阅读说明：本技术 一种利用超细钻杆、油管内涂环氧粉末废料制备的粉末涂料组合物 (Powder coating composition prepared by coating epoxy powder waste in superfine drill pipe and oil pipe ) 是由 孙健 蒋灿 陈海林 于 2021-01-04 设计创作，主要内容包括：本发明涉及油气开采技术领域,具体是一种利用超细钻杆、油管内涂环氧粉末废料制备的粉末涂料组合物,由以下成分按如下重量百分比组成：双酚A环氧树脂10-25％,钛酸酯螯合剂1-3％,脲醛树脂1-3％,填料5-25％,超细粉末涂料废料30-50％,噁唑烷酮环氧树脂10-20％,酚醛树脂5-15％,咪唑类促进剂0.5-2％,气相二氧化硅0.5-1％。本发明还提供所述涂料组合物的制备方法。本发明让回收的钻杆、油管内涂环氧粉末涂料重新利用,制备得到的粉末涂料粒径能够满足20-150微米,并且通过SY/T 6717(2016)以及SY/T 0544(2016)中含N-2和CO-2的高温高压釜测试。(The invention relates to the technical field of oil and gas exploitation, in particular to a powder coating composition prepared by coating epoxy powder waste in superfine drill pipes and oil pipes, which comprises the following components in percentage by weight: bisphenol A epoxy10-25% of resin, 1-3% of titanate chelating agent, 1-3% of urea-formaldehyde resin, 5-25% of filler, 30-50% of superfine powder coating waste, 10-20% of oxazolidone epoxy resin, 5-15% of phenolic resin, 0.5-2% of imidazole accelerator and 0.5-1% of fumed silica. The invention also provides a preparation method of the coating composition. The invention recycles the epoxy powder coating in the recovered drill pipe and oil pipe, the particle size of the prepared powder coating can meet 20-150 microns, and N is contained in SY/T6717 (2016) and SY/T0544(2016) 2 And CO 2 High temperature autoclave test of (2).)

1. A powder coating composition prepared by coating epoxy powder waste in superfine drill pipes and oil pipes is characterized by comprising the following components in percentage by weight:

2. the powder coating composition as claimed in claim 1, wherein the bisphenol A epoxy resin has an epoxy equivalent of 400-1000 and a softening point of 60-105 ℃.

3. A powder coating composition as claimed in claim 1, wherein the titanate chelating agent is selected from an acetylacetonate type titanate coupling agent or an acetoacetoxyethyl ester type titanate coupling agent.

4. The powder coating composition of claim 1, wherein the urea-formaldehyde resin is selected from the group consisting of n-butyl etherified, isobutyl etherified, and methyl etherified urea-formaldehyde resins.

5. The powder coating composition of claim 1, wherein the filler is selected from the group consisting of barium sulfate, wollastonite, and combinations thereof having good chemical resistance commonly used in heavy duty powder coatings.

6. The powder coating composition of claim 1, wherein the ultrafine powder coating waste is epoxy powder waste in an ultrafine drill pipe or an oil pipe.

7. The powder coating composition as recited in claim 1, wherein the oxazolidone epoxy resin has an epoxy equivalent weight of 380-460.

8. The powder coating composition of claim 1, wherein the phenolic resin has a softening point of 85-110 ℃.

9. A powder coating composition as recited in claim 1, wherein the imidazole-based accelerator is selected from the group consisting of imidazole, dimethylimidazole, and phenylimidazole.

10. A process for preparing a powder coating composition according to any one of claims 1 to 9, comprising the steps of:

the bisphenol A epoxy resin, the titanate chelating agent, the urea-formaldehyde resin, the filler and the ultrafine powder coating waste are subjected to melt extrusion at the temperature of 150 ℃ through a screw extruder, an intermediate is obtained after tabletting and crushing, the oxazolidinone epoxy resin, the phenolic aldehyde and the imidazole accelerator are added into the intermediate, mixed and melted, subjected to melt reaction at the temperature of 120 ℃ and extruded, the tablet is crushed, the gas phase silicon dioxide is added in the milling process, and the powder coating with the qualified particle size of 20-150 microns can be obtained through a 100-mesh screen.

Technical Field

The invention relates to the technical field of oil and gas exploitation, in particular to a method for recycling epoxy powder waste materials in an ultra-fine drill rod and an oil pipe through reactive extrusion and a prepared powder coating composition.

Background

The process of preparing epoxy powder coating in drill pipe and oil pipe can easily produce 5-20 micron superfine powder coating with 10% concentration, and this kind of powder coating can not be electrostatically sprayed and can easily cause the powder coating to suspend in air when vacuum adsorption internal spraying is adopted.

The method for recycling epoxy powder waste in the inner surfaces of the ultra-fine drill pipe and the oil pipe through reactive extrusion and the prepared powder coating composition are not reported at present.

Disclosure of Invention

The invention aims to provide a method for recycling epoxy powder coating waste materials in superfine drill pipes and oil pipes by reactive extrusion, which comprises the steps of adding bisphenol A epoxy resin and a high-adhesion branching auxiliary agent into recycled powder, extruding prepolymerized branched epoxy resin by reaction, adding other resins, curing agents, fillers and the like, melting again, extruding, tabletting, crushing and grinding again to recycle the recycled epoxy powder coating waste materials in the drill pipes and the oil pipes, and enabling the recycled epoxy powder coating waste materials in the drill pipes and the oil pipes to contain N by SY/T6717 (2016) and SY/T0544(2016)₂And CO₂High temperature autoclave test of (2).

The invention provides a powder coating composition prepared by epoxy powder waste materials in superfine drill pipes and oil pipes, which comprises the following components in percentage by weight:

furthermore, the bisphenol A epoxy resin with the epoxy equivalent of 400-1000 and the softening point of 60-105 ℃ is adopted. South Asia NPES 901, 903 resins may be used.

Further, the titanate chelating agent is selected from an acetylacetone type titanate coupling agent or an acetoacetic ester type titanate coupling agent. The series titanate can react with epoxy resin, can wet a coating filler, and can remarkably inhibit the phenomenon that the epoxy resin is subjected to implosion or excessive crosslinking between the epoxy resin and recycled powder to cause gelation in the process of pre-extruding the epoxy resin and superfine powder in a combined manner. Bis (ethylacetoacetate) di-n-butoxy titanate, bis (ethylacetoacetate) diisobutyl titanate, bis (acetylacetonate) ethoxyisopropoxy titanate, bis (acetylacetonate) diisopropyl titanate may be used.

Further, the urea-formaldehyde resin is selected from n-butyl ether, isobutyl ether and methyl ether urea-formaldehyde resin. Cyanote U-1051 can be used.

Further, the filler is selected from barium sulfate, silica powder and a combination thereof which are commonly used in heavy-duty anticorrosive powder coatings and have good chemical resistance.

Furthermore, the ultrafine powder coating waste is an ultrafine powder coating formed in the grinding process, the particle size of the ultrafine powder coating is less than or equal to 20 micrometers, the ultrafine powder coating is mainly collected from a recovery tower of a manufacturer and a recovery tower of a coating factory, the product cannot be directly used, otherwise, the powder coating has low powder rate, the film thickness and the appearance of a coating are affected, drop marks are easy to appear during internal spraying, and the ultrafine powder coating produced by the company generally comprises bisphenol A epoxy resin, oxazolidone epoxy resin, phenolic resin, latent amine, a curing accelerator, fillers such as silica powder, barium sulfate and pigments. If waste ultrafine powder is directly extruded secondarily by a screw extruder, the feeding material is difficult to enter the screw extruder, and the particle size of the powder coating after being ground is still within 20 microns, which is difficult to meet the expected range of 20-150 microns.

Therefore, the scheme adopts the titanate coupling agent, the urea-formaldehyde resin, the epoxy resin and the like for secondary extrusion to ensure that old powder such as the filler is carried into the screw rod, the phenomenon that the filler is difficult to add in the feeding process of the extruding agent is avoided, the ultra-fine powder is re-fused with the added resin, the curing agent, the filler and the like through the reaction between the urea-formaldehyde resin, the titanate coupling agent and the ultra-fine powder, and the particle size of the powder after being milled reaches between 20 and 150 microns, so that the powder coating has usability.

Further, the epoxy equivalent of the oxazolidone epoxy resin is 380-460. DER 6508, 6510, etc. of Dow chemical can be used.

Furthermore, the softening point of the phenolic resin is 85-110 ℃. The Shandong Shengquan PF-8013/8012/8010/8020 can be used.

Further, the imidazole accelerator is selected from imidazole, dimethyl imidazole, phenyl imidazole and the like. 2-methylimidazole is preferred, and the raw materials are sold by the national medicine group.

Further, the fumed silica is commonly used hydrophilic fumed silica. The specific surface area reaches 200 square meters per gram. A200 fumed silica of degussa and N20 fumed silica of Wacker chemical can be used, and the fumed silica is hydrophilic fumed silica with high cost performance.

The materials used in the present invention are all commercially available materials.

The invention provides a method for recycling epoxy powder waste in the inner surfaces of an ultra-fine drill pipe and an oil pipe by reactive extrusion, which comprises the following steps:

the bisphenol A epoxy resin, the titanate chelating agent, the urea-formaldehyde resin, the filler and the ultrafine powder coating waste are subjected to melt extrusion at the temperature of 150 ℃ through a screw extruder, an intermediate is obtained after tabletting and crushing, the oxazolidinone epoxy resin, the phenolic aldehyde and the imidazole accelerator are added into the intermediate, mixed and melted, subjected to melt reaction at the temperature of 120 ℃ and extruded, the tablet is crushed, the gas phase silicon dioxide is added in the milling process, and the powder coating with the qualified particle size of 20-150 microns can be obtained through a 100-mesh screen.

The innovation point of the invention is that the titanate coupling agent, the urea-formaldehyde resin, the epoxy resin and the superfine powder are extruded at the temperature of 130-150 ℃, the urea-formaldehyde resin and the titanate coupling agent are extruded by reacting with the resin and the superfine powder at the temperature, so that the urea-formaldehyde resin and the titanate can fully wet the superfine powder and are melted and reacted to form a whole, then the whole is extruded and crushed to be used as an intermediate, and the obtained product, the phenolic curing agent and the accelerator are extruded and pressed at the temperature of 120-130 ℃ for the second time, and the particle size can reach 20-150 microns after being crushed; if the superfine powder coating is directly used for secondary extrusion and grinding, the superfine powder coating still can be obtained, and the particle size of the coating is still less than or equal to 20 microns. The titanate coupling agent and the urea-formaldehyde resin are capable of melt reacting with the ultra-fine powder and the epoxy resin and wetting the filler.

The invention has the advantages that:

according to the invention, bisphenol A epoxy resin and a high-adhesion branching auxiliary agent are added into recovered powder, titanate and urea resin can form a sufficient reaction with epoxy resin and an ultrafine powder coating at the temperature of 130-150 ℃, the ultrafine powder can be well coated, the prepolymerized branched epoxy resin is extruded through the reaction, then the mixture is tableted and crushed to be used as an intermediate, phenolic resin and an accelerant which are used as a curing agent are added into the intermediate to be melted, extruded, tableted, crushed and ground again at the temperature of 120-130 ℃, the epoxy powder coating in the recovered drill pipe and oil pipe is reused to obtain the powder coating with qualified performance, the particle size can meet 20-150 micrometers, and the coating performance can pass SY/T6717 (2016) and SY/T0544(2016) containing N₂And CO₂High temperature autoclave test of (2).

The invention can recycle the waste drill rod and oil pipe coating into qualified products, reduces the hazardous waste generation of the powder coating and is environment-friendly. The problem that the ultrafine powder coating can only be discarded in the industry is solved; under the condition of no curing agent and accelerator, the epoxy resin, the coupling agent, the filler and the ultrafine powder coating are subjected to melting reaction at the temperature of 130-150 ℃, the reaction at the temperature cannot cause the implosion of the resin and the powder coating, the branching of the resin and the wetting of the ultrafine powder coating and the filler can be realized, and then the powder coating is subjected to tabletting, crushing and screw extrusion, tabletting, crushing and grinding of the curing agent and the curing accelerator at the temperature of 120-130 ℃, so that the particle size of the powder coating obtained by the method reaches 20-150 micrometers, and the feeding speed in the screw extrusion process cannot be influenced.

Detailed Description

The following examples are provided to illustrate specific embodiments of the present invention.

Example 1:

TABLE 1 EXAMPLE 1 powder coating formulation

The preparation method comprises the following steps: a, B, C, D, E is melt-extruded at 150 ℃ through a screw extruder, an intermediate is obtained after tabletting and crushing, F, G, H mixed melt at 130 ℃ is added into the intermediate for melt-reaction extrusion, tabletting and crushing are carried out, I is added in the process of grinding, and the qualified powder coating with the particle size of 20-150 microns can be obtained through a 100-mesh screen.

The prepared powder coating TG 2120 ℃ has the gelling time of 90S; particle size ranges 15-140 microns, particle size ranges D99140 microns, D5080 microns, D95120 microns. The steel tube was heated to 230 ℃ and the powder coating sprayed and then cured for 90min, the resulting coating passing SY/T6717 (2016) and SY/T0544(2016) standards.

Example 2:

TABLE 2 example 2 powder coating formulation

The preparation method comprises the following steps: a, B, C, D, E is melt-extruded at 150 ℃ through a screw extruder, an intermediate is obtained after tabletting and crushing, F, G, H mixed melt at 130 ℃ is added into the intermediate for melt-reaction extrusion, tabletting and crushing are carried out, I is added in the process of grinding, and the qualified powder coating with the particle size of 20-150 microns can be obtained through a 100-mesh screen.

The prepared powder coating TG 2106 ℃ has the gelling time of 110S; particle size ranges D99140 microns, D5080 microns, D95120 microns. The steel tube was heated to 230 ℃ and the powder coating was sprayed and then cured for 90min, the resulting coating passing SY/T6717 (2016) and SY/T0544(2016) standards.

Example 3:

TABLE 3 example 3 powder coating formulation

The preparation method comprises the following steps: a, B, C, D, E is melt-extruded at 150 ℃ through a screw extruder, an intermediate is obtained after tabletting and crushing, F, G, H mixed melt at 130 ℃ is added into the intermediate for melt-reaction extrusion, tabletting and crushing are carried out, I is added in the process of grinding, and the qualified powder coating with the particle size of 20-150 microns can be obtained through a 100-mesh screen.

The prepared powder coating TG 2105 ℃, gelling time 80S, particle size range 15-140 microns, particle size range D99140 microns, particle size range D5080 microns and particle size range D95120 microns. The steel tube was heated to 230 ℃ and the powder coating sprayed and then cured for 90min, the resulting coating passing SY/T6717 (2016) and SY/T0544(2016) standards.

Example 4:

TABLE 4 example 4 powder coating formulation

The preparation method comprises the following steps: a, B, C, D, E is melt-extruded at 150 ℃ through a screw extruder, an intermediate is obtained after tabletting and crushing, F, G, H mixed melt at 130 ℃ is added into the intermediate for melt-reaction extrusion, tabletting and crushing are carried out, I is added in the process of grinding, and the qualified powder coating with the particle size of 20-150 microns can be obtained through a 100-mesh screen.

The prepared powder coating TG 2115 ℃, gelling time of 100S, particle size range of 15-140 microns, particle size range of D99140 microns, D5080 microns and D95120 microns. The steel tube was heated to 230 ℃ and the powder coating sprayed and then cured for 90min, the resulting coating passing SY/T6717 (2016) and SY/T0544(2016) standards.

Example 5:

TABLE 5 example 5 powder coating formulation

The preparation method comprises the following steps: a, B, C, D, E is melt-extruded at 150 ℃ through a screw extruder, an intermediate is obtained after tabletting and crushing, F, G, H mixed melt at 130 ℃ is added into the intermediate for melt-reaction extrusion, tabletting and crushing are carried out, I is added in the process of grinding, and the qualified powder coating with the particle size of 20-150 microns can be obtained through a 100-mesh screen.

The prepared powder coating TG 2105 ℃, gelling time of 100S, particle size range of 15-140 microns, particle size range of D99140 microns, D5080 microns and D95120 microns. The steel tube was heated to 230 ℃ and the powder coating sprayed and then cured for 90min, the resulting coating passing SY/T6717 (2016) and SY/T0544(2016) standards.

Example 6:

TABLE 6 example 6 powder coating formulation

The preparation method comprises the following steps: a, B, C, D, E is melt-extruded at 150 ℃ through a screw extruder, an intermediate is obtained after tabletting and crushing, F, G, H mixed melt at 130 ℃ is added into the intermediate for melt-reaction extrusion, tabletting and crushing are carried out, I is added in the process of grinding, and the qualified powder coating with the particle size of 20-150 microns can be obtained through a 100-mesh screen.

The prepared powder coating TG 2105 ℃, gelling time of 100S, particle size range of 15-140 microns, particle size range of D99140 microns, D5080 microns and D95120 microns. The steel tube was heated to 230 ℃ and the powder coating sprayed and then cured for 90min, the resulting coating passing SY/T6717 (2016) and SY/T0544(2016) standards.

While the preferred embodiments of the present invention have been described in detail, it will be understood by those skilled in the art that the invention is not limited thereto, and that various changes and modifications may be made without departing from the spirit of the invention, and the scope of the appended claims is to be accorded the full range of equivalents.