CN111635479B - Marine microorganism adhesion-resistant olefin composite material and preparation method thereof - Google Patents
Marine microorganism adhesion-resistant olefin composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an olefin composite material resistant to marine microorganism adhesion and a preparation method thereof, wherein the preparation method comprises the following steps: (1) weighing a copolymerized olefin material, an inorganic nano component and an olefin monomer with a cyclopentadiene structure, blending, and performing ultrasonic dispersion treatment to obtain a blend; (2) and (2) adding the blend obtained in the step (1) and a catalyst into a reactor, uniformly mixing, injecting into a mold, and carrying out polymerization curing molding to obtain the target product. Compared with the prior art, the olefin composite material prepared by the invention has excellent mechanical properties such as better wear resistance, high strength and high toughness, more importantly, can effectively inhibit the attachment of marine microorganisms, has excellent marine corrosion resistance, and is beneficial to the application of the composite material in the field of marine engineering.
Description
Technical Field
The invention belongs to the technical field of modification of high polymer materials, and relates to an olefin composite material resistant to marine microorganism adhesion and a preparation method thereof.
Background
With the development and utilization of marine resources, marine engineering materials face the problems of huge abrasion, microbial corrosion and the like, the problems seriously restrict the development of major marine engineering technologies and equipment, the corrosion failure problem of microorganisms and the like seriously influences the reliability and the service life of the marine engineering and the equipment, and the anti-corrosion and wear-resistant technology of the materials becomes a problem to be solved urgently in the field of marine engineering in China. For example, valves, ship partition plates and the like which are used as key material components directly contacted with seawater are in seawater for a long time and are corroded by severe marine microorganisms and related abrasion in the using process, and the service conditions are quite harsh.
The polycyclic olefin material is a novel engineering thermosetting plastic, can be prepared from dicyclopentadiene and the like in a petroleum cracking C5 fraction and a coal coking byproduct light benzene fraction through ring-opening displacement polymerization reaction, is an environment-friendly engineering plastic with excellent comprehensive performance, particularly has remarkable mechanical property, good wear resistance, high modulus, high impact resistance and high creep resistance, is prepared by a reaction injection molding process (RIM for short), and can be widely applied to parts such as valves, ship partition plates and the like. Although engineering plastics such as polycyclic olefin materials have the functions of insulation, protection, water isolation and the like, when the engineering plastics are applied to the environment contacting with seawater and salt lake water, the seawater and the salt lake water contain various components, particularly acid and alkali components can seriously corrode the appearance of products for ocean engineering, and the ocean safety operation is influenced. Furthermore, the adhesive corrosion of marine microorganisms on materials and the like is also a challenge.
Disclosure of Invention
The invention aims to provide an olefin composite material resistant to marine microorganism adhesion and a preparation method thereof, so as to effectively inhibit the marine microorganism adhesion and have excellent marine corrosion resistance.
The purpose of the invention can be realized by the following technical scheme:
one of the technical schemes of the invention provides a preparation method of an olefin composite material resistant to marine microorganism adhesion, which comprises the following steps:
(1) weighing a copolymerized olefin material, an inorganic nano component and an olefin monomer with a cyclopentadiene structure, blending, and performing ultrasonic dispersion treatment to obtain a blend;
(2) and (2) adding the blend obtained in the step (1) and a catalyst into a reactor, uniformly mixing, injecting into a mold, and carrying out polymerization curing molding to obtain the target product.
Further, in the step (1), the copolymerized olefin material is other non-cyclopentadiene structure olefin material capable of being copolymerized with the cyclopentadiene structure olefin monomer. Further, it is mainly preferably selected from one or a mixture of plural kinds of styrene, butadiene, octadiene, ethylene-styrene copolymer, trimethylolpropane triacrylate or ethylene glycol diacrylate.
Further, in the step (1), the inorganic nano-component is selected from one or more of cuprous oxide nano-particles, silver nitrate nano-particles, nano-silica and nano-alumina.
Further, in the step (1), the olefin monomer having a cyclopentadiene structure is selected from one or more of dicyclopentadiene, norbornene derivatives, cyclobutene, isoprene, and cyclooctadiene.
Further, in the step (1), the olefin monomer having a cyclopentadiene structure is selected from one or more of dicyclopentadiene, norbornene, and norbornene derivatives.
Further, in the step (1), the weight parts of the copolymerized olefin material, the inorganic nano-component and the olefin monomer with the cyclopentadiene structure are as follows: 70-100 parts of olefin with cyclopentadiene structure, 0-30 parts of copolymerized olefin material and 0.01-5 parts of inorganic nano-component, wherein when the copolymerized olefin material is 0 part, the copolymerized olefin material is not added. More preferably, the amount of copolymerized olefin material added is greater than 0.
Furthermore, the mass ratio of the olefin monomer with the cyclopentadiene structure to the catalyst is 1000-10000: 1.
Further, the temperature of polymerization curing molding is 45-75 ℃.
Further, the catalyst is Grubbs ruthenium catalyst.
In the invention, olefin monomers with cyclopentadiene structure can be subjected to Ring Opening to form a Polymerization product, wherein, for example, the Ring tension energy of norbornene is 83.6kJ/mol, the Ring tension energy of cyclopentene is 20.5kJ/mol, the Ring tension energy of cyclopentene is far less than that of norbornene Ring, the structure is relatively stable, in the process of Grubbs ruthenium catalyst catalytic Polymerization, firstly, the norbornene Ring is subjected to Ring-Opening Metathesis Polymerization (ROMP), and then, a part of cyclopentadiene structure is subjected to Ring-Opening crosslinking to obtain a thermosetting Polymerization product with a crosslinking structure. The polymerization product formed by ring opening of the olefin monomer with the cyclopentadiene structure has certain destructive effect on marine microorganism cells, and the marine microorganism has certain 'harmful' effect on the polymerization product, so that the cross-linked polymer can effectively inhibit the attachment of the marine microorganism.
In the invention, the temperature of the sheet material formed by polymerization is controlled to be 45-75 ℃, the low polymerization temperature can cause that the ring opening of the olefin monomer with the cyclopentadiene structure can not be realized, the polymerization is incomplete, and the high polymerization temperature can easily cause serious heat release to cause the fracture of the polymerized sheet material.
The copolymerized olefin and the inorganic nanometer component can be uniformly dispersed in an olefin system with a cyclopentadiene structure, and the occurrence of an agglomeration phenomenon can be effectively avoided. Under the action of polymerization forming, the polyolefin copolymer and the inorganic nano-component can form a full interpenetrating network polymer with the olefin with the cyclopentadiene structure, the interface binding property is excellent, no defect occurs, the wear resistance and toughness of the material are improved, the adhesion of marine microorganisms can be effectively inhibited, and the marine anticorrosive performance is excellent.
The second technical scheme of the invention provides an olefin composite material resistant to marine microorganism adhesion, which is prepared by any one of the preparation methods.
Compared with the prior art, the invention has the following advantages:
(1) the co-polyolefin and inorganic nano-components used in the invention have wide sources and lower cost, the pretreatment of the inorganic material is simple, the production process flow of the olefin composite material does not need to be changed, the olefin composite material can be directly used, the construction efficiency is high, and the popularization and the application of factories are convenient.
(2) The invention can effectively form full interpenetrating network polymer by the polyolefin, inorganic nano-component and olefin monomer with cyclopentadiene structure, promote the inorganic nano-particles to be uniformly dispersed in the matrix material after reaction injection molding, effectively avoid agglomeration and further improve the wear resistance and toughness of the material.
(3) The selected polyolefin and inorganic nano-component can effectively improve the corrosion resistance of the material, particularly the inorganic nano-component has good killing effect on marine microorganisms, and greatly inhibits the attachment of the marine microorganisms on the surface of the composite material.
(4) The marine corrosion prevention type polyolefin composite material prepared by the method has wide market prospect and wide application value in the fields of marine engineering and the like.
Detailed Description
The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, reference is made to patent 201710388225.2 or patent 201910472333.7 for Grubbs ruthenium-based catalysts, the following preparation procedures being preferred in the present invention: taking a Grubbs third-generation catalyst, adding the Grubbs third-generation catalyst and NR 3 into a solvent, and reacting; and separating, purifying and drying the reacted materials to obtain the temperature-sensitive ruthenium carbene complex catalyst.
The abrasion loss of the material is tested by adopting the GB/T3960-2016 standard; the thermal deformation temperature of the material is tested by adopting the GB/T1633 standard; the marine microorganism attachment rate is measured by a fluorescence microscope counting method according to the influence of the surface property of the material on the microorganism attachment behavior.
The remainder, unless otherwise indicated, are all conventional commercial materials or conventional processing techniques in the art.
Comparative example 1
In the example, the polyolefin material is prepared by taking dicyclopentadiene monomer and Grubbs ruthenium catalyst as raw materials and adopting a reaction injection molding process. The dicyclopentadiene monomer is a polymerization grade; the catalyst is Grubbs catalyst ethyl acetate solution; the mass ratio of the dicyclopentadiene monomer to the Grubbs ruthenium catalyst is 3000: 1; the reaction temperature for injection molding was 70 ℃.
The method for preparing the polyolefin material in the embodiment comprises the following steps:
performing ultrasonic dissolution and dispersion on the Grubbs ruthenium catalyst by using ethyl acetate as a solvent to obtain a Grubbs catalyst ethyl acetate solution; uniformly blending the Grubbs catalyst toluene solution and the dicyclopentadiene raw material, and immediately injecting into a mold with the temperature of 70 ℃ for molding to obtain the polyolefin pure material. Finally, the material performance test is carried out, and the test result is shown in table 1.
Comparative example 2
The marine anticorrosive polyolefin composite material is prepared by taking dicyclopentadiene monomer, Grubbs ruthenium catalyst and inorganic nanometer component as raw materials and adopting a reaction injection molding process. The dicyclopentadiene monomer is a polymerization grade; the catalyst is Grubbs catalyst ethyl acetate solution; the mass ratio of the dicyclopentadiene monomer to the Grubbs ruthenium catalyst is 3000: 1; the reaction temperature for injection molding was 70 ℃. The inorganic nanometer component is nanometer cuprous oxide, the adding amount of the inorganic nanometer component is 0.1 percent of the mass of the dicyclopentadiene monomer, and the injection molding temperature is 70 ℃.
The preparation method of the marine organism adhesion resistant olefin composite material comprises the following steps:
performing ultrasonic dissolution and dispersion on the Grubbs ruthenium catalyst by using ethyl acetate as a solvent to form a Grubbs ruthenium catalyst ethyl acetate solution; meanwhile, blending and dispersing the nano cuprous oxide and the dicyclopentadiene. Uniformly dispersing the Grubbs ruthenium catalyst toluene solution and the dicyclopentadiene/nano cuprous oxide blending solution, and immediately injecting into a mold with the temperature of 70 ℃ for molding to obtain the marine anticorrosive polyolefin composite material. Finally, the material performance test is carried out, and the test result is shown in table 1.
Example 1
In the embodiment, the marine anticorrosive polyolefin composite material is prepared by taking dicyclopentadiene monomer, Grubbs ruthenium catalyst and polyolefin as raw materials and adopting a reaction injection molding process. The dicyclopentadiene monomer is a polymerization grade; the catalyst is Grubbs catalyst ethyl acetate solution; the mass ratio of the dicyclopentadiene monomer to the Grubbs ruthenium catalyst is 3000: 1; the reaction temperature for injection molding was 70 ℃. The copolymerized olefin is trimethylolpropane triacrylate, the addition of the copolymerized olefin is 15% of the mass of the dicyclopentadiene monomer, and the injection molding temperature is 70 ℃.
The preparation method of the marine organism adhesion resistant olefin composite material comprises the following steps:
using toluene as a solvent, and carrying out ultrasonic dissolution and dispersion on the Grubbs ruthenium catalyst to form a Grubbs ruthenium catalyst ethyl acetate solution; meanwhile, trimethylolpropane triacrylate and dicyclopentadiene are blended and dispersed. And uniformly dispersing the Grubbs ruthenium catalyst ethyl acetate solution and the dicyclopentadiene/trimethylolpropane triacrylate blended solution, and immediately injecting into a mold with the temperature of 70 ℃ for molding to obtain the marine anticorrosive polyolefin composite material. Finally, the material performance test is carried out, and the test result is shown in table 1.
Example 2
In the embodiment, the marine anticorrosive polyolefin composite material is prepared by taking dicyclopentadiene monomer, Grubbs ruthenium catalyst, copolyolefin and inorganic nanometer components as raw materials and adopting a reaction injection molding process. The dicyclopentadiene monomer is a polymerization grade; the catalyst is Grubbs catalyst ethyl acetate solution; the mass ratio of the dicyclopentadiene monomer to the Grubbs ruthenium catalyst is 3000: 1; the reaction temperature for injection molding was 70 ℃. The polyolefin is trimethylolpropane triacrylate, the addition of the polyolefin is 15% of the mass of the dicyclopentadiene monomer, the inorganic nano-component is nano-cuprous oxide, the addition of the inorganic nano-component is 0.1% of the mass of the dicyclopentadiene monomer, and the injection molding temperature is 70 ℃.
The preparation method of the marine organism adhesion resistant olefin composite material comprises the following steps:
performing ultrasonic dissolution and dispersion on the Grubbs ruthenium catalyst by using ethyl acetate as a solvent to form a Grubbs ruthenium catalyst ethyl acetate solution; meanwhile, trimethylolpropane triacrylate, nano cuprous oxide and dicyclopentadiene are blended and dispersed. Uniformly dispersing the Grubbs ruthenium catalyst toluene solution and the dicyclopentadiene/trimethylolpropane triacrylate/nano cuprous oxide blended solution, and immediately injecting into a mold with the temperature of 70 ℃ for molding to obtain the marine anticorrosive polyolefin composite material. Finally, the material performance test is carried out, and the test result is shown in table 1.
Example 3
In the embodiment, the marine anticorrosive polyolefin composite material is prepared by taking dicyclopentadiene monomer, Grubbs ruthenium catalyst, copolyolefin and inorganic nanometer components as raw materials and adopting a reaction injection molding process. The dicyclopentadiene monomer is a polymerization grade; the catalyst is Grubbs catalyst toluene solution; the mass ratio of the dicyclopentadiene monomer to the Grubbs ruthenium catalyst is 3000: 1; the reaction temperature for injection molding was 70 ℃. The copolymerized olefin is ethylene-styrene copolymer, the addition amount of the copolymerized olefin is 10 percent of the mass of the dicyclopentadiene monomer, the inorganic nano-component is silver nitrate, the addition amount of the inorganic nano-component is 0.1 percent of the mass of the dicyclopentadiene monomer, and the injection molding temperature is 70 ℃.
The preparation method of the marine organism adhesion resistant olefin composite material comprises the following steps:
using toluene as a solvent, and carrying out ultrasonic dissolution and dispersion on the Grubbs ruthenium catalyst to form a Grubbs ruthenium catalyst toluene solution; meanwhile, blending and dispersing the ethylene-styrene copolymer, the silver nitrate and the dicyclopentadiene. Uniformly dispersing the Grubbs ruthenium catalyst toluene solution and the dicyclopentadiene/ethylene-styrene copolymer/silver nitrate blended solution, and immediately injecting into a mold with the temperature of 70 ℃ for molding to obtain the marine anticorrosive polyolefin composite material. Finally, the material performance test is carried out, and the test result is shown in table 1.
Example 4
In the embodiment, the marine anticorrosive polyolefin composite material is prepared by taking dicyclopentadiene/isoprene monomer, Grubbs ruthenium catalyst, copolyolefin and inorganic nanometer components as raw materials and adopting a reaction injection molding process. The dicyclopentadiene/isoprene monomer is in a polymerization grade (the mass ratio of the dicyclopentadiene to the isoprene monomer is 7:3), and the catalyst is Grubbs catalyst toluene solution; the mass ratio of dicyclopentadiene/isoprene monomer to Grubbs ruthenium catalyst is 3000: 1; the reaction temperature for injection molding was 70 ℃. The copolymerized olefin is styrene, the addition amount of the copolymerized olefin is 20 percent of the mass of the dicyclopentadiene/isoprene monomer, the inorganic nano-component is nano titanium dioxide, the addition amount of the inorganic nano-component is 0.1 percent of the mass of the dicyclopentadiene/isoprene monomer, and the injection molding temperature is 70 ℃.
The preparation method of the marine organism adhesion resistant olefin composite material comprises the following steps:
using toluene as a solvent, and carrying out ultrasonic dissolution and dispersion on the Grubbs ruthenium catalyst to form a Grubbs ruthenium catalyst toluene solution; meanwhile, blending and dispersing the nano titanium dioxide and the dicyclopentadiene/isoprene. Uniformly dispersing the Grubbs ruthenium catalyst toluene solution and the dicyclopentadiene/isoprene/nano titanium dioxide blending solution, and immediately injecting into a mold with the temperature of 70 ℃ for molding to obtain the marine anticorrosive polyolefin composite material. Finally, the material performance test is carried out, and the test result is shown in table 1.
TABLE 1 study of olefin composites to prevent marine microbial corrosion
The data in table 1 show that the olefin composite material is uniformly mixed with the co-polyolefin and the inorganic nano material, which is beneficial to inhibiting the attachment of marine microorganisms.
In addition, when the obtained plate after the seawater immersion treatment was observed, the pure olefin material (comparative example 1) plate was severely corroded (surface bending, blackening) by seawater, and the olefin composite material (example 3) added with the co-polyolefin and the inorganic nano material was corroded in a small area after being immersed in seawater for a certain period of time and was able to maintain the original smooth appearance and color of the plate.
Selecting the olefin composite material plates in the embodiment 2, the embodiment 3 and the embodiment 4, and respectively numbering the plates in the corresponding way: sample 1, sample 2, sample 3. Through the test of a fluorescence microscope counting method, the three materials are found to have good adhesion resistance in natural seawater, and the adhesion resistance of the No. 3 material is superior to that of the other two materials in the soaking of a bacteria culture solution and natural river water, as shown in Table 2.
TABLE 2 comparative study on corrosion resistance of olefin composite plate
Examples 5 to 9
Compared with example 2, most of them are the same except that in this example, the olefin monomer having a cyclopentadiene structure is replaced with norbornene, cyclobutene, isoprene, cyclooctadiene or 1, 5-hexadiene, respectively.
Examples 10 to 12
Compared to example 2, most of them are the same except that in this example the copolymerized olefin material is replaced with butadiene, octadiene or ethylene glycol diacrylate, respectively.
Example 13
Compared with example 2, most of them are the same except that in this example, the inorganic nano-component is replaced by nano-alumina.
Example 14
Compared to example 2, most of them are the same except that in this example, the injection molding temperature is changed to 45 ℃.
Example 15
Most of the same is true as in example 2, except that in this example, the injection molding temperature is changed to 75 ℃.
Example 16
Compared with example 2, most of them are the same except that in this example, the mass ratio of the olefin monomer having cyclopentadiene structure to the catalyst is 1000: 1.
Example 17
Compared with example 2, most of them are the same except that in this example, the mass ratio of the olefin monomer having cyclopentadiene structure to the catalyst is 10000: 1.
Example 18
Compared with the embodiment 2, most of the components are the same, except that in the embodiment, the weight parts of the copolymerized olefin material, the inorganic nanometer component and the olefin monomer with the cyclopentadiene structure are as follows: 100 parts of olefin with a cyclopentadiene structure, 30 parts of copolymerized olefin material and 5 parts of inorganic nano-component.
Example 19
Compared with the embodiment 2, most of the components are the same, except that in the embodiment, the weight parts of the copolymerized olefin material, the inorganic nanometer component and the olefin monomer with the cyclopentadiene structure are as follows: 70 parts of olefin with a cyclopentadiene structure, 10 parts of copolymerized olefin material and 0.01 part of inorganic nano-component.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (8)
1. The preparation method of the marine microorganism adhesion resistant olefin composite material is characterized by comprising the following steps:
(1) weighing a copolymerized olefin material, an inorganic nano component and an olefin monomer with a cyclopentadiene structure, blending, and performing ultrasonic dispersion treatment to obtain a blend;
(2) adding the blend obtained in the step (1) and a catalyst into a reactor, uniformly mixing, injecting into a mold, and carrying out polymerization curing molding to obtain a target product;
in the step (1), the inorganic nano-component is one or more of cuprous oxide nano-particles, silver nitrate nano-particles, nano-silica and nano-alumina.
2. The method for preparing the marine microorganism adhesion-resistant olefin composite material according to claim 1, wherein in the step (1), the copolymerized olefin material is selected from one or more of styrene, butadiene, octadiene and ethylene-styrene copolymer.
3. The method for preparing the marine microorganism adhesion-resistant olefin composite material according to claim 1, wherein in the step (1), the olefin monomer having cyclopentadiene structure is selected from one or more of dicyclopentadiene, norbornene and norbornene derivatives.
4. The method for preparing the marine microorganism adhesion resistant olefin composite material as claimed in claim 1, wherein in the step (1), the weight parts of the copolymerized olefin material, the inorganic nano-component and the olefin monomer with cyclopentadiene structure are as follows: 70-100 parts of olefin with a cyclopentadiene structure, 0-30 parts of copolymerized olefin material, 0.01-5 parts of inorganic nano-component, and the addition amount of the copolymerized olefin material is more than 0.
5. The preparation method of the marine microorganism adhesion-resistant olefin composite material as claimed in claim 1, wherein the mass ratio of the olefin monomer with cyclopentadiene structure to the catalyst is 1000-10000: 1.
6. The method for preparing the marine microorganism adhesion resistant olefin composite material as claimed in claim 1, wherein the temperature for polymerization curing molding is 45-75 ℃.
7. The method of claim 1, wherein the catalyst is a Grubbs ruthenium catalyst.
8. An olefin composite material resistant to marine microorganism attachment, which is produced by the production method according to any one of claims 1 to 7.
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