JP2017008187A - Resin having hybrid characteristic improving thermal deformation temperature and breaking elongation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin which is a thermosetting resin used for an FRP-made oil well pipe, is formed by blending a plurality of resins having heat resistance of at least 150°C or higher and acid resistance of pH2 level and imparts a physical structural change such as tangling of a molecular structure without deterioration in characteristics, produces a synergistic effect, and has such a hybrid effect that heat resistance is improved by approximately 20% and elongation performance is improved by approximately 10%.SOLUTION: A hybridization thermosetting composition produces such a hybrid (synergistic effect) that high temperature characteristics equal to or more than an original mixed performance is improved by approximately 18% at the maximum and elongation is improved by approximately 19% at the maximum by mixing a plurality of resins of which physical characteristics of high temperature/low elongation and low temperature/high depth are inversely proportional to each other, and applying a hybridization condition; and can control necessary performance of heat resistance and elongation according to the ratio.SELECTED DRAWING: Figure 1

Description

   The present invention relates to high temperature, high elongation and acid resistant resin materials used in oil well pipes. The present invention relates to an effect of improving performance by mixing different characteristics of epoxy-modified thermosetting resin with different molecular weights.

In the development of oil well pipe resins in the high temperature and high pressure region, for example, it is known that even if two types of resins are simply mixed, the required performance characteristics are deteriorated due to phase separation. As a solution, for example, a method of obtaining a polymer blend (polymer alloy) by using a compatibilizing agent or utilizing a chemical bond is known, but usually only performance (deterioration) lower than each function can be obtained. In other words, it is said that it is difficult to draw out the added amount proportional effect characteristics (composite rule) such as heat resistance, elongation and corrosion resistance of each resin without adapting to the compound rule.
The market supplies resins with different characteristics to the market due to the cost reduction effect due to mass production, but there is no system that requires intermediate properties from individual users. On the other hand, even if different resins are simply blended, the desired result cannot be obtained. An invention that allows polymer blending of characteristic materials in which the physical properties of the final cured product (resin) are proportional, such as mixing a resin with excellent heat resistance but poor elongation performance, and a resin with excellent elongation performance but poor heat resistance Need.
That is, according to the mixing ratio, the heat resistance and elongation performances are prevented from at least deterioration due to blending, and ideally, a synergistic effect (herein referred to as hybrid effect) resin by blending is obtained.

   Many studies have been conducted on mixed resins called polymer blends and polymer alloys (References 3-5). However, in addition to general oil drilling applications, there are no examples of polymer blends and polymer alloys aimed at FRP oil well pipe materials with high heat resistance and corrosion resistance such as deep wells and EOR in recent years. There are no published documents.

JP-T-2004-504446

JP 2008-531789 A

Junichi Inada, et al. "Phase structure analysis of epoxy resin / acrylic polymer alloy and its application to die bonding film" Hitachi Chemical Technical Report No.47 Hitachi Chemical Co., Ltd. 2006

Yasuaki Tsuji, Kanako Takenishi, et al. “Evaluation of acid resistance of EOR-compatible high-temperature and high-pressure resins” 5th symposium of the Global Management Society Lecture and paper collection November 1, 2014

Yasuaki Tsuji, Kanako Takenishi, et al. "GPI Standard Simple Corrosion Resistance Evaluation Method" Global Management Society 5th Symposium Lecture and Proceedings November 1, 2014

   Oil well pipes for oil drilling need to be strong enough to withstand the applied pressure and to withstand the heat resistance and corrosion of the pressure fluid. In other words, a material that has durability against high-pressure corrosive fluids (petroleum gas) in the pipe, and has a function to guarantee heat resistance according to the location of use and durability against corrosion degradation (pH 2) of the constituent materials (more than 10 years) A structure is needed. Steel pipes currently widely used as oil well pipes are said to have problems in corrosion resistance, such as stress corrosion cracking under acidic conditions stronger than pH 3. Although acid-resistant steel pipes such as sour-resistant steel are also used, there are many expensive ones. Therefore, there is a demand for oil well pipe materials that are inexpensive, have high durability, and have excellent corrosion resistance.

   Although FRP has been used as an oil well pipe material that shows acid resistance, there is a resin that can achieve an allowable elongation of 18% at around 80 ° C, but it is 8% and 150 ° C in the high temperature region above 110 ° C. In 2% to 3%, the elongation decreases as the temperature rises, and there is no single resin having excellent high temperature performance and elongation. Furthermore, high temperature performance resins have the problem of being expensive.

Thermosetting resins used in FRP oil well pipes, etc., aim for deep well drilling and oilfield regeneration (EOR) in order to increase the amount of oil drilling, so heat resistance at 150 ° C and pH2 level is indispensable. In order to prevent breakage, the resin must have an elongation performance of about 6% or more. Furthermore, geothermal EOR requires heat resistance exceeding 200 ° C.
In the present invention, a low-cost resin using a general-purpose product is provided by improving the required performance by the hybrid effect.
And, it is an invention that makes it possible to obtain two or more types of resins having different characteristics by combining a resin having a high temperature characteristic having at least necessary and sufficient acid resistance and a resin having a high elongation characteristic to obtain a hybrid effect. .
The basis is that they have similar reactive groups with different molecular weights that allow mixing, can cure with the same reaction rate with a common peroxide, and when different molecular structures and lengths polymerize, By polymerizing while maintaining a high density in a state where molecules are entangled, it is possible to obtain a molecular motion suppressing effect that is considered to improve deformation at high temperature (high temperature characteristics). The effect of the invention was confirmed to be nearly 10%. Similarly, the elongation at break increases due to the increased molecular weight of the blended resin. The effect follows a compound law. In other words, scientific reactive groups are similar and have different physical properties. Mixing multiple resins, the solidification reaction can be completed in a short time and at the same time solidified without physical separation of the mixture. We have invented the idea that the desired high-temperature / high-elongation hybrid effect can be obtained by obtaining the entanglement effect of the molecular structure by physical different molecules to compensate for the blend deterioration effect.

   The basic result of the present invention is the heat resistance of a resin made by blending a plurality of resins A (161 ° C. * 2.5%) and resin B (120 ° C. * 12.8%) shown in FIGS. 1 and 2 in a 4: 6 ratio. -Elongation performance characteristics are shown. The discovery of a synergistic effect (hybrid effect) accelerating beyond the compound law effect (143 ° C * 6.7%) proportional to the addition amount, which was previously impossible, and the results of a high-strength resin that could not be achieved with high-temperature properties 2. A resin having a hybrid effect with a heat deformation temperature of 153 ° C. (17.5% synergistic effect) and a breaking elongation of 10.6% (22% synergistic effect) was invented in FIG. Furthermore, since the resins A and Z are made of an inexpensive material, the price is low while obtaining a hybrid effect (quality improvement).

   Figure 1 shows an example of the results. The characteristic of the composite rule proportional to the amount of addition that the characteristics inherent to resins A and Z do not change is indicated by a broken line. It is indicated by a one-dot chain line deterioration curve, and an assumed curve of a hybrid result in which a plurality of synergistic effects by the blend invented this time is generated is indicated by a dotted line. The basic conditions for hybridization invented to produce this result are as follows: 1: common reactive group (in this example, epoxy group, ester), 2: different molecular weight (different in molecular weight and structure), 3: polymerization reaction rate 4: The applied reaction catalyst is the same, 5: Specific gravity separation of the mixed material does not occur, and the compatibility can be maintained, 6: The polymerization reaction is carried out while maintaining the mixed state of different molecules Completing promptly, 7: Necessary addition of interface material (coupling material) between different materials.

   The inventors have invented that a hybrid effect is produced by satisfying all or more than half of these conditions. As a result, the resin developed in the present invention has no change in the curing characteristics and viscosity characteristics of the resin from the original, and is suitable not only for FRP oil well pipes but also for all FRP products, FRP molding products, and molding resin materials. .

   Figures 3 and 4 are blends of resin B (175 ° C * 2.5%) and resin Z. Hybridization conditions 3: different reaction rates, 6: longer curing time, 7: no addition results is there. The high temperature characteristic of FIG. 3 has a synergistic effect of 17.5%, but the elongation of FIG. 4 is a reduction effect of −5.5%.

   FIG. 5 and FIG. 6 are the results when a blend of resin Y (112 ° C., 9%) and resin Z and similar products having different molecular weights and structures under hybridization condition 2: are used. From FIG. 5, there is a synergistic effect of about 19% on the high temperature characteristics, but from FIG. 6, the elongation is reduced by -5%.

   FIG. 7 and FIG. 8 show the results when a blend of Resin X (210 ° C. * 2.5%) and Resin Y did not meet the hybrid condition 5 · 6 mixed state maintenance curing conditions and 7: addition. FIG. 7 shows that the high temperature characteristic has a synergistic effect of about 8.3%, but FIG. 8 shows that the elongation is reduced by -5%.

Figure 1 is a resin A / Z heat distortion temperature hybrid characteristic diagram. FIG. 2 is a resin A / Z break elongation hybrid characteristic diagram. Fig. 3 is a characteristic diagram of resin B / Z heat distortion temperature hybrid. FIG. 4 is a resin B / Z fracture elongation hybrid characteristic diagram. FIG. 5 is a characteristic diagram of resin Y / Z heat distortion temperature hybrid. FIG. 6 is a hybrid characteristic diagram of resin Y / Z breaking elongation. FIG. 7 is a resin X / Y heat distortion temperature hybrid characteristic diagram. FIG. 8 is a resin X / Y breaking elongation hybrid characteristic diagram.

The results of the invention shown in FIG. 1 and FIG. 2 show that a hybrid effect is provided in which a plurality of characteristics are improved together. The resin used at this time has a hybridization condition of 1 to 7 applied by A and Z, and these conditions are the best mode for carrying out the invention.
1. Common reactive group (this example is epoxy group, ester).
2. Different molecular weights (different molecular weights and structures).
3. The polymerization reaction rate is equivalent.
4. The applied reaction catalyst is the same.
5. Specific gravity separation of the mixed material does not occur and compatibility is maintained.
6. The polymerization reaction is completed quickly while maintaining the mixed state of different types of molecules.
7. Add necessary interface material (coupling material) between different materials.

   We discovered an accelerating synergistic effect (hybrid effect) over the combined rule effect (143 ° C * 6.7%) proportional to the addition amount, which was previously impossible, and invented it with a hybrid effect. Since this resin is made of an inexpensive material, the price is low while obtaining a hybrid effect (quality improvement). As a result, industrial use is sufficiently conceivable.

pH2 An indicator for acidity and alkalinity.
℃ Celsius temperature display.
Resin A Thermal deformation temperature 162 ° C, elongation at break 3%, novolac ester modified resin.
Resin B Thermal deformation temperature 175 ° C, elongation at break 2.5%, novolak ester-based modified resin.
Resin X Thermal deformation temperature 112 ° C, elongation at break 9%, epoxy / urethane / ester modified resin.
Resin Y Heat deformation temperature 210 ° C, elongation at break 2%, novolak ester modified resin.
Resin Z Thermal deformation temperature 120 ℃, elongation at break 12.8%, epoxy / urethane / ester modified resin.

Claims (4)

   In thermosetting resins used for FRP oil well pipes, etc., at least two kinds of resins having different and sufficient acid resistance, for example, modified urethane resins having low-temperature and high-elongation properties by ester-bonding epoxy groups ( Epoxy / urethane resin) and modified novolak resin (epoxy / novolak resin) with high temperature and low elongation properties that ester-bond with epoxy groups having similar reactive groups with different molecular weights. Although it has a common reactive group epoxy group and ester bond function but has different characteristics and molecular weight, epoxy group, and further, for example, at 100 ° C, it can be cured as short as possible within 30 minutes with a common catalyst such as BPO-based peroxide. As a result, different molecules solidify in an entangled state, and the mixture does not cause specific gravity separation and the resin reaction rate is the same. This is a resin blended under conditions that allow a curing reaction while maintaining a uniform body.Contrary to the general characteristics that are less than the proportional control of the addition amount of the composite rule, the heat resistance is improved by at least 5% and the allowable elongation is minus 5 Resin and production method with characteristics that can achieve hybrid effect characteristics of over%.    Resins that have a hybrid effect, including vinyl ester resins (including bisphenol and novolac), unsaturated polyester resins (including isophthalic acid and bisphenol), and epoxy resins (including those having a modified structure) , Epoxy vinyl ester resins (including bisphenol-based and novolak-based resins), epoxy-modified resins (polyimide-biased and acrylic-biased resins), etc. have a reaction rate with the same reaction system and blend separation occurs. A resin for molding FRP, characterized in that it is formulated for the purpose of producing no hybrid effect.    In order to obtain a hybrid effect molded product using multiple resins, different resins have the same reactive groups, different molecular weights, the same polymerization reaction rate, the same applied reaction catalyst, and the specific gravity separation of the mixed material occurs. The polymerization reaction is completed quickly while maintaining the compatibility and compatibility of different molecules, and the addition of interface materials (coupling materials) between different materials, etc. Molded products made of composite resin    As an additive for obtaining a hybrid effect in an ester basic reaction resin having an epoxy group that can use a plurality of common reaction catalysts having different molecular weights, for example, 0.5 to 1 part of a silane coupling agent is added to obtain surface activity. For example, 0.5-1.5 parts of a catalyst that quickly cures at medium temperature within a short time of about 20 minutes, such as BPO, can be used to promote the effect of the catalyst, such as dimethylaniline, 0.05-0.3%. A resin having a constitutional characteristic of an additive that is a hybrid resin added to adjust the reaction rate of the curing temperature.

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