A sealing leather ring grouting pipe and a preparation method thereof

Abstract

The application relates to the technical field of grouting pipes, and discloses a grouting pipe with a sealing leather ring and a preparation method thereof. The grouting pipe comprises a pipe body, at least one group of grouting holes is arranged on the outer peripheral wall of the pipe body, at least one annular groove is arranged at the position of the outer periphery of the pipe body in connection with the at least one group of grouting holes, and the number of the group of grouting holes is multiple; a grouting head is fixed to one end of the pipe body, the grouting head is provided with a connecting structure matched with a sounding pipe; and at least one sealing leather ring is arranged in the at least one annular groove of the pipe body. The grouting pipe is optimized by adopting the sealing leather ring and the grouting head, has high structure matching property, is simple to install, can effectively prevent the problems of backflow and blockage caused by the falling of adhesive tapes, improves the sealing reliability and construction efficiency of grouting, and simultaneously reduces construction cost and engineering risk.

Description

Technical Field

[0001] This invention relates to the field of grouting pipe technology, and in particular to a grouting pipe with a sealing ring and its preparation method. Background Technology

[0002] In civil engineering, especially in pile foundation construction and grouting with sonic logging pipes, grouting pipes play a crucial role in enhancing the bearing capacity of the foundation and ensuring the integrity of concrete piles. By setting grouting channels at the pile tip or side and applying cement-based grout, not only can soil compaction and fracturing consolidation be achieved, but the problem of sediment at the pile tip can also be effectively mitigated, thereby enhancing the ultimate bearing capacity of the pile foundation and reducing settlement. This method is widely used in deep foundation construction for high-rise buildings, bridges, and railway engineering. With the improvement of engineering standards, the comprehensive requirements for grouting systems in terms of sealing effect, ease of construction, and material performance are constantly increasing.

[0003] Currently, most common grouting systems use metal grouting pipes. During construction, these metal grouting pipes typically require an external adapter to connect to the sonic logging pipes. Due to significant differences in pipe diameter (grouting pipes are mostly φ20~φ32mm, while sonic logging pipes are mostly φ50~φ57mm), direct installation is not feasible. Furthermore, traditional methods for sealing grouting holes involve wrapping waterproof tape for initial sealing, relying on the high-pressure filling effect of cement grout to achieve final sealing. While theoretically feasible, in practical engineering environments, the tape can shift or detach, leading to unstable sealing and often resulting in concrete backflow into the grouting hole or pipe blockage, affecting subsequent grouting operations and even causing project failure.

[0004] Therefore, this invention proposes a grouting pipe with a sealing ring and its preparation method to overcome the shortcomings of the prior art. Summary of the Invention

[0005] The purpose of this invention is to provide a grouting pipe with a sealing ring and its preparation method, which solves the problems of unstable sealing performance and mismatch between the specifications of existing grouting pipes and sonic logging pipes.

[0006] To achieve the above objectives, the present invention provides the following technical solution: a grouting pipe with a sealing ring, comprising:

[0007] The pipe body has at least one set of grouting holes on its outer peripheral wall, and at least one annular groove is provided on the outer peripheral position of the pipe body associated with the at least one set of grouting holes. The number of grouting holes in one set is multiple.

[0008] The presence of at least one set of grouting holes with multiple grout outlets on the outer circumferential wall of the pipe body is key to achieving efficient and uniform grout distribution. This design departs from traditional single-point or sparse grouting methods, promoting a wider and more uniform grout coverage in the target area through multi-point, diffused grouting, thus improving the effectiveness and controllability of grouting. Simultaneously, the annular grooves, designed in conjunction with the grouting holes, provide precise positioning and a stable load-bearing foundation for the sealing ring, ensuring reliable operation of the seal under pressure and environmental changes—a testament to the synergistic optimization of structure and function.

[0009] The grouting head is fixed at one end of the pipe body, and the grouting head has a connection structure that matches the sonic logging pipe;

[0010] The key design feature of the grouting head is its integrated connection structure that matches the sonic logging pipe. This reduces the need for adapters, simplifies construction, and lowers costs.

[0011] At least one sealing ring is installed in the at least one annular groove of the tube body;

[0012] The sealing ring installed within the annular groove of the pipe body is the core of this invention for achieving long-lasting active sealing. This is due to the TPE material, after special modification (specific modifications will be described later), possessing the characteristic of spontaneously expanding in volume upon contact with moisture. When the sealing ring comes into contact with moisture in the environment, it actively expands and tightly fills the gap between the grouting pipe and the surrounding medium, forming a dynamic and highly adaptable waterproof barrier. This proactive sealing method not only prevents grout leakage during grouting but also compensates for potential leakage paths over the long term.

[0013] The sealing ring comprises the following components in parts by weight:

[0014] Thermoplastic elastomer matrix resin: 100 parts;

[0015] Moisture-responsive components with dual functionalization modified on the surface: 1.0 to 15.0 parts;

[0016] Plasticizer: 10 to 80 parts;

[0017] First antioxidant: 0.1 to 0.5 parts;

[0018] Second antioxidant: 0.1 to 0.5 parts;

[0019] Ultraviolet light absorber: 0.2 to 0.8 parts;

[0020] Interface modifier: 0.5 to 5.0 parts by weight.

[0021] The superior performance of the sealing ring of this invention stems from the synergistic effect of its specific components. A 100-part thermoplastic elastomer matrix resin provides the necessary elasticity and mechanical strength, which is fundamental for its use as a dynamic seal. The molecular chain structure of the matrix resin itself endows the material with macroscopic resilience.

[0022] 1.0 to 15.0 parts of a surface-modified, dual-functionalized moisture-responsive component are key to achieving water-swellable sealing. This component possesses strong water absorption; by performing dual-functionalization on its surface, its dispersion uniformity within the hydrophobic elastomer matrix is ​​significantly improved, and its water absorption and swelling rate and extent are effectively controlled. This precise surface engineering ensures the effective distribution and controllable function of moisture-responsive points within the material.

[0023] The plasticizer, ranging from 10 to 80 parts, reduces the interaction forces between elastomer macromolecular chains and increases chain segment mobility, thereby regulating the material's flexibility and processing fluidity to ensure long-term performance.

[0024] The first antioxidant (0.1 to 0.5 parts) and the second antioxidant (0.1 to 0.5 parts) work synergistically to delay thermo-oxidative aging. The former captures free radicals and the latter decomposes peroxides.

[0025] The ultraviolet light absorber (0.2 to 0.8 parts) protects the material from photodegradation by absorbing ultraviolet light and converting it into harmless energy.

[0026] The interface modifier, at concentrations of 0.5 to 5.0, reduces the interfacial tension between the moisture-responsive component and the elastomer matrix, thereby enhancing the adhesion between the two phases. This not only improves the overall mechanical properties and component dispersion stability of the composite material but also further optimizes its moisture-responsive function.

[0027] Preferably, the thermoplastic elastomer matrix resin is a styrene-ethylene-butene-styrene block copolymer.

[0028] In the material system of the sealing ring of this invention, the selection of the thermoplastic elastomer matrix resin is a key factor in achieving its comprehensive performance. The use of styrene-ethylene-butene-styrene block copolymer (SEBS) as the matrix resin is based on the multifaceted performance advantages brought about by its unique molecular structure, which directly contributes to the final performance and durability of the sealing ring.

[0029] SEBS, as a saturated thermoplastic elastomer, is characterized by its unique molecular chain structure. It consists of hard polystyrene (PS) segments and flexible polyethylene-butene (EB) segments. At room temperature, the hard polystyrene segments at both ends of the molecular chain form physical cross-linking points through physical entanglement or microcrystallization. These cross-linking points endow the material with elasticity and strength similar to vulcanized rubber. Meanwhile, the flexible EB segments in the middle give the material excellent flexibility and rubber-like elastic recovery. This physical cross-linking structure allows SEBS to exhibit excellent elasticity without chemical vulcanization and allows for melt processing at high temperatures, exhibiting good thermoplastic processing properties.

[0030] A key innovative consideration in choosing SEBS as the matrix resin lies in its saturated polyethylene-butene flexible midsegment. Compared to unsaturated rubber midsegments (such as the polybutadiene segment in SBS), the saturated structure of SEBS gives it excellent weather resistance, resistance to heat and oxygen aging, and ozone resistance. This is because saturated C=C single bonds have higher chemical stability than unsaturated C=C double bonds, making them less susceptible to aging reactions such as chain breakage or cross-linking caused by oxygen, ozone, and ultraviolet light. Therefore, sealing rings based on SEBS can better resist corrosion from humid and hot environments, temperature changes, and potential chemical media during long-term use, thus ensuring the long-term stability of their elasticity and sealing performance. This is a key factor in improving the reliability and service life of grouting pipe seals used in complex engineering environments.

[0031] Furthermore, SEBS typically exhibits good compatibility with other polymer components and additives, especially when combined with other specific functional components in this invention (such as moisture-responsive components, plasticizers, antioxidants, etc.), which helps to form a homogeneous and stable composite material system. Its good dispersibility facilitates the full utilization of the functions of each component, ultimately resulting in the optimization of the overall performance of the sealing ring.

[0032] Preferably, the surface-modified moisture-responsive component is cross-linked polyacrylate ultrafine superabsorbent polymer particles, and the average particle size of the ultrafine superabsorbent polymer particles is 5 to 45 micrometers.

[0033] In the sealing ring of this invention, the key to achieving its crucial water-swelling function lies in the preferred use of cross-linked polyacrylate as ultrafine superabsorbent polymer particles. Polyacrylate itself contains a large number of hydrophilic groups (such as carboxylate ions), which is the molecular basis for its ability to absorb and lock in large amounts of water. Water molecules bind to these hydrophilic groups through hydrogen bonds and other interactions, and then penetrate into the polymer network.

[0034] Choosing "crosslinked" polyacrylates is crucial. This is because chemical crosslinking creates a three-dimensional network structure between the polymer chains. This network structure allows the resin to significantly swell and form a hydrogel after absorbing water, but it does not dissolve in water, thus maintaining its solid particle shape and structural strength. This controlled swelling behavior is key to its effective filling of voids without leakage in sealing applications, ensuring that the expanded volume can continuously provide a sealing effect.

[0035] Controlling the average particle size of the ultrafine superabsorbent polymer microparticles within the range of 5 to 45 micrometers is primarily achieved in the following ways: First, a smaller particle size means a larger specific surface area, allowing the microparticles to contact the surrounding moisture more quickly and fully, thereby improving the water absorption and swelling response rate. Second, microparticles within this particle size range are more likely to achieve uniform dispersion in the thermoplastic elastomer matrix, avoiding stress concentration points or uneven dispersion caused by excessively large particles, thus ensuring the stability and uniformity of the overall mechanical properties of the composite material.

[0036] The dual functionalization modification includes: a first functionalization treatment, which involves surface treatment using a hydrophobic modifier; and a second functionalization treatment, which involves surface treatment using a swelling-regulating modifier.

[0037] The first functionalization process involves surface treatment of the superabsorbent polymer (SAP) microparticles with a hydrophobic modifier. This involves introducing hydrophobic groups or forming a thin hydrophobic layer on the surface of the originally highly hydrophilic SAP microparticles. The main purpose of this step is to improve the interfacial compatibility between the SAP microparticles (which are inherently hydrophilic) and the hydrophobic thermoplastic elastomer matrix. By reducing the interfacial tension between the two, the hydrophobic treatment helps the SAP microparticles to be more uniformly dispersed in the elastomer matrix during melt blending, reducing agglomeration and thus ensuring the uniformity of the final sealing ring material structure and the stability of its performance. Furthermore, appropriate surface hydrophobication may also affect the wetting behavior during initial water contact.

[0038] Following this, the second functionalization process involves further surface treatment of the microparticles after the first treatment using a swelling-regulating modifier. This modifies the surface structure or chemical properties of the superabsorbent polymer (SAP) microparticles to precisely control their subsequent swelling rate, degree of swelling, or gel strength upon contact with water. For example, this can be achieved by forming a shell with specific permeability or introducing additional cross-linking points on the microparticle surface, thus regulating the rate at which water penetrates the microparticles and the final swelling volume. The innovative significance of this step lies in the fact that it allows the swelling behavior of the SAP to be "customized" according to actual application needs, rather than simply absorbing water rapidly. This avoids stress concentration or structural damage within the material that may result from excessively rapid or excessive swelling, ensuring the controllability and reliability of the sealing ring when it performs its water-swelling function.

[0039] Preferably, the hydrophobic modifier is selected from at least one of γ-aminopropyltriethoxysilane or stearic acid; the swelling control modifier is selected from at least one of glutaraldehyde or low molecular weight polyethylene glycol diglycidyl ether.

[0040] γ-Aminopropyltriethoxysilane: This silane coupling agent molecule contains both an organophilic group (aminopropyl) and a hydrolyzable alkoxy group (ethoxy). The alkoxy group hydrolyzes in the presence of water to generate silanol groups. These silanol groups can undergo condensation reactions with the hydroxyl or carboxyl groups on the surface of the superabsorbent polymer (SAP) particles, forming stable chemical bonds. Simultaneously, its aminopropyl terminus exhibits good organic compatibility, improving the interfacial bonding between the SAP particles and the hydrophobic TPE matrix. Through this "bridging" effect, a hydrophobic siloxane structure and organic groups are introduced onto the surface of the SAP, thereby achieving surface hydrophobicity.

[0041] Stearic acid, as a long-chain fatty acid, is characterized by its long, nonpolar hydrocarbon chain (hydrophobic end) and terminal carboxyl group (hydrophilic end). Stearic acid can coat the surface of superabsorbent polymer (SAP) particles with its hydrophobic long chain through physical adsorption or weak chemical reactions such as esterification with certain groups on the surface of SAP, forming a hydrophobic film. This reduces the surface energy of the particles and improves their dispersibility in a hydrophobic matrix.

[0042] Glutaraldehyde: Glutaraldehyde is a bifunctional aldehyde compound that can undergo cross-linking reactions with the amine, hydroxyl, or amide groups on the surface of superabsorbent resins (such as polyacrylates), forming a layer on the particle surface or further enhancing the density of the surface cross-linking network. This enhanced surface cross-linking effectively restricts the rapid penetration of water into the particle interior and limits the final swelling volume of the particle, thereby achieving the purpose of controlling the swelling rate and degree of swelling.

[0043] Low molecular weight polyethylene glycol diglycidyl ether: Its epoxide groups at both ends of the molecule possess high reactivity, allowing it to undergo ring-opening addition reactions with carboxyl, hydroxyl, or amine groups (containing active hydrogen) on the surface of superabsorbent polymers, forming new chemical bonds. This can also introduce new cross-linked structures or form a shell with specific permeability on the particle surface. The polyethylene glycol segments themselves possess a certain degree of hydrophilicity and flexibility. By controlling its dosage and the degree of reaction, the pore structure and water permeability of the surface layer can be finely adjusted, thereby effectively controlling the swelling behavior of the superabsorbent polymer.

[0044] Preferably, the interface modifier is polyethylene glycol octylphenyl ether.

[0045] In the composite material system of the sealing ring of the present invention, polyethylene glycol octylphenyl ether is preferably used as an interface modifier. This choice aims to optimize the interfacial interaction between different components, especially the surface-modified moisture-responsive component, and the thermoplastic elastomer matrix.

[0046] Polyethylene glycol octylphenyl ether is a nonionic surfactant whose molecular structure contains both a hydrophilic portion (polyethylene glycol chain) and a lipophilic / hydrophobic portion (octylphenyl group). Its core lies in this amphiphilic structure:

[0047] Hydrophobic end (octylphenyl): It can generate good physical adsorption or intermolecular forces with hydrophobic TPE matrix resin.

[0048] Hydrophilic end (polyethylene glycol chain): capable of interacting with moisture-responsive components (which retain a certain degree of polarity or sites that can form hydrogen bonds even after surface modification) or their surface-modified layers.

[0049] In this way, polyethylene glycol octylphenyl ether can be enriched at the interface between the moisture-responsive component particles and the TPE matrix, acting as a "bridge" to connect two phases with significantly different chemical properties.

[0050] This interfacial modification reduces the interfacial tension between the two phases, promoting a more uniform and stable dispersion of the moisture-responsive components in the TPE matrix.

[0051] The present invention also provides a method for preparing a grouting pipe with a sealing ring, comprising the following steps:

[0052] S1. The ultrafine superabsorbent polymer particles, which are moisture-responsive components, undergo a first and second functionalization treatment to obtain a moisture-responsive component with a surface that has undergone dual functionalization modification.

[0053] In step S1, the ultrafine superabsorbent polymer particles, which are the moisture-responsive component, undergo first and second functionalization treatments. This step is the starting point for realizing the water-swelling function of the sealing ring core. It involves precisely modifying the surface chemically to impart good compatibility between the superabsorbent polymer particles and the hydrophobic elastomer matrix, and effectively controlling their water absorption and swelling behavior. This is a crucial pretreatment to ensure that the moisture-responsive component can be uniformly dispersed in the subsequent composite material and function as expected, reflecting the innovation of customized material functionality.

[0054] S2. The surface-modified moisture-responsive component with dual functionalization is melt-blended and granulated with thermoplastic elastomer matrix resin, plasticizer, first antioxidant, second antioxidant, ultraviolet light absorber and interface modifier in a specified mass ratio to prepare TPE composite material.

[0055] In step S2, the dual-functionalized moisture-responsive component is melt-blended and granulated with the thermoplastic elastomer matrix resin, plasticizer, antioxidants (first and second), UV absorber, and interface modifier according to a pre-set mass ratio. The purpose of this step is to prepare homogeneous TPE composite material particles with specific properties. This is achieved through high-temperature melting and strong shear mixing, ensuring that the components are fully dispersed and interact at the molecular level, forming a synergistic whole. Precise proportioning and uniform blending are fundamental to ensuring the consistency and reliability of the final sealing ring performance.

[0056] S3. The TPE composite material is injection molded to obtain a sealing ring;

[0057] In step S3, the obtained TPE composite material is processed into a sealing ring using injection molding. Injection molding allows for precise control of the sealing ring's size, shape, and surface quality. It utilizes the thermoplasticity of TPE material, injecting it under high pressure into a mold cavity while it is in a molten state, and then cooling and solidifying it to obtain a product of the desired shape. This step transforms the macroscopic properties of the composite material into a sealing element with a specific geometry and function.

[0058] S4. Prepare the pipe body, open multiple grouting holes on its outer peripheral wall, and form at least one annular groove at the part associated with the grouting holes;

[0059] Step S4 includes preparing the tube body and creating multiple key grouting holes and annular grooves for installing the sealing ring on its outer peripheral wall. These structures are crucial for achieving uniform grouting and ring positioning.

[0060] S5. Prepare the grouting head and fix the grouting head to one end of the pipe body;

[0061] Step S5 involves preparing the grouting head and fixing it to one end of the pipe body, thus completing the basic construction and connection function of the grout delivery channel. These steps ensure the precise manufacturing of the main structure of the grouting pipe.

[0062] S6. Install the sealing ring in the annular groove of the pipe body to obtain the grouting pipe with the sealing ring.

[0063] In step S6, the previously prepared sealing ring is precisely installed in the annular groove of the pipe body. This assembly step organically combines the core water-swellable sealing element with the main structure of the grouting pipe, ultimately resulting in a grouting pipe with a complete sealing ring.

[0064] Preferably, the first functionalization treatment involves reacting the ultrafine superabsorbent polymer particles with at least one hydrophobic modifier selected from γ-aminopropyltriethoxysilane or stearic acid at 60 to 100°C for 0.5 to 2 hours; the second functionalization treatment involves reacting the ultrafine superabsorbent polymer particles that have undergone the first functionalization treatment with at least one swelling-regulating modifier selected from glutaraldehyde or low molecular weight polyethylene glycol diglycidyl ether at 40 to 80°C for 0.5 to 2.5 hours.

[0065] The preferred first functionalization treatment involves reacting ultrafine superabsorbent polymer particles with a selected hydrophobic modifier (γ-aminopropyltriethoxysilane or stearic acid) at a temperature of 60 to 100°C for 0.5 to 2 hours.

[0066] Temperature range (60-100℃): The mechanism for choosing this temperature range is that it provides sufficient activation energy to promote the effective reaction between the hydrophobic modifier and the surface of the superabsorbent polymer particles (such as silane hydrolysis, condensation, or fatty acid adsorption / esterification), ensuring that the modified layer can be formed uniformly and firmly; at the same time, this temperature is relatively mild, avoiding potential thermal degradation or damage to the bulk structure of the ultrafine superabsorbent polymer particles at this stage, thus maintaining their original water-absorbing core capabilities. This is an optimized range that balances reaction rate and material stability.

[0067] Reaction time (0.5-2 hours): This time range is set to ensure that the hydrophobication reaction can proceed fully, allowing the modifier sufficient time to diffuse, orient, and complete bonding or coating on the particle surface to form an effective hydrophobic layer. Too short a time may result in incomplete modification and poor hydrophobic effect; too long a time may not provide significant additional benefits and instead increase energy consumption and production cycle. This time window is crucial for achieving efficient and complete surface hydrophobication.

[0068] The preferred second functionalization process involves reacting the microparticles that have undergone the first treatment with a selected swelling modifier (glutaraldehyde or low molecular weight polyethylene glycol diglycidyl ether) at a temperature of 40 to 80°C for 0.5 to 2.5 hours.

[0069] Temperature range (40-80℃): This temperature range provides suitable reaction conditions for swelling-regulating modifiers (such as the crosslinking reaction of glutaraldehyde or the ring-opening addition reaction of epoxy groups) to form an effective regulating layer on the particle surface. Compared to the first treatment, this temperature range is usually slightly lower or overlaps, because the surface crosslinking or shell formation reaction may be more sensitive and needs to be carried out under more precisely controlled conditions to avoid over-reaction that would lead to a significant decrease in water absorption or the formation of an overly dense shell that would hinder water penetration.

[0070] Reaction time (0.5-2.5 hours): This time range ensures that the swelling modifier can fully act on the particle surface to form a control layer with the desired permeability and structural strength. By precisely controlling the reaction time, the density of surface crosslinking or the thickness of the shell can be adjusted, thereby finely regulating the swelling rate, final swelling degree, and gel strength of the water-absorbing resin particles. This is key to achieving "on-demand customization" of the water-induced swelling behavior of sealing rings.

[0071] Preferably, the melt blending is performed using a twin-screw extruder, wherein the surface-modified moisture-responsive component is added through a downstream side feed port of the twin-screw extruder, the set temperature range of each heating zone of the twin-screw extruder is 130 to 210°C, and the set screw speed range is 150 to 450 rpm.

[0072] Twin-screw extruders are widely used in the preparation of polymer composites due to their superior mixing and dispersing capabilities and precise control over material residence time distribution. The mechanism lies in the strong shearing, kneading, and stretching effects generated by the meshing of the twin screws, effectively breaking down and uniformly dispersing different components within the polymer matrix. This is crucial for the TPE system containing various functional additives (especially surface-modified moisture-responsive components) in this invention, ensuring uniform distribution of each component at the microscopic level, thereby enabling the composite material to exhibit uniform and predictable macroscopic properties.

[0073] A key technological innovation of this invention lies in adding the surface-modified moisture-responsive component through a downstream side feed port of a twin-screw extruder. Specifically:

[0074] Protecting functional components: Moisture-responsive components (even modified ones) can be sensitive to excessive shear stress or prolonged heating time. Adding them from the downstream side to the feed port allows them to avoid the high-shear zone and initial melt section near the main feed port of the extruder, reducing potential mechanical damage or excessive heat exposure during extrusion and thus better preserving their original water absorption and swelling properties.

[0075] Optimized dispersion and distribution: After the TPE matrix resin and other heat-resistant additives have been fully melted and pre-mixed in the front section of the extruder, the moisture-responsive component is added from the side. This allows it to be dispersed in the already formed melt, which helps to achieve a more uniform distribution and avoids agglomeration or unevenness that may be caused by early addition.

[0076] Heating Zone Temperature (130-210℃): The temperature range of each heating zone in the twin-screw extruder is set from 130 to 210℃, based on the melt characteristics and thermal stability of the selected TPE matrix resin (such as SEBS) and other components. This temperature range ensures that the TPE matrix resin melts fully, forming a melt with good flowability, providing the necessary conditions for effective dispersion of the components. Simultaneously, by setting the heating zone temperature in stages, precise control of the melt viscosity and the thermal history experienced by the material in different areas of the extruder can be achieved, avoiding polymer degradation or functional additive failure due to excessively high temperatures, or insufficient mixing due to excessively low temperatures. This is an optimized temperature range that seeks a balance between ensuring sufficient plasticization of the material and avoiding thermal damage.

[0077] Screw speed (150-450 rpm): Setting the screw speed range to 150 to 450 rpm directly affects the shear rate, mixing intensity, and residence time of the material within the extruder. Higher screw speeds generally mean stronger shearing and shorter residence times, which helps improve dispersion efficiency and reduce the risk of thermal degradation of the material. However, excessively high speeds can also lead to excessive shearing, damaging certain sensitive components. Therefore, the selection of this speed range is the result of a trade-off between ensuring adequate mixing and dispersion and protecting the integrity of the components, aiming to achieve optimal blending results and production efficiency.

[0078] Preferably, the tube body is prepared by extrusion molding or injection molding, and the injection head is prepared by injection molding; the barrel temperature setting range for injection molding is 165 to 195°C, and the mold temperature setting range is 30 to 55°C; the temperature setting range for each zone of the extruder for extrusion molding is 150 to 190°C.

[0079] Extrusion Molding: For regularly shaped and long tubular structures, extrusion molding is a highly efficient continuous production method. It involves extruding uniformly plasticized PVC melt through a specific die, followed by cooling and shaping to obtain a pipe with the desired cross-sectional shape. In this process, the temperature setting range for each zone of the extruder is 150 to 190°C. This temperature setting ensures that the PVC material is fully and uniformly plasticized at each stage (feeding, compression, melting, metering), forming a melt with suitable fluidity, while minimizing PVC degradation due to overheating, thus guaranteeing the mechanical properties and chemical stability of the pipe material.

[0080] Injection molding: Injection molding can also be used if the tube structure is complex or if higher precision is required in certain areas. The barrel temperature setting range is 165 to 195°C, and the mold temperature setting range is 30 to 55°C. The barrel temperature ensures that the PVC is fully melted and has good fluidity to fill the mold cavity; the lower mold temperature helps the melt cool and solidify quickly, shortening the molding cycle and obtaining a tube with stable dimensions and a smooth surface.

[0081] Because grouting heads typically have more complex shapes to achieve connection with the pipe body and guide grout flow, they are preferably manufactured by injection molding. The process parameters are similar to those for injection molding the pipe body: the barrel temperature is set between 165 and 195°C, and the mold temperature is set between 30 and 55°C. These parameter settings are consistent with the design to accurately replicate the complex cavity of the mold, resulting in a precisely sized and structurally complete grouting head component that ensures good fit with the pipe body and subsequent grouting equipment.

[0082] Preferably, the process parameters for injection molding of the sealing ring include: a barrel temperature setting range of 160 to 205°C and a mold temperature setting range of 20 to 50°C.

[0083] The preferred barrel temperature range is 160 to 205°C. This range ensures that the specially formulated TPE composite material is fully and uniformly melted and plasticized in the barrel, forming a melt with good flowability. This is crucial for completely filling the mold cavity, especially for potentially complex or intricate structures. Simultaneously, controlling this upper temperature limit prevents thermal degradation or performance decline of the TPE matrix resin (such as SEBS) or its heat-sensitive functional components (such as moisture-responsive components, antioxidants, etc.) at prolonged high temperatures, thus ensuring the integrity of the sealing ring's elasticity and water-swellable function. This is an optimized range that strikes a balance between ensuring material flowability and maintaining material performance stability.

[0084] The preferred mold temperature range is 20 to 50°C. This is because a relatively low mold temperature helps the melt cool and solidify rapidly after being injected into the mold cavity, thus shortening the molding cycle and improving production efficiency. More importantly, an appropriate mold temperature can control the rate and extent of crystallization or physical cross-linking network formation in the TPE material (for block copolymers such as SEBS), which directly affects the final mechanical properties (such as hardness and resilience) and dimensional stability of the sealing ring. Excessively high or low mold temperatures can lead to defects in the product, such as uneven shrinkage, surface imperfections, or excessive internal stress. This temperature range is designed to obtain sealing rings with good surface quality and accurate dimensions.

[0085] In summary, the present invention has at least one of the following beneficial technical effects:

[0086] 1. This invention employs injection molding to manufacture the grouting head and sealing ring. The grouting head uses PVC as the base material, directly matching existing sonic logging pipe specifications without the need for additional adapters, significantly simplifying the construction process and reducing assembly errors and costs. Simultaneously, the sealing ring, made of TPE material and formulated with controlled processes, possesses excellent elasticity and sealing response capabilities, adapting to sealing requirements under different grouting pressures. This significantly improves construction efficiency and sealing reliability, effectively solving the problem of backflow and blockage caused by tape detachment in traditional processes.

[0087] 2. This invention, by introducing an interface modifier, effectively improves the compatibility between the moisture-responsive component and the TPE matrix, promoting the uniform dispersion of functional particles at the microscopic level. This strategy significantly improves the structural consistency of the composite material, helps alleviate stress concentration, and enables the sealing ring to maintain stable mechanical response and flexibility under dynamic loads or complex stress environments, demonstrating high reliability and applicability.

[0088] 3. The dual-functionalization process employed in this invention significantly enhances the interfacial affinity of the moisture-responsive components and effectively suppresses the excessively rapid expansion of the sealing ring in water through the introduction of cross-linking structures. This avoids the instability of the sealing ring in an aqueous environment, ensures that the material exhibits controllable expansion under the influence of moisture, and guarantees the durability and performance stability of the sealing ring in sealing applications.

[0089] 4. This invention employs a downstream side-feeding process, avoiding the degradation of moisture-responsive components under high-temperature shear conditions. This process optimization provides better protection for the sealing ring, reducing potential deactivation and degradation caused by prolonged exposure to high temperatures. Improved interfacial bonding between the sealing ring and the TPE matrix enhances the overall performance of the composite material, ensuring the stability and reliability of the sealing ring. Attached Figure Description

[0090] Figure 1 This is a schematic diagram of the preparation process of the present invention;

[0091] Figure 2 This is a schematic diagram of the tube body structure of the present invention;

[0092] Figure 3 This is a schematic diagram of the grouting hole structure of the present invention.

[0093] The components include: 1. Pipe body; 2. Grouting hole; 3. Annular groove; 4. Grouting head; 5. Sealing ring. Detailed Implementation

[0094] The following is in conjunction with the appendix Figure 1 -Appendix Figure 3 The present invention will be further described in detail below.

[0095] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0096] Example 1:

[0097] Step S1: Preparation of dual-functionalized moisture-responsive components

[0098] First functionalization treatment: Take ultrafine superabsorbent polymer particles with an average particle size of 25 micrometers and react them with the hydrophobic modifier γ-aminopropyltriethoxysilane at 80°C for 1.5 hours.

[0099] Second functionalization treatment: The microparticles that have undergone the first treatment are reacted with the swelling regulator glutaraldehyde at 60°C for 1.5 hours to obtain a moisture-responsive component with a surface that has undergone dual functionalization modification.

[0100] Step S2: Preparation of TPE composite material

[0101] Ingredients (parts by weight):

[0102] Thermoplastic elastomer matrix resin: 100 parts;

[0103] Surface-modified moisture-responsive component: 8.0 parts;

[0104] Plasticizer (naphthenic oil): 45 parts;

[0105] First antioxidant (phosphite auxiliary antioxidant 168): 0.3 parts;

[0106] Second antioxidant (hindered phenolic antioxidant 1010): 0.3 parts;

[0107] Ultraviolet light absorber (benzotriazole UV-326): 0.5 parts;

[0108] Interface modifier (polyethylene glycol octylphenyl ether): 2.75 parts.

[0109] Melt blending and granulation: Performed using a twin-screw extruder. The surface-modified moisture-responsive component is added via a downstream side feed port. The heating zones of the twin-screw extruder are set to 170°C (average range, e.g., segmented settings from 140-200°C), and the screw speed is set to 300 rpm. Granulation follows blending.

[0110] Step S3: Injection molding of the sealing ring

[0111] TPE composite material injection molding. The barrel temperature setting range is 180℃ (average range, for example, 170-195℃ segmented setting), and the mold temperature setting is 35℃.

[0112] Step S4: Preparation of the tube body

[0113] The tube body is prepared by extrusion molding. The temperature of each zone of the extruder is set to 170°C (average range, for example, segmented settings of 155-185°C). Multiple injection holes are opened on its outer peripheral wall, and at least one annular groove is formed at the location associated with the injection holes.

[0114] Step S5: Preparation of the grouting head

[0115] The injection head is prepared by injection molding. The barrel temperature is set to 180℃ (average range, for example, 170-190℃ in segments), and the mold temperature is set to 40℃.

[0116] Step S6: Assembly of the sealing ring grouting pipe

[0117] Fix the grouting head to one end of the pipe body, and then install the sealing ring in the annular groove of the pipe body.

[0118] Example 2:

[0119] Step S1: Preparation of dual-functionalized moisture-responsive components

[0120] First functionalization treatment: Take ultrafine superabsorbent polymer particles with an average particle size of 5 micrometers and react them with the hydrophobic modifier stearic acid at 60°C for 0.5 hours.

[0121] Second functionalization treatment: The microparticles that have undergone the first treatment are reacted with the swelling regulator low molecular weight polyethylene glycol diglycidyl ether at 40°C for 0.5 hours.

[0122] Step S2: Preparation of TPE composite material

[0123] Ingredients (parts by weight):

[0124] Thermoplastic elastomer matrix resin: 100 parts;

[0125] Moisture-responsive component with dual functionalization modified surface: 1.0 part;

[0126] 10 parts plasticizer (naphthenic oil);

[0127] First antioxidant (phosphite auxiliary antioxidant 168): 0.1 parts;

[0128] Second antioxidant (hindered phenolic antioxidant 1010): 0.1 parts;

[0129] Ultraviolet light absorber (benzotriazole UV-326): 0.2 parts;

[0130] Interface modifier (polyethylene glycol octylphenyl ether): 0.5 parts.

[0131] Melt blending and granulation: carried out using a twin-screw extruder with side feeding. The temperature range for each heating zone of the twin-screw extruder is set from 130°C (initial zone) to approximately 160°C, and the screw speed is set to 150 rpm.

[0132] Step S3: Injection molding of the sealing ring

[0133] The barrel temperature setting range is from 160℃ (initial stage) to approximately 170℃, and the mold temperature setting is 20℃.

[0134] Step S4: Preparation of the tube body

[0135] The tube body is manufactured by injection molding. The barrel temperature is set from 165°C (initial stage) to approximately 175°C, and the die temperature is set to 30°C. Injection holes and annular grooves are created. (If extrusion molding is used, the initial temperature setting for each zone of the extruder is 150°C.)

[0136] Step S5: Preparation of the grouting head

[0137] Injection molding. The barrel temperature is set from 165°C (initial stage) to approximately 175°C, and the mold temperature is set to 30°C.

[0138] Step S6: Assembly of the sealing ring grouting pipe

[0139] Same as Example 1.

[0140] Example 3:

[0141] Step S1: Preparation of dual-functionalized moisture-responsive components

[0142] First functionalization treatment: Take ultrafine superabsorbent polymer particles with an average particle size of 45 micrometers and react them with the hydrophobic modifier γ-aminopropyltriethoxysilane at 100°C for 2 hours.

[0143] Second functionalization treatment: The microparticles that have undergone the first treatment are reacted with the swelling regulator glutaraldehyde at 80°C for 2.5 hours.

[0144] Step S2: Preparation of TPE composite material

[0145] Ingredients (parts by weight):

[0146] Thermoplastic elastomer matrix resin: 100 parts;

[0147] Surface-modified moisture-responsive component: 15.0 parts;

[0148] Plasticizer (naphthenic oil) 80 parts;

[0149] First antioxidant (phosphite auxiliary antioxidant 168): 0.5 parts;

[0150] Second antioxidant (hindered phenolic antioxidant 1010): 0.5 parts;

[0151] Ultraviolet light absorber (benzotriazole UV-326): 0.8 parts;

[0152] Interface modifier (polyethylene glycol octylphenyl ether): 5.0 parts.

[0153] Melt blending and granulation: carried out using a twin-screw extruder with side feeding. The temperature range of each heating zone of the twin-screw extruder can be set up to 210℃ (e.g., 170-210℃ segmented setting), and the screw speed is set to 450 rpm.

[0154] Step S3: Injection molding of the sealing ring

[0155] The barrel temperature setting range can reach 205℃ (e.g., 180-205℃ segmented setting), and the mold temperature setting is 50℃.

[0156] Step S4: Preparation of the tube body

[0157] The tube body is manufactured by extrusion molding. The temperature settings in each zone of the extruder can reach 190℃. Injection holes and annular grooves are provided. (If injection molding is used, the barrel temperature can reach 195℃, and the die temperature can reach 55℃.)

[0158] Step S5: Preparation of the grouting head

[0159] Injection molding. The barrel temperature can be set up to 195℃, and the mold temperature can be set to 55℃.

[0160] Step S6: Assembly of the sealing ring grouting pipe

[0161] Same as Example 1.

[0162] Comparative Example 1:

[0163] Compared with Example 1, the difference is that in step S2, the interface modifier (polyethylene glycol octylphenyl ether) is not added to the formulation of the TPE composite material, while the rest are the same.

[0164] Comparative Example 2:

[0165] Compared with Example 1, the difference is that in the preparation of the TPE composite material in step S2, the "moisture-responsive component" used is an ultrafine superabsorbent polymer microparticle (average particle size of 25 micrometers, the same as the raw material used in step S1 of Example 1, but without the first and second functionalization treatments) that has not undergone any functionalization treatment. Its addition amount is still 8.0 parts by mass, and the rest are the same.

[0166] Comparative Example 3:

[0167] Compared with Example 1, the difference is that in the preparation of the TPE composite material in step S2, the "moisture-responsive component" used is an ultrafine superabsorbent polymer microparticle that has only undergone the first functionalization treatment (i.e., treated with γ-aminopropyltriethoxysilane at 80°C for 1.5 hours), but has not undergone the second functionalization treatment (i.e., not treated with glutaraldehyde). Its addition amount is still 8.0 parts by mass, and the rest are the same.

[0168] Comparative Example 4:

[0169] Compared with Example 1, the difference is that in the melt blending and granulation process of preparing TPE composite material in step S2, the surface-modified moisture-responsive component is added together with the thermoplastic elastomer matrix resin and other additives from the main feed port of the twin-screw extruder, instead of being added through the downstream side feed port. All other aspects are the same.

[0170] Experiment 1:

[0171] Experimental steps:

[0172] Sample preparation:

[0173] Sealing ring samples (6 mm thick, 30 mm in diameter) were prepared according to the formulations and processes of Example 1, Comparative Example 1, and Comparative Example 4.

[0174] Environmental adjustment:

[0175] All samples were placed in an environment with a temperature of 23±2℃ and a humidity of 50±5% for 24 hours to eliminate processing stress.

[0176] Hardness test:

[0177] Using a Shore A hardness tester, measurements were taken at three different locations randomly selected on the sample surface.

[0178] Each position is spaced at least 8mm apart, and the value is read after the pressure head has been in contact for 15 seconds.

[0179] A total of 9 data points were recorded for each group of 3 samples, and the mean and standard deviation were calculated.

[0180] Data Records:

[0181] Record the three measurements for each sample and the average value within the group, retaining one decimal place.

[0182] Experimental data (see Table 1):

[0183] Table 1: Hardness test results of TPE composite materials in Example 1, Comparative Example 1 and Comparative Example 4;

[0184]

[0185] The experimental data show that the sealing ring prepared in Example 1 exhibits a relatively soft and uniform hardness, indicating that the interface modifier and optimized feeding method introduced into its formulation played a key role. The interface modifier improves the compatibility between the moisture-responsive component and the TPE matrix resin, promoting the uniform dispersion of functional particles and thus mitigating the risk of localized stress concentration. Simultaneously, the downstream side-feeding method avoids prolonged high-temperature shearing of the moisture-responsive component during twin-screw extrusion, effectively protecting the integrity of its surface dual-functionalized structure. This process design not only reduces the risk of functional component degradation but also further enhances its interfacial bonding with the matrix resin, enabling the composite material to maintain overall mechanical strength while achieving more stable flexibility and elastic response.

[0186] In Comparative Example 1, because the use of interface modifiers was completely omitted, the distribution of moisture-responsive components in the TPE matrix became uneven, easily forming micro-agglomerates and leading to localized stiffness enhancement. This poor dispersion may cause an imbalance of internal stress in the material at the microscopic level, ultimately resulting in a significant increase in hardness. This also indirectly confirms the important role of interface regulation in ensuring the stability of mechanical properties.

[0187] Furthermore, Comparative Example 4, by altering the feeding method and adding the moisture-responsive component along with the main ingredient through the main feed inlet, experienced a prolonged residence time under high temperature and high shear conditions, which easily led to the destruction of some surface functionalized structures. Although it still maintained the basic formulation structure, the partial deactivation or thermal degradation of the functional components weakened its softening effect on the matrix, resulting in a slightly higher hardness value than the examples. This also reveals the sensitivity of the feeding position to the final performance control, further emphasizing the synergistic mechanism of processing technology in exerting the effect of functional components.

[0188] Experiment 2:

[0189] Experimental steps:

[0190] Sample preparation:

[0191] Sealing ring samples (6 mm thick, 30 mm in diameter) were prepared according to the formulations and processes of Example 1, Comparative Example 2, and Comparative Example 3.

[0192] Three samples were prepared for each group, for a total of nine samples.

[0193] Pre-drying treatment:

[0194] All samples were dried in a 60°C oven to constant weight (approximately 4 hours), and the initial mass was recorded. ) and volume ( ).

[0195] Immersion test:

[0196] Immerse the sample completely in deionized water (25±1℃), remove it every 24 hours, and blot the surface moisture with filter paper. Measure the mass after immersion ( ) and volume ( ), calculate the expansion rate:

[0197] Expansion rate ;

[0198] The testing period was 72 hours, and each sample was tested three times.

[0199] Data Records:

[0200] Record the expansion rate of each sample at 24h, 48h, and 72h, and retain one decimal place.

[0201] The experimental data are shown in Table 2:

[0202] Table 2: Water swelling rate test results (%) of TPE composite materials in Example 1, Comparative Example 2 and Comparative Example 3.

[0203]

[0204] The experimental results show that the TPE composite material in Example 1 exhibits moderate expansion capacity under the influence of moisture, with a stable expansion rate of approximately 45% after 72 hours and minimal fluctuations. This controlled and uniform expansion behavior stems from the dual functionalization treatment of the moisture-responsive component, which not only provides good interfacial affinity but also forms a certain cross-linked structure. This cross-linked structure, on the one hand, inhibits the excessively rapid swelling of the functional component in water, and on the other hand, enhances its distribution stability in the matrix, ensuring the predictability of the moisture response, thereby achieving stable performance release of the flexible sealing structure in an aqueous environment.

[0205] In Comparative Example 2, because the moisture-responsive component used was not functionalized, its surface lacked chemical or physical anchoring with the TPE matrix, causing the particles to rapidly absorb water and swell during immersion. Although this swelling initially responds quickly, it lacks a restraining mechanism, easily leading to local particle breakage or structural discontinuity, which may result in instability in the overall performance of the composite material. The swelling rate was significantly higher than in Example 1, indicating that the unmodified component cannot effectively synergize with the matrix, potentially leading to risks such as unsustainable sealing and structural failure in engineering applications.

[0206] In Comparative Example 3, the moisture-responsive component underwent only one functionalization treatment. Although it showed some surface activation compared to Comparative Example 2, it lacked further cross-linking stabilization steps, and its interfacial regulation ability and swelling behavior did not reach the ideal state. The experiment showed a moderate swelling rate, reflecting that single functionalization treatment improved the initial compatibility of the component to some extent, but its ability to maintain structure in an aqueous environment remained insufficient. In contrast, the dual functionalization strategy in Example 1 improved interfacial affinity and introduced a structural constraint mechanism, demonstrating the synergistic optimization effect of formulation and interfacial regulation technology, ensuring the controllability of the material's response and its safety in use.

[0207] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A grouting pipe with a sealing ring, characterized in that, include: The pipe body has at least one set of grouting holes on its outer peripheral wall, and at least one annular groove is provided on the outer peripheral position of the pipe body associated with the at least one set of grouting holes. The number of grouting holes in one set is multiple. The grouting head is fixed at one end of the pipe body, and the grouting head has a connection structure that matches the sonic logging pipe; At least one sealing ring is installed in the at least one annular groove of the tube body; The sealing ring comprises the following components in parts by weight: Thermoplastic elastomer matrix resin: 100 parts; Moisture-responsive components with dual functionalization modified on the surface: 1.0 to 15.0 parts; Plasticizer: 10 to 80 parts; First antioxidant: 0.1 to 0.5 parts; Second antioxidant: 0.1 to 0.5 parts; Ultraviolet light absorber: 0.2 to 0.8 parts; Interface modifier: 0.5 to 5.0 parts by weight; The surface-modified moisture-responsive component is cross-linked polyacrylate ultrafine superabsorbent polymer particles, and the average particle size of the ultrafine superabsorbent polymer particles is 5 to 45 micrometers. The dual functionalization modification includes: a first functionalization treatment, which involves surface treatment using a hydrophobic modifier; and a second functionalization treatment, which involves surface treatment using a swelling-regulating modifier. The hydrophobic modifier is selected from at least one of γ-aminopropyltriethoxysilane or stearic acid; the swelling control modifier is selected from at least one of glutaraldehyde or low molecular weight polyethylene glycol diglycidyl ether. The interface modifier is polyethylene glycol octylphenyl ether.

2. The grouting pipe with a sealing ring according to claim 1, characterized in that, The thermoplastic elastomer matrix resin is a styrene-ethylene-butene-styrene block copolymer.

3. A method for preparing a grouting pipe with a sealing ring, used to prepare a grouting pipe with a sealing ring as described in any one of claims 1-2, characterized in that, Includes the following steps: The ultrafine superabsorbent polymer particles, which are moisture-responsive components, are subjected to first and second functionalization treatments to obtain moisture-responsive components with dual functionalization modification on their surface. A moisture-responsive component with a surface that has undergone dual functionalization modification is melt-blended and granulated with a thermoplastic elastomer matrix resin, plasticizer, first antioxidant, second antioxidant, ultraviolet light absorber and interface modifier in a specified mass ratio to produce a TPE composite material. The TPE composite material is injection molded to obtain a sealing ring; Prepare the pipe body, open multiple grouting holes on its outer peripheral wall, and form at least one annular groove at the part associated with the grouting holes; Prepare the grouting head and fix it to one end of the pipe body; The sealing ring is installed in the annular groove of the pipe body to obtain the grouting pipe with the sealing ring.

4. The method for preparing a grouting pipe with a sealing ring according to claim 3, characterized in that, The first functionalization treatment involves reacting the ultrafine superabsorbent polymer particles with at least one hydrophobic modifier selected from γ-aminopropyltriethoxysilane or stearic acid at 60 to 100°C for 0.5 to 2 hours; the second functionalization treatment involves reacting the ultrafine superabsorbent polymer particles that have undergone the first functionalization treatment with at least one swelling-regulating modifier selected from glutaraldehyde or low molecular weight polyethylene glycol diglycidyl ether at 40 to 80°C for 0.5 to 2.5 hours.

5. The method for preparing a grouting pipe with a sealing ring according to claim 3, characterized in that, The melt blending is carried out using a twin-screw extruder, wherein the surface-modified moisture-responsive component is added through the downstream side feed port of the twin-screw extruder, the set temperature range of each heating zone of the twin-screw extruder is 130 to 210°C, and the set screw speed range is 150 to 450 rpm.

6. The method for preparing a grouting pipe with a sealing ring according to claim 3, characterized in that, The tube body is prepared by extrusion molding or injection molding, and the injection head is prepared by injection molding; the barrel temperature setting range for injection molding is 165 to 195°C, and the mold temperature setting range is 30 to 55°C; the temperature setting range for each zone of the extruder for extrusion molding is 150 to 190°C.

7. The method for preparing a grouting pipe with a sealing ring according to claim 3, characterized in that, The process parameters for injection molding of the sealing ring include: the barrel temperature setting range is 160 to 205°C, and the mold temperature setting range is 20 to 50°C.

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