Biomass compound modified waste tire rubber powder, and preparation method and application thereof

Abstract

The present application relates to biomass compound modified waste tire rubber powder and its preparation method and application. The rubber activator is fully contacted with the waste tire rubber powder under the action of high-speed shearing and the surface of the waste tire rubber powder is activated, and the activated rubber powder is obtained after uniform stirring for a certain time; the biomass modifier is slowly added into the reaction container containing the activated rubber powder in the process of uniform stirring, and the mixed solution is obtained after uniform stirring; the catalyst is added into the mixed solution, and the product obtained by the reaction is centrifuged, washed, suction filtered and dried to obtain the biomass compound modified waste tire rubber powder. Compared with the prior art, the waste tire rubber powder is subjected to reactive surface modification by using the biomass compound as the surface modifier, the biomass modifier is loaded on the surface of the rubber powder through the chemical action between the hydroxyl groups in the molecular structure of the biomass compound and the oxygen-containing groups on the surface of the activated rubber powder, and the activated rubber powder is effectively modified.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of materials, and in particular relates to a biomass compound modified waste tire rubber powder and a preparation method and application thereof. BACKGROUND

[0002] Global industrial development is rapid, leading to a sudden rise in greenhouse effect. In order to improve the environment, all walks of life are improving towards clean energy, and the automobile industry is also undergoing a transformation towards new energy vehicles. In the process of global automobile upgrading, many waste tires, rubber products and their leftover waste materials will be generated, and the recycling and reuse thereof is a huge and arduous task. In recent years, the application technology and range of rubber powder have developed very rapidly, and the modification treatment of waste tire rubber powder is a key step. Waste tire rubber powder is most commonly used for the composite modification of asphalt, which can improve its high-temperature resistance and deformation resistance and other properties. The modified rubber powder can be used to prepare rubber products again, such as tires, conveyor belts, etc. The modified rubber powder can also be compounded with other materials to achieve a reinforcing effect, thereby greatly reducing the raw material cost of the rubber industry and greatly improving economic efficiency. Therefore, the modification treatment and recycling of rubber powder are a key link in protecting the environment and purifying environmental sanitation, and their social benefits are immeasurable.

[0003] Biomass resources are a renewable resource with a large storage capacity, which are chemical active substances extracted from biological bodies (including animals, plants, microorganisms, etc.), and have the characteristics of non-toxicity, non-pollution and recyclability. Biomass modifier refers to a monomer derivative or oligomer prepared by using chemical active components extracted from biomass resources, which can be directly used or prepared by chemical synthesis. Among them, the chemical active components extracted from plants are relatively stable, have a wide source, low cost and can be recycled and regenerated, and thus are the main source for preparing biomass modifiers.

[0004] Rubber powder is a three-dimensional cross-linked network structure material mainly composed of rubber, carbon black and the like, and has low surface activity, and thus needs to be modified to be used in composite materials. Some modification methods of rubber powder have been reported previously, such as in patent CN202011180974.4, waste rubber powder is modified by a prepolymer and applied to road asphalt to improve the performance of modified asphalt; and in patent CN201710707103.5, silica is in-situ generated by the reaction of tetraethyl orthosilicate and n-butylamine and grafted on the surface of rubber powder. However, the existing rubber powder modification technology has the problems of complex modification process and environmental pollution in the modification process. SUMMARY

[0005] In view of the problems of complex modification process and environmental pollution in the modification process of the existing rubber powder modification technology, the present application provides a biomass compound modified waste tire rubber powder and a preparation method and application thereof.

[0006] The biomass compound modified waste tire rubber powder provided by the application is a natural plant polyphenol modified waste tire rubber powder.

[0007] The application realizes full contact between the waste tire rubber powder and the activator by high-speed shearing and activates the surface of the waste tire rubber powder to obtain activated rubber powder.

[0008] The application further provides application of the biomass compound modified waste tire rubber powder.

[0009] The preparation process of the application is simple and easy to operate.

[0010] The application can be realized by the following technical scheme.

[0011] The application provides a preparation method of biomass compound modified waste tire rubber powder.

[0012] (1) under a certain temperature, rubber activator is added into a kneader containing waste tire rubber powder for high-speed mixing, so that the rubber activator fully contacts with the waste tire rubber powder under high-speed shearing and activates the surface of the waste tire rubber powder, and after uniform stirring for a certain time, activated rubber powder is obtained, and after further drying, the activated rubber powder is reserved;

[0013] (2) the surface of the activated rubber powder contains a large number of oxygen-containing groups, and further, a biomass modifier is slowly added into a reaction container containing the activated rubber powder in a uniform stirring process, and after uniform stirring, a mixed solution is obtained;

[0014] (3) a certain amount of catalyst is added into the mixed solution, and after constant temperature stirring for a certain time under a certain temperature, the obtained product is centrifuged, washed, suction filtered and dried to obtain the biomass compound modified waste tire rubber powder.

[0015] In some embodiments of the present application, the waste tire rubber powder in step (1) has a mesh size of 10-200 mesh.

[0016] In some embodiments of the present application, the rubber activator in step (1) is selected from one or more of persulfate, peroxide, potassium dichromate, potassium permanganate, chlorate, fuming sulfuric acid, etc.

[0017] In some embodiments of the present application, the amount of the rubber activator in step (1) is 0.1-5wt% of the amount of the waste tire rubber powder.

[0018] In some embodiments of the present application, the biomass modifier in step (2) is selected from one or more of tea polyphenol, apple polyphenol, tannic acid, cardanol, proanthocyanidin or derivatives thereof, and the relative molecular mass of the biomass modifier in step (2) is 300-3000.

[0019] In some embodiments of the present application, the amount of the waste tire rubber powder to the biomass modifier in step (2) is (0.5-50):1.

[0020] In some embodiments of the present application, the catalyst in step (3) is selected from one or more of dibutyl tin dilaurate, bis(dodecylthio) dibutyl tin, dibutyl tin diacetate or stannous octoate.

[0021] In some embodiments of the present application, the amount of the catalyst to the biomass modifier in step (3) is (0.01-0.1):1.

[0022] In some embodiments of the present application, in step (1), the high-speed shearing refers to a condition of a rotation speed of 500-2000 rpm.

[0023] The present application further provides the biomass compound modified waste tire rubber powder obtained based on the above preparation method.

[0024] The present application further provides the application of the biomass compound modified waste tire rubber powder obtained based on the above preparation method, which is applied in natural rubber or various synthetic rubbers to prepare rubber / waste rubber powder composite materials.

[0025] The application uses biomass compounds as surface modifiers to carry out reactive surface modification on waste tire rubber powder, and the biomass modifier is loaded on the surface of the rubber powder through the chemical action between the hydroxyl groups in the molecular structure of the biomass compound and the oxygen-containing groups on the surface of the activated rubber powder, thereby effectively modifying the activated rubber powder, better improving the interface bonding between the waste tire rubber powder and rubber, and effectively improving the performance of the composite material.

[0026] The biomass modifier is selected from one or more of tea polyphenol, apple polyphenol, tannic acid, cardanol, proanthocyanidin or derivatives thereof, is a chemical active substance extracted from organisms (including animals, plants, microorganisms, etc.), has the characteristics of non-toxicity, non-pollution and recyclability, and can effectively improve the surface activity of the waste tire rubber powder.

[0027] Compared with the prior art, the application has the following advantages and beneficial effects:

[0028] 1、The application is easy to operate and has a simple process, directly contacts the waste tire rubber powder with the activator through high-speed shearing to activate the surface of the waste tire rubber powder, and contains a large number of oxygen-containing groups on the surface of the waste tire rubber powder after modification, and then the biomass modifier is slowly added to the reaction container containing the activated rubber powder in the uniform stirring process, and the surface of the rubber powder is chemically modified through the action between the biomass modifier and the oxygen-containing groups on the surface of the rubber powder under certain conditions, to obtain the biomass compound modified waste tire rubber powder, and further composite with the rubber matrix to obtain a rubber / modified rubber powder composite material, which improves the mechanical properties and DIN abrasion resistance, flex resistance and other properties of the composite material, and the process is simple and can be used for industrial production.

[0029] 2、The biomass modifier used in the application is a chemical active substance extracted from organisms (including animals, plants, microorganisms, etc.), has the characteristics of non-toxicity, non-pollution and recyclability, and can be directly used or prepared into monomer derivatives or oligomers by chemical synthesis method. Since the chemical active components of the biomass compound are relatively stable, the source is wide, the cost is low, and it can be recycled, the biomass modifier is the main source of preparing the biomass modifier.

[0030] 3、The application uses chemically modified rubber powder to retain its original structure and performance; the surface of the modified rubber powder has more active groups, which can be used in combination with other materials, and the modified rubber powder can replace or partially replace existing rubber and fillers, and can maintain stable performance. To a certain extent, it can reduce the cost of raw materials, protect the environment, and improve economic benefits. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 Figure is the surface morphology contrast diagram of the rubber powder before and after modification, figure (a) is the unmodified rubber powder, figure (b) is the modified rubber powder.

[0032] Figure 2 Figure is the wear resistance performance analysis of the NR / RP composite material.

[0033] Figure 3 Figure is the flex cracking resistance performance analysis of the NR / RP composite material. DETAILED DESCRIPTION

[0034] The application will be described in detail below in combination with the drawings and specific examples. The protection scope of the application is applicable but not limited to the following examples.

[0035] The tensile strength of the rubber composite material prepared below is tested according to the GB / T 528-2009 standard. The wear resistance performance is tested according to the GB / T 9867-2008 standard. The flex cracking resistance performance is tested according to the GB / T 12586-2003 standard.

[0036] Example 1

[0037] The embodiment provides a preparation method of biomass compound modified waste tire rubber powder and application thereof, comprising the following steps:

[0038] Step (1): 30g of 60 mesh waste rubber powder, 1g of benzoyl peroxide, 1g of cardanol, and 0.5g of dibutyltin dilaurate were weighed and reserved for use;

[0039] Step (2): The benzoyl peroxide was added to the kneader containing the waste rubber powder at a high speed of 1000 rpm to mix, so that the peroxide activator was fully contacted with the waste rubber powder under the action of high speed shearing and the surface of the waste rubber powder was activated. After uniform stirring for 1h, the activated rubber powder was obtained, and after further drying, it was reserved for use;

[0040] Step (3): The activated and modified waste rubber powder was added to a reaction container containing 200ml of deionized water and stirred uniformly, and the biomass modifier cardanol was slowly added to the reaction container in the process of uniform stirring at a speed of 200 rpm. After uniform stirring, a mixed solution was obtained;

[0041] Step (4): 0.5g of catalyst dibutyltin dilaurate was added to the above mixed solution, and after constant temperature stirring at 60℃ for 2h, the reaction product was centrifuged, washed, suction filtered and dried to obtain the biomass compound modified waste tire rubber powder. The microstructure morphology change of the rubber powder before and after modification is as follows: Figure 1As shown, the surface of the modified rubber powder becomes rougher, which is due to the strong oxidation of the activator and the chemical combination of the modifier on the surface of the rubber powder. After modification, the interface between the rubber powder and the rubber matrix is more firmly bonded.

[0042] Step (5): The biomass modified waste tire rubber powder obtained in step (4) is mixed with rubber, small molecule additives to prepare a rubber composite (NR / m-RP). The basic formula of each component is shown in Table 1 (unit: phr). According to the basic formula of rubber, the activator (ZnO+SA), modified rubber powder (m-RP), accelerator (NS), antioxidant (RD+4020), and sulfur (S) are added in sequence using an open mill. After vulcanization at 143°C, a biomass compound modified rubber powder and rubber composite vulcanized rubber is obtained. The physical and mechanical properties of the rubber composite samples with modified and unmodified rubber powder are compared as shown in Table 2. It can be seen that compared with the unmodified rubber powder system, the mechanical properties of the rubber composite are enhanced, and the wear resistance and flex cracking resistance are also improved. Figure 2 、 Figure 3 as shown.

[0043] Table 1 Rubber / Rubber Powder Composite Formula

[0044]

[0045] Table 2 Physical and Mechanical Properties of Rubber / Rubber Powder Composite

[0046]

[0047] Example 2

[0048] The present embodiment provides a preparation method of biomass compound modified waste tire rubber powder and its application, which comprises the following steps:

[0049] Step (1): 30g of 80 mesh rubber powder, 1g of potassium persulfate activator, 2g of tea polyphenol, and 0.5g of dibutyltin dilaurate were weighed and reserved for use;

[0050] Step (2): The potassium persulfate activator was added to the kneader containing the waste rubber powder and mixed at a high speed of 800 rpm to make the potassium persulfate activator fully contact with the waste rubber powder under high-speed shearing and activate the surface. After uniform stirring for 0.5h, the activated rubber powder was obtained and further dried for use;

[0051] Step (3): The activated and modified waste rubber powder was added to a reaction vessel containing 100ml of deionized water and stirred uniformly. The biomass modifier tea polyphenol was slowly added to the reaction vessel under uniform stirring at a speed of 300 rpm. After stirring uniformly, a mixed solution was obtained;

[0052] Step (4) 0.5 g of catalyst dibutyl tin dilaurate was added to the above mixed solution, after constant temperature stirring reaction at 50°C for 3h, the product obtained by the reaction was centrifuged, washed, suction filtered and dried to obtain the biomass compound modified waste tire rubber powder.

[0053] Step (5) The biomass modified waste tire rubber powder obtained in step (4) was mixed with rubber and small molecule additives to prepare a rubber composite (NR / m-RP). The basic formula of each component is shown in Table 3 (unit: phr). According to the basic formula of rubber, the activator (ZnO+SA), modified rubber powder (m-RP), accelerator (NS), antioxidant (RD+4020), and sulfur (S) were added in sequence using an open mill, and the vulcanized rubber composite of biomass compound modified rubber powder and rubber was obtained after vulcanization at 143°C. The physical and mechanical properties of the rubber composite samples with and without modified rubber powder are shown in Table 4. It can be seen that compared with the unmodified rubber powder system, the mechanical properties of the rubber composite are enhanced.

[0054] Table 3

[0055]

[0056] Table 4

[0057]

[0058] Example 3

[0059] The present embodiment provides a preparation method of biomass compound modified waste tire rubber powder and its application, which comprises the following steps:

[0060] Step (1) 20 g of 60 mesh waste rubber powder, 0.5 g of potassium permanganate activator, 1 g of procyanidine, and 0.5 g of bis(dodecylthio) dibutyl tin were weighed and reserved for use;

[0061] Step (2) The potassium permanganate activator was added to the kneader containing the waste rubber powder at a high speed of 1200 rpm to mix, so that the potassium permanganate activator was fully contacted with the waste rubber powder under high speed shearing and the surface of the waste rubber powder was activated. After uniform stirring for 0.5 h, the activated rubber powder was obtained and further dried for use;

[0062] Step (3) The activated and modified waste rubber powder was added to a reaction vessel containing 200 ml of deionized water and stirred uniformly. The biomass modifier procyanidine was slowly added to the reaction vessel at a uniform speed under stirring at a speed of 300 rpm. After stirring uniformly, a mixed solution was obtained.

[0063] In step (4), 0.5 g of the catalyst dibutyltin bis(dodecylsulfide) was added to the mixed solution, and the mixture was stirred at a constant temperature of 70° C. for 2 h. The product obtained by the reaction was centrifuged, washed, filtered, and dried to obtain biomass compound-modified waste tire rubber powder.

[0064] Step (5): The biomass-modified waste tire rubber powder obtained in step (4) is mixed with rubber and a small molecule additive to prepare a rubber composite material (NR / m-RP). The basic formula of each component is shown in Table 5 (unit: phr). According to the basic rubber formula, the activator (ZnO+SA), modified rubber powder (m-RP), accelerator (NS), antioxidant (RD+4020), and sulfur (S) are added in the order of mixing using an open mill. After vulcanization at 143°C, a composite vulcanized rubber of biomass compound modified rubber powder and rubber is obtained. The physical and mechanical properties of the rubber composite samples with modified and unmodified rubber powder are compared in Table 6. It can be seen that the mechanical properties of the rubber composite are enhanced compared to the unmodified rubber powder system.

[0065] Table 5

[0066]

[0067]

[0068] Table 6

[0069]

[0070] Example 4

[0071] This embodiment provides a method for preparing waste tire rubber powder modified with a biomass compound and its application, comprising the following steps:

[0072] Step (1): weigh 30 g of 60-mesh rubber powder, 1 g of potassium dichromate activator, 1 g of tannic acid, and 0.75 g of stannous octoate, and set aside for later use;

[0073] Step (2) adding potassium dichromate activator to a kneader containing waste rubber powder and mixing at a high speed of 1200 rpm to allow the potassium dichromate activator to fully contact the waste rubber powder under the action of high-speed shearing and activate its surface, and uniformly stirring for 1.5 hours to obtain activated rubber powder, which is further dried for later use;

[0074] Step (3) adding the activated and modified waste rubber powder into a reaction vessel containing 300 ml of deionized water and stirring uniformly, and slowly adding the biomass modifier tannic acid dropwise into the reaction vessel at a speed of 100 rpm while stirring uniformly, and stirring uniformly to obtain a mixed solution;

[0075] Step (4) 0.75 g of catalyst stannous octoate is added to the above mixed solution, after constant temperature stirring at 80°C for 1.5 h, the reaction product is centrifuged, washed, filtered and dried to obtain the biomass compound modified waste tire rubber powder.

[0076] Step (5) The biomass modified waste tire rubber powder obtained in step (4) is mixed with rubber and small molecule additives to prepare a rubber composite (NR / m-RP). The basic formula of each component is shown in Table 7 (unit: phr). According to the basic formula of rubber, the activator (ZnO+SA), modified rubber powder (m-RP), accelerator (CZ), antioxidant (4020), and sulfur (S) are added in sequence on an open mill, and the vulcanized rubber composite of biomass compound modified rubber powder and rubber is obtained after vulcanization at 143°C. The physical and mechanical properties of the rubber composite samples with modified and unmodified rubber powder are compared as shown in Table 8. It can be seen that compared with the unmodified rubber powder system, the mechanical properties of the rubber composite are enhanced.

[0077] Table 7

[0078]

[0079] Table 8

[0080]

[0081] Example 5

[0082] The present embodiment provides a preparation method of biomass compound modified waste tire rubber powder and its application, which comprises the following steps:

[0083] Step (1) 40 g of 120 mesh rubber powder, 1 g of methyl ethyl ketone peroxide, 5 g of cardanol, and 1 g of stannous octoate are weighed and reserved for use;

[0084] Step (2) The peroxide activator is added to the kneader containing the waste rubber powder at a speed of 500 rpm for high-speed mixing, so that the peroxide activator fully contacts and activates the surface of the waste rubber powder under the action of high-speed shearing. After uniform stirring for 2 h, the activated rubber powder is obtained and further dried for use;

[0085] Step (3) The activated and modified waste rubber powder is added to a reaction vessel containing 200 ml of deionized water and stirred uniformly. The biomass modifier cardanol is slowly added to the reaction vessel under uniform stirring at a speed of 200 rpm. After stirring uniformly, a mixed solution is obtained.

[0086] Step (4) 1 g of catalyst stannous octoate is added to the above mixed solution, after constant temperature stirring at 60°C for 2 h, the reaction product is centrifuged, washed, filtered and dried to obtain the biomass compound modified waste tire rubber powder.

[0087] Step (5): The biomass modified waste tire rubber powder obtained in step (4) is mixed with rubber and small molecule additives to prepare a rubber composite (NR / m-RP). The basic formula of each component is shown in Table 9 (unit: phr). According to the basic formula of rubber, the activator (ZnO+SA), modified rubber powder (m-RP), accelerator (CZ), antioxidant (4020), and sulfur (S) are added in sequence on an open mill, and the vulcanized rubber composite of biomass compound modified rubber powder and rubber is obtained after vulcanization at 143°C. The physical and mechanical properties of the rubber composite samples with modified and unmodified rubber powder are compared as shown in Table 10. It can be seen that compared with the unmodified rubber powder system, the mechanical properties of the rubber composite are enhanced.

[0088] Table 9

[0089]

[0090] Table 10

[0091]

[0092] Example 6

[0093] The present embodiment provides a preparation method of biomass compound modified waste tire rubber powder and its application, which comprises the following steps:

[0094] Step (1): weigh 10 g of 150 mesh rubber powder, 0.3 g of hydrogen peroxide, 1 g of procyanidine, and 0.25 g of dibutyltin diacetate, and reserve them for use;

[0095] Step (2) Add peroxide activator to the kneader containing waste rubber powder and mix at a speed of 800 rpm to make the peroxide activator fully contact with the waste rubber powder under high-speed shearing and activate the surface. After uniform stirring for 1 h, the activated rubber powder is obtained and further dried for use;

[0096] Step (3) Add the activated and modified waste rubber powder to a reaction vessel containing 300 ml of deionized water and stir uniformly. Slowly add the biomass modifier procyanidine to the reaction vessel at a uniform stirring speed under a rotation speed of 300 rpm. After stirring uniformly, a mixed solution is obtained.

[0097] Step (4) 0.25 g of catalyst dibutyl tin diacetate is added to the above mixed solution, after constant temperature stirring at 50°C for 5 h, the reaction product is centrifuged, washed, filtered and dried to obtain biomass compound modified waste tire rubber powder.

[0098] Step (5) Biomass modified waste tire rubber powder obtained in step (4) is mixed with rubber and small molecule additives to prepare rubber composite (SBR / SiO2 / m-RP). The basic formula of each component is shown in Table 11 (unit: phr). According to the basic formula of rubber, the activator (ZnO+SA), white carbon black (SiO2), modified rubber powder (m-RP), accelerator (CZ), antioxidant (4020), and sulfur (S) are mixed in the order of addition by using an open mill, and the vulcanized rubber is obtained after vulcanization at 150°C. The mechanical properties of each sample are shown in Table 12, which shows that the mechanical properties of the rubber composite are enhanced compared with the unmodified rubber powder system.

[0099] Table 11 Basic formula of rubber / rubber powder composite

[0100]

[0101] Table 12

[0102]

[0103] The above description of the embodiments is to facilitate the understanding and use of the invention by those skilled in the art. Those skilled in the art can easily make various modifications to these embodiments, and apply the general principles described herein to other embodiments without creative labor. Therefore, the present invention is not limited to the above embodiments, and the improvements and modifications made by those skilled in the art according to the disclosure of the present invention without departing from the scope of the present invention should be within the scope of protection of the present invention.

Claims

1. A method for preparing a biomass compound-modified waste tire rubber powder, characterized by, The method comprises the following steps: (1) activating the rubber activator under high-speed shearing and making it fully contact with the waste tire rubber powder and activating the surface, and obtaining the activated rubber powder after uniform stirring for a certain time; (2) slowly adding the biomass modifier to the reaction container containing the activated rubber powder during uniform stirring, and obtaining the mixed solution after uniform stirring; (3) adding a catalyst to the mixed solution, stirring and reacting, and obtaining the biomass compound modified waste tire rubber powder after centrifugation, washing, suction filtration and drying of the reaction product; The amount of the rubber activator in step (1) is 0.1-5 wt% of the amount of the waste tire rubber powder; The biomass modifier in step (2) is selected from one or more of tea polyphenol, apple polyphenol, tannic acid, cardanol, procyanidin or its derivatives, the relative molecular mass of the biomass modifier in step (2) is 300-3000, and the mass ratio of the amount of the waste tire rubber powder to the biomass modifier in step (2) is (0.5-50):1; The catalyst in step (3) is selected from one or more of dibutyltin dilaurate, bis(dodecylthio) dibutyltin, dibutyltin diacetate or stannous octoate, and the mass ratio of the amount of the catalyst to the biomass modifier in step (3) is (0.01~0.1):

1.

2. The method for preparing waste tire rubber powder modified by a biomass compound according to claim 1, characterized in that: The mesh number of the waste tire rubber powder in step (1) is 10-200 mesh.

3. The method of claim 1, wherein the biomass compound is selected from the group consisting of cellulose, hemicellulose, lignin, starch, chitin, chitosan, and combinations thereof. The rubber activator in step (1) is selected from one or more of persulfate, peroxide, potassium dichromate, potassium permanganate, chlorate, fuming sulfuric acid.

4. The biomass compound modified waste tire rubber powder obtained by the preparation method according to any one of claims 1-3.

5. Use of the biomass compound modified scrap tire rubber powder according to claim 4, characterized in that, The biomass compound modified waste tire rubber powder is applied to natural rubber or various synthetic rubbers to prepare rubber / waste rubber powder composites.

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