CN109749123B - Rubber powder with vulcanization promoting effect and preparation method thereof - Google Patents
Rubber powder with vulcanization promoting effect and preparation method thereof Download PDFInfo
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Abstract
The invention discloses modified rubber powder with a vulcanization promoting effect and a preparation method thereof. The preparation method comprises the following steps: treating the rubber powder with concentrated sulfuric acid to obtain rubber powder treated with concentrated sulfuric acid; dispersing the rubber powder treated by concentrated sulfuric acid in deionized water to obtain a rubber powder suspension, and adding a silane coupling agent containing chlorine into the suspension to obtain activated rubber powder treated by the coupling agent; adding a vulcanization accelerator into the activated rubber powder, and further reacting to load the vulcanization accelerator on the surface of the rubber powder to prepare the modified rubber powder with the vulcanization accelerating effect. The rubber powder loaded with the vulcanization accelerator can promote the vulcanization of the rubber powder and a rubber matrix interface and promote the interface interaction when the accelerator is applied to the rubber, so that the rubber/rubber powder composite material is reinforced, and the modified rubber powder has dual functions of vulcanization promotion and filling reinforcement.
Description
Technical Field
The invention relates to the field of rubber powder functional modification, in particular to a preparation method and application of rubber powder modified by a vulcanization accelerator.
Background
China is the first major rubber consuming country in the world, and simultaneously, countries with relatively scarce rubber resources rely on import of nearly 80% of natural rubber and 40% of synthetic rubber, wherein the import dependence of the natural rubber is higher than that of petroleum, iron ore, grain and the like and is the first place, and the consumption of tires accounts for more than 70% of the total rubber. With the increasing prices of natural rubber and synthetic rubber, the waste tires are fully utilized and applied to rubber materials, and the rubber material has important significance for relieving the pressure of rubber resource shortage in China and reducing environmental pollution. At present, the waste rubber is mainly reclaimed rubber, and accounts for about 71 percent of the total amount. Compared with reclaimed rubber, the production of rubber powder is more environment-friendly, the rubber powder produced by waste rubber is a recovery mode with development prospect integrating environmental protection and resource recycling, is also an optimal utilization mode advocating development of circular economy, and has very wide application prospect. The rubber powder can be applied to rubber, plastics, asphalt, cellulose and the like, and can also be applied to inorganic substances such as cement, and certain effect is achieved.
The rubber powder is a material containing a cross-linking structure and composed of rubber, carbon black and the like. The rubber powder has low surface activity, and when the rubber powder is added into a matrix material, the interaction force between the rubber powder and the matrix material is weak, so that the performance of the material is reduced, and the rubber powder needs to be modified when in use. At present, the following methods are mainly adopted: rubber powder is desulfurized and modified, for example, in CN201610054645.2, the rubber powder is desulfurized through microwave treatment and is applied to natural rubber; mechanochemical modification, for example, in the documents [ Linzhen et al [ J ] special rubber products, 2013(1):62-65 ], the influence of the dosage of a regenerant, the regeneration temperature and time, and the open milling temperature and time on the rubber powder activation effect is researched by adopting a mechanochemical method; modifying a grafted or interpenetrating polymer network, for example, in patent CN201710707103.5, by the reaction of ethyl orthosilicate and n-butylamine, in-situ generating silica to be grafted on the surface of rubber powder, wherein the modified rubber powder is used for natural rubber, and in [ Yangli et al [ J ] environmental science and technology, 2012,35(3):63-67 ] the rubber powder is modified by an interpenetrating polymer network technology, and three components of natural rubber/public network/waste rubber powder conjugate are prepared; the modification methods all achieve certain effects, but the technology of treating the rubber powder by concentrated sulfuric acid to increase active groups on the surface of the rubber powder, and then connecting the vulcanization accelerator with the active groups on the rubber powder by a coupling agent so as to load the vulcanization accelerator on the rubber powder, so that the rubber powder has dual functions of filling, reinforcing and vulcanization accelerating, and is not reported in patent and non-patent documents.
Disclosure of Invention
Aiming at the problem that the interface bonding of rubber powder and rubber is weak at present, the invention treats the rubber powder by using concentrated sulfuric acid, then modifies the rubber powder by using a silane coupling agent containing chlorine and a vulcanization accelerator, and loads the vulcanization accelerator on the surface of the rubber powder to prepare the modified rubber powder with dual functions of vulcanization acceleration and filling reinforcement.
The technical scheme of the invention is as follows.
A method for preparing modified rubber powder with vulcanization acceleration effect comprises the following steps:
(1) adding concentrated sulfuric acid into the rubber powder, and rapidly and mechanically stirring for 5-60min at room temperature to obtain rubber powder treated by concentrated sulfuric acid;
(2) dispersing the rubber powder treated by concentrated sulfuric acid into deionized water, adding a silane coupling agent containing chlorine, and rapidly and mechanically stirring for 1-24 hours at 25-100 ℃ to obtain activated rubber powder;
(3) adding a vulcanization accelerator into the activated rubber powder, reacting for 1-24 h at 60-100 ℃ in a nitrogen atmosphere, washing, filtering and drying the product to obtain the modified rubber powder with the vulcanization accelerating effect.
In the method, in the step (1), the mass ratio of the concentrated sulfuric acid to the rubber powder is 0.01-0.05: 1.
In the method, in the step (2), the mass ratio of the deionized water to the rubber powder is 1-2: 1, and the mass ratio of the coupling agent to the rubber powder is 0.03-0.12: 1.
In the method, in the step (3), the mass ratio of the accelerator to the rubber powder is 0.01-0.1: 1.
In the method, the chlorosilane-containing coupling agent comprises chloropropyl trimethoxy silane, chloropropyl triethoxy silane, chloromethyl trimethoxy silane, chloromethyl triethoxy silane, chloroethyl trimethoxy silane, chloroethyl triethoxy silane, chloropropyl trichlorosilane, chloropropyl dimethoxysilane and chloroethyl dimethoxysilane.
In the above method, the vulcanization accelerator includes at least one of 2-mercaptobenzothiazole, dibenzothiazyl disulfide, zinc dimethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc diethyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc dibenzyldithiocarbamate, iron dibutyldithiocarbamate, and copper dibutyldithiocarbamate.
The present invention provides a specific reaction mechanism, but is not limited thereto, when the coupling agent is Chloropropyltriethoxysilane (CTS) and the vulcanization accelerator is 2-mercaptobenzothiazole, the reaction mechanism is as follows:
compared with the prior art, the invention has the advantages that:
(1) according to the invention, the rubber powder is loaded with the vulcanization accelerator, so that the rubber powder is endowed with a vulcanization acceleration effect;
(2) the invention loads the vulcanization accelerator on the rubber powder surface, and the modified rubber powder is applied and filled in rubber, thereby promoting the vulcanization of the rubber powder and the rubber matrix interface, shortening the vulcanization time and improving the vulcanization speed;
(3) the interface interaction between the rubber powder and the rubber matrix is promoted, so that the rubber/rubber powder composite material is reinforced;
(4) the prepared modified rubber powder with the vulcanization acceleration effect has double effects of filling reinforcement and vulcanization acceleration in the rubber/rubber powder composite material, and the comprehensive performance of the composite material is effectively improved.
Drawings
FIG. 1 is a water contact angle chart of unmodified rubber powder, comparative rubber powder 1 and modified rubber powder 1 in example 1.
FIG. 2 is a DSC of styrene-butadiene rubber, styrene-butadiene rubber/unmodified rubber powder, styrene-butadiene rubber/comparative rubber powder 2, styrene-butadiene rubber/modified rubber powder 2 of example 2.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
The glue powder in the examples of the present invention was purchased from Guangzhou Aishi scientific Co.
Example 1
Weighing 100g of 80-mesh rubber powder, adding concentrated sulfuric acid, and rapidly and mechanically stirring at room temperature for 60min, wherein the mass ratio of the concentrated sulfuric acid to the rubber powder is 0.01:1, so as to obtain the rubber powder treated by the concentrated sulfuric acid; dispersing rubber powder treated by concentrated sulfuric acid into deionized water, adding a coupling agent chloropropyltriethoxysilane, wherein the mass ratio of the deionized water to the rubber powder is 1:1, the mass ratio of the coupling agent to the rubber powder is 0.03:1, rapidly and mechanically stirring for 12 hours at 50 ℃, reacting to obtain activated rubber powder, adding an accelerator 2-mercaptobenzothiazole, the mass ratio of the accelerator to the rubber powder is 0.1:1, reacting for 24 hours at 60 ℃ in a nitrogen atmosphere, washing, filtering and drying a product to obtain modified rubber powder 1 with a vulcanization acceleration effect.
In order to compare the influence of the modification process on the structure and performance of the rubber powder, the activated rubber powder obtained in the preparation process is washed, filtered and dried to obtain the comparative rubber powder 1. The water contact angle test is carried out on the unmodified rubber powder, the comparative rubber powder 1 and the modified rubber powder 1, and the experimental result is shown in figure 1. The water contact angle of the unmodified rubber powder is 116.0 degrees, the comparative rubber powder 1 after the activation of sulfuric acid and a coupling agent is 133.1 degrees, the further improvement of the accelerator modified rubber powder 1 is 147.2 degrees, which indicates that the accelerator is successfully grafted to the surface of the rubber powder.
Example 2
Weighing 105g of rubber powder, adding concentrated sulfuric acid, and rapidly and mechanically stirring at room temperature for 5min, wherein the mass ratio of the concentrated sulfuric acid to the rubber powder is 0.05:1, so as to obtain rubber powder treated by the concentrated sulfuric acid; dispersing rubber powder treated by concentrated sulfuric acid into deionized water, adding a coupling agent chloroethyl trimethoxy silane, wherein the mass ratio of the deionized water to the rubber powder is 2:1, the mass ratio of the coupling agent to the rubber powder is 0.12:1, rapidly and mechanically stirring for 24 hours at 25 ℃ to obtain activated rubber powder, adding accelerators zinc diethyldithiocarbamate and zinc ethylphenyldithiocarbamate at the mass ratio of 2:1, the mass ratio of the accelerators to the rubber powder is 0.01:1, reacting for 1 hour at 100 ℃ in a nitrogen atmosphere, washing, filtering and drying a product to obtain modified rubber powder 2.
In order to compare the influence of each rubber powder on the performance of the rubber/rubber powder composite material, the activated rubber powder obtained in the preparation process is washed, filtered and dried to obtain the comparative rubber powder 2.
The modified rubber powder 2, the styrene-butadiene rubber and the rubber additives are subjected to open milling on an open mill to obtain a styrene-butadiene rubber/modified rubber powder composite material, the styrene-butadiene rubber/comparative rubber powder 2 material, the styrene-butadiene rubber/unmodified rubber powder material and the unfilled styrene-butadiene rubber material are obtained by the same method, the styrene-butadiene rubber material, the styrene-butadiene rubber/unmodified rubber powder material, the styrene-butadiene rubber/comparative rubber powder 2 material and the styrene-butadiene rubber/modified rubber powder 2 material are vulcanized, and the vulcanized rubber is taken for DSC test, wherein the result is shown in figure 2. The calculated mass fractions (Chiim) of the rubber limited molecular layer are respectively 0, 5.2%, 9.3% and 16.9%, and the styrene butadiene rubber/modified rubber powder 2 material has the highest limited molecular mass fraction, which indicates that the interfacial interaction between the modified rubber powder 2 and the rubber matrix is strongest.
Example 3
Weighing 110g of rubber powder, adding concentrated sulfuric acid, and rapidly and mechanically stirring at room temperature for 25min, wherein the mass ratio of the concentrated sulfuric acid to the rubber powder is 0.04:1, so as to obtain rubber powder treated by the concentrated sulfuric acid; dispersing rubber powder treated by concentrated sulfuric acid into deionized water, adding coupling agents of chloromethyltriethoxysilane and chloroethyltrimethoxysilane in a mass ratio of 1:1, wherein the mass ratio of the deionized water to the rubber powder is 1.2:1, the mass ratio of the coupling agents to the rubber powder is 0.10:1, quickly and mechanically stirring for 18 hours at 60 ℃ to obtain active rubber powder through reaction, adding an accelerator of dibenzothiazole disulfide, wherein the mass ratio of the accelerator of dibenzothiazole disulfide to the rubber powder is 0.08:1, reacting for 18 hours at 70 ℃ in a nitrogen atmosphere, and washing, filtering and drying a product to obtain modified rubber powder 3.
In order to compare the influence of each rubber powder on the performance of the rubber/rubber powder composite material, the activated rubber powder obtained in the preparation process is washed, filtered and dried to obtain the comparative rubber powder 3.
Example 4
Weighing 115g of rubber powder, adding concentrated sulfuric acid, and rapidly and mechanically stirring at room temperature for 40min, wherein the mass ratio of the concentrated sulfuric acid to the rubber powder is 0.03:1, so as to obtain rubber powder treated by the concentrated sulfuric acid; dispersing rubber powder treated by concentrated sulfuric acid into deionized water, adding a coupling agent chloroethyl dimethoxysilane, wherein the mass ratio of the deionized water to the rubber powder is 1.5:1, the mass ratio of the coupling agent to the rubber powder is 0.08:1, quickly and mechanically stirring for 12 hours at 80 ℃ to obtain activated rubber powder, adding an accelerant iron dibutyldithiocarbamate, wherein the mass ratio of the accelerant to the rubber powder is 0.05:1, reacting for 8 hours at 60 ℃ in a nitrogen atmosphere, and washing, filtering and drying a product to obtain modified rubber powder 4.
In order to compare the influence of each rubber powder on the performance of the rubber/rubber powder composite material, the activated rubber powder obtained in the preparation process is washed, filtered and dried to obtain the comparative rubber powder 4.
Example 5
Weighing 120g of rubber powder, adding concentrated sulfuric acid, and rapidly and mechanically stirring at room temperature for 50min, wherein the mass ratio of the concentrated sulfuric acid to the rubber powder is 0.02:1, so as to obtain rubber powder treated by the concentrated sulfuric acid; dispersing rubber powder treated by concentrated sulfuric acid into deionized water, adding a coupling agent chloroethyl triethoxysilane, wherein the mass ratio of the deionized water to the rubber powder is 1.8:1, the mass ratio of the coupling agent to the rubber powder is 0.06:1, rapidly and mechanically stirring for 1h at 100 ℃ to obtain activated rubber powder, adding an accelerator zinc diethyldithiocarbamate, wherein the mass ratio of the accelerator to the rubber powder is 0.03:1, reacting for 6h at 90 ℃ in a nitrogen atmosphere, and washing, filtering and drying a product to obtain modified rubber powder 5.
In order to compare the influence of each rubber powder on the performance of the rubber/rubber powder composite material, the activated rubber powder obtained in the preparation process is washed, filtered and dried to obtain the comparative rubber powder 5.
The unmodified rubber powder, the comparative rubber powder 2-5 and the modified rubber powder 2-5 in the above examples 2-5 are respectively applied to styrene butadiene rubber, nitrile butadiene rubber and natural rubber, the added rubber powder is 40 parts, the vulcanization curve of the rubber compound is tested, the performance of the material is determined according to the national standard GB/T528-.
TABLE 1 test results of rubber Material Properties
The embodiment can obtain that the rubber powder loaded with the vulcanization accelerator is added into a rubber system, so that the vulcanization speed of the rubber/rubber powder composite material can be increased, the vulcanization time is shortened, the filling effect is achieved, and the tensile strength of the rubber/rubber powder composite material is increased.
Claims (6)
1. A preparation method of modified rubber powder with vulcanization acceleration effect is characterized by comprising the following steps:
(1) adding concentrated sulfuric acid into the rubber powder, and rapidly and mechanically stirring for 5-60min at room temperature to obtain rubber powder treated by concentrated sulfuric acid;
(2) dispersing the rubber powder treated by concentrated sulfuric acid into deionized water, adding a silane coupling agent containing chlorine, and rapidly and mechanically stirring for 1-24 hours at 25-100 ℃ to obtain activated rubber powder;
(3) adding a vulcanization accelerator into the activated rubber powder, reacting for 1-24 h at 60-100 ℃ in a nitrogen atmosphere, washing, filtering and drying the product to obtain modified rubber powder with a vulcanization accelerating effect;
the vulcanization accelerator comprises more than one of 2-mercaptobenzothiazole, dibenzothiazyl disulfide, zinc dimethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc diethyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc dibenzyldithiocarbamate, iron dibutyldithiocarbamate and copper dibutyldithiocarbamate.
2. The method for preparing modified rubber powder with vulcanization acceleration effect according to claim 1, characterized in that in step (1), the mass ratio of the concentrated sulfuric acid to the rubber powder is 0.01-0.05: 1.
3. The preparation method of the modified rubber powder with the vulcanization acceleration effect as claimed in claim 1, wherein in the step (2), the mass ratio of the deionized water to the rubber powder is 1-2: 1, and the mass ratio of the coupling agent to the rubber powder is 0.03-0.12: 1.
4. The preparation method of modified rubber powder with vulcanization acceleration effect as claimed in claim 1, characterized in that in step (3), the mass ratio of the accelerator to the rubber powder is 0.01-0.1: 1.
5. The method for preparing modified rubber powder with vulcanization acceleration effect according to claim 1, wherein the chlorosilane-containing coupling agent comprises chloropropyltrimethoxysilane, chloropropyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, chloroethyltrimethoxysilane, chloroethyltriethoxysilane, chloropropyltrichlorosilane, chloropropyldimethoxysilane, chloroethyldimethoxysilane.
6. The modified rubber powder with the vulcanization acceleration effect is prepared by the preparation method of any one of claims 1 to 5.
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| JP4581116B2 (en) * | 2007-09-10 | 2010-11-17 | 住友ゴム工業株式会社 | Vulcanized rubber composition, pneumatic tire, and production method thereof |
| CN103736465B (en) * | 2013-12-12 | 2016-04-13 | 华中科技大学 | A kind of modification waste Crumb rubber for Adsorption of Heavy Metals and preparation method thereof |
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