CN109401716B - Preparation method of rapid crystallization waterborne polyurethane adhesive - Google Patents

Preparation method of rapid crystallization waterborne polyurethane adhesive Download PDF

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CN109401716B
CN109401716B CN201811224816.7A CN201811224816A CN109401716B CN 109401716 B CN109401716 B CN 109401716B CN 201811224816 A CN201811224816 A CN 201811224816A CN 109401716 B CN109401716 B CN 109401716B
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CN109401716A (en
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邱元进
郑力铭
陈国栋
饶长贵
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Fujian Huaxialan New Material Technology Co ltd
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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  • Adhesives Or Adhesive Processes (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a preparation method of a rapid crystallization aqueous polyurethane adhesive, wherein the rapid crystallization aqueous polyurethane adhesive is prepared by adding a certain amount of auxiliary agent into a rapid crystallization aqueous polyurethane dispersoid, the rapid crystallization aqueous polyurethane dispersoid is prepared by polymerizing monohydric alcohol, short-chain bifunctional compound, polyisocyanate, polyalcohol, carboxyl hydrophilic agent and chain extender, and the aqueous polyurethane adhesive has the advantages of rapid crystallization speed, strong initial adhesion, good later-stage adhesion and good storage stability, and is beneficial to industrial mass production.

Description

Preparation method of rapid crystallization waterborne polyurethane adhesive
Technical Field
The invention relates to a preparation method of a rapid crystallization aqueous polyurethane adhesive.
Background
With the development of science and technology, the waterborne polyurethane adhesive has made great progress, and the waterborne polyurethane adhesive replaces a solvent-based polyurethane adhesive in a plurality of fields. The aqueous polyurethane adhesive has the advantages of extremely low solvent content, environmental protection, convenient use and high bonding strength, and more people begin to pay attention to the use of the aqueous polyurethane adhesive.
At present, compared with a solvent type polyurethane adhesive, the biggest defect of the water-based polyurethane adhesive is that the crystallization speed of the water-based polyurethane adhesive is slow, which directly reflects that the initial bonding strength is lower. This characteristic makes the consumer's willingness of aqueous polyurethane adhesives to replace solvent-borne polyurethane adhesives low.
CN108084945A proposes a polyurethane emulsion adhesive containing nano organic montmorillonite, which takes the effect of reinforcing and inducing polyurethane molecular chain crystallization by using the nano organic montmorillonite as a blocking agent, improves the initial adhesion of the adhesive, and utilizes acetophenone oxime to block isocyanate as a potential reactive group, which can further react with an active group of a bonding interface, thereby improving the bonding strength of the adhesive.
CN108300402A proposes a polyurethane emulsion adhesive containing nano-silica, which adopts nano-organic montmorillonite as a blocking agent to reinforce and induce polyurethane molecular chain crystallization, thereby improving the initial adhesion of the adhesive, and utilizes acetophenone oxime to block isocyanate as a potential reactive group, thereby further reacting with the active group of the bonding interface and improving the bonding strength of the adhesive.
According to the technical scheme, the nano inorganic substance is used as a blocking agent of the polyurethane emulsion and matched with polyester polyol with a specific molecular weight, so that the nano inorganic substance is uniformly and stably dispersed in the polyurethane emulsion to induce polyurethane crystallization, and the initial bonding strength of the adhesive is improved.
However, the compatibility between inorganic substances and organic substances is poor, and although the specific raw materials are matched with the inorganic substances in the technical scheme, flocculation, precipitation and other phenomena can be caused by batch difference of the raw materials even storage condition change and the like, and serious consequences can be caused in actual production.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a rapid crystallization aqueous polyurethane adhesive. According to the invention, isocyanate and a short-chain bifunctional compound are reacted to generate a hard segment, and the hard segment is used as a crystal nucleus to induce self-crystallization, so that the initial bonding strength of the adhesive is improved.
The invention adopts the technical scheme that the invention provides a preparation method of the rapid crystallization waterborne polyurethane adhesive, which comprises the following steps:
step 1, adding a proper amount of 5A molecular sieve into monohydric alcohol, a short-chain bifunctional compound, polyol and a carboxyl hydrophilic agent respectively for treatment, and standing until the water content is 0.05-0.1%. Slowly dripping 1mol of dehydrated 1mol of monohydric alcohol into 1mol of polyisocyanate, heating to 60-95 ℃ after dripping, reacting for 1-5 hours, and cooling to 40-50 ℃ to obtain prepolymer A;
step 2, adding 1-6 mol of the short-chain bifunctional compound subjected to water removal treatment and polyisocyanate with equal mass into the prepolymer A obtained in the step 1, heating to 60-95 ℃, carrying out heat preservation reaction for 1-12 hours, and cooling to 40-50 ℃; adding 18-29 mol of polyol, 1-5 mol of carboxyl hydrophilic agent and 19-34 mol of polyisocyanate, heating to 60-95 ℃, carrying out heat preservation reaction for 1-12 hours, and then cooling to 40-50 ℃ to obtain prepolymer B;
step 3, adding 0.3-0.9 mol of chain extender and 1000ml of acetone into the prepolymer B obtained in the step 2, heating to 60-95 ℃, carrying out heat preservation reaction for 1-12 hours, then cooling to 40-50 ℃, slowly dropwise adding a pH regulator to adjust the pH to be 6-9, then carrying out reduced pressure distillation to remove the acetone, and simultaneously dropwise adding water until the solid content is 40-60%, thus obtaining the aqueous polyurethane dispersion C;
and 4, adding 98-99.8 parts by weight of the aqueous polyurethane dispersion C obtained in the step 3 into a stirring container, sequentially adding 0.1-0.5 part by weight of a wetting agent, 0.1-0.5 part by weight of a defoaming agent and 0-1 part by weight of a thickening agent, controlling the stirring speed at 500-800 rpm, and carrying out dispersion mixing for 10-30 min to obtain the fast-crystallization aqueous polyurethane adhesive D.
The molar ratio of the monohydric alcohol to the short-chain bifunctional compound to the polyisocyanate to the polyol to the carboxyl hydrophilizing agent to the chain extender is 1: 1-6: 21-40: 18-29: 1-5: 0.3 to 0.9.
The monohydric alcohol is a straight chain saturated monohydric alcohol with 4-12 carbon atoms.
The short-chain bifunctional compound is one or a combination of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol and ethylenediamine.
Further, the polyisocyanate is one or a combination of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and 4,4' -dicyclohexylmethane diisocyanate.
Further, the polyol is one or a combination of more of polyoxypropylene glycol, polyethylene glycol, polytetrahydrofuran ether glycol, polycaprolactone glycol and polybutadiene glycol.
The carboxyl hydrophilic agent is one of dimethylolpropionic acid and dimethylolbutyric acid.
The chain extender is one or a combination of more of ethylenediamine, butanediamine and hexanediamine.
The wetting agent is commonly chemical CoaddTM W-1866、CoaddTM W-1855、CoaddTMW138 and CoaddTMOne or a combination of more of W110;
the defoaming agent is a chemical CoaddTM DF-420、CoaddTM DF-460、CoaddTMDF-860 and CoaddTMOne or more combinations of DF 825;
the thickening agent is Wanhua chemical Vesmody® U605、Vesmody®U505 and Vesmody®One or more of U905.
The invention has the beneficial effects that: according to the invention, the self structure of polyurethane is adjusted, the hard segment in the polyurethane molecular chain is used as a crystal nucleus, and crystallization is induced in the polyurethane cooling process, so that the initial crystallinity of the polyurethane adhesive is improved, and the initial bonding strength of the adhesive is improved; the polyurethane adhesive prepared by the invention has good storage stability and is beneficial to industrial mass production.
Detailed Description
In order to explain the technical content, the objects and the effects of the present invention in detail, the following description will be given with reference to the embodiments.
Example 1
Step 1, adding a proper amount of 5A molecular sieve into 1-butanol, ethylene glycol, polyoxypropylene glycol 1000 and dimethylolpropionic acid respectively for treatment, and standing until the water content is 0.05%. Taking 1mol of isophorone diisocyanate, slowly dropwise adding 1mol of 1-butanol subjected to water removal treatment, heating to 75 ℃ after dropwise adding, reacting for 5 hours, and cooling to 50 ℃ to obtain a prepolymer A1;
step 2, adding 1mol of dehydrated ethylene glycol and 1mol of isophorone diisocyanate into the prepolymer A1 obtained in the step 1, heating to 60 ℃, carrying out heat preservation reaction for 12 hours, and then cooling to 50 ℃; adding 18mol of polyoxypropylene glycol 1000, 5mol of dimethylolpropionic acid and 23mol of isophorone diisocyanate, heating to 80 ℃, carrying out heat preservation reaction for 6 hours, and then cooling to 40 ℃ to obtain prepolymer B1;
step 3, adding 0.8mol of ethylenediamine and 1000ml of acetone into the prepolymer B1 obtained in the step 2, heating to 75 ℃, carrying out heat preservation reaction for 1 hour, cooling to 40 ℃, slowly dropwise adding ammonia water to adjust the pH to be =7.5, then carrying out reduced pressure distillation to remove acetone, and simultaneously dropwise adding water until the solid content is about 50% to obtain an aqueous polyurethane dispersoid C1;
step 4, adding 198 parts by weight of the aqueous polyurethane dispersion C obtained in the step 3 into a stirring container, and then sequentially adding a wetting agent CoaddTMW-18660.5 parts by weight, defoamer CoaddTMDF 8250.5 parts by weight and Vesmody as thickening agent®U6051 weight portions, controlling the stirring speed at 500rpm, and dispersing and mixing for 30min to obtain the fast crystallization water-based polyurethane adhesive D1.
Example 2
Step 1, adding a proper amount of 5A molecular sieve into 1-octanol, 1, 3-propanediol, polyethylene glycol 2000 and dimethylolbutyric acid respectively for treatment, and standing until the water content is 0.07%. Taking 1mol of toluene diisocyanate, slowly dropwise adding 1mol of dehydrated 1-octanol, raising the temperature to 60 ℃ after the dropwise adding is finished, reacting for 1 hour, and cooling to 40 ℃ to obtain a prepolymer A2;
step 2, adding 6mol of dehydrated 1, 3-propylene glycol and 6mol of hexamethylene diisocyanate into the prepolymer A2 obtained in the step 1, heating to 95 ℃, carrying out heat preservation reaction for 1 hour, and cooling to 40 ℃; adding 18mol of polyethylene glycol 2000, 1mol of dimethylolbutyric acid and 19mol of hexamethylene diisocyanate, heating to 95 ℃, carrying out heat preservation reaction for 3 hours, and then cooling to 50 ℃ to obtain prepolymer B2;
step 3, adding 0.3mol of butanediamine and 1000ml of acetone into the prepolymer B2 obtained in the step 2, heating to 60 ℃, carrying out heat preservation reaction for 12 hours, then cooling to 45 ℃, slowly dropwise adding a triethylamine aqueous solution to adjust the pH to be =6, then carrying out reduced pressure distillation to remove the acetone, and simultaneously dropwise adding water until the solid content is about 40% to obtain an aqueous polyurethane dispersion C2;
step 4, adding the aqueous polyurethane dispersion C299 parts by weight obtained in the step 3 into a stirring container, and then sequentially adding a wetting agent CoaddTMW1100.1 parts by weight, defoamer CoaddTMDF-4600.1 weight portions and Vesmody as thickening agent®U5050.8 weight parts, controlling the stirring speed at 500rpm, and dispersing and mixing for 10min to obtain the fast crystallization water-based polyurethane adhesive D2.
Example 3
Step 1, adding a proper amount of 5A molecular sieve into 1-dodecanol, 1, 4-butanediol, polyoxypropylene glycol 2000 and dimethylolpropionic acid respectively for treatment, and standing until the water content is lower than 0.1%. 1mol of toluene diisocyanate is taken, 1mol of 1-dodecanol subjected to water removal treatment is slowly dripped, the temperature is raised to 95 ℃ after the dripping is finished, the reaction is carried out for 5 hours, and the temperature is lowered to 45 ℃ to obtain prepolymer A3;
step 2, adding 3mol of 1, 4-butanediol subjected to water removal treatment and 3mol of 4,4' -dicyclohexylmethane diisocyanate into the prepolymer A3 obtained in the step 1, heating to 70 ℃, carrying out heat preservation reaction for 6 hours, and then cooling to 45 ℃; adding 29mol of polyoxypropylene glycol 2000, 5mol of dimethylolpropionic acid and 34mol of 4,4' -dicyclohexylmethane diisocyanate, heating to 60 ℃, carrying out heat preservation reaction for 8 hours, and cooling to 40 ℃ to obtain prepolymer B3;
step 3, adding 0.5mol of hexamethylene diamine and 1000ml of acetone into the prepolymer B3 obtained in the step 2, heating to 80 ℃, carrying out heat preservation reaction for 6 hours, then cooling to 50 ℃, slowly dropwise adding a triethylamine aqueous solution to adjust the pH to =9, then carrying out reduced pressure distillation to remove the acetone, and simultaneously dropwise adding water to adjust the solid content to 50% to obtain an aqueous polyurethane dispersion C3;
step 4, adding 399.8 parts by weight of the aqueous polyurethane dispersion C obtained in the step 3 into a stirring container, and then sequentially adding a wetting agent CoaddTMW-18550.1 parts by weight, defoamer CoaddTMDF-8600.1 weight portions, controlling the stirring speed at 650rpm, and dispersing and mixing for 10min to obtain the fast crystallization water-based polyurethane adhesive D3.
Example 4
Step 1, respectively adding a proper amount of 5A molecular sieve into n-amyl alcohol, 1, 4-butanediol, polyethylene glycol 2000 and dimethylolbutyric acid for treatment, and standing until the water content is lower than 0.1%. Taking 1mol of hexamethylene diisocyanate, slowly dropwise adding 1mol of n-amyl alcohol subjected to water removal treatment, heating to 80 ℃ after dropwise adding, reacting for 3 hours, and cooling to 45 ℃ to obtain a prepolymer A4;
step 2, adding 4mol of dehydrated 1, 4-butanediol and 4mol of toluene diisocyanate into the prepolymer A4 obtained in the step 1, heating to 75 ℃, carrying out heat preservation reaction for 8 hours, and cooling to 48 ℃; adding 20mol of polyethylene glycol 2000, 3mol of dimethylolbutyric acid and 25mol of toluene diisocyanate, heating to 65 ℃, carrying out heat preservation reaction for 8.5 hours, and then cooling to 50 ℃ to obtain prepolymer B4;
step 3, adding 0.4mol of butanediamine and 1000ml of acetone into the prepolymer B4 obtained in the step 2, heating to 65 ℃, carrying out heat preservation reaction for 8 hours, then cooling to 50 ℃, slowly dropwise adding a triethylamine aqueous solution to adjust the pH to be =9, then carrying out reduced pressure distillation to remove the acetone, and simultaneously dropwise adding water until the solid content is 60% to obtain an aqueous polyurethane dispersion C4;
step 4, adding 498.5 parts by weight of the aqueous polyurethane dispersion C obtained in the step 3 into a stirring container, and then sequentially adding a wetting agent CoaddTMW-1380.5 parts by weight, defoamer CoaddTMDF-4200.2 weight portions and Vesmody as thickening agent®U9050.8 weight parts, controlling the stirring speed at 800rpm, and dispersing and mixing for 30min to obtain the fast crystallization water-based polyurethane adhesive D4.
Example 5
Step 1, respectively adding a proper amount of 5A molecular sieve into n-hexanol, 1, 3-propylene glycol, polytetrahydrofuran ether glycol and dimethylolpropionic acid for treatment, and standing until the water content is lower than 0.1%. Taking 1mol of hexamethylene diisocyanate, slowly dropwise adding 1mol of n-hexanol subjected to water removal treatment, heating to 80 ℃ after dropwise adding, reacting for 3 hours, and cooling to 50 ℃ to obtain a prepolymer A5;
step 2, adding 2.5mol of dehydrated 1, 3-propylene glycol and 2.5mol of hexamethylene diisocyanate into the prepolymer A5 obtained in the step 1, heating to 60-95 ℃, carrying out heat preservation reaction for 1 hour, and cooling to 43 ℃; adding 25mol of polytetrahydrofuran ether glycol, 1mol of dimethylolpropionic acid and 30mol of hexamethylene diisocyanate, heating to 85 ℃, carrying out heat preservation reaction for 7.5 hours, and cooling to 50 ℃ to obtain a prepolymer B5;
step 3, adding 0.9mol of ethylenediamine and 1000ml of acetone into the prepolymer B5 obtained in the step 2, heating to 70 ℃, carrying out heat preservation reaction for 6 hours, then cooling to 50 ℃, slowly dropwise adding a triethylamine aqueous solution to adjust the pH to =8, then carrying out reduced pressure distillation to remove the acetone, and simultaneously dropwise adding water to adjust the solid content to 53% to obtain an aqueous polyurethane dispersion C5;
step 4, adding 599.3 parts by weight of the aqueous polyurethane dispersion C obtained in the step 3 into a stirring container, and then sequentially adding a wetting agent CoaddTMW-18550.2 parts by weight, defoamer CoaddTMDF-4200.3 weight portions and Vesmody as thickening agent®U5050.2 weight parts, controlling the stirring speed at 500rpm, and dispersing and mixing for 20min to obtain the fast crystallization water-based polyurethane adhesive D5.
Example 6
Step 1, respectively adding a proper amount of 5A molecular sieve into 2-hexanol, 1, 4-butanediol, polycaprolactone diol 1000 and dimethylolbutyric acid for treatment, and standing until the water content is lower than 0.1%. Taking 1mol of hexamethylene diisocyanate, slowly dropwise adding 1mol of dehydrated 2-hexanol, heating to 72 ℃ after dropwise adding, reacting for 2 hours, and cooling to 46 ℃ to obtain prepolymer A6;
step 2, adding 1.5mol of dehydrated 1, 4-butanediol and 1.5mol of 4,4' -dicyclohexylmethane diisocyanate into the prepolymer A6 obtained in the step 1, heating to 85 ℃, carrying out heat preservation reaction for 12 hours, and then cooling to 50 ℃; adding 25mol of polycaprolactone diol 1000, 2.5mol of dimethylolbutyric acid and 22mol of 4,4' -dicyclohexylmethane diisocyanate, heating to 75 ℃, carrying out heat preservation reaction for 11 hours, and cooling to 40-50 ℃ to obtain a prepolymer B6;
step 3, adding 0.7mol of butanediamine and 1000ml of acetone into the prepolymer B6 obtained in the step 2, heating to 70 ℃, carrying out heat preservation reaction for 8 hours, then cooling to 50 ℃, slowly dropwise adding a triethylamine aqueous solution to adjust the pH to =7, then carrying out reduced pressure distillation to remove the acetone, and simultaneously dropwise adding water to adjust the solid content to 45% to obtain an aqueous polyurethane dispersion C6;
step 4, adding the aqueous polyurethane dispersoid C698.8 weight parts obtained in the step 3 into a stirring container, and then sequentially adding a wetting agent CoaddTMW-1100.1 parts by weight, defoamer CoaddTMDF-8250.1 weight portions and Vesmody as thickening agent®U5051 weight portion, controlling stirring speed at 650rpm, dispersing and mixing for 15min, and obtaining the fast crystallization water-based polyurethane adhesive D6.
Testing initial adhesion and later adhesion of the rapid crystallization waterborne polyurethane adhesives D1-D6 and the commercial waterborne polyurethane adhesive products E1 and E2 according to GB/T30779-2014 waterborne polyurethane adhesives, treating a standard rubber strip with a rubber treating agent, drying for 4 minutes at 70 ℃, taking out, thinly brushing the rapid crystallization waterborne polyurethane adhesives D1-D6 and the commercial waterborne polyurethane adhesive products E1 and E2 on the rubber strip, drying for 4 minutes at 70 ℃, immediately pressing the rubber strip with 1MPa pressure for 12 seconds after taking out. 5 minutes after pressure relief, testing the initial adhesion of the rubber strip on a tensile machine; and (4) after 24 hours of pressure relief, testing the later-stage adhesive force of the rubber strip on a tensile machine. 6 rubber strips were made for each adhesive sample, with 3 strips for the initial tack and 3 strips for the later tack. The test results were averaged as shown in table 1.
Table 1 comparison of the adhesion of the waterborne polyurethane adhesives D1-D6 prepared in the examples with commercial products E1 and E2
Sample name Initial viscous force, N/mm Late stage viscous force, N/mm
Adhesive D1 14.6 22.1
Adhesive D2 15.1 20.3
Adhesive D3 14.7 22.3
Adhesive D4 14.9 21.9
Adhesive D5 13.9 19.8
Adhesive D6 14.9 20.6
Adhesive E1 10.9 22.3
Adhesive E2 11.4 21.7
As can be seen from Table 1, the initial adhesive force of the adhesives D1-D6 is generally more than 14N/mm and is much higher than that of the commercial products E1 and E2; and the adhesives D1-D6 are basically close to the adhesives E1 and E2 from later stage adhesion comparison. This fully demonstrates that the adhesives D1-D8 have a strong ability to crystallize rapidly, can rapidly increase the initial strength, and have no effect on the later stage adhesive strength.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention in the specification or directly or indirectly applied to the related technical field are included in the scope of the present invention.

Claims (7)

1. A fast crystallization aqueous polyurethane adhesive is characterized in that: the preparation method of the rapid crystallization waterborne polyurethane adhesive comprises the following steps:
step 1, respectively adding a proper amount of 5A molecular sieve into monohydric alcohol, a short-chain bifunctional compound, polyol and a carboxyl hydrophilic agent for treatment, and standing until the water content is 0.05-0.1%;
slowly dripping 1mol of dehydrated 1mol of monohydric alcohol into 1mol of polyisocyanate, heating to 60-95 ℃ after dripping, reacting for 1-5 hours, and cooling to 40-50 ℃ to obtain prepolymer A;
step 2, adding 1-6 mol of the short-chain bifunctional compound subjected to water removal treatment and polyisocyanate with equal mass into the prepolymer A obtained in the step 1, heating to 60-95 ℃, carrying out heat preservation reaction for 1-12 hours, and cooling to 40-50 ℃; adding 18-29 mol of polyol, 1-5 mol of carboxyl hydrophilic agent and 19-34 mol of polyisocyanate, heating to 60-95 ℃, carrying out heat preservation reaction for 1-12 hours, and then cooling to 40-50 ℃ to obtain prepolymer B;
step 3, adding 0.3-0.9 mol of chain extender and 1000ml of acetone into the prepolymer B obtained in the step 2, heating to 60-95 ℃, carrying out heat preservation reaction for 1-12 hours, then cooling to 40-50 ℃, slowly dropwise adding a pH regulator to adjust the pH to be 6-9, then carrying out reduced pressure distillation to remove the acetone, and simultaneously dropwise adding water until the solid content is 40-60%, thus obtaining the aqueous polyurethane dispersion C;
step 4, adding 98-99.8 parts of the aqueous polyurethane dispersion C obtained in the step 3 into a stirring container, sequentially adding 0.1-0.5 part of wetting agent, 0.1-0.5 part of defoaming agent and 0-1 part of thickening agent, controlling the stirring speed at 500-800 rpm, and carrying out dispersion mixing for 10-30 min to obtain a fast crystallization aqueous polyurethane adhesive D;
the monohydric alcohol is straight chain saturated monohydric alcohol with 4-12 carbon atoms;
the short-chain bifunctional compound is one or a composition of more of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol and ethylenediamine;
the polyisocyanate is one or a composition of more of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and 4,4' -dicyclohexylmethane diisocyanate;
the polyalcohol is one or a composition of more of polyoxypropylene glycol, polyethylene glycol, polytetrahydrofuran ether glycol, polycaprolactone glycol and polybutadiene glycol;
the carboxyl hydrophilic agent is one of dimethylolpropionic acid and dimethylolbutyric acid;
the chain extender is one or a composition of more of ethylenediamine, butanediamine and hexanediamine;
the wetting agent is commonly chemical CoaddTM W-1866、CoaddTM W-1855、CoaddTMW138 and CoaddTMOne or a combination of more of W110; the defoaming agent is a chemical CoaddTM DF-420、CoaddTM DF-460、CoaddTMDF-860 and CoaddTMOne or more combinations of DF 825; the thickening agent is Wanhua chemical Vesmody® U605、Vesmody®U505 and Vesmody®One or more of U905.
2. The fast crystallizing aqueous polyurethane adhesive of claim 1, wherein: the preparation method of the rapid crystallization waterborne polyurethane adhesive comprises the following steps:
step 1, respectively adding a proper amount of 5A molecular sieve into 1-butanol, ethylene glycol, polyoxypropylene glycol 1000 and dimethylolpropionic acid for treatment, and standing until the water content is 0.05%;
slowly dropwise adding 1mol of 1-butanol subjected to water removal treatment into 1mol of isophorone diisocyanate, heating to 75 ℃ after dropwise adding, reacting for 5 hours, and cooling to 40-50 ℃ to obtain a prepolymer A1;
step 2, adding 1mol of dehydrated ethylene glycol and 1mol of isophorone diisocyanate into the prepolymer A1 obtained in the step 1, heating to 60 ℃, carrying out heat preservation reaction for 12 hours, and then cooling to 40-50 ℃; adding 18mol of polyoxypropylene glycol, 5mol of dimethylolpropionic acid and 23mol of isophorone diisocyanate, heating to 80 ℃, carrying out heat preservation reaction for 6 hours, and then cooling to 50 ℃ to obtain prepolymer B1;
step 3, adding 0.8mol of ethylenediamine and 1000ml of acetone into the prepolymer B1 obtained in the step 2, heating to 75 ℃, carrying out heat preservation reaction for 12 hours, then cooling to 50 ℃, slowly adding dropwise ammonia water to adjust the pH to be =7.5, then carrying out reduced pressure distillation to remove acetone, and simultaneously adding dropwise water until the solid content is 50% to obtain an aqueous polyurethane dispersion C1;
step 4, adding 198 parts of the aqueous polyurethane dispersion C obtained in the step 3 into a stirring container in parts by weight, and then sequentially adding a wetting agent CoaddTMW-18660.5 parts, defoaming agent CoaddTMDF 8250.5 parts and thickening agent Vesmody®U6051 parts, controlling the stirring speed at 500rpm, and dispersing and mixing for 30min to obtain the fast crystallization water-based polyurethane adhesive D1.
3. The fast crystallizing aqueous polyurethane adhesive of claim 1, wherein: the preparation method of the rapid crystallization waterborne polyurethane adhesive comprises the following steps:
step 1, respectively adding a proper amount of 5A molecular sieve into 1-octanol, 1, 3-propanediol, polyethylene glycol 2000 and dimethylolbutyric acid for treatment, and standing until the water content is 0.07%;
slowly dripping 1mol of dehydrated 1-octanol into 1mol of toluene diisocyanate, heating to 60 ℃ after dripping, reacting for 1 hour, and cooling to 40-50 ℃ to obtain prepolymer A2;
step 2, adding 6mol of dehydrated 1, 3-propylene glycol and 6mol of hexamethylene diisocyanate into the prepolymer A2 obtained in the step 1, heating to 95 ℃, carrying out heat preservation reaction for 1 hour, and cooling to 40-50 ℃; adding 18mol of polyethylene glycol 2000, 1mol of dimethylolbutyric acid and 19mol of hexamethylene diisocyanate, heating to 95 ℃, carrying out heat preservation reaction for 3 hours, and then cooling to 40 ℃ to obtain prepolymer B2;
step 3, adding 0.3mol of butanediamine and 1000ml of acetone into the prepolymer B2 obtained in the step 2, heating to 60 ℃, carrying out heat preservation reaction for 12 hours, then cooling to 40 ℃, slowly dropwise adding a triethylamine aqueous solution to adjust the pH to be =6, then carrying out reduced pressure distillation to remove the acetone, and simultaneously dropwise adding water until the solid content is 40% to obtain an aqueous polyurethane dispersion C2;
step 4, adding the aqueous polyurethane dispersion C299 parts by weight obtained in the step 3 into a stirring container, and then sequentially adding a wetting agent CoaddTMW1100.1 parts by weight, defoamer CoaddTMDF-4600.1 weight portions and Vesmody as thickening agent®U5050.8 weight parts, controlling the stirring speed at 500rpm, and dispersing and mixing for 10min to obtain the fast crystallization water-based polyurethane adhesive D2.
4. The fast crystallizing aqueous polyurethane adhesive of claim 1, wherein: the preparation method of the rapid crystallization waterborne polyurethane adhesive comprises the following steps:
step 1, respectively adding a proper amount of 5A molecular sieve into 1-dodecanol, 1, 4-butanediol, polyoxypropylene glycol 2000 and dimethylolpropionic acid for treatment, and standing until the water content is lower than 0.1%;
1mol of toluene diisocyanate is taken, 1mol of 1-dodecanol subjected to water removal treatment is slowly dripped, the temperature is raised to 95 ℃ after the dripping is finished, the reaction is carried out for 5 hours, and the temperature is lowered to 45 ℃ to obtain prepolymer A3;
step 2, adding 3mol of 1, 4-butanediol subjected to water removal treatment and 3mol of 4,4' -dicyclohexylmethane diisocyanate into the prepolymer A3 obtained in the step 1, heating to 70 ℃, carrying out heat preservation reaction for 6 hours, and then cooling to 45 ℃; adding 29mol of polyoxypropylene glycol 2000, 5mol of dimethylolpropionic acid and 34mol of 4,4' -dicyclohexylmethane diisocyanate, heating to 60 ℃, carrying out heat preservation reaction for 8 hours, and cooling to 40 ℃ to obtain prepolymer B3;
step 3, adding 0.5mol of hexamethylene diamine and 1000ml of acetone into the prepolymer B3 obtained in the step 2, heating to 80 ℃, carrying out heat preservation reaction for 6 hours, then cooling to 50 ℃, slowly dropwise adding a triethylamine aqueous solution to adjust the pH to =9, then carrying out reduced pressure distillation to remove the acetone, and simultaneously dropwise adding water to adjust the solid content to 50% to obtain an aqueous polyurethane dispersion C3;
step 4, adding the aqueous polyurethane dispersion C399.8 weight obtained in the step 3 into a stirring containerThe wetting agent Coadd is added after the weight portionTMW-18550.1 parts by weight, defoamer CoaddTMDF-8600.1 weight portions, controlling the stirring speed at 650rpm, and dispersing and mixing for 10min to obtain the fast crystallization water-based polyurethane adhesive D3.
5. The fast crystallizing aqueous polyurethane adhesive of claim 1, wherein: the preparation method of the rapid crystallization waterborne polyurethane adhesive comprises the following steps:
step 1, respectively adding a proper amount of 5A molecular sieve into n-amyl alcohol, 1, 4-butanediol, polyethylene glycol 2000 and dimethylolbutyric acid for treatment, and standing until the water content is lower than 0.1%;
taking 1mol of hexamethylene diisocyanate, slowly dropwise adding 1mol of n-amyl alcohol subjected to water removal treatment, heating to 80 ℃ after dropwise adding, reacting for 3 hours, and cooling to 45 ℃ to obtain a prepolymer A4;
step 2, adding 4mol of dehydrated 1, 4-butanediol and 4mol of toluene diisocyanate into the prepolymer A4 obtained in the step 1, heating to 75 ℃, carrying out heat preservation reaction for 8 hours, and cooling to 48 ℃; adding 20mol of polyethylene glycol 2000, 3mol of dimethylolbutyric acid and 25mol of toluene diisocyanate, heating to 65 ℃, carrying out heat preservation reaction for 8.5 hours, and then cooling to 50 ℃ to obtain prepolymer B4;
step 3, adding 0.4mol of butanediamine and 1000ml of acetone into the prepolymer B4 obtained in the step 2, heating to 65 ℃, carrying out heat preservation reaction for 8 hours, then cooling to 50 ℃, slowly dropwise adding a triethylamine aqueous solution to adjust the pH to be =9, then carrying out reduced pressure distillation to remove the acetone, and simultaneously dropwise adding water until the solid content is 60% to obtain an aqueous polyurethane dispersion C4;
step 4, adding 498.5 parts by weight of the aqueous polyurethane dispersion C obtained in the step 3 into a stirring container, and then sequentially adding a wetting agent CoaddTMW-1380.5 parts by weight, defoamer CoaddTMDF-4200.2 weight portions and Vesmody as thickening agent®U9050.8 weight parts, controlling the stirring speed at 800rpm, and dispersing and mixing for 30min to obtain the fast crystallization water-based polyurethane adhesive D4.
6. The fast crystallizing aqueous polyurethane adhesive of claim 1, wherein: the preparation method of the rapid crystallization waterborne polyurethane adhesive comprises the following steps:
step 1, respectively adding a proper amount of 5A molecular sieve into n-hexanol, 1, 3-propylene glycol, polytetrahydrofuran ether glycol and dimethylolpropionic acid for treatment, and standing until the water content is lower than 0.1%;
taking 1mol of hexamethylene diisocyanate, slowly dropwise adding 1mol of n-hexanol subjected to water removal treatment, heating to 80 ℃ after dropwise adding, reacting for 3 hours, and cooling to 50 ℃ to obtain a prepolymer A5;
step 2, adding 2.5mol of dehydrated 1, 3-propylene glycol and 2.5mol of hexamethylene diisocyanate into the prepolymer A5 obtained in the step 1, heating to 60-95 ℃, carrying out heat preservation reaction for 1 hour, and cooling to 43 ℃; adding 25mol of polytetrahydrofuran ether glycol, 1mol of dimethylolpropionic acid and 30mol of hexamethylene diisocyanate, heating to 85 ℃, carrying out heat preservation reaction for 7.5 hours, and cooling to 50 ℃ to obtain a prepolymer B5;
step 3, adding 0.9mol of ethylenediamine and 1000ml of acetone into the prepolymer B5 obtained in the step 2, heating to 70 ℃, carrying out heat preservation reaction for 6 hours, then cooling to 50 ℃, slowly dropwise adding a triethylamine aqueous solution to adjust the pH to =8, then carrying out reduced pressure distillation to remove the acetone, and simultaneously dropwise adding water to adjust the solid content to 53% to obtain an aqueous polyurethane dispersion C5;
step 4, adding 599.3 parts by weight of the aqueous polyurethane dispersion C obtained in the step 3 into a stirring container, and then sequentially adding a wetting agent CoaddTMW-18550.2 parts by weight, defoamer CoaddTMDF-4200.3 weight portions and Vesmody as thickening agent®U5050.2 weight parts, controlling the stirring speed at 500rpm, and dispersing and mixing for 20min to obtain the fast crystallization water-based polyurethane adhesive D5.
7. The fast crystallizing aqueous polyurethane adhesive of claim 1, wherein: the preparation method of the rapid crystallization waterborne polyurethane adhesive comprises the following steps:
step 1, respectively adding a proper amount of 5A molecular sieve into 2-hexanol, 1, 4-butanediol, polycaprolactone diol 1000 and dimethylolbutyric acid for treatment, and standing until the water content is lower than 0.1%;
taking 1mol of hexamethylene diisocyanate, slowly dropwise adding 1mol of dehydrated 2-hexanol, heating to 72 ℃ after dropwise adding, reacting for 2 hours, and cooling to 46 ℃ to obtain prepolymer A6;
step 2, adding 1.5mol of dehydrated 1, 4-butanediol and 1.5mol of 4,4' -dicyclohexylmethane diisocyanate into the prepolymer A6 obtained in the step 1, heating to 85 ℃, carrying out heat preservation reaction for 12 hours, and then cooling to 50 ℃; adding 25mol of polycaprolactone diol 1000, 2.5mol of dimethylolbutyric acid and 22mol of 4,4' -dicyclohexylmethane diisocyanate, heating to 75 ℃, carrying out heat preservation reaction for 11 hours, and cooling to 40-50 ℃ to obtain a prepolymer B6;
step 3, adding 0.7mol of butanediamine and 1000ml of acetone into the prepolymer B6 obtained in the step 2, heating to 70 ℃, carrying out heat preservation reaction for 8 hours, then cooling to 50 ℃, slowly dropwise adding a triethylamine aqueous solution to adjust the pH to =7, then carrying out reduced pressure distillation to remove the acetone, and simultaneously dropwise adding water to adjust the solid content to 45% to obtain an aqueous polyurethane dispersion C6;
step 4, adding the aqueous polyurethane dispersoid C698.8 weight parts obtained in the step 3 into a stirring container, and then sequentially adding a wetting agent CoaddTMW-1100.1 parts by weight, defoamer CoaddTMDF-8250.1 weight portions and Vesmody as thickening agent®U5051 weight portion, controlling stirring speed at 650rpm, dispersing and mixing for 15min, and obtaining the fast crystallization water-based polyurethane adhesive D6.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1406997A (en) * 2001-08-21 2003-04-02 三井武田化学株式会社 Polyurethane water dispersant and water soluble polyurethane adhesive
WO2005100427A1 (en) * 2004-04-13 2005-10-27 Lamberti S.P.A. Adhesive aqueous compositions
CN104031225A (en) * 2013-03-06 2014-09-10 万华化学集团股份有限公司 Aqueous polyurethane dispersoid for synthetic leather adhesive and preparation method thereof
CN106221649A (en) * 2016-08-15 2016-12-14 汕头市龙湖昌丰化工有限公司 Waterborne polyurethane shoe adhesive of low viscosity high-adhesive-strength and preparation method thereof
CN107406724A (en) * 2015-04-07 2017-11-28 科思创德国股份有限公司 With the method for adhesive bonding base material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1406997A (en) * 2001-08-21 2003-04-02 三井武田化学株式会社 Polyurethane water dispersant and water soluble polyurethane adhesive
WO2005100427A1 (en) * 2004-04-13 2005-10-27 Lamberti S.P.A. Adhesive aqueous compositions
CN104031225A (en) * 2013-03-06 2014-09-10 万华化学集团股份有限公司 Aqueous polyurethane dispersoid for synthetic leather adhesive and preparation method thereof
CN107406724A (en) * 2015-04-07 2017-11-28 科思创德国股份有限公司 With the method for adhesive bonding base material
CN106221649A (en) * 2016-08-15 2016-12-14 汕头市龙湖昌丰化工有限公司 Waterborne polyurethane shoe adhesive of low viscosity high-adhesive-strength and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Influence of the Chain Extender Nature on Adhesives";Orgiles-Calpena等;《JOURNAL OF DISPERSION SCIENCE AND TECHNOLOGY》;20111220;第33卷(第1期);第147-154页 *
"扩链剂对水性聚氨酯胶膜结晶性能的影响";姚机艳等;《聚氨酯工业》;20161028;第31卷(第5期);第22-25页 *

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