Polyurethane adhesive for pavement paving and polyurethane mixture containing polyurethane adhesive

Abstract

The invention provides a polyurethane adhesive for pavement paving and a polyurethane mixture containing the polyurethane adhesive. The polyurethane adhesive for pavement paving is prepared from the following raw materials in parts by mass: 28 to 50 parts of isocyanate, 35 to 57 parts of polyether polyol, 10 to 20 parts of solvent and 0.5 to 2.5 parts of coupling agent, the isocyanate is prepared from aromatic isocyanate; the solvent comprises a combination of a hydrophilic compound and a hydrophobic compound, and the hydrophobic compound has a structure as shown in a formula I. Through the design of the solvent and the compounding of the solvent, the isocyanate, the polyether polyol and the coupling agent, the polyurethane adhesive has the characteristics of high strength, high toughness, controllable curing speed and good curing uniformity, is low in cost, has a small addition amount in a polyurethane mixture, improves the mixing uniformity and production efficiency of the polyurethane mixture containing the polyurethane adhesive, and is suitable for industrial production. The large-scale construction possibility is realized, and the excellent high-temperature rutting resistance and low-temperature deformation resistance are realized.

Description

Technical Field

[0001] The present invention belongs to the technical field of pavement materials, and particularly relates to a polyurethane adhesive for pavement paving and a polyurethane mixture containing the same. Background Art

[0002] With the gradual intensification of climate change and the continuous rise of global temperatures, obvious changes have occurred in climate phenomena in various regions. High-temperature phenomena in summer occur frequently, and the pavement temperature in some areas can even reach above 70°C, which makes asphalt pavements more prone to rutting. At the same time, due to the overloading of vehicles, this further exacerbates the rutting deformation of asphalt pavements; moreover, due to the inherent properties of asphalt, it is very easy to crack in low-temperature environments; the above two situations further exacerbate the damage of asphalt pavements and reduce the service life of asphalt pavements. In addition, with the increasingly strict environmental protection requirements, there is an urgent need for a new green and high-performance pavement paving material to solve the problems existing in existing asphalt pavement materials. Polymer-modified asphalt can effectively improve the problems of asphalt softening to form ruts at high temperatures and cracking at low temperatures. Among them, polyurethane is a polymer material with excellent comprehensive properties and has great application potential in pavement materials.

[0003] CN113307936A discloses a preparation method of a two-component modified polyurethane and mixture, including the following steps: preparing component A, which includes 100 parts of solvent, 0.2 - 5 parts of dibutyltin dilaurate catalyst, 50 - 250 parts of polytetrahydrofuran, and 220 - 400 parts of isocyanate monomer. After the above materials are mixed, they are reacted at 80°C to obtain component A; preparing component B, which includes 100 parts of solvent, 1 - 5 parts of BYK 320, 1 - 5 parts of 5005, 1 - 10 parts of dibutyltin dilaurate catalyst, and 800 - 1000 parts of special resin. The foregoing materials are mixed evenly to obtain component B; mixing component A and component B to obtain a two-component modified polyurethane, which has good deformation ability, fatigue resistance, water impermeability, corrosion resistance, etc., can be cured at room temperature, is convenient for construction, and provides good road performance when used in mixtures. However, this two-component modified polyurethane adhesive uses a large amount of substances with high toxicity such as benzene and xylene, and does not have characteristics such as green environmental protection. At the same time, it uses all raw materials such as special isocyanates such as H 12 MDI, IPDI, HDI, XDI, and polytetrahydrofuran polyol. The raw material production capacity is low, which greatly increases the cost of the polyurethane adhesive; in addition, the amount of the adhesive in this polyurethane mixture exceeds 9%, and there are problems such as high adhesive dosage, fast adhesive reaction speed, and uneven curing, which limit the application of this material in the field of road paving.

[0004] CN109180071A discloses a high-performance cold mix for road surface courses, which consists of mineral aggregates, polyurethane binder, carboxylic acid and anti-stripping agent. Among them, the carboxylic acid is isooctanoic acid, and the anti-stripping agent is a phosphorus-containing hydroxyl anti-stripping agent. The polyurethane binder is prepared from the following components: 50-70 parts of isocyanate, 50-60 parts of ethyl acetate, 30-40 parts of polyol, 5-10 parts of chemical absorbent, 1-5 parts of catalyst, 1-3 parts of surfactant, and 1-3 parts of chain extender. This mixture can be mixed at normal temperature, which has environmental significance. However, due to the need to add additives such as carboxylic acid and anti-stripping agent during the production process of the mixture, the mixing process becomes complicated, the practical operability is reduced, and the pot life of the mixture is short, and the high and low temperature resistance is insufficient, which greatly limits the application scenarios of the mixture.

[0005] CN114409307A discloses a high-strength and high-toughness polyurethane concrete and its preparation method and application, which is prepared from 100 parts of polyisocyanate, 100 parts of oligomeric polyol, 10-15 parts of chain extender, 2-3 parts of catalyst, 7-8 parts of molecular sieve activated powder, 6-8 parts of silicone, 120-200 parts of fly ash, 140-160 parts of fine aggregate, 300-320 parts of coarse aggregate, 5-10 parts of carbon fiber powder and 20-40 parts of chitosan surface-grafted hyperbranched polymer. Among them, the oligomeric polyol is aliphatic terminal amino polyether, which increases the viscosity of the adhesive and makes the mixing difficult; and it contains filler substances, which further increases the viscosity of the adhesive and affects the mixing effect. Moreover, the use of chitosan surface-grafted hyperbranched polymer in this polyurethane concrete makes the preparation process cumbersome and costly, which is not conducive to large-scale application.

[0006] Therefore, it is of great significance for the application of polyurethane materials in the paving field to develop a polyurethane adhesive with relatively low cost, less addition amount in the mixture, easy to mix, possibility of large-scale construction, simple synthesis method, and high strength and high toughness characteristics to solve the problems of high-temperature rutting and low-temperature deformation of asphalt pavements. Summary of the Invention

[0007] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a polyurethane adhesive for road paving and a polyurethane mixture containing the same. Through the design of solvents of specific components and their mutual compounding with isocyanate, polyether polyol and coupling agent, the polyurethane adhesive for road paving has the characteristics of high strength, high toughness, controllable curing speed, good curing uniformity, good heat resistance and water resistance, and relatively low cost and less addition amount in the polyurethane mixture, improving the mixing uniformity and production efficiency of the polyurethane mixture containing the same, having the possibility of large-scale construction, and having excellent high-temperature rutting resistance and low-temperature deformation resistance.

[0008] To achieve this purpose, the present invention adopts the following technical solutions:

[0009] In a first aspect, the present invention provides a polyurethane adhesive for pavement paving. The raw materials for preparing the polyurethane adhesive for pavement paving include the following components by mass:

[0010]

[0011] The isocyanate includes aromatic isocyanate;

[0012] The solvent includes a combination of a hydrophilic compound and a hydrophobic compound. The hydrophobic compound has a structure shown in Formula I:

[0013]

[0014] In Formula I, ring Ar is selected from any one of C6-C16 aromatic rings;

[0015] In Formula I, R is selected from any one of C8-C20 straight-chain or branched-chain alkyl groups.

[0016] In Formula I, m represents the number of Rs, which is an integer selected from 1-3. For example, it can be 1, 2, or 3; when m≥2, multiple Rs are the same or different groups.

[0017] In the polyurethane adhesive for pavement paving provided by the present invention, a combination including a hydrophilic compound and a hydrophobic compound is used as a solvent, which realizes the adjustment of the pot life and curing speed of the polyurethane adhesive, and effectively improves the comprehensive performance of the polyurethane adhesive. Specifically, the hydrophobic compound has the structure shown in Formula I, which is an aromatic compound substituted by a long-chain alkyl R. According to the principle of similar compatibility, it can be miscible with the adhesive to reduce the viscosity of the adhesive. At the same time, the long-chain alkyl side chain it carries reduces the hydrophilicity of ether bonds, urethane bonds, urea bonds, etc. in the adhesive, prolongs the retention time of the adhesive, and can be inserted between macromolecular chain segments to increase the slipperiness between the molecular chains of the polyurethane adhesive and improve the visco-temperature performance of the polyurethane adhesive. Moreover, the electron-rich ring contained in the hydrophobic compound itself can absorb, resonate, and disperse energy, which can effectively improve the heat and oxygen aging resistance of the polyurethane adhesive. In addition, the aromatic ring structure contained in the hydrophobic compound can improve the bonding strength of the polyurethane adhesive, and its long-chain alkyl side chain can prevent the intrusion of water into the adhesive and improve the water resistance stability of the adhesive. The hydrophilic compound is characterized by high polarity and strong hydrophilicity. It is uniformly dispersed in the polyurethane adhesive, which can reduce the difficulty of contact between water molecules and the adhesive and improve the uniformity of contact between the adhesive and water molecules, thereby promoting the curing of the polyurethane adhesive. By combining and compounding the hydrophilic compound and the hydrophobic compound, the present invention can, on the one hand, reduce the viscosity of the polyurethane adhesive and prevent the uneven curing of the adhesive caused by too strong hydrophobicity of the solvent, and improve the curing uniformity of the polyurethane adhesive.

[0018] In the present invention, based on the design of the solvent and its mutual compounding with isocyanates including aromatic isocyanates, polyether polyols, and coupling agents, the polyurethane adhesive has the characteristics of low viscosity, controllable pot life and curing speed, and high curing uniformity. Its cured product is high-strength and high-toughness, with excellent water resistance and high-temperature resistance, and relatively low cost and less addition amount in the polyurethane mixture, which improves the mixing uniformity and production efficiency of the polyurethane mixture containing it, has the possibility of large-scale construction, effectively solves the problems of high-temperature rutting and low-temperature deformation and brittle cracking of asphalt pavement materials, and significantly improves the high-temperature rutting resistance, low-temperature deformation resistance, and low-temperature crack / brittle cracking resistance of pavement materials.

[0019] The following are the preferred technical solutions of the present invention, but do not limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the purpose and beneficial effects of the present invention can be better achieved and realized.

[0020] In the raw materials for preparing the polyurethane adhesive for pavement paving provided by the present invention, the mass parts of the isocyanate are 28-50 parts, for example, it can be 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts or 48 parts, and the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range. Preferably, it is 30-48 parts.

[0021] The mass parts of the polyether polyol are 35-57 parts, for example, it can be 38 parts, 40 parts, 42 parts, 45 parts, 48 parts, 50 parts, 53 parts or 55 parts, and the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range. Preferably, it is 40-52 parts.

[0022] The mass parts of the solvent are 10-20 parts, for example, it can be 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts or 19 parts, and the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range. Preferably, it is 12-18 parts.

[0023] The mass parts of the coupling agent are 0.5-2.5 parts, for example, it can be 0.6 parts, 0.8 parts, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts or 2.4 parts, and the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range. Preferably, it is 1-2 parts.

[0024] In formula I, the ring Ar is selected from any one of C6-C16 aromatic rings, for example, it can be aromatic rings of C6, C9, C10, C12, C14, C16, etc. Exemplarily, it includes but is not limited to: benzene ring, biphenyl ring, naphthalene ring, anthracene ring, etc.

[0025] In formula I, the R is selected from C8-C20 straight-chain or branched-chain alkyl groups, for example, it can be straight-chain or branched-chain alkyl groups of C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20. Exemplarily, it includes but is not limited to: nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, etc. The foregoing groups include straight-chain structures or branched-chain structures.

[0026] Preferably, the isocyanate includes a combination of polymethylene polyphenyl isocyanate and diisocyanate.

[0027] As a preferred technical solution of the present invention, the isocyanate is composed of polymethylene polyphenyl isocyanate and diisocyanate. Different active isocyanates are combined with a mixed solvent of hydrophilic compound - hydrophobic compound to further adjust the pot life and curing speed of the polyurethane adhesive to meet the construction requirements of polyurethane pavements in different scenarios. At the same time, the polymethylene polyphenyl isocyanate acts together with the coupling agent and is compounded with other components, which can further improve the high-temperature rutting resistance of the polyurethane mixture.

[0028] Preferably, the mass percentage content of polymethylene polyphenyl isocyanate in the isocyanate is 6 - 22%, for example, it can be 7%, 8%, 10%, 12%, 14%, 15%, 16%, 18%, 20% or 21%, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range. Further preferably, it is 8 - 20%.

[0029] Preferably, the average functionality of the polymethylene polyphenyl isocyanate is 2.3 - 3.0, for example, it can be 2.4, 2.5, 2.6, 2.7, 2.8 or 2.9, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range. Further preferably, it is 2.5 - 2.9.

[0030] Preferably, the viscosity of the polymethylene polyphenyl isocyanate is 100 - 1000 mPa·s, for example, it can be 200 mPa·s, 300 mPa·s, 400 mPa·s, 500 mPa·s, 600 mPa·s, 700 mPa·s, 800 mPa·s or 900 mPa·s, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range. Further preferably, it is 150 - 500 mPa·s.

[0031] In the present invention, the parameters related to viscosity are measured under the condition of 25°C.

[0032] Preferably, the mass percentage content of the NCO group in the polymethylene polyphenyl isocyanate is 29 - 32%, for example, it can be 29.2%, 29.5%, 29.8%, 30%, 30.2%, 30.5%, 30.8%, 31%, 31.2%, 31.5% or 31.8%, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range. Further preferably, it is 29.5 - 31.5%.

[0033] Preferably, the polymethylene polyphenyl isocyanate is a commercially available product, and examples include but are not limited to: any one or a combination of at least two of PM-100, PM-130, PM-200, PM-300, PM-400, PM-2010, PM-2025, PM-6302, and PM-6304 of Wanhua Chemical. Further preferably, it is any one or a combination of at least two of PM-100, PM-130, PM-200, PM-300, PM-2010, and PM-2025.

[0034] Preferably, the functionality of the diisocyanate is 2.

[0035] Preferably, the mass percentage content of the diisocyanate in the isocyanate is 78-94%, for example, it can be 79%, 80%, 82%, 85%, 88%, 90%, 91%, or 93%, as well as the specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the above range. Further preferably, it is 80-92%.

[0036] Preferably, the viscosity of the diisocyanate is 3-40 mPa·s, for example, it can be 4 mPa·s, 5 mPa·s, 8 mPa·s, 10 mPa·s, 12 mPa·s, 15 mPa·s, 18 mPa·s, 20 mPa·s, 22 mPa·s, 25 mPa·s, 28 mPa·s, 30 mPa·s, 32 mPa·s, 35 mPa·s, or 38 mPa·s, as well as the specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the above range. Further preferably, it is 3.5-38 mPa·s.

[0037] Preferably, the mass percentage content of the NCO group in the diisocyanate is 30-60%, for example, it can be 33%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, 52%, 55%, 57%, or 59%, as well as the specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the above range. Further preferably, it is 32-58%.

[0038] Preferably, the diisocyanate includes any one or a combination of at least two of diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), and 1,6-hexamethylene diisocyanate (HDI). Further preferably, it is diphenylmethane diisocyanate (MDI) and / or toluene diisocyanate (TDI).

[0039] Preferably, the diisocyanate is a commercially available product, including but not limited to, for example: any one or a combination of at least two of MDI-100, MDI-50, MDI-10, MDI-6001, TDI-80, TDI-65, IPDI, HDI from Wanhua Chemical; more preferably, any one or a combination of at least two of MDI-100, MDI-50, TDI-80, MDI-6001, TDI-65.

[0040] Preferably, the functionality of the polyether polyol is ≥2, more preferably 2-3.

[0041] Preferably, the number average molecular weight of the polyether polyol is 1000-5000, for example, it can be 1200, 1500, 1800, 2000, 2200, 2500, 2800, 3000, 3200, 3500, 3800, 4000, 4200, 4500 or 4800, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range. More preferably, it is 1500-4500.

[0042] Preferably, the hydroxyl value of the polyether polyol is 20-200 mg KOH / g, for example, it can be 30 mg KOH / g, 50 mg KOH / g, 80 mg KOH / g, 100 mg KOH / g, 110 mg KOH / g, 120 mg KOH / g, 130 mg KOH / g, 140 mg KOH / g, 150 mg KOH / g, 160 mg KOH / g, 180 mg KOH / g or 190 mg KOH / g, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range. More preferably, it is 25-150 mg KOH / g.

[0043] Preferably, the polyether polyol is a commercially available product, including but not limited to, for example: C2010D, C2020, C2030, C2040, C2140, F3147, F3156, F3056D, F3135 of Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd., PTMG-2000, Poly THF1400, Poly THF1800, Poly THF2000, Poly THF2900 of BASF, PTMG-1300 of Mitsubishi Chemical Corporation of Japan, and any one or a combination of at least two of HM-130, HM-140, HM-1070, HM-13150B, HM-13160A, HM-13160 of Herima. Further preferably, it is any one or a combination of at least two of C2020, C2040, C2140, F3156, F3135, F3056D, PTMG-2000, Poly THF1800, Poly THF2000. More preferably, it is any one or a combination of at least two of C2020, F3156, F3056D, PTMG-2000, Poly THF1800, Poly THF2000.

[0044] Preferably, the hydrophilic compound includes any one or a combination of at least two of sulfone compounds, compounds with the structure shown in Formula II, and compounds with the structure shown in Formula III;

[0045]

[0046] In Formula II, X1, X2, and X3 are each independently selected from O or S.

[0047] In Formula II, R1 is selected from any one of H, C1-C4 (such as C1, C2, C3, C4) straight-chain or branched-chain alkyl groups.

[0048] In Formula III, R2 and R3 are the same or different and are each independently selected from any one of C1-C6 (such as C1, C2, C3, C4, C5, C6) straight-chain or branched-chain alkyl groups.

[0049] Preferably, in Formula II, X1, X2, and X3 are O.

[0050] Preferably, in Formula II, R1 is selected from any one of H, C1-C3 straight-chain or branched-chain alkyl groups, and more preferably any one of C1-C3 straight-chain or branched-chain alkyl groups.

[0051] Preferably, in Formula III, R2 and R3 are each independently selected from any one of C1-C3 straight-chain or branched-chain alkyl groups.

[0052] As a preferred technical solution of the present invention, the hydrophilic compound includes any one of sulfone compounds, cyclic carbonates, and chain carbonates, or a combination of at least two thereof, and contains a large number of ester bonds in its molecular structure. It can be evenly dispersed in the polyurethane adhesive, and utilizes its own high polarity and strong hydrophilicity to reduce the difficulty of contact between water molecules and the polyurethane adhesive, and improve the uniformity of contact between the polyurethane adhesive and water molecules, thereby promoting the curing (wet curing) of the polyurethane adhesive.

[0053] Preferably, the hydrophilic compound includes any one of sulfolane, propylene carbonate, ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, and dimethyl carbonate, or a combination of at least two thereof.

[0054] Preferably, the hydrophilic compound is a commercially available product, illustratively including but not limited to: sulfolane of Mingwei, propylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate of Shandong Lixing New Materials, electronic grade propylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate of Shandong Shida Shenghua, any one of propylene carbonate of LyondellBasell or a combination of at least two thereof.

[0055] Preferably, the mass percentage of the hydrophilic compound in the solvent is 30-55%, for example, it can be 32%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, 52% or 54%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range, and 35-50% is further preferred.

[0056] Preferably, in Formula I, the ring Ar is selected from any one of a benzene ring, a naphthalene ring or an anthracene ring, that is, the hydrophobic compound includes any one of alkylnaphthalene, alkylbenzene and alkylanthracene or a combination of at least two thereof.

[0057] Preferably, in Formula I, the ring Ar is a benzene ring or a naphthalene ring.

[0058] Preferably, the hydrophobic compound comprises any one or a combination of at least two of the compound of the structure shown in Formula IA (alkylbenzene) and the compound of the structure shown in Formula IB (alkylnaphthalene);

[0059]

[0060] Preferably, the R is selected from any one of C10-C18 straight chain or branched chain alkyl groups.

[0061] Preferably, m is 1 or 2.

[0062] Preferably, the hydrophobic compound includes any one or a combination of at least two of branched dodecylbenzene, n-dodecylbenzene, undecylbenzene, T801 alkylnaphthalene, and Synesstic alkylnaphthalene base oil.

[0063] Preferably, the hydrophobic compound is a commercially available product, and exemplarily includes, but is not limited to, any one or a combination of at least two of branched dodecylbenzene from Shandong Shunhao Chemical Industry, n-dodecylbenzene from Jining Sanshi Biotechnology Co., Ltd., undecylbenzene from Tianmen Hengchang Chemical Co., Ltd., T801 alkylnaphthalene from Shandong Shangwei Chemical Industry, and Synesstic alkylnaphthalene base oil from ExxonMobil Chemical. Further preferably, it is any one or a combination of at least two of n-dodecylbenzene from Jining Sanshi Biotechnology Co., Ltd., T801 alkylnaphthalene from Shandong Shangwei Chemical Industry, and Synesstic alkylnaphthalene base oil from ExxonMobil Chemical.

[0064] Preferably, the mass percentage content of the hydrophobic compound in the solvent is 45 - 70%, for example, it can be 46%, 48%, 50%, 52%, 55%, 58%, 60%, 62%, 65%, or 68%, as well as the specific point values between the above point values. Due to space limitations and for the sake of brevity, the specific point values included in the scope of the present invention are not exhaustively listed herein. Further preferably, it is 50 - 65%.

[0065] As a preferred technical solution of the present invention, the solvent is prepared by compounding 45 - 70% of the hydrophobic compound and 30 - 55% of the hydrophilic compound. Further preferably, it is a combination of 50 - 65% of the hydrophobic compound and 35 - 50% of the hydrophilic compound, so that the solvent can not only reduce the viscosity of the adhesive, but also prevent the situation that the solvent such as alkylbenzene and / or alkylnaphthalene is too hydrophobic, resulting in uneven curing of the adhesive, and improve the curing uniformity of the polyurethane adhesive. If the amount of the hydrophobic compound in the solvent is too much, the curing speed of the adhesive will be greatly reduced, and at the same time, the curing uniformity of the adhesive will be reduced, and the strength and toughness of the polyurethane adhesive will be insufficient, affecting the high-temperature rutting resistance and low-temperature cracking resistance of the polyurethane mixture; if the amount of the hydrophilic compound in the solvent is too much, the curing speed of the adhesive will be accelerated, shortening the construction operation period of the polyurethane mixture, reducing the construction quality of the polyurethane pavement, and at the same time, too much hydrophilic compound will increase the water absorption of the adhesive, making the polyurethane mixture more likely to absorb water, affecting the water resistance stability of the polyurethane mixture, and ultimately reducing the service life of the polyurethane pavement.

[0066] Preferably, the coupling agent includes any one or a combination of at least two of silane coupling agents, titanate coupling agents, aluminate coupling agents, and zirconate coupling agents. Further preferably, it is any one or a combination of at least two of silane coupling agents, titanate coupling agents, and aluminate coupling agents. More preferably, it is a silane coupling agent and / or a titanate coupling agent.

[0067] Preferably, the silane coupling agent includes any one or a combination of at least two of amino-containing silane coupling agents, epoxy group-containing silane coupling agents, vinyl group-containing silane coupling agents, mercapto group-containing silane coupling agents, (meth)acryloyloxy group-containing silane coupling agents, urea group-containing silane coupling agents, and isocyanate group-containing silane coupling agents.

[0068] Preferably, the silane coupling agent has a structure shown in Formula IV:

[0069]

[0070] In Formula IV, R4, R5, and R6 are each independently selected from any one of C1-C4 (such as C1, C2, C3, C4) straight-chain or branched-chain alkyl groups. Further preferably, it is any one of C1-C3 straight-chain or branched-chain alkyl groups. Exemplarily, it includes but is not limited to: methyl, ethyl, isopropyl, etc. R4, R5, and R6 are respectively connected to O, and the formed -OR4, -OR5, and -OR6 are hydrolyzable groups.

[0071] In Formula IV, L is selected from any one of a single bond, C1-C10 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9, C10) straight-chain or branched-chain alkylene groups, or a group in which at least one CH2 in the C1-C10 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9, C10) straight-chain or branched-chain alkylene group is replaced by O. Further preferably, it is any one of C1-C6 straight-chain or branched-chain alkylene groups, or a group in which at least one CH2 in the C1-C6 straight-chain or branched-chain alkylene group is replaced by O.

[0072] In Formula IV, Y1 is a non-hydrolyzable group, and is selected from any one of an amino group, an acryloyloxy group, a methacryloyloxy group, an epoxy group, a hydroxyl group, a C2-C6 (such as C2, C3, C4, C5, C6) alkenyl group, a mercapto group, a C1-C6 (such as C1, C2, C3, C4, C5, C6) straight-chain or branched-chain alkyl group, a phenyl group, a thio group, a urea group, or an isocyanate group.

[0073] Preferably, Y1 is selected from any one of amino, acryloyloxy, methacryloyloxy, epoxy, hydroxyl, vinyl, mercapto, alkyl, phenyl, thiol, urea or isocyanate, more preferably any one of amino, epoxy, mercapto, phenyl, urea or isocyanate, further preferably epoxy, mercapto, urea or isocyanate.

[0074] Preferably, the silane coupling agent is a commercially available product, illustratively including but not limited to: any one or a combination of at least two of SICO-A119 from Shandong SICO, SCA-E87M from Nanjing Nengde, Silquest A-189 from Momentive, KBE9007 and KBM-603 from Shin-Etsu of Japan, and Geniosil GF40 from Wacker Chemie of Germany.

[0075] Preferably, the titanate coupling agent includes any one of a fatty acid type titanate coupling agent, a phosphate type titanate coupling agent, and a pyrophosphate type titanate coupling agent, or a combination of at least two of them.

[0076] Preferably, the titanate coupling agent is a commercially available product, illustratively including but not limited to: any one or a combination of at least two of TCA-L01 and TCA-K238T from Nanjing Nengde, GR-102 from Nanjing Tianlan New Materials, and KR-38S from Kenrich Company of the United States.

[0077] Preferably, the viscosity of the polyurethane adhesive for road paving is ≤1600 mPa·s, and can be 943-1534 mPa·s.

[0078] In a second aspect, the present invention provides a method for preparing the polyurethane adhesive for road paving as described in the first aspect, the preparation method comprising:

[0079] The isocyanate is reacted with the polyether polyol to obtain the polyurethane; the polyurethane is evenly mixed with the solvent and the coupling agent to obtain the polyurethane adhesive for road paving.

[0080] Preferably, the polyether polyol is dehydrated to have a water content of ≤2000ppm. For example, the water content may be 0, 50ppm, 100ppm, 200ppm, 300ppm, 500ppm, 800ppm, 1000ppm, 1200ppm, 1500ppm, 1800ppm or 1900ppm, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0081] Preferably, the dehydration treatment is carried out under vacuum conditions.

[0082] Preferably, the temperature of the dehydration treatment is 100-120 °C, for example, it can be 102 °C, 105 °C, 108 °C, 110 °C, 112 °C, 115 °C or 118 °C, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0083] Preferably, the temperature of the reaction is 80-100 °C, for example, it can be 82 °C, 84 °C, 85 °C, 88 °C, 90 °C, 92 °C, 94 °C, 96 °C or 98 °C, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range. Further preferably, it is 85-95 °C.

[0084] Preferably, the time of the reaction is 1-3 h, for example, it can be 1.2 h, 1.5 h, 1.8 h, 2 h, 2.2 h, 2.5 h or 2.8 h, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range. Further preferably, it is 1.5-2 h.

[0085] Preferably, the reaction is carried out under stirring conditions.

[0086] Preferably, the rotation speed of the stirring is 150-300 r / min, for example, it can be 160 r / min, 180 r / min, 200 r / min, 220 r / min, 250 r / min or 280 r / min, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0087] Preferably, the mixing is carried out under stirring conditions, and the rotation speed of the stirring is preferably 150-300 r / min, for example, it can be 160 r / min, 180 r / min, 200 r / min, 220 r / min, 250 r / min or 280 r / min, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0088] Preferably, first mix the polyurethane with the hydrophilic compound and the coupling agent, and then add the hydrophobic compound and mix evenly to obtain the polyurethane adhesive for road paving.

[0089] Preferably, the mixing time of the polyurethane with the hydrophilic compound and the coupling agent is 0.5-1 h, for example, it can be 0.6 h, 0.7 h, 0.8 h or 0.9 h, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0090] Preferably, the mixing time after adding the hydrophobic compound is 0.5 - 1 h, for example, it can be 0.6 h, 0.7 h, 0.8 h, or 0.9 h, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the said range.

[0091] In a third aspect, the present invention provides a polyurethane mixture, which comprises a combination of mineral materials and the polyurethane adhesive for pavement paving as described in the first aspect.

[0092] Preferably, the mass percentage content of the mineral materials in the polyurethane mixture is ≥90%, for example, it can be 91%, 92%, 92.5%, 93%, 93.5%, 94%, 94.5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, 99%, or 99.5%, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the said range. Further preferably, it is 93 - 98%.

[0093] Preferably, the mineral materials include a combination of coarse aggregates, fine aggregates, and mineral powder.

[0094] Preferably, the polyurethane mixture comprises the following components by mass parts:

[0095]

[0096]

[0097] Among them, the particle size of the first coarse aggregate is d1, 9.5 mm < d1 ≤ 16 mm, for example, d1 can be 9.6 mm, 9.8 mm, 10 mm, 11 mm, 12 mm, 13 mm, 14 mm, 15 mm, or 15.5 mm, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the said range.

[0098] The particle size of the second coarse aggregate is d2, 4.75 mm < d2 ≤ 9.5 mm, for example, d2 can be 4.8 mm, 5 mm, 5.5 mm, 6 mm, 6.5 mm, 7 mm, 7.5 mm, 8 mm, 8.5 mm, 9 mm, 9.2 mm, or 9.4 mm, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the said range.

[0099] The particle size of the third coarse aggregate is d3, where 2.36 mm < d3 ≤ 4.75 mm. For example, d3 can be 2.38 mm, 2.4 mm, 2.5 mm, 2.6 mm, 2.8 mm, 3 mm, 3.2 mm, 3.5 mm, 3.8 mm, 4 mm, 4.2 mm, 4.5 mm or 4.7 mm, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0100] The particle size of the fine aggregate is d4, where d4 ≤ 2.36 mm. For example, it can be 1 mm, 1.2 mm, 1.5 mm, 1.8 mm, 2 mm, 2.2 mm or 2.3 mm, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0101] Preferably, the particle size of the mineral powder is 500 - 800 μm. For example, it can be 520 μm, 530 μm, 550 μm, 580 μm, 600 μm, 620 μm, 650 μm, 680 μm, 700 μm, 720 μm, 750 μm or 780 μm, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0102] Preferably, in the polyurethane mixture provided by the present invention, the mass fraction of the first coarse aggregate is 25 - 31 parts. For example, it can be 26 parts, 26.5 parts, 27 parts, 27.5 parts, 28 parts, 28.5 parts, 29 parts, 29.5 parts, 30 parts or 30.5 parts, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0103] The mass fraction of the second coarse aggregate is 22 - 36 parts. For example, it can be 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts or 35 parts, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0104] The mass fraction of the third coarse aggregate is 6 - 14 parts. For example, it can be 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts or 13 parts, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0105] The mass portion of the fine aggregate is 20 - 40 parts. For example, it can be 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts or 38 parts, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the said range.

[0106] The mass portion of the mineral powder is 1 - 5 parts. For example, it can be 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts or 4.5 parts, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the said range.

[0107] The mass portion of the polyurethane adhesive for road paving is 3 - 5 parts. For example, it can be 3.2 parts, 3.5 parts, 3.8 parts, 4 parts, 4.2 parts, 4.5 parts or 4.8 parts, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the said range.

[0108] Preferably, the method for preparing the polyurethane mixture includes: mixing the mineral materials and the polyurethane adhesive for road paving evenly to obtain the polyurethane mixture.

[0109] Preferably, the preparation method includes: mixing the first coarse aggregate, the second coarse aggregate, the third coarse aggregate, the fine aggregate, the mineral powder and the polyurethane adhesive for road paving evenly according to the formula amount to obtain the polyurethane mixture.

[0110] Preferably, the mixing time is 30 - 90 s. For example, it can be 35 s, 40 s, 45 s, 50 s, 55 s, 60 s, 65 s, 70 s, 75 s, 80 s or 85 s, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the said range.

[0111] Fourthly, the present invention provides a road paving material, which includes at least one of the polyurethane adhesive for road paving as described in the first aspect and the polyurethane mixture as described in the third aspect.

[0112] Compared with the prior art, the present invention has the following beneficial effects:

[0113] (1) In the polyurethane adhesive for pavement paving provided by the present invention, through the design of the solvent and its mutual compounding with specific isocyanates, polyether polyols, and coupling agents, it has the characteristics of low viscosity, adjustable operation time, and controllable curing speed, so as to meet the construction requirements of polyurethane pavements in different scenarios. At the same time, the polyurethane adhesive for pavement paving has high curing uniformity, high-strength and high-toughness cured products, excellent water resistance and high-temperature resistance, and relatively low cost and less addition amount in the polyurethane mixture, effectively improving the mixing uniformity and production efficiency of the polyurethane mixture containing it, having the possibility of large-scale construction, effectively solving the problems of high-temperature rutting and low-temperature deformation and brittle cracking of asphalt pavement materials, and significantly improving the high-temperature rutting resistance, low-temperature deformation resistance, and low-temperature crack resistance of pavement materials.

[0114] (2) Through the component design and formula optimization of the polyurethane adhesive for pavement paving of the present invention, its viscosity ≤ 1550 mPa·s, the surface drying time at 30°C and 90% RH is 76 - 90 h, the tensile strength ≥ 20 MPa, the elongation at break is 332 - 880%, the water resistance stability of the polyurethane mixture containing it after curing is 85 - 92%, the Marshall stability is 80 - 115 kN, the splitting strength is 3.2 - 4 MPa, the low-temperature bending strain is 4810 - 10910 με, the Hamburg rut depth ≤ 0.94 mm, with high strength and toughness, high Marshall stability, good water resistance, and excellent rutting resistance and low-temperature crack resistance. Specific Embodiments

[0115] The technical solutions of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations to the present invention.

[0116] In the following specific embodiments of the present invention, the materials involved are as follows:

[0117] (1) Isocyanate

[0118] Polymethylene polyphenyl isocyanate: PM-130, PM-200 of Wanhua Chemical;

[0119] Diisocyanate: MDI-50, MDI-100 of Wanhua Chemical.

[0120] (2) Polyether polyol

[0121] C2020: Polyoxypropylene polyol, with a number average molecular weight of 2000, functionality of 2, hydroxyl value of 56.1 mg KOH / g, using propylene glycol as the initiator and PO as the repeating unit; purchased from Wanhua Rongwei;

[0122] F3056D, with a number-average molecular weight of 3000, functionality of 3, and hydroxyl value of 56.1 mg KOH / g; purchased from Wanhua Rongwei;

[0123] PTMG-2000, polytetrahydrofuran diol, with a number-average molecular weight of 2000 and hydroxyl value of 56.1 mg KOH / g; purchased from BASF.

[0124] (3) Solvent

[0125] Hydrophilic compounds: Propylene carbonate and dimethyl carbonate from Shandong Lixing New Materials, and sulfolane from Mingwei;

[0126] Hydrophobic compounds: T801 alkylnaphthalene from Shandong Shangwei Chemical Industry, Synesstic alkylnaphthalene base oil solvent from ExxonMobil Chemical, and n-dodecylbenzene from Jining Sanshi Biology.

[0127] (4) Coupling agent

[0128] Silane coupling agent: SCA-E87M from Nanjing Nengde;

[0129] Titanate coupling agent: GR-102 from Nanjing Tianlan New Materials.

[0130] Example 1

[0131] This example provides a polyurethane adhesive for road paving, and its preparation raw materials include the following components by mass:

[0132]

[0133] The preparation method of the polyurethane adhesive for road paving is as follows:

[0134] (1) According to the formula amount, vacuum dehydrate each polyether polyol at 120 °C until the water content is lower than 2000 ppm, and then cool the polyether polyol to 90 °C for standby;

[0135] (2) Mix and heat the various isocyanates to 90 °C, add the dehydrated polyether polyol obtained in step (1) thereto, and react at 90 °C for 1.5 h under stirring at 200 r / min to end the reaction and obtain polyurethane;

[0136] (3) Start to cool the polyurethane obtained in step (2) to 50 °C, add the hydrophilic compound propylene carbonate and the coupling agent thereto, and stir for 0.5 h under the condition of 200 r / min; after the stirring is completed, add the hydrophobic compound T801 alkylnaphthalene and continue to stir for 0.5 h under the stirring condition of 200 r / min to obtain the polyurethane adhesive for road paving.

[0137] This embodiment also provides a polyurethane mixture, which includes the combination of the polyurethane adhesive for pavement paving provided in this embodiment and mineral aggregates. The mass ratio of the polyurethane adhesive for pavement paving to the mineral aggregates is 4.8:100. The mineral aggregates adopt the graded mineral aggregates of dense-graded asphalt mixture AC-13, and the components of the mineral aggregates are shown in Table 1 below:

[0138] Table 1

[0139]

[0140] The preparation method of the polyurethane mixture is as follows: Place each aggregate and mineral powder in a mixing pot according to the formula in Table 1, add the polyurethane adhesive for pavement paving, and stir for 60 s to obtain the polyurethane mixture.

[0141] Perform performance tests on the aforementioned polyurethane adhesive for pavement paving and the polyurethane mixture. The specific methods are as follows:

[0142] (1) Viscosity of the adhesive: Test the viscosity of the polyurethane adhesive according to "GB / T 2794-2013 Determination of Viscosity of Adhesives", and the test temperature is 25°C.

[0143] (2) Test for surface drying time of the adhesive: Refer to the test method for surface drying time in "GB / T 16777-2008 Building Waterproof Coatings" to test the surface drying time of the adhesive, and the test conditions are 30°C / 90% RH.

[0144] (3) Tensile property test: Refer to the method in "GB / T 1040-2018 Determination of Tensile Properties of Plastics" to test the tensile strength and elongation at break of the polyurethane adhesive.

[0145] (4) Test of the polyurethane mixture

[0146] Prepare Marshall specimens with reference to "Test Procedures for Bitumen and Bituminous Mixtures in Highway Engineering" (JTGE20-2011). The diameter of the specimens is 101.6 mm and the thickness is 63.5 mm. Cure them at room temperature for 48 h, and then place them in an environment of 50°C / 90% RH for accelerated curing for 4 days. Prepare rutting plate specimens with reference to "Test Procedures for Bitumen and Bituminous Mixtures in Highway Engineering" (JTGE20-2011). The size of the specimens is: length × width × height = 300 mm × 300 mm × 50 mm. Cure them at room temperature for 48 h, and then place them in an environment of 50°C / 90% RH for accelerated curing for 4 days. After the rutting plate specimens are cured, cut the rutting plates into beam specimens with a size of length × width × height = 250 mm × 30 mm × 35 mm according to the bending test method of asphalt mixtures.

[0147] Test the water resistance stability of the polyurethane mixture according to the method in "T0729-2000 Asphalt Mixture Freeze-Thaw Split Test" in "Specifications for Tests of Bitumen and Bituminous Mixtures for Highway Engineering" (JTGE20-2011), test the Marshall stability of the polyurethane mixture according to the method in "T0709-2011 Marshall Stability Test of Asphalt Mixtures" in "Specifications for Tests of Bitumen and Bituminous Mixtures for Highway Engineering" (JTGE20-2011), test the splitting strength of the polyurethane mixture according to the method in "T0716-2011 Asphalt Mixture Splitting Test" in "Specifications for Tests of Bitumen and Bituminous Mixtures for Highway Engineering" (JTGE20-2011), and test the low-temperature bending strain of the polyurethane mixture according to the method in "T0715-2011 Asphalt Mixture Bending Test" in "Specifications for Tests of Bitumen and Bituminous Mixtures for Highway Engineering" (JTGE20-2011).

[0148] Test the Hamburg rut depth of the polyurethane mixture according to the AASHTO T324 Hamburg rut test procedure.

[0149] The test data are shown in Table 2.

[0150] Examples 2-9, Comparative Examples 1-4

[0151] A polyurethane adhesive for pavement paving and a polyurethane mixture containing the same are different from Example 1 only in that the raw materials for preparing the polyurethane adhesive for pavement paving are different, and the specific formulations are shown in Table 2 and Table 3; wherein, the dosage unit of each component is "parts by mass"; the preparation methods and performance test methods of the polyurethane adhesive for pavement paving and the polyurethane mixture are the same as those in Example 1.

[0152] Table 2

[0153]

[0154]

[0155]

[0156] Table 3

[0157]

[0158]

[0159] Combined with the foregoing performance test data, it can be seen that through the component design and formula optimization of the polyurethane adhesive for pavement paving, especially by introducing a combination of solvents with specific components and isocyanates with different activities, and compounding with polyether polyols and coupling agents, the polyurethane adhesive has a low viscosity, with a viscosity of 943 - 1534 mPa·s. The pot life and curing speed can be adjusted and controlled. The surface drying time at 30°C and 90% RH is 76 - 90 h, and it has the characteristics of high strength and high toughness, with a tensile strength of 20 - 32 MPa and an elongation at break of 332 - 880%. The water resistance stability of the polyurethane mixture containing the polyurethane adhesive for pavement paving in Examples 1 - 7 after curing is 85 - 92%, the Marshall stability is 80 - 115 kN, the splitting strength is 3.2 - 4 MPa, the low-temperature bending strain is 4810 - 10910 με, and the Hamburg rut depth is 0.80 - 0.94 mm. It has a high Marshall stability, good water resistance, and excellent rutting resistance and low-temperature crack resistance. In addition, in the present invention, by adjusting the ratio of hydrophilic compounds and hydrophobic compounds in the solvent, further optimization of the performance of the polyurethane adhesive can be achieved; in Example 8, the amount of hydrophilic propylene carbonate is too small, resulting in a slower curing speed of the polyurethane adhesive, and a certain degree of reduction in the strength and toughness of the adhesive, thereby affecting the splitting strength, Marshall stability, and Hamburg rut depth of the polyurethane mixture; in Example 9, the amount of propylene carbonate is too large, resulting in a greatly shortened surface drying time of the polyurethane adhesive. At the same time, due to the excessive amount of hydrophilic propylene carbonate in the polyurethane adhesive, the adhesive is easily absorbed by water, damaging the interfacial bonding effect between the stone and the adhesive, and thus reducing the splitting strength and water resistance stability of the polyurethane mixture.

[0160] In Comparative Examples 1 and 4, although they also contain hydrophobic solvents, they are different from the specific type of hydrophobic compounds with the structure shown in Formula I defined in the present invention, resulting in easier intrusion of moisture into the bonding interface between the adhesive and the stone, thus affecting the splitting strength and water resistance stability of the polyurethane mixture. In Comparative Example 2, a single hydrophobic solvent is used, resulting in a slower curing speed of the adhesive and a reduction in the tensile strength of the adhesive, ultimately affecting the Marshall stability, splitting strength, and Hamburg rut depth of the polyurethane mixture. In Comparative Example 3, a single hydrophilic solvent is used, resulting in a greatly shortened surface drying time of the polyurethane adhesive. Due to the presence of a large amount of hydrophilic solvent, the adhesive is extremely easy to absorb moisture, thereby affecting the water resistance stability, splitting strength, Marshall stability, and low-temperature bending strain of the polyurethane mixture.

[0161] The applicant declares that the present invention uses the above embodiments to illustrate the polyurethane adhesive for pavement paving and the polyurethane mixture containing the same, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent replacement of each raw material of the present invention's product, the addition of auxiliary components, the selection of specific methods, etc. all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A polyurethane adhesive for pavement paving, characterized in that, The raw materials for preparing the polyurethane adhesive for pavement paving include the following components by mass: The isocyanate includes aromatic isocyanate; The solvent includes a combination of hydrophilic compounds and hydrophobic compounds, and the hydrophobic compound has the structure shown in Formula I: Ring Ar is selected from any one of C6-C16 aromatic rings; R is selected from any one of C8-C20 straight-chain or branched-chain alkyl groups; m is an integer selected from 1-3; when m≥2, multiple Rs are the same or different groups.

2. The polyurethane adhesive for pavement paving according to claim 1, wherein, The isocyanate includes a combination of polymethylene polyphenyl isocyanate and diisocyanate; Preferably, the mass percentage content of polymethylene polyphenyl isocyanate in the isocyanate is 6-22%, and further preferably 8-20%; Preferably, the average functionality of the polymethylene polyphenyl isocyanate is 2.3-3.0, and further preferably 2.5-2.9; Preferably, the viscosity of the polymethylene polyphenyl isocyanate is 100-1000 mPa·s, and further preferably 150-500 mPa·s; Preferably, the mass percentage content of the NCO group in the polymethylene polyphenyl isocyanate is 29-32%, and further preferably 29.5-31.5%; Preferably, the mass percentage content of diisocyanate in the isocyanate is 78-94%, and further preferably 80-92%; Preferably, the viscosity of the diisocyanate is 3-40 mPa·s, and further preferably 3.5-38 mPa·s; Preferably, the mass percentage content of the NCO group in the diisocyanate is 30-60%, and further preferably 32-58%; Preferably, the diisocyanate includes any one or a combination of at least two of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, and further preferably diphenylmethane diisocyanate and / or toluene diisocyanate.

3. The polyurethane adhesive for pavement paving according to claim 1 or 2, characterized in that, The functionality of the polyether polyol ≥2, preferably 2-3; Preferably, the number average molecular weight of the polyether polyol is 1000-5000, and further preferably 1500-4500; Preferably, the hydroxyl value of the polyether polyol is 20-200 mg KOH / g, and further preferably 25-150 mg KOH / g.

4. The polyurethane adhesive for pavement paving according to any one of claims 1-3, characterized in that The hydrophilic compound includes any one or a combination of at least two of sulfone compounds, compounds with the structure shown in Formula II, and compounds with the structure shown in Formula III; Among them, X1, X2, and X3 are each independently selected from O or S; R1 is selected from any one of H, C1-C4 straight-chain or branched-chain alkyl groups; R2 and R3 are each independently selected from any one of C1-C6 straight-chain or branched-chain alkyl groups; Preferably, X1, X2, and X3 are O; Preferably, R1 is selected from any one of H, C1-C3 straight-chain or branched-chain alkyl groups; Preferably, R2 and R3 are each independently selected from any one of C1-C3 straight-chain or branched-chain alkyl groups; Preferably, the hydrophilic compound includes any one or a combination of at least two of sulfolane, propylene carbonate, ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, and dimethyl carbonate; Preferably, the mass percentage content of the hydrophilic compound in the solvent is 30 - 55%, more preferably 35 - 50%.

5. The polyurethane adhesive for pavement paving according to any one of claims 1-4, characterized in that, In formula I, the ring Ar is selected from any one of a benzene ring, a naphthalene ring, and an anthracene ring, preferably a benzene ring or a naphthalene ring; Preferably, the hydrophobic compound includes any one or a combination of at least two of the compounds having the structure shown in formula IA and the compounds having the structure shown in formula IB; Preferably, R is selected from any one of C10 - C18 straight-chain or branched-chain alkyl groups; Preferably, m is 1 or 2; Preferably, the hydrophobic compound includes any one or a combination of at least two of branched dodecylbenzene, n-dodecylbenzene, undecylbenzene, T801 alkylnaphthalene, and Synesstic alkylnaphthalene base oil; Preferably, the mass percentage content of the hydrophobic compound in the solvent is 45 - 70%, more preferably 50 - 65%.

6. The polyurethane adhesive for pavement paving according to any one of claims 1-5, characterized in that, The coupling agent includes any one or a combination of at least two of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, and a zirconate coupling agent, preferably a silane coupling agent and / or a titanate coupling agent; Preferably, the silane coupling agent includes any one or a combination of at least two of an amino-containing silane coupling agent, an epoxy group-containing silane coupling agent, a vinyl group-containing silane coupling agent, a mercapto group-containing silane coupling agent, a (meth)acryloyloxy group-containing silane coupling agent, a urea group-containing silane coupling agent, and an isocyanate group-containing silane coupling agent; Preferably, the titanate coupling agent includes any one or a combination of at least two of a fatty acid type titanate coupling agent, a phosphate type titanate coupling agent, and a pyrophosphate type titanate coupling agent.

7. A preparation method of the polyurethane adhesive for pavement paving according to any one of claims 1-6, characterized in that, The preparation method includes: Reacting an isocyanate with a polyether polyol to obtain a polyurethane; mixing the polyurethane with a solvent and a coupling agent uniformly to obtain the polyurethane adhesive for road paving; Preferably, the temperature of the reaction is 80 - 100 °C, more preferably 85 - 95 °C; Preferably, the time of the reaction is 1 - 3 h, more preferably 1.5 - 2 h; Preferably, first mix the polyurethane with the hydrophilic compound and the coupling agent, and then add the hydrophobic compound and mix uniformly to obtain the polyurethane adhesive for road paving.

8. A polyurethane mixture, characterized in that, The polyurethane mixture includes a combination of mineral materials and the polyurethane adhesive for road paving as described in any one of claims 1 - 6.

9. The polyurethane mixture according to claim 8, characterized in that, The mass percentage content of the mineral materials in the polyurethane mixture is ≥90%; Preferably, the mineral materials include a combination of coarse aggregates, fine aggregates, and mineral powder; Preferably, the polyurethane mixture includes the following components by mass parts: Among them, the particle size of the first coarse aggregate is d1, 9.5 mm < d1 ≤ 16 mm; the particle size of the second coarse aggregate is d2, 4.75 mm < d2 ≤ 9.5 mm; the particle size of the third coarse aggregate is d3, 2.36 mm < d3 ≤ 4.75 mm; the particle size of the fine aggregate is d4, d4 ≤ 2.36 mm.

10. A pavement paving material, characterized in that, The pavement paving material includes at least one of the polyurethane adhesives for pavement paving as described in any one of claims 1-6 and the polyurethane mixture as described in claim 8 or 9.

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