Ethoxyquinoline polyether polyol as well as preparation method and application thereof

Abstract

The invention discloses ethyoxyl quinoline polyether polyol which is prepared by the following method: carrying out aminolysis reaction on an ethyoxyl quinoline polymer and epoxypropane to prepare amino alcohol; and carrying out polymerization reaction on amino alcohol serving as an initiator and epoxypropane to prepare the ethyoxyl quinoline polyether polyol. The invention also discloses application of the polyether polyol in preparation of a waterproof material, a UV coating, printing ink or an adhesive. The method comprises the following steps: dissolving ethoxyquin distillation still residues by using an organic solvent selected from xylene or butyl acetate, extracting organic molecules, filtering to remove high-temperature carbides, carrying out aminolysis reaction on ethoxyquin polymer secondary amine functional groups and epoxypropane, and introducing hydroxyl to prepare amino alcohol; and further taking amino alcohol as an initiator, and carrying out polymerization reaction with epoxypropane under the action of a catalyst to prepare the polyether polyol. According to the method, resource utilization of the ethoxyquin distillation still residues is realized.

Description

Technical Field

[0001] The invention belongs to the field of materials, and relates to an ethoxyquinoline polyether polyol and a preparation method and application thereof, and specifically relates to a polyether polyol prepared by using an ethoxyquinoline polymer and a preparation method and application thereof. Background Art

[0002] Ethoxyquin is a very economical and effective antioxidant, which is currently widely used. It is not only used for food preservation, but also can slow down rubber aging, inhibit vitamin oxidation, and prevent fruit skin from discoloring due to oxidation. However, for every ton of ethoxyquin crude oil produced, 0.2 to 0.25 tons of distillation heavy component polymers will be produced, that is, distillation kettle residue, which is solid at room temperature and begins to melt into a viscous liquid when heated to 90 to 100°C. It is a hazardous waste. Treating it as solid waste not only puts pressure on the ecological environment, but also requires capital costs to treat solid waste. The resource utilization of heavy component polymers has always been a technical problem that has plagued the development of the industry.

[0003] Polymers with ether bonds (—R—O—R—) in the main chain of polymer molecules and more than 2 hydroxyl groups (—OH) in the end or side groups are collectively referred to as polyether polyols. They are colorless to brown viscous liquids at room temperature, usually soluble in aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ketones, and hygroscopic. They are synthesized by homopolymerization or copolymerization with oxidized olefins using polyhydroxy or polyamine compounds as initiators under the action of a catalyst. Polyether polyols are widely used and are often used in the manufacture of general-purpose polyurethane foams, adhesives, and elastomers. Special polyether polyols are also used as defoamers, surfactants, etc.

[0004] If the application technology of polyether polyols can be combined with the heavy components of ethoxyquinoline distillation to achieve the resource utilization of the heavy components of ethoxyquinoline distillation polymers, then a feasible solution will be found to the technical problems that have been plaguing the development of the industry. Summary of the invention

[0005] The object of the present invention is to provide a polyether polyol prepared by using ethoxyquinoline polymer in view of the above-mentioned deficiencies in the prior art.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] An ethoxyquinoline polyether polyol is prepared by the following method: an ethoxyquinoline polymer undergoes an aminolysis reaction with propylene oxide to prepare an amino alcohol; and the amino alcohol is used as an initiator to undergo a polymerization reaction with propylene oxide to prepare the ethoxyquinoline polyether polyol.

[0008] Preferably, the ethoxyquinoline polyether polyol is prepared by the following method: using one selected from xylene or butyl acetate as a reaction solvent, under the action of a catalyst, ethoxyquinoline polymer and propylene oxide undergo an aminolysis reaction to prepare an amino alcohol; then using one selected from xylene or butyl acetate as a reaction solvent and amino alcohol as an initiator, under the action of a catalyst, amino alcohol and propylene oxide undergo a polymerization reaction to prepare the ethoxyquinoline polyether polyol.

[0009] Ethoxyquinoline is generally prepared by condensing p-aminophenyl ether with acetone under the action of p-toluenesulfonic acid as a catalyst, using toluene as a reaction solvent. After the reaction is completed, a Na2CO3 aqueous solution with a concentration of about 0.1 g / mL is added to stand for stratification, and the upper organic layer is taken. The organic layer enters a distillation kettle for distillation, and toluene, a fraction 1 with an ethoxyquinoline content of less than 78%, a fraction 2 with an ethoxyquinoline content of 78% or less and less than 88% (the distillation temperature is 190±5°C and the vacuum degree is -0.096MPa±0.001MPa), and a finished product with an ethoxyquinoline content of 88% or less (the distillation temperature is 190±5°C and the vacuum degree is -0.096MPa±0.001MPa) are distilled out in sequence, and the ethoxyquinoline distillation kettle residue is obtained in a distillation tower.

[0010] The ethoxyquinoline polymer is obtained by extraction using the residue of ethoxyquinoline distillation kettle as raw material and one selected from xylene or butyl acetate as extraction solvent.

[0011] Preferably, the ethoxyquinoline polymer is prepared by the following method: mixing the ethoxyquinoline distillation kettle residue with an organic solvent selected from butyl acetate or xylene, stirring and heating to 50-100° C., dissolving at a temperature of 50-100° C. for 1-3 hours, cooling after uniform dissolution, and filtering to obtain an ethoxyquinoline polymer solution.

[0012] Preferably, the ethoxyquinoline polymer is prepared by the following method: adding the ethoxyquinoline distillation kettle residue and an organic solvent selected from butyl acetate or xylene into a dissolution kettle, stirring and heating to 60-90° C., dissolving at a temperature of 60-90° C. for 1-2 hours, cooling after uniform dissolution, filtering, and obtaining an ethoxyquinoline polymer solution.

[0013] The xylene can be various isomers of xylene, the most commonly used is industrial grade mixed xylene

[0014] Preferably, the mixture is cooled to 40°C and filtered.

[0015] The filtration adopts filter paper with a pore size of 20 microns.

[0016] Another object of the present invention is to provide a method for preparing the ethoxyquinoline polyether polyol, comprising:

[0017] Step (1), pretreatment of ethoxyquinoline still residue: mixing an organic solvent selected from xylene or butyl acetate with the ethoxyquinoline still residue, stirring and heating to 50-100° C., dissolving at 50-100° C. for 1-3 hours, cooling after uniform dissolution, filtering, and obtaining an ethoxyquinoline polymer solution;

[0018] Step (2), using one selected from xylene or butyl acetate as a reaction solvent, in the presence of a catalyst, the ethoxyquinoline polymer and propylene oxide undergo an aminolysis reaction to prepare an amino alcohol;

[0019] Step (3), using one selected from xylene or butyl acetate as a reaction solvent and the amino alcohol prepared in step (2) as an initiator, the amino alcohol and propylene oxide undergo a polymerization reaction in the presence of a catalyst to prepare an ethoxyquinoline polyether polyol.

[0020] In step (1), the mass ratio of the organic solvent selected from xylene or butyl acetate to the ethoxyquinoline distillation kettle residue is 1:0.5 to 1:2.0, preferably 1:1.0 to 1:1.6.

[0021] The theoretical amine value of ethoxyquinoline is 258 mgKOH / g.

[0022] The amine value of the ethoxyquinoline polymer solution is usually 80 to 110 mgKOH / g.

[0023] In step (2), represents ethoxyquinoline polymer, ethoxyquinoline polymer and propylene oxide undergo aminolysis reaction to obtain an amino alcohol with a structure as shown in formula I, and the synthesis route is as follows:

[0024]

[0025] The mass ratio of the ethoxyquinoline polymer solution to propylene oxide is (56.1×1000 / Av):[58.08×(1.0~1.1)]; wherein 56.1 is the relative molecular weight of KOH, Av is the amine value measured by the ethoxyquinoline polymer solution, and 58.08 is the relative molecular weight of propylene oxide.

[0026] The ethoxyquinoline polymer solution is a xylene or butyl acetate solution of the ethoxyquinoline polymer.

[0027] The temperature of the aminolysis reaction is 80°C to 120°C, the pressure is 0.1 to 0.4 MPa, and the end point of the reaction is when the pressure of the reaction system drops to a constant level. Generally, the time of the aminolysis reaction is 1 to 8 hours, when the pressure in the kettle drops to a constant level.

[0028] The catalyst is one or two or more of trifluoromethanesulfonates such as lanthanum trifluoromethanesulfonate, neodymium trifluoromethanesulfonate, erbium trifluoromethanesulfonate, ytterbium trifluoromethanesulfonate, scandium trifluoromethanesulfonate, cerium trifluoromethanesulfonate, stannous trifluoromethanesulfonate, bismuth trifluoromethanesulfonate, etc., and the mixture is preferably one or two or more of lanthanum trifluoromethanesulfonate, ytterbium trifluoromethanesulfonate, and scandium trifluoromethanesulfonate. The amount of the catalyst is 0.1wt% to 1wt% of the total mass of the ethoxyquinoline polymer solution and propylene oxide.

[0029] Specifically, the amino alcohol is prepared by the following method: in a pressure reactor, in the presence of a catalyst, an ethoxyquinoline polymer solution and propylene oxide are reacted at a temperature of 80°C to 120°C and a pressure of 0.1 to 0.4 MPa until the pressure in the reactor drops to a constant level. After the reaction is completed, the reaction is cooled to below 50°C to obtain the amino alcohol.

[0030] Under the reaction conditions of the present invention, the epoxy group of propylene oxide is ring-opened and reacts with the secondary amine group of the ethoxyquinoline polymer to undergo addition reaction. When the pressure of the reaction system drops to a constant value, that is, the absorption of propylene oxide is completed, the reaction is considered to be finished.

[0031] In step (3), the amino alcohol with a structure as shown in formula I undergoes polymerization reaction with propylene oxide to obtain an ethoxyquinoline polyether polyol with a structure as shown in formula II. The synthesis route is as follows:

[0032]

[0033] The amount of amino alcohol is calculated based on the ethoxyquinoline polymer solution, and the mass ratio of the ethoxyquinoline polymer solution to propylene oxide is (56.1×1000 / Av):[58.08×(1.0~50)], preferably (56.1×1000 / Av):[58.08×(3~40)]; wherein 56.1 is the relative molecular weight of KOH, Av is the amine value measured by the ethoxyquinoline polymer solution, and 58.08 is the relative molecular weight of propylene oxide. In step (3), the amount of propylene oxide used does not include the amount of propylene oxide used in step (2).

[0034] The polymerization temperature is 100°C to 165°C, preferably 140°C to 155°C, the polymerization pressure is 0.1 to 0.6 MPa, preferably 0.2 to 0.5 MPa, and the polymerization time is 1 to 8 hours, preferably 3 to 7 hours. Generally, the end point of the polymerization is when the pressure of the reaction system drops to a constant level.

[0035] The catalyst is one of sodium formate, potassium formate, sodium benzoate and potassium benzoate or a mixture of two or more of them in any proportion; the amount of the catalyst is 1wt% to 5wt% of the total mass of amino alcohol and propylene oxide.

[0036] After the reaction is completed, the organic solvent is removed by distillation under reduced pressure, activated clay is added for stirring, and then cyclic pressure filtration is performed until the solution is clear and transparent to obtain ethoxyquinoline polyether polyol.

[0037] The conditions for removing the organic solvent by reduced pressure distillation are: vacuum degree -0.098MPa, temperature 120°C.

[0038] After the reaction in step (2) is completed, there is no need to purify the amino alcohol. When the reaction liquid drops to ≤50°C, a catalyst is added, and then the temperature is raised to the set reaction temperature, and propylene oxide is continuously and slowly added dropwise to carry out a polymerization reaction.

[0039] Specifically, the ethoxyquinoline polyether polyol is prepared by the following method: in a pressure reactor, using xylene or butyl acetate as a reaction solvent, under the action of a catalyst, amino alcohol (I) and propylene oxide undergo a polymerization reaction, until the pressure in the reactor drops to a constant, the temperature is lowered to 80° C., and reduced pressure distillation is started to recover the organic solvent to 120° C., and no solvent is distilled out for 10 minutes at a vacuum degree of -0.098 MPa and a temperature of 120° C., and the distillation is terminated, the temperature is lowered to 60° C., activated clay is added and stirred for 30 minutes, and cyclic pressure filtration is performed until it is clear and transparent to obtain the ethoxyquinoline polyether polyol.

[0040] More specifically, the ethoxyquinoline polyether polyol is prepared by the following method: after the reaction in step (2) is completed, when the reaction liquid drops to ≤50°C, a catalyst is added, and then the temperature is raised to a set reaction temperature, and propylene oxide is continuously and slowly added dropwise to carry out a polymerization reaction until the pressure in the kettle drops to a constant level, the temperature is lowered to 80°C, and reduced pressure distillation is started to recover the solvent to 120°C. At a vacuum degree of -0.098MPa and a temperature of 120°C, no solvent is distilled out for 10 minutes, the distillation is terminated, the temperature is lowered to 60°C, activated clay is added and stirred for 30 minutes, and cyclic pressure filtration is carried out until it is clear and transparent to obtain the ethoxyquinoline polyether polyol.

[0041] Another object of the present invention is to provide the use of the ethoxyquinoline polyether polyol in the preparation of waterproof materials, UV coatings, inks or adhesives.

[0042] A one-component polyether polyurethane adhesive is prepared by using ethoxyquinoline polyether polyol and phenylene diisocyanate compounds as raw materials, reacting at 60-85°C under nitrogen protection and with the action of a catalyst until the isocyanate group (-CNO) content is 2%-10%.

[0043] The mass ratio of the ethoxyquinoline polyether polyol to the isocyanate group (-CNO) in the phenylene diisocyanate compound is (56.1×1000 / V OH ):[42×(0.5~3)], preferably (56.1×1000 / V OH):[42×(2~3)]; where V OH is the hydroxyl value of the polyether polyol, 56.1 is the relative molecular weight of KOH, and 42 is the relative molecular weight of the isocyanate group (-CNO).

[0044] The phenylene diisocyanate compound is at least one of diphenylmethane-4,4'-diisocyanate (MDI), 2,4-toluene diisocyanate, and 2,6-toluene diisocyanate. Specifically, the phenylene diisocyanate compound is MDI or TDI-80.

[0045] The catalyst is dibutyltin dilaurate; the dosage of the catalyst is 0.02wt% to 0.025wt% of the mass of the ethoxyquinoline polyether polyol.

[0046] Specifically, the one-component polyether polyurethane adhesive is prepared by the following method: the ethoxyquinoline polyether polyol and the phenylene diisocyanate compound are used as raw materials, the phenylene diisocyanate compound and the catalyst are mixed, and the mixture is stirred and heated to 60-65° C. under nitrogen protection, and the ethoxyquinoline polyether polyol is added dropwise through a constant temperature dropping funnel at a temperature of 60-65° C. After the addition is completed, the mixture is slowly heated to 80-85° C., and the mixture is reacted at a temperature of 80-85° C. until the -NCO content in the one-component polyether polyurethane adhesive is 2%-10%.

[0047] Beneficial effects of the present invention:

[0048] Ethoxyquinoline distillation kettle residue is a chemical solid waste. The present invention uses xylene or butyl acetate to dissolve the ethoxyquinoline distillation kettle residue, extracts organic molecules, filters to remove high-temperature carbides, and then makes the secondary amine functional group of the ethoxyquinoline polymer react with propylene oxide to introduce hydroxyl groups to obtain amino alcohol; further, the amino alcohol is used as an initiator and is polymerized with propylene oxide under the action of a catalyst to obtain polyether polyol, and the molecular structure is improved by chain extension through the polymerization reaction, the softening point and viscosity of the polyether polyol are reduced, and the Tg is reduced to improve brittleness, and further the rigid nitrogen-containing heteroatom quinoline ring structure and the flexible ether chain are rigid-flexible combined to achieve a rigid-flexible balance, which is more beneficial to its application performance.

[0049] The adhesive prepared by using the ethoxyquinoline polyether polyol as the main raw material has good performance indicators such as open time, elongation at break, tensile shear strength, etc., and meets the requirements of practical application. The prepolymer prepared by using the ethoxyquinoline polyether polyol as the main raw material has excellent properties such as high hardness, wear resistance, scratch resistance, heat resistance, weather resistance, etc. after being cured, and can be used as a raw material for waterproof materials, coatings, and inks.

[0050] The invention realizes the resource utilization of the ethoxyquinoline distillation kettle residue and "turns waste into treasure". DETAILED DESCRIPTION

[0051] Determination of amine value by perchloric acid-acetic acid titration:

[0052] Weigh about 0.2g (accurate to 0.0001g) of sample, place it in a 250mL conical flask, add about 25mL of glacial acetic acid, stir magnetically to fully dissolve, add 2-3 drops of crystal violet indicator (dissolve 0.5g of crystal violet in 100mL of glacial acetic acid), and titrate with the prepared calibrated 0.1mol / L perchloric acid standard solution until the solution changes from purple to pure blue, which is the titration end point. Titrate in parallel two or three times and take the average value [1] .

[0053] The calculation formula of amine value is:

[0054] Where:

[0055] C—concentration of perchloric acid standard solution, mol / L;

[0056] V—volume of perchloric acid standard solution consumed by the sample, mL;

[0057] m—mass of sample, g;

[0058] 56.1—The mass of potassium hydroxide per mole.

[0059] Example 1

[0060] The first step is to add 800 g of xylene and 800 g of ethoxyquinoline distillation kettle residue into a 2L dissolving kettle, stir and heat to 90° C., dissolve at 90° C. for 2 hours, and after uniform dissolution, cool to 40° C., filter with filter paper with a pore size of 20 μm, filter out black solid particles formed by high-temperature carbonization of organic matter, and obtain 1515 g of xylene solution of ethoxyquinoline polymer, and the amine value is 93.2 mgKOH / g determined by perchloric acid-acetic acid titration method;

[0061] In the second step, 1203.86 grams of the xylene solution of the ethoxyquinoline polymer prepared in the first step and 4 grams of lanthanum trifluoromethanesulfonate (CAS No. 52093-26-2) were added to a 5L pressure reactor, stirring was started, the temperature was raised to 110°C, and 127 grams of propylene oxide was added dropwise for reaction. During the addition, the temperature was controlled at 110°C to 120°C and the pressure was controlled at 0.10 to 0.40 MPa. The addition was completed within 2 hours. After the addition was completed, the temperature was kept at 110°C to 120°C for 2 hours until the pressure in the reactor dropped to a constant value, and then cooled to below 50°C to obtain amino alcohol. No separation or purification was required, and the next step of reaction was directly carried out.

[0062] The third step is to drop 20 grams of sodium formate into the 5L pressure reactor, start stirring, heat to 150°C, start to drip 696.96 grams of propylene oxide to react, control the temperature at 150°C to 155°C and the pressure at 0.10 to 0.40MPa during the dropping process, and complete the dropwise addition within 4 hours. After completion of the dropwise addition, keep at 150°C to 155°C for 3 hours until the pressure in the reactor drops to a constant level, cool to 80°C, start underpressure distillation to recover xylene to 120°C, and distill without xylene for 10 minutes at a vacuum degree of -0.098MPa and a temperature of 120°C, terminate distillation, cool to 60°C, add 20 grams of activated clay and stir for 30 minutes, perform circulating filter press, and obtain 1398 grams of clear and transparent ethoxyquinoline polyether polyols, and recover 590 grams of xylene.

[0063] The designed hydroxyl equivalent (the mass number of a compound containing 1 mol of hydroxyl group) of ethoxyquinoline polyether polyol is 712.76 g / mol, and the measured hydroxyl equivalent is 713.22 g / mol; wherein, the conversion relationship between the hydroxyl equivalent and the hydroxyl value is hydroxyl equivalent = 56.1 × 1000 / hydroxyl value; the hydroxyl value is measured in accordance with the national standard "GB / T 12008.3-2009 Plastic polyether polyols Part 3: Determination of hydroxyl value".

[0064] Example 2

[0065] Preparation of one-component polyether polyurethane adhesive with a designed -NCO content of 4.32%.

[0066] The preparation of the adhesive was carried out under the condition of heating with a thermostatic electric heater. 249 g of diphenylmethane-4,4'-diisocyanate (MDI, CAS No.101-68-8, relative molecular weight 250.25), 0.16 g of dibutyltin dilaurate (CAS No.77-58-7) were added to a four-necked flask, and the corresponding stirring device, heating device, temperature control device and nitrogen protection device were connected. Under nitrogen protection, the temperature was stirred and raised to 60°C. 713.22 g of the ethoxyquinoline polyether polyol prepared in Example 1 was added dropwise to the four-necked flask through a constant pressure dropping funnel. The temperature was controlled at 60-65°C during the addition. After the addition of the ethoxyquinoline polyether polyol was completed, the temperature was slowly raised to 80°C, and the reaction was kept at 80-85°C for 3 hours. When the residual -NCO content of the system reached the designed value of 4.32%, it was cooled to 60°C under nitrogen protection, and the material was discharged (the air in the container was blown out with nitrogen during the discharge process, and the nitrogen was cut off and sealed after the discharge was completed), and the material was stored in a sealed bottle.

[0067] Example 3

[0068] Preparation of one-component polyether polyurethane adhesive with a designed -NCO content of 4.72%.

[0069] The preparation of the adhesive was carried out under the condition of heating with a thermostatic electric heater. 174 g of TDI-80 (containing 80% 2,4-toluene diisocyanate, CAS No. 584-84-9, 20% 2,6-toluene diisocyanate, CAS No.91-08-7, relative molecular weight 174.16), 0.15 g of dibutyltin dilaurate were added to a four-necked flask, and the corresponding stirring device, heating device, temperature control device and nitrogen protection device were connected. Under nitrogen protection, the temperature was stirred and raised to 60°C. 713.22 g of the ethoxyquinoline polyether polyol prepared in Example 1 was added dropwise to the four-necked flask through a constant pressure dropping funnel. The temperature was controlled to be 60-65°C during the addition process. After the addition of the ethoxyquinoline polyether polyol was completed, the temperature was slowly raised to 80°C, and the reaction was kept at 80-85°C for 3 hours. When the residual -NCO content of the system reached the designed value of 5.81%, it was cooled to 60°C under nitrogen protection, and the material was discharged (the air in the container was blown out with nitrogen during the discharge process, and the nitrogen was cut off and sealed after the discharge was completed), and it was stored in a sealed bottle.

[0070] Comparative Example 1

[0071] A polyether polyol having the same hydroxyl equivalent as that in Example 1 was designed and prepared, using commonly used glycerol as an initiator and reacting with propylene oxide.

[0072] In a 3L pressure reactor, 92.09 g of glycerol (relative molecular weight 92.09) and 20 g of sodium formate were added, stirring was started, the temperature was raised to 150°C, and 2046.19 g of propylene oxide was added dropwise for reaction. During the addition, the temperature was controlled at 150°C to 155°C and the pressure was 0.10 to 0.40 MPa. The addition was completed within 4 hours. After the addition was completed, the temperature was kept at 150°C to 155°C for 3 hours until the pressure in the reactor dropped to a constant value, the temperature was lowered to 60°C, 10 g of activated clay was added, and stirring was carried out for 30 minutes. Circulation filter pressing was performed to obtain 2095 g of clear and transparent polyether polyol.

[0073] The designed hydroxyl equivalent (the mass number of a compound containing 1 mol of hydroxyl group) of the polyether polyol is 712.76 g / mol, and the measured hydroxyl equivalent is 713.31 g / mol; wherein, the conversion relationship between the hydroxyl equivalent and the hydroxyl value is hydroxyl equivalent = 56.1 × 1000 / hydroxyl value; the hydroxyl value is measured in accordance with the national standard "GB / T 12008.3-2009 Plastic polyether polyols Part 3: Determination of hydroxyl value".

[0074] Comparative Example 2

[0075] Preparation of one-component polyether polyurethane adhesive with a designed -NCO content of 4.32%.

[0076] The preparation of the adhesive is carried out under the condition of heating by a thermostatic electric heater. 249 grams of diphenylmethane-4,4'-diisocyanate and 0.16 grams of dibutyltin dilaurate are added to a four-necked flask, and the corresponding stirring device, heating device, temperature control device, and nitrogen protection device are connected. Under nitrogen protection, the temperature is stirred and raised to 60°C. 713.31 grams of the polyether polyol prepared in Comparative Example 1 is added dropwise to the four-necked flask through a constant pressure dropping funnel. The temperature is controlled at 60-65°C during the addition process. After the polyether polyol is added dropwise, the temperature is slowly raised to 80°C, and the reaction is kept at 80-85°C for 3 hours. When the residual -NCO content of the system reaches the designed value of 4.32%, it is cooled to 60°C under nitrogen protection, and the material is discharged (the air in the container is blown out with nitrogen during the discharge process, and the nitrogen is cut off and sealed after the discharge is completed), and it is stored in a sealed bottle.

[0077] Comparative Example 3

[0078] Preparation of one-component polyether polyurethane adhesive with a designed -NCO content of 4.72%.

[0079] The preparation of the adhesive was carried out under the condition of heating by a thermostatic electric heater. 174 g of TDI-80 and 0.15 g of dibutyltin dilaurate were added to a four-necked flask, and the corresponding stirring device, heating device, temperature control device, and nitrogen protection device were connected. Under nitrogen protection, the temperature was stirred and raised to 60°C. 713.31 g of the polyether polyol prepared in Comparative Example 1 was added dropwise to the four-necked flask through a constant pressure dropping funnel. The temperature was controlled at 60-65°C during the addition process. After the polyether polyol was added dropwise, the temperature was slowly raised to 80°C, and the reaction was kept at 80-85°C for 3 hours. When the residual -NCO content of the system reached the designed value of 5.81%, it was cooled to 60°C under nitrogen protection, and the material was discharged (the air in the container was blown out with nitrogen during the discharge process, and the nitrogen was cut off and sealed after the discharge was completed), and it was stored in a sealed bottle.

[0080] The one-component polyurethane adhesives prepared in Example 2, Example 3, Comparative Example 2, and Comparative Example 3 were tested for their application performance.

[0081] Test method:

[0082] (1) Determination of adhesive open time

[0083] According to GB / T13477.57-2002 standard, glue is applied to a smooth glass plate (polytetrafluoroethylene plate) with a thickness of 0.1mm. The time when the surface of the glue layer is sticky is the open time.

[0084] (2) Determination of elongation at break of adhesive

[0085] According to GB / T 1040-92 standard, the film is cut into dumbbell shape (according to Type I in GB / T 528 standard). The sample thickness needs to be accurately measured by electronic vernier caliper, the speed is set at 50mm / min, and there are 3 parallel samples.

[0086] (3) Determination of tensile shear strength of adhesive

[0087] According to GB / T 7124-2008 standard, the homemade ABS board needs to be treated with acetone for 1 minute and dried for use. The test environment is room temperature 25℃, humidity 50-60%, the length specification of the bonding surface of the board is 12.50mm±0.25mm, the width specification of the bonding surface is 25.00mm±0.25mm, the glue layer is about 0.2mm, the tensile speed of the universal tensile testing machine is set to 5mm / min, the tensile shear strength is measured, and the number of parallel test samples is 5.

[0088] Test results:

[0089] Table 1. Application performance test results of the one-component polyurethane adhesives prepared in Example 2 and Example 3

[0090]

[0091]

[0092] The performance test results are shown in Table 1, which show that the performance of the one-component polyurethane adhesives prepared in Examples 2 and 3 is better than that of the adhesives prepared in Comparative Examples 2 and 3. In terms of key performance, the tensile shear strength of the one-component polyurethane adhesive prepared in Example 2 is 2.8 MPa, which is higher than the 1.9 MPa and 1.7 MPa of the adhesives prepared in Comparative Examples 2 and 3.

[0093] References:

[0094] [1] Zhang Lanfen, Zhou Xiuli. Determination of amine value of epoxy curing agent [J]. Coatings Technology and Abstracts, 2004, (1): 40-41.

Claims

1. An ethoxyquinoline polyether polyol, characterized in that: The method is prepared by the following method: an ethoxyquinoline polymer undergoes an aminolysis reaction with propylene oxide to prepare an amino alcohol; and the amino alcohol is used as an initiator to undergo a polymerization reaction with propylene oxide to prepare an ethoxyquinoline polyether polyol.

2. A method for preparing the ethoxyquinoline polyether polyol according to claim 1, characterized in that: include: Step (1), pretreatment of ethoxyquinoline still residue: mixing an organic solvent selected from xylene or butyl acetate with the ethoxyquinoline still residue, stirring and heating to 50-100° C., dissolving at 50-100° C. for 1-3 hours, cooling, filtering, and obtaining an ethoxyquinoline polymer solution; Step (2), using one selected from xylene or butyl acetate as a reaction solvent, in the presence of a catalyst, the ethoxyquinoline polymer and propylene oxide undergo an aminolysis reaction to prepare an amino alcohol; Step (3), using one selected from xylene or butyl acetate as a reaction solvent and amino alcohol as an initiator, the amino alcohol and propylene oxide undergo a polymerization reaction in the presence of a catalyst to prepare an ethoxyquinoline polyether polyol.

3. The preparation method of ethoxyquinoline polyether polyol according to claim 2, characterized in that: In step (1), the mass ratio of the organic solvent selected from xylene or butyl acetate to the ethoxyquinoline distillation kettle residue is 1:0.5 to 1:2.0, preferably 1:1.0 to 1:1.

6.

4. The preparation method of ethoxyquinoline polyether polyol according to claim 2, characterized in that: In step (1), the amine value of the ethoxyquinoline polymer solution is 80-110 mgKOH / g.

5. The preparation method of ethoxyquinoline polyether polyol according to claim 2, characterized in that: In step (2), the mass ratio of the ethoxyquinoline polymer solution to propylene oxide is (56.1×1000 / Av):[58.08×(1.0-1.1)]; wherein Av is the amine value of the ethoxyquinoline polymer solution; The temperature of the aminolysis reaction is 80°C to 120°C, the pressure is 0.1 to 0.4 MPa, and the end point of the reaction is when the pressure of the reaction system drops to a constant value; The catalyst is at least one of lanthanum trifluoromethanesulfonate, neodymium trifluoromethanesulfonate, erbium trifluoromethanesulfonate, ytterbium trifluoromethanesulfonate, scandium trifluoromethanesulfonate, cerium trifluoromethanesulfonate, stannous trifluoromethanesulfonate and bismuth trifluoromethanesulfonate, preferably at least one of lanthanum trifluoromethanesulfonate, ytterbium trifluoromethanesulfonate and scandium trifluoromethanesulfonate; the amount of the catalyst is 0.1wt% to 1wt% of the total mass of the ethoxyquinoline polymer solution and propylene oxide.

6. The preparation method of ethoxyquinoline polyether polyol according to claim 2, characterized in that: In step (3), the mass ratio of the ethoxyquinoline polymer solution to propylene oxide is (56.1×1000 / Av):[58.08×(1.0-50)], preferably (56.1×1000 / Av):[58.08×(3-40)]; wherein Av is the amine value of the ethoxyquinoline polymer solution; The polymerization reaction temperature is 100°C to 165°C, preferably 140°C to 155°C, the polymerization reaction pressure is 0.1 to 0.6 MPa, preferably 0.2 to 0.5 MPa, and the polymerization reaction time is 1 to 8 hours, preferably 3 to 7 hours; The catalyst is at least one of sodium formate, potassium formate, sodium benzoate and potassium benzoate; the amount of the catalyst is 1wt% to 5wt% of the total mass of the amino alcohol and propylene oxide.

7. The preparation method of ethoxyquinoline polyether polyol according to claim 2, characterized in that: In step (3), after the reaction is completed, the organic solvent is removed by distillation under reduced pressure, activated clay is added and stirred, and then cyclic pressure filtration is performed until the mixture becomes clear and transparent to obtain ethoxyquinoline polyether polyol.

8. Use of the ethoxyquinoline polyether polyol according to claim 1 in the preparation of waterproof materials, UV coatings, inks or adhesives.

9. A one-component polyether polyurethane adhesive, characterized in that: The ethoxyquinoline polyether polyol as claimed in claim 1 and phenylene diisocyanate compounds are used as raw materials, and reacted at 60-85° C. under nitrogen protection and the action of a catalyst until the -NCO content reaches 2%-10%.

10. The one-component polyether polyurethane adhesive according to claim 9, characterized in that: The mass ratio of the ethoxyquinoline polyether polyol to the isocyanate group in the phenylene diisocyanate compound is (56.1×1000 / V OH ):[42×(0.5~3)], preferably (56.1×1000 / V OH ):[42×(2~3)]; where V OH is the hydroxyl value of the polyether polyol; The phenylene diisocyanate compound is at least one of diphenylmethane-4,4'-diisocyanate, 2,4-toluene diisocyanate, and 2,6-toluene diisocyanate; The catalyst is dibutyltin dilaurate; the dosage of the catalyst is 0.02wt% to 0.025wt% of the mass of the ethoxyquinoline polyether polyol.

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