阅读说明：本技术 一种消光剂和消光尼龙6材料及其制备方法 (Delustering agent, delustering nylon 6 material and preparation method thereof ) 是由 伍千新 李先华 肖朝晖 姚亮红 于 2018-07-30 设计创作，主要内容包括：本发明公开了一种消光剂和消光尼龙6材料及其制备方法,消光剂包括由三聚氰胺类化合物和三聚氰酸类化合物反应生成三聚氰胺三聚氰酸盐类；采用消光剂用于制备纤维级消光尼龙6材料的方法：将三聚氰胺类化合物、三聚氰酸类化合物、二元羧酸、二元伯胺及水加入到熔融己内酰胺液体中,剪切分散,得到分散液；所述分散液与熔融己内酰胺液体一起进入聚合系统进行开环聚合,即得消光尼龙6材料。该消光剂成本低廉,与己内酰胺互溶,分散稳定,具有较好的消光性能,制备的聚己内酰胺具有更好的力学性能,如冲击强度和拉伸强度等性能优异。(The invention discloses a delustering agent, a delustering nylon 6 material and a preparation method thereof, wherein the delustering agent comprises melamine cyanurate which is generated by the reaction of melamine compounds and cyanuric acid compounds; the method for preparing the fiber-grade extinction nylon 6 material by adopting the extinction agent comprises the following steps: adding a melamine compound, a cyanuric acid compound, dicarboxylic acid, primary diamine and water into molten caprolactam liquid, and shearing and dispersing to obtain a dispersion liquid; and (3) allowing the dispersion liquid and the molten caprolactam liquid to enter a polymerization system for ring-opening polymerization to obtain the extinction nylon 6 material. The delustering agent is low in cost, is mutually soluble with caprolactam, is stable in dispersion, has good delustering performance, and the prepared polycaprolactam has better mechanical properties, such as excellent impact strength, tensile strength and the like.)

1. A matting agent for fiber-grade matting nylon 6 material, characterized in that: comprises melamine cyanurate salt generated by the reaction of melamine compound and cyanuric acid compound;

the melamine compound has a structure of formula 1:

the cyanuric acid compound has the structure of formula 2:

wherein R is ₁～R ₉Independently selected from hydrogen, alkyl or aryl.

2. A matting agent for fibre grade matting nylon 6 material according to claim 1 characterised in that: the alkyl group is C ₁～C ₁₀Alkyl groups of (a); the aryl is phenyl or substituted phenyl.

3. A matting agent for fibre grade matting nylon 6 material according to claim 1 or 2 characterised in that: the melamine compound comprises melamine, monoalkyl substituted melamine or dialkyl substituted melamine; the cyanuric acid compound comprises cyanuric acid, monoalkyl cyanuric acid and dialkyl cyanuric acid.

4. A matting agent for fibre grade matting nylon 6 material according to claim 3 characterised in that: the melamine compound is melamine; the cyanuric acid compound is cyanuric acid.

5. A matting agent for fiber grade matting nylon 6 material according to any one of claims 1 to 4, characterized in that: the molar ratio of the melamine compound to the cyanuric acid compound is 1-3: 1-3.

6. A matting agent for fibre grade matting nylon 6 material according to claim 5 characterised in that: the molar ratio of the melamine compound to the cyanuric acid compound is 1: 1.

7. A fiber-grade delustering nylon 6 material is characterized in that: the matting agent is obtained by carrying out melt ring-opening polymerization on raw materials comprising the matting agent as defined in any one of claims 1 to 6, dicarboxylic acid, primary diamine, caprolactam and water.

8. The fiber grade matted nylon 6 material of claim 7, wherein: the mass of the flatting agent accounts for 1-6% of the mass of caprolactam.

9. The fiber grade matted nylon 6 material of claim 7, wherein: the mass of the water accounts for 0.5-10% of the mass of the caprolactam.

10. A fiber grade matting nylon 6 material according to claim 12 characterized in that: the mass of the dicarboxylic acid accounts for 1-3% of the mass of caprolactam; the mass of the primary diamine accounts for 1-3% of the mass of caprolactam.

11. A fiber grade matting nylon 6 material according to claim 10, characterized in that: the dicarboxylic acid comprises saturated aliphatic hydrocarbon dicarboxylic acid and/or dicarboxyl substituted aromatic hydrocarbon; the primary diamine includes saturated aliphatic hydrocarbon primary diamine and/or diamino substituted aromatic hydrocarbon.

12. A fiber grade matting nylon 6 material according to claim 11, characterized in that: the saturated aliphatic hydrocarbon dicarboxylic acid comprises at least one of malonic acid, succinic acid, glutaric acid and adipic acid; the dicarboxy substituted aromatic hydrocarbon comprises terephthalic acid and/or isophthalic acid; the saturated aliphatic hydrocarbon dibasic primary amine comprises at least one of propane diamine, butane diamine, pentane diamine and 1, 6-hexane diamine; the diamino substituted aromatic hydrocarbon comprises p-phenylenediamine and/or m-phenylenediamine.

13. The preparation method of the fiber-grade extinction nylon 6 material as claimed in any one of claims 7 to 12, is characterized in that: adding a melamine compound, a cyanuric acid compound, dicarboxylic acid, primary diamine and water into molten caprolactam liquid, and shearing and dispersing to obtain a dispersion liquid; and (3) allowing the dispersion liquid and the molten caprolactam liquid to enter a polymerization system for ring-opening polymerization to obtain the extinction nylon 6 material.

14. The method for preparing the fiber-grade delustered nylon 6 material as claimed in claim 13, wherein the method comprises the following steps: the ring-opening polymerization adopts a VK tube continuous polymerization mode of polymerization before pressurization and polymerization after depressurization.

Technical Field

The invention relates to a delustering agent, in particular to a delustering agent containing a triazine structure, a delustering nylon 6 material prepared by using the triazine delustering agent and a preparation method of the delustering nylon 6 material, and belongs to the technical field of preparation of nylon 6 materials.

Background

According to the classification of the industry standard FZ/T5104-2011 fiber grade polycaprolactam slices, the nylon 6 slices are generally divided into bright slices (the mass percentage of titanium dioxide is less than or equal to 0.05%), semi-dull slices (the mass percentage of titanium dioxide is more than 0.1% and less than 0.6%) and full-dull slices (the mass percentage of titanium dioxide is more than or equal to 1.2%) according to the mass fraction of titanium dioxide added into a nylon 6 matrix resin; the light, semi-dull and full dull filaments and the engineering plastics thereof can be respectively prepared by using the slices.

The existing methods for preparing the nylon extinction slice comprise the following two methods: one is titanium dioxide as delustering agent, titanium dioxide powder is dispersed in melted caprolactam and ground by a ball mill or other mechanical dispersing equipment, and then the titanium dioxide powder is added into a caprolactam hydrolytic ring-opening system to be prepared in a continuous polymerization mode; the other method is to pre-mix the superfine titanium dioxide powder, the surface treating agent and the nylon 6 chip resin, and then melt, blend and granulate the mixture through a double-screw extruder to obtain the titanium dioxide powder. The flatting agent adopted by the two methods is titanium dioxide powder, and the titanium dioxide is a high-strength inorganic metal oxide, so that the material is high in price and high in stability, and the material is unevenly and unstably dispersed in caprolactam or nylon 6 melt, so that special equipment is required to be adopted for grinding and dispersing to ensure that the slice quality meets the spinning requirement, the difficulty in equipment selection is increased, the time consumption and the manufacturing cost are increased, and the nylon 6 slice is subjected to secondary heating by adopting a blending method to influence the comprehensive performance of the material.

Disclosure of Invention

Aiming at the defects that the existing matting agents made of metal oxides such as titanium dioxide and the like have uneven and unstable dispersion, increase the processing cost of polycaprolactam and influence the performance of the polycaprolactam in the use process of fiber-grade polycaprolactam materials, the invention aims to provide the matting agent which is mutually soluble with caprolactam, stable in dispersion, better in matting performance, free from influencing the performances such as the impact strength, the tensile strength and the like of the polycaprolactam and low in cost.

The second purpose of the invention is to provide a fiber-grade full-dull nylon material which has better mechanical properties compared with the existing dull nylon material, and particularly has obvious advantages in the aspects of impact strength, tensile strength and the like.

The third purpose of the invention is to provide a method for preparing the fiber-grade full-dull nylon material, which is simple to operate and low in cost.

In order to achieve the technical purpose, the invention provides a flatting agent for a fiber-grade flatting nylon 6 material, which comprises melamine cyanurate salts generated by the reaction of a melamine compound and a cyanuric acid compound;

the melamine compound has a structure of formula 1:

the cyanuric acid compound has the structure of formula 2:

wherein R is ₁～R ₉Independently selected from hydrogen, alkyl Or aryl radicals。

In a preferred embodiment, the alkyl group is C ₁～C ₁₀The alkyl group of (2) is preferably a short chain alkyl group, and the alkyl group may be a straight chain alkyl group or a branched chain alkyl group. Preferred alkyl is C ₁～C ₅Alkyl group of (1). Such as methyl, ethyl, propyl, n-butyl, isobutyl, and the like.

In a preferred embodiment, the aryl group is phenyl or substituted phenyl. The substituted phenyl group is generally a phenyl group having the usual groups, e.g. halogen, alkyl (C) ₁～C ₅) Alkoxy (C) ₁～C ₅) And the like.

More preferably, the melamine compound comprises melamine, mono-alkyl substituted melamine or dialkyl substituted melamine. Most preferred is melamine.

In a preferred embodiment, the cyanuric acid compound comprises cyanuric acid, monoalkyl cyanuric acid or dialkyl substituted cyanuric acid. Cyanuric acid is most preferred.

The organic quaternary ammonium salt has good extinction property and good compatibility with polycaprolactam, can be dispersed in polycaprolactam in a molecular level, has good dispersion stability, and does not influence the mechanical property of the polycaprolactam. Compared with the existing common flatting agent titanium dioxide, the titanium dioxide has obvious advantages in both cost and performance.

Preferably, the molar ratio of the melamine compound to the cyanuric acid compound is 1-3: 1-3. Most preferably 1: 1. Within the preferred ratio ranges, stable melamine cyanurate salts are most readily obtained.

The invention also provides a fiber-grade extinction nylon 6 material which is prepared by carrying out melt ring-opening polymerization on raw materials including an extinction agent, dicarboxylic acid, primary diamine, caprolactam and water.

In a preferable scheme, the mass of the flatting agent accounts for 1-6% of the mass of caprolactam. Preferably 1 to 2%. Compared with the titanium dioxide delustering agent with the same effect, the delustering agent has the advantage that the manufacturing cost of raw materials is greatly reduced.

In a preferred scheme, the mass of the water accounts for 0.5-10% of the mass of the caprolactam.

In a preferred embodiment, the starting material comprises a dicarboxylic acid and a diprimary amine. The dicarboxylic acid and the diprotic primary amine are mainly used for adjusting the molecular weight of the polycaprolactam so as to enable the polycaprolactam to reach the spinning grade requirement.

In a preferred scheme, the mass of the dicarboxylic acid accounts for 1-3% of the mass of caprolactam. The preferable dicarboxylic acid includes any one or more of saturated aliphatic dicarboxylic acid, dicarboxylic substituted aromatic hydrocarbon, etc. The saturated aliphatic hydrocarbon dicarboxylic acid is common malonic acid, succinic acid, glutaric acid, adipic acid and the like. Such as common terephthalic acid, isophthalic acid, and the like.

In a preferred scheme, the mass of the primary diamine accounts for 1-3% of the mass of caprolactam. The preferable primary diamine includes any one or more of saturated aliphatic hydrocarbon primary diamine, diamino substituted aromatic hydrocarbon and the like. The saturated aliphatic hydrocarbon dibasic primary amine is common propane diamine, butane diamine, pentane diamine, 1, 6-hexane diamine, etc. The diamino substituted aromatic hydrocarbon is common p-phenylenediamine, m-phenylenediamine and the like.

The invention also provides a preparation method of the fiber-grade delustering nylon 6 material, which comprises the steps of adding a melamine compound, a cyanuric acid compound, dicarboxylic acid, primary diamine and water into the molten caprolactam liquid, and shearing and dispersing to obtain a dispersion liquid; and (3) allowing the dispersion liquid and the molten caprolactam liquid to enter a polymerization system for ring-opening polymerization to obtain the extinction nylon 6 material.

In a preferred embodiment, the ring-opening polymerization is carried out by a VK tube continuous polymerization method using polymerization before pressurization and polymerization after depressurization.

The preparation method of the fiber-grade extinction nylon 6 material comprises the following specific steps:

1) adding cyanuric acid, melamine, adipic acid, 1, 6-hexanediamine and water into molten caprolactam liquid, and firstly dispersing and dissolving by using a high-shear dispersion emulsifier to form a solution with stable dispersion and homogeneous phase, which is marked as solution A;

2) continuous polymerization preparation of extinction slice

Conveying the solution prepared in the step 1) and main caprolactam molten liquid raw materials into a polymerization system, and polymerizing according to a VK tube continuous polymerization mode of caprolactam hydrolytic ring opening before pressurization and after depressurization.

Compared with the prior art, the invention has the following obvious advantages:

1) the raw materials of the flatting agent such as the melamine compound, the cyanuric acid compound and the like adopted by the invention are common organic raw materials sold in the market, and the cost is far lower than that of the existing superfine titanium dioxide powder.

2) The flatting agent is used for preparing fiber-grade flatting nylon 6 materials, and compared with the existing titanium dioxide flatting agent, the flatting agent can simplify the process, reduce the equipment investment and reduce the production cost. Mainly because titanium dioxide is a high-strength inorganic metal oxide, the titanium dioxide is unevenly and unstably dispersed in caprolactam or nylon 6 melt, and special equipment is needed to be adopted for grinding and dispersing in order to ensure that the slice quality meets the spinning requirement, so that the difficulty in selecting the type of the equipment is increased, the time is consumed, and the manufacturing cost is increased; the matting agent can be mutually soluble in the molten caprolactam, is stable in dispersion, and can be uniformly dispersed without special dispersing equipment.

3) The fiber-grade extinction nylon 6 material prepared by the extinction agent has more stable and better product performance, such as better material impact strength and tensile strength. The delustering agent can be dispersed and dissolved in a molten caprolactam liquid in a molecular state or a nano-scale dispersion state, so that the property of a polymer is not reduced and the stability of a spinning process is not influenced due to the existence of trace coarse particles in a titanium dioxide dispersion system. . .

Drawings

FIG. 1 is a polymerization system of the present invention for preparing fiber grade matte nylon 6 material;

wherein 0 is a liquid caprolactam storage tank; 1 is a dulling agent caprolactam solution preparation tank; 2 is a mixing tank of delustering agent caprolactam solution and caprolactam; 3 is a fine filter; 4 is a preheater; 5 is a static mixer; 6 is a front gathering tower; 7 is a rear polymerization tower; 8, a granulator; 9 is a pre-extraction tower; 10 is an extraction tower; 11 is a drying tower.

Detailed Description

The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.