CN112538192B - Modified nano MCA composite flame retardant, preparation method thereof and application thereof in preparation of halogen-free flame-retardant nylon composition for spinning - Google Patents
Modified nano MCA composite flame retardant, preparation method thereof and application thereof in preparation of halogen-free flame-retardant nylon composition for spinning Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/12—Applications used for fibers
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- Polymers & Plastics (AREA)
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Abstract
The invention discloses a modified nano MCA composite flame retardant, a preparation method thereof and application thereof in preparing a halogen-free flame-retardant nylon composition for spinning. The preparation method comprises the following steps: mixing melamine, cyanuric acid, a modifier and water, heating to 90-100 ℃ for reaction, and then carrying out post-treatment; the modifier is selected from diorganophosphinates. The invention discloses a preparation method of a modified nano MCA composite flame retardant, which has the advantages of simple preparation process, low energy consumption, safety and controllability, the particle size of the prepared modified nano MCA composite flame retardant can be as low as 40-60 nm, the flame retardant property is better and excellent, and the preparation method is particularly suitable for preparing a halogen-free flame retardant nylon material for spinning.
Description
Technical Field
The invention belongs to the field of manufacturing of halogen-free flame retardants, and particularly relates to a modified nano MCA composite flame retardant, a preparation method thereof and application thereof in preparing a halogen-free flame retardant nylon composition for spinning.
Background
Melamine Cyanurate (MCA) is a nitrogen-containing halogen-free environmentally friendly flame retardant, which is a white powdery solid. The preparation technology of MCA is well established, and the method mainly adopts the direct reaction of melamine and cyanuric acid to generate MCA, but the grain size of MCA produced by the method is generally 1-50 μm.
MCA is particularly suitable for nylon 6 and nylon 66 without filler. The product has the advantages of economical use, high efficiency, excellent electrical property and mechanical property. Meanwhile, the composite material is low in toxicity, safe for users, good in environmental compatibility and good in thermal stability, and is very suitable for processing materials.
At present, in the field of nylon spinning, in order to improve the flame retardant property of textiles, a flame retardant also needs to be added, but the mechanical property of nylon is greatly influenced by the addition of the conventional flame retardant MCA, and the spinning is easy to break, so that continuous spinning is difficult to form. This is due to the poor compatibility of conventional MCAs with nylon, which are in the micron scale. When the size of the MCA reaches the nanometer level, the effect of strengthening and plasticizing rigid particles is achieved, so that the preparation of the MCA at the nanometer level is necessary in the application field of spinning nylon.
For example, chinese patent publication No. CN 101914220A discloses a method for preparing nano melamine cyanurate, which includes two steps, the first step: reacting melamine and cyanuric acid in a mixed solvent consisting of water and an organic solvent to prepare nano MCA particles; the second step is that: adding MCA surface modifier into the reaction system, stirring and coating, and then filtering, separating and drying. The surfactant is silane coupling agent or stearic acid. In the technical scheme, raw materials are reacted in a mixed solvent so as to control the formation process of MCA crystals to enable the particles to be precipitated in a nanometer scale, and after the particles are precipitated, a surfactant is added to enable the particles not to be agglomerated so as to obtain the nanometer MCA. However, since the solvent used contains an organic solvent, the potential risk increases.
Also, for example, chinese patent publication No. CN 102757393A discloses a method for synthesizing nano-scale melamine cyanurate by a hydrothermal method, which comprises the steps of uniformly stirring melamine, cyanuric acid, water and a surfactant, adding the mixture into a hydrothermal reaction kettle, performing hydrothermal reaction at 120-180 ℃ to obtain melamine cyanurate slurry, and performing centrifugation and drying to obtain nano-scale melamine cyanurate. The technical scheme also adopts the surfactant, so that the surfactant is adsorbed on the surface of the nano melamine cyanurate particles to prevent the nano melamine cyanurate particles from continuously growing into micron particles and prevent the nano particles from agglomerating. Although the melamine cyanurate generated by the technical scheme is nano-scale, the particle size is 40 nm-200 nm, the particle size distribution range is wide, and the adverse effect on the performance of nylon spinning can be still generated.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses a preparation method of a modified nano MCA composite flame retardant, which has the advantages of simple preparation process, low energy consumption, safety and controllability, and the particle size of the prepared modified nano MCA composite flame retardant can be as low as 40-60 nm, the particle size distribution range is narrow, the flame retardant property is more excellent, and the preparation method is particularly suitable for preparing a halogen-free flame retardant nylon material for spinning.
The specific technical scheme is as follows:
a preparation method of a modified nano MCA composite flame retardant comprises the following steps:
mixing melamine, cyanuric acid, a modifier and water, heating to 90-100 ℃ for reaction, and performing post-treatment to obtain the modified nano MCA composite flame retardant;
the modifier is selected from diorganophosphinates.
The invention firstly provides that diorganophosphinate is added as a modifier in the MCA preparation process, and the particle size of the prepared MCA can be controlled in a nanometer level and the particle size distribution of the MCA can be controlled in a very narrow range by only mixing the specific modifier without changing the raw materials and process conditions of the original MCA preparation process, thereby providing possibility for further preparing the halogen-free flame-retardant nylon composite material for spinning with more excellent flame retardance and spinning performance.
Experiments show that the diorganophosphinic salt used as a modifier is added in the preparation process of MCA, so that the formation of a hydrogen bond network structure of the MCA can be disturbed and reduced, the particle size of the prepared MCA is in a nanometer level, and the particle size distribution range is extremely narrow.
The structural formula of the diorganophosphinic salt is shown as the following formula:
in the formula: r 1 、R 2 Independently selected from linear, branched or cyclic C 1 ～C 18 Alkyl radical, C 6 ～C 18 Aryl radical, C 7 ～C 18 Arylalkyl radical or C 7 ～C 18 An alkylaryl group;
m represents Na, mg, al, ca, fe, zn, sb;
m＝1～3。
preferably: the diorganophosphinic acid salt is one or more selected from aluminum diethylphosphinate, aluminum methylethylphosphinate, aluminum methylbutylphosphinate, aluminum diisobutylphosphinate, sodium diethylphosphinate and ferrous diethylphosphinate.
The preferable diorganophosphinic acid salt is used as a modifier, and the prepared MCA is nano-sized, has the particle size of 40-60 nm and narrow particle size distribution.
Further preferably: the diorganophosphinic acid salt is selected from aluminum diethylphosphinate, aluminum diisobutylphosphinate, aluminum methylbutylphosphinate or sodium diethylphosphinate.
Tests show that the MCA prepared by using the further preferable diorganophosphinic salt as the modifier has a particle size of 40-50 nm.
Preferably:
the mass ratio of the melamine to the cyanuric acid is 1:0.9 to 1.1; more preferably 1:0.95 to 1.05.
Preferably:
the addition amount of the diorgano phosphinate is 0.1 to 1 percent of the total mass of the melamine and the cyanuric acid; more preferably 0.1 to 0.5%.
The mass of the water is 2 to 5 times of the total mass of the melamine and the cyanuric acid; more preferably 2 to 3 times.
Experiments show that when the using amount of the diorgano phosphinate is too large, or the using amount of water is too large, the particle size distribution of the prepared nano MCA composite flame retardant is widened. Thereby causing the reduction of the full-curl rate when preparing the halogen-free flame-retardant nylon composite material for spinning.
The post-treatment comprises centrifugation, filtration, drying and crushing.
The invention also discloses the modified nano MCA composite flame retardant prepared by the method, and the particle size is 40-60 nm.
The invention also discloses a halogen-free flame-retardant nylon composition for spinning, which comprises the modified nano MCA composite flame retardant, and the halogen-free flame-retardant nylon composition comprises the following raw materials in parts by weight:
85-95 parts of nylon;
5-15 parts of modified nano MCA composite flame retardant;
0.2 to 0.5 percent of processing aid.
The nylon is selected from nylon 6 or nylon 66.
The processing aid is selected from an antioxidant and/or a lubricant.
Further preferably, the raw materials comprise:
88 to 92 portions of nylon;
8-12 parts of modified nano MCA composite flame retardant;
0.2 to 0.3 percent of processing aid.
The halogen-free flame-retardant nylon composition for spinning prepared by the invention has excellent spinning performance and good flame-retardant performance.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of the modified nano MCA composite flame retardant disclosed by the invention takes diorganophosphinic acid salt as a modifier, not only controls the particle size of the prepared MCA to be 40-60 nm and improves the spinnability when the prepared MCA is applied to nylon spinning, but also plays a flame-retardant synergistic effect with the MCA through the addition of the modifier and further improves the flame retardant property of the MCA.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes and modifications can be made by those skilled in the art after reading the disclosure of the present invention, and equivalents also fall within the scope of the invention defined by the claims.
Example 1
100g of melamine, 100g of cyanuric acid, 400g of water and 1g of aluminum diethylphosphinate were added to a reaction apparatus, stirred continuously, and the reaction temperature was raised to 95 ℃ for 2 hours. After the reaction is finished, cooling to room temperature, and then centrifuging, filtering, drying and crushing the product to obtain the modified nano MCA composite flame retardant.
The particle size of the modified nano MCA composite flame retardant obtained in the embodiment is 40-50 nm through tests.
850g of nylon 6, 150g of the modified nano MCA composite flame retardant prepared by the method, 2g of antioxidants 1010 and 168 (the mass ratio is 1); the melt extrusion temperature is 230-240 ℃.
Comparative example 1
100g of melamine, 100g of cyanuric acid and 400g of water were charged into a reaction apparatus. The reaction temperature was raised to 95 ℃ with continuous stirring, and the reaction was carried out for 2 hours. And after the reaction is finished, cooling to room temperature, and then centrifuging, filtering, drying and crushing the product to obtain the MCA flame retardant.
The MCA flame retardant prepared in this comparative example was tested to have a particle size of 1 to 40 μm.
Comparative example 2
850g of nylon 6, 150g of MCA flame retardant prepared in comparative example 1, 1g of aluminum diethylphosphinate, 2g of antioxidants 1010 and 168 (the mass ratio is 1; the melt extrusion temperature is 230-240 ℃.
Comparative example 3
850g of nylon 6, 150g of MCA flame retardant prepared in comparative example 1, 2g of antioxidants 1010 and 168 (mass ratio is 1); the melt extrusion temperature is 230-240 ℃.
Example 2
100g of melamine, 110g of cyanuric acid, 1050g of water and 0.22g of aluminum methyl ethyl phosphinate are added into a reaction device, the mixture is stirred continuously, the reaction temperature is raised to 100 ℃, and the reaction is carried out for 5 hours. After the reaction is finished, cooling to room temperature, and then centrifuging, filtering, drying and crushing the product to obtain the modified nano MCA composite flame retardant.
The particle size of the modified nano MCA composite flame retardant obtained in the embodiment is 50-60 nm through tests.
Mixing 900g of nylon 6, 100g of the modified nano MCA composite flame retardant prepared by the method, 1g of antioxidant 1010 and 1g of lubricant EBS, and then performing melt extrusion granulation to prepare the halogen-free flame retardant nylon composite material; the melt extrusion temperature is 230-240 ℃.
Example 3
100g of melamine, 90g of cyanuric acid, 500g of water and 1.9g of diisobutylphosphinic aluminum are added into a reaction device, stirred continuously, and the reaction temperature is raised to 90 ℃ for reaction for 3 hours. After the reaction is finished, cooling to room temperature, and then centrifuging, filtering, drying and crushing the product to obtain the modified nano MCA composite flame retardant.
Through tests, the particle size of the modified nano MCA composite flame retardant obtained in the embodiment is 40-50 nm.
950g of nylon 6, 50g of the modified nano MCA composite flame retardant prepared by the method, 2g of the antioxidant 168 and 2g of the lubricant EBS are blended and then subjected to melt extrusion granulation to prepare the halogen-free flame retardant nylon composite material for spinning; the melt extrusion temperature is 230-240 ℃.
Comparative example 4
950g of nylon 6, 50g of the nano MCA flame retardant (with wide particle size distribution and 40-200 nm size) prepared according to example 1 of the Chinese patent document with the application publication number CN 102757393A, 2g of the antioxidant 168 and 2g of the lubricant EBS are blended and then subjected to melt extrusion granulation to prepare the halogen-free flame retardant nylon composite material for spinning; the melt extrusion temperature is 230-240 ℃.
Example 4
100g of melamine, 95g of cyanuric acid, 500g of water and 0.5g of sodium diethylhypophosphite are added into a reaction device, stirred continuously, the reaction temperature is raised to 95 ℃, and the reaction is carried out for 3 hours. After the reaction is finished, cooling to room temperature, and then centrifuging, filtering, drying and crushing the product to obtain the modified nano MCA composite flame retardant.
The particle size of the modified nano MCA composite flame retardant obtained in the embodiment is 40-50 nm through tests.
920g of nylon 6, 80g of the modified nano MCA composite flame retardant prepared by the method, 2g of antioxidants 1010 and 168 (the mass ratio is 2; the melt extrusion temperature is 230-240 ℃.
Example 5
100g of melamine, 105g of cyanuric acid, 600g of water and 0.6g of aluminum methylbutylphosphinate are added into a reaction device, stirred continuously, the reaction temperature is raised to 95 ℃, and the reaction is carried out for 3 hours. After the reaction is finished, cooling to room temperature, and then centrifuging, filtering, drying and crushing the product to obtain the modified nano MCA composite flame retardant.
Through tests, the particle size of the modified nano MCA composite flame retardant obtained in the embodiment is 40-50 nm.
880g of nylon 6, 120g of the modified nano MCA composite flame retardant prepared in the embodiment, 1g of antioxidant 1010 and 2g of lubricant PETS are blended and then subjected to melt extrusion granulation to prepare the halogen-free flame retardant nylon composite material for spinning; the melt extrusion temperature is 230-240 ℃.
Comparative example 5
100g of melamine, 105g of cyanuric acid, 2050g of water and 2.46g of aluminum methylbutylphosphinate are added to a reaction apparatus, stirred continuously, the reaction temperature is raised to 95 ℃ and the reaction is carried out for 3 hours. After the reaction is finished, cooling to room temperature, and then centrifuging, filtering, drying and crushing the product to obtain the modified nano MCA composite flame retardant.
Through tests, the particle size of the modified nano MCA composite flame retardant obtained in the comparative example is 40-90 nm.
880g of nylon 6, 120g of the modified nano MCA composite flame retardant prepared by comparison, 1g of antioxidant 1010 and 2g of lubricant PETS are blended and then subjected to melt extrusion granulation to prepare the halogen-free flame retardant nylon composite material for spinning; the melt extrusion temperature is 230-240 ℃.
The halogen-free flame-retardant nylon composite material for spinning prepared in each embodiment and the comparative example is subjected to flame retardant performance test, and the material is subjected to spinning experiment.
Flame retardant properties the flame behaviour part 2 was determined according to GB/T2406.2-2009 "oxygen index for plastics: testing according to the standard of Room temperature test;
the spinning experiment is to use a spinning machine to spin the prepared halogen-free flame-retardant nylon composite material for spinning to obtain the full lap rate of each sample, wherein the spinning speed is 1000 m/min, and the higher the full lap rate is, the less the yarn breakage phenomenon is.
The performance data are listed in table 1 below.
TABLE 1
| Test item | Flame retardant Properties (oxygen index/%) | Percentage of full lap (%) |
| Example 1 | 24.8 | 93 |
| Comparative example 2 | 24.3 | 68 |
| Comparative example 3 | 23.2 | 69 |
| Example 2 | 23.8 | 95 |
| Example 3 | 22.6 | 96 |
| Comparative example 4 | 22.3 | 82 |
| Example 4 | 23.7 | 96 |
| Example 5 | 24.2 | 95 |
| Comparative example 5 | 24.0 | 88 |
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (8)
1. A preparation method of a modified nano MCA composite flame retardant is characterized by comprising the following steps:
mixing melamine, cyanuric acid, a modifier and water, heating to 90-100 ℃ for reaction, and performing post-treatment to obtain the modified nano MCA composite flame retardant;
the modifier is selected from diorganophosphinates;
the mass ratio of the melamine to the cyanuric acid is 1:0.9 to 1.1;
the addition amount of the diorganophosphinic acid salt is 0.1 to 1 percent of the total mass of the melamine and the cyanuric acid;
the mass of the water is 2.0 to 5.0 times of the total mass of the melamine and the cyanuric acid.
2. The preparation method of the modified nano MCA composite flame retardant of claim 1, wherein:
the structural formula of the diorganophosphinic salt is shown as the following formula:
in the formula: r 1 、R 2 Independently selected from linear, branched or cyclic C 1 ~C 18 Alkyl radical, C 6 ~C 18 Aryl radical, C 7 ~C 18 Arylalkyl radical or C 7 ~C 18 An alkylaryl group;
m represents Na, mg, al, ca, fe, zn, sb;
m=1~3。
3. the preparation method of the modified nano MCA composite flame retardant of claim 2, wherein: the diorganophosphinic acid salt is one or more selected from aluminum diethylphosphinate, aluminum methylethylphosphinate, aluminum methylbutylphosphinate, aluminum diisobutylphosphinate, sodium diethylphosphinate and ferrous diethylphosphinate.
4. The method for preparing the modified nano MCA composite flame retardant of claim 1, wherein the post-treatment comprises centrifugation, filtration, drying and crushing.
5. The modified nano MCA composite flame retardant prepared by the method according to any one of claims 1 to 4, wherein the particle size of the modified nano MCA composite flame retardant is 40 to 60nm.
6. The halogen-free flame retardant nylon composition for spinning is characterized by comprising the modified nano MCA composite flame retardant of claim 5, and the halogen-free flame retardant nylon composition comprises the following raw materials in parts by weight:
85 to 95 parts of nylon;
5 to 15 percent of modified nano MCA composite flame retardant;
0.2-0.5 percent of processing aid.
7. Halogen free flame retardant nylon composition according to claim 6, characterized in that the nylon is selected from nylon 6 or nylon 66.
8. The halogen-free flame retardant nylon composition of claim 6, wherein the processing aid is an antioxidant and/or a lubricant.
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| CN100341941C (en) * | 2005-11-10 | 2007-10-10 | 四川大学 | Trimeric cyanamide cyanureate fire retarding polyamide nano-composite meterial and its preparation method |
| CN102757393B (en) * | 2012-07-05 | 2014-07-16 | 同济大学 | Method for synthesizing nano-scale melamine cyanurate (MCA) through hydrothermal method |
| CN107903622A (en) * | 2017-11-23 | 2018-04-13 | 宁波七诺新材料科技有限公司 | Flame-retardant modified nylon and preparation method thereof |
| CN111662323A (en) * | 2019-03-07 | 2020-09-15 | 黎杰 | Dialkyl phosphinic acid-alkyl phosphorous acid metal composite salt, preparation method and application thereof |
| CN111410840A (en) * | 2020-05-15 | 2020-07-14 | 四川大学 | Halogen-free flame-retardant nylon low-dimensional product material and preparation method thereof |
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