Ethoxyquinoline polyurethane acrylate as well as preparation method and application thereof

Abstract

The invention discloses ethyoxyl quinoline polyurethane acrylate, which is prepared by the following method: carrying out aminolysis reaction on an ethyoxyl quinoline polymer and epoxypropane to prepare amino alcohol; taking amino alcohol as an initiator, and carrying out polymerization reaction on the amino alcohol and epoxypropane to prepare ethyoxyl quinoline polyether polyol; the preparation method comprises the following steps: carrying out a polyurethane reaction on ethoxyquin polyether polyol and diisocyanate to prepare a polyurethane intermediate; and reacting the polyurethane intermediate with acrylate containing a hydroxyl functional group to prepare the ethyoxyl quinoline polyurethane acrylate. The invention also discloses an application of the ethyoxyl quinoline polyurethane acrylate in preparation of UV coatings, printing ink and adhesives. After being cured, polyurethane acrylate prepared from the ethoxyquin polymer has the excellent properties of high hardness, wear resistance, scratch resistance, heat resistance, weather resistance and the like, and can be used as a raw material of UV coatings, printing ink and adhesives.

Description

Technical Field

[0001] The invention belongs to the field of materials, and relates to an ethoxyquinoline polyurethane acrylate and a preparation method and application thereof, and specifically relates to a polyurethane acrylate 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 after cooling to 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] With the rapid development of science and technology and the strict restrictions on solvents by environmental protection laws and regulations, ultraviolet (UV) light-curing polymer materials are gaining more and more attention. UV light-curing materials have excellent properties such as fast curing, low energy consumption, less pollution, and high efficiency, so they are widely used in coatings, printing, and electronic industries, and have developed rapidly in recent years.

[0004] Polyurethane acrylate (PUA) is made of polyether or polyester polyols, isocyanates, and acrylates containing hydroxyl functional groups as raw materials, and is prepared by the reaction of isocyanate groups (-NCO) and hydroxyl groups (-OH). It is an important photocurable oligomer with excellent properties such as low irritation, adjustable curing speed, high transparency, high flexibility, and adjustable hardness. It is widely used in photocurable inks, coatings, adhesives and other fields.

[0005] If UV technology can be combined with the heavy components of ethoxyquinoline distillation to achieve resource utilization of the heavy components of ethoxyquinoline distillation polymers, then the technical problems that have been plaguing the development of the industry will find a feasible solution. Summary of the invention

[0006] The object of the present invention is to provide a polyurethane acrylate prepared by using ethoxyquinoline polymer in view of the above-mentioned deficiencies in the prior art.

[0007] The purpose of the present invention can be achieved through the following technical solutions:

[0008] An ethoxyquinoline polyurethane acrylate is prepared by the following method: an ethoxyquinoline polymer is subjected to an aminolysis reaction with propylene oxide to prepare an amino alcohol; the amino alcohol is used as an initiator to undergo a polymerization reaction with propylene oxide to prepare an ethoxyquinoline polyether polyol; the ethoxyquinoline polyether polyol is subjected to a polyurethane reaction with diisocyanate to prepare a polyurethane intermediate; the polyurethane intermediate is reacted with an acrylate containing a hydroxyl functional group to prepare the ethoxyquinoline polyurethane acrylate.

[0009] Preferably, the ethoxyquinoline polyurethane acrylate 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; using one selected from xylene or butyl acetate as a reaction solvent, under the action of a catalyst, using the amino alcohol as an initiator, and propylene oxide undergo a polymerization reaction to prepare an ethoxyquinoline polyether polyol; under the action of a catalyst, ethoxyquinoline polyether polyol and diisocyanate undergo a polyurethane reaction to prepare a polyurethane intermediate; under the action of a catalyst and an inhibitor, the polyurethane intermediate reacts with an acrylate containing a hydroxyl functional group to prepare the ethoxyquinoline polyurethane acrylate.

[0010] 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.

[0011] 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.

[0012] 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.

[0013] More 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.

[0014] The xylene can be various isomers of xylene, and the most commonly used is industrial grade mixed xylene.

[0015] Preferably, the mixture is cooled to 40°C and filtered.

[0016] The filtration adopts filter paper with a pore size of 20 microns.

[0017] Another object of the present invention is to provide a method for preparing the ethoxyquinoline polyurethane acrylate, comprising the following steps:

[0018] 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, filtering out black solid particles formed by high-temperature carbonization of organic matter, and obtaining an ethoxyquinoline polymer solution;

[0019] 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;

[0020] Step (3), using one selected from xylene or butyl acetate as a reaction solvent, and using the amino alcohol prepared in step (2) as an initiator to undergo a polymerization reaction with propylene oxide in the presence of a catalyst to prepare an ethoxyquinoline polyether polyol;

[0021] Step (4), in the presence of a catalyst, the ethoxyquinoline polyether polyol prepared in step (3) is subjected to a polyurethane reaction with diisocyanate to prepare a polyurethane intermediate;

[0022] Step (5), under the action of a catalyst and an inhibitor, the polyurethane intermediate reacts with an acrylate containing a hydroxyl functional group to prepare ethoxyquinoline polyurethane acrylate.

[0023] In step (1), the mass ratio of the organic solvent to the ethoxyquinoline distillation kettle residue is 1:0.5 to 1:2.0, preferably 1:1.0 to 1:1.6.

[0024] The theoretical amine value of ethoxyquinoline is 258 mgKOH / g.

[0025] The amine value of the ethoxyquinoline polymer solution is usually 80 to 110 mgKOH / g.

[0026] 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 56.1 is the relative molecular weight of KOH (in the amine value calculation formula), Av is the amine value measured by the ethoxyquinoline polymer solution, and 58.08 is the relative molecular weight of propylene oxide.

[0027] The ethoxyquinoline polymer solution is a xylene or butyl acetate solution of the ethoxyquinoline polymer.

[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.

[0029] The dosage of the catalyst is 0.1wt% to 1wt% of the total mass of the ethoxyquinoline polymer solution and propylene oxide.

[0030] The temperature of the aminolysis reaction is 80°C to 120°C, the pressure of the aminolysis reaction is 0.1 to 0.4 MPa, and the end point of the aminolysis 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, until the pressure in the kettle drops to a constant level.

[0031] Specifically, the amino alcohol is prepared by the following method: an ethoxyquinoline polymer solution, propylene oxide and a catalyst are put into a pressure reactor, and under the action of the catalyst, the ethoxyquinoline polymer and propylene oxide undergo an aminolysis reaction until the pressure in the reactor drops to a constant level, thereby obtaining the amino alcohol.

[0032] 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.

[0033] In step (3), the amount of the amino alcohol is calculated based on the ethoxyquinoline polymer solution. 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×(3.0~40)]; 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 does not include the amount of propylene oxide in step (2).

[0034] 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.

[0035] 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.

[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 becomes 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] Specifically, the ethoxyquinoline polyether polyol is prepared by the following method: in a pressure reactor, in the presence of a catalyst, amino alcohol and propylene oxide undergo polymerization reaction until the pressure in the reactor drops to a constant level, the temperature is lowered to 80° C., reduced pressure distillation is started to recover the organic solvent to 120° C., no organic solvent is distilled out for 10 minutes at a vacuum degree of -0.098 MPa and a temperature of 120° C., 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.

[0039] More specifically, the ethoxyquinoline polyether polyol is prepared by the following method: after the reaction of step (2) is completed, the amino alcohol does not need to be purified, and when the kettle temperature drops to ≤50° C., the catalyst of step (3) is directly added, and then the temperature is raised to a set temperature, and propylene oxide is continuously and slowly added dropwise to carry out a polymerization reaction, and the reaction pressure is controlled to be within a set range. After the addition of propylene oxide is completed, the reaction is continued by heat preservation until the pressure in the kettle drops to a constant value, the temperature is lowered to 80° C., and reduced pressure distillation is started to recover the organic solvent to 120° C., and at a vacuum degree of -0.098 MPa and a temperature of 120° C., no organic solvent is distilled out for 10 minutes, the distillation is terminated, the temperature is lowered to 60° C., activated white 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.

[0040] In step (4), the mass ratio of the ethoxyquinoline polyether polyol to the diisocyanate is (56.1×1000 / V OH ):[(1~1.5)×M], preferably (56.1×1000 / V OH ):[(1~1.25)×M]; where 56.1 is the relative molecular weight of KOH, V OH It is the hydroxyl value of ethoxyquinoline polyether polyol, and the hydroxyl value of ethoxyquinoline polyether polyol is measured according to the national standard "GB / T 12008.3-2009 Plastic polyether polyol Part 3: Determination of hydroxyl value"; M is the relative molecular weight of diisocyanate.

[0041] The diisocyanate is IPDI, HMDI, HDI, MDI, TDI (toluene diisocyanate), etc., preferably TDI.

[0042] The toluene diisocyanate has two isomers, 2,4-toluene diisocyanate and 2,6-toluene diisocyanate. According to the different contents of the two isomers, there are three specifications of products: TDI-65 (containing 2,4-TDI 65%, 2,6-TDI 35%), TDI-80 (containing 2,4-TDI 80%, 2,6-TDI 20%), and TDI-100 (containing 2,4-TDI 100%). TDI-80 is preferred in the present invention.

[0043] The catalyst is dibutyltin dilaurate; the amount of the catalyst used is 100 to 3000 ppm, preferably 100 to 1000 ppm, of the total mass of ethoxyquinoline polyether polyol and diisocyanate.

[0044] The temperature of the polyurethane reaction is 50°C to 95°C, preferably 60°C to 85°C, and the time of the polyurethane reaction is 1 to 6.

[0045] Preferably, the polyurethane intermediate is prepared by the following method: ethoxyquinoline polyether polyol and diisocyanate react at 50°C to 95°C for 1 to 6 hours to obtain a polyurethane intermediate; wherein the mass ratio of the ethoxyquinoline polyether polyol to the diisocyanate is (56.1×1000 / V OH ):[(1~1.5)×m].

[0046] Further preferably, the polyurethane intermediate is prepared by the following method: ethoxyquinoline polyether polyol and diisocyanate react at 60°C to 85°C for 1 to 6 hours to obtain a polyurethane intermediate; wherein the mass ratio of the ethoxyquinoline polyether polyol to the diisocyanate is (56.1×1000 / V OH ):[(1~1.25)×m].

[0047] In step (5), the mass ratio of the polyurethane intermediate (based on ethoxyquinoline polyether polyol) to the hydroxyl-functional acrylate is (56.1×1000 / V OH ):[(1~2.2)×(56.1×1000 / V OH ′)], preferably (56.1×1000 / V OH ):[(1~1.8)×(56.1×1000 / V OH ′)]; where V OH is the hydroxyl value of ethoxyquinoline polyether polyol (II), V OH ' is the hydroxyl value of acrylate containing hydroxyl functional group, and the hydroxyl value of hydroxy acrylate is determined by acid-catalyzed acetylation method.

[0048] The acrylate containing hydroxyl functional group is a acrylate containing one or more acryloyloxy groups. The acrylic ester organic substance containing one hydroxyl group (-OH) is preferably hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), 4-hydroxybutyl acrylate (4-HBA), caprolactone acrylate (Photomer 4034), and more preferably caprolactone acrylate (Photomer 4034).

[0049] The caprolactone acrylate (Photomer 4034) is a monofunctional UV acrylate monomer produced by IGM. It is an addition reaction product of hydroxyethyl acrylate (CAS NO: 818-61-1) and ε-caprolactone (CAS NO: 502-44-3). ε-caprolactone is ring-opened to form an ester bond with the hydroxyl group of hydroxyethyl acrylate. At the same time, the other end of the cyclic ester ring is opened to form a hydroxyl group, that is, the molecular structure contains one terminal hydroxyl group (-OH) and one acryloyloxy group. With two different functional active groups, Caprolactone acrylate (Photomer 4034) has enhanced flexibility, improved chemical resistance and excellent hydrolytic stability. It can be used in UV formulation products, and can also be used as a raw material to synthesize and modify new UV materials or other polymer materials to provide special properties.

[0050] The polymerization inhibitor may be p-hydroxyanisole or 2,6-di-tert-butyl-p-methylphenol; the dosage of the polymerization inhibitor is 100-5000 ppm of the total mass of ethoxyquinoline polyether polyol, diisocyanate and acrylate containing hydroxyl functional group.

[0051] The catalyst is dibutyltin dilaurate; the dosage of the catalyst is 100-3000ppm of the total mass of ethoxyquinoline polyether polyol, diisocyanate and acrylate containing hydroxyl functional group.

[0052] The reaction temperature is 50°C to 95°C, preferably 60°C to 85°C; the reaction time is 3 to 9 hours.

[0053] After the reaction is completed, add active diluent, stir evenly and filter.

[0054] The active diluent is tripropylene glycol diacrylate (TPGDA).

[0055] The active diluent is 10-30% of the total mass of ethoxyquinoline polyether polyol, diisocyanate, acrylate containing hydroxyl functional group, TPGDA, catalyst and inhibitor, preferably 20%.

[0056] Preferably, ethoxyquinoline polyurethane acrylate is prepared by the following method: a polyurethane intermediate is reacted with an acrylate containing a hydroxyl functional group at 50° C. to 95° C. for 3 to 9 hours, a reactive diluent is added, stirred and dissolved for 30 minutes, and filtered to obtain ethoxyquinoline polyurethane acrylate; wherein the polyurethane intermediate is obtained by step (4), the amount of the polyurethane intermediate is calculated based on ethoxyquinoline polyether polyol, and the mass ratio of ethoxyquinoline polyether polyol to hydroxyl acrylate is (56.1×1000 / V OH ):[(1~2.2)×(56.1×1000 / V OH ′)].

[0057] Further preferably, ethoxyquinoline polyurethane acrylate is prepared by the following method: a polyurethane intermediate is reacted with an acrylate containing a hydroxyl functional group at 60° C. to 85° C. for 3 to 9 hours, a reactive diluent is added, stirred and dissolved for 30 minutes, and filtered to obtain ethoxyquinoline polyurethane acrylate; wherein the polyurethane intermediate is obtained by step (4), the amount of the polyurethane intermediate is calculated based on ethoxyquinoline polyether polyol, and the mass ratio of ethoxyquinoline polyether polyol to hydroxyl acrylate is (56.1×1000 / V OH ):[(1~1.8)×(56.1×1000 / V OH ′)].

[0058] Another object of the present invention is to provide the use of the ethoxyquinoline polyurethane acrylate in the preparation of UV coatings, inks and adhesives.

[0059] Beneficial effects of the present invention:

[0060] Ethoxyquinoline still residue is a chemical solid waste. The present invention uses xylene or butyl acetate to dissolve the ethoxyquinoline still residue, extracts organic molecules, filters and removes high-temperature carbides, and then uses the secondary amine functional group of the ethoxyquinoline polymer to undergo an aminolysis reaction with propylene oxide to introduce a hydroxyl group, and further uses amino alcohol as an initiator to undergo a polymerization reaction with propylene oxide under the action of a catalyst to prepare polyether polyols, and the polyether polyols are further reacted with diisocyanates and hydroxy acrylates to prepare polyurethane acrylates, thereby realizing the resource utilization of the ethoxyquinoline still residue and "turning waste into treasure".

[0061] The present invention introduces polar urethane bonds (-NH-COO-) through diisocyanate. The urethane bonds have high cohesive energy, provide adhesion and hard segments, and form a soft-hard combination structure with the polyether chain soft segment, so that the molecular chain has good strength and wear resistance. Hydrogen bonds are formed between the imino group (-NH-) in the urethane bond (-NH-COO-) and the carbonyl group in the hard segment and the ether group in the soft segment. Compared with the bonding force of the intramolecular chemical bond, the hydrogen bond is a physical attraction. The close arrangement of the polar chain segments promotes the formation of hydrogen bonds; at higher temperatures, the chain segments receive energy and move, and the hydrogen bonds disappear. The hydrogen bonds play a physical cross-linking role, which can make the polyurethane material have higher strength and wear resistance. The more hydrogen bonds there are, the stronger the intermolecular force is, and the higher the strength of the material.

[0062] The invention introduces acrylate containing hydroxyl functional groups to make the molecular chain have enhanced flexibility, improved chemical resistance and excellent hydrolysis stability.

[0063] At the same time, due to the introduction of the nitrogen-containing heteroatom quinoline ring structure with stable rigidity and chemical resistance, the polyurethane acrylate prepared from the ethoxyquinoline polymer of the present invention has excellent properties such as high hardness, wear resistance, scratch resistance, heat resistance, and weather resistance after curing, and can be used as a raw material for UV coatings, inks, and adhesives. DETAILED DESCRIPTION

[0064] Determination of amine value by perchloric acid-acetic acid titration [1] :

[0065] Weigh about 0.2g (accurate to 0.0001g) of sample, place it in a 250mL conical flask, add about 25mL of glacial acetic acid solution, stir magnetically to fully dissolve, add 2 to 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.

[0066] The calculation formula of amine value is:

[0067] Where:

[0068] C—concentration of perchloric acid standard solution, mol / L;

[0069] V—volume of perchloric acid standard solution consumed by the sample, mL;

[0070] m—mass of sample, g;

[0071] 56.1—The mass of potassium hydroxide per mole.

[0072] Example 1

[0073] 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;

[0074] Step 2: The ethoxyquinoline polymer obtained in the first step The amino alcohol having a structure as shown in formula I is prepared by an aminolysis reaction with propylene oxide. The synthetic route is as follows:

[0075]

[0076] In a 5L pressure reactor, 1203.86g of ethoxyquinoline polymer xylene solution and 4g of lanthanum trifluoromethanesulfonate (CAS No.52093-26-2) were added, stirring was started, the temperature was raised to 110°C, and 127g of propylene oxide was added dropwise for reaction. The temperature during the addition was controlled at 110°C to 120°C and the pressure was 0.10 to 0.40MPa. 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.

[0077] In the third step, 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:

[0078]

[0079] 20 g of sodium formate was added to a 5L pressure reactor, stirring was started, the temperature was raised to 150°C, 696.96 g of propylene oxide was added dropwise to react, the temperature during the addition 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, and 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 80°C, and underpressure distillation was started to recover xylene to 120°C. Under a vacuum degree of -0.098 MPa and a temperature of 120°C, no xylene was distilled out for 10 minutes, the distillation was terminated, and the temperature was then lowered to 60°C, 20 g of activated clay was added and stirred for 30 minutes, and 1398 g of ethoxyquinoline polyether polyol was obtained by circulating filter press until clear and transparent, and 590 g of xylene was recovered.

[0080] In this embodiment, the designed hydroxyl equivalent (the mass number of the compound containing 1 mol of hydroxyl group) of the 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 according to the national standard "GB / T 12008.3-2009 Plastic polyether polyol Part 3: Determination of hydroxyl value".

[0081] Step 4: Preparation of polyurethane intermediates:

[0082]

[0083] The preparation reaction is carried out under the condition of heating by a thermostatic electric heater, 183 g of TDI-80 (containing 80% of 2,4-toluene diisocyanate, CAS No.584-84-9, 20% of 2,6-toluene diisocyanate, CAS No.91-08-7, relative molecular weight 174.16) and 0.18 g of dibutyltin dilaurate (CAS No.77-58-7) are added to a four-necked flask, and the corresponding stirring device, heating device and temperature control device are connected, and the temperature is stirred and raised to 60° C., and 713.22 g of the ethoxyquinoline polyether polyol prepared in Example 1 is added dropwise to the four-necked flask through a constant pressure dropping funnel, and the temperature is controlled at 60-65° C. during the dropping process. After the ethoxyquinoline polyether polyol is added dropwise, the reaction is carried out at 60-65° C. for 1 hour to obtain polyurethane intermediates (IIIa, IIIb);

[0084] Step 5: Preparation of ethoxyquinoline polyurethane acrylate:

[0085]

[0086] 0.5 g of p-hydroxyanisole was added to a three-necked flask, and 280 g of caprolactone acrylate (Photomer 4034) was added dropwise to the three-necked flask through a constant pressure dropping funnel. The temperature was controlled at 60-65° C. during the addition, and the addition was completed within 2 hours. After the addition of caprolactone acrylate (Photomer 4034) was completed, the temperature was slowly raised to 80° C., and the reaction was continued at 80-85° C. for 4 hours. When the residual -NCO content of the system was ≤0.1%, 294.3 g of TPGDA was added, stirred for 30 minutes, dissolved evenly, cooled to 60° C., and filtered through a 100-mesh gauze to obtain 1459 g of ethoxyquinoline polyurethane acrylate (total feed amount of 1471.2 g).

[0087] Acid catalyzed acetylation [2] The hydroxyl value of caprolactone acrylate (Photomer 4034) was measured to be 240.43 mgKOH / g, and the hydroxyl equivalent (the mass number of a compound containing 1 mol of hydroxyl group) was 233.33. The conversion relationship between the hydroxyl equivalent and the hydroxyl value is: hydroxyl equivalent = 56.1 × 1000 / hydroxyl value.

[0088] Example 2

[0089] raw materials

[0090] UV resin: ethoxyquinoline polyurethane acrylate prepared in Example 1; difunctional polyurethane acrylate (Photomer 6582, Agenmon Group, with good flexibility and good reactivity).

[0091] UV monomers: pentaerythritol triacrylate (PETA, Jiangsu Litian Technology Co., Ltd. of Agenmon Group); tripropylene glycol diacrylate (TPGDA, Jiangsu Litian Technology Co., Ltd. of Agenmon Group); tetrahydrofuran acrylate (THFA, Jiangsu Litian Technology Co., Ltd. of Agenmon Group).

[0092] Photoinitiator: 1173, Aigenmeng Anqing Technology Development Co., Ltd.

[0093] Additives: Tego432, Tego920, German Tego, Tego432 and Tego920 are added in a mass ratio of 1:1.

[0094] Mixed solvent: Butyl acetate, toluene, and methyl isobutyl ketone are mixed in a mass ratio of 1:1:1.

[0095] Instruments and Equipment

[0096] LT-1002 UV curing machine, Lantian Special Light Development Co., Ltd.; QFZ paint film adhesion tester, Tianjin Kelian Material Testing Machine Factory; RCA paper tape abrasion tester, Shanghai Modern Environmental Engineering Technology Research Institute; water bath; hot and cold cycle equipment.

[0097] Coating preparation

[0098] Weigh a certain amount of UV resin, then add UV monomer, photoinitiator, and additives, stir evenly, and prepare the coating. The coating ratio is shown in Table 1.

[0099] Table 1: Coating ratio

[0100]

[0101] Coating preparation and curing

[0102] A 10cm×10cm ABS plastic sheet was selected, and a layer of thermoplastic acrylic resin white primer was first sprayed on its surface and baked at 60℃ for 3h. Then, a UV topcoat was sprayed on its surface. The coating thickness was about 20μm. It was cured on a light curing machine to make the cured film surface dry. The dry-to-touch method was used to characterize it, and the curing time was recorded.

[0103] Performance Testing

[0104] Curing time: The experiment adopts the finger-touch drying method, which is to touch the surface of the paint film with your finger. If it does not feel sticky, it is considered that the surface of the paint film has been cured.

[0105] Pencil hardness: Determined according to GB 6739-86 coating pencil hardness method.

[0106] Adhesion: Determined according to GB / T 1720-88 coating adhesion test method. Divided into 7 levels, with 1 being the best and 7 being the worst.

[0107] Abrasion resistance: RCA test, 175g, 500±50 times.

[0108] Boiling water resistance: refer to the national standard GB / T 1733 "Determination of water resistance of paint films".

[0109] Resistant to hot and cold cycles:

[0110] (1) Scope and description: Plastic paints tend to crack due to moisture-heat cycles or loss of plasticizers, or both. Whether the paint film cracks and the extent of cracking can be determined by alternating exposure to a warm and cold box.

[0111] (2) Instruments: Humidity chamber, freezer, colorimeter, grid marker.

[0112] (3) Determination method: Place the test sample in a hot box with a relative humidity of 100% and a temperature of 38°C. The sample should be placed at an angle of 0 to 30° to the vertical direction, and the panels are required not to touch each other during the test. After 24 hours, transfer the sample to a freezer at (-23±1.5)°C within 30 seconds for 20 hours. Take out the sample and place it at room temperature for 4 hours. A total of 48 hours constitutes one cycle. Perform 15 cycles in total and test the appearance, color and adhesion of the sample. Stage evaluation can be carried out during the cold and hot cycle resistance.

[0113] (4) Result indication: The coating should be free of cracking, discoloration, decreased adhesion or other defects.

[0114] (5) Reference standard: American standard AAMA 615-02 "Industry specifications, performance requirements and test methods for high-performance organic coatings on plastic profiles" [3] .

[0115] Results and Discussion

[0116] UV resin is the main body of UV coating, and its performance basically determines the main performance of the cured coating. This experiment uses ethoxyquinoline polyurethane acrylate prepared in Example 2 and flexible difunctional polyurethane acrylate to form different formulations, and the coating performance is shown in Table 2.

[0117] Table 2: Effect of different ratios of ethoxyquinoline polyurethane acrylate and difunctional polyurethane acrylate on coating performance

[0118]

[0119]

[0120] Photoinitiator 1173 Description:

[0121] Manufacturer: Aijianmeng Anqing Technology Development Co., Ltd.;

[0122] Chemical name: 2-Hydroxy-2-methyl-1-phenyl-1-propanone;

[0123] English name: 2-Hydroxy-2-methyl-1-phenyl-propan-1-one;

[0124] CAS No: 7473-98-5;

[0125] Molecular formula: C 10 H 12 O;

[0126] Relative molecular weight: 164.2;

[0127] Chemical structure:

[0128] Technical indicators:

[0129] Appearance: Colorless to light yellow transparent liquid;

[0130] Purity: ≥99.0%;

[0131] Boiling point: 80-81°C;

[0132] Light transmittance: 425nm ≥ 99.0%; 500nm ≥ 99.3%;

[0133] Volatile matter: ≤0.2%;

[0134] Ash content: ≤0.10%;

[0135] application:

[0136] 1173 is suitable for acrylic light-curing varnish systems, such as varnishes for wood, metal, paper, plastic, etc. 1173 is especially recommended for UV-curing coatings that need to withstand long-term sunlight and resist yellowing. Since 1173 is a liquid and very easy to blend, it is suitable for compounding with other photoinitiators. The recommended addition amount is 1-4% w / w.

[0137] References:

[0138] [1] Zhang Lanfen, Zhou Xiuli. Determination of amine value of epoxy curing agent [J]. Coatings Technology and Abstracts, 2004, (1): 40-41.

[0139] [2] Zeng Zhaoxun. Rapid determination of hydroxyl value of alcohols[J]. Daily Chemical Industry, 1980, (02): 34-35.

[0140] [3] Yu Yingying. Complete list of inspection methods and instruments for coatings industry. Beijing: Chemical Industry Press, 2007: 525.

Claims

1. An ethoxyquinoline polyurethane acrylate, characterized in that: The preparation method is as follows: an ethoxyquinoline polymer is subjected to an aminolysis reaction with propylene oxide to prepare an amino alcohol; the amino alcohol is used as an initiator to undergo a polymerization reaction with propylene oxide to prepare an ethoxyquinoline polyether polyol; the ethoxyquinoline polyether polyol is subjected to a polyurethane reaction with diisocyanate to prepare a polyurethane intermediate; the polyurethane intermediate is reacted with an acrylate containing a hydroxyl functional group to prepare an ethoxyquinoline polyurethane acrylate.

2. A method for preparing the ethoxyquinoline polyurethane acrylate according to claim 1, characterized in that: The following steps are involved: 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, using an amino alcohol as an initiator, and reacting with propylene oxide in the presence of a catalyst to prepare an ethoxyquinoline polyether polyol; Step (4), in the presence of a catalyst, ethoxyquinoline polyether polyol and diisocyanate undergo a polyurethane reaction to prepare a polyurethane intermediate; Step (5), under the action of a catalyst and an inhibitor, the polyurethane intermediate reacts with an acrylate containing a hydroxyl functional group to prepare ethoxyquinoline polyurethane acrylate.

3. The method for preparing ethoxyquinoline polyurethane acrylate according to claim 2, characterized in that: In step (1), the mass ratio of butyl acetate to ethoxyquinoline distillation kettle residue is 1:0.5 to 1:2.0, preferably 1:1.0 to 1:1.

6.

4. The method for preparing ethoxyquinoline polyurethane acrylate according to claim 2, characterized in that: In step (1), the amine value of the ethoxyquinoline polymer solution is usually 80 to 110 mgKOH / g.

5. The method for preparing ethoxyquinoline polyurethane acrylate according to claim 2, characterized in that: In step (1), 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 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; The temperature of the aminolysis reaction is 80° C. to 120° C., the pressure of the aminolysis reaction is 0.1 to 0.4 MPa, and the end point of the aminolysis reaction is when the pressure of the reaction system drops to a constant level.

6. The method for preparing ethoxyquinoline polyurethane acrylate 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×(3.0-40)]; wherein Av is the amine value of the ethoxyquinoline polymer solution; 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; 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.

7. The method for preparing the ethoxyquinoline polyurethane acrylate according to claim 2 or 6, 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 with stirring, and then cyclic pressure filtration is performed until the mixture becomes clear and transparent to obtain ethoxyquinoline polyether polyol.

8. The method for preparing ethoxyquinoline polyurethane acrylate according to claim 2, characterized in that: In step (4), the mass ratio of the ethoxyquinoline polyether polyol to the diisocyanate is (56.1×1000 / V OH ):[(1~1.5)×M], preferably (56.1×1000 / V OH ):[(1~1.25)×M]; Among them, V OH is the hydroxyl value measured for ethoxyquinoline polyether polyol; M is the relative molecular weight of diisocyanate; The diisocyanate is IPDI, HMDI, HDI, MDI, TDI, preferably TDI; The catalyst is dibutyltin dilaurate; the amount of the catalyst is 100 to 3000 ppm of the total mass of ethoxyquinoline polyether polyol and diisocyanate, preferably 100 to 1000 ppm; The temperature of the polyurethane reaction is 50°C to 95°C, preferably 60°C to 85°C, and the time of the polyurethane reaction is 1 to 6.

9. The method for preparing ethoxyquinoline polyurethane acrylate according to claim 2, characterized in that: In step (5), the mass ratio of the polyurethane intermediate (based on ethoxyquinoline polyether polyol) to the hydroxyl-functional acrylate is (56.1×1000 / V OH ):[(1~2.2)×(56.1×1000 / V OH ′)], preferably (56.1×1000 / V OH ):[(1~1.8)×(56.1×1000 / V OH ′)]; Among them, V OH is the hydroxyl value of ethoxyquinoline polyether polyol, V OH ' is the hydroxyl value measured for acrylate containing hydroxyl functional groups; The acrylate containing a hydroxyl functional group is an organic acrylate containing one or more acryloxy groups and one hydroxyl group, preferably hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, caprolactone acrylate, and more preferably caprolactone acrylate; The polymerization inhibitor is p-hydroxyanisole or 2,6-di-tert-butyl-p-methylphenol; the dosage of the polymerization inhibitor is 100-5000ppm of the total mass of ethoxyquinoline polyether polyol, diisocyanate and acrylate containing hydroxyl functional group; The catalyst is dibutyltin dilaurate; the amount of the catalyst is 100 to 3000 ppm of the total mass of ethoxyquinoline polyether polyol, diisocyanate and acrylate containing hydroxyl functional group; The reaction temperature is 50°C to 95°C, preferably 60°C to 85°C; the reaction time is 3 to 9 hours; After the reaction is completed, add active diluent, stir evenly, and filter; The active diluent is tripropylene glycol diacrylate.

10. Use of the ethoxyquinoline polyurethane acrylate according to claim 1 in the preparation of UV coatings, inks and adhesives.

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