Mcpp acid-terminated silane coupling agent, its preparation method and application
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- KESHUN WATERPROOF TECH CO LTD
- Filing Date
- 2025-09-28
- Publication Date
- 2026-06-02
Smart Images
Figure CN121342861B_ABST
Abstract
Description
Technical Field
[0001] This application relates to the field of waterproof membrane technology, specifically to an MCPP acid-terminated silane coupling agent, its preparation method, and its application. Background Technology
[0002] Waterproof membranes are mainly used in building walls, roofs, tunnels, highways, landfills, etc. They are flexible building materials that can be rolled up to prevent the seepage of external rainwater and groundwater. As a leak-proof connection between the foundation of the project and the building, they are the first line of defense for waterproofing the entire project and play a vital role in the overall project.
[0003] During use, waterproof membranes are often prone to damage, insufficient strength, and poor adhesion due to punctures by plant roots. Therefore, in addition to good waterproofing performance, waterproof membranes should also have good root-blocking properties.
[0004] MCPP acid (2-methyl-4-chlorophenoxypropionic acid) is a very stable herbicide. It can be added to waterproof membranes in various ways, such as mixing it into modified bitumen layers or coatings as a root-blocking material applied to the surface of the waterproof layer, thereby inhibiting plant root growth and reducing the invasion and damage of plant roots to the membrane. However, as a small molecule, it has poor compatibility in modified bitumen or root-blocking material systems, which may lead to uneven dispersion of the root-blocking agent and affect its root-blocking effect. Furthermore, heating during construction and high-temperature stirring during production can damage the root-blocking agent. In addition, the durability and stability of the root-blocking agent may be affected by environmental factors (such as rainwater erosion), causing its root-blocking effect to weaken over time. Therefore, current technologies make it difficult to achieve a long-lasting root-blocking effect by directly adding it to modified bitumen layers or coatings.
[0005] Therefore, there is a need to provide a root-blocking agent that can provide a long-lasting root-blocking effect. Summary of the Invention
[0006] This application provides an MCPP acid-terminated silane coupling agent, its preparation method, and its application. The MCPP acid-terminated silane coupling agent can be used as a root inhibitor for any surface requiring root inhibition, and has a long-lasting root inhibition effect.
[0007] In a first aspect, this application provides an MCPP acid-terminated silane coupling agent having a structure as shown in Formula I:
[0008] Formula I,
[0009] Wherein, R1 represents a substituted or unsubstituted C2-C8 alkylene group, R2 represents a substituted or unsubstituted C8-C18 alkylene group, R3 and R4 independently represent one of alkyl and alkylacyl groups, and R5 represents one of alkyl, alkoxy and alkylacyloxy groups.
[0010] According to this application, the structure of the MCPP acid-terminated silane coupling agent consists of an MCPP acid with good root-blocking effect at one end and a silane group with good reactivity at the other end. The silane group can be hydrolyzed to form silanol, which then undergoes a coupling reaction with the material and is bonded through chemical bonds, thereby fixing the MCPP acid with good root-blocking effect to the material surface. This effectively reduces the dissolution and loss of MCPP acid during use, thus achieving a long-lasting root-blocking effect.
[0011] In some embodiments, R2 represents an unsubstituted C8-C18 alkylene group.
[0012] In some embodiments, R2 represents a substituted C8-C18 alkylene group, and the substituent includes at least one of amino, carboxyl, methoxy, and ethoxy groups.
[0013] Secondly, this application provides a method for preparing MCPP acid-terminated silane coupling agents, comprising the following steps:
[0014] S10: MCPP acid is esterified with C8~C18 enol to obtain MCPP acid with grafted alkenyl groups;
[0015] S20: The grafted alkenyl MCPP acid is reacted with a thiol-alkene click reaction to obtain an MCPP acid-terminated silane coupling agent.
[0016] In some implementations, S10 specifically includes:
[0017] C8-C18 enols and MCPP acids in a molar ratio of 1:(1.05~1.5) are mixed evenly. Under a nitrogen atmosphere, heating conditions, and catalysis by concentrated sulfuric acid, the carboxyl groups in the MCPP acids undergo an esterification reaction with the hydroxyl groups in the C8-C18 enols to obtain MCPP acids with grafted alkenyl groups.
[0018] In some implementations, S20 specifically includes:
[0019] A MCPP acid grafted with alkenyl groups in a molar ratio of 1:(1.05~1.5) is mixed with a silane coupling agent containing mercapto groups. Under the catalysis of triethylamine, the alkenyl groups in the grafted alkenyl MCPP acid and the mercapto groups in the silane coupling agent containing mercapto groups undergo a mercapto-alkene click reaction to obtain an MCPP acid-terminated silane coupling agent.
[0020] Thirdly, this application provides the application of the MCPP acid-terminated silane coupling agent according to any embodiment of the first aspect or the MCPP acid-terminated silane coupling agent prepared by the method according to any embodiment of the second aspect as a root inhibitor in the preparation of waterproof materials.
[0021] Fourthly, this application provides a root-barrier material, including the MCPP acid-terminated silane coupling agent according to any embodiment of the first aspect or the MCPP acid-terminated silane coupling agent prepared by the method according to any embodiment of the second aspect.
[0022] In some embodiments, the MCPP acid-terminated silane coupling agent has a mass percentage content of 0.1% to 10% in the waterproof material.
[0023] Fifthly, this application provides a root-penetration-resistant waterproof material, comprising a substrate and a coating formed of a root-barrier material according to any embodiment of the fourth aspect, disposed on the surface of the substrate. Detailed Implementation
[0024] The various embodiments or implementation schemes in this specification are described in a progressive manner, with each embodiment focusing on the differences from other embodiments.
[0025] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "illustrative embodiment," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with an embodiment or example is included in at least one embodiment or example of this application. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.
[0026] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of that feature. In the description of this application, "multiple" means at least two, such as two, three, etc., unless otherwise explicitly specified.
[0027] As described in the background section above, waterproof membranes may be damaged by plant roots during use, rendering them ineffective at preventing waterproofing. Therefore, root inhibitors can be added to the modified bitumen of the waterproof membrane or to the root-inhibiting material to mitigate plant root intrusion. However, commonly used root inhibitors, such as MCPP acid, have a small molecular weight and poor compatibility in the system, potentially leading to uneven dispersion and affecting their root-inhibiting effect. Furthermore, heating during construction and high-temperature stirring during production of modified bitumen waterproof membranes can damage the root inhibitor structure, significantly impacting its effectiveness. Additionally, MCPP acid is prone to leaching from the adhesive or coating layer, failing to provide a long-lasting root-inhibiting effect.
[0028] Therefore, related technologies involve modifying MCPP acid, for example, by reacting the carboxyl groups on MCPP acid with the hydroxyl groups on the polyether end groups to graft longer polyether segments, thereby improving its compatibility in root-blocking materials. Simultaneously, a higher molecular weight also slows down its dissolution rate, thus prolonging its root-blocking effect. However, the problem is that slowing down the dissolution rate by increasing molecular weight and chain length is limited; the root-blocking agent will still dissolve and be lost during use, making it difficult to achieve a long-lasting root-blocking effect. On the other hand, root-blocking agents confined within the coating cannot directly contact plant roots, resulting in a poor root-blocking effect, while those migrating to the surface are also prone to loss, making it difficult to simultaneously achieve both root-blocking effectiveness and long-lasting effect.
[0029] Based on this, this application provides an MCPP acid-terminated silane coupling agent, in which the silane at the end group can be fixed to the material surface by chemical bonds, effectively reducing the loss of root inhibitors and thus achieving a long-lasting root-inhibiting effect. The specific embodiments provided in this application are described in detail below.
[0030] In a first aspect, this application provides an MCPP acid-terminated silane coupling agent having a structure as shown in Formula I:
[0031] Formula I,
[0032] Wherein, R1 represents a substituted or unsubstituted C2-C8 alkylene group, R2 represents a substituted or unsubstituted C8-C18 alkylene group, R3 and R4 independently represent one of alkyl and alkylacyl groups, and R5 represents one of alkyl, alkoxy and alkylacyloxy groups.
[0033] According to this application, the structure of the MCPP acid-terminated silane coupling agent consists of an MCPP acid with good root-blocking effect at one end and a silane group with good reactivity at the other end. The silane group can be hydrolyzed to form silanol, which then undergoes a coupling reaction with the material and is bonded through chemical bonds, thereby fixing the MCPP acid with good root-blocking effect to the material surface. This effectively reduces the dissolution and loss of MCPP acid during use, thus achieving a long-lasting root-blocking effect.
[0034] Specifically, R1 represents substituted or unsubstituted C2~C8 alkylene groups, and R2 represents substituted or unsubstituted C8~C18 alkylene groups. An appropriate carbon chain length is beneficial to ensure the root-barrier effect of the terminal MCPP acid and the coupling effect of the silane group. At the same time, R1 and R2 can also affect the polarity of the MCPP acid-terminated silane coupling agent. They can be adjusted according to actual needs to obtain MCPP acid-terminated silane coupling agents suitable for different systems.
[0035] In some alternative embodiments, R3 and R4 independently represent one of methyl, ethyl, and acetyl groups, and R5 represents one of methyl, ethyl, methoxy, ethoxy, and acetoxy groups.
[0036] R3 and R4 independently represent one of methyl, ethyl, and acetyl groups. In this case, the silanoxy group is more likely to undergo hydrolysis to form silanol, thereby undergoing coupling reactions with other materials and making the MCPP acid more stably fixed to the target system. It is understood that the siloxane group has at least two hydrolyzable branches, thus enabling stable fixation to the material surface; when it contains three hydrolyzable branches, the fixation effect is even better, making it less likely for the root-barrier MCPP acid to be lost. Therefore, R5 can represent one of methyl, ethyl, methoxy, ethoxy, and acetyloxy groups.
[0037] It is worth noting that the MCPP acid-terminated silane coupling agent provided in this application can not only be used as an additive in waterproof materials, but also directly applied to the surface of waterproof materials or substrates. It is directly fixed to the target material surface through a coupling reaction with silane groups. Compared to root inhibitors fixed inside the waterproof material, surface-grafted MCPP acid can better exert its root-blocking effect. Furthermore, because it is directly fixed through chemical bonds, the surface root inhibitor is also less prone to loss, thus achieving a good balance between root-blocking ability and long-lasting effect. In addition, when used as an additive in waterproof materials, since inorganic fillers are generally added to waterproof materials, this MCPP acid-terminated silane coupling agent can also be fixed on the surface of the inorganic fillers in the waterproof material. The MCPP acid can be evenly distributed in the waterproof material, so even if part of the waterproof material surface is damaged, the waterproof material still has a good barrier effect, and the MCPP acid-terminated silane coupling agent is not easily lost, achieving long-lasting root-blocking ability.
[0038] It is worth noting that, for waterproof membranes, applying the MCPP acid-terminated silane coupling agent provided in this application directly to the surface requiring root inhibition may be more flexible and have a better root inhibition effect than adding it as an additive to the waterproof material, especially at the overlap of the membrane.
[0039] It should also be noted that, in the context of this application, alkylene includes straight-chain and branched alkylene, and the substituents of the compounds are disclosed by groups or ranges, and such description is expressly intended to include every individual subcombination of members of these groups and ranges. For example, the term "C1-C8 alkylene" is explicitly intended to separately disclose C1, C2, C3, C4, C5, C6, C7, C8, C1-C8, C1-C7, C1-C6, C1-C5, C1-C4, C1-C3, C1-C2, C2-C8, C2-C7, C2-C6, C2-C5, C2-C4, C2-C3, C3-C8, C3-C7, C3-C6, C3-C5, C3-C4, C4-C8, C4-C7, C4-C6, C4-C5, C5-C8, C5-C7, C5-C6, C6-C8, C6-C7, and C7-C8 alkylene.
[0040] In some embodiments, R2 represents an unsubstituted C8-C18 alkylene group.
[0041] In some of the above embodiments, R2 represents an unsubstituted C8~C18 alkylene group. In this case, the segments in the MCPP acid-terminated silane coupling agent are mainly non-polar alkylene segments. Therefore, this silane coupling agent is more suitable for non-polar waterproofing materials, such as bitumen-based waterproof coatings, and has better compatibility. Thus, while improving the root barrier effect, it will not significantly affect other properties of non-polar waterproof coatings.
[0042] In some embodiments, R2 represents a substituted C8-C18 alkylene group, and the substituent includes at least one of amino, carboxyl, methoxy, and ethoxy groups.
[0043] In some of the above embodiments, R2 may also represent a substituted C8-C18 alkylene group. The substituent may include at least one of amino, carboxyl, methoxy, and ethoxy groups with a certain degree of polarity. In this case, the MCPP acid-terminated silane coupling agent obtained has a certain degree of polarity. Therefore, the silane coupling agent is more suitable for waterproof materials in polar systems, such as polyurethane waterproof coatings, and has better compatibility. Thus, while improving the root-barrier effect, it will not significantly affect other properties of non-polar waterproof coatings.
[0044] Secondly, this application provides a method for preparing MCPP acid-terminated silane coupling agents, comprising the following steps:
[0045] S10: MCPP acid is esterified with C8~C18 enol to obtain MCPP acid with grafted alkenyl groups;
[0046] S20: The MCPP acid grafted with alkenyl groups undergoes a mercapto-alkene click reaction with a silane coupling agent containing mercapto groups to obtain an MCPP acid-terminated silane coupling agent.
[0047] According to this application, an MCPP acid-terminated silane coupling agent is obtained by first undergoing an esterification reaction with C8-C18 enols to graft alkenes onto the MCPP acid, and then reacting it with a silane coupling agent containing thiols via a thiol-alkene click reaction to graft the silane coupling agent onto the MCPP acid. One end of this MCPP acid-terminated silane coupling agent is an MCPP acid with good root-barrier properties, and the other end is a silaneoxy group with good reactivity. The silaneoxy group can be hydrolyzed to form silanols, which then undergo a coupling reaction with the material and bond through chemical bonds. This fixes the MCPP acid with good root-barrier properties to the material surface, effectively reducing the dissolution and loss of MCPP acid during use, thus achieving a long-lasting root-barrier effect.
[0048] In some embodiments, the MCPP acid-terminated silane coupling agent has the structure of the MCPP acid-terminated silane coupling agent in any embodiment of the first aspect. This method can obtain a structure having the structure of the MCPP acid-terminated silane coupling agent according to any embodiment of the first aspect, and therefore has the beneficial effects of the first aspect, which will not be repeated here.
[0049] Additionally, it can be understood that R2 in Formula I can be adjusted by using different C8~C18 enols, and R2, R3, R4, and R5 can be adjusted by using different silane coupling agents containing mercapto groups, thereby obtaining MCPP acid-terminated silane coupling agents with different structures.
[0050] As an example, MCPP acid is esterified with octadecenol to obtain alkenyl-grafted MCPP acid, as shown in Formula II:
[0051] Formula II
[0052] Wherein, R represents a straight-chain heptadecanyl group.
[0053] The MCPP acid grafted with alkenyl groups then undergoes a mercapto-alkene click reaction with KH590 to obtain an MCPP acid-terminated silane coupling agent, as shown in Formula III:
[0054] Formula III
[0055] Wherein, R represents a straight-chain pineneheptadecyl, and R' represents a straight-chain heptadecylene.
[0056] In some implementations, S10 specifically includes:
[0057] C8-C18 enols and MCPP acids in a molar ratio of 1:(1.05~1.5) are mixed evenly. Under a nitrogen atmosphere, heating conditions, and catalysis by concentrated sulfuric acid, the carboxyl groups in the MCPP acids undergo an esterification reaction with the hydroxyl groups in the C8-C18 enols to obtain MCPP acids with grafted alkenyl groups.
[0058] In the above steps, the heating temperature is 120 to 160 degrees Celsius.
[0059] In some of the above embodiments, specific conditions for the reaction of MCPP acid with C8-C18 enols are defined. An appropriate excess of MCPP acid can promote the forward esterification reaction, increasing the yield of the grafted alkenyl MCPP acid. Simultaneously, excess MCPP acid is easily removed by alkaline washing, improving the purity of the grafted alkenyl MCPP acid. Alternatively, an EDC-DMAP system (containing 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and 4-dimethylaminopyridine) can be used to react C8-C18 enols with MCPP acid at room temperature. After either of these reactions, the product, the grafted alkenyl MCPP acid, needs to be separated by column chromatography to remove impurities that may affect subsequent reactions.
[0060] In some embodiments, S20 specifically includes: mixing a grafted alkenyl MCPP acid and a thiol-containing silane coupling agent in a molar ratio of 1:(1.05~1.3), and, under the catalysis of triethylamine, causing the alkenyl group in the grafted alkenyl MCPP acid to undergo a thiol-alkene click reaction with the thiol group in the thiol-containing silane coupling agent to obtain an MCPP acid-terminated silane coupling agent. Furthermore, the grafted alkenyl MCPP acid and the thiol-containing silane coupling agent can be reacted directly using a solvent-free system, or by mixing with low-polarity organic solvents such as dichloromethane or trichloromethane.
[0061] In some of the above embodiments, the specific conditions for the reaction between the grafted alkenyl MCPP acid and the silane coupling agent containing mercapto groups are specifically defined. An appropriate excess of the silane coupling agent containing mercapto groups can allow the grafted alkenyl MCPP acid to react fully, thereby increasing the yield of the MCPP acid-terminated silane coupling agent.
[0062] Thirdly, this application provides the application of MCPP acid-terminated silane coupling agent prepared according to any embodiment of the first aspect or the method prepared according to any embodiment of the second aspect as a long-lasting root inhibitor in the preparation of root-penetration resistant waterproof materials.
[0063] According to this application, the MCPP acid-terminated silane coupling agent prepared according to any embodiment of the first aspect or the method prepared according to any embodiment of the second aspect can fix MCPP acid in or on the surface of waterproof materials through chemical bonds. Therefore, when used as a root inhibitor in waterproof materials, it can play a long-lasting root-inhibiting role.
[0064] When MCPP acid-terminated silane coupling agent is applied directly to the surface requiring root inhibition, it can be applied by brushing or spraying, with the dosage controlled between 1 and 50 g of root inhibitor per square meter. Both brushing and spraying can be diluted. If spraying is chosen, it can be diluted with solvent before being sprayed onto the material surface, with the spraying dosage controlled between 5 and 250 g per square meter.
[0065] Fourthly, this application provides a root-barrier material, comprising an MCPP acid-terminated silane coupling agent according to any embodiment of the first aspect or an MCPP acid-terminated silane coupling agent prepared by a method according to any embodiment of the second aspect. This improves the root penetration resistance of the waterproof material.
[0066] In some embodiments, the waterproofing material includes asphalt, resin, mineral oil, filler, and other functional additives to obtain a root-barrier material with root-barrier effect, which can form a waterproof layer with long-lasting root-barrier effect.
[0067] In some embodiments, the waterproofing material includes polyurethane prepolymer, fillers, and other functional additives to obtain a waterproofing material with root-barrier effect, which can form a waterproofing layer with long-lasting root-barrier effect.
[0068] In some embodiments, the MCPP acid-terminated silane coupling agent has a mass percentage content of 0.1% to 10% in the waterproof material. Preferably, the MCPP acid-terminated silane coupling agent has a mass percentage content of 0.1% to 5% in the waterproof material.
[0069] In some of the above embodiments, the mass percentage content of MCPP acid-terminated silane coupling agent in the waterproofing material is specifically defined. It is understood that MCPP acid-terminated silane coupling agent can be used as an additive in waterproofing materials or as a main component in root-barrier materials; therefore, its mass percentage content can be selected according to actual needs. When used as an additive, its dosage can be appropriately reduced to avoid affecting the performance of the waterproofing material; when used as a main component, its mass percentage content in the root-barrier material can be appropriately increased to achieve a better root-barrier effect.
[0070] Fifthly, this application provides a root-penetration-resistant waterproof material, comprising a substrate and a coating formed of a root-barrier material according to any embodiment of the fourth aspect, disposed on the surface of the substrate.
[0071] According to this application, since the membrane includes a waterproof layer formed from the waterproof material according to any embodiment of the fourth aspect, it has the beneficial effects of the fourth aspect. Because the waterproof layer has a good root-blocking effect, it is not easily damaged by plant roots, thus effectively improving the service life of the waterproof layer. The substrate can be an organic substrate or an inorganic substrate. Organic substrates can be polymer waterproof membranes, asphalt waterproof membranes, waterproof coatings, etc. Inorganic substrates can be metal materials, such as steel / aluminum substrates, etc.
[0072] The following describes embodiments of this application. The embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments used, unless otherwise specified, are all conventional products that can be obtained commercially.
[0073] Example 1
[0074] Preparation of MCPP acid-terminated silane coupling agent:
[0075] S10, octadecenol and 2-methyl-4-chlorophenoxypropionic acid were reacted in a molar ratio of 1:1.05 under a nitrogen atmosphere and catalyzed by concentrated sulfuric acid (2% of the mass of MCPP acid). The mixture was stirred at 120°C, with nitrogen continuously introduced to remove the water produced during the reaction. After 3 hours of reaction, the carboxyl group in 2-methyl-4-chlorophenoxypropionic acid and the hydroxyl group in octadecenol underwent an esterification reaction to obtain MCPP acid with grafted alkenyl groups.
[0076] S20: Grafted alkenyl MCPP acid and KH590 in a molar ratio of 1:1.05 are dissolved in ethanol. Under the catalysis of triethylamine, the mass of triethylamine added is 2% of the mass of the grafted alkenyl MCPP acid. The mixture is stirred at 65°C for 0.5 h to allow the alkenyl group in the grafted alkenyl MCPP acid to undergo a mercapto-alkene click reaction with the mercapto group of KH590, thus obtaining an MCPP acid-terminated silane coupling agent. KH590, also known as 3-mercaptopropyltriethoxysilane, is a typical silane coupling agent containing a mercapto group (-SH).
[0077] Example 2
[0078] The difference between this embodiment and Example 1 is that the raw materials used in S10 are different. Octadectenyl alcohol and 2-methyl-4-chlorophenoxypropionic acid are reacted in a nitrogen atmosphere at a molar ratio of 1:1.5.
[0079] Example 3
[0080] The difference between this embodiment and Embodiment 1 is that the molar ratio of the raw materials used in S10 is different. The grafted alkenyl MCPP acid and KH590 with a molar ratio of 1:1.3 are dissolved in ethanol.
[0081] Example 4
[0082] The difference between this embodiment and Embodiment 1 is that the raw materials used in S10 are different, with hexadeceneol being replaced by an equimolar amount.
[0083] Example 5
[0084] The difference between this embodiment and Embodiment 1 is that the raw materials used in S10 are different, with dodecenol being used in an equal molar amount to replace octadecenol.
[0085] Example 6
[0086] The difference between this embodiment and embodiment 1 is that the raw materials used in S10 are different, with KH590 replaced by an equal molar amount of KH580.
[0087] Example 7
[0088] The difference between this embodiment and Embodiment 1 is that the raw materials used in S10 are different, with KH590 replaced by an equal molar amount of 3-mercaptopropylmethyldimethoxysilane.
[0089] Comparative Example 1
[0090] The difference between this comparative example and Example 1 is that the raw materials used in S10 are different, with allyl alcohol being used in an equal molar amount to replace octadecenol.
[0091] Comparative Example 2
[0092] The silane coupling agent provided in this comparative example is: the grafted alkenyl MCPP acid obtained in Example 1 mixed with an equal amount of KH590.
[0093] Comparative Example 3
[0094] The comparative example provided is PREVENTOL, a polymer-based root inhibitor manufactured by Lanxess AG, Germany. ® B2.
[0095] Application 1
[0096] The silane coupling agents (root inhibitors) obtained in Examples 1-7 or Comparative Examples 1-3 were subjected to root-inhibiting effect tests, including: mixing the final silane coupling agent from the examples or comparative examples with acetonitrile to prepare root-inhibiting agent solutions of the same concentration (20% by mass). Root penetration resistance tests were conducted according to Appendix A of GB / T 35468-2017, using Keshun 3mm APF-500 self-adhesive polymer-modified bitumen waterproof membrane (non-root-inhibiting type). After laying the membrane sample, the surface release film was removed, and the entire surface was sprayed with the root-inhibiting agent solution. After drying, planting soil was evenly placed on top.
[0097] Root inhibitor loss rate: The above 2-year test period was used as the test period. The root inhibitor content of the root barrier layer was tested before and after the test. According to the industry standard T / CBMF 49 / T / CWA301—2019 "Test method for root inhibitor content of bitumen-based root-penetration resistant waterproof membrane", the root inhibitor loss rate = (root inhibitor content before test - root inhibitor content after test) / root inhibitor content before test.
[0098] Water impermeability of the membrane after root barrier test: The test period is 2 years. After the test, the water impermeability of the membrane is tested according to Method B in GB / T 328.10—2007. A seven-hole sheet is used, the test pressure is 0.3 MPa, and the test time is 2 hours.
[0099] The test results are shown in Table 1.
[0100] Table 1
[0101]
[0102] As shown in Table 1, the MCPP acid-terminated silane coupling agent in the examples has an MCPP acid with good root-blocking effect at one end and a silane oxygen group with good reactivity at the other end. The silane oxygen group can be hydrolyzed to form silanol, which then undergoes a coupling reaction with the material and bonds through chemical bonds, thereby fixing the MCPP acid with good root-blocking effect to the material surface. This effectively reduces the dissolution and loss of MCPP acid during use, thus achieving a long-lasting root-blocking effect. In contrast, the coupling agent in the comparative example does not have the end groups of the examples, such as MCPP acid or silane oxygen, resulting in a higher root-blocking agent loss rate and a poorer root-blocking effect.
[0103] Application 2
[0104] The silane coupling agent / root inhibitors of Example 1 and Comparative Example 3 were added to the asphalt waterproof membrane coating for root inhibition testing:
[0105] The silane coupling agent / root inhibitor was added at 0.5% of the total mass of the coating formulation. The coating formulation was prepared according to the following parts by mass: 48 parts of 70# asphalt, 6 parts of SBS, 8 parts of naphthenic oil, 37.5 parts of calcium carbonate filler, and 0.5 parts of the silane coupling agent / root inhibitor from Example 1 or Comparative Example 3; the base material used was 250 g / cm³. 3 The polyester-based waterproof membrane has a thickness of 3mm.
[0106] The obtained bitumen waterproof membrane was used as a root-penetration resistant waterproof material. Root-penetration resistance performance tests were conducted according to Appendix A of GB / T 35468-2017.
[0107] The method for testing the root inhibitor loss rate is the same as in Application 1.
[0108] The method for testing the impermeability of the membrane after the root barrier test is the same as in Application 1.
[0109] Table 2
[0110]
[0111] As shown in Table 2, the MCPP acid-terminated silane coupling agent in the embodiments, when applied to the surface of the asphalt waterproof membrane, can further reduce the root inhibitor loss rate, improve the stability of the asphalt waterproof membrane, and maintain the asphalt waterproof membrane's impermeability.
[0112] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.
Claims
1. An MCPP acid-terminated silane coupling agent, characterized in that, It has a structure as shown in Equation I: Equation I, Wherein, R1 represents an unsubstituted C2-C8 alkylene group, R2 represents an unsubstituted C8-C18 alkylene group, R3 and R4 independently represent one of methyl and ethyl; and R5 represents one of methyl, ethyl, methoxy, and ethoxy.
2. A method for preparing the MCPP acid-terminated silane coupling agent of claim 1, characterized in that, Includes the following steps: S10: MCPP acid is esterified with C8~C18 enol to obtain MCPP acid with grafted alkenyl groups; S20: The grafted alkenyl MCPP acid is reacted with a thiol-alkene click reaction to obtain an MCPP acid-terminated silane coupling agent.
3. The method according to claim 2, characterized in that, S10 specifically includes: C8-C18 enols and MCPP acids in a molar ratio of 1:(1.05~1.5) are mixed evenly. Under an inert gas atmosphere, heating conditions, and catalysis by a first catalyst, the carboxyl groups in the MCPP acids undergo an esterification reaction with the hydroxyl groups in the C8-C18 enols to obtain MCPP acids with grafted alkenyl groups.
4. The method according to claim 3, characterized in that, S20 specifically includes: A MCPP acid grafted with alkenyl groups in a molar ratio of 1:(1.05~1.5) is mixed with a silane coupling agent containing mercapto groups. Under the catalysis of a second catalyst, the alkenyl groups in the MCPP acid grafted with alkenyl groups undergo a mercapto-alkene click reaction with the mercapto groups in the silane coupling agent containing mercapto groups to obtain an MCPP acid-terminated silane coupling agent.
5. The application of the MCPP acid-terminated silane coupling agent according to claim 1 or the MCPP acid-terminated silane coupling agent prepared by the method according to any one of claims 2 to 4 in the preparation of root inhibitors for waterproof materials.
6. A root-barrier material, characterized in that, Includes the MCPP acid-terminated silane coupling agent according to claim 1 or the MCPP acid-terminated silane coupling agent prepared by the method according to any one of claims 2 to 4.
7. The root-barrier material according to claim 6, characterized in that, The MCPP acid-terminated silane coupling agent has a mass percentage content of 0.1% to 10% in the waterproof material.
8. A root-penetration-resistant waterproof material, characterized in that, It includes a substrate and a coating formed of the root-barrier material according to claim 6 or 7 disposed on the surface of the substrate.