Polyurethane composite coiled material as well as preparation method and application thereof

Abstract

The invention relates to the technical field of functional coiled materials, in particular to a polyurethane composite coiled material and a preparation method and application thereof. The invention provides a polyurethane composite coiled material. The polyurethane composite coiled material comprises a bottom layer, a middle layer and a surface layer which are sequentially arranged, the preparation raw materials of the surface layer comprise a component A and a component B in a mass ratio of (3-4): 1, and the component B is isocyanate; the component A comprises the following components in parts by weight: 25-35 parts of bio-based polyol, 45-55 parts of flame-retardant polyester polyol, 3-9 parts of polyester polyol, 3-8 parts of an alcohol chain extender, 1-5 parts of a delayed thermosensitive catalyst, 1-12 parts of an auxiliary agent and 0-5 parts of color paste; the characteristics and proportions of important components in the surface layer and the middle layer are different, the surface layer and the middle layer with different characteristics are obtained by means of specific component matching and component proportions, and the surface layer and the middle layer are compounded to achieve a synergistic effect, so that the performance of the composite coiled material is further improved.

Description

Technical Field

[0001] This invention relates to the field of functional roll material technology, specifically to a polyurethane composite roll material, its preparation method, and its application. Background Technology

[0002] The marine environment places extremely stringent demands on the durability of flooring products. Ships are constantly exposed to corrosive atmospheres with high humidity and high salt spray, requiring frequent deck washing and cleaning, while also needing to withstand potential oil spills and chemical splashes. Furthermore, the continuous vibrations and impacts during ship operation, as well as mandatory regulations on fire safety for materials, all necessitate that flooring materials possess exceptional durability, mechanical stability, and long-term reliability.

[0003] Currently, commonly used marine flooring products, such as wood / wood-plastic composite flooring, rubber or plastic sheets, PVC flooring, and coated flooring, generally suffer from insufficient durability in practical applications. Specifically: wood or wood-plastic composite flooring is highly susceptible to moisture absorption, deformation, and rot in humid environments, and is also flammable, resulting in a short service life. Rubber or plastic sheets also present flammability issues, have poor fatigue resistance, and are prone to permanent deformation or cracking under long-term vibration. PVC flooring has poor heat resistance, abrasion resistance, and solvent resistance, and is prone to scratches, stain penetration, and aging and embrittlement, making it difficult to meet the long-term use requirements of the marine environment.

[0004] In the realm of coated flooring, epoxy flooring materials present a dilemma: achieving a balance between hardness and flexibility. Their coatings are prone to cracking and peeling due to insufficient toughness, and they exhibit poor weather resistance, easily yellowing and chalking, impacting long-term aesthetics and protective effects. While polyurethane flooring offers improvements in wear resistance and ease of application, its on-site construction quality is heavily influenced by environmental factors, its curing period is long, and the overall performance of existing materials, particularly their durability in corrosion resistance, tear resistance, and resistance to long-term dynamic loads, still requires improvement.

[0005] Therefore, there is an urgent need in this field to develop a new type of ship floor material that combines excellent mechanical properties, superior corrosion and wear resistance, good dimensional stability, and efficient and convenient construction, in order to overcome the bottleneck of existing technology in terms of the long-term durability of floor products. Summary of the Invention

[0006] The present invention aims to overcome the shortcomings of poor durability of existing flooring by providing a polyurethane composite roll material, its preparation method, and its application.

[0007] To achieve the above objectives, the present invention provides the following technical solution: This invention provides a polyurethane composite roll material, comprising a bottom layer, a middle layer, and a top layer arranged sequentially; the raw materials for preparing the top layer include component A and component B in a mass ratio of (3~4):1, wherein component B is isocyanate; by weight, component A comprises: 25~35 parts of bio-based polyol, 45~55 parts of flame-retardant polyester polyol, 3~9 parts of polyester polyol, 3~8 parts of alcohol chain extender, 1~5 parts of delayed-type thermosensitive catalyst, 1~12 parts of additives, and 0~5 parts of color paste; the alcohol chain extender has a symmetrical structure.

[0008] The composite roll material provided by this invention consists of three layers: bottom, middle, and top. The top layer is responsible for wear resistance, scratch resistance, and aesthetics. The middle layer determines the overall toughness and strength of the composite roll material, while the bottom layer serves to reduce shock and level the surface.

[0009] In the topcoat formulation, three different types of polyols—bio-based polyol, flame-retardant polyester polyol, and polyester polyol—are blended to determine the main soft segments of the topcoat. Furthermore, a less reactive alcohol chain extender reacts with isocyanate to form urethane bonds (-NHCOO-). The urethane bond has low cohesive energy and relatively better molecular chain mobility, which helps to form a harder segment region with a more uniform microstructure and lower internal stress. This structure effectively reduces microcracks caused by internal stress, thereby improving aging resistance. Simultaneously, the alcohol chain extender's reaction is mild, providing a longer working time for application. A delayed-action thermosensitive catalyst can initiate the curing reaction at high temperatures, completing curing slowly at first and then rapidly, ensuring curing is completed within the appropriate temperature and time. Furthermore, during the reaction between the alcohol chain extender and the isocyanate curing agent, the delayed-action thermosensitive catalyst (such as SO1) exhibits a certain degree of delayed thermal activity. Compared to the more reactive T12, it can extend the curing time of both the alcohol chain extender and the isocyanate curing agent, maintaining a low viscosity state for a certain period. That is, in the early stage of high-temperature curing, the catalytic activity of the catalyst has not been fully released, which ensures that the reaction is slow before gelation after mixing. This longer flowable time is beneficial for the filling, leveling and wetting of the raw material components.

[0010] In summary, this invention provides a surface layer formulation design with a specific component ratio, ultimately resulting in a highly durable polyurethane composite roll material.

[0011] Preferably, the polyester polyol is at least one of XCP-244, XCP-3000H or XCP-R4500H.

[0012] Preferably, the alcohol chain extender is selected from at least one of 1,4-butanediol or 1,6-hexanediol.

[0013] Preferably, the delayed-type thermosensitive catalyst is selected from at least one of SO1, SO19 or S130.

[0014] Preferably, the isocyanate comprises at least a trimer form of isocyanate.

[0015] Preferably, the isocyanate in the trimer form is a hexamethylene diisocyanate-based polyisocyanate trimer.

[0016] Preferably, the isocyanate comprises hexamethylene diisocyanate-based polyisocyanate trimer and isophorone diisocyanate monomer.

[0017] Preferably, the mass ratio of the hexamethylene diisocyanate-based polyisocyanate trimer to the isophorone diisocyanate monomer is (1~2):1.

[0018] Preferably, the mass ratio of the hexamethylene diisocyanate-based polyisocyanate trimer to the isophorone diisocyanate monomer is (1.5~2):1.

[0019] Preferably, the mass ratio of the hexamethylene diisocyanate-based polyisocyanate trimer to the isophorone diisocyanate monomer is 2:1.

[0020] The mixture consists of hexamethylene diisocyanate-based polyisocyanate trimer and isophorone diisocyanate monomer. The isophorone diisocyanate monomer can regulate the rate of the curing reaction and prevent the reaction from being too fast, while the hexamethylene diisocyanate-based polyisocyanate trimer can ensure that the obtained surface layer has a certain strength.

[0021] Preferably, the bio-based polyol is a plant oil-based polyol.

[0022] Preferably, the vegetable oil-based polyol is selected from at least one of castor oil polyol, soybean oil polyol, palm oil polyol, and olive oil polyol.

[0023] Preferably, the castor oil polyol is selected from at least one of CF-275T, CF-220T, or CF-260T.

[0024] Preferably, the flame-retardant polyester polyol is selected from at least one of PF-2012, PF-2021, and PF-2014.

[0025] Preferably, the additives include at least one of leveling agents, defoamers, and dehydrating agents.

[0026] Preferably, the raw materials for preparing the middle layer include component C and component D in a mass ratio of (2~2.5):1, wherein component D is isocyanate; by weight, component C includes: 10~30 parts of bio-based polyol, 15~35 parts of flame-retardant polyester polyol, 1~10 parts of polycaprolactone polyol, 5~20 parts of aromatic diamine chain extender, 10~15 parts of flame retardant, 20~50 parts of inorganic filler, 1~10 parts of instant thermosensitive catalyst, 0~5 parts of color paste and 0~15 parts of additives.

[0027] The middle layer, located between the top and bottom layers, primarily functions to bear stress, absorb impact, enhance adhesion, and provide strong support for the top layer. In the middle layer formulation of this invention, the proportions of each component have changed significantly compared to the top layer. Inorganic fillers that provide strength have been introduced, and the proportion of the curing agent has been increased, thereby effectively controlling the curing reaction rate. Specifically, a more crystalline polycaprolactone polyol is introduced to enhance the toughness and tear resistance of the middle layer. Furthermore, a highly active aromatic diamine chain extender is selected, which facilitates the formation of a strong and tough three-dimensional network within a suitable time, allowing the middle layer to effectively disperse and absorb external impact energy, ensuring the overall flexibility and impact resistance of the composite roll material. An instantaneous thermosensitive catalyst, such as S12, has a strong catalytic effect on the gelled isocyanate and active hydrogen, enabling the aromatic diamine chain extender and isocyanate curing agent to rapidly increase in strength within a short time, ensuring the high strength and toughness of the middle layer.

[0028] Ultimately, by combining the surface and intermediate layer formulations provided by this invention, a composite roll material with good durability and toughness can be obtained.

[0029] Preferably, the bio-based polyol is a plant oil-based polyol.

[0030] Preferably, the vegetable oil-based polyol is selected from at least one of castor oil polyol, soybean oil polyol, palm oil polyol, and olive oil polyol.

[0031] Preferably, the castor oil polyol is selected from at least one of CF-275T, CF-220T or CF-260T.

[0032] Preferably, the flame-retardant polyester polyol is selected from at least one of PF-2021, PF-2014, and PF-2012.

[0033] Preferably, the polycaprolactone polyol is polycaprolactone polyol PCL-2053.

[0034] Preferably, the aromatic diamine chain extender is 3,5-dimethylthiotoluene diamine.

[0035] Preferably, the flame retardant is a phosphorus-based halogen-free flame retardant.

[0036] Preferably, the inorganic filler is selected from at least one of calcium carbonate, talc, aluminum hydroxide, silica, and white corundum.

[0037] Preferably, the particle size of the inorganic filler is 600~1500 mesh.

[0038] Preferably, the instantaneous thermosensitive catalyst is S12.

[0039] Preferably, the additives include at least one of leveling agents, defoamers, and dehydrating agents.

[0040] Preferably, the isocyanate comprises hexamethylene diisocyanate-based polyisocyanate trimer and isophorone diisocyanate monomer.

[0041] Preferably, the mass ratio of the hexamethylene diisocyanate-based polyisocyanate trimer to the isophorone diisocyanate monomer is (0.5~2):1.

[0042] Preferably, the mass ratio of the hexamethylene diisocyanate-based polyisocyanate trimer to the isophorone diisocyanate monomer is (1.5~2):1.

[0043] Preferably, the mass ratio of the hexamethylene diisocyanate-based polyisocyanate trimer to the isophorone diisocyanate monomer is 2:1.

[0044] Preferably, the raw materials for preparing the bottom layer include component E and component F in a mass ratio of (1~3):1, wherein component E is isocyanate; and component F, by weight, includes: 1~10 parts of bio-based polyol, 10~20 parts of flame-retardant polyester polyol, 20~30 parts of polyester polyol, 10~15 parts of flame retardant, 20~50 parts of inorganic filler, 0~5 parts of color paste and 0~15 parts of additives.

[0045] Preferably, the bio-based polyol is castor oil polyol of model CF-275T.

[0046] Preferably, the flame-retardant polyester polyol is selected from at least one of PF-2021, PF-2014 or PF-2012.

[0047] Preferably, the polyester polyol is of model HDPOL-5520M.

[0048] Preferably, the inorganic filler is selected from at least one of calcium carbonate, talc, aluminum hydroxide, silica, and white corundum.

[0049] Preferably, the particle size of the inorganic filler is 600~1200 mesh.

[0050] Preferably, the flame retardant is selected from at least one of ammonium polyphosphate, magnesium hydroxide, aluminum hydroxide, tris(2-chloropropyl) phosphate, phosphorus-based halogen-free flame retardant, nano carbon black, and cenospheres.

[0051] Preferably, the additives include at least one of leveling agents, defoamers, and dehydrating agents.

[0052] Preferably, the isocyanate is diphenylmethane diisocyanate.

[0053] This invention provides a method for preparing a polyurethane composite roll material, comprising: S1. Mix component A and add component B to obtain the topcoat; mix component C and add component D to obtain the intermediate coat; mix component E and add component F to obtain the base coat. S2. The topcoat is applied to the base film, then heat-cured, and the release film is removed to obtain the topcoat. S3. Apply a middle layer coating to the top layer and heat-cur it to obtain a reinforcing layer; a mesh fabric is added during the coating process; S4. Apply the base coat to the middle layer, heat cure, cool, trim the edges and roll up to obtain polyurethane composite roll material.

[0054] Preferably, in S2, the thermosetting method is as follows: curing at 80°C for 10-30 min, heating to 100°C for 10-30 min, and then heating to 120°C for 10-30 min. And / or, in S3~S4, the thermosetting temperature is 80~120℃ and the thermosetting time is 10~30 min; And / or, in S2, the base film is a polyethylene terephthalate film; And / or, in S3, the mesh fabric is a polyester mesh fabric.

[0055] This invention also provides the application of polyurethane composite rolls in ship flooring.

[0056] Therefore, the present invention has the following beneficial effects: (1) The present invention uses slow-reacting alcohol chain extenders in combination with a variety of polyols and uses a delayed thermosensitive catalyst to start the reaction, so that the curing reaction of the surface layer is controlled within the required time, ensuring the full integration of soft and hard segments, and the final composite roll material has high wear resistance and high corrosion resistance.

[0057] (2) The present invention adjusts the formulation of the middle layer and the top layer to match the two layers, so that the final composite roll material has the dual functions of durability and high toughness. Among them, the middle layer uses a fast-reacting amine chain extender combined with polycaprolactone polyol, and selects an instantaneous thermosensitive catalyst that can quickly start the reaction at high temperature, so that the middle layer forms a high-strength and stable three-dimensional network structure, allowing the middle layer to play the role of supporting the top layer. The final composite roll material has high strength and high toughness.

[0058] (3) The present invention selects a compound curing agent as the curing agent for the top layer and the middle layer. By taking advantage of the different characteristics of different curing agents, the different mass ratios and total weight percentages of hexamethylene diisocyanate-based polyisocyanate trimer and isophorone diisocyanate monomer in the top layer and the middle layer curing agent are adjusted to meet the different needs of the top layer and the middle layer, so that the final composite roll material has better durability and flexibility by matching the top layer and the middle layer.

[0059] (4) The characteristics of the important components in the surface layer and the middle layer of the present invention are different and their respective proportions are different. By using specific component combinations and component proportions, surface layers and middle layers with different characteristics can be obtained. The two are combined and their synergistic effect further improves the performance of the composite roll.

[0060] (5) The polyurethane composite roll provided by the present invention has a multi-layer structure. The surface layer has the functions of wear resistance and scratch resistance, and the middle layer can adjust the type and amount of polyol according to the needs, so that the material can be adjusted in terms of softness and hardness, and also has the functions of shock absorption and sound insulation.

[0061] (6) The polyurethane composite roll provided by the present invention can realize factory finished product production and on-site paving, and the paving speed is fast, which is better than polyurethane self-leveling flooring.

[0062] (7) The present invention uses polyester mesh fabric as the fiber reinforcement material of the middle layer, which can improve the mechanical properties of the middle layer on the one hand, and can fully meet the requirements of material vibration when applied to ship flooring on the other hand. Attached Figure Description

[0063] Figure 1 This is a real-world test image of the abrasion resistance of the polyurethane composite roll material obtained by this invention. Figure 2 This is a real-world bending test diagram of the polyurethane composite roll material obtained by the present invention. Detailed Implementation

[0064] The present invention will be further described below with reference to specific embodiments. Those skilled in the art will be able to implement the present invention based on these descriptions. Furthermore, the embodiments of the present invention described below are generally only some, not all, of the embodiments of the present invention. Therefore, all other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort should fall within the scope of protection of the present invention.

[0065] The raw materials used in this section are as follows: Bio-based polyol CF-275T and flame-retardant polyester polyol PF-2021 were purchased from Zibo Ruinuo New Materials Co., Ltd.; Polycaprolactone polyol PCL-2053 was purchased from Hunan Juren New Materials Co., Ltd.; Polyether polyol C2020 was purchased from Guangzhou Wenlong Chemical Co., Ltd.; Polyester polyol HDPOL-5520M was purchased from Shanghai Huide Technology Co., Ltd.; Polyester polyol XCP-244 was purchased from Asahikawa Chemical (Suzhou) Co., Ltd.; Ammonium polyphosphate (APP) was purchased from Shandong Haoyao New Materials Co., Ltd.; Phosphorus-based halogen-free flame retardant F936 was purchased from Jiaxing Jingzuan New Materials Technology Co., Ltd.; Catalyst WCAT-S12 and catalyst CUCAT-S01 were purchased from Guangzhou Yourun Synthetic Materials Co., Ltd.; Catalyst H05 was purchased from Shanghai Zhengui New Materials Technology Co., Ltd.; Heavy calcium carbonate GY808 1200 mesh was purchased from Jiangyin Guangyuan Ultrafine Powder Co., Ltd.; Talc powder 800 mesh was purchased from Lingshou Junkai New Materials Co., Ltd. Hexamethylene diisocyanate-based polyisocyanate trimer (HT100) was purchased from Shandong Jiaying Chemical Technology Co., Ltd. Isophorone diisocyanate monomer (IPDI) and diphenylmethane diisocyanate monomer MDI (PM200) were purchased from Jinan Xinhuakai New Material Technology Co., Ltd. Diphenylmethane diisocyanate monomer (MDI50) was purchased from Jining Ribuluo Biotechnology Co., Ltd. 1,4-Butanediol was purchased from Shandong Jintai Hongfa Biotechnology Co., Ltd. Trimethylolpropane was purchased from Shanghai Huichao New Material Co., Ltd. 3,5-Dimethylthiotoluene diamine (DMTDA, E-300) was purchased from Jinan Linyan Mandi New Material Co., Ltd. Leveling agent BYK-333 was purchased from Foshan Qianyou Chemical Co., Ltd., and defoamer BYK-088 was purchased from Guangzhou Haoliangda International Trade Co., Ltd. Dehydrating agent K-3A activating powder was purchased from Guangzhou Xincheng Environmental Protection Technology Co., Ltd. Metallic gray paste was purchased from Hangzhou Gangliu New Material Co., Ltd.

[0066]

Example

[0067] Surface layer component A: Bio-based polyol CF-275T, 30 parts; Flame-retardant polyester polyol PF-2021, 44 parts; Polyester polyol XCP-244, 8 parts; 1,4-Butanediol, 5 parts; Leveling agent BYK-333, 3 parts; Defoamer BYK-088, 3 parts; Dehydrating agent K-3A activating powder, 4 parts; CUCAT-S01, 1 copy; Surface layer component B: IPDI, 10 copies; HT100, 20 servings.

[0068] S2. Preparation of intermediate coating: Weigh each raw material in intermediate component C according to the following mass parts, mix them thoroughly in a stirrer, let them stand, filter to obtain a premixed liquid, and then slowly add the following mass parts of curing agent intermediate component D, stir thoroughly to obtain intermediate coating.

[0069] Composition of middle layer C component: Bio-based polyol CF-275T, 15 parts; Flame-retardant polyester polyol PF-2021, 25 parts; Polycaprolactone polyol PCL-2053, 5 parts; DMTDA, 10 copies; Trihydrated calcium carbonate GY808, 1200 mesh, 35 portions; F936, 10 copies; Leveling agent BYK-333, 2 parts; Defoamer BYK-088, 3 parts; K-3A dehydrating agent activating powder, 3 parts; WCAT-S12, 1 copy; Metallic gray paste, 2 parts; Middle layer D component: IPDI, 16.7 copies; HT100, 33.3 copies.

[0070] S3. Preparation of the base coat: Weigh each raw material in the base component E according to the following mass parts, mix them thoroughly in a stirrer, let them stand, filter them to obtain a premixed liquid, and then slowly add the following mass parts of the curing agent base component F, stir thoroughly to obtain the base coat.

[0071] The composition of the bottom layer E component: Bio-based polyol CF-275T, 5 parts; Flame-retardant polyester polyol PF-2021, 15 parts; Polyester polyol HDPOL-5520M, 25 parts; Talc powder, 800 mesh, 35 parts; APP, 10 copies; Leveling agent BYK-333, 3 parts; Defoamer BYK-088, 2 parts; K-3A dehydrating agent activating powder, 3 parts; Metallic gray paste, 2 parts; Bottom layer F component: MDI (PM200), 50 portions.

[0072] S4. Preparation of polyurethane composite roll material: (1) Apply the topcoat coating to a PET film with a gloss (60°) of 20 GU, cure at 80°C for 15 min, raise the temperature to 100°C for 20 min, and then raise the temperature to 120°C for 30 min. After curing, remove the release film to form the topcoat. (2) Apply a middle layer coating on the surface layer and bond it to the polyester mesh fabric. After curing at 120°C for 30 min, a mesh fabric reinforcement layer is formed. (3) Apply the base coat to the mesh reinforcement layer and cure at 120°C for 30 min to form the base coat layer; (4) Cool, trim and roll up to obtain the following: Figure 1 The polyurethane composite roll shown.

[0073] Comparative Examples 1-12 were prepared using the preparation scheme of Example 1. The coating formulations for the middle and bottom layers were the same as those in Example 1, while the coating formulations for the top layer were prepared according to Tables 1-2 below, resulting in composite rolls with different top layer coating formulations.

[0074] Examples 2-3 and Comparative Examples 13-14 were prepared using the same preparation scheme as Example 1. The coating formulations for the top and bottom layers were the same as in Example 1, while the coating formulation for the middle layer was prepared according to Tables 3-4 below, resulting in composite rolls with different middle layer coating formulations.

[0075] Table 1 Formulations of Different Topcoat Coatings

[0076] Table 2 Formulations of Different Topcoat Coatings

[0077] Table 3 Formulations for Different Intermediate Coatings (Table 1)

[0078] Table 4 Formulations of Different Intermediate Coatings (Table 2)

[0079] [Performance Testing] The test methods used in this section are as follows: Abrasion resistance: determined using the rotating rubber wheel method (GB / T1768-2006 Determination of abrasion resistance of paints and varnishes). Salt spray resistance (neutral salt spray test, NSS): tested using the salt spray test method (GB / T10125-2021 Artificial atmosphere corrosion test). Tensile properties and elongation at break: determined using the tensile stress-strain properties of vulcanized rubber or thermoplastic rubber (GB / T 528-2009). Flexibility: determined using the standard (GB / T 11982.1-2015 Polyvinyl chloride roll flooring - Part 1: Non-homogeneous polyvinyl chloride roll flooring).

[0080] The test results are shown in Table 5 below. Analysis reveals that different polyols were used in Example 1 and Comparative Examples 1-3; different alcohol chain extenders were used in Comparative Examples 4-6; different catalysts were used in Comparative Example 7; and different curing agents were used in Comparative Examples 8-12. Comparing the above data, it can be found that the selection and compounding ratio of polyester polyols, specific alcohol chain extenders, curing agents, and delayed-action thermosensitive catalysts are key to obtaining a high-durability surface layer. They significantly influence the adjustment of the soft and hard segments of the surface layer, and only suitable soft and hard segments allow the material surface layer to simultaneously meet the requirements of wear resistance and strength.

[0081] Furthermore, the choice of curing agent in the intermediate layer has a significant impact on its toughness. Changing the curing agent formulation can drastically affect the toughness of the intermediate layer, making the polyurethane roll material highly susceptible to cracking. This is because the curing agent formulation used in the intermediate layer allows for more efficient chain segment reactions, resulting in higher chain segment strength and better material ductility at high temperatures. Simultaneously, when the curing agent formulation ratio is within a specific range, the flexibility of the intermediate layer can be further improved.

[0082] In summary, the selection and compounding ratio of polyester polyols and curing agents, along with the synergistic effect of specific alcohol chain extenders and delayed-action thermosensitive catalysts, can significantly improve the abrasion and corrosion resistance of polyurethane composite roll surfaces while also maintaining scratch resistance. In the formulation of the abrasion-resistant surface layer, the synergistic effect of polycaprolactone polyols, specific curing agents, instantaneous thermosensitive catalysts, highly reactive aromatic diamine chain extenders, and inorganic fillers can significantly improve the flexibility of polyurethane composite rolls while also maintaining tensile and tear resistance. Ultimately, this results in a durable and highly tough polyurethane composite roll.

[0083] Table 5. Effects of different coating formulations on the performance of composite roll materials

Claims

1. A high-durability polyurethane composite roll material, characterized in that, It includes a bottom layer, a middle layer and a top layer arranged in sequence; the raw materials for preparing the top layer include component A and component B in a mass ratio of (3~4):1, wherein component B is isocyanate; By weight, component A comprises: 25-35 parts of bio-based polyol, 45-55 parts of flame-retardant polyester polyol, 3-9 parts of polyester polyol, 3-8 parts of alcohol chain extender, 1-5 parts of delayed-type thermosensitive catalyst, 1-12 parts of additives and 0-5 parts of color paste; the alcohol chain extender has a symmetrical structure.

2. The high-durability polyurethane composite roll material as described in claim 1, characterized in that, The polyester polyol is at least one of XCP-244, XCP-3000H or XCP-R4500H; Preferably, the alcohol chain extender is selected from at least one of 1,4-butanediol or 1,6-hexanediol; Preferably, the delayed-type thermosensitive catalyst is selected from at least one of SO1, SO19, or S130; Preferably, the isocyanate comprises hexamethylene diisocyanate-based polyisocyanate trimer and isophorone diisocyanate monomer; Preferably, the mass ratio of the hexamethylene diisocyanate-based polyisocyanate trimer to the isophorone diisocyanate monomer is (1~2):

1.

3. The high-durability polyurethane composite roll material as described in claim 1, characterized in that, The bio-based polyol is a plant oil-based polyol; Preferably, the vegetable oil-based polyol is selected from at least one of castor oil polyol, soybean oil polyol, palm oil polyol, and olive oil polyol; Preferably, the castor oil polyol is selected from at least one of CF-275T, CF-220T or CF-260T; Preferably, the flame-retardant polyester polyol is selected from at least one of PF-2012, PF-2021, and PF-2014; Preferably, the additives include at least one of leveling agents, defoamers, and dehydrating agents.

4. The high-durability polyurethane composite roll material as described in any one of claims 1 to 3, characterized in that, The raw materials for preparing the middle layer include component C and component D in a mass ratio of (2~2.5):1, wherein component D is isocyanate; By weight, component C comprises: 10-30 parts of bio-based polyol, 15-35 parts of flame-retardant polyester polyol, 1-10 parts of polycaprolactone polyol, 5-20 parts of aromatic diamine chain extender, 10-15 parts of flame retardant, 20-50 parts of inorganic filler, 1-10 parts of instant thermosensitive catalyst, 0-5 parts of color paste and 0-15 parts of additives.

5. The high-durability polyurethane composite roll material as described in claim 4, characterized in that, The bio-based polyol is a plant oil-based polyol; Preferably, the vegetable oil-based polyol is selected from at least one of castor oil polyol, soybean oil polyol, palm oil polyol, and olive oil polyol; Preferably, the castor oil polyol is selected from at least one of CF-275T, CF-220T or CF-260T; Preferably, the flame-retardant polyester polyol is selected from at least one of PF-2021, PF-2014, and PF-2012; Preferably, the polycaprolactone polyol is polycaprolactone polyol PCL-2053; Preferably, the aromatic diamine chain extender is 3,5-dimethylthiotoluenediamine; Preferably, the flame retardant is a phosphorus-based halogen-free flame retardant; Preferably, the inorganic filler is selected from at least one of calcium carbonate, talc, aluminum hydroxide, silica, and white corundum; Preferably, the particle size of the inorganic filler is 600~1500 mesh; Preferably, the instantaneous thermosensitive catalyst is S12; Preferably, the additives include at least one of leveling agents, defoamers, and dehydrating agents; Preferably, the isocyanate comprises hexamethylene diisocyanate-based polyisocyanate trimer and isophorone diisocyanate monomer; Preferably, the mass ratio of the hexamethylene diisocyanate-based polyisocyanate trimer to the isophorone diisocyanate monomer is (0.5~2):

1.

6. The high-durability polyurethane composite roll material as described in any one of claims 1 to 3, characterized in that, The raw materials for preparing the bottom layer include component E and component F in a mass ratio of (1~3):1, wherein component E is an isocyanate; By weight, component F comprises: 1-10 parts of bio-based polyol, 10-20 parts of flame-retardant polyester polyol, 20-30 parts of polyester polyol, 10-15 parts of flame retardant, 20-50 parts of inorganic filler, 0-5 parts of color paste, and 0-15 parts of additives.

7. The high-durability polyurethane composite roll material as described in claim 6, characterized in that, The bio-based polyol is castor oil polyol of model CF-275T; Preferably, the flame-retardant polyester polyol is selected from at least one of PF-2021, PF-2014 or PF-2012; Preferably, the polyester polyol is of type HDPOL-5520M; Preferably, the inorganic filler is selected from at least one of calcium carbonate, talc, aluminum hydroxide, silica, and white corundum; Preferably, the particle size of the inorganic filler is 600~1200 mesh; Preferably, the flame retardant is selected from at least one of ammonium polyphosphate, magnesium hydroxide, aluminum hydroxide, tris(2-chloropropyl) phosphate, phosphorus-based halogen-free flame retardant, nano carbon black, and cenospheres; Preferably, the additives include at least one of leveling agents, defoamers, and dehydrating agents; Preferably, the isocyanate is diphenylmethane diisocyanate.

8. A method for preparing a high-durability polyurethane composite roll material as described in any one of claims 1 to 7, characterized in that, include: S1. After mixing component A, add component B to obtain the topcoat coating; After mixing component C, component D is added to obtain the intermediate coating; After mixing component E, component F is added to obtain the base coat; S2. The topcoat is applied to the base film, then heat-cured, and the release film is removed to obtain the topcoat. S3. Apply a middle layer coating to the top layer and heat-cur it to obtain a reinforcing layer; a mesh fabric is added during the coating process; S4. Apply the base coat to the middle layer, heat cure, cool, trim the edges, and roll up to obtain a high-durability polyurethane composite roll.

9. The preparation method according to claim 8, characterized in that, In S2, the thermosetting method is as follows: cure at 80℃ for 10~30 min, raise the temperature to 100℃ for 10~30 min, and then raise the temperature to 120℃ for 10~30 min. And / or, in S3~S4, the thermosetting temperature is 80~120℃ and the thermosetting time is 10~30 min; And / or, in S2, the base film is a polyethylene terephthalate film; And / or, in S3, the mesh fabric is a polyester mesh fabric.

10. Application of the high-durability polyurethane composite roll material as described in any one of claims 1 to 7 or the high-durability polyurethane composite roll material prepared by the preparation method as described in any one of claims 8 to 9 in ship flooring.

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