Polyurethane industrial production and application. Building insulation anti-corrosion asphalt polyurethane rigid foam plastic Zhang Shuhua (Qingdao Jinbeiyang Engineering Co., Ltd. focused on the role of polyoxyethylene triol, rosin aromatic polyester polyol in the formulation. Asphalt polyurethane rigid foam not only has the insulation of ordinary polyurethane rigid foam It has the properties of anti-corrosion, anti-weathering and anti-penetration of asphalt. It has been successfully used for exterior wall insulation, roof waterproofing, heat preservation and anti-corrosion and heat preservation of oil pipelines. Zheqing Polyurethane Rigid Foam is a research and development project to solve the corrosion and perforation of oilfield oil pipelines. 111. Halogen-containing stabilizers and halogen-containing foaming agents in ordinary polyurethane rigid foam and all-water polyurethane rigid foam formulations. Easy to dechlorinate to form hydrochloric acid and water and polyisocyanate foaming reaction, C) reacts with water to form carbonic acid, which corrodes the pipeline and causes perforation of the pipeline. Polyurethane rigid foam blended with coal, because of the phenolic, alcoholic hydroxyl, amine and imine groups and other alkaline active hydrogen compounds, the mass fraction of which is between 08% and 1.0%, the active hydrogen compound Participate in the chemical foaming reaction and become part of the foam skeleton, making the foam a hard foam with high hand strength and high compressive strength. The hard foam body has a high crosslink density and improves the foam polymer. Dimensional stability reduces the shrinkage of the foam; on the other hand, the coal contains a variety of basic substances such as amine groups and imine groups, which can neutralize the acidic substances released in the foam, such as foaming agents and resistance. The acidic substances released by the fuel, etc., greatly reduce the acid corrosion perforation of the steel pipeline; at the same time, the amine and imine components in the coal sapphire act as catalysts in the chemical foaming process. Zheqing polyurethane rigid foam is chemically reacted by a combination of polyol and polyisocyanate, and chain-crosslinking forms a crosslinked network. The foam is formed by three processes of nucleation, opalescence and gelation. Based on the continuous improvement and improvement of the performance of Zheqing polyurethane rigid foam, this material has been widely used in the fields of building insulation, waterproofing and anti-corrosion. 1 Asphalt polyurethane rigid foam composition and preparation process 11 basic formula cyan, foaming agent and other composition of the composition (AS) and isocyanate (B component by chemical reaction foaming. Its formula is shown in Table 1 Table 1 asphalt polyurethane Hard foam basic formula component parts by weight eight component sucrose polyether polyol rosin aromatic hydrocarbon polyester polyol high activity crosslinker polyoxyethylene triol coal tar pitch silicone foam stabilizer composite catalyst flame retardant water B component isocyanate Preparation of index 12 preparation process 121 coal pitch dispersion First, the solid coal is crushed, put into the reaction kettle, and melted at 180 ~ 200 ° C. After the coal is completely melted, the temperature is lowered to 80 ~ 100 ° C, and the input is low. Relative molecular mass polyol and ester diluent, prepare coal sapling dispersion with mass fraction of about 70%, filter packaging. Preparation of 122 combined polyols In the reactor, sucrose polyether polyol, rosin aromatic hydrocarbon polyester Alcohol, polyoxyethylene triol, pre-mixing with stirring, adding coal sapphire, silicone foam stabilizer and composite catalyst while stirring, mixing at uniform speed, and then adding foaming agent Hd1411 and water Stirring and mixing evenly. Determine the foaming speed and the free coal-forming Zheqing and Muzhaqing dispersion to prepare the Zheqing polyurethane rigid foam composition, seal it in a container, and place it in an oven at 50 °C for accelerated storage stability test. Table 2 2 Selection of main raw materials 21 Selection and dosage of asphalt This work uses ordinary petroleum sapphire, low temperature coal, sapphire, high temperature meter 2 asphalt polyurethane combination polyether material storage stability mass parts sucrose polyether polyol rosin aromatics Polyester polyol polyoxyethylene triol organosilicon bubble stabilizer composite catalyst ordinary petroleum asphalt dispersion low temperature coal asphalt dispersion liquid temperature coal pitch dispersion wood asphalt dispersion composition After 48h, floc appeared, there was no precipitation after 96h precipitation of small particles and a small amount of floc appeared after 72h of floc. It can be seen from Table 2 that the storage stability of high temperature coal and green was better in the accelerated storage stability experiment, followed by It is a wood-Zheqing, and the storage stability of the common petroleum-yellow formula composition is poor. The Zheqing polyurethane rigid foam composition prepared with high-temperature coal and purple is sprayed on the roof and exterior wall. The dosage of Zheqing also has a great influence on the storage stability of the composite. The suitable dosage of Zheqing in the combination should be that Zheqing is dispersed as a dispersed phase in the combined polyether, that is, the combined polyol is the continuous phase, and the green is dispersed. Phase, if the dosage of Zheqing is increased to become a continuous phase, the storage stability of the composite material will be greatly reduced, and the greening is prone to flocculation, skinning, sedimentation, agglomeration and the like; the hard foam obtained by using the composite material The body is crisp, flexible and has poor resilience. Especially when used in the one-step production line of oil fiber foam tube, the hard foam insulation layer is easy to crack and debonded from the outer jacket tube. 22 high-activity cross-linking agent polyoxyethylene triol polyoxyethylene triol is prepared by ring-opening polymerization of ethylene oxide with glycerol as a starting agent, which is both high activity and low relative. The molecular weight cross-linking agent is also a non-ionic surfactant, the relative molecular mass of which is 246 hydroxyl value of 680 mKOH/g, and the primary hydroxyl group content of 1% polyoxyethylene triol plays the following role in the formulation: Because polyoxyethylene triol has affinity to the green particles, it is easy to adsorb and enrich and reduce the surface tension of the material on the surface of the green particles, improve the interface state, and facilitate the dispersion of the green particles in the combined polyol. Improve the storage stability of the combined polyether polyol system; Second, due to the surface activity of the polyoxyethylene triol, the atomization performance of the polyisocyanate and the polyol in the spraying operation is improved, that is, the dispersion of the droplet is improved. It is beneficial for the polyisocyanate to fully react with the polyol. During the formation of the rigid polyurethane foam, as the polymerization of the polyether polyol and the polyisocyanate proceeds, the relative molecular mass increases, and the blowing agent vaporizes under the action of the reaction heat and is combined with the C gas released in the reaction. A large number of gas cores are generated in the gelation, and the polyoxyethylene triol cooperates with the silicone foam stabilizer to sufficiently disperse the bubbles to form a fine and uniform foamed rigid polyurethane foam; and third, the polyoxyethylene triol is a high activity. The cross-linking agent has three primary hydroxyl groups to make the chain-extension cross-linking reaction more fully, and forms a polyurethane polymer network with relatively high cross-linking density, which is beneficial to resist the solubilization of HCFC44lb foaming agent and effectively improve the dimensional stability of the hard foam body. Sex. The rosin aromatic hydrocarbon polyester polyol used in the rosin aromatic polyester polyol formulation is a rosin aromatic hydrocarbon polyester polyol obtained by polycondensation reaction of first-grade rosin, phthalic anhydride, diethylene glycol and glycerin under the action of a catalyst, and its appearance is deep. Brown viscous liquid, hydroxyl value 400mgH / g acid value < 5mgKH / g viscosity at ambient temperature of about 4000mpas due to the adhesion of rosin itself, the coating between the hard foam layer and the layer has better adhesion Overcome the hard foaming degree caused by the HCFC141b foaming agent; at the same time, the rosin polyester polyol can greatly improve the flatness of the sprayed hard foam surface and overcome the HCFC! 4lb foaming system sprays the defects of "popcorn" on the surface of hard foam, and the sprayed and cast polyurethane rigid foam cells are fine and uniform, basically without pinholes and holes; non-polar in rosin polyester polyol molecules With the polar segment, the rosin polyester polyol has good miscibility with the green and other components, and the prepared composition is stable in storage; due to the rosin's own tricyclic phenanthrene heat-resistant structure, it can improve the green polyurethane hardness. Flame retardant and heat resistant properties of the foam. The high-efficiency catalyst used in the composite catalyst formulation is a potassium alkoxide compound synthesized from a small molecular polyol and potassium hydroxide, and then compounded with triethylenediamine and tris-(dimethylaminomethyl)phenol. The catalyst can effectively improve defects such as shrinkage, drumming, and adhesion between layers of the rigid polyurethane foam of the HCFC141b water-foaming system. In particular, spraying the outer wall surface and the inclined roof surface at a lower ambient temperature will increase the foaming speed and will not be effective as a general catalyst. 3Asphalt polyurethane rigid foam plastic application 1 pipeline anti-corrosion and thermal insulation coal Zheqing has been used in oilfield pipeline anti-corrosion coating for many years, and is still using a large number of Zheqing paint, Zheqing polyurethane anti-corrosion paint, and epoxy coal Pipeline coating. Zheqing polyurethane rigid foam forms a thin and dense Zhejiang polyurethane coating on the outer side of the steel pipe during the foaming process of the foam jacket tube insulation layer such as “one-step methodâ€, “two-step method†and “tube tubeâ€. The layer acts as an anti-corrosion coating. The oil pipe foam jacket tube adopts the "one-step" foam jacket tube construction process parameters and technical indicators. See Table 3 and Table 4. The recommended formula is made of Zheqing polyurethane rigid foam cell with fine pores, soft handfeel, small thermal conductivity and heat transfer. low efficiency. Experiments show that the thermal conductivity of the new polyurethane foam made of HCFC-l4lb foaming agent is 0 019Wm.K), the skin is cut off and exposed to air for a long time, the gas in the cell changes with time. It is replaced by air or intrusion of moisture, resulting in an increase in thermal conductivity and stability around 0027WAm.K). Petroleum Pipe Foam Jacket Zheqing Polyurethane Rigid Bubble Sample Tested by China National Petroleum Corporation Anti-corrosion and Insulation Product Quality Supervision and Inspection Center, Daqing Oilfield Corrosion and Protection Inspection Center and China National Petroleum Pipeline Bureau Inspection Technology Center, in line with oil and gas industry standards Technical standard requirements for SY/T0415-96 buried steel pipe rigid polyurethane foam anti-corrosion insulation layer. The oil pipeline of Jiangsu Oilfield is laid under the paddy field. The jacket tube is almost rust-free in the humid environment for many years, which is obviously superior to the ordinary foam jacket tube. Table 3 "One-step" foam jacket tube construction process parameters project process parameters steel pipe heating temperature / ° c foaming liquid surface distance from the core barrel / m combination polyol and polyisocyanate liquid preheating temperature / c jacket protective layer extrusion Machine heating temperature / ° c jacket protective layer cooling water temperature / C spray gun supply pressure / MPa combined polyol and polyisocyanate mass ratio tube end head / nm Table 4 project indicators apparent density / kgm compressive strength / MPa water absorption /gcm3 thermal conductivity / W. (mK) heat resistance (100C dimensional change rate /% weight change rate strength change rate /% 32 external wall insulation and roof waterproof construction using spray foaming, spray pressure > rnMPa combination polyol The mass ratio of polyisocyanate to L0:1.0~1.05 is 8kg/mn, and the construction temperature is 15%. The technical indicators of the product are shown in Table 5. The sample is subject to the National Construction Engineering Quality Supervision and Inspection Center and the national building materials industry insulation and sealing material products. Quality Supervision, Inspection and Testing Center test, in line with GB/T20219! 2006 standard requirements for spraying rigid polyurethane foam. Table 5 exterior wall. Roof waterproofing, temperature-temperature asphalt polyurethane rigid foam technical index project index foaming parameters foaming time / s gel time / s bubble physical compressive strength (compression deformation 10%) / kPa thermal conductivity / W. (mK) 1 water vapor transmission Wet coefficient / g (Pam.s) I water absorption rate (v / v /% vertical combustion method average burning time / s average burning height / mm horizontal burning method average burning time / s average burning range / mm 4 in the end, in During the maintenance process of the ramp, the zinc-polyurethane foam blishing, which has been running for 3 years, is blended with polyether or polyester polyol with excellent anti-corrosion performance, and the obtained rigid polyurethane foam is used for anti-corrosion. It has a new role in the polyurethane hard foam family by coating action, anti-weathering and penetration resistance. It has improved the rigid polyurethane foam by adding polyoxyethylene triol, rosin aromatic polyester polyol and high-efficiency composite catalyst. 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Building insulation anti-corrosion asphalt polyurethane rigid foam