阅读说明：本技术 一种高效润湿水性异氰酸酯固化剂 (Efficient wetting water-based isocyanate curing agent ) 是由 邱元进 饶长贵 陈国栋 于 2019-10-26 设计创作，主要内容包括：本发明公开了一种高效润湿水性异氰酸酯固化剂;所述高效润湿水性异氰酸酯固化剂的三聚体结构中含有相邻的炔基和磺酸基；炔基提供强极性,磺酸基提供强亲水性;炔基作为强极性的疏水基团,可进一步提高炔基体系中的电子云浓度,降低亲水基团的电子云密度,增加所述水性异氰酸酯固化剂中的极性,提高其离子化程度,进而加强水性异氰酸酯固化剂的乳化效果;所述高效润湿水性异氰酸酯固化剂可将水的表面张力降低至26-29 mN/m,加入常规水性聚氨酯胶粘剂中,可增大水性聚氨酯胶粘剂在基材上的接触面积,进而提高贴合强度,对难贴合的硬质TPR、聚丙烯、聚乙烯等材料均有很好的贴合效果。(The invention discloses a high-efficiency wetting water-based isocyanate curing agent, wherein a tripolymer structure of the high-efficiency wetting water-based isocyanate curing agent contains adjacent alkynyl and sulfonic group; the high-efficiency wetting water-based isocyanate curing agent can reduce the surface tension of water to 26-29 mN/m, can increase the contact area of the water-based polyurethane adhesive on a substrate by adding the high-efficiency wetting water-based isocyanate curing agent into a conventional water-based polyurethane adhesive, further improves the bonding strength, and has a good bonding effect on hard TPR, polypropylene, polyethylene and other materials which are difficult to bond.)

1. An efficient wetting water-based isocyanate curing agent is characterized in that: the structural general formula of the efficient wetting water-based isocyanate curing agent is as follows:

wherein R is ₁Is composed of

R ₂is composed of ，

m is [ N (CH) ₂CH ₃) ₄] ⁺，[N(CH ₂CH ₂CH ₂CH ₃) ₄] ⁺，[N(CH ₃) ₃C ₁₆H ₃₃] ⁺，[N(CH ₃) ₃C ₁₂H ₂₅] ⁺And [ N (CH) ₃) ₃C ₁₈H ₃₇] ⁺One of (1);

the preparation method of the high-efficiency wetting water-based isocyanate curing agent comprises the following steps:

(1) a mol contains R ₂Dissolving a dihydroxy compound with a structure in tetrahydrofuran to prepare a solution with the mass concentration of 25-40%, cooling the solution to-50 to-30 ℃, slowly dropwise adding B mol of chlorinating agent, keeping the temperature unchanged, and continuously stirring for 2-5 hours;

(2) adding C mol of sulfonating agent solid into the filtrate, slowly heating to room temperature within 2-4 hours, violently stirring for 0.5-1 hour, heating to 50-65 ℃, reacting for 6-12 hours, cooling to 20-30 ℃, filtering to remove redundant sulfonating agent, and collecting the filtrate; b mol of halogenated salt containing a group M is added into the filtrate, white fine precipitate appears in the system, and colorless transparent clear liquid is obtained after filtration;

(3) adding the clear liquid into B mol containing R at one time ₁Reacting the isocyanate tripolymer with the structure for 1 to 3 hours at the temperature of between 50 and 75 ℃; distilling under reduced pressure to remove tetrahydrofuran to obtain colorless transparent viscous liquid, namely the high-efficiency wetting water-based isocyanate curing agent;

according to the molar ratio, B is more than or equal to 0.98A and less than or equal to A, and C is more than or equal to 1.4B and less than or equal to 3B;

wherein the chlorinating agent is one of phosphorus trichloride, phosphorus pentachloride and 4-methoxytriphenylmethane chloride; the sulfonating agent is one or a combination of two of sodium bisulfite, sodium sulfite, potassium bisulfite and potassium sulfite; the halogenated salt is one of a chloride salt and a bromide salt.

2. The efficient wetting water-based isocyanate curing agent according to claim 1, wherein the efficient wetting water-based isocyanate curing agent is prepared by the following steps:

(1) dissolving 1mol of 1, 4-butynediol in 129g of tetrahydrofuran to prepare a solution with the mass concentration of 40%, cooling the solution to-50 ℃, slowly dropwise adding 0.98 mol of phosphorus trichloride, keeping the temperature unchanged, and continuously stirring for 5 hours;

(2) adding 1.4 mol of sodium sulfite solid into the filtrate, slowly heating to room temperature within 4 hours, violently stirring for 1 hour, heating to 60 ℃, reacting for 9 hours, cooling to 30 ℃, filtering to remove redundant sodium sulfite, and collecting the filtrate; adding 0.98 mol of tetrabutylammonium chloride into the filtrate to obtain white and fine precipitate sodium chloride in the system, and filtering to obtain colorless and transparent clear liquid;

(3) adding the clear liquid into 0.98 mol hexamethylene diisocyanate tripolymer at one time, and reacting for 3 hours at 50 ℃; and distilling under reduced pressure to remove tetrahydrofuran to obtain colorless transparent viscous liquid, namely the efficient wetting water-based isocyanate curing agent F1.

3. The efficient wetting water-based isocyanate curing agent according to claim 1, wherein the efficient wetting water-based isocyanate curing agent is prepared by the following steps:

(1) dissolving 1.2mol of 2, 5-dimethyl-3-hexyne-2, 5-diol in 510g of tetrahydrofuran to prepare a solution with the mass concentration of 25%, cooling the solution to-30 ℃, slowly dropwise adding 1.19 mol of phosphorus pentachloride, keeping the temperature unchanged, and continuously stirring for 2 hours;

(2) adding 3.57 mol of sodium bisulfite into the filtrate, slowly heating to room temperature within 2 hours, vigorously stirring for 1 hour, heating to 65 ℃, reacting for 6 hours, cooling to 25 ℃, filtering to remove excessive sodium bisulfite, and collecting the filtrate; adding 1.19 mol of tetraethylammonium bromide into the filtrate to enable the system to generate white fine precipitates, and filtering to obtain colorless transparent clear liquid;

(3) adding the clear liquid into 1.2mol of isophorone diisocyanate tripolymer at one time, and reacting for 1.5 hours at 75 ℃; and distilling under reduced pressure to remove tetrahydrofuran to obtain colorless transparent viscous liquid, namely the efficient wetting water-based isocyanate curing agent F2.

4. The efficient wetting water-based isocyanate curing agent according to claim 1, wherein the efficient wetting water-based isocyanate curing agent is prepared by the following steps:

(1) dissolving 1mol of 3-hexyne-2, 5-diol in 210g of tetrahydrofuran to prepare a solution with the mass concentration of 35%, cooling the solution to-46 ℃, slowly dropwise adding 1mol of 4-methoxytriphenylmethane chloride, keeping the temperature unchanged, and continuously stirring for 2 hours;

(2) adding 2mol of sodium sulfite solid into the filtrate, slowly raising the temperature to room temperature within 4 hours, violently stirring for 1 hour, raising the temperature to 55 ℃, reacting for 8 hours, then cooling to 20 ℃, filtering to remove redundant sodium sulfite, and collecting the filtrate; adding 1mol of hexadecyl trimethyl ammonium bromide into the filtrate, allowing a white fine precipitate to appear in the system, and filtering to obtain a colorless transparent clear solution;

(3) adding the clear liquid into 1mol of 4,4' -dicyclohexylmethane diisocyanate trimer at one time, and reacting for 1.5 hours at 65 ℃; and distilling under reduced pressure to remove tetrahydrofuran to obtain colorless transparent viscous liquid, namely the efficient wetting water-based isocyanate curing agent F3.

5. The efficient wetting water-based isocyanate curing agent according to claim 1, wherein the efficient wetting water-based isocyanate curing agent is prepared by the following steps:

(1) dissolving 3-hexyne-2, 5-diol 2mol in tetrahydrofuran 265g to prepare a solution with the mass concentration of 30%, cooling the solution to-35 ℃, slowly dropwise adding phosphorus pentachloride 1.99 mol, keeping the temperature unchanged, and continuously stirring for 3 hours;

(2) adding 3.6 mol of potassium sulfite solid into the filtrate, slowly heating to room temperature within 3 hours, violently stirring for 0.5 hour, heating to 58 ℃, reacting for 9 hours, cooling to 20 ℃, filtering to remove redundant potassium sulfite, and collecting the filtrate; adding 1.99 mol of octadecyl trimethyl ammonium chloride into the filtrate to obtain white fine precipitate, and filtering to obtain colorless transparent clear liquid;

(3) adding the clear liquid into 2mol of isophorone diisocyanate trimer at one time, and reacting for 3 hours at 55 ℃; and distilling under reduced pressure to remove tetrahydrofuran to obtain colorless transparent viscous liquid, namely the efficient wetting water-based isocyanate curing agent F4.

6. The efficient wetting water-based isocyanate curing agent according to claim 1, wherein the efficient wetting water-based isocyanate curing agent is prepared by the following steps:

(1) dissolving 0.8 mol of 1, 4-butynediol in 147g of tetrahydrofuran to prepare a solution with the mass concentration of 32%, cooling the solution to-40 ℃, slowly dropwise adding 4-methoxytriphenylmethane chloride in the solution, keeping the temperature unchanged, and continuously stirring for 3 hours;

(2) adding 2mol of potassium bisulfite into the filtrate, slowly heating to room temperature within 3.5 hours, violently stirring for 0.5 hour, heating to 62 ℃, reacting for 7 hours, cooling to 27 ℃, filtering to remove redundant potassium bisulfite, and collecting the filtrate; adding 0.79 mol of dodecyl trimethyl ammonium bromide into the filtrate to enable a system to generate white fine precipitates, and filtering to obtain colorless transparent clear liquid;

(3) adding the clear liquid into 0.79 mol hexamethylene diisocyanate trimer at one time, and reacting for 2.5 hours at 63 ℃; and distilling under reduced pressure to remove tetrahydrofuran to obtain colorless transparent viscous liquid, namely the efficient wetting water-based isocyanate curing agent F5.

7. The efficient wetting water-based isocyanate curing agent according to claim 1, wherein the efficient wetting water-based isocyanate curing agent is prepared by the following steps:

(1) dissolving 1.5 mol of 2, 5-dimethyl-3-hexyne-2, 5-diol in 347g of tetrahydrofuran to prepare a solution with the mass concentration of 38%, cooling the solution to-36 ℃, slowly dropwise adding 1.48 mol of phosphorus trichloride, keeping the temperature unchanged, and continuously stirring for 4 hours;

(2) adding 4mol of sodium bisulfite solid into the filtrate, slowly heating to room temperature within 2 hours, violently stirring for 0.5 hour, heating to 55 ℃, reacting for 12 hours, cooling to 20 ℃, filtering to remove redundant sodium bisulfite, and collecting the filtrate; adding 1.48 mol of tetraethylammonium bromide into the filtrate to enable the system to generate white fine precipitates, and filtering to obtain colorless transparent clear liquid;

(3) adding the clear liquid into 1.48 mol of 4,4' -dicyclohexylmethane diisocyanate trimer at one time, and reacting for 1.5 hours at 70 ℃; and distilling under reduced pressure to remove tetrahydrofuran to obtain colorless transparent viscous liquid, namely the efficient wetting water-based isocyanate curing agent F6.

Technical Field

The invention relates to an efficient wetting water-based isocyanate curing agent and a preparation method thereof.

Background

With the development of science and technology, the waterborne polyurethane adhesive makes great progress, and the waterborne polyurethane adhesive is matched with a waterborne curing agent for use, so that the bonding requirements of multiple fields can be met; meanwhile, as people's awareness of environmental protection is improved, the aqueous polyurethane adhesive is replacing the solvent type polyurethane adhesive in more and more fields. It is expected that aqueous polyurethane adhesives will develop more rapidly in the future.

The aqueous polyurethane adhesive takes water as a dispersing medium, and because the surface tension of the water is high (72 mN/m), the aqueous polyurethane adhesive cannot be wetted and spread in partial base materials, particularly plastics or synthetic resins, so that the aqueous polyurethane adhesive is easy to have serious quality problems of uneven adhesion, low bonding strength and the like in the base materials.

Disclosure of Invention

In order to solve the technical problems, the invention provides a high-efficiency wetting water-based isocyanate curing agent. The technical scheme adopted by the invention is that the structural general formula of the high-efficiency wetting water-based isocyanate curing agent is as follows:

；

wherein R is ₁Is composed of

、

And

one of (1);

R ₂is composed of

，

And

one of (1);

m is [ N (CH) ₂CH ₃) ₄] ⁺，[N(CH ₂CH ₂CH ₂CH ₃) ₄] ⁺，[N(CH ₃) ₃C ₁₆H ₃₃] ⁺，[N(CH ₃) ₃C ₁₂H ₂₅] ⁺And [ N (CH) ₃) ₃C ₁₈H ₃₇] ⁺One of (1);

the preparation method of the high-efficiency wetting water-based isocyanate curing agent comprises the following steps:

(1) a mol contains R ₂Dissolving a dihydroxy compound with a structure in tetrahydrofuran to prepare a solution with the mass concentration of 25-40%, cooling the solution to-50 to-30 ℃, slowly dropwise adding B mol of chlorinating agent, keeping the temperature unchanged, and continuously stirring for 2-5 hours;

(2) adding C mol of sulfonating agent solid into the filtrate, slowly heating to room temperature within 2-4 hours, violently stirring for 0.5-1 hour, heating to 50-65 ℃, reacting for 6-12 hours, cooling to 20-30 ℃, filtering to remove redundant sulfonating agent, and collecting the filtrate; b mol of halogenated salt containing a group M is added into the filtrate, white fine precipitate appears in the system, and colorless transparent clear liquid is obtained after filtration;

(3) adding the clear liquid into B mol containing R at one time ₁Reacting the isocyanate tripolymer with the structure for 1 to 3 hours at the temperature of between 50 and 75 ℃; distilling under reduced pressure to remove tetrahydrofuran to obtain colorless transparent viscous liquid, namely the high-efficiency wetting water-based isocyanate curing agent;

according to the molar ratio, B is more than or equal to 0.98A and less than or equal to A, and C is more than or equal to 1.4B and less than or equal to 3B;

wherein the chlorinating agent is one of phosphorus trichloride, phosphorus pentachloride and 4-methoxytriphenylmethane chloride; the sulfonating agent is one or a combination of two of sodium bisulfite, sodium sulfite, potassium bisulfite and potassium sulfite; the halogenated salt is one of a chloride salt and a bromide salt.

The invention has the beneficial effects that: the trimer structure of the high-efficiency wetting water-based isocyanate curing agent contains adjacent alkynyl and sulfonic group; the alkynyl group provides strong polarity and the sulfonic acid group provides strong hydrophilicity. Compared with the conventional alkane and alkene hydrophobic groups, the alkynyl is used as the hydrophobic group with strong polarity, so that the electron cloud concentration in an alkynyl system can be further improved, the electron cloud density of the hydrophilic group is reduced, the polarity in the aqueous isocyanate curing agent is increased, the ionization degree of the aqueous isocyanate curing agent is improved, and the emulsification effect of the aqueous isocyanate curing agent is further enhanced. The high-efficiency wetting water-based isocyanate curing agent can reduce the surface tension of water to 26-29 mN/m, can increase the contact area of the water-based polyurethane adhesive on a base material when being added into the conventional water-based polyurethane adhesive, further improves the bonding strength, and has good bonding effect on hard TPR, polypropylene, polyethylene and other materials which are difficult to bond.

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.