阅读说明：本技术 一种磷腈衍生物改性mc尼龙及其制备方法 (Phosphonitrile derivative modified MC nylon and preparation method thereof ) 是由 李爱元 孙向东 董艳杰 陈碧芬 彭振博 苏倡 张慧波 于 2021-06-25 设计创作，主要内容包括：本发明涉及一种磷腈衍生物改性MC尼龙及其制备方法,属于高分子材料改性技术领域。本发明公开了一种磷腈衍生物改性MC尼龙,包括质量百分比分别为85-95％的己内酰胺和5-15％的磷腈衍生物,还包括催化剂、助催化剂。本发明同时公开了磷腈衍生物改性MC尼龙的制备方法,包括将己内酰胺和磷腈衍生物加入反应器,加热熔融后加入催化剂,在真空下反应,待熔体温度升至140-160℃保温15-30min,解除真空并停止加热,再加入助催化剂,搅匀后迅速注入已预热的模具中,将装有反应体系的模具置于干燥箱中进行聚合反应,反应完毕,冷却脱模,得到磷腈衍生物改性MC尼龙。本发明通过简单的工艺提升了MC尼龙的拉伸强度等性能。(The invention relates to phosphonitrile derivative modified MC nylon and a preparation method thereof, belonging to the technical field of modification of high polymer materials. The invention discloses a phosphonitrile derivative modified MC nylon, which comprises 85-95% of caprolactam and 5-15% of phosphonitrile derivative by mass, a catalyst and a cocatalyst. Adding caprolactam and phosphazene derivative into a reactor, heating and melting, adding a catalyst, reacting under vacuum, keeping the temperature of the melt at 160 ℃ for 15-30min after the temperature of the melt rises to 140-. The invention improves the properties of the MC nylon such as tensile strength and the like through a simple process.)

1. The phosphonitrile derivative modified MC nylon is characterized by comprising 85-95% of caprolactam and 5-15% of phosphonitrile derivative by mass percent respectively.

2. The modified MC nylon of claim 1, wherein the phosphazene derivative comprises one or more of hexaphenoxycyclotriphosphazene, hexaanilinocyclotriphosphazene, hexafluorocyclotriphosphazene, pentafluoro (phenoxy) cyclotriphosphazene, and hexap-carboxyphenoxycyclotriphosphazene.

3. The modified MC nylon of claim 1, further comprising one or both of a catalyst and a co-catalyst.

4. The modified MC nylon of claim 3, wherein the mass ratio of the catalyst, the cocatalyst and the caprolactam is (1-3): (4-7): 1000.

5. the modified MC nylon of claim 3 or claim 4, wherein the catalyst comprises one or more of sodium hydroxide and sodium methoxide.

6. The modified MC nylon of claim 3 or 4, wherein the co-catalyst comprises one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate.

7. A method for preparing the phosphazene derivative modified MC nylon of claim 1, which is characterized by comprising: adding caprolactam and phosphazene derivative into a reactor, heating and melting, adding a catalyst, reacting under vacuum, keeping the temperature for 15-30min when the temperature of a melt rises to 140-160 ℃, removing the vacuum and stopping heating, adding a cocatalyst, uniformly stirring, quickly injecting into a preheated mold, placing the mold filled with a reaction system into a drying box for polymerization reaction, and cooling and demolding after the reaction is finished to obtain the phosphazene derivative modified MC nylon.

8. The method as claimed in claim 7, wherein the heating and melting temperature is 140-160 ℃.

9. The method as claimed in claim 7, wherein the mold preheating temperature is 170-190 ℃.

10. The method as claimed in claim 7, wherein the polymerization process temperature is 170 ℃ and 190 ℃ and the time is 25-45 min.

Technical Field

The invention belongs to the technical field of high polymer material modification, and particularly relates to phosphonitrile derivative modified MC nylon and a preparation method thereof.

Background

MC nylon, also known as cast nylon, is a widely used engineering plastic, can replace steel and has excellent properties, has various unique properties such as light weight, high strength, self-lubrication, wear resistance, corrosion resistance, insulation and the like, and is almost applied to all industrial fields. However, MC nylon also has the disadvantages of poor acid resistance, low-temperature impact strength, high water absorption, flammability, etc., thus limiting its application.

CN110872380B discloses a graphene/MC nylon nanocomposite and a preparation method thereof, in the scheme, a dispersing agent is used to physically peel off a graphite raw material to prepare a graphene dispersion solution, so that graphene can be stably and uniformly dispersed in MC nylon without performing surface treatment on graphene, and the mechanical properties of the graphene/MC nylon nanocomposite are improved. CN103232595A discloses a modified MC nylon, which is improved in performance by adding a catalyst and an activator by adopting techniques such as reinforcement, toughening and the like, but has more additives and a complex process. Therefore, a novel modification mode which has easily available raw materials, simple and safe preparation process and suitability for industrialization is researched to improve the performance of the MC nylon.

Disclosure of Invention

The invention aims to solve the problems in the prior art and provide a phosphonitrile derivative modified MC nylon, which can improve the toughness of the MC nylon due to good compatibility of the phosphonitrile derivative and the MC nylon.

The above object of the present invention can be achieved by the following technical solutions:

the modified MC nylon comprises 85-95% of caprolactam and 5-15% of phosphazene derivative by mass percent respectively.

Preferably, the phosphazene derivative comprises one or more of hexaphenoxycyclotriphosphazene, hexaanilinocyclotriphosphazene, hexafluorocyclotriphosphazene, pentafluoro (phenoxy) cyclotriphosphazene and hexap-carboxyphenoxy cyclotriphosphazene.

Preferably, the modified MC nylon further comprises one or two of a catalyst and a cocatalyst.

Further preferably, the mass ratio of the catalyst, the cocatalyst and the caprolactam is (1-3): (4-7): 1000.

further preferably, the catalyst comprises one or more of sodium hydroxide and sodium methoxide.

Further preferably, the cocatalyst comprises one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate and dicyclohexylmethane diisocyanate.

The preparation method of the phosphonitrile derivative modified MC nylon comprises the following steps: adding caprolactam and phosphazene derivative into a reactor, heating and melting, then adding a catalyst, reacting under vacuum, keeping the temperature for 15-30min when the temperature of a melt rises to 140-160 ℃, removing the vacuum, stopping heating, adding a cocatalyst, stirring uniformly, then quickly injecting into a preheated mold, placing the mold filled with a reaction system into a drying box for polymerization reaction, and cooling and demolding after the reaction is finished to obtain the phosphazene derivative modified MC nylon.

Preferably, the heating and melting temperature is 140-160 ℃.

In this temperature range, the MC nylon is completely molten and does not evaporate due to excessive temperatures.

Preferably, the preheating temperature of the mold is 170-190 ℃.

The preheating of the die can protect the die from damage, difficult forming, cracks and the like caused by large temperature change.

Preferably, the temperature of the polymerization process is 170-190 ℃ and the time is 25-45 min.

At this polymerization temperature, the cocatalyst starts to act, and if the temperature is too low, the polymerization is not allowed, while if the temperature is too high, the raw material is vaporized and even imploded.

The invention has the beneficial effects that:

1. the phosphazene derivative has flame retardant property and good compatibility with MC nylon, and the combination of the phosphazene derivative and MC nylon can be used for preparing MC nylon modified products, so that the application field of the phosphazene derivative is widened, and the tensile strength, the notch impact strength, the acid resistance and the water absorption performance of the MC nylon products are greatly improved.

2. The preparation method of the modified MC nylon reduces the production cost by 5 percent, has high economic benefit and good application prospect, and is suitable for industrial production.

Detailed Description

The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.

Example 1

Adding caprolactam accounting for 95% of the total mass of the materials and hexaphenoxycyclotriphosphazene accounting for 5% of the total mass of the materials into a reactor, starting a vacuum pump, decompressing, heating and melting, adding sodium hydroxide at 140 ℃, reacting under vacuum, maintaining for 20min when the temperature of a melt rises to 140 ℃, relieving the vacuum, stopping heating, adding a cocatalyst of diphenylmethane diisocyanate, uniformly stirring, quickly injecting into a mold preheated to 180 ℃, placing the mold filled with a reaction system into a constant-temperature drying oven at 180 ℃, polymerizing for 30min, cooling and demolding to obtain the modified MC nylon.

Example 2

Adding caprolactam accounting for 90% of the total mass of the materials and hexaphenoxycyclotriphosphazene accounting for 10% of the total mass of the materials into a reactor, starting a vacuum pump, decompressing, heating and melting, adding sodium hydroxide at 160 ℃, reacting under vacuum, maintaining for 23min when the temperature of the melt rises to 160 ℃, removing the vacuum, stopping heating, adding a cocatalyst of toluene diisocyanate, uniformly stirring, quickly injecting into a mold preheated to 190 ℃, placing the mold filled with a reaction system into a constant-temperature drying oven at 190 ℃ for polymerization for 28min, cooling and demolding to obtain the modified MC nylon.

Example 3

Adding caprolactam accounting for 93 percent of the total mass of the materials and hexaaniline cyclotriphosphazene accounting for 7 percent of the total mass of the materials into a reactor, starting a vacuum pump to reduce pressure, heat and melt, adding sodium hydroxide at 160 ℃, reacting under vacuum, maintaining for 23min when the temperature of the melt rises to 160 ℃, relieving the vacuum, stopping heating, adding a cocatalyst of toluene diisocyanate, uniformly stirring, quickly injecting into a mold preheated to 190 ℃, placing the mold filled with a reaction system into a constant-temperature drying oven at 190 ℃ to polymerize for 28min, cooling and demolding to obtain the modified MC nylon.

Example 4

Adding caprolactam accounting for 91 percent of the total mass of the materials and pentafluoro (phenoxy) cyclotriphosphazene accounting for 9 percent of the total mass of the materials into a reactor, starting a vacuum pump to reduce pressure, heat and melt, adding sodium methoxide at 155 ℃, reacting under vacuum, maintaining for 26min when the temperature of the melt rises to 155 ℃, relieving vacuum, stopping heating, adding a cocatalyst of toluene diisocyanate, uniformly stirring, quickly injecting into a mold preheated to 165 ℃, placing the mold filled with a reaction system into a constant-temperature drying oven at 165 ℃ to polymerize for 25min, cooling and demolding to obtain the modified MC nylon.

Example 5

Adding caprolactam accounting for 75% of the total mass of the materials and hexafluorocyclotriphosphazene accounting for 25% of the total mass of the materials into a reactor, starting a vacuum pump, decompressing, heating and melting, adding sodium methoxide at 150 ℃, reacting under vacuum, maintaining the temperature of a melt at 150 ℃ for 30min, removing the vacuum, stopping heating, adding a cocatalyst dicyclohexylmethane diisocyanate, uniformly stirring, quickly injecting into a mold preheated to 180 ℃, placing the mold filled with a reaction system into a constant-temperature drying oven at 180 ℃ for polymerization for 40min, cooling and demolding to obtain the modified MC nylon.

Comparative example 1

The feed was changed to 100% caprolactam and the other steps were the same as in example 1.

Comparative example 2

The batch was changed to 94% caprolactam and 6% magnesium oxide by total mass, otherwise the same as in example 1.

The detection method of each technical index of the invention comprises the following steps:

(1) the tensile strength is tested according to GB/T1040-;

(2) the notch impact strength is tested according to GB/T1043-;

(3) the water absorption is tested according to GB/T1034-2008;

(4) and (3) testing acid resistance: and (3) placing the sample in octadecanoic acid at 25 ℃ for 48h, taking out, airing and weighing, and calculating the loss rate.

The results of the performance tests of the MC nylons of examples 1-5 and comparative examples 1-2 of the present invention are shown in Table 1:

table 1: performance test results of MC nylons in examples 1-5 and comparative examples 1-2

From the test results in table 1, it can be seen that the tensile strength of the modified MC nylon with the inorganic filler is significantly lower than that of the nylon body; the phosphazene derivative is adopted to modify MC nylon, and various performance indexes of the MC nylon are greatly improved, and particularly when the mass percentages of caprolactam and the phosphazene derivative are respectively 90% and 10%, the indexes are obviously improved.

In conclusion, the phosphonitrile derivative modified MC nylon has good tensile strength, and when the mass percentage of the caprolactam and the phosphonitrile derivative is in the range, various performance indexes are greatly improved. The preparation method is low in production cost, more economical and practical and suitable for industrial production.

The technical means disclosed by the scheme of the invention are not limited to the technical means disclosed by the technical means, and the technical scheme also comprises the technical scheme formed by any combination of the technical characteristics. While the foregoing is directed to embodiments of the present invention, it will be appreciated by those skilled in the art that various changes may be made in the embodiments without departing from the principles of the invention, and that such changes and modifications are intended to be included within the scope of the invention.

The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.