Cold-mixed and cold-laid mixture based on polyurethane modified petroleum resin and preparation method of cold-mixed and cold-laid mixture

Abstract

The invention discloses a cold-mixed and cold-laid mixture based on polyurethane modified petroleum resin and a preparation method of the cold-mixed and cold-laid mixture, and belongs to the technical field of road materials. The mixture is prepared from the following components in parts by mass: 4 to 8 parts of polyurethane modified petroleum resin, 88 to 94 parts of mineral aggregate and 2 to 4 parts of toner. The preparation method comprises the following steps: reacting hydroxyl-terminated polybutadiene with diisocyanate to prepare a polyurethane prepolymer; under the action of a free radical initiator, carrying out copolymerization reaction on the prepolymer and C5 / C9 petroleum resin to prepare chemically modified petroleum resin; and finally, mixing the mixture with a polyurethane curing agent to obtain a premix, and mixing the premix with mineral aggregate and toner at normal temperature. Through chemical grafting modification, the flexibility, the binding power and the water damage resistance of the material are remarkably improved, the obtained mixture is high in Marshall stability and strong in adhesive force, cold mixing and cold paving construction is completely achieved, and the material has the advantages of being low in energy consumption, free of pollution, convenient and fast to construct and high in cost effectiveness and is particularly suitable for road maintenance, emergency repair and colored pavement paving.

Description

Technical Field

[0001] This invention belongs to the field of road materials technology, specifically relating to a cold-mix cold-laying compound based on polyurethane modified petroleum resin and its preparation method. Background Technology

[0002] Asphalt mixtures are one of the most widely used core materials in road construction and maintenance projects. Traditional hot-mix asphalt mixtures require mixing and paving at high temperatures, which not only consumes a large amount of energy but also emits a large amount of harmful gases and dust, causing serious environmental pollution. Furthermore, the high-temperature construction conditions pose a threat to the safety of construction workers. In addition, hot-mix asphalt mixtures are prone to temperature decay during transportation and construction in cold seasons or remote road sections, making it difficult to guarantee the quality of pavement construction and greatly limiting their application in special scenarios.

[0003] To address the aforementioned issues, cold-mix cold-pave asphalt mixtures have emerged. These materials can be mixed and paved at room temperature, offering significant advantages such as low energy consumption, convenient construction, and environmental friendliness. They are particularly suitable for emergency road repairs, small-area maintenance, and road projects in low-temperature and remote areas, and have become a research hotspot and development trend in the field of road materials. However, existing cold-mix asphalt mixtures still face numerous technical bottlenecks. On the one hand, the base asphalt or ordinary modified asphalt commonly used in traditional cold-mix asphalt mixtures suffers from insufficient bonding performance and poor flexibility, resulting in the Marshall stability of the mixture often failing to meet engineering requirements. Although my country's JTG F40 "Technical Specification for Construction of Highway Asphalt Pavement" stipulates that the Marshall stability of cold-mix asphalt mixtures should not be less than 3kN, most existing products are prone to loosening, peeling, and other defects in practical applications, affecting the service life of the pavement. On the other hand, in order to reduce material costs, some technical solutions use petroleum resin as a modifying component. However, traditional modification methods are mostly physical blending, and petroleum resin and the main binder material fail to form a stable chemical bond. When the amount of petroleum resin is high, it is easy to remain free in the system, reducing the intermolecular interaction force, which in turn leads to a decline in the mechanical properties of the material, making it impossible to balance cost-effectiveness and performance.

[0004] Petroleum resins, as byproducts of petroleum refining, possess advantages such as low cost, strong hydrophobicity, and resistance to acid and alkali corrosion, making them promising for applications in road materials. C5 and C9 petroleum resins, in particular, are frequently used for asphalt modification due to their wide availability of raw materials and mature preparation processes. However, unmodified petroleum resins suffer from high brittleness and insufficient bonding strength, making them unsuitable for meeting the load-bearing and anti-aging requirements of road surfaces when directly applied to cold-mix asphalt mixtures. While existing technologies have attempted to modify petroleum resins with polyurethane, these methods primarily involve incorporating petroleum resins as non-reactive fillers into the polyurethane system. This simple blending approach fails to form a cross-linked network structure, resulting in limited improvements in the flexibility and adhesion of the modified materials. Furthermore, the dosage of petroleum resins is strictly limited, hindering the full realization of their cost advantages.

[0005] Therefore, how to achieve efficient chemical bonding between petroleum resin and polyurethane through innovative modification technology, while retaining the low-cost advantage of petroleum resin, significantly improve the flexibility, adhesion and bonding strength of the modified material, and thus develop a cold-mixed paving material that is easy to construct, low in energy consumption, environmentally friendly and has excellent road performance, has become an urgent technical problem to be solved in the field of road materials.

[0006] Currently, research on the modification of petroleum resins using polyurethane as a modifier through chemical modification methods is relatively scarce, and existing polyurethane modification technologies mostly focus on asphalt systems. The invention patent "A Two-Component Polyurethane Warm-Mix Composite Modified Asphalt, Asphalt Mixture and its Preparation Method" discloses a polyurethane modified asphalt mixture and its preparation method. The composite modified asphalt raw material includes the following components by weight: 100 parts of base asphalt, 0-3 parts of compatibilizer, 3-20 parts of two-component polyurethane raw material, and 0.3-4 parts of warm-mix agent; the warm-mix agent is at least one of Sasobit, Aspha-min, and DWMA-1. This invention patent utilizes a compatibilizer to make asphalt and two-component polyurethane raw material compatible, but the modification of polyurethane and asphalt remains at the level of physical blending modification. The compatibilizer simply increases the compatibility between polyurethane and asphalt; no chemical bond occurs between the three components. The patent description does not state that these three components will undergo a chemical reaction to form a bond, so it remains at the level of physical modification, which can easily cause material stratification or precipitation, affecting the overall performance of the material.

[0007] Currently, polyurethane-modified petroleum resins are rarely used in mixtures. Huang Chaoming's invention, "A Modified Polyurethane Waterproof Coating, Its Preparation Method and Construction Method," includes Group A and Group B. Group A is prepared by mixing and reacting polyether polyol or polyester polyol with isocyanate; Group B is prepared by mixing and reacting petroleum resin, petroleum-based rubber oil, dibutyl phthalate and / or diisononyl phthalate, filler, di-o-chlorodiphenylmethane diamine, and catalyst. The reaction mechanism of this invention mainly involves the chemical reaction between the isocyanate groups in the polyurethane and certain hydroxyl and amine groups in the petroleum resin molecules, forming chemical bonds that combine the two. The patent document "Modified C9 Hydrogenated Petroleum Resin, Its Preparation Method and Application" (Patent No.: CN202211707389) points out that petroleum resin contains a large number of unsaturated bonds but no polar groups, resulting in poor compatibility with polar materials and poor thermal stability. The document also mentions that the acid value of acid-modified petroleum resin is low (<1.0 mg KOH / g resin), further reflecting the scarcity of active groups in petroleum resin itself, which is consistent with the extremely low content of active groups such as hydroxyl and amino groups. Therefore, in the "A Modified Polyurethane Waterproof Coating, Its Preparation Method and Construction Method," there is a large amount of free polyurethane after the reaction, resulting in poor mixing between polyurethane and petroleum resin. The uniformity of the film after formation cannot be guaranteed, leading to poor performance of the polyurethane-modified petroleum resin.

[0008] Other invention patents include "Preparation of a Petroleum Resin-Modified Polyamine Epoxy Resin Curing Agent" (202210883997.4), "An Oil-Based Epoxy Asphalt Colored Road Anti-Slip Coating Based on Epoxy-Modified Petroleum Resin and Its Preparation Method" (202210895331.0), and "An Water-Based Epoxy Asphalt Colored Road Anti-Slip Coating Based on Epoxy-Modified Petroleum Resin and Its Preparation Method" (202210883989.X). All three patents focus on the field of epoxy resin modification technology. Among them, "Preparation of a Petroleum Resin-Modified Polyamine Epoxy Resin Curing Agent" uses C5 or C9 fractions as the main raw material, introduces allyl glycidyl ether to prepare modified petroleum resin, and then reacts it with polyamine end-capping products to finally obtain the epoxy resin curing agent. The latter two patents prepare epoxy-modified petroleum resin composite materials through chemical modification processes, with their core application being epoxy asphalt colored road anti-skid coatings. The core technology of this invention is the field of modified petroleum resin, which is significantly different from the field of epoxy resin modification focused on by the above three patents. The core innovation lies in the chemical modification of petroleum resin through polyurethane, optimizing key performance indicators such as flexibility and adhesion of petroleum resin, and thus preparing high-performance cold-mix cold-lay mixture suitable for road engineering applications. It is fundamentally different from the above patents in terms of technical field, core modification system and technical objectives. Summary of the Invention

[0009] The purpose of this invention is to overcome the technical shortcomings of existing cold-mix cold-pavement mixtures, such as insufficient binder performance, low modification efficiency of petroleum resin and polyurethane, poor material compatibility, and difficulty in balancing construction and performance. This invention provides a cold-mix cold-pavement mixture based on polyurethane-modified petroleum resin and its preparation method. This method achieves efficient and stable bonding of petroleum resin and polyurethane through an innovative chemical modification pathway. The prepared mixture exhibits excellent flexibility, adhesion, and bonding strength, and can be mixed and paved at room temperature. It also features low cost, low energy consumption, and environmental friendliness, meeting the engineering needs of road construction and maintenance.

[0010] The technical solution adopted in this invention is:

[0011] A cold-mix paving compound based on polyurethane-modified petroleum resin, comprising the following components by weight parts:

[0012] 4-8 parts polyurethane modified petroleum resin, 88-94 parts mineral powder, and 2-4 parts color powder.

[0013] The polyurethane-modified petroleum resin comprises the following components in parts by weight:

[0014] 100 parts of hydroxyl-terminated polybutadiene polyurethane prepolymer modified petroleum resin and 18-163 parts of polyurethane curing agent.

[0015] The hydroxyl-terminated polybutadiene polyurethane prepolymer modified petroleum resin is composed of the following components by mass parts: 30-45 parts of at least one of C5 or C9 petroleum resin, 20-41.5 parts of solvent, 0.2-0.5 parts of azobisisobutyronitrile, 5-15 parts of diisocyanate, and 11-33 parts of hydroxyl-terminated polybutadiene.

[0016] The method for preparing the polyurethane-modified petroleum resin includes the following steps:

[0017] Step 1: Preparation of hydroxyl-terminated polybutadiene polyurethane prepolymer

[0018] Accurately weigh 11-33 parts of hydroxyl-terminated polybutadiene, dehydrate it for 2 hours at 120℃ and -0.09MPa, cool it down to 50℃, add 5-15 parts of diisocyanate, react at 50℃ for 1 hour, raise the temperature to 80℃ and continue the reaction for 3 hours, degas for 30 minutes, and obtain a hydroxyl-terminated polybutadiene polyurethane prepolymer with a -NCO content of 6.4%-9.6%.

[0019] Step 2: Preparation of petroleum resin modified with hydroxyl-terminated polybutadiene polyurethane prepolymer

[0020] Add 30-45 parts of at least one of C5 or C9 petroleum resin and 20-41.5 parts of solvent to a reaction vessel, control the temperature at 70-80℃, stir until completely dissolved, add 0.2-0.5 parts of azobisisobutyronitrile, and dropwise add 16-48 parts of the hydroxyl-terminated polybutadiene polyurethane prepolymer obtained in the first step, which is added over 3 hours. Continue the reaction for 1 hour to obtain hydroxyl-terminated polybutadiene polyurethane prepolymer modified petroleum resin.

[0021] Step 3: Preparation of polyurethane-modified petroleum resin premix

[0022] 100 parts of the hydroxyl-terminated polybutadiene polyurethane prepolymer modified petroleum resin obtained in the second step are mixed and stirred evenly with 18-163 parts of polyurethane curing agent to obtain a polyurethane modified petroleum resin premix for later use.

[0023] The solvent is an organic solvent with a boiling point above 80°C under normal pressure.

[0024] The diisocyanate is either toluene diisocyanate or diphenylmethane diisocyanate.

[0025] The polyurethane curing agent is one or more of polypropylene glycol with a relative molecular mass of 1000, polypropylene glycol with a relative molecular mass of 2000, and di-o-chlorodiphenylmethane diamine.

[0026] The C5 petroleum resin is a thermoplastic resin obtained by pretreatment, polymerization, and distillation of C5 fraction.

[0027] The C9 petroleum resin is a thermoplastic resin obtained by pretreatment, polymerization, and distillation of C9 fraction.

[0028] The mineral material is composed of 48-62 parts of 5-8mm first coarse aggregate, 21-27 parts of 3-5mm second coarse aggregate, and 17-25 parts of 0-3mm fine aggregate; and the mineral material is any one of basalt, granite, and diabase.

[0029] A method for preparing the aforementioned cold-mix cold-laying compound based on polyurethane modified petroleum resin includes the following steps:

[0030] At room temperature, 88-94 parts of mineral aggregate and 2-4 parts of color powder are mixed for 10-15 seconds to obtain aggregate. The aggregate is then sprayed into 4-8 parts of the prepared polyurethane-modified petroleum resin premix while being mixed for 30-45 seconds to ensure that the polyurethane-modified petroleum resin premix coats the aggregate, thus obtaining the cold-mixed and cold-laid polyurethane-modified petroleum resin mixture.

[0031] The mixture uses the following gradations: 100% passing through a 9.5mm sieve, 35-75% passing through a 4.75mm sieve, 15-35% passing through a 2.36mm sieve, 8-25% passing through a 1.18mm sieve, 6-20% passing through a 0.6mm sieve, 5-15% passing through a 0.3mm sieve, 4-12% passing through a 0.015mm sieve, and 4-10% passing through a 0.075mm sieve.

[0032] The cold-mix cold-laying compound based on polyurethane modified petroleum resin and its preparation method provided by this invention have the following significant advantages and positive effects:

[0033] Innovative Modification Mechanism and Robust Chemical Bonding: This invention abandons the traditional modification approach that relies on the low content of polar groups in petroleum resins. Instead, it innovatively utilizes a free radical initiator (such as azobisisobutyronitrile) to copolymerize a hydroxyl-terminated polybutadiene polyurethane prepolymer (whose molecular chain contains carbon-carbon double bonds from hydroxyl-terminated polybutadiene) with the abundant carbon-carbon double bonds in petroleum resin molecules. This process achieves chemical grafting between polyurethane segments and petroleum resin molecules, forming stable chemical bonds. This chemical modification method fundamentally solves the problems of material stratification and component release that easily occur with physical blending, ensuring a uniform and stable modified system and significantly improving the material's bulk properties and adhesion durability with aggregates.

[0034] Excellent material properties and outstanding road performance:

[0035] Excellent flexibility and crack resistance: The chemically introduced long polyurethane chains endow the material with excellent flexibility and elastic recovery. As shown in Table 1, the binder elongation of the mixture of the present invention (D mixture) is far superior to that of traditional SBS modified petroleum resin mixtures and ordinary asphalt mixtures, which can better adapt to base deformation and temperature stress, and effectively reduce the risk of low-temperature cracking and reflective cracking of the pavement.

[0036] Superior bonding performance and structural strength: The chemically bonded network structure greatly enhances the cohesion of the binder and its adhesion to the aggregate. Marshall stability tests show that the stability of the mixture of this invention far exceeds the basic requirements of traditional cold-mix asphalt mixtures and is significantly better than the comparative SBS modified petroleum resin and ordinary asphalt mixtures (see Table 1), providing sufficient structural strength and rutting resistance for the pavement.

[0037] Strong adhesion and resistance to water damage: Through boiling water peel test (referencing relevant standard methods, a higher rating indicates stronger adhesion, with level 5 being the optimal), the interfacial adhesion between the binder and aggregates in this invention reached the highest level (level 5), significantly superior to the control group (see Table 1). This indicates its extremely strong resistance to water erosion, effectively preventing aggregate peeling in humid or rainy environments, significantly reducing the probability of road surface water damage, and extending road service life.

[0038] Convenient and environmentally friendly construction, with a wide range of applications:

[0039] True cold mix and cold paving: The entire mixing and paving process is carried out at room temperature, without the need for high-temperature heating of aggregates and binders, thus completely avoiding the high energy consumption problem of traditional hot mix processes.

[0040] Environmentally friendly: The construction process produces no high-temperature emissions of harmful gases such as asphalt fumes and dust, which improves the working environment, reduces the impact on the health of construction workers, and conforms to the concept of green construction.

[0041] Highly adaptable: Particularly suitable for emergency road repairs, winter low-temperature construction, road maintenance in remote areas, and scenarios requiring rapid reopening of traffic under heavy traffic pressure. The addition of pigments facilitates the preparation of colored pavements, meeting diverse needs such as municipal beautification, traffic warnings, and the construction of pedestrian and bicycle lanes.

[0042] Significant comprehensive benefits, balancing performance and cost: As shown in Table 1, the performance comparison of this invention's mixture (Mixture D) is slightly inferior to the high-performance pure polyurethane mixture (Mixture A) in key properties such as flexibility, adhesion, and bonding strength, but comprehensively surpasses the traditional SBS-modified petroleum resin mixture (Mixture B) and ordinary asphalt mixture (Mixture C). More importantly, this invention efficiently utilizes low-cost petroleum resin through chemical modification, achieving near-pure polyurethane mixture performance while significantly reducing raw material costs. This overcomes the bottleneck of high-priced pure polyurethane materials being difficult to apply on a large scale in ordinary road engineering, achieving a good balance between high performance and low cost, and possessing broad prospects for engineering applications and market promotion.

[0043] Table 1 Comparison of Key Performance Tests for Various Mixtures

[0044] Performance indicators Test Project Mixture A (Polyurethane) Mixture B (SBS modified petroleum resin) C-mixture (ordinary asphalt) D-mixture (this invention) flexibility Bonding material elongation (cm) 50 25 11 34 Adhesion Marshall stability (kN) 15 4 5 12 Adhesion Boiling water peel test levels (1-5) 4 3 3 5 Detailed Implementation

[0045] The present invention will be further described below with reference to embodiments.

[0046] Example 1

[0047] The cold-mix cold-laying compound based on polyurethane modified petroleum resin described in this embodiment includes the following components in parts by weight:

[0048] 8 parts polyurethane modified petroleum resin, 88 parts mineral powder, and 4 parts color powder.

[0049] The above-mentioned method for preparing a cold-mix and cold-laying compound based on polyurethane modified petroleum resin includes the following steps:

[0050] Step 1: Preparation of hydroxyl-terminated polybutadiene polyurethane prepolymer

[0051] 23.2 parts of hydroxyl-terminated polybutadiene were accurately weighed and dehydrated at 120℃ and -0.09MPa for 2 hours. When the temperature dropped to 50℃, 9 parts of diphenylmethane diisocyanate were accurately added and reacted at 50℃ for 1 hour. Then the temperature was raised to 80℃ and reacted for 3 hours. After degassing for 30 minutes, a hydroxyl-terminated polybutadiene polyurethane prepolymer with a -NCO% content of 6.4% was obtained.

[0052] Step 2: Preparation of petroleum resin modified with hydroxyl-terminated polybutadiene polyurethane prepolymer

[0053] 42 parts of C5 petroleum resin and 25.4 parts of solvent were added to a reaction vessel, and the temperature of the reaction vessel was controlled at 70-80℃. The mixture was stirred until the C5 petroleum resin was completely dissolved. Then, 0.4 parts of azobisisobutyronitrile were added at the reaction temperature of 70-80℃, and 32.2 parts of prepolymer containing hydroxyl-terminated polybutadiene were added dropwise. The addition was controlled to be completed in 3 hours, and the reaction was continued for 1 hour to prepare hydroxyl-terminated polybutadiene polyurethane prepolymer modified petroleum resin.

[0054] Step 3: Preparation of polyurethane-modified petroleum resin premix

[0055] 100 parts of hydroxyl-terminated polybutadiene polyurethane prepolymer modified petroleum resin were mixed with 2 parts of di-o-chlorodiphenylmethane diamine and 16 parts of polyoxypropylene glycol to prepare a polyurethane modified petroleum resin premix.

[0056] Step 4: The ore is prepared by mixing 48 parts of 5-8mm basalt, 27 parts of 3-5mm basalt, and 25 parts of 0-3mm basalt.

[0057] Step 5: At room temperature, mix 88 parts of mineral material and 4 parts of color powder for 10-15 seconds until uniformly mixed to obtain aggregate. Spray the aggregate into 8 parts of the prepared polyurethane modified petroleum resin premix while mixing for 30-45 seconds to ensure that the polyurethane modified petroleum resin premix coats the aggregate, thus obtaining the cold-mixed and cold-laid polyurethane modified petroleum resin mixture.

[0058] Example 2

[0059] The cold-mix cold-laying compound based on polyurethane modified petroleum resin described in this embodiment includes the following components in parts by weight:

[0060] 8 parts polyurethane modified petroleum resin, 88 parts mineral powder, and 4 parts color powder.

[0061] The above-mentioned method for preparing a cold-mix and cold-laying compound based on polyurethane modified petroleum resin includes the following steps:

[0062] Step 1: Preparation of hydroxyl-terminated polybutadiene polyurethane prepolymer

[0063] 27.5 parts of hydroxyl-terminated polybutadiene were accurately weighed and dehydrated at 120℃ and -0.09MPa for 2 hours. When the temperature dropped to 50℃, 9.8 parts of toluene diisocyanate were accurately added and reacted at 50℃ for 1 hour. Then the temperature was raised to 80℃ and reacted for 3 hours. After degassing for 30 minutes, a hydroxyl-terminated polybutadiene polyurethane prepolymer with a -NCO% content of 9.6% was obtained.

[0064] Step 2: Preparation of petroleum resin modified with hydroxyl-terminated polybutadiene polyurethane prepolymer

[0065] 40 parts of C9 petroleum resin and 22.5 parts of solvent were added to a reaction vessel, and the temperature of the reaction vessel was controlled at 70-80℃. The mixture was stirred until the C9 petroleum resin was completely dissolved. Then, 0.4 parts of azobisisobutyronitrile were added at the reaction temperature of 70-80℃, and 37.3 parts of prepolymer containing hydroxyl-terminated polybutadiene were added dropwise. The addition was controlled to be completed in 3 hours, and the reaction was continued for 1 hour to prepare hydroxyl-terminated polybutadiene polyurethane prepolymer modified petroleum resin.

[0066] Step 3: Preparation of polyurethane-modified petroleum resin premix

[0067] 100 parts of hydroxyl-terminated polybutadiene polyurethane prepolymer modified petroleum resin were mixed with 40 parts of polyoxypropylene glycol to prepare a polyurethane modified petroleum resin premix.

[0068] Step 4: The ore is prepared by mixing 48 parts of 5-8mm granite, 27 parts of 3-5mm granite, and 25 parts of 0-3mm granite.

[0069] Step 5: At room temperature, mix 88 parts of mineral material and 4 parts of color powder for 10-15 seconds until uniformly mixed to obtain aggregate. Spray the aggregate into 8 parts of the prepared polyurethane modified petroleum resin premix while mixing for 30-45 seconds to ensure that the polyurethane modified petroleum resin premix coats the aggregate, thus obtaining the cold-mixed and cold-laid polyurethane modified petroleum resin mixture.

[0070] Example 3

[0071] The cold-mix cold-laying compound based on polyurethane modified petroleum resin described in this embodiment includes the following components in parts by weight:

[0072] It is prepared by mixing 8 parts of polyurethane modified petroleum resin, 88 parts of mineral material, and 4 parts of color powder;

[0073] The above-mentioned method for preparing a cold-mix and cold-laying compound based on polyurethane modified petroleum resin includes the following steps:

[0074] Step 1: Preparation of hydroxyl-terminated polybutadiene polyurethane prepolymer

[0075] 24.5 parts of hydroxyl-terminated polybutadiene were accurately weighed and dehydrated at 120℃ and -0.09MPa for 2 hours. When the temperature dropped to 50℃, 6 parts of toluene diisocyanate were accurately added and reacted at 50℃ for 1 hour. Then the temperature was raised to 80℃ and reacted for 3 hours. After degassing for 30 minutes, a hydroxyl-terminated polybutadiene polyurethane prepolymer with a -NCO% content of 8.7% was obtained.

[0076] Step 2: Preparation of petroleum resin modified with hydroxyl-terminated polybutadiene polyurethane prepolymer

[0077] 44 parts of C5 petroleum resin and 25 parts of solvent were added to a reaction vessel. The temperature of the reaction vessel was controlled at 70-80℃. The mixture was stirred until the C5 petroleum resin was completely dissolved. Then, 0.5 parts of azobisisobutyronitrile were added at the reaction temperature of 70-80℃, and 30.5 parts of prepolymer containing hydroxyl-terminated polybutadiene were added dropwise. The addition was controlled to be completed in 3 hours. The reaction was then continued for 1 hour to prepare hydroxyl-terminated polybutadiene polyurethane prepolymer modified petroleum resin.

[0078] Step 3: Preparation of polyurethane-modified petroleum resin premix

[0079] 100 parts of hydroxyl-terminated polybutadiene polyurethane prepolymer modified petroleum resin were mixed with 45 parts of polyoxypropylene glycol to prepare a polyurethane modified petroleum resin premix.

[0080] Step 4: The ore is prepared by mixing 48 parts of 5-8mm diabase, 27 parts of 3-5mm diabase, and 25 parts of 0-3mm diabase.

[0081] Step 5: At room temperature, mix 88 parts of mineral material and 4 parts of color powder for 10-15 seconds until uniformly mixed to obtain aggregate. Spray the aggregate into 8 parts of the prepared polyurethane modified petroleum resin premix while mixing for 30-45 seconds to ensure that the polyurethane modified petroleum resin premix coats the aggregate, thus obtaining the cold-mixed and cold-laid polyurethane modified petroleum resin mixture.

[0082] Example 4

[0083] The cold-mix cold-laying compound based on polyurethane modified petroleum resin described in this embodiment includes the following components in parts by weight:

[0084] It is prepared by mixing 6 parts of polyurethane modified petroleum resin, 91 parts of minerals, and 3 parts of color powder.

[0085] The above-mentioned method for preparing a cold-mix and cold-laying compound based on polyurethane modified petroleum resin includes the following steps:

[0086] Step 1: Preparation of hydroxyl-terminated polybutadiene polyurethane prepolymer

[0087] 11.1 parts of hydroxyl-terminated polybutadiene were accurately weighed and dehydrated at 120℃ and -0.09MPa for 2 hours. When the temperature dropped to 50℃, 5 parts of diphenylmethane diisocyanate were accurately added and reacted at 50℃ for 1 hour. Then the temperature was raised to 80℃ and reacted for 3 hours. After degassing for 30 minutes, a hydroxyl-terminated polybutadiene polyurethane prepolymer with a -NCO% content of 7.6% was obtained.

[0088] Step 2: Preparation of petroleum resin modified with hydroxyl-terminated polybutadiene polyurethane prepolymer

[0089] 42 parts of C9 petroleum resin and 41.5 parts of solvent were added to a reaction vessel, and the temperature of the reaction vessel was controlled at 70-80℃. The mixture was stirred until the C9 petroleum resin was completely dissolved. Then, 0.4 parts of azobisisobutyronitrile were added at the reaction temperature of 70-80℃, and 16.1 parts of prepolymer containing hydroxyl-terminated polybutadiene were added dropwise. The addition was controlled to be completed in 3 hours, and the reaction was continued for 1 hour to prepare hydroxyl-terminated polybutadiene polyurethane prepolymer modified petroleum resin.

[0090] Step 3: Preparation of polyurethane-modified petroleum resin premix

[0091] 100 parts of hydroxyl-terminated polybutadiene polyurethane prepolymer modified petroleum resin were mixed with 26 parts of polyoxypropylene glycol to prepare a polyurethane modified petroleum resin premix.

[0092] Step 4: The ore is prepared by mixing 55 parts of 5-8mm granite, 25 parts of 3-5mm granite, and 20 parts of 0-3mm granite.

[0093] Step 5: At room temperature, mix 91 parts of mineral material and 3 parts of color powder for 10-15 seconds until uniformly mixed to obtain aggregate. Spray the aggregate into 6 parts of the prepared polyurethane modified petroleum resin premix while mixing for 30-45 seconds to ensure that the polyurethane modified petroleum resin premix coats the aggregate, thus obtaining the cold-mixed and cold-laid polyurethane modified petroleum resin mixture.

[0094] Example 5

[0095] The cold-mix cold-laying compound based on polyurethane modified petroleum resin described in this embodiment includes the following components in parts by weight:

[0096] It is prepared by mixing 6 parts of polyurethane modified petroleum resin, 91 parts of minerals, and 3 parts of color powder.

[0097] The above-mentioned method for preparing a cold-mix and cold-laying compound based on polyurethane modified petroleum resin includes the following steps:

[0098] Step 1: Preparation of hydroxyl-terminated polybutadiene polyurethane prepolymer

[0099] Accurately weigh 33 parts of hydroxyl-terminated polybutadiene and dehydrate it at 120℃ and -0.09MPa for 2 hours. When the temperature drops to 50℃, accurately add 11.2 parts of toluene diisocyanate and react at 50℃ for 1 hour. Then, raise the temperature to 80℃ and react for 3 hours. After degassing for 30 minutes, a hydroxyl-terminated polybutadiene polyurethane prepolymer with a -NCO% content of 9.1% is obtained.

[0100] Step 2: Preparation of petroleum resin modified with hydroxyl-terminated polybutadiene polyurethane prepolymer

[0101] 30 parts of C9 petroleum resin and 25.4 parts of solvent were added to a reaction vessel, and the temperature of the reaction vessel was controlled at 70-80℃. The mixture was stirred until the C9 petroleum resin was completely dissolved. Then, 0.4 parts of azobisisobutyronitrile were added at the reaction temperature of 70-80℃, and 44.2 parts of prepolymer containing hydroxyl-terminated polybutadiene were added dropwise. The addition was controlled to be completed in 3 hours, and the reaction was continued for 1 hour to prepare hydroxyl-terminated polybutadiene polyurethane prepolymer modified petroleum resin.

[0102] Step 3: Preparation of polyurethane-modified petroleum resin premix

[0103] 100 parts of hydroxyl-terminated polybutadiene polyurethane prepolymer modified petroleum resin were mixed with 163 parts of polyethylene glycol to prepare a polyurethane modified petroleum resin premix.

[0104] Step 4: The ore is prepared by mixing 55 parts of 5-8mm basalt, 25 parts of 3-5mm basalt, and 20 parts of 0-3mm basalt.

[0105] Step 5: At room temperature, mix 91 parts of mineral material and 3 parts of color powder for 10-15 seconds until uniformly mixed to obtain aggregate. Spray the aggregate into 6 parts of the prepared polyurethane modified petroleum resin premix while mixing for 30-45 seconds to ensure that the polyurethane modified petroleum resin premix coats the aggregate, thus obtaining the cold-mixed and cold-laid polyurethane modified petroleum resin mixture.

[0106] Example 6

[0107] The cold-mix cold-laying compound based on polyurethane modified petroleum resin described in this embodiment includes the following components in parts by weight:

[0108] It is prepared by mixing 6 parts of polyurethane modified petroleum resin, 91 parts of minerals, and 3 parts of color powder.

[0109] The above-mentioned method for preparing a cold-mix and cold-laying compound based on polyurethane modified petroleum resin includes the following steps:

[0110] Step 1: Preparation of hydroxyl-terminated polybutadiene polyurethane prepolymer

[0111] Accurately weigh 33 parts of hydroxyl-terminated polybutadiene and dehydrate it at 120℃ and -0.09MPa for 2 hours. When the temperature drops to 50℃, accurately add 15 parts of diphenylmethane diisocyanate and react at 50℃ for 1 hour. Then, raise the temperature to 80℃ and react for 3 hours. After degassing for 30 minutes, a hydroxyl-terminated polybutadiene polyurethane prepolymer with a -NCO% content of 7.1% is obtained.

[0112] Step 2: Preparation of petroleum resin modified with hydroxyl-terminated polybutadiene polyurethane prepolymer

[0113] 31.8 parts of C5 petroleum resin and 20 parts of solvent were added to a reaction vessel, and the temperature of the reaction vessel was controlled at 70-80℃. The mixture was stirred until the C5 petroleum resin was completely dissolved. Then, 0.2 parts of azobisisobutyronitrile were added at the reaction temperature of 70-80℃, and 48 parts of prepolymer containing hydroxyl-terminated polybutadiene were added dropwise. The addition was controlled to be completed in 3 hours, and then the reaction was continued for 1 hour to prepare hydroxyl-terminated polybutadiene polyurethane prepolymer modified petroleum resin.

[0114] Step 3: Preparation of polyurethane-modified petroleum resin premix

[0115] 100 parts of hydroxyl-terminated polybutadiene polyurethane prepolymer modified petroleum resin were mixed with 80 parts of polyethylene glycol and 20 parts of polyoxypropylene glycol to prepare a polyurethane modified petroleum resin premix.

[0116] Step 4: The ore is prepared by mixing 55 parts of 5-8mm diabase, 25 parts of 3-5mm diabase, and 20 parts of 0-3mm diabase.

[0117] Step 5: At room temperature, mix 91 parts of mineral material and 3 parts of color powder for 10-15 seconds until uniformly mixed to obtain aggregate. Spray the aggregate into 6 parts of the prepared polyurethane modified petroleum resin premix while mixing for 30-45 seconds to ensure that the polyurethane modified petroleum resin premix coats the aggregate, thus obtaining the cold-mixed and cold-laid polyurethane modified petroleum resin mixture.

[0118] Example 7

[0119] The cold-mix cold-laying compound based on polyurethane modified petroleum resin described in this embodiment includes the following components in parts by weight:

[0120] It is prepared by mixing 4 parts of polyurethane modified petroleum resin, 94 parts of mineral material, and 2 parts of color powder;

[0121] The above-mentioned method for preparing a cold-mix and cold-laying compound based on polyurethane modified petroleum resin includes the following steps:

[0122] Step 1: Preparation of hydroxyl-terminated polybutadiene polyurethane prepolymer

[0123] Accurately weigh 33 parts of hydroxyl-terminated polybutadiene and dehydrate it at 120℃ and -0.09MPa for 2 hours. When the temperature drops to 50℃, accurately add 11.2 parts of toluene diisocyanate and react at 50℃ for 1 hour. Then, raise the temperature to 80℃ and react for 3 hours. After degassing for 30 minutes, a hydroxyl-terminated polybutadiene polyurethane prepolymer with a -NCO% content of 9.1% is obtained.

[0124] Step 2: Preparation of petroleum resin modified with hydroxyl-terminated polybutadiene polyurethane prepolymer

[0125] 30 parts of C9 petroleum resin and 25.4 parts of solvent were added to a reaction vessel, and the temperature of the reaction vessel was controlled at 70-80℃. The mixture was stirred until the C9 petroleum resin was completely dissolved. Then, 0.4 parts of azobisisobutyronitrile were added at the reaction temperature of 70-80℃, and 44.2 parts of prepolymer containing hydroxyl-terminated polybutadiene were added dropwise. The addition was controlled to be completed in 3 hours, and the reaction was continued for 1 hour to prepare hydroxyl-terminated polybutadiene polyurethane prepolymer modified petroleum resin.

[0126] Step 3: Preparation of polyurethane-modified petroleum resin premix

[0127] 100 parts of hydroxyl-terminated polybutadiene polyurethane prepolymer modified petroleum resin were mixed with 70 parts of polyoxypropylene glycol and 5 parts of di-o-chlorodiphenylmethane diamine to prepare a polyurethane modified petroleum resin premix.

[0128] Step 4: The ore is prepared by mixing 62 parts of 5-8mm basalt, 21 parts of 3-5mm basalt, and 17 parts of 0-3mm basalt.

[0129] Step 5: At room temperature, mix 94 parts of mineral material and 2 parts of color powder for 10-15 seconds until uniformly mixed to obtain aggregate. Spray the aggregate into 4 parts of the prepared polyurethane modified petroleum resin premix while mixing for 30-45 seconds to ensure that the polyurethane modified petroleum resin premix coats the aggregate, thus obtaining the cold-mixed and cold-laid polyurethane modified petroleum resin mixture.

[0130] Example 8

[0131] The cold-mix cold-laying compound based on polyurethane modified petroleum resin described in this embodiment includes the following components in parts by weight:

[0132] It is prepared by mixing 4 parts of polyurethane modified petroleum resin, 94 parts of mineral material, and 2 parts of color powder;

[0133] The above-mentioned method for preparing a cold-mix and cold-laying compound based on polyurethane modified petroleum resin includes the following steps:

[0134] Step 1: Preparation of hydroxyl-terminated polybutadiene polyurethane prepolymer

[0135] 27.5 parts of hydroxyl-terminated polybutadiene were accurately weighed and dehydrated at 120℃ and -0.09MPa for 2 hours. When the temperature dropped to 50℃, 9.8 parts of toluene diisocyanate were accurately added and reacted at 50℃ for 1 hour. Then the temperature was raised to 80℃ and reacted for 3 hours. After degassing for 30 minutes, a hydroxyl-terminated polybutadiene polyurethane prepolymer with a -NCO% content of 9.6% was obtained.

[0136] Step 2: Preparation of petroleum resin modified with hydroxyl-terminated polybutadiene polyurethane prepolymer

[0137] 40 parts of C9 petroleum resin and 22.5 parts of solvent were added to a reaction vessel, and the temperature of the reaction vessel was controlled at 70-80℃. The mixture was stirred until the C9 petroleum resin was completely dissolved. Then, 0.4 parts of azobisisobutyronitrile were added at the reaction temperature of 70-80℃, and 37.3 parts of prepolymer containing hydroxyl-terminated polybutadiene were added dropwise. The addition was controlled to be completed in 3 hours, and the reaction was continued for 1 hour to prepare hydroxyl-terminated polybutadiene polyurethane prepolymer modified petroleum resin.

[0138] Step 3: Preparation of polyurethane-modified petroleum resin premix

[0139] 100 parts of hydroxyl-terminated polybutadiene polyurethane prepolymer modified petroleum resin were mixed with 50 parts of polyoxypropylene glycol and 7 parts of di-o-chlorodiphenylmethane diamine to prepare a polyurethane modified petroleum resin premix.

[0140] Step 4: The mineral material is prepared by mixing 62 parts of 5-8mm granite, 21 parts of 3-5mm granite, and 17 parts of 0-3mm granite.

[0141] Step 5: At room temperature, mix 94 parts of mineral material and 2 parts of color powder for 10-15 seconds until uniformly mixed to obtain aggregate. Spray the aggregate into 4 parts of the prepared polyurethane modified petroleum resin premix while mixing for 30-45 seconds to ensure that the polyurethane modified petroleum resin premix coats the aggregate, thus obtaining the cold-mixed and cold-laid polyurethane modified petroleum resin mixture.

[0142] Example 9

[0143] The cold-mix cold-laying compound based on polyurethane modified petroleum resin described in this embodiment includes the following components in parts by weight:

[0144] It is prepared by mixing 4 parts of polyurethane modified petroleum resin, 94 parts of mineral material, and 2 parts of color powder;

[0145] The above-mentioned method for preparing a cold-mix and cold-laying compound based on polyurethane modified petroleum resin includes the following steps:

[0146] Step 1: Preparation of hydroxyl-terminated polybutadiene polyurethane prepolymer

[0147] Accurately weigh 33 parts of hydroxyl-terminated polybutadiene and dehydrate it at 120℃ and -0.09MPa for 2 hours. When the temperature drops to 50℃, accurately add 11.2 parts of toluene diisocyanate and react at 50℃ for 1 hour. Then, raise the temperature to 80℃ and react for 3 hours. After degassing for 30 minutes, a hydroxyl-terminated polybutadiene polyurethane prepolymer with a -NCO% content of 9.1% is obtained.

[0148] Step 2: Preparation of petroleum resin modified with hydroxyl-terminated polybutadiene polyurethane prepolymer

[0149] 30 parts of C9 petroleum resin and 25.4 parts of solvent were added to a reaction vessel, and the temperature of the reaction vessel was controlled at 70-80℃. The mixture was stirred until the C9 petroleum resin was completely dissolved. Then, 0.4 parts of azobisisobutyronitrile were added at the reaction temperature of 70-80℃, and 44.2 parts of prepolymer containing hydroxyl-terminated polybutadiene were added dropwise. The addition was controlled to be completed in 3 hours, and the reaction was continued for 1 hour to prepare hydroxyl-terminated polybutadiene polyurethane prepolymer modified petroleum resin.

[0150] Step 3: Preparation of polyurethane-modified petroleum resin premix

[0151] 100 parts of hydroxyl-terminated polybutadiene polyurethane prepolymer modified petroleum resin were mixed with 70 parts of polyoxypropylene glycol and 5 parts of di-o-chlorodiphenylmethane diamine to prepare a polyurethane modified petroleum resin premix.

[0152] Step 4: The ore is prepared by mixing 62 parts of 5-8mm diabase, 21 parts of 3-5mm diabase, and 17 parts of 0-3mm diabase.

[0153] Step 5: At room temperature, mix 94 parts of mineral material and 2 parts of color powder for 10-15 seconds until uniformly mixed to obtain aggregate. Spray the aggregate into 4 parts of the prepared polyurethane modified petroleum resin premix while mixing for 30-45 seconds to ensure that the polyurethane modified petroleum resin premix coats the aggregate, thus obtaining the cold-mixed and cold-laid polyurethane modified petroleum resin mixture.

Claims

1. A cold-mix cold-laying compound based on polyurethane-modified petroleum resin, characterized in that, Includes the following components by parts by mass: 4-8 parts polyurethane modified petroleum resin, 88-94 parts mineral powder, and 2-4 parts color powder.

2. The cold-mix cold-laying compound based on polyurethane-modified petroleum resin according to claim 1, characterized in that, The polyurethane-modified petroleum resin comprises the following components in parts by weight: 100 parts of hydroxyl-terminated polybutadiene polyurethane prepolymer modified petroleum resin and 18-163 parts of polyurethane curing agent. The hydroxyl-terminated polybutadiene polyurethane prepolymer modified petroleum resin is composed of the following components by mass parts: 30-45 parts of at least one of C5 or C9 petroleum resin, 20-41.5 parts of solvent, 0.2-0.5 parts of azobisisobutyronitrile, 5-15 parts of diisocyanate, and 11-33 parts of hydroxyl-terminated polybutadiene.

3. The cold-mix cold-laying compound based on polyurethane-modified petroleum resin according to claim 2, characterized in that, The method for preparing the polyurethane-modified petroleum resin includes the following steps: Step 1: Preparation of hydroxyl-terminated polybutadiene polyurethane prepolymer Accurately weigh 11-33 parts of hydroxyl-terminated polybutadiene, dehydrate it for 2 hours at 120℃ and -0.09MPa, cool it down to 50℃, add 5-15 parts of diisocyanate, react at 50℃ for 1 hour, raise the temperature to 80℃ and continue the reaction for 3 hours, degas for 30 minutes, and obtain a hydroxyl-terminated polybutadiene polyurethane prepolymer with a -NCO content of 6.4%-9.6%. Step 2: Preparation of petroleum resin modified with hydroxyl-terminated polybutadiene polyurethane prepolymer Add 30-45 parts of at least one of C5 or C9 petroleum resin and 20-41.5 parts of solvent to a reaction vessel, control the temperature at 70-80℃, stir until completely dissolved, add 0.2-0.5 parts of azobisisobutyronitrile, and dropwise add 16-48 parts of the hydroxyl-terminated polybutadiene polyurethane prepolymer obtained in the first step, which is added over 3 hours. Continue the reaction for 1 hour to obtain hydroxyl-terminated polybutadiene polyurethane prepolymer modified petroleum resin. Step 3: Preparation of polyurethane-modified petroleum resin premix 100 parts of the hydroxyl-terminated polybutadiene polyurethane prepolymer modified petroleum resin obtained in the second step are mixed and stirred evenly with 18-163 parts of polyurethane curing agent to obtain a polyurethane modified petroleum resin premix for later use.

4. The cold-mix cold-laying compound based on polyurethane-modified petroleum resin according to claim 1, characterized in that: The solvent is an organic solvent with a boiling point above 80°C under normal pressure.

5. The cold-mix cold-laying compound based on polyurethane-modified petroleum resin according to claim 1, characterized in that: The diisocyanate is either toluene diisocyanate or diphenylmethane diisocyanate.

6. The cold-mix cold-laying compound based on polyurethane-modified petroleum resin according to claim 1, characterized in that: The polyurethane curing agent is one or more of polypropylene glycol with a relative molecular mass of 1000, polypropylene glycol with a relative molecular mass of 2000, and di-o-chlorodiphenylmethane diamine.

7. The cold-mix cold-laying compound based on polyurethane-modified petroleum resin according to claim 1, characterized in that: The C5 petroleum resin is a thermoplastic resin obtained by pretreatment, polymerization, and distillation of C5 fraction.

8. The cold-mix cold-laying compound based on polyurethane-modified petroleum resin according to claim 1, characterized in that: The C9 petroleum resin is a thermoplastic resin obtained by pretreatment, polymerization, and distillation of C9 fraction.

9. The cold-mix cold-laying compound based on polyurethane-modified petroleum resin according to claim 1, characterized in that: The mineral material is composed of 48-62 parts of 5-8mm first coarse aggregate, 21-27 parts of 3-5mm second coarse aggregate, and 17-25 parts of 0-3mm fine aggregate; and the mineral material is any one of basalt, granite, and diabase.

10. A method for preparing the cold-mix cold-laying compound based on polyurethane-modified petroleum resin according to any one of claims 1 to 9, characterized in that: Includes the following steps: At room temperature, 88-94 parts of mineral aggregate and 2-4 parts of color powder are mixed for 10-15 seconds to obtain aggregate. The aggregate is then sprayed into 4-8 parts of the prepared polyurethane-modified petroleum resin premix while being mixed for 30-45 seconds to ensure that the polyurethane-modified petroleum resin premix coats the aggregate, thus obtaining the cold-mixed and cold-laid polyurethane-modified petroleum resin mixture.