agent are used in amounts such that, in the obtained modified peroxide curing agent, the content of the structure provided by the peroxide curing agent is 0.5-35 wt%, the content of the structure provided by the silane coupling agent is 1-60 wt%, and the balance is the content of the structure provided by silica, based on the total weight of the modified peroxide curing agent.
In a fourth aspect, the present invention provides a modified peroxide curing agent prepared by the method of the second or third aspect.
A fifth aspect of the present invention provides the use of the modified peroxide curing agent of the first or fourth aspect as described above in the vulcanization of rubber.
The modified peroxide vulcanizing agent provided by the invention is obtained by modifying silica with a peroxide vulcanizing agent, and the peroxide vulcanizing agent and the silica are coupled through a silane coupling agent to carry out the modification, wherein the peroxide vulcanizing agent and the silane coupling agent as well as the silane coupling agent and the silica are connected through chemical bonds, and the chemical bonds between the silane coupling agent and the silica are formed through condensation reaction, so that the modified peroxide vulcanizing agent has high grafting amount and excellent extraction resistance, and further more peroxide vulcanizing agents can be loaded, thereby improving the vulcanization performance of the modified peroxide vulcanizing agent, and the modified peroxide vulcanizing agent has stronger volatilization resistance and chemical stability.
The preparation method provided by the invention can be used for preparing the modified peroxide vulcanizing agent with the specific structure, and has the advantages of simple operation, easily obtained raw materials, strong controllability of material properties, low cost and suitability for industrial production.
Drawings
FIG. 1 is a TEM image of a modified peroxide curing agent S1 prepared in example 1;
FIG. 2 is a TEM image of a modified peroxide curing agent S2 prepared in example 2;
FIG. 3 is a thermogravimetric plot of intermediate A and modified peroxide curative S1 prepared in example 1;
FIG. 4 is a representation of the modified peroxide curative S2 prepared in example 229SiNMR diagram.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a modified peroxide curing agent obtained by modifying silica with a peroxide curing agent, and the peroxide curing agent and the silica are coupled by a silane coupling agent to perform the modification, wherein the peroxide curing agent and the silane coupling agent, and the silane coupling agent and the silica are all linked by a chemical bond, and the chemical bond between the silane coupling agent and the silica is formed by a condensation reaction;
wherein, based on the total weight of the modified peroxide curing agent, the content of the structure provided by the peroxide curing agent is 0.5-35 wt%, the content of the structure provided by the silane coupling agent is 1-60 wt%, and the balance is the content of the structure provided by the silica.
In the present invention, the peroxide curing agent and the silane coupling agent are connected by forming a chemical bond through reaction of the groups contained in each of them, and the specific type and manner of forming a chemical bond through reaction of the peroxide curing agent and the silane coupling agent are not particularly limited as long as they are connected by a chemical bond. For example, aminopropyltriethoxysilane is bonded to a chlorine-containing peroxide curing agent by reaction of the amino group with chlorine to form a bond; the present invention is not described in detail for all cases, and those skilled in the art should not be construed as limiting the present invention.
The specific type and properties of the silica are not particularly limited in the present invention, and the silica may be known silica in the art, and is preferably silica obtained by a silicate reaction.
In the present invention, the condensation reaction in which the silane coupling agent and the silica are linked by forming a chemical bond by means of a condensation reaction is not particularly limited, and it is preferable that the silane coupling agent and a raw material for forming the silica, such as silicate, are linked by performing a dehydration condensation reaction to form a chemical bond between the silane coupling agent and the silica.
According to the invention, the silane coupling agent and the silicon dioxide form a chemical bond for connection in a condensation reaction mode, and meanwhile, the peroxide vulcanizing agent is connected with the silane coupling agent through a reaction bonding, so that the peroxide vulcanizing agent and the silicon dioxide are coupled through the silane coupling agent, and the modified peroxide vulcanizing agent is obtained.
According to the present invention, preferably, the peroxide curing agent is 2, 4-dichlorobenzoyl peroxide.
According to the present invention, preferably, the silane coupling agent is at least one selected from the group consisting of compounds having a structure represented by formula (I),
Figure BDA0002728126280000061
wherein, in the formula (I), each R' is independently selected from halogen atom and C1-10R is selected from amino and/or epoxy group-containing groups, and n is selected from 1 to 10.
In the present invention, the halogen atom is selected from fluorine, chlorine, bromine and iodine; chlorine, bromine and iodine are preferred.
In the present invention, said C1-10Alkoxy in (b) means an alkoxy group containing 1 to 10 carbon atoms, which may be linear, branched or cyclic, and includes, for example, but is not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, cyclopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, cyclobutoxy, n-pentoxy, iso-pentoxyPentyloxy, neopentyloxy, cyclopentyloxy, n-hexyloxy, isohexyloxy, cyclohexyloxy, and the like.
In the present invention, n is selected from 1 to 10, and n is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
More preferably, the silane coupling agent is selected from aminopropyltriethoxysilane and/or gamma-glycidoxypropyltrimethoxysilane.
Preferably, the particle size of the modified peroxide curing agent is 10nm to 100 μm.
The modified peroxide vulcanizing agent provided by the invention has high grafting amount and excellent extraction resistance, and further can load more peroxide vulcanizing agents, so that the vulcanizing performance of the modified peroxide vulcanizing agent is improved, and the modified peroxide vulcanizing agent has stronger volatility resistance and chemical stability.
As previously noted, a second aspect of the present invention provides a process for preparing a modified peroxide curative comprising:
(1) in the presence of a first solvent, carrying out a first reaction on silicate ester and a silane coupling agent to obtain an intermediate product A, wherein the intermediate product A is co-condensed silicon dioxide;
(2) in the presence of a second solvent, carrying out a second reaction on a peroxide vulcanizing agent and the intermediate product A to obtain the modified peroxide vulcanizing agent;
wherein the conditions of the first reaction comprise: the reaction temperature is 20-70 ℃, and the reaction time is 30 min-24 h; the conditions of the second reaction include: the reaction temperature is 20-140 ℃, and the reaction time is 6-48 h;
the silicate, the peroxide curing agent and the silane coupling agent are used in amounts such that, in the obtained modified peroxide curing agent, the content of the structure provided by the peroxide curing agent is 0.5-35 wt%, the content of the structure provided by the silane coupling agent is 1-60 wt%, and the balance is the content of the structure provided by silica, based on the total weight of the modified peroxide curing agent.
In the method of the second aspect of the present invention, the types of the silane coupling agent and the peroxide curing agent are the same as those of the silane coupling agent and the peroxide curing agent of the first aspect, and the description of the present invention is omitted here.
In the present invention, the silicate is not limited, and any silicate capable of producing silica existing in the art may be used, and for example, at least one selected from the group consisting of methyl orthosilicate, ethyl orthosilicate, and propyl orthosilicate.
Preferably, in step (1), the first reaction is carried out under stirring at a rate of 50rpm to 1000 rpm.
According to the present invention, preferably, in the step (1), the silicate and the silane coupling agent are used in a molar ratio of 1:0.1 to 10.
According to the present invention, preferably, the conditions of the first reaction further comprise: the pH value is 7-12.
In a preferred embodiment of the present invention, in step (1), the first reaction is carried out in the presence of a first catalyst selected from at least one of an acidic reagent and a buffer thereof, and a basic reagent and a buffer thereof.
Preferably, in the step (1), the first catalyst is used in an amount such that the reaction system of the first reaction has a pH of 7 to 12.
According to the method provided by the invention, the selectable range of the first solvent is wide as long as the reaction in the step (1) can be performed; preferably, in step (1), the first solvent is selected from at least one of anhydrous ethanol, isopropanol, acetone, butanone, N-dimethylformamide, and tetrahydrofuran. The amount of the first solvent used in the present invention is not limited as long as silicate and the silane coupling agent can be dissolved; for example, the first solvent may be preferably used in an amount of 0.1 to 1mol/L relative to the total amount of the silicate and the silane coupling agent.
According to another preferred embodiment of the invention, step (1) is carried out in the absence of a catalyst.
According to the invention, in step (2), the second reaction is carried out with stirring at a rate of 50rpm to 500 rpm.
Preferably, in step (2), the weight ratio of the intermediate product A to the peroxide curing agent is 1: 0.25-1.5.
According to the present invention, preferably, the second solvent is at least one selected from the group consisting of benzene, toluene, xylene, methanol, ethanol, chloroform, dichloromethane, dimethylformamide, dimethylacetamide, dioxane, acetone, dimethyl sulfoxide, tetrahydrofuran and acetonitrile.
The amount of the second solvent used in the present invention is not limited as long as the peroxide curing agent and the intermediate product A can be dissolved.
As previously noted, a third aspect of the present invention provides a process for preparing a modified peroxide curative comprising:
(a) in the presence of a third solvent, carrying out first contact on a peroxide vulcanizing agent and a silane coupling agent to obtain an intermediate product B, wherein the intermediate product B is a functionalized silane coupling agent;
(b) in the presence of a fourth solvent, carrying out second contact on silicate and the intermediate product B to obtain the modified peroxide vulcanizing agent;
wherein the conditions of the first contacting include: the reaction temperature is 20-140 ℃, and the reaction time is 6-48 h; the conditions of the second contacting include: the reaction temperature is 20-70 ℃, and the reaction time is 30 min-24 h;
the silicate, the peroxide curing agent and the silane coupling agent are used in amounts such that, in the obtained modified peroxide curing agent, the content of the structure provided by the peroxide curing agent is 0.5-35 wt%, the content of the structure provided by the silane coupling agent is 1-60 wt%, and the balance is the content of the structure provided by silica, based on the total weight of the modified peroxide curing agent.
In the method according to the third aspect of the present invention, the types of the silane coupling agent, the peroxide curing agent, and the silicate are the same as those of the silane coupling agent, the peroxide curing agent, and the silicate according to the first aspect, and the description thereof is omitted.
Preferably, in step (a), the first contacting is carried out under agitation at a rate of from 50rpm to 500 rpm.
According to the present invention, preferably, in step (a), the silane coupling agent and the peroxide vulcanizing agent are used in a molar ratio of 1:1.05 to 1.5.
Preferably, the third solvent is selected from at least one of benzene, toluene, xylene, methanol, ethanol, chloroform, dichloromethane, dimethylformamide, dimethylacetamide, dioxane, acetone, dimethylsulfoxide, tetrahydrofuran, triethylamine, and acetonitrile. The amount of the third solvent used in the present invention is not limited as long as the peroxide curing agent and the silane coupling agent can be dissolved.
According to the present invention, preferably, in step (b), said second contacting is carried out under stirring at a rate of 50rpm to 1000 rpm.
Preferably, in step (B), the silicate is used in a weight ratio of 1:0.1-10 to the intermediate product B.
According to the present invention, preferably, the conditions of the second contacting further include: the pH value is 2-12.
In a preferred embodiment of the present invention, the second contacting is performed in the presence of a second catalyst selected from at least one of an acidic reagent and a buffer thereof, a basic reagent and a buffer thereof.
Preferably, the second catalyst is used in an amount such that the pH of the reaction system of the second contact is 2 to 12.
According to another preferred embodiment of the invention, step (b) is carried out in the absence of a catalyst.
According to the present invention, preferably, in step (b), the fourth solvent is at least one selected from the group consisting of N, N-dimethylformamide, tetrahydrofuran and ethanol. The amount of the fourth solvent used in the present invention is not limited as long as silicate and the intermediate product B can be dissolved; for example, the amount of the fourth solvent may be preferably 0.1 to 1mol/L with respect to the total amount of the silicate and the intermediate product B.
The method according to the second aspect or the third aspect of the present invention further includes conventional post-treatment operations known in the art, such as filtration, washing, drying, etc., and the present invention is not particularly limited thereto, and those skilled in the art can perform the method according to the conventional art, and the present invention will not be described in detail herein, and the present invention will be described in detail hereinafter by way of a specific operation procedure, and those skilled in the art should not be construed as limiting the present invention.
As previously mentioned, a fourth aspect of the present invention provides a modified peroxide curing agent prepared by the method of the second or third aspect.
The modified peroxide vulcanizing agent prepared by the invention has higher peroxide vulcanizing agent loading capacity, and the loading capacity is adjustable; the rubber has good hydrophobicity and can be well dispersed in a rubber matrix; has good volatility resistance, solvent extraction resistance and self chemical stability; when the rubber is used for preparing rubber, the vulcanization performance of the rubber can be effectively improved.
As previously mentioned, a fifth aspect of the present invention provides the use of a modified peroxide curing agent as described in the first or fourth aspects above in the vulcanization of rubber.
The present invention is not particularly limited in the way of the specific operation of the application, and more specifically, the present invention is not particularly limited in the way of the preparation of the vulcanized rubber using the modified peroxide curing agent, and can be carried out by a method existing in the art for preparing rubber, for example, a method used in the preparation of the vulcanized rubber using a conventional curing agent (2, 4-dichlorobenzoyl peroxide), and the present invention will not be described in detail herein, and the present invention is exemplified in the following examples by specific procedures, and those skilled in the art should not be construed as limiting the present invention.
The present invention will be described in detail below by way of examples. The starting materials used, unless otherwise specified, are all commercially available and are in analytical purity. The room temperatures referred to in the examples below all represent 25. + -. 3 ℃.
Matrix rubber: methyl vinyl silicone rubber (hereinafter referred to as silicone rubber), brand 110, hejiang Heishi silicon industries, Ltd;
silicate ester: tetraethoxysilane, content (SiO) of Shirong chemical Co., Ltd2) Greater than 28 wt%, molecular weight 208 g/mol;
silane coupling agent: aminopropyltriethoxysilane, Afaha Elisa, purity 97% by weight, molecular weight 221 g/mol;
si 69: bis- (gamma-triethoxysilylpropyl) tetrasulfide, available from alatin reagent;
peroxide vulcanizing agent: 2, 4-dichlorobenzoyl peroxide, Jiangsu pexing chemical Co., Ltd;
filling: white carbon black, degussa inc.
In the following examples, the vulcanization properties were determined according to GB/T16584-1996 using a rotorless vulcameter, test temperature 160 ℃. Wherein the minimum torque is represented by ML, the maximum torque is represented by MH, and the scorch time is represented by ts1Expressed as the initial cure time tc10Indicated as positive cure time in tc90And (4) showing.
Particle size observations were made by Transmission Electron Microscope (TEM) testing of JEOL corporation, JEM-2200FS, Japan.
In the following examples, the information on the instruments and apparatuses is specifically shown in table 1.
TABLE 1
Serial number Device name Model number Manufacturer of the product
1 Internal mixer BR1600 Farrel America Ltd
2 Open mill XK-160 Qingdao Xincheng Yiming mechanical Co Ltd
3 Rotor-free vulcanizer GT-M2000-A type Taiwan high speed railway, China
Example 1
This example illustrates the modified peroxide curative and the method of making the same according to the present invention.
(1) Sequentially adding tetraethoxysilane and aminopropyltriethoxysilane into 300ml of ethanol to obtain a mixed solution, wherein the molar ratio of the tetraethoxysilane to the aminopropyltriethoxysilane is 1:7, and the concentration of total silicon elements in the mixed solution is 0.8 mol/L;
adding 10ml of distilled water into the mixed solution, stirring for 6 hours at 30 ℃ and 500rpm to carry out a first reaction, filtering a product of the first reaction, washing with ethanol, and drying to obtain an intermediate product A;
(2) dispersing 10g of the intermediate product A in 500ml of toluene, adding 6g of 2, 4-dichlorobenzoyl peroxide and 0.2g of triethylamine, stirring at 110 ℃ and 300rpm for 12h to perform a second reaction, filtering the product of the second reaction, washing with ethanol, and drying to obtain a modified peroxide vulcanizing agent S1.
A TEM image of the modified peroxide curing agent S1 is shown in FIG. 1, and it was measured that the average particle diameter was 46 nm.
The intermediate product A and the modified peroxide curative S1 were tested for thermogravimetric properties and the TGA profile is shown in FIG. 3.
In the S1, the content of the structure provided by 2, 4-dichlorobenzoyl peroxide was 10% by weight by TGA test (the test apparatus is a thermogravimetric analyzer of TA Co., Ltd., the same applies hereinafter).
Example 2
This example illustrates the modified peroxide curative and the method of making the same according to the present invention.
(1) Mixing 0.5mol of gamma-glycidoxypropyltrimethoxysilane and 0.6mol of 2, 4-dichlorobenzoyl peroxide, adding 0.6g of triethylamine, stirring at 100 ℃ and 250rpm for 24 hours, and carrying out first contact to obtain an intermediate product B;
(2) sequentially adding tetraethoxysilane and the intermediate product B into 500ml of ethanol to obtain a mixed solution, wherein the mass ratio of tetraethoxysilane to the intermediate product B is 1:0.3, and the total silicon concentration is 0.52 mol/L; then adding 15ml of ammonia water to adjust the pH value to about 8, stirring for 3h at 60 ℃ and 300rpm for second contact, filtering the product of the second reaction, washing with ethanol, and drying to obtain the modified peroxide vulcanizing agent S2.
A TEM image of the modified peroxide curing agent S2 is shown in FIG. 2, and the average particle diameter is measured to be 98 nm.
Process for producing the above-mentioned modified peroxide curing agent S229SiNMR is shown in FIG. 4.
In said S2, by29The SiNMR test shows that the content of the structure provided by the 2, 4-dichlorobenzoyl peroxide in the S2 is about 7.3 wt% through peak separation calculation; the silane coupling agent provides a structure content of about 8.5 wt.%.
Comparative example 1
A peroxide curing agent DS1 was prepared in a similar manner to example 1, except that silica was used in place of the ethyl orthosilicate and the procedure was otherwise the same as in example 1.
The peroxide curative DS1 had an average particle size of 67nm as measured by TEM analysis.
In the DS1, the content of structural units provided by 2, 4-dichlorobenzoyl peroxide was 4.5% by weight by TGA test.
Test example 1
Vulcanized rubbers L1, L2, DL1 and DL2 were prepared by using the vulcanizing agents (i.e., S1, S2, DS1) obtained in the above examples 1-2 and comparative example 1 and 2, 4-dichlorobenzoyl peroxide, respectively, according to the following procedures:
the temperature of the first-stage mixing of the internal mixer is set to be 70 ℃, and the rotating speed of a rotor is 90 rpm. Adding the silicon rubber into an open mill for plastication for 30 s. Then, adding white carbon black and Si69, mixing for 240s, and discharging.
Standing the obtained rubber material for 4h, plasticating for 1min at the set temperature of 40 ℃ and the rotor speed of 60rpm in two-stage mixing, adding a vulcanizing agent and an accelerant, mixing for 4min, and discharging to obtain vulcanized rubber.
The amounts of the raw materials involved in the above treatment are shown in Table 2.
The vulcanizates were tested for vulcanization performance as shown in table 3.
TABLE 2
Figure BDA0002728126280000141
TABLE 3
Sample (I) ML/dN.m MH/dN.m t10/min t90/min
L1 4.39 14.36 0:16 1:32
DL1 5.21 16.76 0:18 2:23
L2 4.40 15.82 0:15 1:52
DL2 4.86 16.32 0:18 2:47
As can be seen from Table 3 and the results shown in the figure, the modified peroxide curing agent provided by the present invention has excellent high grafting amount and good volatility resistance and thermal stability.
In addition, the above comparative examples are not all prior arts, are only provided for comparison with the present invention, and are not to be construed as limiting the present invention.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (15)

1. A modified peroxide curing agent, which is obtained by modifying silica with a peroxide curing agent, wherein the peroxide curing agent and the silica are coupled by a silane coupling agent to perform the modification, wherein the peroxide curing agent and the silane coupling agent, and the silane coupling agent and the silica are both connected by a chemical bond, and the chemical bond between the silane coupling agent and the silica is formed by a condensation reaction;
wherein, based on the total weight of the modified peroxide curing agent, the content of the structure provided by the peroxide curing agent is 0.5-35 wt%, the content of the structure provided by the silane coupling agent is 1-60 wt%, and the balance is the content of the structure provided by the silica.
2. The modified peroxide curing agent of claim 1, wherein the peroxide curing agent is 2, 4-dichlorobenzoyl peroxide;
preferably, the silane coupling agent is at least one selected from compounds having a structure represented by formula (I),
Figure FDA0002728126270000011
wherein, in the formula (I), each R' is independently selected from halogen atom and C1-10R is selected from amino and/or epoxy group-containing groups, n is selected from 1 to 10;
preferably, the silane coupling agent is selected from aminopropyltriethoxysilane and/or gamma-glycidoxypropyltrimethoxysilane.
3. The modified peroxide curing agent according to claim 1 or 2, wherein the particle size of the modified peroxide curing agent is 10nm to 100 μm.
4. A process for preparing a modified peroxide curative, comprising:
(1) in the presence of a first solvent, carrying out a first reaction on silicate ester and a silane coupling agent to obtain an intermediate product A, wherein the intermediate product A is co-condensed silicon dioxide;
(2) in the presence of a second solvent, carrying out a second reaction on a peroxide vulcanizing agent and the intermediate product A to obtain the modified peroxide vulcanizing agent;
wherein the conditions of the first reaction comprise: the reaction temperature is 20-70 ℃, and the reaction time is 30 min-24 h; the conditions of the second reaction include: the reaction temperature is 20-140 ℃, and the reaction time is 6-48 h;
the silicate, the peroxide curing agent and the silane coupling agent are used in amounts such that, in the obtained modified peroxide curing agent, the content of the structure provided by the peroxide curing agent is 0.5-35 wt%, the content of the structure provided by the silane coupling agent is 1-60 wt%, and the balance is the content of the structure provided by silica, based on the total weight of the modified peroxide curing agent.
5. The process according to claim 4, wherein, in step (1), the first reaction is carried out under stirring at a rate of 50-1000 rpm;
preferably, in the step (1), the silicate and the silane coupling agent are used in a molar ratio of 1: 0.1-10;
preferably, the conditions of the first reaction further comprise: the pH value is 7-12;
preferably, in step (1), the first reaction is carried out in the presence of a first catalyst selected from at least one of an acidic reagent and a buffer thereof, a basic reagent and a buffer thereof;
preferably, in the step (1), the first catalyst is used in an amount such that the reaction system of the first reaction has a pH of 7 to 12.
6. The method according to claim 4 or 5, wherein the first solvent is selected from at least one of anhydrous ethanol, isopropanol, acetone, butanone, N-dimethylformamide, and tetrahydrofuran;
preferably, the silicate is selected from at least one of methyl orthosilicate, ethyl orthosilicate and propyl orthosilicate;
preferably, the silane coupling agent is at least one selected from compounds having a structure represented by formula (I),
Figure FDA0002728126270000031
wherein, in the formula (I), each R' is independently selected from halogen atom and C1-10R is selected from amino and/or epoxy group-containing groups, n is selected from 1 to 10;
preferably, the silane coupling agent is selected from aminopropyltriethoxysilane and/or gamma-glycidoxypropyltrimethoxysilane.
7. The process according to any one of claims 4 to 6, wherein, in step (2), the second reaction is carried out under stirring at a rate of 50rpm to 500 rpm;
preferably, in step (2), the weight ratio of the intermediate product A to the peroxide curing agent is 1: 0.25-1.5.
8. The method according to any one of claims 4 to 7, wherein the second solvent is selected from at least one of benzene, toluene, xylene, methanol, ethanol, chloroform, dichloromethane, dimethylformamide, dimethylacetamide, dioxane, acetone, dimethylsulfoxide, tetrahydrofuran, and acetonitrile;
preferably, the peroxide curing agent is 2, 4-dichlorobenzoyl peroxide.
9. A process for preparing a modified peroxide curative, comprising:
(a) in the presence of a third solvent, carrying out first contact on a peroxide vulcanizing agent and a silane coupling agent to obtain an intermediate product B, wherein the intermediate product B is a functionalized silane coupling agent;
(b) in the presence of a fourth solvent, carrying out second contact on silicate and the intermediate product B to obtain the modified peroxide vulcanizing agent;
wherein the conditions of the first contacting include: the reaction temperature is 20-140 ℃, and the reaction time is 6-48 h; the conditions of the second contacting include: the reaction temperature is 20-70 ℃, and the reaction time is 30 min-24 h;
the silicate, the peroxide curing agent and the silane coupling agent are used in amounts such that, in the obtained modified peroxide curing agent, the content of the structure provided by the peroxide curing agent is 0.5-35 wt%, the content of the structure provided by the silane coupling agent is 1-60 wt%, and the balance is the content of the structure provided by silica, based on the total weight of the modified peroxide curing agent.
10. The process of claim 9, wherein in step (a), the first contacting is carried out under agitation at a rate of 50rpm to 500 rpm;
preferably, in step (a), the silane coupling agent and the peroxide curing agent are used in a molar ratio of 1:1.05 to 1.5.
11. The method according to claim 9 or 10, wherein the third solvent is selected from at least one of benzene, toluene, xylene, methanol, ethanol, chloroform, dichloromethane, dimethylformamide, dimethylacetamide, dioxane, acetone, dimethyl sulfoxide, tetrahydrofuran, and acetonitrile;
preferably, the peroxide vulcanizing agent is 2, 4-dichlorobenzoyl peroxide;
preferably, the silane coupling agent is at least one selected from compounds having a structure represented by formula (I),
Figure FDA0002728126270000041
wherein, in the formula (I), each R' is independently selected from halogen atom and C1-10R is selected from amino and/or epoxy group-containing groups, n is selected from 1 to 10;
preferably, the silane coupling agent is selected from at least one of aminopropyltriethoxysilane and gamma-glycidoxypropyltrimethoxysilane.
12. The process of any one of claims 9-11, wherein in step (b), the second contacting is carried out under agitation at a rate of 50rpm to 1000 rpm;
preferably, in step (B), the silicate is used in a weight ratio of 1:0.1-10 to the intermediate product B;
preferably, the conditions of the second contacting further comprise: the pH value is 2-12;
preferably, the second contacting is performed in the presence of a second catalyst selected from at least one of an acidic reagent and a buffer thereof, a basic reagent and a buffer thereof;
preferably, the second catalyst is used in an amount such that the pH of the reaction system of the second contact is 2 to 12.
13. The process according to any one of claims 9 to 12, wherein, in step (b), the fourth solvent is selected from at least one of N, N-dimethylformamide, tetrahydrofuran and ethanol;
preferably, the silicate is selected from at least one of methyl orthosilicate, ethyl orthosilicate, and propyl orthosilicate.
14. A modified peroxide curing agent prepared by the process of any one of claims 4 to 8 and 9 to 13.
15. Use of a modified peroxide curing agent as defined in any one of claims 1 to 3 and 14 in the vulcanization of rubber.
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030178600A1 (en) * 2002-03-22 2003-09-25 Geo Specialty Chemicals, Inc. Encapsulated peroxide compositions
US20030178599A1 (en) * 2002-03-22 2003-09-25 Dluzneski Peter R. Supported peroxides
WO2013094719A1 (en) * 2011-12-21 2013-06-27 住友化学株式会社 Anti-aging agent for rubbers
CN103360628A (en) * 2013-07-11 2013-10-23 华南理工大学 Loaded-type rubber vulcanization accelerant as well as preparation method and application thereof
CN104497360A (en) * 2014-12-02 2015-04-08 华南理工大学 Nano-silica immobilized hindered phenol antioxidant as well as preparation method and application of antioxidant
CN106700160A (en) * 2016-11-21 2017-05-24 华南理工大学 Preparation method of supported rubber vulcanizing agent and application thereof
CN109265749A (en) * 2018-07-23 2019-01-25 华南理工大学 A kind of rubber chemicals and the preparation method and application thereof loading carbon sulphur compound
CN109265780A (en) * 2018-08-27 2019-01-25 华南理工大学 A kind of support type rubber processing aids and the preparation method and application thereof
CN110643072A (en) * 2019-08-21 2020-01-03 北京化工大学 Supported sulfur, preparation method and application thereof, and rubber composition

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030178600A1 (en) * 2002-03-22 2003-09-25 Geo Specialty Chemicals, Inc. Encapsulated peroxide compositions
US20030178599A1 (en) * 2002-03-22 2003-09-25 Dluzneski Peter R. Supported peroxides
WO2013094719A1 (en) * 2011-12-21 2013-06-27 住友化学株式会社 Anti-aging agent for rubbers
CN103360628A (en) * 2013-07-11 2013-10-23 华南理工大学 Loaded-type rubber vulcanization accelerant as well as preparation method and application thereof
CN104497360A (en) * 2014-12-02 2015-04-08 华南理工大学 Nano-silica immobilized hindered phenol antioxidant as well as preparation method and application of antioxidant
CN106700160A (en) * 2016-11-21 2017-05-24 华南理工大学 Preparation method of supported rubber vulcanizing agent and application thereof
CN109265749A (en) * 2018-07-23 2019-01-25 华南理工大学 A kind of rubber chemicals and the preparation method and application thereof loading carbon sulphur compound
CN109265780A (en) * 2018-08-27 2019-01-25 华南理工大学 A kind of support type rubber processing aids and the preparation method and application thereof
CN110643072A (en) * 2019-08-21 2020-01-03 北京化工大学 Supported sulfur, preparation method and application thereof, and rubber composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
吴文剑;杨树颜;蔡海宁;李红强;曾幸荣;: "负载型抗氧剂的制备及应用研究进展", 高分子材料科学与工程, no. 10, pages 170 - 176 *

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