CN112126041A - Solvent-free hydrophilic modification method for oil-based polyurethane high polymer - Google Patents
Solvent-free hydrophilic modification method for oil-based polyurethane high polymer Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/771—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur oxygen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08G18/4202—Two or more polyesters of different physical or chemical nature
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
Abstract
The invention discloses a solvent-free hydrophilic modification method of an oil-based polyurethane polymer, which comprises the following steps: s1, hydrophilic grafting modification of diisocyanate; s2, preheating and pre-polymerizing the synthetic material; s3, reducing the system temperature in the S2 to 60-80 ℃, adding a catalyst for reaction at the reaction temperature of 80-110 ℃, and continuing the reaction for 2-6 h; s4, chain extension: reducing the temperature of the system to 40-80 ℃, and adding the rest chain extender for further chain extension reaction; s5, terminating the reaction; s6, emulsification: and (3) cooling the solution in the S5 to normal temperature, adding the solution into a high-speed dispersion kettle, adding deionized water in batches at normal temperature and normal pressure according to the final solid content of the formula, and shearing and emulsifying at the rotating speed of 500-900 r/min. The solvent-free hydrophilic modification method of the oil-based polyurethane high polymer has strong applicability, can realize the water-based modification process of the oil-based polyurethane on the premise of not replacing the original solvent-based resin formula, and has the molecular weight of 20 ten thousand orders of magnitude higher than that of the conventional solvent-based resin.
Description
Technical Field
The invention relates to the technical field of water-based high-molecular polymer materials, in particular to a solvent-free hydrophilic modification method for an oil-based polyurethane high polymer.
Background
Polyurethane resin compositions have high adhesion to various materials and excellent physical properties, and therefore are widely used in the fields of coating agents, paints, adhesives, printing inks, and the like.
The traditional solvent type high molecular weight polyurethane resin is generally prepared by dissolving PEBA2000 (polyhydric alcohol) and EG (ethylene glycol) in DMF (xylene, solvent), heating and reacting with MDI (diphenylmethane diisocyanate) under a catalyst, diluting and adjusting the resin viscosity by adding DMF (dimethylformamide), and finally adding toluene and cosolvent and then adding methanol to terminate the reaction. The reaction system contains a large amount of organic solvent, and the prepared resin is easy to generate VOCs in the using process and is not environment-friendly.
In recent years, due to social and industrial demands, an aqueous (water-based) composition that does not use an organic solvent has been desired, and the composition is economically advantageous by not using an organic solvent. Therefore, recently, the conversion of a polyurethane resin composition using an organic solvent into an aqueous polyurethane resin composition using an aqueous dispersion has been widely performed.
The existing water-based modification method of polyurethane resin generally designs a PUD formula in advance, then carries out prepolymerization in an acetone solvent, then introduces DMPA or sulfonic acid groups in the prepolymerization process for hydrophilic chain extension, introduces amine substances for alkali neutralization after the reaction is finished, adds deionized water for emulsification, removes acetone in vacuum, and further realizes the hydrophilic and emulsification of the resin. However, in the above method, the synthesis process involves the formation of salts of amines, and the molecular weight is generally not more than 10 ten thousand.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, one purpose of the invention is to provide a solvent-free hydrophilic modification method for an oil-based polyurethane polymer, which has strong applicability, can realize the aqueous modification process of the oil-based polyurethane on the premise of not replacing the original solvent-based resin formula, and has the molecular weight of 20 ten thousand orders of magnitude higher than that of the conventional solvent-based resin.
The technical scheme of the invention is as follows:
a solvent-free hydrophilic modification method for an oil-based polyurethane polymer comprises the following steps:
s1, hydrophilic grafting modification of diisocyanate;
s2, preheating and pre-polymerization of synthetic materials: stirring and preheating the polyol to 50-55 ℃, and adding all diisocyanate in S1 into the polyol for stirring and reacting for 1-3 h;
s3, reducing the system temperature in S2, adding a catalyst for reaction, wherein the reaction temperature is 80-110 ℃, and the continuous reaction time is 2-6 h;
s4, chain extension: reducing the temperature of the system to 60-80 ℃, and adding a chain extender to carry out chain extension reaction;
s5, terminating the reaction: adding a terminator to terminate the reaction
S6, emulsification: adding the solution in the S5 into a high-speed dispersion kettle, adding deionized water in several times at normal temperature and normal pressure according to the final solid content of the formula, and shearing and emulsifying at the rotating speed of 500-900 r/min;
the mass percentage of the components in the total mass of the reaction system is as follows:
further, the diisocyanate in step S1 is one or a combination of modified MDI, IPDI, TDI, HDI and HMDI.
Further, the above-mentioned diisocyanate modification method is as follows,
adding the diisocyanate serving as a raw material into a four-neck flask with a condensation reflux device, slowly heating to 55 ℃, introducing nitrogen for protection, dropwise adding polyethylene glycol monomethyl ether, polyethylene glycol monomethyl ether and polyethylene glycol monomethyl ether sequentially within 40min, reacting at the constant temperature of 80-85 ℃ for 2 hours, cooling to 65 ℃, dropwise adding a catalyst, reacting at the constant temperature of 80-85 ℃ for 2 hours, cooling and discharging to obtain the modified diisocyanate.
Further, an antioxidant is added in step S2.
Further, in step S2, the polyol is selected from the group consisting of polyethylene glycol adipate diol, 1, 4-butanediol adipate diol, polytetrahydrofuran diol, polyoxypropylene polyol, polycaprolactone diol, polycaprolactone triol, polycarbonate diol, polyethylene glycol adipate diol, neopentyl glycol adipate diol, 3-methyl-1, 5-pentanediol adipate diol, 1, 6-hexanediol adipate diol, polyethylene glycol neopentyl glycol adipate diol, polyethylene glycol 1, 4-butanediol neopentyl glycol adipate diol, polyethylene glycol adipate diethylene glycol adipate diol, One or a combination of 1,4 butanediol adipate diglycol glycol, 2-methyl-1, 3 propylene glycol adipate glycol, polyethylene glycol phthalate diglycol glycol, polyethylene glycol terephthalate adipate glycol diglycol glycol, modified polytetrahydrofuran polyol with side groups, tetrahydrofuran-ethylene oxide copolymer glycol, polyethylene glycol oxide glycol, special polyester polyol with side groups, polyacrylate polyol, caprolactone modified polyacrylate polyol, polybutadiene polyol, polystyrene polyol and soybean oil polyol.
Further, in step S3, the catalyst is an organotin catalyst, organobismuth, organolead, organozinc or silver salt catalyst.
Further, in step S4, the chain extender is a small molecule diol or a small molecule diamine.
Further, the chain extender is ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 3-butanediol, neopentyl glycol, 1, 6-hexanediol, 1, 2-propanediol, 2-methyl-1, 3-propanediol, hydroquinone dihydroxyethyl ether, resorcinol bis (hydroxyethyl) ether, resorcinol dihydroxypropyl ether, trimethylpentanediol, 1, 3-propanediol, dipropylene glycol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 4-dimethylolcyclohexane, cyclohexanediol, TCD tricyclo diol, hydroxypivalyl hydroxypivalate, butylethylpropanediol, diethylpentanediol, ethylhexanediol, dodecanediol, trimethylolpropane, 1,2, 3-propanetriol, Trimethylolethane, 1,2, 6-hexanetriol, trishydroxyethyl isocyanurate, pentaerythritol, xylitol, sorbitol, mannitol, sucrose, methyl glucoside, triethanolamine, diethanolamine, triisopropanolamine, methyldiethanolamine, dimethylolpropionic acid, dimethylolbutyric acid, 3 '-dichloro-4, 4' -diphenylmethanediamine, 3, 5-dimethylthiotoluenediamine, 3, 5-diethyltoluenediamine, 4 '-methylenebis (3-chloro-2, 6-diethylaniline), 4' -methylenebis (2, 6-diethyl) aniline, 4 '-methylenebis (2, 6-diisopropyl) aniline, 4' -methylenebis (2-isopropyl-6-methyl) aniline.
Further, the terminator is methanol or morpholine.
The invention is characterized in that: on the basis of an oil polyurethane formula, by modifying diisocyanate and completing the stepwise polymerization reaction without greatly changing the original oil formula and related process parameters, the shearing of deionized water can be performed, so that the emulsification of polyurethane resin is completed, DMPA or other hydrophilic chain-extended small molecules are not introduced in the prepolymerization stage, and alkali neutralization is not required; in addition, the physical and chemical properties of the PUD produced by the method are similar to those of the original oily PUD.
The invention has the following beneficial effects: on the premise of not greatly adjusting the formula and process parameters of the original oily polyurethane resin, the aqueous modification of the oily polyurethane can be completed, meanwhile, the problem of solvent residue caused by the introduction of a solvent (acetone) as in the traditional aqueous modification method is not needed, and the molecular weight of the prepared resin is limited;
in addition, the resin prepared by the modification method has better mechanical strength and weather resistance.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
A solvent-free hydrophilic modification method for an oil-based polyurethane polymer comprises the following steps:
s1, hydrophilic grafting modification of diisocyanate, and the method comprises the following steps: adding the diisocyanate serving as a raw material into a four-neck flask with a condensation reflux device, slowly heating to 50-55 ℃, introducing nitrogen for protection, dripping polyethylene glycol monomethyl ether, polyethylene glycol monomethyl ether and polyethylene glycol monomethyl ether in sequence within 40min, reacting at the constant temperature of 80-100 ℃ for 2 hours, cooling to 65 ℃, dripping a catalyst, reacting at the constant temperature of 80-100 ℃ for 2 hours, cooling and discharging to obtain the modified diisocyanate.
In the process, the diisocyanate is one or a combination of MDI, IPDI, TDI, HDI and HMDI;
taking TDI as an example: 500g of tolylene diisocyanate (TDI-80 BASF, Germany) were introduced into a 1500ml four-necked flask with a reflux condenser, the temperature was slowly raised to 55 ℃ and nitrogen was passed through. 290g of polyethylene glycol monomethyl ether (Haian petrochemical MPEG350), 71.69g of polyethylene glycol monomethyl ether (Haian petrochemical MPEG550), 133.57g of polyethylene glycol monomethyl ether (Haian petrochemical MPEG350) and 109.84g of polyethylene glycol monomethyl ether (Haian petrochemical MPEG550) are respectively dripped in turn within 40 min. Keeping the temperature at 80-85 ℃ for 2 hours. Cooling to 65 deg.C, adding 0.54g catalyst (CuCAT-U2, Guangzhou Yougun synthetic material), and maintaining at 80-85 deg.C for 2 hr. And (5) cooling and discharging to obtain the modified TDI. Whether the hydrophilic grafting modification process of other raw materials is similar or not.
S2, preheating and pre-polymerization of synthetic materials: stirring and preheating the polyol to 50-55 ℃ until the polyol is completely dissolved, adding all diisocyanate in S1 into the polyol, stirring and reacting for 1-3h, melting and uniformly mixing different raw materials, and simultaneously carrying out pre-polymerization reaction on the polyol and the diisocyanate, wherein the reaction belongs to exothermic reaction, and heat is released in the process, so that the reaction is promoted, and the temperature range of 80-110 ℃ is reached. In addition, when the temperature in the reaction kettle reaches 80-110 ℃, the reaction is started to time. Meanwhile, an antioxidant can be added into the reaction system to reduce the generation of byproducts.
The polyol can be selected from polyethylene glycol adipate glycol, polyethylene glycol 1,4 butanediol adipate glycol, polytetrahydrofuran glycol, polypropylene oxide polyol, polycaprolactone glycol, polycaprolactone triol, polycarbonate diol, polyethylene glycol adipate glycol, polyethylene glycol neopentyl glycol adipate glycol, polyethylene glycol 1,4 butanediol adipate glycol, polyethylene glycol neopentyl glycol adipate glycol, 3-methyl-1, 5 pentanediol adipate, polyethylene glycol 1,6 hexanediol adipate glycol, polyethylene glycol neopentyl glycol adipate glycol, polyethylene glycol 1,4 butanediol adipate glycol, polyethylene glycol diethylene glycol adipate glycol 1,4 butanediol neopentyl glycol adipate glycol, polyethylene glycol adipate glycol diethylene glycol diol, polyethylene glycol adipate 1,4 butanediol diethylene glycol diglycol diol, Polyethylene glycol adipate-diethylene glycol trimethylolpropane ester polyol, polyethylene glycol adipate-1, 4-butanediol 2-methyl-1, 3-propylene glycol diol, polyethylene glycol adipate-2-methyl-1, 3-propylene glycol diol, polyethylene glycol phthalate-diethylene glycol diol, polyethylene glycol terephthalate adipate-diethylene glycol diol, modified polytetrahydrofuran polyol with side groups, tetrahydrofuran-ethylene oxide copolymer diol, polyethylene oxide diol, special polyester polyol with side groups, polyacrylate polyol, caprolactone modified polyacrylate polyol, polybutadiene polyol, polystyrene polyol and soybean oil polyol.
S3, after the system temperature in the S2 is reduced to 60-80 ℃ (side reaction caused by excessive temperature fluctuation is avoided), adding a catalyst for reaction (the catalyst is an organic tin catalyst, organic bismuth, organic lead, organic zinc or silver salt catalyst), wherein the reaction temperature is 80-110 ℃, and continuing the reaction for 2-6 hours;
s4, chain extension: reducing the temperature of the system to 60-80 ℃, adding a chain extender to carry out chain extension reaction, wherein the chain extender is micromolecular diol or micromolecular diamine, such as: ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 3-butanediol, neopentyl glycol, 1, 6-hexanediol, 1, 2-propanediol, 2-methyl-1, 3-propanediol, hydroquinone dihydroxyethyl ether, resorcinol bis (hydroxyethyl) ether, resorcinol dihydroxypropyl ether, trimethylpentanediol, 1, 3-propanediol, dipropylene glycol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 4-dimethylolcyclohexane, cyclohexanediol, TCD tricyclo diol, hydroxypivalyl hydroxypivalate, butylethylpropanediol, diethylpentanediol, ethylhexanediol, dodecanediol, trimethylolpropane, 1,2, 3-propanetriol, trimethylolethane, 1,2, 6-hexanetriol, trihydroxyethyl isocyanurate, pentaerythritol, xylitol, sorbitol, mannitol, sucrose, methyl glucoside, triethanolamine, diethanolamine, triisopropanolamine, one or a combination of methyldiethanolamine, dimethylolpropionic acid, dimethylolbutyric acid, 3 '-dichloro-4, 4' -diphenylmethanediamine, 3, 5-dimethylthiotoluenediamine, 3, 5-diethyltoluenediamine, 4 '-methylenebis (3-chloro-2, 6-diethylaniline), 4' -methylenebis (2, 6-diethyl) aniline, 4 '-methylenebis (2, 6-diisopropyl) aniline, 4' -methylenebis (2-isopropyl-6-methyl) aniline.
S5, terminating the reaction: adding a terminator to terminate the reaction; the terminator can be one or more of methanol, morpholine ethanol, propanol, ethylene glycol, 1, 3-butanediol, 1, 4-butanediol or isopropanol
S6, emulsification: adding the solution in the S5 into a high-speed dispersion kettle, adding deionized water in several times at normal temperature and normal pressure according to the final solid content of the formula, and shearing and emulsifying at the rotating speed of 500-1500 r/min;
the mass percentage of the components in the total mass of the reaction system is as follows:
the first embodiment is as follows:
665g of poly 1, 4-butanediol adipate (Zhejiang Hexin new material, 1000 molecular weight) is put into a dry reaction kettle, heated to 50-55 ℃, and fully stirred and mixed for about 30min until the polyhydric alcohol is completely dissolved; under the condition of stirring, adding modified MDI (modified diphenylmethane diisocyanate) into a reaction kettle at intervals of 1768g, 502g and 312.3g for 10min for three times, and providing heat for the materials in the reaction kettle by utilizing the heat release of chemical reaction; slowly heating to 75-85 ℃ after the temperature of the kettle is stable, starting timing, carrying out constant temperature reaction for 2h, cooling to 65 ℃, adding 5.69g of an organic bismuth catalyst (Jiangsu Han Shang Co.), carrying out constant temperature reaction for 4h at 75-85 ℃, cooling to 65 ℃, adding 138g of ethylene glycol (sold in the market), carrying out constant temperature reaction for 2h at 75-80 ℃, cooling to 50 ℃, adding 2.5g of methanol (national medicine group), stopping excessive-NCO groups in the reaction, and finishing the gradual polymerization stage; and cooling the materials in the reaction kettle to normal temperature, discharging the materials into a high-speed dispersion shearing kettle, adjusting the rotating speed to 500r/min-900r/min, gradually adding 4137.59g of deionized water, and shearing and emulsifying. Thus, an aromatic PUD emulsion having a solid content of 45 wt% was prepared.
Example two:
adding 135.2g polycaprolactone diol (Japan xylonite chemical, 2000 molecular weight) and 84.1g polytetrahydrofuran diol (Germany BASF, 2000 molecular weight) and 1.3g antioxidant JPP100 (Japan northern Japan chemical) (Irganox 1010, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, BHT 264, Irganox245, Irganox1098, Irgafos168, TPP, TNPP, DPDP, ODPP, TDP, PDDP) into a dry reaction kettle, heating to 50-55 deg.C, and mixing for about 30min until the polyhydric alcohol is completely dissolved; under the condition of stirring, respectively adding 87.62g of modified IPDI (modified isophorone diisocyanate) and 128.7g of modified MDI (modified diphenylmethane diisocyanate) into a reaction kettle, and utilizing the heat release of chemical reaction to provide heat for the materials in the reaction kettle to continuously carry out the reaction; after the temperature of the kettle is stable, slowly heating to 95-105 ℃, starting timing, and reacting for 2 hours at constant temperature; cooling to 65 ℃, adding 5.12g of organic bismuth catalyst (Jiangsu Han dynasty commercial), and reacting at the constant temperature of 95-105 ℃ for 5 hours; cooling to 65 ℃, adding 10g of isophorone diamine (Yingchuang in Germany), keeping the temperature for constant temperature reaction, reacting at an interval of 15min, adding 15.35g of 1, 4-butanediol (Shanxi three-dimensional), reacting at a constant temperature of 60-65 ℃ for 2h, cooling to 45 ℃, adding 1.4g of morpholine (national drug group), terminating excessive NCO groups in the reaction, and finishing the polymerization stage step by step. And cooling the materials in the reaction kettle to normal temperature, discharging the materials into the high-speed dispersion shearing kettle, adjusting the rotating speed to 500-900r/min, gradually adding 563.4g of deionized water, and shearing and emulsifying. Thus, an aliphatic PUD emulsion having a solid content of 45 wt% was prepared.
Example three:
28g of poly (1, 4-butylene adipate) glycol (Zhejiang Hexin new material, 1000 molecular weight), 40g of polytetrahydrofuran glycol (Mitsubishi chemical, 2000 molecular weight), 792g of polycaprolactone glycol (Pastol, England, 3000 molecular weight) and 4.82g of antioxidant PP100 (Mitsubishi chemical) are put into a dry reaction kettle, heated to 50-55 ℃ and fully stirred and mixed for about 30min until the polyol is completely dissolved, which is a physical mixing process. Because the poly 1, 4-butanediol adipate glycol, the polytetrahydrofuran glycol and the polycaprolactone glycol are waxy solids, the poly 1, 4-butanediol adipate glycol, the polytetrahydrofuran glycol and the polycaprolactone glycol are required to be heated and melted and are uniformly mixed with a heat-resistant oxidant, and the next-stage chemical reaction is favorably carried out;
then adding 289.824g of modified TDI (toluene diisocyanate) into a reaction kettle under the condition of stirring, utilizing the heat release of chemical reaction to provide heat for materials in the reaction kettle to continuously perform reaction, slowly heating to 80-90 ℃ after the temperature of the reaction kettle is stable, and reacting at constant temperature for 2 h; the stepwise polymerization reaction of polyurethane, two-NCO in modified TDI with a large amount of hydrophilic groups on the molecular chain reacts with-OH groups in polyol to generate the molecular chain with the hydrophilic groups, and the molecular weight is gradually increased from small to small.
Cooling to 65 ℃, adding 4.81g of organic bismuth catalyst (Jiangsu Han dynasty commercial), and reacting for 3 hours at the constant temperature of 80-90 ℃; as the reaction proceeds, the residual small molecules in the system tend to decrease, at which time a catalyst may be added to facilitate the synthesis of the remaining monomers or small molecular chains to large molecular chains. A certain amount of chemical heat is generated due to the accelerating effect of the catalyst on the reaction. Therefore, the temperature needs to be lowered in advance so as to effectively utilize the heat of the heat exchanger and prevent the temperature from being too high and adverse reactions from occurring.
Cooling to 65 ℃, adding 1038.5g of modified MDI (modified diphenylmethane diisocyanate), and reacting at the constant temperature of 75-85 ℃ for 2 h; the modified diisocyanate TDI and MDI are added separately, different diisocyanates are distributed in different positions of a molecular chain controllably according to the physicochemical property requirement of a formula, and the addition of the modified MDI can cause the heat release and the temperature rise of a system for the same reason. Therefore, the temperature is reduced in advance so as to fully utilize the heat, the reaction time is increased adaptively so as to ensure that the reaction is as complete as possible, and residual monomer micromolecules in the system are as few as possible.
When the temperature is reduced to 50 ℃, 3.3g of methanol (national drug group) is added, the excessive NCO group in the reaction is stopped, and the polymerization stage is completed step by step; according to the formulation process, the-NCO/-OH (1.07-1.2): 1-NCO is usually in excess, so that when the reaction is complete, the excess-NCO needs to be terminated with methanol.
And cooling the materials in the reaction kettle to normal temperature, discharging the materials into a high-speed dispersion shearing kettle, adjusting the rotating speed to 500r/min-900r/min, gradually adding 2675g of deionized water, and shearing and emulsifying to complete the preparation of the aromatic PUD emulsion with the solid content of 45 wt%.
Parameter detection
1. GB/T1040-2006, determination of the tensile properties of plastics;
2. GB/T528-2009, determination of tensile stress strain performance of vulcanized rubber or thermoplastic rubber;
3. QB _ T4671-;
test sample size: 150mm
The test method comprises the following steps:
and (3) hoisting the sample in a constant temperature and humidity box for damp heat aging, wherein the constant temperature and humidity temperature is 70 +/-2 ℃, and the relative humidity is more than 95%.
After 3-10 weeks of hot flash treatment (cycle time error within +/-2H), taking out the test piece, and placing the test piece under the conditions of temperature 23 +/-2 ℃ and relative humidity 45-55% for 2H:
1) and observing the change condition of the surface.
2) The peel load of the test sample is tested by a tensile machine, and 60 percent of the performance before the test is qualified.
4. The acetone and amine content is determined by gas-liquid chromatography according to relevant documents.
TABLE one result of the measurement of the relevant Performance parameters of examples 1 to 3 and comparative example
Note: the comparative example was commercially available product AH-1618.
From the results in table one, it is clear that in examples 1 to 3 of the present application, acetone and amine were not detected, and both of them had good storage stability and excellent film-forming properties.
Molecular weight determination test method: viscosity method for measuring relative molecular weight (viscosity average molecular weight M eta) the intrinsic viscosity [ eta ] of the high molecular diluted solution is measured by an Ubbelohde viscometer, k and alpha values are found out from the literature or a related manual according to the Mark-Houwink formula [ eta ] ═ kM alpha, and the molecular weight of the high molecular is calculated. Wherein, the k and alpha values have different values due to different solvents and different experimental temperatures, and the molecular weight is more than 20 ten thousand orders of magnitude in the application.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (9)
1. A solvent-free hydrophilic modification method of an oil-based polyurethane polymer is characterized by comprising the following steps:
the method comprises the following steps:
s1, hydrophilic grafting modification of diisocyanate;
s2, preheating and pre-polymerization of synthetic materials: stirring and preheating the polyol and a proper amount of chain extender to 50-55 ℃ until the polyol and the chain extender are completely dissolved, adding all diisocyanate in S1 into the polyol according to the formula design, and stirring and reacting for 1-3 hours;
s3, catalytic reaction: reducing the system temperature in S2 to 60-80 ℃, adding a catalyst for reaction at the reaction temperature of 80-110 ℃, and continuing the reaction for 2-6 h;
s4, chain extension: reducing the temperature of the system to 40-80 ℃, and adding the rest chain extender for further chain extension reaction;
s5, terminating the reaction: cooling to 40-50 ℃, and adding a terminator to terminate the reaction;
s6, emulsification: cooling the solution in the S5 to normal temperature, adding the solution into a high-speed dispersion kettle, adding deionized water in batches at normal temperature and normal pressure according to the final solid content of the formula, and shearing and emulsifying at the rotating speed of 500-900 r/min;
the mass percentage of the components in the total mass of the reaction system is as follows:
2. the solvent-free hydrophilic modification method of an oil-based polyurethane polymer according to claim 1, wherein: the diisocyanate in the step S1 is one or a combination of modified MDI, IPDI, TDI, HDI and HMDI.
3. The solvent-free hydrophilic modification method of an oil-based polyurethane polymer according to claim 2, wherein:
the diisocyanate modification method in step S1 is as follows,
adding the diisocyanate serving as a raw material into a four-neck flask with a condensation reflux device, slowly heating to 50-55 ℃, introducing nitrogen for protection, dripping polyethylene glycol monomethyl ether, polyethylene glycol monomethyl ether and polyethylene glycol monomethyl ether in sequence within 40min, reacting at the constant temperature of 80-100 ℃ for 2 hours, cooling to 65 ℃, dripping a catalyst, reacting at the constant temperature of 80-100 ℃ for 2 hours, cooling and discharging to obtain the modified diisocyanate.
4. The solvent-free hydrophilic modification method of an oil-based polyurethane polymer according to claim 1, wherein: in step S2, an antioxidant is added, which is 0.05-0.1% of the total mass of the reaction system.
5. The solvent-free hydrophilic modification method of an oil-based polyurethane polymer according to claim 1, wherein: the polyol in the step S2 is polyethylene glycol adipate diol, 1, 4-butanediol adipate diol, polytetrahydrofuran diol, polyoxypropylene polyol, polycaprolactone diol, polycaprolactone triol, polycarbonate diol, polyethylene glycol adipate diol, polytetramethylene glycol adipate diol, 3-methyl-1, 5-pentanediol adipate diol, 1, 6-hexanediol adipate diol, polyethylene glycol adipate neopentyl glycol ester diol, polyethylene glycol adipate 1, 4-butanediol neopentyl glycol diester diol, polyethylene glycol adipate diethylene glycol diol, 1-adipic acid adipate, 4 butanediol diglycol, polyethylene adipate glycol trimethylolpropane ester polyol, 1,4 butanediol adipate 2-methyl-1, 3 propanediol glycol, polyethylene adipate glycol 2-methyl-1, 3 propanediol glycol, poly phthalic anhydride diglycol glycol, polyethylene adipate terephthalate glycol diglycol glycol, modified polytetrahydrofuran polyol with side groups, tetrahydrofuran-ethylene oxide copolymer glycol, polyethylene oxide glycol, special polyester polyol with side groups, polyacrylate polyol, caprolactone modified polyacrylate polyol, polybutadiene polyol, polystyrene polyol and soybean oil polyol.
6. The solvent-free hydrophilic modification method of an oil-based polyurethane polymer according to claim 1, wherein: in step S3, the catalyst is organic tin catalyst, organic bismuth, organic lead, organic zinc or silver salt catalyst.
7. The solvent-free hydrophilic modification method of an oil-based polyurethane polymer according to claim 1, wherein: in step S4, the chain extender is a small molecule diol or a small molecule diamine.
8. The solvent-free hydrophilic modification method of an oil-based polyurethane polymer according to claim 7, wherein: the chain extender is ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 3-butanediol, neopentyl glycol, 1, 6-hexanediol, 1, 2-propanediol, 2-methyl-1, 3-propanediol, hydroquinone dihydroxyethyl ether, resorcinol bis (hydroxyethyl) ether, resorcinol dihydroxypropyl ether, trimethylpentanediol, 1, 3-propanediol, dipropylene glycol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 4-dimethylolcyclohexane, cyclohexanediol, TCD tricyclo-diol, hydroxypivalyl hydroxypivalate, butylethylpropanediol, diethylpentanediol, ethylhexanediol, dodecanediol, trimethylolpropane, 1,2, 3-propanetriol, trimethylolethane, 1,2, 6-hexanetriol, trihydroxyethyl isocyanurate, pentaerythritol, xylitol, sorbitol, mannitol, sucrose, methyl glucoside, triethanolamine, diethanolamine, triisopropanolamine, one or a combination of methyldiethanolamine, dimethylolpropionic acid, dimethylolbutyric acid, 3 '-dichloro-4, 4' -diphenylmethanediamine, 3, 5-dimethylthiotoluenediamine, 3, 5-diethyltoluenediamine, 4 '-methylenebis (3-chloro-2, 6-diethylaniline), 4' -methylenebis (2, 6-diethyl) aniline, 4 '-methylenebis (2, 6-diisopropyl) aniline, 4' -methylenebis (2-isopropyl-6-methyl) aniline.
9. The solvent-free hydrophilic modification method of an oil-based polyurethane polymer according to claim 1, wherein: the terminator is one or a combination of methanol, morpholine ethanol, propanol, ethylene glycol, 1, 3-butanediol, 1, 4-butanediol or isopropanol.
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