Root inhibitor modified filler, butyl pressure-sensitive adhesive, preparation method and application

Abstract

The invention belongs to the field of pressure-sensitive adhesives, and discloses a root inhibitor modified filler, a butyl pressure-sensitive adhesive, and a preparation method and application of the butyl pressure-sensitive adhesive. The root inhibitor modified filler is prepared by stirring a layered double hydroxide composition and a root inhibitor in the presence of a solvent; the chemical structural formula of the layered double hydroxide composition is # imgabs0 #, wherein M < 2 + > is at least one of Mg < 2 + >, Zn < 2 + >, Ni < 2 + >, Co < 2 + > and Mn < 2 + >; m < 3 + > is at least one of Al < 3 + >, Ga < 3 + >, Fe < 3 + > and Mn < 3 + >; an <-> is at least one of F <->, CO3 < 2->, Cl <->, SO4 < 2-> and organic acid ions; x ranges from 0.2 to 0.4, and the root inhibitor is a micromolecular chemical root inhibitor. According to the invention, a novel powder material is introduced and is modified by using the root inhibitor, so that the obtained root inhibitor modified filler not only has a better dispersion condition in the butyl pressure-sensitive adhesive, but also has the performance of slowly releasing the root inhibitor.

Description

Technical Field

[0001] The invention belongs to the field of pressure-sensitive adhesives (PSA), and more specifically, relates to a root inhibitor-modified filler and a butyl pressure-sensitive adhesive, and a preparation method and application thereof. Background Art

[0002] Root-penetration-resistant polymer self-adhesive waterproofing membranes (HDPE, TPO, etc.) are widely used in the waterproofing layer of planting top plates and planting roofs. Polymer sheets such as HDPE and TPO have excellent puncture resistance and therefore have a physical root barrier effect. However, the joint area of ​​this type of physical root barrier polymer self-adhesive membrane is a weak point. At present, hot air welding is generally used in the overlap area to ensure sufficient joint integrity and joint strength. Hot air welding construction requires a high level of professionalism from construction equipment and personnel. Relatively speaking, self-adhesive overlap of the overlap area using a pressure-sensitive adhesive is a more efficient and simple construction method. Adding a chemical root barrier to the pressure-sensitive adhesive can make the polymer self-adhesive membrane have both physical and chemical root barrier functions, improve the reliability of root barrier, and greatly improve the convenience of construction.

[0003] At present, the commonly used chemical root inhibitors on the market include metal powders and small molecule ester chemical root inhibitors. CN215435397U introduces a copper powder conductive adhesive, in which the copper powder contained in the copper powder conductive adhesive will generate basic copper carbonate to play a root inhibitor role in the presence of roots. CN117511408A introduces a rubber asphalt waterproof coating, which uses a 2-(4-chloro-2-methylphenoxy) propionic acid small molecule mono / diester chemical root inhibitor, which will chemically bond with other components in the coating to play a root inhibitor role.

[0004] Both metal powder and small molecule ester chemical root inhibitors have poor compatibility with the commonly used butyl pressure-sensitive adhesive system, resulting in poor dispersion uniformity of the root inhibitor components in the adhesive. At the same time, the use of chemical root inhibitors also needs to be considered in dosage. Excessive dosage will cause toxic risks to plants and soil, while too little dosage will not have a puncture-resistant effect.

[0005] Therefore, it is urgent to propose a new type of root inhibitor modified filler and apply it to butyl pressure-sensitive adhesive, so as to finally obtain a butyl pressure-sensitive adhesive with high bonding peel strength, root penetration resistance and environmental friendliness. Summary of the invention

[0006] The purpose of the present invention is to address the deficiencies of the prior art and to provide a root inhibitor modified filler and a butyl pressure-sensitive adhesive as well as a preparation method and application. The present invention introduces a new type of powder and uses a root inhibitor to modify it. The obtained root inhibitor modified filler not only has a good dispersion in the butyl pressure-sensitive adhesive, but also has the performance of slow-release root inhibitor.

[0007] In order to achieve the above-mentioned object, the first aspect of the present invention provides a root inhibitor modified filler, wherein the root inhibitor modified filler is prepared by stirring a layered double hydroxide composition and a root inhibitor under solvent conditions;

[0008] The chemical structural formula of the layered double hydroxide composition is shown in formula (1):

[0009]

[0010] In the formula (1):

[0011] M 2+ Mg 2+ 、Zn 2+ 、Ni 2+ 、Co 2+ and Mn 2+ At least one of;

[0012] M 3+ For Al 3+ , Ga 3+ , Fe 3+ and Mn 3+ At least one of;

[0013] A n- F - 、CO3 2- , Cl - 、SO4 2- and at least one of an organic acid ion (whereby n is the charge number of the selected anion);

[0014] The value of x ranges from 0.2 to 0.4; m is the content of crystalline water carried in the layered double hydroxide composition, and the amount of crystalline water contained is controlled by the synthesis process of the layered double hydroxide composition;

[0015] The root inhibitor is a small molecule chemical root inhibitor.

[0016] According to the present invention, preferably, the mass ratio of the layered double hydroxide composition to the root inhibitor is (60-80):(20-40).

[0017] According to the present invention, preferably, the root inhibitor is a phenoxycarboxylic acid root inhibitor, preferably, the root inhibitor is at least one of 2-methyl-4-chlorophenoxypropionic acid (MCPP), 2-methyl-4-chlorophenoxyacetic acid (MCPA), 2,4-dichlorophenoxyacetic acid (2,4-D) and 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB).

[0018] According to the present invention, preferably, the solvent is at least one of methanol, ethanol and deionized water.

[0019] According to the present invention, preferably, the preparation method of the root inhibitor modified filler comprises:

[0020] 1) mixing the layered double hydroxide composition with a solvent to obtain a first suspension;

[0021] 2) mixing the root inhibitor with a solvent to obtain a second suspension;

[0022] 3) mixing the second suspension with the first suspension and stirring to obtain a mixed suspension; centrifugally washing, drying and grinding the mixed suspension to obtain the root inhibitor modified filler.

[0023] According to the present invention, preferably, in the step 1), the ratio of the layered double hydroxide composition to the solvent is (5-45): (300-400) g / mL.

[0024] According to the present invention, preferably, in the step 2), the mass fraction of the root inhibitor in the second suspension is 15-35%.

[0025] According to the present invention, preferably, in said step 3):

[0026] The stirring time is 45-90 min, preferably 60-75 min;

[0027] The speed of centrifugal washing is 1500-3000 rpm, and the washing solvent used in the centrifugal washing is at least one of methanol, ethanol and acetone;

[0028] The drying temperature should be 40-50℃.

[0029] The second aspect of the present invention provides a butyl pressure-sensitive adhesive, wherein the butyl pressure-sensitive adhesive comprises the root inhibitor modified filler.

[0030] According to the present invention, preferably, the butyl pressure-sensitive adhesive comprises the following components in parts by weight: 10-40 parts of butyl rubber component, 20-40 parts of plasticizer, 10-30 parts of hydrogenated tackifying resin, 0-3 parts of antioxidant, 10-50 parts of inorganic filler and 2-6 parts of the root inhibitor modified filler.

[0031] According to the present invention, preferably, the Mooney viscosity ML (1+8) of the butyl rubber component at 125°C is between 20 and 60.

[0032] According to the present invention, preferably, the plasticizer is a low molecular weight polyisobutylene rubber and / or naphthenic oil having a number average molecular weight of 400-2400 g / mol.

[0033] In the present invention, the low molecular weight polyisobutylene rubber has good compatibility with the butyl rubber component.

[0034] According to the present invention, preferably, the hydrogenated tackifying resin is selected from at least one of hydrogenated C5 resin, aromatic modified hydrogenated C5 resin, hydrogenated C9 resin, hydrogenated dicyclopentadiene resin, aromatic modified hydrogenated dicyclopentadiene resin and α-methylstyrene pure monomer resin; the hydrogenation degree of the hydrogenated tackifying resin is above 90%, and the softening point is 80°C-140°C.

[0035] According to the present invention, preferably, the antioxidant is at least one of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tris[2,4-di-tert-butylphenyl]phosphite and n-octadecylβ-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

[0036] According to the present invention, preferably, the inorganic filler is selected from at least one of calcium carbonate powder, talc powder, kaolin, mica powder and titanium dioxide.

[0037] The third aspect of the present invention provides a method for preparing the butyl pressure-sensitive adhesive, comprising the following steps:

[0038] a) mixing a butyl rubber component, a portion of a plasticizer, a hydrogenated tackifying resin and an optional antioxidant and heating and stirring to obtain a first uniform colloid;

[0039] b) mixing the first uniform colloid, the inorganic filler, the root inhibitor modified filler and the remaining plasticizer, heating and stirring the mixture to obtain a second uniform colloid, and cooling and molding the mixture to obtain the butyl pressure-sensitive adhesive product.

[0040] According to the present invention, preferably, in the step a), the temperature of heating and stirring is 120-160° C., and the time is 45-120 min.

[0041] According to the present invention, preferably, in the step b), the temperature of heating and stirring is 120-160° C., and the time is 45-60 min.

[0042] According to the present invention, preferably, the ratio of the amount of the plasticizer in step a) to the amount of the plasticizer in step b) is (8-12):(10-25).

[0043] The fourth aspect of the present invention provides the use of the butyl pressure-sensitive adhesive in the self-adhesive overlap of a polymer waterproofing membrane, wherein the polymer waterproofing membrane is a polymer waterproofing membrane used as a waterproof layer of a planting top plate and / or a planting roof.

[0044] According to the present invention, preferably, the coating thickness of the butyl pressure-sensitive adhesive is 280-500 μm.

[0045] The beneficial effects of the technical solution of the present invention are as follows:

[0046] The root inhibitor modified filler of the present invention introduces a new type of powder, namely layered double hydroxide (LDH), whose special layered structure can "sandwich" anions between layers, so the powder itself has excellent thermal stability and anion exchange performance. By utilizing its anion exchange performance, the anions of the phenoxycarboxylic acid root inhibitor are intercalated between the layered double hydroxide layers to form an intermolecular force, which plays a fixing role on the root inhibitor and achieves the slow release effect of the root inhibitor ( Figure 1 It can be seen that the filler modified by the root inhibitor of the present invention has a higher retention amount of the root inhibitor than the direct use of the root inhibitor, and the effect of releasing the root inhibitor is slower. ). Therefore, compared with the use of the phenoxycarboxylic acid small molecule root inhibitor, the filler modified by the root inhibitor of the present invention can effectively prevent the root inhibitor from being lost in large quantities after encountering soil and water, and maximize the root inhibition effect.

[0047] When the root inhibitor modified filler of the present invention is used in butyl pressure-sensitive adhesive, compared with the phenoxycarboxylic acid type small molecule root inhibitor, the solid form of the layered double hydroxide helps the root inhibitor small molecule to have better dispersion and better compatibility in the butyl pressure-sensitive adhesive (phenoxycarboxylic acid type small molecules are easy to agglomerate during the mixing process and are unevenly dispersed; and during use, due to their own small molecular weight, they are easy to quickly migrate out of the pressure-sensitive adhesive (poor compatibility). Therefore, the present invention considers using solid fillers to modify small molecules, and the physical form of the solid fillers themselves can be used to help disperse and retain small molecules (that is, have better dispersibility and compatibility)). And due to the excellent thermal stability of the root inhibitor modified filler, it is not easy to decompose and fail during application and processing.

[0048] The root barrier modified filler of the present invention is mixed with butyl rubber, plasticizer, hydrogenated tackifying resin, antioxidant and inorganic filler in a specific ratio to obtain a chemical root barrier butyl pressure-sensitive adhesive product with a slow-release function. The finished product has higher joint bonding strength and better water-impermeability than general butyl pressure-sensitive adhesives.

[0049] During use of the butyl pressure-sensitive adhesive product of the present invention, the root inhibitor anions between the inner layers of the root inhibitor modified filler will be exchanged with the anions in the soil, achieving the effect of slowly releasing the root inhibitor, effectively reducing its toxic impact on the soil, being environmentally friendly, and extending its effective time, so that the finished product has a longer resistance to root penetration.

[0050] The butyl pressure-sensitive adhesive product of the present invention is suitable for cold-bonding construction, thereby improving the convenience of construction.

[0051] Other features and advantages of the present invention will be described in detail in the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] The above and other objects, features and advantages of the present invention will become more apparent through a more detailed description of exemplary embodiments of the present invention with reference to the accompanying drawings.

[0053] Figure 1 A schematic diagram showing the change in the content of the internal root inhibitor MCPP of the butyl pressure-sensitive adhesive of Examples 1-2 and Comparative Examples 2-4 with the immersion time in the sustained-release performance test of the present invention. DETAILED DESCRIPTION

[0054] The preferred embodiments of the present invention will be described in more detail below. Although the preferred embodiments of the present invention are described below, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments set forth herein. On the contrary, these embodiments are provided to make the present invention more thorough and complete, and to fully convey the scope of the present invention to those skilled in the art.

[0055] In the following embodiments and comparative examples:

[0056] 2-Methyl-4-chlorophenoxypropionic acid (MCPP) root inhibitor, purchased from Merck (MERCK), CAS No.: 93-65-2;

[0057] 2-Methyl-4-chlorophenoxyacetic acid (MCPA) and 2,4-dichlorophenoxyacetic acid (2,4-D) were purchased from Jiangsu Changfeng Agrochemical Co., Ltd., with the brand names of 2-Methyl-4-chlorophenoxyacetic acid and 2,4-D technical respectively;

[0058] The layered double hydroxide composition, magnesium aluminum hydroxide composition, was purchased from Kyowa Chemical Industry Co., Ltd. under the brand name KYOWAAD TM 500;

[0059] The layered double hydroxide compositions, namely the zinc-aluminum hydroxide composition, the manganese-iron hydroxide composition, and the cobalt-iron hydroxide composition, were all purchased from Jiangsu Xianfeng Nanomaterial Technology Co., Ltd., with the brands XFL04, XFL08, and XFL09, respectively.

[0060] The methanol was purchased from Jinan Century Tongda Chemical Co., Ltd. with a purity of 99.9%;

[0061] The butyl rubber component is purchased from Arlanxeo with a brand name of RB100;

[0062] The plasticizer was purchased from Daelim Co., Ltd. of South Korea with a brand name of PB1300;

[0063] The hydrogenated tackifying resin is purchased from ExxonMobil Chemical and has the brand name ESCROEZ 5300;

[0064] The antioxidant was purchased from BASF and its brand name was Irganox 1010;

[0065] The commercially available root inhibitor described in Comparative Examples 2-4 is selected from LANXESS, with a brand name of

[0066] Example 1

[0067] This embodiment provides a root inhibitor modified filler, wherein the root inhibitor modified filler is prepared by stirring a layered double hydroxide composition and a root inhibitor under solvent conditions;

[0068] The layered double hydroxide composition is the magnesium aluminum hydroxide composition (MgAl-LDH);

[0069] The root inhibitor is 2-methyl-4-chlorophenoxypropionic acid (MCPP).

[0070] The preparation method of the root inhibitor modified filler comprises:

[0071] 1) adding 20 g of magnesium aluminum hydroxide composition (MgAl-LDH) into 400 mL of methanol, stirring and dispersing at room temperature to obtain a first suspension;

[0072] 2) Add 10 g of the root inhibitor into 50 mL of methanol, stir and disperse at room temperature to obtain a second suspension;

[0073] 3) adding the second suspension dropwise into the first suspension, stirring for 60 minutes after the addition is completed to obtain a mixed suspension; centrifuging the mixed suspension and washing it three times with methanol, after washing, pouring out the supernatant, drying it in a vacuum oven at 50° C., and then grinding it to obtain the root inhibitor modified filler MCPP-MgAl LDH.

[0074] This embodiment also provides a butyl pressure-sensitive adhesive, which includes the following components in parts by weight: 25 parts of butyl rubber component, 30 parts of plasticizer, 20 parts of hydrogenated tackifying resin, 1 part of antioxidant, 20 parts of calcium carbonate powder and 4 parts of the root inhibitor modified filler MCPP-MgAl LDH.

[0075] The preparation method of the above-mentioned butyl pressure-sensitive adhesive comprises the following steps:

[0076] a) adding a butyl rubber component, a portion of a plasticizer, a hydrogenated tackifying resin and an antioxidant into a kneader, and stirring and mixing them at a heating condition of 145° C. for 120 minutes to obtain a first uniform colloid;

[0077] b) adding inorganic filler, root inhibitor modified filler MCPP-MgAl LDH and the remaining plasticizer to the first uniform colloid, and continuing to stir and mix under heating conditions of 145° C. for 60 minutes to obtain a second uniform colloid, and cooling and molding to obtain the butyl pressure-sensitive adhesive product.

[0078] The amount ratio of the plasticizer in step a) to the plasticizer in step b) is 1:2.

[0079] Example 2

[0080] This embodiment provides a root inhibitor modified filler. The difference between this embodiment and embodiment 1 is that:

[0081] The layered double hydroxide composition is the zinc aluminum hydroxide composition (ZnAl-LDH);

[0082] In the preparation method of the root inhibitor modified filler:

[0083] Step 1), adding 25 g of zinc aluminum hydroxide composition (ZnAl-LDH) into 400 mL of methanol, stirring and dispersing at room temperature to obtain a first suspension;

[0084] In step 3), the stirring time is 70 min;

[0085] The root inhibitor modified filler MCPP-ZnAl LDH is obtained.

[0086] This embodiment also provides a butyl pressure-sensitive adhesive, and the difference between this embodiment and embodiment 1 is only that:

[0087] The butyl rubber component is 20 parts, the inorganic filler is 25 parts, and the amounts of other components remain unchanged.

[0088] The preparation method of the above butyl pressure-sensitive adhesive is the same as that of Example 1.

[0089] Example 3

[0090] This embodiment provides a root inhibitor modified filler. The difference between this embodiment and embodiment 1 is that:

[0091] The layered double hydroxide composition is the manganese-iron hydroxide combination (MnFe-LDH);

[0092] In the preparation method of the root inhibitor modified filler:

[0093] Step 1), adding 40g of manganese iron hydroxide combination into 400mL of methanol, stirring and dispersing at room temperature to obtain a first suspension;

[0094] Step 2), adding 15 g of root inhibitor into 50 mL of methanol, stirring and dispersing at room temperature to obtain a second suspension;

[0095] Step 3), the stirring time is 70min;

[0096] The root inhibitor modified filler MCPP-MnFe LDH is obtained.

[0097] This embodiment also provides a butyl pressure-sensitive adhesive, and the difference between this embodiment and embodiment 1 is only that:

[0098] 25 parts of plasticizer, 25 parts of inorganic filler, and the amounts of other components remain unchanged.

[0099] The preparation method of the above-mentioned butyl pressure-sensitive adhesive differs from that of Example 1 only in that:

[0100] The amount ratio of the plasticizer in step a) to the plasticizer in step b) is 10:15.

[0101] Example 4

[0102] This embodiment provides a root inhibitor modified filler. The difference between this embodiment and embodiment 1 is that:

[0103] The layered double hydroxide composition is the cobalt iron hydroxide composition (CoFe-LDH);

[0104] In the preparation method of the root inhibitor modified filler:

[0105] Step 1), adding 45 g of magnesium aluminum hydroxide composition (MgAl-LDH) into 400 mL of methanol, stirring and dispersing at room temperature to obtain a first suspension;

[0106] Step 2), adding 15 g of root inhibitor into 50 mL of methanol, stirring and dispersing at room temperature to obtain a second suspension;

[0107] Step 3), the stirring time is 70min;

[0108] The root inhibitor modified filler MCPP-CoFe LDH is obtained.

[0109] This embodiment also provides a butyl pressure-sensitive adhesive, and the difference between this embodiment and embodiment 1 is only that:

[0110] 25 parts of plasticizer, 25 parts of hydrogenated tackifying resin, and the amounts of other components remain unchanged.

[0111] The preparation method of the above-mentioned butyl pressure-sensitive adhesive differs from that of Example 1 only in that:

[0112] The amount ratio of the plasticizer in step a) to the plasticizer in step b) is 10:15.

[0113] Example 5

[0114] This embodiment provides a root inhibitor modified filler. The difference between this embodiment and embodiment 1 is that:

[0115] The root inhibitor is 2-methyl-4-chlorophenoxyacetic acid (MCPA).

[0116] In the preparation method of the root inhibitor modified filler:

[0117] In step 3), the stirring time is 70 min;

[0118] The root inhibitor modified filler MCPA-MgAl LDH is obtained.

[0119] This embodiment also provides a butyl pressure-sensitive adhesive, and the difference between this embodiment and embodiment 1 is only that:

[0120] The root inhibitor modified filler is 4 parts of MCPA-MgAl LDH.

[0121] The preparation method of the above butyl pressure-sensitive adhesive is the same as that of Example 1.

[0122] Example 6

[0123] This embodiment provides a root inhibitor modified filler. The difference between this embodiment and embodiment 1 is that:

[0124] The root inhibitor is 2,4-dichlorophenoxyacetic acid (2,4-D).

[0125] In the preparation method of the root inhibitor modified filler:

[0126] Step 1), adding 25 g of magnesium aluminum hydroxide composition (MgAl-LDH) into 400 mL of methanol, stirring and dispersing at room temperature to obtain a first suspension;

[0127] The root inhibitor modified filler 2,4-D-MgAl LDH is obtained.

[0128] This embodiment also provides a butyl pressure-sensitive adhesive. The difference between this embodiment and embodiment 1 is that the root inhibitor modified filler is 4 parts of 2,4-D-MgAl LDH.

[0129] The preparation method of the above butyl pressure-sensitive adhesive is the same as that of Example 1.

[0130] Comparative Example 1

[0131] This comparative example provides a butyl pressure-sensitive adhesive, which includes the following components in parts by weight: 25 parts of butyl rubber component, 30 parts of plasticizer, 20 parts of hydrogenated tackifying resin, 1 part of antioxidant, and 24 parts of calcium carbonate powder.

[0132] That is, the difference between this comparative example and Example 1 is that an inorganic filler is used to replace the root inhibitor modified filler in Example 1.

[0133] The preparation method of the above butyl pressure-sensitive adhesive is the same as that of Example 1.

[0134] Comparative Example 2

[0135] This comparative example provides a butyl pressure-sensitive adhesive, which includes the following components in parts by weight: 30 parts of butyl rubber component, 30 parts of plasticizer, 20 parts of hydrogenated tackifying resin, 1 part of antioxidant, 18 parts of calcium carbonate powder and 1 part of the commercially available root inhibitor (the reason for using 1 part of the commercially available root inhibitor is to ensure that the effective root inhibitor content in 4 parts of the root inhibitor modified filler is consistent with the effective content of 1 part of the commercially available root inhibitor. This is also consistent with the subsequent Figure 1 Among them, the effective content of the root inhibitor is basically the same at the beginning, corresponding to the following comparative examples 3-4).

[0136] The preparation method of the above butyl pressure-sensitive adhesive is the same as that of Example 1.

[0137] Comparative Example 3

[0138] This comparative example provides a butyl pressure-sensitive adhesive, and the difference between this comparative example and Example 1 is only that:

[0139] 45 parts of butyl rubber component, 17 parts of plasticizer, 8 parts of hydrogenated tackifying resin, 1 part of the commercially available root inhibitor, and other components and their amounts remain unchanged.

[0140] The preparation method of the above-mentioned butyl pressure-sensitive adhesive differs from that of Example 1 only in that:

[0141] The amount ratio of the plasticizer in step a) to the plasticizer in step b) is 10:7.

[0142] Comparative Example 4

[0143] This comparative example provides a butyl pressure-sensitive adhesive, and the difference between this comparative example and Example 1 is only that:

[0144] 5 parts of butyl rubber component, 45 parts of plasticizer, 35 parts of hydrogenated tackifying resin, 1 part of the commercially available root inhibitor, and other components and their amounts remain unchanged.

[0145] The preparation method of the above-mentioned butyl pressure-sensitive adhesive differs from that of Example 1 only in that:

[0146] The amount ratio of the plasticizer in step a) to the plasticizer in step b) is 20:25.

[0147] Test Case

[0148] In this test example, the butyl pressure-sensitive adhesive of the above embodiment and comparative example is coated on a substrate with a thickness of 300 μm, and covered with a release film to obtain a self-adhesive waterproof roll. The butyl pressure-sensitive adhesive of the above embodiment and comparative example is tested for peeling performance and water-impermeability performance, root penetration resistance performance test, and sustained release effect performance test;

[0149] (1) Peeling performance and water-tightness test

[0150] According to the T / CWA "Test Methods for Engineering Requirements of Building Waterproof Materials" standard, the joint peel strength and lap joint impermeability tests are carried out.

[0151] When the joint is peeled off, cohesive failure of the adhesive layer itself occurs, which is recorded as CF; when the joint is peeled off, interfacial failure between the adhesive layer and the coil occurs, which is recorded as AF.

[0152] The lap joint impermeability is 0.2MPa, and if there is no water penetration on the surface after 30 minutes, it passes the impermeability test.

[0153] (2) Root penetration resistance test

[0154] According to GB / T 35468-2017 "Root penetration resistant waterproof membrane for green roofs", the root penetration resistance performance test is carried out.

[0155] (3) Sustained release performance test

[0156] After bonding the self-adhesive membrane to the waterproof membrane backing, cure for 3 days under standard environment. After curing, soak the bonded membrane in irrigation water. The irrigation water should meet the requirements of irrigation water in Appendix A-4.8 of GB / T 35468-2017 "Root-penetration-resistant waterproof membrane for green roofs", and the adhesive membrane should be placed at a distance of more than 10 cm from the water surface. Take adhesive samples every 2 weeks for a total of 6 months.

[0157] According to the standard T / CWA 301-2019 "Test Method for Root Inhibitor Content in Asphalt-based Root Penetration Resistant Waterproofing Membrane", a standard curve was developed and the MCPP content in the glue was measured after different treatments. The test results are as follows: Figure 1 The other non-MCPP modified rubber samples were only tested for the initial effective root inhibitor content inside the rubber samples and the effective root inhibitor content after immersion for 6 months.

[0158] The results are shown in Tables 1 and 2.

[0159] Table 1

[0160]

[0161]

[0162] Table 2

[0163]

[0164]

[0165] From Table 1, we can see that:

[0166] In Examples 1-6, different combinations of layered double hydroxides and root inhibitors were used to prepare different types of root inhibitor modified fillers. The root inhibitor modified fillers were used in butyl pressure sensitive adhesives, and the final products all passed the root penetration resistance test.

[0167] Comparing Table 1 and Table 2, we can see that:

[0168] Compared with Examples 1-6, the seam peel strength of Comparative Example 1-2 is reduced to a certain extent, which shows that the introduction of the root inhibitor modified filler into the butyl pressure-sensitive adhesive does not reduce the seam peel strength of the finished product, but has a positive effect. After heat aging and water immersion treatment, the positive effect still exists.

[0169] Compared with Examples 1-6, the seam peeling strength of Comparative Examples 3 and 4 is significantly reduced, and the seam water permeability occurs. This shows that for the final product butyl pressure-sensitive adhesive, the component ratio of butyl rubber component, plasticizer and hydrogenated tackifying resin is more important to its bonding performance. Excessive butyl rubber component will increase the cohesive strength of the butyl pressure-sensitive adhesive, deteriorate the bonding performance, and the bonding phenomenon will change from cohesive failure to interfacial failure; while too little butyl rubber component and too much plasticizer / hydrogenated tackifying resin component will make the cohesive strength of the finished butyl pressure-sensitive adhesive too small, and face the situation of water permeability at the seam after heat aging.

[0170] The composition analysis of the adhesive samples of Examples 1-6 and Comparative Examples 2-4 shows that the initial effective root inhibitor content in the above adhesives is about 10wt‰. As the time of soaking the adhesive samples in the irrigation water increases, the effective root inhibitor content in the adhesive samples will be lost to a certain extent. After 6 months of testing, the effective root inhibitor components in the adhesives of Examples 1-6 averaged 8.1wt‰, with a retention rate of about 80%; while the adhesives of Comparative Examples 2-4 using commercially available root inhibitors, the effective root inhibitor content averaged 3.3wt‰, with a retention rate of about 33%. This shows that the root inhibitor modified filler of the present invention has a better retention effect on the root inhibitor and a longer service life.

[0171] According to market research, the amount of root blockers added to the market is generally at least 5wt‰, which also means that when the content of root blockers in the finished butyl pressure-sensitive adhesive product is greater than 5wt‰, the finished product will have better resistance to root penetration. Comparing the effective root blocker content of butyl pressure-sensitive adhesives after immersion in Examples 1-6 and Comparative Examples 2-4, the effective root blocker content in the glue of Examples 1-6 reached 8wt‰ after immersion for 6 months, meeting the root blocker content requirement. On the contrary, the effective root blocker content in the glue of Comparative Examples 2-4 using commercially available root blockers was only 3.3wt‰ after immersion for 6 months, which did not meet the above-mentioned 5wt‰ addition requirement. Corresponding to the results in Table 2, the root penetration resistance performance of the finished coiled material was unqualified.

[0172] pass Figure 1 It can be seen that:

[0173] By comparing the changes in the content of the root inhibitor MCPP in the butyl pressure-sensitive adhesives of Examples 1-2 and Comparative Examples 2-4 during the 6-month immersion process, it can be clearly seen that the butyl pressure-sensitive adhesive using the root inhibitor modified filler of the present invention has a slow-release effect on the root inhibitor.

[0174] The embodiments of the present invention have been described above, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A root inhibitor modified filler, It is characterized in that The root inhibitor modified filler is prepared by stirring a layered double hydroxide composition and a root inhibitor under solvent conditions; The chemical structural formula of the layered double hydroxide composition is shown in formula (1): In the formula (1): M 2 +Mg 2+ 、Zn 2+ 、Ni 2+ 、Co 2+ and Mn 2+ At least one of; M 3 + for Al 3+ , Ga 3+ , Fe 3+ and Mn 3+ At least one of; An- is F - , CO 3 2- , Cl - 、SO 4 2- and at least one of an organic acid ion; The value range of x is between 0.2 and 0.4; The root inhibitor is a small molecule chemical root inhibitor.

2. The root inhibitor modified filler according to claim 1, in, The mass ratio of the layered double hydroxide composition to the root inhibitor is (60-80): (20-40); The root inhibitor is a phenoxycarboxylic acid root inhibitor, preferably, the root inhibitor is at least one of 2-methyl-4-chlorophenoxypropionic acid, 2-methyl-4-chlorophenoxyacetic acid, 2,4-dichlorophenoxyacetic acid and 4-(2,4-dichlorophenoxy)butyric acid; The solvent is at least one of methanol, ethanol and deionized water.

3. The root inhibitor modified filler according to claim 1 or 2, in, The preparation method of the root inhibitor modified filler comprises: 1) mixing the layered double hydroxide composition with a solvent to obtain a first suspension; 2) mixing the root inhibitor with a solvent to obtain a second suspension; 3) mixing the second suspension with the first suspension and stirring to obtain a mixed suspension; centrifugally washing, drying and grinding the mixed suspension to obtain the root inhibitor modified filler.

4. The root inhibitor modified filler according to claim 3, in, In the step 1), the ratio of the layered double hydroxide composition to the solvent is (5-45): (300-400) g / mL; In the step 2), the mass fraction of the root inhibitor in the second suspension is 15-35%; In the step 3): The stirring time is 45-90min; The speed of centrifugal washing is 1500-3000 rpm, and the washing solvent used in the centrifugal washing is at least one of methanol, ethanol and acetone; The drying temperature should be 40-50℃.

5. A butyl pressure-sensitive adhesive, It is characterized in that The butyl pressure-sensitive adhesive comprises the root inhibitor modified filler as described in any one of claims 1 to 4.

6. The butyl pressure-sensitive adhesive according to claim 5, in, The butyl pressure-sensitive adhesive comprises the following components in parts by weight: 10-40 parts of butyl rubber component, 20-40 parts of plasticizer, 10-30 parts of hydrogenated tackifying resin, 0-3 parts of antioxidant, 10-50 parts of inorganic filler and 2-6 parts of root barrier modified filler.

7. The butyl pressure-sensitive adhesive according to claim 6, in, The Mooney viscosity ML (1+8) of the butyl rubber component at 125° C. is between 20 and 60; The plasticizer is a low molecular weight polyisobutylene rubber and / or naphthenic oil having a number average molecular weight of 400-2400 g / mol; The hydrogenated tackifying resin is selected from at least one of hydrogenated C5 resin, aromatic modified hydrogenated C5 resin, hydrogenated C9 resin, hydrogenated dicyclopentadiene resin, aromatic modified hydrogenated dicyclopentadiene resin and α-methylstyrene pure monomer resin; the hydrogenated tackifying resin has a hydrogenation degree of more than 90% and a softening point of 80°C-140°C; The antioxidant is at least one of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tris[2,4-di-tert-butylphenyl]phosphite and β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate; The inorganic filler is selected from at least one of calcium carbonate powder, talc powder, kaolin, mica powder and titanium dioxide.

8. A method for preparing a butyl pressure-sensitive adhesive according to any one of claims 5 to 7, It is characterized in that The preparation method comprises the following steps: a) mixing a butyl rubber component, a portion of a plasticizer, a hydrogenated tackifying resin and an optional antioxidant and heating and stirring to obtain a first uniform colloid; b) mixing the first uniform colloid, the inorganic filler, the root inhibitor modified filler and the remaining plasticizer, heating and stirring the mixture to obtain a second uniform colloid, and cooling and molding the mixture to obtain the butyl pressure-sensitive adhesive product.

9. The method for preparing the butyl pressure-sensitive adhesive according to claim 8, in, In the step a), the heating and stirring temperature is 120-160° C. and the time is 45-120 min; In the step b), the heating and stirring temperature is 120-160° C. and the time is 45-60 min; The amount ratio of the plasticizer in step a) to the plasticizer in step b) is (8-12):(10-25).

10. Use of the butyl pressure-sensitive adhesive according to any one of claims 5 to 7 in the self-adhesive overlap of a polymer waterproofing membrane, wherein the polymer waterproofing membrane is a polymer waterproofing membrane used as a waterproof layer of a planting top plate and / or a planting roof; Preferably, the coating thickness of the butyl pressure-sensitive adhesive is 280-500 μm.

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