CN112708167A - Surface modification method for waste rubber powder - Google Patents
Surface modification method for waste rubber powder Download PDFInfo
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- CN112708167A CN112708167A CN202011556947.2A CN202011556947A CN112708167A CN 112708167 A CN112708167 A CN 112708167A CN 202011556947 A CN202011556947 A CN 202011556947A CN 112708167 A CN112708167 A CN 112708167A
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- rubber powder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2319/00—Characterised by the use of rubbers not provided for in groups C08J2307/00 - C08J2317/00
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
- Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention relates to a surface modification method of waste rubber powder, which comprises the following specific steps: 1) washing the waste rubber powder with clear water, and drying; 2) mixing and reacting the dried waste rubber powder with an acid solution, and then drying the waste rubber powder at a high temperature; 3) and crushing the waste rubber powder dried at the high temperature to 100-200 meshes to obtain the rubber powder with the modified surface. The waste rubber modification treatment method provided by the invention is simple in process, easy to operate, economical and practical, and the obtained modified rubber powder is high in mechanical property, good in reaction activity, good in compatibility with epoxy resin when used for preparing rubber modified epoxy adhesive, large in interface bonding strength, and capable of remarkably improving the mechanical property and durability of the epoxy adhesive.
Description
Technical Field
The invention belongs to the technical field of waste recovery or processing, and particularly relates to a waste rubber powder surface modification method.
Background
With the development of industrial and modern civilization, the treatment of various wastes has become a great problem to people, and particularly for chemically crosslinked rubber, the rubber cannot be degraded even if being stacked in a natural environment for hundreds of years due to a crosslinked network structure inside the rubber, so that the environmental safety and beautification are seriously influenced. How to efficiently and reasonably treat waste rubber to change waste into valuable is a common problem in all countries today.
The waste rubber powder is doped into the epoxy adhesive to prepare the rubber modified epoxy adhesive which is used in building engineering, and the method is a very promising disposal method. The epoxy structural adhesive is widely applied to steel bonding reinforcement of various components, including repairing of bridges, beam column defect reinforcement of old plants, cantilever beam bonding, bracket bonding, cement pile head lengthening and the like. For a building located on a stratum structure belt with a lot of earthquakes, the use of the epoxy adhesive can improve the earthquake resistance level of the building, the epoxy adhesive is large in brittleness and poor in toughness, and the epoxy adhesive can be toughened after being doped into rubber, and the reason is mainly that a structural deformation center capable of absorbing strain energy can be formed in the rubber modified epoxy adhesive, so that the impact resistance of the building is obviously improved, and various diseases caused by internal stress are reduced.
But the adhesive strength of the epoxy adhesive can be obviously reduced by directly doping the waste rubber powder, and the interface adhesive force with the epoxy adhesive is weak mainly because the interaction force between the rubber and the epoxy adhesive is weak, so that the large-scale application of the waste rubber powder in products is hindered, and therefore, the waste rubber powder is pretreated firstly, and some chemical groups are introduced, so that the modified rubber can generate strong chemical bonding effect with the epoxy adhesive.
At present, NaOH solution and CCl are mainly adopted by a plurality of scientific researchers4The surface of the waste rubber powder is modified by a solution, polyacrylamide, polyvinyl acetal, a silane coupling agent and the like to strengthen the interaction between the rubber powder and the epoxy adhesive, but with the increase of the mixing amount of the rubber, the mixing amount of the rubber powder generally reaches about 5%, the bonding strength of the epoxy adhesive is obviously reduced, and the aim of large-scale utilization is difficult to achieve.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for modifying the surface of waste rubber powder, aiming at the defects in the prior art, the method can effectively improve the compatibility of the waste rubber powder and an epoxy glue cementing material, and obviously improve the interface bonding strength between the waste rubber powder and the epoxy glue cementing material.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the method for modifying the surface of the waste rubber powder comprises the following specific steps:
1) washing the waste rubber powder with clear water, and drying;
2) mixing and reacting the dried waste rubber powder with an acid solution, and then drying the waste rubber powder at a high temperature;
3) and crushing the waste rubber powder dried at the high temperature to 100-200 meshes to obtain the rubber powder with the modified surface.
According to the scheme, the waste rubber powder in the step 1) is 100-200-mesh superfine rubber powder.
According to the scheme, the drying mode in the step 1) is natural drying or drying at 50-60 ℃.
According to the scheme, the method for washing the waste rubber powder by using the clean water in the step 1) comprises the following steps: soaking the waste rubber powder in clear water and stirring for more than 10 minutes. The clean water washing is used for removing floating dust and pollutants on the surface of the waste rubber powder.
According to the scheme, the acid solution in the step 2) is prepared by mixing concentrated sulfuric acid with the mass concentration of 98% and deionized water according to the volume ratio of 1: 1, mixing to obtain; the mass volume ratio of the waste rubber powder to the acidic solution is 1-2 g/mL.
According to the scheme, the method for mixing and reacting the dried waste rubber powder with the acidic solution in the step 2) comprises the following steps: adding the acidic solution into the waste rubber powder in batches for a few times, stirring while adding, and stirring for 5-10 minutes after adding.
According to the scheme, the high-temperature drying conditions in the step 2) are as follows: baking at 60 deg.C for 12 hr, and baking at 120 deg.C for 3 hr.
According to the scheme, the method for crushing the waste rubber powder in the step 3) comprises the following steps: grinding for 3-5 minutes by adopting a planetary ball mill at the rotating speed of 5000-6000 r/min.
The invention also comprises the modified rubber powder obtained by the modification method.
And the application of the modified rubber powder in the aspect of preparing the rubber modified epoxy adhesive, the specific use method is as follows: and adding the modified rubber powder into an epoxy adhesive according to the mixing amount of 15-20%. The toughness of the obtained rubber modified epoxy adhesive is greatly improved under the condition of ensuring that the bonding strength is not reduced, and the defect of high brittleness of the epoxy adhesive is effectively overcome.
The rubber has good toughness, can be used for improving the defect of high brittleness of the epoxy adhesive, but the surface of the rubber is inert and has poor interface compatibility with the epoxy adhesive, so that the application of the rubber in the epoxy adhesive is hindered. According to the invention, the surface of the waste rubber powder is pretreated by acid to graft active functional groups such as carboxyl, hydroxyl and the like on the surface of the rubber powder, so that the interface compatibility of the rubber powder and the epoxy adhesive is improved, and the interface bonding strength of the rubber powder and the epoxy adhesive is improved.
The invention has the beneficial effects that: 1. the method for modifying and treating the waste rubber has simple process, easy operation, economy and practicability, and provides an effective solution for solving the problem of black pollution in the current society; 2. the modified rubber powder provided by the invention has high mechanical property and good reaction activity, is good in compatibility with epoxy resin when used for preparing rubber modified epoxy adhesive, is high in interface bonding strength, and can remarkably improve the mechanical property and durability of the epoxy adhesive.
Drawings
FIG. 1 is an infrared spectrum of the waste rubber powder treated in step 1) of example 2 of the present invention;
FIG. 2 is an infrared spectrum of the surface-modified rubber powder obtained in step 3) of example 2;
FIG. 3 is a graph showing the morphology of the interface between the modified rubber powder and the epoxy resin prepared in example 2;
FIG. 4 is a graph showing the morphology of the interface between the modified rubber powder and the epoxy resin prepared in comparative example 1.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention is further described in detail below with reference to the accompanying drawings.
The acid solution used in the embodiment of the invention is prepared by mixing 98% concentrated sulfuric acid and deionized water according to the volume ratio of 1: 1 are mixed to obtain the product.
Example 1
A surface modification method for waste rubber powder comprises the following specific steps:
1) washing waste rubber powder with clear water, soaking 200g of waste rubber powder (100 meshes) in 200mL of clear water, stirring for 10 minutes, and naturally drying;
2) adding 100mL of acid solution into the dried waste rubber powder in batches in a small amount for multiple times, stirring while adding, stirring for 10 minutes, and then drying the stirred mixture at 60 ℃ for 12 hours and at 120 ℃ for 3 hours;
3) and (3) grinding the waste rubber powder dried at high temperature for 3 minutes at the rotating speed of 5000 rpm by adopting a planetary ball mill to obtain the rubber powder (the particle size is 100-200 meshes) with modified surface.
Example 2
A surface modification method for waste rubber powder comprises the following specific steps:
1) washing waste rubber powder with clear water, soaking 200g of waste rubber powder (150 meshes) in 200mL of clear water, stirring for 10 minutes, and drying at 50 ℃;
2) adding 100mL of acid solution into the dried waste rubber powder in batches in a small amount for multiple times, stirring while adding, stirring for 10 minutes, then drying the stirred mixture at 60 ℃ for 12 hours, and then drying at 120 ℃ for 3 hours;
3) and (3) grinding the waste rubber powder dried at high temperature for 3 minutes at the rotating speed of 5000 rpm by adopting a planetary ball mill to obtain the rubber powder (the particle size is 100-200 meshes) with modified surface.
FIG. 1 is an infrared spectrum of the waste rubber powder treated in step 1) of this example, and FIG. 2 is an infrared spectrum of the surface-modified rubber powder obtained in step 3) of this example, wherein the infrared spectrum of the modified rubber powder is 1715cm-1，3420cm-1，1083cm-1Has strong absorption peak, which shows that the surface modified rubber powder has the activity of carboxyl, hydroxyl and the likeThe functional group and the rubber powder treated in the step 1) have no strong absorption peak in an infrared spectrogram.
Comparative example 1 (No treatment with acidic solution)
A surface modification method for waste rubber powder comprises the following specific steps:
1) washing waste rubber powder with clear water, soaking 200g of waste rubber powder (150 meshes) in 200mL of clear water, stirring for 10 minutes, drying the waste rubber powder at 60 ℃ for 12 hours, and drying at 120 ℃ for 3 hours;
2) and grinding the waste rubber powder dried at high temperature for 3 minutes at the rotating speed of 5000 revolutions per minute by adopting a planetary ball mill to obtain the surface modified rubber powder (the particle size is 100-200 meshes).
The modified rubber powder obtained in example 2 and the modified rubber powder obtained in comparative example 1 were mixed with liquid bisphenol a epoxy resin, epoxy diluent AGE, and amine curing agent diethylenetriamine (the mass ratio of bisphenol a epoxy resin, epoxy diluent AGE, and diethylenetriamine is 20: 3: 4), and the amount of rubber powder was 10% (based on the total mass of liquid bisphenol a epoxy resin, epoxy diluent AGE, and amine curing agent, the amount of rubber powder was reduced for easy observation under a microscope), and two rubber modified epoxy adhesives were obtained by mixing uniformly, followed by curing at 100 ℃ for 0.5h to obtain two rubber powder-epoxy resin composite products. The interface condition of the modified rubber powder and the epoxy resin in the two rubber powder-epoxy resin composite products is observed by adopting an MV3000 optical microscope, and an interface image is acquired by adopting a magnification of 400 times. Fig. 3 and 4 are respectively a morphology chart of an interface between the modified rubber powder and the epoxy resin obtained in example 2 and a morphology chart of an interface between the modified rubber powder and the epoxy resin obtained in comparative example 1, and it can be seen from fig. 3 that the interface between the rubber powder and the epoxy resin adhesive obtained in example 2 is fuzzy and complex, and the interface transition region is large, indicating that the compatibility of the rubber powder-epoxy resin system is good and the interface has no obvious weak region. In fig. 4, the interface between the rubber powder and the epoxy resin adhesive obtained in comparative example 1 is clear and single, the rubber powder-epoxy resin system has an obvious boundary and a narrow transition region, which indicates that the compatibility between the rubber powder and the epoxy resin is poor and the interface region between the rubber powder and the epoxy resin is weak.
The tensile strength of two rubber powder-epoxy resin composite products was measured according to the method in GBT 6329-1996-measurement of tensile strength of adhesive butt joint, and the tensile strength of the product obtained by compounding the modified rubber powder with the epoxy resin in example 2 was 9.76MPa, and the tensile strength of the product obtained by compounding the modified rubber powder with the epoxy resin in comparative example 1 was 4.32 MPa.
According to the method, the modified rubber powder obtained in the example 2 is mixed with liquid bisphenol A epoxy resin, epoxy diluent AGE and amine curing agent diethylenetriamine (the mass ratio of the bisphenol A epoxy resin to the epoxy diluent AGE to the diethylenetriamine is 20: 3: 4), the mixing amount of the rubber powder is increased to 20% (based on the mass sum of the liquid bisphenol A epoxy resin, the epoxy diluent AGE and the amine curing agent), the rubber modified epoxy adhesive obtained after uniform mixing is cured for 0.5h at 100 ℃, and the bonding strength of the cured product is 6.78 MPa.
Claims (10)
1. A waste rubber powder surface modification method is characterized by comprising the following specific steps:
1) washing the waste rubber powder with clear water, and drying;
2) mixing and reacting the dried waste rubber powder with an acid solution, and then drying the waste rubber powder at a high temperature;
3) and crushing the waste rubber powder dried at the high temperature to 100-200 meshes to obtain the rubber powder with the modified surface.
2. The method for modifying the surface of the waste rubber powder according to claim 1, wherein the waste rubber powder in the step 1) is 100-200 mesh superfine rubber powder.
3. The method for modifying the surface of the waste rubber powder according to claim 1, wherein the drying manner in the step 1) is natural drying or drying at 50-60 ℃.
4. The method for modifying the surface of the waste rubber powder according to claim 1, wherein the method for washing the waste rubber powder with clean water in the step 1) comprises the following steps: soaking the waste rubber powder in clear water and stirring for more than 10 minutes. The clean water washing is used for removing floating dust and pollutants on the surface of the waste rubber powder.
5. The method for modifying the surface of the waste rubber powder according to claim 1, wherein the acidic solution in the step 2) is prepared by mixing concentrated sulfuric acid with a mass concentration of 98% and deionized water according to a volume ratio of 1: 1, mixing to obtain; the mass volume ratio of the waste rubber powder to the acidic solution is 1-2 g/mL.
6. The method for modifying the surface of the waste rubber powder according to claim 1, wherein the method for mixing and reacting the dried waste rubber powder with the acidic solution in the step 2) comprises the following steps: adding the acidic solution into the waste rubber powder in batches for a few times, stirring while adding, and stirring for 5-10 minutes after adding.
7. The method for modifying the surface of the waste rubber powder according to claim 1, wherein the high-temperature drying conditions in the step 2) are as follows: baking at 60 deg.C for 12 hr, and baking at 120 deg.C for 3 hr.
8. The method for modifying the surface of the waste rubber powder according to claim 1, wherein the method for crushing the waste rubber powder in the step 3) comprises the following steps: grinding for 3-5 minutes by adopting a planetary ball mill at the rotating speed of 5000-6000 r/min.
9. A modified rubber crumb obtained by the method for surface modification of crumb rubber according to any one of claims 1 to 8.
10. The application of the modified rubber powder of claim 9 in preparing rubber modified epoxy adhesive is characterized in that the specific application method is as follows: and adding the modified rubber powder into an epoxy adhesive according to the mixing amount of 15-20%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113667179A (en) * | 2021-08-20 | 2021-11-19 | 山西省交通科技研发有限公司 | Preparation method of nano titanium dioxide coated modified waste rubber powder |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113667179A (en) * | 2021-08-20 | 2021-11-19 | 山西省交通科技研发有限公司 | Preparation method of nano titanium dioxide coated modified waste rubber powder |
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