Preparation method of environmentally-friendly aqueous polyurethane adhesive

A water-based polyurethane and adhesive technology, applied in the direction of polyurea/polyurethane adhesives, adhesives, adhesive types, etc., can solve the problems of inconvenience for large-scale production, increase production costs, and difficulty in operation, and achieve energy saving, The initial viscosity is strong, and the effect of not easy to agglomerate and precipitate

Active Publication Date: 2011-06-22

JIAXING HEXIN CHEM IND

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AI-Extracted Technical Summary

Problems solved by technology

The process required by the preparation method is very complicated, the operation is difficult, and the requirements for workers are very high, it is not convenient for large-scale produc...

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Method used

1, polyadipate-ethylene glycol-1,4-butylene glycol ester diol 180g (number average molecular weight is 3000), polyadipate-1,4-butylene glycol ester diol 20g (the number-average molecular weight is 1000), 40g of polyε-caprolactone diol (the number-average molecular weight is 2000), hydrophobic small molecule chain extender 1,3-butanediol 4.50g and hydrazine hydrate 0.05g, hydrophilic Add 9.38g of dimethylolpropionic acid (DMPA), a non-toxic chain extender, into the reaction kettle. Under the protection of nitrogen, heat up to 120°C, vacuum dehydrate for 30 minutes, cool to 60°C, add 48.27g of 1,6-hexane Diisocyanate (HDI) (the molar ratio of diisocyanate to active hydrogen compound is 1.3:1), reacted at 100°C for 2.5 hours, then lowered the temperature to 80°C, added 0.05g tetrabutyl stannous titanate, reaction 3 Hours, when the viscosity increased, 40 g of ethyl acetate (ETAC) was added to reduce the viscosity of the polymer.

As can be seen from the above table, 100% tensile modulus, tensile strength, elongation at break physical index of waterborne polyurethane adhesive all exceed common oily polyurethane adhesive, wherein elongation at break is particularly high, illustrate that waterborne polyurethane has Ver...

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Abstract

The invention discloses a preparation method of an environmentally-friendly aqueous polyurethane adhesive. The environmentally-friendly aqueous polyurethane adhesive is prepared from the following raw materials: polydiol with a number-average molecular weight between 500 and 5,000, a hydrophobic chain extender with a number-average molecular weight between 61 and 400, an inner-crosslinking agent,a hydrophilic chain extender, diisocyanate, a catalyst, an organic solvent, a neutralizing agent and deionized water. The preparation process comprises: heating the polydiol, the hydrophobic chain extender, the inner-crosslinking agent and the hydrophilic chain extender in a protective atmosphere of nitrogen, dewatering under vacuume and cooling; adding diisocyanate for reaction, cooling and adding a catalyst for a reaction; adding a proper amount of organic solvent for regulating viscosity; and adding aqueous solution of the neutralizing agent under the action of a high-speed shearing force to obtain the product. The product has the advantages of extremely low organic solvent content, high stability, insusceptibility to agglomeration and sedimentation, long storage period and low thermalactivation temperature, can be used for dry type combination and has the characteristics of high initial viscosity, high flexibility, high breathability, light odor and the like.

Application Domain

Polyureas/polyurethane adhesives

Technology Topic

IonPolyurethane adhesive +10

Image

Examples

Experimental program(9)

Example Embodiment

[0022] The raw material composition of this environmentally-friendly waterborne polyurethane adhesive preparation method is calculated by mass percentage:

[0023] 10-50% of polymerized diols with a number average molecular weight of 500-5000,

[0024] A hydrophobic chain extender with a number average molecular weight of 61-400 0.1-10%,

[0025] Internal crosslinking agent 0~5%,

[0026] Hydrophilic chain extender 0.1~10%,

[0027] Diisocyanate 2~30%,

[0028] Catalyst 0.001~0.1%,

[0029] Organic solvent 0~10%,

[0030] Neutralizer 0.2~5%;

[0031] Deionized water 40~80%;

[0032] The preparation process is as follows:

[0033] (a) Add the polymerized glycol, hydrophobic chain extender, internal crosslinking agent, and hydrophilic chain extender into the reactor, under the protection of nitrogen, heat up to 110~120℃, vacuum dehydration for 15~30 minutes ;

[0034] (b) Cool to 50~60℃, add diisocyanate, the molar ratio of diisocyanate to active hydrogen compound can be controlled at (1.1~3.5):1, react at 80℃~100℃ for 1~5 hours;

[0035] (c) Lower the temperature to 60℃~80℃, and add catalyst to react for 1~3 hours;

[0036] (d) Depending on the viscosity, no organic solvent is added, or an appropriate amount of organic solvent is added to make the viscosity lower than 60000cps/60℃;

[0037] (e) Under the action of high-speed shearing force (1500~5000r/min), add the aqueous solution of neutralizer into the reactor (the molar ratio of neutralizer and hydrophilic chain extender is 0.6~1.3:1 ), stirring for 5-60 minutes to obtain a water-based polyurethane adhesive.

[0038] The polymerized diol with a number average molecular weight between 500 and 5000 used in the present invention can be polyester diol, polyε-caprolactone diol, polyether diol, polycarbonate diol, poly One or several mixed diols of ester polyether diol and polyester polycarbonate diol.

[0039] The polyester diols mentioned above can be synthesized by stepwise polymerization using dibasic acids and their derivatives, and diols and their derivatives. The dibasic acids and their derivatives used can be adipic acid, One or several mixed dibasic acids of azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, terephthalic acid, etc.; the diols and their derivatives used have a molecular weight of 50~ Compounds between 500, can be ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, methyl One or more mixed diols of propylene glycol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, dipropylene glycol, bisphenol A, etc.

[0040] The polyether diol used in the present invention may be polyoxyethylene diol, polyoxypropylene diol, polyoxyethylene propylene diol, polytetrahydrofuran diol.

[0041] The hydrophobic chain extender with a number average molecular weight between 61 and 400 according to the present invention can be a small molecule glycol or amine including 1-hydroxy 2-amino-ethane, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, methyl propylene glycol, 1,6-hexanediol, neopentyl glycol, diacetate Ethylene glycol, triethylene glycol, dipropylene glycol, bisphenol A, 3,3′-dichloro-4,4′-diamino-diphenylmethane (MOCA), hydroquinone-bis(β) -Hydroxyethyl) ether (HQEE), ethylenediamine, melamine, 1,4-butanediamine, propylenediamine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, hydrazine hydrate One or more of the others.

[0042] The internal crosslinking agent of the present invention can be one or more of trimethylolpropane, glycerin, 1,2,6-hexanetriol and the like.

[0043] The hydrophilic chain extender of the present invention can be a water-soluble small molecule compound containing a carboxylic acid group or a sulfonic acid group. The small molecule compound containing a carboxylic acid group includes dimethylolpropionic acid (DMPA), dimethylol Butyric acid (DMBA), dimethylolvaleric acid, dimethyloloctanoic acid; small molecule compounds containing sulfonic acid groups include N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid, two One or more of aminobutanesulfonic acid, sodium ethylenediaminoethanesulfonate or sodium 1,4-butanediol-2-sulfonate.

[0044] The diisocyanate of the present invention can be 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), hydrogenated diphenylmethane diisocyanate (HDI) 12 One or more of MDI) and xylylene diisocyanate (XDI).

[0045] The catalyst of the present invention is one or more of dibutyl tin dilaurate (DBTDL), tetrabutyl stannous titanate octoate, and tetraisopropanol titanate.

[0046] The organic solvent of the present invention is acetone (ACET), methyl ethyl ketone (MEK), N-methylpyrrolidone (NMP), ethyl acetate (ETAC), ethyl glycol ethyl ether, N-butyl glycol ethyl ether One or more of propylene glycol methyl ether, etc.

[0047] The neutralizer of the present invention can be ammonia, sodium carbonate, sodium bicarbonate, dimethylethanolamine, trimethylamine, triethylamine, triethanolamine, sodium hydroxide, potassium hydroxide, calcium hydroxide and the like.

Example Embodiment

[0048] Example one

[0049] 1. The polyoxypropylene glycol 160g (number average molecular weight is 2000), the hydrophobic small molecule chain extender neopentyl glycol 4.16g, the internal crosslinking agent trimethylolpropane 0.54g, the hydrophilic chain extender two Add 8.58g of DMPA to a four-neck reactor equipped with a thermometer, a condenser and a stirring device. Under the protection of nitrogen, the temperature is raised to 120°C, dehydrated under vacuum for 30 minutes, cooled to 60°C, and added 45.91g isophorone diisocyanate (IPDI) (the molar ratio of diisocyanate to active hydrogen compound is 1.1:1), react at 90°C for 2 hours, then lower the temperature to 80°C, add 0.05g tetraisopropyl titanate Alcohol ester, react for 3 hours.

[0050] 2. Under the action of high-speed shearing force (stirring speed at 2000r/min), add the neutralizer triethylamine aqueous solution (triethylamine 3.88g, deionized water 520g) into the reaction kettle, neutralizer three The molar ratio of ethylamine to the hydrophilic chain extender dimethylolpropionic acid (DMPA) is 0.6:1, stirred for 15 minutes, and the viscosity is 45CPS/25℃, solid content is 30.18%, and pH value is 7.5. Organic solvent translucent water-based polyurethane adhesive.

Example Embodiment

[0051] Example two

[0052] 1. Add 160g of polyoxyethylene glycol (number average molecular weight of 2000), 4.16g of neopentyl glycol, 0.54g of trimethylolpropane, and 8.58g of dimethylolpropionic acid into the reactor, under the protection of nitrogen After heating to 120°C, vacuum dehydration for 30 minutes, cooling to 60°C, adding 45.91g of isophorone diisocyanate (the molar ratio of diisocyanate to active hydrogen compound is 1.1:1), reacting at 90°C for 2 hours, and then The temperature was lowered to 80° C., 0.05 g of tetraisopropanol titanate was added and reacted for 3 hours.

[0053] 2. Under the action of high-speed shearing force (stirring speed at 2000r/min), add the aqueous solution of triethylamine (triethylamine 3.88g, deionized water 520g) into the reaction kettle and stir for 15 minutes to obtain a viscosity of A translucent waterborne polyurethane adhesive with 40CPS/25°C, 30.10% solid content, 7.5 pH, and no organic solvents.

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PUM

Property	Measurement	Unit
Viscosity	80.0	cps
tensile		MPa
Particle size		Pa
strength	10

Description & Claims & Application Information

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the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine

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