A composite material for wet insulation and providing solid buoyancy and a method of making the same

Abstract

The application discloses a composite material for wet thermal insulation and solid buoyancy and a preparation method thereof. The composite material for wet thermal insulation and solid buoyancy comprises the following preparation raw materials in parts by weight: 100 parts of a matrix resin, 30-60 parts of microbeads, 5-30 parts of a curing agent, 0-10 parts of reinforcing fillers and 0-10 parts of modified phenolic aerogel fillers; the matrix resin is a phenolic resin; and the microbeads are hollow glass microbeads which are surface modified by a coupling agent. The modified phenolic aerogel powder is introduced as the filler, and compared with the traditional inorganic aerogel filler, since the phenolic aerogel is an organic aerogel and the resin matrix is the same, the resin-filler system is compatible, the internal heat conduction path and interface defects are effectively reduced, the effect of the filler is significantly improved, and the mechanical strength and thermal insulation performance of the composite material are comprehensively improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of organic and inorganic blended materials, in particular to a composite material for wet thermal insulation and providing solid buoyancy and a preparation method thereof. BACKGROUND

[0002] Deep-sea oil and gas pipelines are called "lifeline of offshore oil and gas fields", and are an important part of the offshore oil and gas collection, transportation and storage system. The basic form of the single-wall pipe thermal insulation structure currently used at home and abroad is: steel pipe-corrosion resistant layer-thermal insulation layer-waterproof protective layer, wherein the thermal insulation layer and the protective layer are connected by an adhesive, forming a "three-proofing system" of the pipeline, so that the steel pipe, the corrosion resistant layer, the thermal insulation layer and the protective layer are firmly combined into one, improving the corrosion and thermal insulation effect of the pipeline.

[0003] Thermal insulation material is the core of the pipeline thermal insulation structure. Unlike traditional sandwich thermal insulation structure, since the wet thermal insulation material of the pipeline directly contacts with seawater and bears huge hydrostatic pressure in deep sea, the wet thermal insulation material for deep-sea oil and gas pipelines must consider its thermal insulation performance, water absorption rate, tensile and compressive yield strength, high temperature adaptability, and creep resistance, etc. Composite foam is a material composed of hollow spherical fillers in a resin matrix, such as epoxy composite foam, polyurethane composite foam and phenolic composite foam, which has been widely used in oil pipelines of offshore platforms. However, the production of composite foam thermal insulation materials for deep-sea pipelines is basically monopolized by foreign companies, such as AIS Company in the United Kingdom. At the same time, there are still technical problems to be improved in the use of wet thermal insulation composite foam materials for deep-sea pipeline thermal insulation, the most important of which is to ensure excellent thermal insulation performance under deep-sea conditions.

[0004] In addition, in order to ensure the stable operation of oil development devices in deep sea, solid buoyancy materials need to be installed to provide sufficient static buoyancy. However, the solid buoyancy materials prepared in China still have many gaps compared with international advanced technology, for example, the buoyancy materials developed in the early stage generally use polyurethane foam, epoxy resin foam or other foaming plastics, which have low compressive strength and poor reliability compared with the same materials abroad, and the maximum working depth is only 400 m.

[0005] Chinese patent CN103665768A discloses a preparation method of high-strength solid buoyancy material, although the hollow microbeads are modified by using a coupling agent, but it does not consider to study the addition of other targeted fillers to further enhance the comprehensive performance of the material. Chinese patent CN109796840A discloses a reaction kettle external insulation material, which adds silica aerogel as a filler, but since the silica aerogel still belongs to inorganic aerogel, it is difficult to blend between inorganic and organic materials, resulting in the problem of uneven mixing. Therefore, on this basis, it is of great significance to select specific fillers for the specific performance of the composite material, solve the interface compatibility problem, and develop a composite material for wet insulation and solid buoyancy, which is of great significance to the safe operation of China's marine pipeline and the development of marine energy. SUMMARY

[0006] In order to overcome the technical problems existing in the prior art, the present application provides a composite material for wet insulation and solid buoyancy and a preparation method thereof, which has excellent compressive strength and thermal insulation performance; and the whole preparation process is simple, easy to operate and low in cost, and is suitable for small batch sample preparation.

[0007] In order to achieve the above purpose, the technical scheme adopted by the present application is:

[0008] The first aspect of the present application provides a composite material for wet insulation and solid buoyancy, which comprises the following preparation raw materials in parts by weight:

[0009] 100 parts of base resin, 30-60 parts of microbeads, 5-30 parts of curing agent, 0-10 parts of reinforcing filler and 0-10 parts of modified phenolic aerogel filler;

[0010] The base resin is phenolic resin.

[0011] The microbeads are coupling agent surface modified hollow glass microbeads.

[0012] Preferably, the composite material for wet insulation and solid buoyancy comprises the following preparation raw materials in parts by weight:

[0013] 100 parts of base resin, 30-60 parts of microbeads, 5-30 parts of curing agent, 1-5 parts of reinforcing filler and 0.5-5 parts of modified phenolic aerogel filler.

[0014] Further preferably, the composite material for wet insulation and solid buoyancy comprises the following preparation raw materials in parts by weight:

[0015] 100 parts of base resin, 44-46 parts of microbeads, 10-12 parts of curing agent, 1-2 parts of reinforcing filler and 0.8-1.2 parts of modified phenolic aerogel filler.

[0016] Preferably, the phenolic resin has a density of 1.10-1.50 g / cm 3 , a solid content of 50%-80%, and a viscosity of 500-5000 mPa·s / 25℃.

[0017] Preferably, the microbeads are silane coupling agent modified hollow glass microbeads, and the silane coupling agent is at least one of γ-aminopropyl triethoxysilane (KH550), γ-glycidyl ether propyl trimethoxysilane (KH560), and γ-methacryloyloxy propyl trimethoxysilane (KH570). The specific source and preparation process of the silane coupling agent modified hollow glass microbeads are not limited in the present application.

[0018] Further preferably, the hollow glass microbeads have a density of 0.30-0.70 g / cm 3 , a particle size of 10-200 μm, and a compressive strength of 10-100 MPa. The specific source and preparation process of the hollow glass microbeads are not limited in the present application, and the hollow glass microbeads prepared by known methods or commercially available hollow glass microbeads can be used.

[0019] Preferably, the curing agent includes at least one of p-toluenesulfonic acid, benzene sulfonic acid, and propylene carbonate.

[0020] Preferably, the reinforcing filler is at least one of nano-silica, glass fiber, and carbon black.

[0021] Preferably, the modified phenolic aerogel filler is at least one of boron modified phenolic resin-formaldehyde aerogel powder, benzoxazine resin-formaldehyde aerogel powder, and epoxy modified phenolic resin-formaldehyde aerogel powder.

[0022] Preferably, the preparation method of the modified phenolic aerogel filler is mixing and stirring the modified phenolic resin, ethanol, and urotropine (by weight) in a ratio of 1:(3-3.4):(0.2-0.4), transferring to an autoclave, and reacting at 100-160℃ for 15-20 h. After the reaction is completed, the modified phenolic aerogel filler is obtained by grinding and fine screening. The modified phenolic resin is one of boron modified phenolic resin, benzoxazine resin, and epoxy modified phenolic resin. The specific source of the modified phenolic resin is not limited in the present application, and the modified phenolic resin prepared by self or commercially available can be used.

[0023] The second aspect of the present application provides a preparation method of the composite material for wet thermal insulation and providing solid buoyancy, which comprises the following steps:

[0024] (1) mixing the base resin with the curing agent, and then adding other raw materials for preparation, mixing and stirring to obtain a mixture;

[0025] (2) After the mixture is degassed, it is transferred into a mold, and cured and demolded to obtain the composite material for wet thermal insulation and solid buoyancy.

[0026] Preferably, the curing step is room temperature curing for 10-24 h, followed by curing at 60-120℃ for 10-24 h.

[0027] Compared with the prior art, the present application has the following advantages:

[0028] 1. The composite material for wet thermal insulation and solid buoyancy provided by the present application uses a silane coupling agent to modify the surface of hollow glass microspheres. The "molecular bridge" of the silane coupling agent introduces the hollow glass microspheres into the resin crosslinking system, improves the dispersibility of the hollow glass microspheres in the resin system, limits the dispersibility of different fillers in the resin system, and improves the interface defects between the matrix resin and the microspheres, between the microspheres and the fillers, and between the matrix resin and the fillers, thereby synergistically enhancing the mechanical properties and thermal insulation properties of the composite material. In addition, by innovatively introducing modified phenolic aerogel powder as a filler, compared with traditional inorganic aerogel fillers, firstly, since the phenolic aerogel is an organic aerogel and the resin matrix is the same, the resin-filler system is compatible, effectively reducing the internal heat conduction path and interface defects, and significantly improving the effect of the filler, thereby comprehensively improving the mechanical strength and thermal insulation properties of the composite material. Secondly, since the phenolic resin in the phenolic aerogel is further modified, the filler has more excellent heat resistance and thermal insulation properties. Therefore, the composite material of the present application has excellent mechanical strength and thermal insulation properties while having a low density.

[0029] 2. The preparation method of the composite material for wet thermal insulation and solid buoyancy provided by the present application uses a stirring and degassing machine and an oven to stir and degas the mixture and to cure and demold to obtain a phenolic composite foam with uniform mixing of various materials. The entire process requires low equipment, is simple to operate, and is non-toxic and harmless. The entire preparation process is simple, easy to operate, and low in cost. In addition, the preparation method of the present application does not have strict requirements for the order of adding materials, and a mixture without obvious bubbles can be obtained after stirring and degassing treatment, thereby avoiding the problem of a sharp decrease in the mechanical properties of the thermal insulation material caused by the presence of large bubbles inside. DETAILED DESCRIPTION

[0030] The specific embodiments of the present application are further described below. It should be noted that the description of these embodiments is used to help understand the present application, but does not constitute a limitation on the present application. In addition, the technical features involved in each embodiment of the present application described below can be combined with each other as long as they do not conflict with each other.

[0031] The experimental methods in the following examples are all conventional methods unless otherwise specified. The experimental materials used in the following examples are all commercially available unless otherwise specified.

[0032] Example 1

[0033] The composite material for wet insulation and solid buoyancy provided in this example is prepared from the following raw materials and in the following weight proportions:

[0034] Phenolic resin 100 parts, KH550 modified S38HS 45 parts, p-toluenesulfonic acid 12 parts, glass fiber 1 part, nano-silicon dioxide 1 part, boron-modified phenolic resin-formaldehyde aerogel powder 1 part.

[0035] The preparation method comprises the following steps:

[0036] S1: Hollow glass microbeads (model: S38HS; manufacturer: 3M) are pretreated with γ-aminopropyltriethoxysilane (KH550), and the KH550 modified S38HS is obtained by filtration and drying. The amount of coupling agent is 50wt% of the mass of the glass microbeads;

[0037] S2: Boron-modified phenolic resin (appearance: yellow solid; manufacturer: Wangxin Plastic), ethanol, and urotropine (in weight parts) are mixed and stirred in a ratio of 1:3.2:0.3, transferred to an autoclave, and reacted at 120°C for 15h. After the reaction is completed, the boron-modified phenolic resin-formaldehyde aerogel powder is obtained by grinding and sieving;

[0038] S3: After mixing the phenolic resin with p-toluenesulfonic acid, the KH550 modified S38HS, glass fiber, nano-silicon dioxide, and boron-modified phenolic resin-formaldehyde aerogel powder are added, and stirred for 6min until they are uniformly mixed;

[0039] S4: The mixture is transferred to a planetary stirring defoaming machine and stirred at 1000rpm for 10min to defoam;

[0040] S5: After the mixture is defoamed, it is transferred to a mold, solidified at room temperature for 10h, and then solidified at 60°C for 24h. The composite material is obtained by demolding.

[0041] Example 2

[0042] The composite material for wet insulation and solid buoyancy provided in this example is prepared from the following raw materials and in the following weight proportions:

[0043] Phenolic resin 100 parts, KH550 modified S38HS 45 parts, p-toluenesulfonic acid 10 parts, glass fiber 1 part, nano-silicon dioxide 1 part, boron-modified phenolic resin-formaldehyde aerogel powder 1 part.

[0044] The preparation method comprises the following steps:

[0045] S1: S38HS is pretreated with gamma-aminopropyl triethoxysilane, and the KH550 modified S38HS is obtained by filtration and drying, wherein the amount of the coupling agent is 50wt% of the mass of the glass beads;

[0046] S2: The boron-modified phenolic resin, ethanol and urotropin (by weight) are mixed and stirred in a ratio of 1:3.2:0.3, transferred to an autoclave for reaction at 120 DEG C for 15 hours, and after the reaction is completed, the boron-modified phenolic resin-formaldehyde aerogel powder is obtained by grinding and fine screening;

[0047] S3: The phenolic resin is mixed with p-toluenesulfonic acid, and then the KH550 modified S38HS, glass fiber, nano-silicon dioxide and boron-modified phenolic resin-formaldehyde aerogel powder are added and stirred for 6 minutes until they are uniformly mixed;

[0048] S4: The mixture is transferred to a planetary stirring defoaming machine and stirred and defoamed at 1000 rpm for 10 minutes;

[0049] S5: After the mixture is free of obvious bubbles, it is transferred to a mold, and then cured at room temperature for 10 hours and at 60 DEG C for 24 hours, and the composite material is obtained by demolding.

[0050] Example 3

[0051] The composite material for wet thermal insulation and providing solid buoyancy is prepared from the following raw materials and weight parts:

[0052] phenolic resin 100 parts, KH550 modified S38HS 45 parts, p-toluenesulfonic acid 12 parts, glass fiber 1 part, and boron-modified phenolic resin-formaldehyde aerogel powder 1 part.

[0053] The preparation method comprises the following steps:

[0054] S1: S38HS is pretreated with gamma-aminopropyl triethoxysilane, and the KH550 modified S38HS is obtained by filtration and drying, wherein the amount of the coupling agent is 50wt% of the mass of the glass beads;

[0055] S2: The boron-modified phenolic resin, ethanol and urotropin (by weight) are mixed and stirred in a ratio of 1:3.2:0.3, transferred to an autoclave for reaction at 120 DEG C for 15 hours, and after the reaction is completed, the boron-modified phenolic resin-formaldehyde aerogel powder is obtained by grinding and fine screening;

[0056] S3: After mixing the phenolic resin with p-toluenesulfonic acid, add KH550 modified S38HS, glass fiber and boron modified phenolic resin-formaldehyde aerogel powder, stir for 6 min until mixed evenly;

[0057] S4: Transfer the mixture to a planetary stirring defoaming machine and stir for 10 min at 1000 rpm;

[0058] S5: After the mixture is free of obvious bubbles, transfer it to a mold, first cure at room temperature for 10 h, then cure at 60°C for 24 h, and the composite material can be obtained after demolding.

[0059] Example 4

[0060] The present example provides a composite material for wet thermal insulation and providing solid buoyancy, the preparation raw materials and weight parts are as follows:

[0061] Phenolic resin 100 parts, KH550 modified S38HS 45 parts, p-toluenesulfonic acid 12 parts, glass fiber 1 part, and silica aerogel powder 1 part (specification: particle size 15 microns; manufacturer: Zhongning Technology).

[0062] The preparation method comprises the following steps:

[0063] S1: Pretreat S38HS with γ-aminopropyltriethoxysilane, filter and dry to obtain the KH550 modified S38HS, and the amount of coupling agent is 50wt% of the mass of glass beads;

[0064] S2: After mixing the phenolic resin with p-toluenesulfonic acid, add KH550 modified S38HS, glass fiber and silica aerogel powder, stir for 6 min until mixed evenly;

[0065] S3: Transfer the mixture to a planetary stirring defoaming machine and stir for 10 min at 1000 rpm;

[0066] S4: After the mixture is free of obvious bubbles, transfer it to a mold, first cure at room temperature for 10 h, then cure at 60°C for 24 h, and the composite material can be obtained after demolding.

[0067] Example 5

[0068] The present example provides a composite material for wet thermal insulation and providing solid buoyancy, the preparation raw materials and weight parts are as follows:

[0069] Phenolic resin 100 parts, KH550 modified S38HS 45 parts, p-toluenesulfonic acid 12 parts, glass fiber 1 part, and silica aerogel powder 1 part (specification: particle size 15 microns; manufacturer: Zhongning Technology).

[0070] The preparation method comprises the following steps:

[0071] S1: The S38HS was pretreated with γ-aminopropyl triethoxysilane, and the KH550 modified S38HS was obtained by filtration and drying, and the amount of coupling agent was 50wt% of the mass of glass beads;

[0072] S2: After mixing the phenolic resin with p-toluenesulfonic acid, KH550 modified S38HS, glass fiber and nano silicon dioxide were added, and stirred for 6 min until mixed uniformly;

[0073] S3: The mixture was transferred to a planetary stirring defoaming machine and stirred at 1000 rpm for 10 min;

[0074] S4: After the mixture was transferred to the mold, it was first cured at room temperature for 24 h, and then cured at 60℃ for 24 h, and the composite material was obtained by demolding.

[0075] Comparative Example 1

[0076] This comparative example provides a composite material for wet thermal insulation and providing solid buoyancy, and the preparation raw materials and weight parts are as follows:

[0077] Phenolic resin 100 parts, S38HS 45 parts, p-toluenesulfonic acid 12 parts, glass fiber 1 part.

[0078] The preparation method comprises the following steps:

[0079] S1: After mixing the phenolic resin with p-toluenesulfonic acid, S38HS and glass fiber were added, and stirred for 6 min until mixed uniformly;

[0080] S2: The mixture was transferred to a planetary stirring defoaming machine and stirred at 1000 rpm for 10 min;

[0081] S3: After the mixture was transferred to the mold, it was first cured at room temperature for 24 h, and then cured at 60℃ for 24 h, and the composite material was obtained by demolding.

[0082] Comparative Example 2

[0083] This comparative example provides a composite material for wet thermal insulation and providing solid buoyancy, and the preparation raw materials and weight parts are as follows:

[0084] Phenolic resin 100 parts, S38HS 45 parts, p-toluenesulfonic acid 10 parts.

[0085] The preparation method comprises the following steps:

[0086] S1: After mixing the phenolic resin with p-toluenesulfonic acid, S38HS was added, and stirred for 6 min until mixed uniformly;

[0087] S2: The mixture was transferred to a planetary stirring defoaming machine and stirred and defoamed at 1000 rpm for 10 min;

[0088] S3: After the mixture was free of obvious bubbles, it was transferred to a mold, first cured at room temperature for 24 h, then cured at 60°C for 24 h, and the composite material was obtained after demolding.

[0089] The performance tests were carried out on Examples 1-5 and Comparative Examples 1-2; the density test was carried out according to the ISO 1183 standard; the thermal insulation performance test was carried out according to the ISO 8301 standard; the compression performance test was carried out according to the ISO 844 standard, and the test results are shown in Table 1 below.

[0090] Table 1

[0091]

[0092]

[0093] Result analysis:

[0094] (1) From Examples 1-2, when the content of the curing agent increases, the phenolic composite foam insulation material prepared has lower density, flat thermal conductivity, and better compression strength, indicating that the degree of curing and crosslinking is significantly improved. In addition, it is found that the composite material prepared has good thermal insulation performance and compression strength while having low density, with the lowest thermal conductivity of 0.1694 W / (m·K) and the highest compression strength of 45.303 MPa, reaching the performance requirements of C55 type phenolic composite foam produced by British AIS Company, and the service water depth can reach more than 3000 meters, indicating that it can be used in deep-sea oil and gas pipeline wet insulation and solid buoyancy material field.

[0095] (2) From Examples 3 and 4, compared with the addition of silica aerogel filler, the compression strength of the composite material with modified phenolic aerogel filler is greatly improved, and the addition of modified phenolic aerogel filler can effectively reduce the interface defects between the filler and the matrix.

[0096] (3) From Examples 1, 3 and 5, the addition of reinforcing filler can effectively improve the compression strength of the composite material, the addition of modified phenolic aerogel filler can effectively reduce the heat conduction path, significantly reduce the thermal conductivity of the composite material and improve its compression strength, and when both are added, the comprehensive performance of the composite material can reach a good balance point. Although the overall compression strength of the material will decrease due to the decrease in the density of the material, its thermal insulation performance is better than that of the composite foam with only thermal insulation aerogel filler, indicating that there is a synergistic effect between the two different types of fillers.

[0097] (4) From the combination of Examples 1-5 and Comparative Examples 1-2, it can be seen that after the surface modification of the filler, the addition of phenolic aerogel filler and the confined dispersion, the thermal insulation performance and the compression performance of the composite material are both significantly enhanced while the density remains little changed, effectively showing that the thermal insulation performance and the mechanical properties of the composite material can be significantly enhanced by the above preparation method.

[0098] The embodiments of the present application are described in detail above, but the present application is not limited to the described embodiments. For those skilled in the art, various changes, modifications, replacements and variations of the embodiments can be made without departing from the principles and spirits of the present application, and still fall within the protection scope of the present application.

Claims

1. A composite material for wet insulation and providing solid buoyancy, characterized in that, The preparation raw materials include the following by weight parts: 100 parts of a base resin, 30-60 parts of microbeads, 5-30 parts of a curing agent, 1-5 parts of a reinforcing filler, and 0.5-5 parts of a modified phenolic aerogel filler; The base resin is a phenol resin, the phenol resin has a density of 1.1-1.5 g / cm 3 , a solid content of 50%-80%, and a viscosity of 500-5000 mPa·s / 25℃; The microbeads are surface modified hollow glass microbeads with a coupling agent, a density of 0.3-0.7 g / cm 3 , a particle size of 10-200 μm, and a compressive strength of 10-100 MPa. The modified phenolic aerogel filler is at least one of boron-modified phenolic resin-formaldehyde aerogel powder, benzoxazine resin-formaldehyde aerogel powder, and epoxy-modified phenolic resin-formaldehyde aerogel powder; The preparation method of the modified phenolic aerogel filler is: mixing and stirring the modified phenolic resin, ethanol, and urotropin at a mass ratio of 1:3-3.4:0.2-0.4, transferring to an autoclave at 100-160℃ for 15-20h, and after the reaction is completed, grinding and fine screening to obtain the modified phenolic aerogel filler; the modified phenolic resin is one of boron-modified phenolic resin, benzoxazine resin, and epoxy-modified phenolic resin.

2. The composite material for wet insulation and providing solid buoyancy according to claim 1, characterized in that, The microbeads are hollow glass microbeads modified by a silane coupling agent, and the silane coupling agent is at least one of γ-aminopropyl triethoxysilane, γ-glycidyl ether oxypropyl trimethoxysilane, and γ-methacryloyloxypropyl trimethoxysilane.

3. The composite material for wet insulation and providing solid buoyancy according to claim 1, characterized in that, The curing agent includes at least one of p-toluenesulfonic acid, benzene sulfonic acid, and propylene carbonate.

4. The composite material for wet insulation and providing solid floatation according to claim 1, characterized in that, The reinforcing filler is at least one of nanosilica, glass fiber, and carbon black.

5. A process for the production of a composite material for wet insulation and solid floatation according to any one of claims 1 to 4, characterized in that The method includes the following steps: (1) mixing the base resin with the curing agent, then adding other preparation raw materials, mixing and stirring to obtain a mixture; (2) transferring the mixture after degassing to a mold, curing and demolding to obtain the composite material for wet thermal insulation and providing solid buoyancy.

6. A method of producing a composite material for thermal insulation and solid floatation according to claim 5, characterized in that, The curing step is room temperature curing for 10-24h, and then curing at 60-120℃ for 10-24h.

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