Epoxy resin modified waterborne hyperbranched polyurethane and preparation method thereof
A hyperbranched polyurethane and epoxy resin technology, applied in polyurea/polyurethane coatings, polyurea/polyurethane adhesives, adhesive types, etc., can solve the problems of insufficient stability of the emulsion, cumbersome steps, and easy cross-linking
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[0084] The preparation method of epoxy resin modified waterborne hyperbranched polyurethane of the present invention, concrete steps are as follows:
[0085] 1) The organic acid (a) containing one carboxyl group and two hydroxyl groups and the alcohol (b) containing multiple hydroxyl groups are reacted at a certain reaction temperature (such as 140-160 ° C) for a period of time (such as 8-24 hours), under vacuum conditions (such as below 740mmHg), the molar ratio between (a) and (b) used is 12 / 1-4 / 1, thereby forming a large amount of hydroxyl-terminated reaction intermediates (referred to as A1 , namely the hyperbranched polyester A-(OH) of the present invention n );
[0086] Wherein, used (a), its structure is as follows:
[0087]
[0088] Among them, R 5 Can be:
[0089]
[0090]Wherein, m is an integer ≥ 1 (preferably an integer of 1-10).
[0091] (b) used may be:
[0092] ethylene glycol, diethylene glycol,
[0093] Glycerol, Trimethylolpropane,
[00...
Embodiment 1
[0142] 1.1 Preparation of epoxy resin modified waterborne hyperbranched polyurethane 1
[0143] 1) Add 13.6g (0.1mol) of pentaerythritol and 53.64g (0.4mol) of dimethylolpropionic acid (DMPA) in a four-necked flask equipped with mechanical stirring, a thermometer, and a condenser tube. (740mmHg), react at 140-160°C for 2.5h to obtain a transparent yellowish liquid;
[0144] Then add 107.28g (0.8mol) DMPA to the transparent yellowish liquid, and react at 140-160°C under vacuum conditions (below 740mmHg), until the acid value of the resin is measured to be less than 20mg KOH / g, and the reaction is terminated , discharging, cooling to obtain light yellow transparent or translucent solid, denoted as A1-1 (the molar ratio of pentaerythritol and dimethylolpropionic acid is 1 / 12).
[0145] 2) Dissolve 18.94g of A1-1 (0.0121mol) in 50g of N-methylpyrrolidone, add 8.57g (0.085mol) of succinic anhydride, and react at 100°C for 36 hours to obtain a light yellow transparent liquid, which...
Embodiment 2
[0164] 2.1 Preparation of epoxy resin modified waterborne hyperbranched polyurethane 2
[0165] 1) Add 13.6g (0.1mol) of pentaerythritol and 53.64g (0.4mol) of dimethylolpropionic acid (DMPA) into a four-necked flask equipped with mechanical stirring, a thermometer, and a condenser, and react at 140-160°C after mixing 2.5h, under vacuum conditions (below 740mmHg), a transparent yellowish liquid is obtained;
[0166] Then add 107.28g (0.8mol) DMPA to the transparent yellowish liquid, and react at 140-160°C under vacuum conditions (below 740mmHg), until the acid value of the resin is less than 20mg KOH / g, and the reaction is terminated , poured out, and after cooling, a yellowish transparent or translucent solid was obtained, which was denoted as A1-2 (the molar ratio of dimethylol propionic acid and pentaerythritol was 12 / 1).
[0167] 2) Dissolve 18.94g of A1-2 (0.0121mol) in 50g of N-methylpyrrolidone, add 8.57g (0.085mol) of succinic anhydride, and react at 100°C for 36 hour...
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