阅读说明：本技术 一种耐海洋微生物附着的烯烃复合材料及其制备方法 (Marine microorganism adhesion-resistant olefin composite material and preparation method thereof ) 是由 杨维成 罗勇 乔新峰 付宏伟 刘建 李秀君 段高坤 方超立 于 2020-05-26 设计创作，主要内容包括：本发明涉及一种耐海洋微生物附着的烯烃复合材料及其制备方法,该制备方法包括以下步骤：(1)称取共聚烯烃材料、无机纳米组分和具有环戊二烯结构的烯烃单体进行共混,超声分散处理,得到共混物；(2)将步骤(1)所得共混物与催化剂加入到反应器中,均匀混合,注入模具中,聚合固化成型,即得到目的产物。与现有技术相比,本发明制备的烯烃复合材料具有较好的耐磨性、高强高韧性等优异的机械性能,更重要的是,可以有效抑制海洋微生物的附着,具有优异的海洋防腐蚀性能,有利于该复合材料在海洋工程领域方面的应用。(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.)

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) 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.

2. The method for preparing the marine microorganism adhesion-resistant olefin composite material as claimed in claim 1, wherein in the step (1), the copolymerized olefin material is selected from one or more of styrene, butadiene, octadiene, ethylene-styrene copolymer, trimethylolpropane triacrylate or ethylene glycol diacrylate.

3. The method for preparing the olefin composite material with marine microorganism adhesion resistance, as claimed in claim 1, wherein 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 or nano-alumina.

4. 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 a cyclopentadiene structure is one or more selected from dicyclopentadiene, norbornene derivatives, cyclobutene, isoprene, cyclooctadiene and 1, 5-hexadiene.

5. The method for preparing the marine microorganism adhesion-resistant olefin composite material according to claim 4, wherein in the step (1), the olefin monomer having cyclopentadiene structure is selected from one or more of dicyclopentadiene, norbornene or norbornene derivatives.

6. 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 cyclopentadiene structure, 0-30 parts of copolymerized olefin material and 0.01-5 parts of inorganic nanometer component, wherein when the copolymerized olefin material is 0 part, the copolymerized olefin material is not added.

7. 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.

8. 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 ℃.

9. The method of claim 1, wherein the catalyst is a Grubbs ruthenium catalyst.

10. An olefin composite material resistant to marine microorganism attachment, which is produced by the production method according to any one of claims 1 to 9.

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 structures 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 rings, the structure is relatively stable, in the process of catalytic polymerization of Grubbs ruthenium catalyst, the norbornene rings are subjected to Ring-Opening metathesis polymerization (ROMP), and then a part of cyclopentadiene structures are 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.