阅读说明：本技术 一种聚氨酯高分子分散剂的制备方法 (Preparation method of polyurethane polymer dispersant ) 是由 颜承法 黄井然 黄启宾 张凯 王宾 张德东 于 2021-08-30 设计创作，主要内容包括：本发明公开了一种聚氨酯高分子分散剂的制备方法,包括以下步骤：将多聚磷酸与磷酸按1：0.8比例混合配制成无水磷酸；无水磷酸在40～46℃下搅拌；将脱脂纤维加入无水磷酸混合液中进行液化与聚乙二醇及丙三醇混合均匀；料液后与二异氰酸酯混合均匀进行聚合反应,得到聚合产物料液；封端反应得到聚氨酯高分子分散剂；将二元醇、催化剂和有机溶剂混合,之后与二异氰酸酯混合进行聚合反应,聚氨酯高分子分散剂与聚氨酯纤维分散剂混合,本发明的高分子分散剂制备方法通过纤维素液化后成为多元醇,将其用于聚氨酯的合成,选材成本低,能够节约成本,具有良好的阻燃性,燃烧时产生的有毒烟气较少,对环境友好,与粘合剂有良好的相容性。(The invention discloses a preparation method of a polyurethane polymer dispersant, which comprises the following steps: mixing polyphosphoric acid and phosphoric acid according to the proportion of 1: 0.8 proportion to prepare anhydrous phosphoric acid; stirring anhydrous phosphoric acid at 40-46 ℃; adding the degreased fiber into the anhydrous phosphoric acid mixed solution for liquefaction, and uniformly mixing with polyethylene glycol and glycerol; uniformly mixing the feed liquid with diisocyanate to perform polymerization reaction to obtain a polymerization product feed liquid; carrying out end-capping reaction to obtain a polyurethane macromolecular dispersant; the preparation method of the high molecular dispersing agent has the advantages that the high molecular dispersing agent is liquefied by the cellulose to form the polyol, and the polyol is used for synthesizing the polyurethane.)

1. A preparation method of a polyurethane polymer dispersant is characterized by comprising the following steps:

mixing polyphosphoric acid and phosphoric acid according to the proportion of 1: 0.8 proportion to prepare anhydrous phosphoric acid;

stirring anhydrous phosphoric acid at 40-46 ℃, naturally cooling for 2 hours, and then freezing, wherein the freezing temperature is controlled at 1-2 ℃;

adding the degreased fiber into the anhydrous phosphoric acid mixed solution for liquefaction, carrying out neutralization reaction, drying and crushing into powder;

uniformly mixing the powder with polyethylene glycol and glycerol, adding a foaming agent and a stabilizer and a catalyst, and uniformly stirring to obtain a feed liquid;

uniformly mixing the feed liquid with diisocyanate to perform polymerization reaction to obtain a polymerization product feed liquid;

mixing the polymerization product liquid with a blocking agent, and carrying out blocking reaction to obtain a polyurethane fiber dispersing agent;

(7) mixing dihydric alcohol, a catalyst and an organic solvent, then mixing the mixture with diisocyanate for polymerization reaction to obtain a polymerization product feed liquid, mixing the polymerization product feed liquid with a blocking agent, and then carrying out blocking reaction to obtain a polyurethane high molecular dispersant, wherein the content of the polyurethane high molecular dispersant and the polyurethane fiber dispersant is 4-10%: (90-96%) by mixing.

2. The method for producing a polyurethane polymer dispersant according to claim 1, wherein: the diisocyanate is one or a mixture of TDI, MDI, IPDI, HDI and NDI.

3. The method for producing a polyurethane polymer dispersant according to claim 1, wherein: the degreased fiber is flocculent plant containing more than 80% of cellulose.

4. The method for producing a polyurethane polymer dispersant according to claim 1, wherein: the mass ratio of the diisocyanate to the dihydric alcohol to the blocking agent to the catalyst to the organic solvent is (17-55): (12-24): (9-18): (0.1-2): (24-45).

5. The method for producing a polyurethane polymer dispersant according to claim 1, wherein: the temperature of the polymerization reaction is 65-75 ℃.

6. The method for producing a polyurethane polymer dispersant according to claim 1, wherein: and (4) carrying out neutralization reaction on the anhydrous phosphoric acid mixed solution in the step (3) by using ammonia water until the pH is = 7-7.5.

7. The method for producing a polyurethane polymer dispersant according to claim 1, wherein: and (7) foaming, solidifying and cooling the dispersant solution.

Technical Field

The invention relates to the technical field of high polymer materials, in particular to a preparation method of a polyurethane high polymer dispersant.

Background

The organic colorant has wide application, but common organic colorants generally have lipophilic benzene ring or heterocyclic ring structures, contain active amine groups, amide groups, carboxylic acid groups, ester groups, hydroxyl groups and the like on the surface, have strong intermolecular attraction force and are easy to agglomerate in a solution, so that a dispersing agent is often added to serve as a bridge between the organic colorant and a dispersing medium, so that the organic colorant can be stably dispersed in the solution. The waterborne polyurethane coating takes water as a main medium, has the characteristics of low VOC content, low or no environmental pollution, convenient construction and the like, is one of the main substitutes of solvent-based coatings, and has been widely applied in many fields, such as: wood lacquer and wood floor lacquer; coating paper; building coatings; coating leather; fabric coatings, and the like; however, the existing polyurethane has low flame retardance, and toxic smoke is generated if the polyurethane is burnt, so that the polyurethane is easy to cause damage to people and the environment.

Disclosure of Invention

The invention aims to provide a preparation method of a polyurethane polymer dispersant.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of a polyurethane polymer dispersant comprises the following steps:

(1) mixing polyphosphoric acid and phosphoric acid according to the proportion of 1: 0.8 proportion to prepare anhydrous phosphoric acid;

(2) stirring anhydrous phosphoric acid at 40-46 ℃, naturally cooling for 2 hours, and then freezing, wherein the freezing temperature is controlled at 1-2 ℃;

(3) adding the degreased fiber into the anhydrous phosphoric acid mixed solution for liquefaction, carrying out neutralization reaction, drying and crushing into powder;

(4) uniformly mixing the powder with polyethylene glycol and glycerol, adding a foaming agent and a stabilizer and a catalyst, and uniformly stirring to obtain a feed liquid;

(5) uniformly mixing the feed liquid with diisocyanate to perform polymerization reaction to obtain a polymerization product feed liquid;

(6) mixing the polymerization product feed liquid with a terminal capping agent, and then carrying out a terminal capping reaction to obtain a polyurethane macromolecular dispersant, wherein in the polycondensation reaction, active functional groups usually exist at two ends of a formed polymer, when a proper functional group exists, the chain end of a polymer molecule can still continuously participate in the reaction to grow the chain, and in order to eliminate the activity of the terminal group, a monofunctional compound can be added to eliminate the terminal group functional group;

(7) mixing dihydric alcohol, a catalyst and an organic solvent, then mixing the mixture with diisocyanate for polymerization reaction to obtain a polymerization product feed liquid, mixing the polymerization product feed liquid with a blocking agent, and then carrying out blocking reaction to obtain a polyurethane high molecular dispersant, wherein the content of the polyurethane high molecular dispersant and the polyurethane fiber dispersant is 4-10%: (90-96%) by mixing.

Preferably, the diisocyanate is one or a mixture of TDI, MDI, IPDI, HDI and NDI.

Preferably, the defatted fiber is a flocculent plant containing more than 80% cellulose.

Preferably, the mass ratio of the diisocyanate to the diol to the blocking agent to the catalyst to the organic solvent is (17-55): (12-24): (9-18): (0.1-2): (24-45).

Preferably, the temperature of the polymerization reaction is 65-75 ℃.

Preferably, in the step (3), the neutralization reaction of the anhydrous phosphoric acid mixed solution is carried out by ammonia water, and the neutralization is carried out until the pH = 7-7.5.

Preferably, the dispersant solution is foamed, solidified and cooled after step (7).

Compared with the prior art, the invention has the advantages that:

the preparation method of the high molecular dispersing agent disclosed by the invention is used for synthesizing polyurethane, has the advantages of low material selection cost, capability of saving cost, good flame retardance, less toxic smoke generated during combustion, environmental friendliness and good compatibility with an adhesive.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.

FIG. 1 is a graph of the thermal conductivity of polyurethane fiber dispersants of the present invention at different substitution rates.

Detailed Description

The preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings so that the advantages and features of the present invention can be more easily understood by those skilled in the art, and the scope of the present invention will be more clearly and clearly defined.

Example one

The invention provides a preparation method of a polyurethane polymer dispersant, which comprises the following steps: mixing polyphosphoric acid and phosphoric acid according to the proportion of 1: 0.8 proportion to prepare anhydrous phosphoric acid; stirring anhydrous phosphoric acid at 40 ℃, naturally cooling for 2h, and then freezing, wherein the freezing temperature is controlled at 1 ℃;

adding the degreased fiber into an anhydrous phosphoric acid mixed solution for liquefaction, carrying out neutralization reaction, drying and crushing into powder after the neutralization reaction is carried out until the pH =7, wherein the anhydrous phosphoric acid mixed solution is neutralized by ammonia water, the degreased fiber is a flocculent plant containing more than 80% of cellulose, can be used cotton wool, has the cellulose content of more than 90%, can perfectly replace polyhydric alcohol, and has low cost;

uniformly mixing the powder with polyethylene glycol and glycerol, adding a foaming agent and a stabilizer and a catalyst, and uniformly stirring to obtain a feed liquid; uniformly mixing the feed liquid with diisocyanate to perform polymerization reaction to obtain a polymerization product feed liquid, wherein the polymerization reaction temperature is 65 ℃, and the diisocyanate is one or a mixture of TDI, MDI, IPDI, HDI and NDI;

mixing the polymerization product liquid with a blocking agent, and carrying out blocking reaction to obtain a polyurethane fiber dispersing agent;

mixing dihydric alcohol, a catalyst and an organic solvent, then mixing the mixture with diisocyanate for polymerization reaction to obtain a polymerization product feed liquid, mixing the polymerization product feed liquid with a blocking agent, and then carrying out blocking reaction to obtain a polyurethane polymer dispersant, wherein the ratio of the polyurethane polymer dispersant to a polyurethane fiber dispersant is 4%: mixing at a ratio of 96%.

And then foaming, solidifying and cooling the dispersant solution, so as to facilitate subsequent storage, processing and experimental work.

The mass ratio of the diisocyanate to the dihydric alcohol to the blocking agent to the catalyst to the organic solvent is 17: 12: 9: 0.1: 24.

example two

Mixing polyphosphoric acid and phosphoric acid according to the proportion of 1: 0.8 proportion to prepare anhydrous phosphoric acid; stirring anhydrous phosphoric acid at 40-46 ℃, naturally cooling for 2 hours, and then freezing, wherein the freezing temperature is controlled at 2 ℃;

adding the degreased fiber into an anhydrous phosphoric acid mixed solution for liquefaction, carrying out neutralization reaction, neutralizing until the pH =7.3, then drying and crushing into powder, wherein the neutralization reaction of the anhydrous phosphoric acid mixed solution is carried out by ammonia water, and the degreased fiber is flocculent plants containing more than 80% of cellulose;

uniformly mixing the powder with polyethylene glycol and glycerol, adding a foaming agent and a stabilizer and a catalyst, and uniformly stirring to obtain a feed liquid; uniformly mixing the feed liquid with diisocyanate to perform polymerization reaction to obtain a polymerization product feed liquid, wherein the polymerization reaction temperature is 65-75 ℃, and the diisocyanate is one or a mixture of TDI, MDI, IPDI, HDI and NDI;

mixing the polymerization product liquid with a blocking agent, and carrying out blocking reaction to obtain a polyurethane fiber dispersing agent;

mixing dihydric alcohol, a catalyst and an organic solvent, then mixing the mixture with diisocyanate for polymerization reaction to obtain a polymerization product feed liquid, mixing the polymerization product feed liquid with a blocking agent, and then carrying out blocking reaction to obtain a polyurethane polymer dispersant, wherein the proportion of the polyurethane polymer dispersant to the polyurethane fiber dispersant is 8%: mixing at a ratio of 92%;

then foaming, solidifying and cooling the dispersant solution, so as to facilitate subsequent storage, processing and experimental work;

the mass ratio of the diisocyanate to the dihydric alcohol to the blocking agent to the catalyst to the organic solvent is 30: 20: 12: 0.15: 30.

EXAMPLE III

Mixing polyphosphoric acid and phosphoric acid according to the proportion of 1: 0.8 proportion to prepare anhydrous phosphoric acid; stirring anhydrous phosphoric acid at 46 ℃, naturally cooling for 2 hours, and then freezing, wherein the freezing temperature is controlled to be 1-2 ℃;

adding the degreased fiber into an anhydrous phosphoric acid mixed solution for liquefaction, carrying out neutralization reaction until the pH is =7.5, then drying and crushing into powder, wherein the neutralization reaction of the anhydrous phosphoric acid mixed solution is carried out by ammonia water, and the degreased fiber is a flocculent plant containing more than 80% of cellulose;

uniformly mixing the powder with polyethylene glycol and glycerol, adding a foaming agent and a stabilizer and a catalyst, and uniformly stirring to obtain a feed liquid; uniformly mixing the feed liquid with diisocyanate to perform polymerization reaction to obtain a polymerization product feed liquid, wherein the polymerization reaction temperature is 75 ℃, and the diisocyanate is one or a mixture of TDI, MDI, IPDI, HDI and NDI;

mixing the polymerization product liquid with a blocking agent, and carrying out blocking reaction to obtain a polyurethane fiber dispersing agent;

mixing dihydric alcohol, a catalyst and an organic solvent, then mixing the mixture with diisocyanate for polymerization reaction to obtain a polymerization product feed liquid, mixing the polymerization product feed liquid with a blocking agent, and then carrying out blocking reaction to obtain a polyurethane polymer dispersant, wherein the proportion of the polyurethane polymer dispersant to the polyurethane fiber dispersant is 10%: mixing at a ratio of 90%;

then foaming, solidifying and cooling the dispersant solution, so as to facilitate subsequent storage, processing and experimental work; and then foaming, solidifying and cooling the dispersant solution.

The mass ratio of the diisocyanate to the dihydric alcohol to the blocking agent to the catalyst to the organic solvent is 55: 24: 18: 2: 45.

the proportion of the polyurethane polymer dispersant to the polyurethane fiber dispersant is selected to be 0 percent as follows: 100%, 4%: 96% and 6%: 94%, 8%: 92% and 10%: carrying out an experiment on the powder after the five 90% mixed solutions are solidified and cooled;

the flame retardance of the five parts of powder can be analyzed by a calorimeter, the ignition time, the heat release speed and the heat release peak value of the five parts are detected, the detection result is shown in figure 1, the flame retardance of polyurethane can be obviously improved by mixing the polyurethane fiber dispersing agent, and when the substitution rate is 6%, each data is far larger than that of a part of 0%.

The ammonium salt formed by neutralizing the phosphoric acid with ammonia water imparts significant flame retardant properties to the polyurethane.

Although the embodiments of the present invention have been described with reference to the accompanying drawings, various changes or modifications may be made by the patentees within the scope of the appended claims, and within the scope of the invention, as long as they do not exceed the scope of the invention described in the claims.