WO2019210528A1 - Preparation method for organic titanium precursor polymer tpp-ii and application thereof in special coating - Google Patents

Abstract

A preparation method for an organic titanium precursor polymer TPP-II and an application thereof in a special coating, relating to the technical field of preparation for and application of new materials. Under the catalysis of gamma-phase nanometer aluminum oxide, a mixture of hydrogenated titanium powder, epoxy resin, a nano-dispersant, a titanate coupling agent, a silane coupling agent, and a solvent is placed in a ball-milling reaction tank for a ball milling reaction under ultrasonic conditions; under the coupling action of mechanical force and ultrasonic waves, not only the micron-sized titanium hydride is refined to the nanometer scale, but also a chain scission, grafting and polymerization of a high-molecular polymer is induced; and an organic titanium precursor polymer TPP-II with a hydroxyl group structure is obtained by ring opening of epoxy groups. The organic titanium precursor polymer TPP-II can be used to prepare an anti-acid corrosion protection material in a high temperature environment, such as primers and finishing coats of a flue gas desulfurization system and a heat exchanger device.

Description

Preparation method of organic titanium precursor polymer TPP-II and its application in special coatings Technical field

The invention belongs to the technical field of preparation and application of new materials.

Background technique

As we all know, titanium is a very active metal element with low density, high specific strength, good ductility, low thermal conductivity, good high and low temperature resistance, non-toxic, non-magnetic, wear-resistant and corrosion-resistant. It is widely used in military and aerospace. Manufacturing fields such as navigation and civil use are known as structural materials for space and ocean. Titanium is arranged in the Group IV subgroup (titanium) element system in the periodic table of chemical elements, and has an atomic number of 22 and an atomic weight of 47.88. The valence has three types: +2, +3, and +4. Therefore, under certain environmental conditions, its vibrancy also provides a multi-reaction response trend.

The standard electrode potential of titanium is very low (E=-1.63V), and the blunt potential is also low, so it is easy to passivate. At room temperature, the titanium surface is very easy to form a passivation film composed of oxides and nitrides. It is very stable in the atmosphere and many etchable media, and has good corrosion resistance. In the atmosphere, aqueous chloride solutions and oxidizing acids (nitric acid, chromic acid, etc.) and most organic acids, the corrosion resistance exceeds that of stainless steel; it is not corroded in seawater, so it is the most ideal material for marine engineering.

Although titanium has such good corrosion resistance, titanium materials are expensive, and so far they have not been prepared as anti-corrosion coatings for industrial anti-corrosion applications.

If the metal titanium is grafted with the organic polymer material to form a polymer alloy polymer, and then applied to the industrial anti-corrosion field in the form of a coating, it can replace the stainless steel and solve the industrial corrosion problem. It is the object and reason of the present invention to reduce manufacturing costs and improve the economic efficiency of the enterprise.

Organotitanium polymer, also known as polytitanoxane, is a general term for organometallic polymers containing titanium atoms in the main chain molecular structure, which can be partially hydrolyzed by the original titanate Ti(OR) ₄ . Polycondensed. Polytetraoxane can be used as a surfactant, water repellent and rust inhibitor to form fibers under mechanical agitation; some can be used as a heat-resistant coating, which is an example of early application of organotitanium-based coatings.

Summary of the invention

A first object of the invention is to prepare an organotitanium precursor polymer TPP-II.

The technical scheme of the invention is: placing a mixture of hydrogen hydride titanium powder, epoxy resin, nano dispersant, titanate coupling agent, silane coupling agent and solvent in a ball milling reaction under the catalysis of γ-phase nano-alumina In the tank, the ball milling reaction is carried out under ultrasonic conditions, and H ₂ is intermittently discharged during the ball milling reaction. After the temperature in the ball milling reaction tank is cooled to 40-50 ° C, the can is taken out to obtain the organic titanium precursor polymer TPP- II.

During the ball milling process, TiH ₂ releases H ₂ , so intermittent H ₂ is required to be discharged during the reaction, and then the operation is continued.

The principle of synthesis of the invention: under the action of the catalyst γ-phase nano-alumina (γ-Al ₂ O _3-x ), the coupling of mechanical force and ultrasonic wave not only refines the micron-sized titanium hydride to the nanometer scale, but also The macromolecular polymer is induced to undergo a broken-chain polymerization, and the epoxy group is opened to form a phenoxy polymer (TPP-II) having a hydroxyl structure; the synthesis product of the reaction product is:

The technical route adopted by the invention is based on the principle of mechanical force chemistry, blending titanium metal with epoxy resin, and preparing nano titanium base material by ultrasonic assisted solid-liquid reaction ball milling technology. According to the principle of "Mechanical Chemistry" (Chen Ding, Chen Zhonghua, published in "Chemical Industry Press" in 2008, under the action of mechanical force, the polymer is concentrated due to uneven distribution of internal stress or impact energy concentrated on individual segments. The critical stress causes the chemical bond to break. The most important feature of the chemical bond cleavage is the formation of the chemical center (free radical). The position of the force degradation (chemical bond cleavage) depends on the stress concentration on the individual segments of the polymer, and the branched polymer and the main chain The junction of the branch, the horizontal bond in the network, the main chain at the point where the hetero atom is contained, and the stress concentration at the time of deformation of the polymer. The preparation of the nano-organic titanium precursor polymer of the present invention utilizes the epoxy The main structure of the resin structure contains a hetero atom, which is broken by a mechanochemical action and bonded to a titanium atom to form a completely new metal polymer.

This reaction is divided into two processes: the first stage is the process in which the titanium nanoparticle interface atoms absorb energy and release the H ₂ during the nanocrystallization process; the second stage is the γ-phase nano-alumina (γ-Al ₂ O). _{The 3-x} ) vacancy bond (under-oxygen bond) competes with the epoxy group for oxygen atoms, releasing energy (exothermic process), forcing the epoxy group to open, thereby causing the CO carbon-oxygen bond to break and occur with the titanium atom. Bonding to form a nanoorganic titanium precursor polymer.

The invention utilizes the activity of titanium metal to cause the chemical bond of the polymer and the lattice bond on the surface of the titanium nanoparticle to be broken during the nanocrystallization process under the action of mechanical force chemistry, thereby generating an ion or base with extremely high surface activity. The group degrades the polymer into small molecular oligomers, which undergo graft polymerization at high temperature and high pressure to realize molecular structure reforming to form a novel structure of precursor polymer. The polymer is a general-purpose titanium. The base material can be used alone as a base material for the coating, or can be blended with various resins (such as EP, PY, PET, PI, EP-PF, PAES, PAEK, etc.) to prepare a polymer alloy composite or copolymer. Used to produce paints.

Further, the mixed mass ratio of the γ-phase nano-alumina, the hydrogenated titanium powder, the epoxy resin, the nano-ultradispersant, the titanate coupling agent and the silane coupling agent of the present invention is 1 to 5:20-25 : 15 to 20: 5 to 10: 1 to 3: 1 to 3. It is very important that the titanium hydride powder (TiH ₂ ) contains two hydrogens, which can provide two hydrogen atoms on the shoulder of the titanium during the polymerization grafting reaction. Not all the added titanium hydride powders can participate in the polymerization reaction. The titanium that has not participated in the reaction is filled with the nano-hybrid particles in the polymer to enhance the modification of the polymer. Since the nanoparticles have high activity and are easily agglomerated, it is suitable. The nano-hyperdispersant is very important. The principle of selection is that it must be a small molecular type of oligomer, that is, its particles are smaller than titanium nanoparticles, so as to cover the surface of titanium nanoparticles to form a corona layer. The principle is that the coated titanium nanoparticles are not agglomerated, but are uniformly and stably dispersed in the polymer system; the coupling agent is also called a "bridge" and plays a role in the compatibility of the inorganic-organic phase.

The titanium hydride powder has a particle diameter of 3 to 5 μm and is an ultra-fine titanium powder, which can greatly shorten the ball milling time. Direct purchase of nano-scale titanium powder can not be directly applied without ball milling. Nano-scale titanium powder can only undergo molecular reforming and graft polymerization with the disordered bond-deformed epoxy polymer under the action of mechanical force to form a new polymer.

The γ-phase nano-alumina has a particle diameter of ≤ 20 μm. The use of the γ-phase nano-alumina having the particle diameter as a catalyst easily causes chemical bond cleavage of the polymer molecules to form an activation center.

The nano hyperdispersant is CI-913.

In the ball milling reaction, the volume ratio of the ball material is about 6:1, and the loading volume of the material in the ball mill reaction tank is one-half.

In the ball milling reaction, the pressure in the ball mill reaction vessel was 0.6 MPa and the temperature was 150 ± 1 °C. The pressure in the ball mill tank is derived from the hydrogen released by the dehydrogenation reaction when the titanium powder is ball milled. The temperature comes from the accumulation of heat during the ball milling process, which provides a source of energy and conditions for mechanochemical conversion to thermochemistry.

The solvent consists of a mixture of DMF, dimethylacetamide (DMAC) and NMP. DMF, DMAC and NMP, these solvents are carriers for solid-liquid reaction ball milling, and the polymerization is carried out in a carrier.

Another object of the present invention is to propose an application of the organotitanium precursor polymer TPP-II prepared by the above method, which can be used for preparing a high temperature environment acid corrosion resistant protective coating, such as a flue gas desulfurization system and a primer and a surface of a heat exchanger device. paint.

Used in the preparation of flue gas desulfurization system and heat exchanger equipment primer, carbonate mixed ester, propylene carbonate, organotitanium precursor polymer TPP-II, epoxy resin, NPCN-704PFEP, Desmophen 670SP, carbon black, graphite The olefin dispersion slurry, the mica powder, the rust preventive pigment, the curing agent, the diaminodiphenyl sulfone, the R-8747MEA and the coating auxiliaries are uniformly mixed, ground, and filtered to obtain a primer.

For the preparation of flue gas desulfurization system and heat exchanger equipment topcoat, carbonate mixed ester, propylene carbonate, organotitanium precursor polymer TPP-II, epoxy resin, NPCN-704PFEP, Desmophen 670SP, carbon black, graphite The olefin dispersion slurry, the mica powder, the rust preventive pigment, the diaminodiphenyl sulfone and the R-8747MEA and the coating auxiliaries are uniformly mixed, ground, and filtered to obtain a top lacquer.

Before painting, the metal surface of the equipment is treated to expose the steel material, and then the primer is sequentially applied.

Painted with the topcoat, dried and cured before being used in equipment operation. After testing, the above coatings fully meet the requirements of heat resistance, wear resistance and chemical resistance of the operation of the desulfurization system equipment.

DRAWINGS

Figure 1 is an electron micrograph of a titanium base before the ball milling reaction.

Figure 2 is an electron micrograph of the ball mill reaction.

3 is a scanning electron microscopy characterization of an organotitanium precursor polymer TPP-II.

4 is a partially enlarged view of a transmission electron microscope of an organic titanium precursor polymer TPP-II.

detailed description

1. Description of planetary ultrasonic assisted solid-liquid ball mill reactor:

Working principle: When it is necessary to apply ultrasonic waves, insert the plug of the ultrasonic generator into the socket of the energy converter, and at the same time open the switch on the ultrasonic generator. At this time, the energy converter starts working and the ultrasonic wave can be input. Because the ultrasonic wave has a strong penetrating ability, it can penetrate a stainless steel plate with a thickness of 2 mm, and has a physical and chemical action on the material in the ball mill tank.

Technical parameters of ultrasonic assisted solid-liquid ball mill reactor:

(1) Planetary transmission mechanism: autobiography 18 ~ 168r / min (turntable); revolution 70 ~ 670r / min (ball mill tank).

(2) Ultrasonic frequency: 40KHz.

(3) Ultrasonic power: 200W.

(4) Ultrasonic intensity: 1.13 W/cm ³ .

2. Preparation of organotitanium precursor polymer TPP-II:

20 to 25 parts by mass of titanium hydride powder (TiH ₂ , particle size Φ3 to 5 μm, content ≥99.5%, produced by Zhongnan Titanium Powder Co., Ltd.), 15 to 20 parts by mass of 128 epoxy resin (produced by Yueyang Petrochemical Co., Ltd.), 10 ～15 parts by mass of DMF, 8 to 12 parts by mass of dimethylacetamide (DMAC), 15 to 20 parts by mass of NMP, 5 to 10 parts by mass of CI-913 nanometer hyperdispersant (German C&I CoeIen ChIme product), 1 ～5 parts by mass of VK-L20Y γ-phase nano-alumina (γ-Al ₂ O _3-x , particle size ≤20μm, produced and sold by Xuancheng Jingrui New Material Co., Ltd.), 1-3 parts by mass of titanate coupling The agent and 1 to 3 parts by mass of the silane coupling agent are uniformly mixed.

The above uniformly mixed mixture is divided into four equal portions and respectively charged into four ball-milling reaction tanks, each of which has a loading capacity of one-half in the ball-milling reaction tank, and then four kinds of stages are respectively filled in each ball-milling reaction tank. With stainless steel beads (Φ5, Φ10, Φ15, Φ20mm) to two-thirds, the volume ratio of the ball is about 6:1. After tightening the bolts, the ball-milling reaction tanks are sealed, and the ultrasonic and ball mill are turned on.

During the ball milling process, TiH ₂ will release H ₂ , so stop after 1h of operation, open the exhaust valve to deflate and continue to run for 2h. During the ball milling reaction, the pressure in the ball mill tank was controlled at 0.6 MPa and the temperature was about 150 °C.

When the temperature in the tank is cooled to 40 to 50 ° C, the can is taken out to obtain a black viscous liquid organic titanium precursor polymer TPP-II. The parameters of each indicator are listed in the table below.

project	TPP-II
Exterior	Black mucus
Solubility	Alcohol/ester/ketone, etc.
Solid content, %	45~50
Nano titanium content, %	15~18
Nano titanium particle size, nm	50～80
Micron titanium residual, %	2 to 5
Viscosity, mPa·s/25°C	2000～2500
Relative density, g/cm 3	1.10~1.15
Volatile organic compounds, %	50~55
OH equivalent, g/mol	20~25

Long-term service temperature, °C	≤250
Chemically resistant to chemical media	Excellent
Weather resistant natural aging	Excellent

Third, the characterization of each material:

It can be seen from the electron micrograph before the ball milling reaction of Fig. 1 that the titanium base material consists of γ-phase nano alumina, hydrogen hydride powder, epoxy resin, nano dispersant, titanate coupling agent, silane coupling agent and solvent. It is a mixed agglomerate state.

It can be seen from the electron micrograph of the ball-milling reaction of Fig. 2 that the material has been completely nanosized after the solid-liquid ball milling reaction.

Scanning electron microscopy characterization of the organotitanium precursor polymer TPP-II of Figure 3 shows the dispersion state of the nanomaterial.

The partially magnified picture of the organic titanium precursor polymer TPP-II of Figure 4 shows that the core in the solid-liquid ball-milling reaction is titanium nanoparticles, the shadow-coated part is a polymer, and the core shell constitutes a titanium nano-precursor. The polymer is the organotitanium precursor polymer TPP-II.

Fourth, the production of flue gas desulfurization system and heat exchanger equipment coating:

1. Primer:

Primer A component: Weigh 5 to 10 parts of carbonate mixed ester (DXC or HEMA), 2 to 8 parts of propylene carbonate (PDC), 10 to 15 parts of TPP-II, and 5 to 10 parts of 609 by mass parts. (E-03) Epoxy Resin (EP), 5-10 parts NPCN-704PFEP, 3-6 parts Desmophen 670SP, 3-5 parts MA-100 Mitsubishi carbon black, 5-10 parts 6% graphene dispersion slurry (GDS ), 5 to 10 parts of 800 mesh mica powder, 15 to 20 parts of TFG-1 composite antirust pigment, 20 to 25 parts of Wanhua TH-100 HDI trimer, 3 to 5 parts of diaminodiphenyl sulfone (DDS), 3 to 5 parts of R-8747MEA and 3 to 5 parts of coating aids are put into the container and dispersed in a high-speed disperser. After mixing, they are ground by a sand mill, and then filtered and packed with a 200-mesh filter cloth.

Primer B component: TH-100 HDI trimer curing agent 20-25 parts, can be directly dispensed.

When used, the primer A component and the primer B are uniformly mixed on the spot, and then applied to the surface of the surface-cleaned flue gas desulfurization equipment or the heat exchanger metal material, and dried at 25 ° C to form a primer layer.

2. Topcoat:

Topcoat A component: Weigh 5-10 parts of carbonate mixed ester (DXC or HEMA), 2-8 parts of propylene carbonate (PDC), 10-15 parts of TPP-II, 5-10 parts of 609 by mass parts. (E-03) Epoxy Resin (EP), 5-10 parts NPCN-704PFEP, 3-6 parts Desmophen 670SP, 3-5 parts MA-100 Mitsubishi carbon black, 5-10 parts 6% graphene dispersion slurry (GDS ), 5 to 10 parts of 800 mesh mica powder, 15 to 20 parts of TFG-1 composite antirust pigment, 3 to 5 parts of diaminodiphenyl sulfone (DDS), 3 to 5 parts of R-8747MEA and 3 to 5 parts of coating aid The agent input container is built in a high-speed disperser for dispersion, and after mixing, it is ground by a sand mill, and then the package is filtered with a 200-mesh filter cloth.

Topcoat B component: 20-25 parts TH-100 HDI trimer curing agent, directly packaged.

When used, the topcoat A component and the topcoat B are uniformly mixed on the spot, and then applied to the surface of the cured primer layer, and dried at 25 ° C to form a top coat coating.

The main components and mass of the above graphene dispersion slurry (GDS) are: graphene (powder) 8%, nano dispersant 8%, silane coupling agent 3%, 128 epoxy resin 20%, suspending agent 1%, The balance is an organic solvent such as N-methylpyrrolidone (NMP), which is ultrasonically assisted by mechanical dispersion.

The performance test results of flue gas desulfurization system and heat exchanger equipment coating are shown in the following table.

Claims (10)

1. A method for preparing an organotitanium precursor polymer TPP-II, characterized in that titanium hydride powder, epoxy resin, nano hyperdispersant, titanate coupling agent, silane are catalyzed by γ-phase nano-alumina The mixture of the coupling agent and the solvent is placed in a ball-milling reaction tank, and the ball-milling reaction is carried out under ultrasonic conditions for 3 hours, and H2 is intermittently discharged during the ball-milling reaction, and the temperature is cooled to 40 to 50 ° C after the ball-milling reaction tank is opened. The organic titanium precursor polymer TPP-II is obtained by taking the material.
2. The method for preparing an organotitanium precursor polymer TPP-II according to claim 1, characterized in that the γ-phase nano-alumina, hydrogen hydride powder, epoxy resin, nano-dispersant, titanate coupling agent and The mixing ratio by mass of the silane coupling agent is from 1 to 5:20 to 25:15 to 20:5 to 10:1 to 3:1 to 3.
3. The method for producing an organotitanium precursor polymer TPP-II according to claim 1 or 2, wherein the titanium hydride powder has a particle diameter of from 3 to 5 μm.
4. The method for producing an organotitanium precursor polymer TPP-II according to claim 1 or 2, wherein the γ-phase nano-alumina has a particle diameter of ≤ 20 μm.
5. The method for producing an organotitanium precursor polymer TPP-II according to claim 1 or 2, wherein the nano hyperdispersant is CI-913.
6. The method for preparing an organotitanium precursor polymer TPP-II according to claim 1 or 2, wherein in the ball milling reaction, the volume ratio of the ball material is about 6:1, and the loading volume of the material in the ball milling reaction tank is Half.
7. The method for producing an organotitanium precursor polymer TPP-II according to claim 1 or 2, wherein in the ball milling reaction, the pressure in the ball-milling reaction tank is 0.6 MPa and the temperature is 150 ± 1 °C.
8. The method for producing an organotitanium precursor polymer TPP-II according to claim 1 or 2, wherein the solvent is composed of a mixture of DMF, dimethylacetamide (DMAC) and NMP.
9. The organotitanium precursor polymer TPP-II prepared by the method of claim 1 is used for preparing a primer for a flue gas desulfurization apparatus and a heat exchanger, characterized in that a carbonate mixed ester, a propylene carbonate, an organotitanium precursor is polymerized. TPP-II, epoxy resin, NPCN-704PFEP, Desmophen 670SP, carbon black, graphene dispersion slurry, mica powder, anti-rust pigment, curing agent, diaminodiphenyl sulfone, R-8747MEA and coating additives are evenly mixed Grinding, filtering, to obtain a primer.
10. The organotitanium precursor polymer TPP-II prepared by the method of claim 1 is used for preparing a topcoat for a flue gas desulfurization apparatus and a heat exchanger, characterized in that a carbonate mixed ester, a propylene carbonate, an organotitanium precursor is polymerized. TPP-II, epoxy resin, NPCN-704PFEP, Desmophen 670SP, carbon black, graphene dispersion slurry, mica powder, anti-rust pigment, diaminodiphenyl sulfone and R-8747MEA and coating additives are uniformly mixed and ground. Filter to obtain a topcoat.

Images