阅读说明：本技术 一种阻燃性的纳米SiO2-超分子量聚乙烯防穿刺纤维的合成方法 (Flame-retardant nano SiO2Synthesis method of-supermolecule polyethylene puncture-proof fiber ) 是由 赵建海 于 2021-08-10 设计创作，主要内容包括：本发明涉及防穿刺纤维技术领域,且公开了一种阻燃性的纳米SiO-(2)-超分子量聚乙烯防穿刺纤维,哌嗪-DOPO改性纳米SiO-(2),与超分子量聚乙烯共混纺丝,得到阻燃性的纳米SiO-(2)-超分子量聚乙烯防穿刺纤维,纳米SiO-(2)的加入可以有效提高超分子量聚乙烯纤维的防穿刺性能,并且纳米SiO-(2)表面修饰的哌嗪和DOPO小分子构成氮磷阻燃体系,在高温下会热分解产生含有含氮不可燃气体和含氧磷酸,促进材料在纳米SiO-(2)表面脱水成炭,与纳米SiO-(2)复合形成稳固的无机炭-硅阻隔层,具有很好的抑烟作用和防熔滴效果,具有更高的极限氧指数,对超分子量聚乙烯防穿刺纤维的阻燃性有很大提高。(The invention relates to the technical field of puncture-resistant fibers and discloses a flame-retardant nano SiO 2 -supermolecule polyethylene puncture-proof fiber, piperazine-DOPO modified nano SiO 2 Blending and spinning with supermolecular weight polyethylene to obtain flame-retardant nano SiO 2 Ultra-molecular weight polyethylene puncture-resistant fiber, nano SiO 2 The addition of the nano SiO can effectively improve the puncture resistance of the super-molecular weight polyethylene fiber 2 The surface-modified piperazine and DOPO micromolecules form a nitrogen-phosphorus flame-retardant system, and can be thermally decomposed at high temperature to generate nitrogen-containing non-combustible gas and oxygen-containing phosphoric acid to promote the material to be in nano SiO 2 Surface dehydration to form carbon, and nano SiO 2 Compounded to form a stable inorganic carbon-silicon barrier layer with good smoke suppression effectThe anti-molten drop fiber has high limiting oxygen index and high fire resistance.)

1. Flame-retardant nano SiO₂-a method for synthesizing ultra-molecular weight polyethylene puncture-resistant fibers, characterized in that: the synthesis method comprises the following steps:

modifying supermolecule polyethylene and piperazine-DOPO with nano SiO₂Pouring the antioxidant 1010 into a double-screw extruder, blending and extruding for granulation at the temperature of 240-280 ℃, then carrying out melt spinning on the materials at the spinning temperature of 280-310 ℃, and carrying out traction and stretching on the obtained nascent fiber to obtain the flame-retardant nano SiO₂Ultra-molecular weight polyethylene puncture-resistant fibers.

2. The flame-retardant nano SiO according to claim 1₂-a method for synthesizing ultra-molecular weight polyethylene puncture-resistant fibers, characterized in that: in the synthesis method, by mass, the super-molecular weight polyethylene is 100 parts, and the piperazine-DOPO modified nano SiO₂1.5-8 parts.

3. The flame-retardant nano SiO according to claim 1₂-a method for synthesizing ultra-molecular weight polyethylene puncture-resistant fibers, characterized in that: the piperazine-DOPO modified nano SiO₂The synthesis method comprises the following steps:

(1) mixing nano SiO₂And toluene diisocyanate toHeating and refluxing in toluene solvent to react to obtain isocyanate modified nano SiO₂；

(2) Isocyanate is modified into nano SiO₂Dispersing into organic solvent by ultrasonic, adding DOPO derivative and catalyst stannous octoate, heating for reaction, distilling under reduced pressure after reaction, washing the product by acetone and ethyl acetate in sequence to obtain DOPO modified nano SiO₂；

(3) Modifying DOPO with nano SiO₂Ultrasonically dispersing into dichloromethane, adding 1-chloroformyl-4-methylpiperazine and a catalyst, reacting at 0-10 ℃ for 10-30 h, decompressing and distilling after the reaction, and washing the product by using tetrahydrofuran and ethyl acetate in sequence to obtain the piperazine-DOPO modified nano SiO₂。

4. The flame-retardant nano SiO of claim 3₂-a method for synthesizing ultra-molecular weight polyethylene puncture-resistant fibers, characterized in that: in the step (2), the isocyanate modified nano SiO is calculated by mass₂100 parts of DOPO derivative 120-300 parts of stannous octoate 8-25 parts of the mixture.

5. The flame-retardant nano SiO of claim 3₂-a method for synthesizing ultra-molecular weight polyethylene puncture-resistant fibers, characterized in that: the reaction in the step (2) is carried out at 65-90 ℃ for 12-36 h.

6. The flame-retardant nano SiO of claim 3₂-a method for synthesizing ultra-molecular weight polyethylene puncture-resistant fibers, characterized in that: the organic solvent in the step (3) is any one of ethyl acetate, 1, 4-dioxane, toluene and xylene.

7. The flame-retardant nano SiO of claim 3₂-a method for synthesizing ultra-molecular weight polyethylene puncture-resistant fibers, characterized in that: in the step (3), the DOPO modified nano SiO is calculated by mass portion₂100 portions of 1-chloroformyl-4-methylpiperazine is 80 to 200 portions20-55 parts of catalyst.

8. The flame-retardant nano SiO of claim 3₂-a method for synthesizing ultra-molecular weight polyethylene puncture-resistant fibers, characterized in that: the catalyst in the step (3) is triethylamine or pyridine.

Technical Field

The invention relates to the technical field of puncture-resistant fibers, in particular to flame-retardant nano SiO₂-a method for synthesizing supermolecule polyethylene puncture-proof fiber.

Background

The supermolecule polyethylene fiber has the advantages of high strength, large specific modulus, strong wear resistance and the like, can be made into puncture-proof clothes, bullet-proof clothes and bullet-proof armor, and can be widely applied in the fields of industrial protection, aerospace, national defense and the like, and the anti-puncture performance of the fabric can be effectively improved by compounding the aramid fiber, the supermolecule polyethylene fiber and the shear thickening liquid containing the nano silicon dioxide.

The supermolecule polyethylene fiber puncture-proof material can effectively prevent sharp instruments such as cutters and the like from penetrating, and has wide application prospects in the aspects of industrial production protection, military police uniform and the like, so that the puncture-proof performance of the supermolecule polyethylene fiber is improved, the nanometer silicon dioxide is compounded with the supermolecule polyethylene fiber, the puncture-proof performance of a fiber fabric can be enhanced, and patent CN106832413B discloses phosphorus-nitrogen-containing polymer modified silicon dioxide nanometer particles, a preparation method and application thereof, and discloses that phosphorus-nitrogen-containing polymer modified SiO is used for modifying₂The nano particles can play a role in strengthening and flame retarding in high polymer materials, so that the nitrogen and phosphorus containing flame retardant modified nano silicon dioxide can be applied to the super-molecular weight polyethylene fibers, and the puncture resistance and the flame retarding performance of the fiber fabric are improved.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a flame-retardant nano SiO₂The supermolecule polyethylene puncture-proof fiber and the synthesis method endow the supermolecule polyethylene fiber with excellent puncture-proof performance and flame retardant performance.

In order to achieve the purpose, the invention provides the following technical scheme: flame-retardant nano SiO₂The supermolecule polyethylene puncture-proof fiber is synthesized by the following steps:

modifying supermolecule polyethylene and piperazine-DOPO with nano SiO₂Pouring the antioxidant 1010 into a double-screw extruder, blending and extruding for granulation at the temperature of 240-280 ℃, then carrying out melt spinning on the materials at the spinning temperature of 280-310 ℃, and carrying out traction and stretching on the obtained nascent fiber to obtain the flame-retardant nano SiO₂Ultra-molecular weight polyethylene puncture-resistant fibers.

Preferably, in the synthesis method, by mass, the super-molecular weight polyethylene is 100 parts, and the piperazine-DOPO modified nano SiO₂1.5-8 parts.

Preferably, the piperazine-DOPO modified nano SiO₂Of (2)The method comprises the following steps:

(1) mixing nano SiO₂Adding the isocyanate and toluene diisocyanate into a toluene solvent, and heating and refluxing to react to obtain isocyanate modified nano SiO₂。

(2) Isocyanate is modified into nano SiO₂Ultrasonically dispersing into organic solvent, adding DOPO derivative and catalyst stannous octoate (Sn (Oct)₂) Heating for reaction, decompressing and distilling after the reaction, washing the product by using acetone and ethyl acetate in sequence to obtain the DOPO modified nano SiO₂。

(3) Modifying DOPO with nano SiO₂Ultrasonically dispersing into dichloromethane, adding 1-chloroformyl-4-methylpiperazine and a catalyst, reacting at 0-10 ℃ for 10-30 h, decompressing and distilling after the reaction, and washing the product by using tetrahydrofuran and ethyl acetate in sequence to obtain the piperazine-DOPO modified nano SiO₂。

Preferably, in the step (2), the isocyanate modified nano SiO is calculated by mass portion₂100 parts of DOPO derivative 120-300 parts of stannous octoate 8-25 parts of the mixture.

Preferably, the reaction in the step (2) is carried out at 65-90 ℃ for 12-36 h.

Preferably, the organic solvent in step (3) is any one of ethyl acetate, 1, 4-dioxane, toluene and xylene.

Preferably, in the step (3), the DOPO modified nano SiO is calculated by mass portion₂100 parts of 1-chloroformyl-4-methylpiperazine, 80-200 parts of catalyst and 20-55 parts of catalyst.

Preferably, the catalyst in the step (3) is triethylamine or pyridine.

Compared with the prior art, the invention has the following beneficial technical effects:

the flame-retardant nano SiO₂Ultra-molecular weight polyethylene puncture-proof fiber, isocyanate modified nano SiO₂The isocyanate group contained on the surface reacts with the hydroxyethyl group of the DOPO derivative under the catalytic action of stannous octoate, so that the nano SiO₂The surface of the DOPO micromolecule containing phenolic hydroxyl is modified,obtaining DOPO modified nano SiO₂Further, under the catalytic action of triethylamine or pyridine, the introduced phenolic hydroxyl and 1-chloroformyl-4-methylpiperazine have esterification reaction, and further in the presence of nano SiO₂Modifying the surface of piperazine micromolecule to obtain piperazine-DOPO modified nano SiO₂Then blended and spun with supermolecular weight polyethylene to obtain the flame-retardant nano SiO₂Ultra-molecular weight polyethylene puncture-resistant fiber, nano SiO₂The addition of the nano SiO can effectively improve the puncture resistance of the super-molecular weight polyethylene fiber₂The surface-modified piperazine and DOPO micromolecules form a nitrogen-phosphorus flame-retardant system, and can be thermally decomposed at high temperature to generate nitrogen-containing non-combustible gas and oxygen-containing phosphoric acid to promote the material to be in nano SiO₂Surface dehydration to form carbon, and nano SiO₂The composite inorganic carbon-silicon barrier layer has good smoke suppression effect and molten drop prevention effect, higher limit oxygen index and greatly improved flame retardance of the ultra-molecular weight polyethylene puncture-proof fiber.

Drawings

FIG. 1 shows isocyanate modified nano SiO₂And a reaction scheme of a DOPO derivative;

FIG. 2 is DOPO modified nano SiO₂And 1-chloroformyl-4-methylpiperazine;

FIG. 3 is a comparison of puncture depth data;

FIG. 4 is a graph comparing limiting oxygen index test data.

Detailed Description

To achieve the above object, the present invention provides the following embodiments and examples: flame-retardant nano SiO₂The supermolecule polyethylene puncture-proof fiber is synthesized by the following steps:

(1) mixing nano SiO₂Adding the isocyanate and toluene diisocyanate into a toluene solvent, and heating and refluxing to react to obtain isocyanate modified nano SiO₂。

(2) Isocyanate modified nano SiO with the mass portion of 100 portions₂Ultrasonically dispersing into an organic solvent, wherein the organic solvent is any one of ethyl acetate, 1, 4-dioxane, toluene and xylene, and adding 120 portions of DOPO-300 portions to deriveHeating the product and 8-25 parts of catalyst stannous octoate (Sn (Oct) 2) to 65-90 ℃, reacting for 12-36 h, carrying out reduced pressure distillation after reaction, washing the product by using acetone and ethyl acetate in sequence to obtain DOPO modified nano SiO₂。

(3) 100 parts by mass of DOPO modified nano SiO₂Ultrasonically dispersing into dichloromethane, adding 80-200 parts of 1-chloroformyl-4-methylpiperazine and 20-55 parts of catalyst, wherein the catalyst is triethylamine or pyridine, reacting at 0-10 ℃ for 10-30 h, decompressing and distilling after the reaction, washing the product by using tetrahydrofuran and ethyl acetate in sequence to obtain the piperazine-DOPO modified nano SiO₂。

(4) 100 parts of supramolecular polyethylene and 1.5-8 parts of piperazine-DOPO modified nano SiO₂Pouring the antioxidant 1010 into a double-screw extruder, blending and extruding for granulation at the temperature of 240-280 ℃, then carrying out melt spinning on the materials at the spinning temperature of 280-310 ℃, and carrying out traction and stretching on the obtained nascent fiber to obtain the flame-retardant nano SiO₂Ultra-molecular weight polyethylene puncture-resistant fibers.

Example 1

(1) 1 g of nano SiO₂Adding 0.5 g of toluene diisocyanate into 20 mL of toluene solvent, and carrying out heating reflux reaction to obtain isocyanate modified nano SiO₂。

(2) 1 g of isocyanate modified nano SiO₂Ultrasonically dispersing into an organic solvent, wherein the organic solvent is ethyl acetate, adding 1.2 g of DOPO derivative and 0.08 g of catalyst stannous octoate, heating to 65 ℃, reacting for 12 hours, carrying out reduced pressure distillation after the reaction, and washing the product by using acetone and ethyl acetate in sequence to obtain the DOPO modified nano SiO₂。

(3) 2 g of DOPO modified nano SiO₂Ultrasonically dispersing into dichloromethane, adding 1.6 g of 1-chloroformyl-4-methylpiperazine and 0.4 g of catalyst which is triethylamine, reacting for 10 hours at 0 ℃, decompressing and distilling after the reaction, washing the product by tetrahydrofuran and ethyl acetate in sequence to obtain the piperazine-DOPO modified nano SiO₂。

(4) 20 g of an ultrahigh molecular weight polymer was addedEthylene, 0.3 g of piperazine-DOPO modified nano SiO₂0.05 g of antioxidant 1010 is poured into a double-screw extruder, and is blended and extruded for granulation at 240 ℃, then the materials are melt spun, the spinning temperature is 280 ℃, the obtained nascent fiber is drawn and stretched, and the flame-retardant nano SiO is obtained₂Ultra-molecular weight polyethylene puncture-resistant fibers.

Example 2

(1) 1 g of nano SiO₂Adding 0.7 g of toluene diisocyanate into 30 mL of toluene solvent, and carrying out heating reflux reaction to obtain isocyanate modified nano SiO₂。

(2) 1 g of isocyanate modified nano SiO₂Ultrasonically dispersing into an organic solvent which is 1, 4-dioxane, adding 1.6 g of DOPO derivative and 0.15 g of catalyst stannous octoate, heating to 70 ℃, reacting for 24 hours, carrying out reduced pressure distillation after the reaction, washing the product by using acetone and ethyl acetate in sequence to obtain the DOPO modified nano SiO₂。

(3) 2 g of DOPO modified nano SiO₂Ultrasonically dispersing into dichloromethane, adding 2.5 g of 1-chloroformyl-4-methylpiperazine and 0.6 g of catalyst which is pyridine, reacting at 5 ℃ for 12 h, decompressing and distilling after the reaction, washing the product by tetrahydrofuran and ethyl acetate in sequence to obtain the piperazine-DOPO modified nano SiO₂。

(4) 20 g of supermolecular weight polyethylene and 1 g of piperazine-DOPO modified nano SiO₂0.08 g of antioxidant 1010 is poured into a double-screw extruder, blended and extruded for granulation at 260 ℃, then the materials are subjected to melt spinning at the spinning temperature of 300 ℃, and the obtained nascent fiber is subjected to traction and stretching to obtain the flame-retardant nano SiO₂Ultra-molecular weight polyethylene puncture-resistant fibers.

Example 3

(1) 1 g of nano SiO₂Adding 1 g of toluene diisocyanate into 40 mL of toluene solvent, and carrying out heating reflux reaction to obtain isocyanate modified nano SiO₂。

(2) 1 g of isocyanate modified nano SiO₂Ultrasonic dispersion into organic solventAdding 2.5 g of DOPO derivative and 0.2 g of catalyst stannous octoate into ethyl acetate serving as an organic solvent, heating to 80 ℃, reacting for 24 hours, carrying out reduced pressure distillation after the reaction, and washing the product by using acetone and ethyl acetate in sequence to obtain the DOPO modified nano SiO₂。

(3) 2 g of DOPO modified nano SiO₂Ultrasonically dispersing into dichloromethane, adding 3.2 g of 1-chloroformyl-4-methylpiperazine and 0.9 g of catalyst which is triethylamine, reacting at 5 ℃ for 12 h, decompressing and distilling after the reaction, and washing the product by using tetrahydrofuran and ethyl acetate in sequence to obtain the piperazine-DOPO modified nano SiO₂。

(4) 20 g of supramolecular polyethylene and 1.2 g of piperazine-DOPO modified nano SiO₂And 0.12 g of antioxidant 1010 are poured into a double-screw extruder, blended and extruded for granulation at 260 ℃, then the materials are subjected to melt spinning at the spinning temperature of 300 ℃, and the obtained nascent fiber is subjected to traction and stretching to obtain the flame-retardant nano SiO 2-super-molecular weight polyethylene puncture-proof fiber.

Example 4

(1) 1 g of nano SiO₂Adding 1.2 g of toluene diisocyanate into 50 mL of toluene solvent, and carrying out heating reflux reaction to obtain isocyanate modified nano SiO₂。

(2) 1 g of isocyanate modified nano SiO₂Ultrasonically dispersing into an organic solvent, wherein the organic solvent is ethyl acetate, adding 3 g of DOPO derivative and 0.25 g of catalyst stannous octoate, heating to 90 ℃, reacting for 36 hours, carrying out reduced pressure distillation after the reaction, and washing the product by using acetone and ethyl acetate in sequence to obtain the DOPO modified nano SiO₂。

(3) 2 g of DOPO modified nano SiO₂Ultrasonically dispersing into dichloromethane, adding 4 g of 1-chloroformyl-4-methylpiperazine and 1.1 g of catalyst which is pyridine, reacting at 10 ℃ for 30 h, decompressing and distilling after reaction, washing the product by tetrahydrofuran and ethyl acetate in sequence to obtain piperazine-DOPO modified nano SiO₂。

(4) 20 g of supramolecular polyethylene and 1.6 g of piperazine-DOPO modified nanoSiO₂0.15 g of antioxidant 1010 is poured into a double-screw extruder, blended and extruded for granulation at 280 ℃, then the materials are subjected to melt spinning at the spinning temperature of 310 ℃, and the obtained nascent fiber is subjected to traction and stretching to obtain the flame-retardant nano SiO₂Ultra-molecular weight polyethylene puncture-resistant fibers.

Comparative example 1

(1) Adding 1 g of nano SiO2 and 0.5 g of toluene diisocyanate into 30 mL of toluene solvent, and carrying out heating reflux reaction to obtain isocyanate modified nano SiO₂。

(2) 1 g of isocyanate modified nano SiO₂Ultrasonically dispersing into an organic solvent, wherein the organic solvent is ethyl acetate, adding 1.2 g of DOPO derivative and 0.08 g of catalyst stannous octoate, heating to 65 ℃, reacting for 24 hours, carrying out reduced pressure distillation after the reaction, and washing the product by using acetone and ethyl acetate in sequence to obtain the DOPO modified nano SiO₂。

(3) 20 g of super molecular weight polyethylene and 0.3 g of DOPO modified nano SiO₂0.05 g of antioxidant 1010 is poured into a double-screw extruder, and is blended and extruded for granulation at 240 ℃, then the materials are subjected to melt spinning, the spinning temperature is 300 ℃, and the obtained nascent fiber is subjected to traction and stretching to obtain the nano SiO₂Ultra-molecular weight polyethylene puncture-resistant fibers.

Comparative example 2

(1) 1 g of nano SiO₂Adding 0.8 g of toluene diisocyanate into 20 mL of toluene solvent, and carrying out heating reflux reaction to obtain isocyanate modified nano SiO₂。

(2) 20 g of supramolecular polyethylene and 0.3 g of isocyanate modified nano SiO₂0.05 g of antioxidant 1010 is poured into a double-screw extruder, and the mixture is blended and extruded for granulation at 250 ℃, then the materials are melt spun, the spinning temperature is 310 ℃, the obtained nascent fiber is drawn and stretched to obtain the nano SiO₂Ultra-molecular weight polyethylene puncture-resistant fibers.

Flame-retardant nano SiO₂Weaving the ultra-molecular weight polyethylene anti-puncture fiber into fabric by adopting GA68-2008 policeThe puncture resistance performance was tested using the puncture resistance standard, and the puncture depth data is shown in fig. 3.

Flame-retardant nano SiO₂Ultra-molecular weight polyethylene puncture-resistant fibers. A square sample with the specification of 2 cm multiplied by 2 cm is prepared, the GB/T2406.1-2008 standard is adopted to test the limit oxygen index, and the test result is shown in figure 4.

Finally, it should be noted that: the above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; it will be understood by those skilled in the art that the present invention may be modified and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.