阅读说明：本技术 一种磷阻燃水性聚氨酯的制备方法 (Preparation method of phosphorus flame-retardant waterborne polyurethane ) 是由 王念贵 王亚红 龚齐瑞 于 2020-05-19 设计创作，主要内容包括：本发明公开了一种磷阻燃水性聚氨酯的制备方法,该方法通过采用9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物开环环氧大豆油制备含磷大豆油基多元醇；再以该多元醇为原料与二异氰酸酯、2,2-二羟甲基丙酸、N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯、中和剂、水和扩链剂等反应,得到具有阻燃性能好的水性聚氨酯。该方法反应时间短、生产效率高,且得到的水性聚氨酯颜色浅,有效降低颜填料对有色水性聚氨酯成膜后光泽度的影响。(The invention discloses a preparation method of phosphorus flame-retardant waterborne polyurethane, which is characterized in that phosphorus-containing soybean oil-based polyol is prepared by adopting 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide ring-opening epoxy soybean oil; and then the polyol is taken as a raw material to react with diisocyanate, 2-dimethylolpropionic acid, N-bis (2-hydroxyethyl) amino diethyl methylenephosphonate, a neutralizer, water, a chain extender and the like to obtain the waterborne polyurethane with good flame retardant property. The method has the advantages of short reaction time and high production efficiency, and the obtained waterborne polyurethane has a light color, so that the influence of the color filler on the glossiness of the colored waterborne polyurethane after film forming is effectively reduced.)

1. A preparation method of phosphorus flame-retardant waterborne polyurethane is characterized by comprising the following steps:

s1, mixing epoxidized soybean oil, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and a catalyst, heating to 180-190 ℃ under the condition of stirring, carrying out heat preservation reaction, sampling at intervals to determine the epoxy value, stopping the reaction until the epoxy value is close to a theoretical value, and obtaining the phosphorus-containing soybean oil-based polyol; the mol ratio of the epoxidized soybean oil to the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:2-2.2, and the content of the catalyst is 0.5-3% of the total mass of the epoxidized soybean oil and the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide;

s2, sequentially adding phosphorus-containing soybean oil-based polyol and diisocyanate into a reaction container, heating to 70-90 ℃, preserving heat for 1-2h, adding 2, 2-dimethylolpropionic acid, preserving heat for 1-2h, cooling to 50-70 ℃, adding N, N-bis (2-hydroxyethyl) amino diethyl methylenephosphonate, preserving heat for 1-2h, cooling to below 40 ℃, adding a neutralizing agent for neutralization to obtain a polyurethane prepolymer, adding deionized water for emulsification, adding a chain extender, and reacting for 0.5-2h to obtain phosphorus flame retardant waterborne polyurethane;

the molar ratio of the diisocyanate, the phosphorus-containing soybean oil-based polyol, the 2, 2-dimethylolpropionic acid, the diethyl N, N-bis (2-hydroxyethyl) aminomethylene phosphonate and the chain extender is 100:25-35:20-30:15-35: 10-20;

the mol ratio of the neutralizing agent to the 2, 2-dimethylolpropionic acid is 0.8-1.2: 1;

the mass ratio of the deionized water to the polyurethane prepolymer is 2-4: 1.

2. The method of preparing the phosphorus flame-retardant waterborne polyurethane of claim 1, wherein the epoxidized soybean oil in step S1 contains an average of 2.2 to 4 epoxy groups per molecule.

3. The method for preparing the phosphorus flame-retardant waterborne polyurethane as claimed in claim 1, wherein the catalyst in step S1 is one of triphenylphosphine, tetrabutylammonium bromide, N-dimethylbenzylamine or triethylamine.

4. The method for preparing the phosphorus flame-retardant waterborne polyurethane as claimed in claim 1, wherein the neutralizing agent in step S2 is one of ammonia, sodium hydroxide, triethylamine, triethanolamine, diethanolamine, and 2-amino-2-methyl-1-propanol, and the reaction time for neutralization is 10-30 min.

5. The method of claim 1, wherein the diisocyanate in step S2 is one of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, or lysine diisocyanate.

6. The method for preparing the phosphorus flame-retardant waterborne polyurethane as claimed in claim 1, wherein the chain extender in step S2 is one of ethylenediamine, diethylenetriamine and isophoronediamine.

7. The phosphorus flame-retardant aqueous polyurethane obtained by the production method according to any one of claims 1 to 6.

Technical Field

The invention belongs to the technical field of waterborne polyurethane, and particularly relates to a preparation method of phosphorus flame-retardant waterborne polyurethane.

Background

The soybean oil has wide sources, and the soybean oil and the derivatives thereof have good environmental protection and resource reproducibility. It contains active site, and can be chemically modified to introduce active functional group, so that it can be used as ideal monomer for synthesizing various polymers, and can be used for making various polymers with wide application range.

Waterborne Polyurethanes (WPUs) have attracted considerable attention as a promising environmentally friendly polymer with excellent processability. However, the use of WPU in coatings, leather, textiles, films and adhesives is greatly limited due to its inherent flammability. Therefore, improvement of poor flame retardancy of WPU is urgently required to increase its applications.

Disclosure of Invention

In view of the above, the invention provides a preparation method of phosphorus flame-retardant waterborne polyurethane, which comprises the steps of ring-opening epoxidized soybean oil by using a phosphorus-containing reagent to obtain a flame-retardant monomer with better flame-retardant performance, and then preparing the waterborne polyurethane by using the monomer as a raw material; the waterborne polyurethane prepared by the method has light color and good flame retardant property.

In order to achieve the above purpose, the technical scheme of the invention is as follows:

a preparation method of phosphorus flame-retardant waterborne polyurethane comprises the following steps:

s1, mixing epoxidized soybean oil, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and a catalyst, heating to 180-190 ℃ under the condition of stirring, carrying out heat preservation reaction, sampling at intervals, measuring the epoxy value, stopping the reaction until the epoxy value is close to a theoretical value, and obtaining phosphorus-containing soybean oil-based polyol (DESO); the mol ratio of the epoxidized soybean oil to the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:2-2.2, and the content of the catalyst is 0.5-3% of the total mass of the epoxidized soybean oil and the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide;

s2, sequentially adding phosphorus-containing soybean oil-based polyol and diisocyanate into a reaction container, heating to 70-90 ℃, preserving heat for 1-2h, adding 2, 2-dimethylolpropionic acid (DMPA), preserving heat for 1-2h, cooling to 50-70 ℃, adding N, N-bis (2-hydroxyethyl) amino diethyl methylenephosphonate (FEC-6), preserving heat for 1-2h, cooling to below 40 ℃, adding a neutralizer for neutralization to obtain a polyurethane prepolymer, adding deionized water for emulsification, adding a chain extender for reaction for 0.5-2h, and obtaining phosphorus flame retardant waterborne polyurethane;

the molar ratio of the diisocyanate, the phosphorus-containing soybean oil-based polyol, the 2, 2-dimethylolpropionic acid, the diethyl N, N-bis (2-hydroxyethyl) aminomethylene phosphonate and the chain extender is 100:25-35:20-30:15-35: 10-20;

the mol ratio of the neutralizing agent to the 2, 2-dimethylolpropionic acid is 0.8-1.2: 1;

the mass ratio of the deionized water to the polyurethane prepolymer is 2-4: 1.

Preferably, the epoxidized soybean oil in step S1 contains an average of 2.2 to 4 epoxy groups per molecule.

Preferably, the catalyst in step S1 is one of triphenylphosphine, tetrabutylammonium bromide, N-dimethylbenzylamine or triethylamine.

Preferably, the neutralizing agent in step S2 is one of ammonia, sodium hydroxide, triethylamine, triethanolamine, diethanolamine, and 2-amino-2-methyl-1-propanol, and the reaction time of the neutralization is 10-30 min;

preferably, the diisocyanate in step S2 is one of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, or lysine diisocyanate.

Preferably, in step S2, the chain extender is one of ethylenediamine, diethylenetriamine, and isophoronediamine.

The invention has the beneficial effects that:

1) the phosphorus-containing soybean oil-based polyol (DESO) is obtained by ring-opening epoxidized soybean oil with 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, the reaction operation steps are simple, the ring opening is sufficient, and the content of the reaction hydroxyl is easy to control. The flame-retardant monomer (DESO) is prepared from bio-based soybean oil as a raw material, has good biocompatibility, is biodegradable, and is beneficial to environmental protection. The DESO has good compatibility with other monomers in the polyurethane.

2) The flame retardant effect is greatly improved by the matching use of the DESO and the FEC-6.

3) The epoxidized soybean oil with high epoxy value has the characteristic of light color, probably because more oxidants are needed for preparing the epoxidized soybean oil with high epoxy value and the reaction time is longer, so that the pigment in the soybean oil is damaged, and the color is lighter; the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is white solid powder, the prepared phosphorus-containing soybean oil-based polyol is basically colorless transparent liquid, so that the prepared waterborne polyurethane also has a light color, the later color blending of the phosphorus-containing soybean oil-based waterborne polyurethane is facilitated, the using amount of the color filler is reduced, and the influence of the color filler on the glossiness of the colored waterborne polyurethane after film forming is effectively reduced.

4) The prepared waterborne polyurethane has low viscosity, is easier to be uniformly mixed with pigment or other substances, and is beneficial to use.

Detailed Description

The present invention is further illustrated below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention.