阅读说明：本技术 一种聚烯烃纤维料用复合助剂及其制备方法 (Composite auxiliary agent for polyolefin fiber material and preparation method thereof ) 是由 孙秀平 李英杰 彭令才 于 2020-06-15 设计创作，主要内容包括：本发明公开了一种聚烯烃纤维料用复合助剂及其制备方法,涉及塑料助剂技术领域,为解决现有技术中的聚烯烃纤维料其本身的强度和耐磨性较为优越,可以用于消防服饰的生产制作,但其本身并不具备阻燃性和抗静电功能的问题。所述按如下比重配比：1-十六烷醇28.5％,氧氯化磷9.5％,蒸馏水4.5％,氢氧化钾7.5％,三羟甲基丙烷16％,亚膦酸三甲酯17.5％,甲基膦酸二甲酯16.5％。将三羟甲基丙烷先投入釜中,加热至130℃使其溶解。随后加入1-十六烷醇,加热至50℃时1-十六烷醇熔解,加热至55℃时加入氧氯化磷。然后加入亚膦酸三甲酯和催化剂,加热至65～70℃,并维持5～6小时,控制加热反应釜温度升至70～75℃,亚膦酸三甲酯与三羟甲基丙烷通过催化剂会生成副产物甲醇。(The invention discloses a composite auxiliary agent for a polyolefin fiber material and a preparation method thereof, relates to the technical field of plastic auxiliary agents, and aims to solve the problems that the polyolefin fiber material in the prior art is superior in strength and wear resistance, can be used for producing fire-fighting clothes, and does not have flame retardance and antistatic function. The formula comprises the following components in percentage by weight: 28.5 percent of 1-hexadecanol, 9.5 percent of phosphorus oxychloride, 4.5 percent of distilled water, 7.5 percent of potassium hydroxide, 16 percent of trimethylolpropane, 17.5 percent of trimethyl phosphonite and 16.5 percent of dimethyl methylphosphonate. Trimethylolpropane is first put into a kettle and heated to 130 ℃ to be dissolved. Adding 1-hexadecanol, heating to 50 deg.C, melting 1-hexadecanol, heating to 55 deg.C, and adding phosphorus oxychloride. And then adding trimethyl phosphonite and a catalyst, heating to 65-70 ℃, maintaining for 5-6 hours, controlling the temperature of the heating reaction kettle to rise to 70-75 ℃, and allowing trimethyl phosphonite and trimethylolpropane to pass through the catalyst to generate a byproduct methanol.)

1. The composite additive for the polyolefin fiber material is characterized by comprising the following components in parts by weight: 28.5 percent of 1-hexadecanol, 9.5 percent of phosphorus oxychloride, 4.5 percent of distilled water, 7.5 percent of potassium hydroxide, 16 percent of trimethylolpropane, 17.5 percent of trimethyl phosphonite and 16.5 percent of dimethyl methylphosphonate.

2. The preparation method of the composite auxiliary agent for the polyolefin fiber material is characterized by comprising the following steps:

the method comprises the following steps: putting trimethylolpropane into a kettle, and heating to 130 ℃ to dissolve the trimethylolpropane;

step two: adding 1-hexadecanol, heating to 50 deg.C, melting 1-hexadecanol, heating to 55 deg.C, and adding phosphorus oxychloride;

step three: then adding trimethyl phosphonite and a catalyst, heating to 65-70 ℃, and maintaining for 5-6 hours;

step four: controlling the temperature of the heating reaction kettle to rise to 70-75 ℃, and allowing trimethyl phosphonite and trimethylolpropane to pass through a catalyst to generate a byproduct methanol;

step five: after the methanol is recovered, adding distilled water, controlling the temperature at 75 ℃, and continuously heating for about one hour;

step six: heating to 80 ℃, adding potassium hydroxide for reaction for one hour, thereby obtaining an alkyl phosphate solution;

step seven: after the solution is prepared, heating to 160 ℃, preserving the heat for 1-2 hours, and adding dimethyl methylphosphonate and a catalyst;

step eight: and finally, after the reaction is carried out for 7-8 hours under the condition of heat preservation, adding a catalyst, and reacting for 4-5 hours to enable the prepared alkyl phosphate solution to be blended with the phosphonate solution, thereby obtaining the antistatic flame-retardant composite additive.

3. The method for preparing the composite auxiliary agent for polyolefin fiber material according to claim 2, wherein the composite auxiliary agent comprises: in the third step, the catalyst is an acidic catalyst, wherein the acidic catalyst comprises one or a mixture of sulfuric acid, sulfonic acid and phosphoric acid.

4. The method for preparing the composite auxiliary agent for polyolefin fiber material according to claim 2, wherein the composite auxiliary agent comprises: in the fourth step, the catalyst used is a mixture of sodium methoxide and sodium ethoxide.

5. The method for preparing the composite auxiliary agent for polyolefin fiber material according to claim 2, wherein the composite auxiliary agent comprises: in the eighth step, the heat preservation temperature needs to be maintained at 160-170 ℃, and under the condition that the molecular structure of the prepared alkyl phosphate salt solution is not changed, the phosphonate solution generated by the reaction of dimethyl methylphosphonate, trimethyl phosphinate and trimethylolpropane and the alkyl phosphate salt solution are mutually fused together.

6. The method for preparing the composite auxiliary agent for polyolefin fiber material according to claim 2, wherein the composite auxiliary agent comprises: in the step eight, the catalyst used is a mixture of halogenated alkane Australian ethane and Australian isobutane.

Technical Field

The invention relates to the technical field of plastic additives, in particular to a composite additive for polyolefin fiber materials and a preparation method thereof.

Background

The plastic additives are compounds which are necessary to be added for improving the processability of polymers (synthetic resins) during molding and processing or for improving the properties of the resins themselves. Wherein the antistatic agent functions to reduce the surface resistance of the polymer article and eliminate the electrostatic hazard that can result from static buildup. The antistatic agent may be classified into an internal type and an application type according to the use pattern. The internal antistatic agent is added or blended into a plastic formula, and is transferred to the surface from the inside of a product or forms a conductive network after being formed, so that the aim of reducing surface resistance and discharging charges is fulfilled. The coating type antistatic agent is attached to the surface of the plastic product in a coating or wetting manner, thereby absorbing moisture in the environment and forming an electrolyte layer capable of discharging charges. From the viewpoint of chemical composition, conventional antistatic agents are almost without exception surfactant compounds including quaternary ammonium salt cationic surfactants, alkyl sulfonate anionic surfactants, nonionic surfactants such as alkanolamines, alkanolamides and polyol fatty acid esters, and the like. However, the recent emergence of "high molecular weight permanent antistatic agents" has broken this convention in that they are generally hydrophilic block copolymers which are compounded in a blended alloy with a base resin to conduct charge by forming conductive channels. Compared with the surfactant antistatic agent, the high molecular weight permanent antistatic agent has no loss caused by migration, volatilization and extraction, so that the antistatic property is durable and stable and is hardly influenced by the environmental humidity.

However, the existing polyolefin fiber material has superior strength and wear resistance, can be used for producing fire-fighting clothes, and does not have the functions of flame retardance and static resistance; therefore, the existing requirements are not met, and a composite auxiliary agent for polyolefin fiber materials and a preparation method thereof are provided.

Disclosure of Invention

The invention aims to provide a composite auxiliary agent for a polyolefin fiber material and a preparation method thereof, and aims to solve the problems that the polyolefin fiber material provided in the background technology has relatively excellent strength and wear resistance, can be used for producing fire-fighting clothes, and does not have flame retardance and antistatic function.

In order to achieve the purpose, the invention provides the following technical scheme: a composite auxiliary agent for polyolefin fiber materials comprises the following components in parts by weight: 28.5 percent of 1-hexadecanol, 9.5 percent of phosphorus oxychloride, 4.5 percent of distilled water, 7.5 percent of potassium hydroxide, 16 percent of trimethylolpropane, 17.5 percent of trimethyl phosphonite and 16.5 percent of dimethyl methylphosphonate.

A preparation method of a composite auxiliary agent for polyolefin fiber materials comprises the following steps:

the method comprises the following steps: putting trimethylolpropane into a kettle, and heating to 130 ℃ to dissolve the trimethylolpropane;

step two: adding 1-hexadecanol, heating to 50 deg.C, melting 1-hexadecanol, heating to 55 deg.C, and adding phosphorus oxychloride;

step three: then adding trimethyl phosphonite and a catalyst, heating to 65-70 ℃, and maintaining for 5-6 hours;

step four: controlling the temperature of the heating reaction kettle to rise to 70-75 ℃, and allowing trimethyl phosphonite and trimethylolpropane to pass through a catalyst to generate a byproduct methanol;

step five: after the methanol is recovered, adding distilled water, controlling the temperature at 75 ℃, and continuously heating for about one hour;

step six: heating to 80 ℃, adding potassium hydroxide for reaction for one hour, thereby obtaining an alkyl phosphate solution;

step seven: after the solution is prepared, heating to 160 ℃, preserving the heat for 1-2 hours, and adding dimethyl methylphosphonate and a catalyst;

step eight: and finally, after the reaction is carried out for 7-8 hours under the condition of heat preservation, adding a catalyst, and reacting for 4-5 hours to enable the prepared alkyl phosphate solution to be blended with the phosphonate solution, thereby obtaining the antistatic flame-retardant composite additive.

Preferably, in the third step, the catalyst used is an acidic catalyst, which includes one or a mixture of sulfuric acid, sulfonic acid and phosphoric acid.

Preferably, in the fourth step, the catalyst used is a mixture of sodium methoxide and sodium ethoxide.

Preferably, in the step eight, the heat preservation temperature needs to be maintained at 160-170 ℃, and under the condition that the molecular structure of the prepared alkylphosphate solution is not changed, the phosphonate solution generated by the reaction of dimethyl methylphosphonate, trimethyl phosphonite and trimethylolpropane and the alkylphosphate solution are mutually fused.

Preferably, in the eighth step, the catalyst used is a mixture of halogenated alkane, namely Austethane and Austenitic isobutane.

Compared with the prior art, the invention has the beneficial effects that:

1. when the mixture of the alkyl phosphate ester salt of the invention is in a molten state, molecules of the antistatic agent form the densest orientation arrangement at the interface between the resin and the air or between the resin and the metal, wherein the lipophilic group extends to the inside of the resin, the hydrophilic group extends to the outside of the resin, after the resin is cured, the hydrophilic groups on the molecules of the antistatic agent are all arranged towards the air side to form a monomolecular conducting layer, the antistatic performance of the antistatic agent molecule layer on the surface of the material is reduced along with the defect after the processing and the use through stretching, rubbing, washing and the like, but different from an external coating type antistatic agent, the molecules of the antistatic agent in the material continuously migrate to the surface after a period of time, so that the defect part is recovered, and the antistatic effect is displayed again, because the antistatic agent of the two types of the antistatic agent can achieve the antistatic purpose through absorbing the environmental moisture and reducing the, therefore, the dependence on the environmental humidity is larger, the higher the environmental humidity is, the stronger the water absorption of antistatic agent molecules is, and the more remarkable the antistatic performance is, and the compound auxiliary agent has the flame retardant and antistatic performance by matching with the traditional cyclic phosphonate solution.

2. The invention has the advantages of perfect process, standard operation, no solvent, no toxicity or harm of reaction medium and by-products, no corrosion to equipment, no halogen in the product, contribution to human health and environmental protection and lower production cost. The flame retardant prepared by the method has high phosphorus content, good water solubility, low volatility and good intermiscibility with most high molecular compounds, can be widely used for the flame retardant treatment of fabrics such as building, automobile interior decoration cloth, curtain cloth, special work clothes and the like, particularly terylene and polyester-cotton blended fabrics and polyurethane coating fabrics, has permanent and washable flame retardant function after the treatment, has wide application, has high thermal stability and has little influence on the hand feeling after the treatment.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments.

The embodiment provided by the invention comprises the following steps: a composite auxiliary agent for polyolefin fiber materials comprises the following components in parts by weight: 28.5 percent of 1-hexadecanol, 9.5 percent of phosphorus oxychloride, 4.5 percent of distilled water, 7.5 percent of potassium hydroxide, 16 percent of trimethylolpropane, 17.5 percent of trimethyl phosphonite and 16.5 percent of dimethyl methylphosphonate.

A preparation method of a composite auxiliary agent for polyolefin fiber materials comprises the following steps:

the method comprises the following steps: putting trimethylolpropane which is an important fine chemical product into a kettle, heating to 130 ℃ to dissolve the trimethylolpropane, wherein the melting point of the trimethylolpropane is 56-60 ℃, 3 hydroxymethyl groups exist in a molecular structure, the trimethylolpropane can react with organic acid to generate monoester or multiester, the multiester can react with aldehyde and ketone to generate acetal and ketal, and the acetal and ketal can react with diisocyanate to generate carbamate;

step two: adding 1-hexadecanol, heating to 50 deg.C, melting 1-hexadecanol, heating to 55 deg.C, and adding phosphorus oxychloride;

step three: then adding trimethyl phosphonite and a catalyst, heating to 65-70 ℃, and maintaining for 5-6 hours, wherein in trimethyl phosphite molecules, a phosphorus atom has a lone pair electron, and the lone pair electron can attack a carbon atom with electropositivity to form a phosphonate compound and can attack other heteroatoms with electropositivity, for example, attack an azide compound to obtain phosphoramide;

step four: controlling the temperature of the heating reaction kettle to rise to 70-75 ℃, and allowing trimethyl phosphonite and trimethylolpropane to pass through a catalyst to generate a byproduct methanol;

step five: the method comprises the following steps of (1) recovering methanol, adding distilled water, detecting the amount of the methanol in a reaction kettle after the methanol is recovered, carrying out subsequent processing reaction after the methanol reaches the standard, controlling the temperature at 75 ℃, and continuously heating for about one hour;

step six: heating to 80 ℃, adding potassium hydroxide for reaction for one hour, thereby obtaining an alkyl phosphate solution;

step seven: after the solution is prepared, heating to 160 ℃, preserving the heat for 1-2 hours, and adding dimethyl methylphosphonate and a catalyst;

step eight: and finally, after the reaction is carried out for 7-8 hours under the condition of heat preservation, adding a catalyst, and reacting for 4-5 hours to enable the prepared alkyl phosphate solution to be blended with the phosphonate solution, thereby obtaining the antistatic flame-retardant composite additive.

Further, in the third step, the catalyst used is an acidic catalyst, which includes one or a mixture of sulfuric acid, sulfonic acid and phosphoric acid.

Further, in the fourth step, the catalyst used is a mixture of sodium methoxide and sodium ethoxide.

Further, in the eighth step, the heat preservation temperature needs to be maintained at 160-170 ℃, and under the condition that the molecular structure of the prepared alkyl phosphate salt solution is not changed, the phosphonate solution generated by the reaction of dimethyl methylphosphonate, trimethyl phosphinate and trimethylolpropane and the alkyl phosphate salt solution are mutually fused together.

Further, in the eighth step, the catalyst used is a mixture of halogenated alkane, namely Austanethane and Austanebutane.

The working principle is as follows: when the catalyst is used, trimethylolpropane is firstly put into a kettle, the trimethylolpropane is heated to 130 ℃ to be dissolved, then 1-hexadecanol is added, the 1-hexadecanol is dissolved when the trimethylolpropane is heated to 50 ℃, phosphorus oxychloride is added when the trimethylolpropane is heated to 55 ℃, then trimethyl phosphonite and a catalyst are added, the type of the catalyst is an acidic catalyst, the catalyst comprises one or two of sulfuric acid, sulfonic acid or phosphoric acid, the trimethyl phosphonite and the phosphoric acid are heated to 65-70 ℃ and maintained for 5-6 hours, the temperature of the heating reaction kettle is controlled to be raised to 70-75 ℃, a byproduct methanol is generated by the trimethyl phosphonite and the trimethylolpropane through the catalyst, the catalyst is a mixture of sodium methoxide and sodium ethoxide, distilled water is added after the methanol is recovered, the temperature is controlled to be 75 ℃, the heating is continued for about one hour, the temperature is raised to 80 ℃, potassium hydroxide is added for reacting for one hour, and therefore, the alkyl phosphate solution is obtained, and heating the prepared solution to 160 ℃, preserving heat for 1-2 hours, adding dimethyl methyl phosphonate and a catalyst, wherein the catalyst is a mixture of sodium methoxide and sodium ethoxide, preserving heat for reaction for 7-8 hours, then adding the catalyst, the catalyst is a mixture of haloalkane Australian ethane and Australian isobutane, reacting for 4-5 hours, and preserving heat at 160-170 ℃, and mutually melting a product phosphonate solution generated by the reaction of dimethyl methyl phosphonate, trimethyl phosphonite and trimethylolpropane and an alkyl phosphate solution under the condition of keeping the molecular structure of the prepared alkyl phosphate solution unchanged, thereby obtaining the antistatic flame-retardant composite additive.

It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.