CN115058116B - Halogen-free flame-retardant corrugated pipe material and preparation method thereof - Google Patents
Halogen-free flame-retardant corrugated pipe material and preparation method thereof Download PDFInfo
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- CN115058116B CN115058116B CN202210391077.0A CN202210391077A CN115058116B CN 115058116 B CN115058116 B CN 115058116B CN 202210391077 A CN202210391077 A CN 202210391077A CN 115058116 B CN115058116 B CN 115058116B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/22—Halogen free composition
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Abstract
The invention discloses a halogen-free flame-retardant corrugated pipe material and a preparation method thereof. The preparation method comprises the following steps of: s1 polyamide, S2 polyamide coated hypophosphite, S3 toughening agent and S4 auxiliary agent package containing lubricant and antioxidant. The polyamide-coated hypophosphite metal salt enables the flame retardant to be tightly coated inside the polyamide, so that on one hand, the heat resistance of the flame retardant is improved, toxic gas is prevented from being generated to harm human bodies, and on the other hand, the compatibility of the flame retardant and matrix resin is improved. The plasticizer is not needed to be added, the crystallization structure of the polyamide is destroyed by utilizing the complexation of the metal chloride to achieve the requirements of plasticizing the polyamide and improving the fluidity of the material. The composite material prepared by the invention can reach V0 level flame retardance, is smokeless and environment-friendly in the process of extruding a pipeline, has smooth surface of the extruded corrugated pipe material, has excellent toughness and molding, and can meet the use requirement.
Description
Technical Field
The invention belongs to the field of high polymer materials and processing, and particularly relates to a halogen-free flame-retardant corrugated pipe material with bright surface and high toughness and a preparation method thereof.
Background
Nylon is a widely used engineering plastic and has numerous excellent properties such as high strength, good toughness, high temperature resistance and the like. However, nylon materials often require the addition of large amounts of plasticizers and flame retardants due to too high hardness, high modulus, flammability, etc. when extruded as piping materials. At present, the plasticizer which is common in the market and has the highest cost performance is N-methylbenzenesulfonamide, and the boiling point of the plasticizer is only 165-170 ℃, so that the plasticizer is easy to volatilize partially in the extrusion process, the smoke of a machine head is slightly larger, and the effect on the health of workers on site is great.
Hypophosphite is a flame retardant with low cost and extremely high phosphorus content (about 40%), and is widely used in PET, PBT, PA, TPU, ABS and other resins. There are several disadvantages in use: (1) PH which is easily decomposed to form extremely toxic when the temperature is slightly higher than 130 DEG C 3 The gas is extremely harmful to human body and environment. The gas generated by the decomposition can reduce the surface glossiness of the particles and generate pores. (2) The hypophosphite is directly added into the polyamide resin, and white pits are formed on the appearance of particles due to the fact that the flame retardant has larger particle size and exists in the form of inorganic matters. (3) The hypophosphite is mainly gas-phase flame retardant, the condensed phase flame retardant capability is slightly poor, and the hypophosphite needs to be matched with a synergist for use in the use process.
There are few literature and patent reports concerning this aspect. Chinese patent CN112457663a reports that the modified material of flame retardant nylon bellows and its preparation method directly selects PA and flame retardant to blend and extrude, so that the prepared pipe is too hard on one hand, and the flame retardant is easy to have many pores and many pits on the surface of particles when untreated. Chinese patent CN110079021a reports a high temperature aging resistant flame retardant polypropylene material for corrugated pipes and a preparation method thereof, which uses halogen flame retardant, and has great harm to environment and human body. Chinese patent CN103242652A reports a flame retardant plastic modified material for extrusion molding of automobile corrugated pipes and a preparation method thereof, wherein PA12, DBDPE and antimony trioxide are added into PA6 to achieve flame retardant and toughening effects, and the pipe prepared by the method uses halogen flame retardants, so that toxic gas generated once a fire disaster is harmful to human bodies. Chinese patent CN1696120A reports that melamine cyanurate is synthesized by taking a polyamide resin solution as a reaction medium and a preparation method thereof, and MCA is generated by adopting the reaction of melamine and cyanuric acid to solve the problem that the grain size of a flame retardant is too large, but the V0 flame retardant cannot be produced by the material prepared by the method, and in addition, a plasticizer still needs to be additionally introduced due to low-temperature impact difference.
Therefore, the problems that inorganic aluminum hypophosphite is easy to decompose, poor in dispersion in a polyamide matrix and air holes and pits are caused to particle appearance are solved; the plasticizer is easy to volatilize and has large smell, and the preparation of the flame-retardant corrugated pipe material with bright surface and high toughness is very important.
Disclosure of Invention
The invention aims to provide a halogen-free flame-retardant corrugated pipe material with bright surface and high toughness and a preparation method thereof. Solves the problems of dispersion of inorganic hypophosphite in polyamide matrix and easy decomposition in the processing process. In addition, the invention does not use volatile plasticizer to soften polyamide, and finally prepares the flame-retardant corrugated pipe material with bright surface and high toughness.
In order to achieve the above object, the present invention has the following technical scheme:
the halogen-free flame-retardant corrugated pipe material with bright surface and high toughness is prepared from the following raw materials:
s1, 65-85 parts of polyamide, preferably 70-80 parts;
s2, 10-35 parts, preferably 15-25 parts, of polyamide-coated hypophosphite;
s3, 5-10 parts, preferably 6-8 parts of toughening agent
S4, the auxiliary agent comprises 0.01 to 0.1 part of lubricant, preferably 0.05 to 0.08 part; 0.2 to 2 parts of antioxidant, preferably 0.4 to 1 part;
the parts are mass parts.
As a preferred embodiment, the halogen-free flame retardant corrugated pipe material of the invention does not contain plasticizer.
In the invention, the polyamide S1 is selected from one or more of PA6, PA66, PA610, PA612, PA1012, PA11 and PA12, and preferably one or more of PA1012, PA11 and PA 12.
In the invention, the preparation method of the S2 polyamide coated hypophosphite comprises the following steps:
(1) Addition of NaH to a phosphoric acid homogeneous solution of a Polyamide resin 2 PO 2 ·H 2 Stirring for 30-80min, preferably 40-60min; then dropwise adding a metal chloride solution for reaction for 30-100min, preferably 50-80min;
(2) Adding ammonia water into the product of the step (1) to neutralize to pH=6-7, so that the dissolved polyamide resin is separated out to form a film, and obtaining polyamide coated hypophosphite;
(3) And (3) filtering, drying and crushing the product obtained in the step (2) to obtain a powdery product.
The preparation method of the phosphoric acid homogeneous solution of the polyamide resin comprises the following steps: mixing and heating polyamide resin and phosphoric acid solution to 40-100deg.C, preferably 60-80deg.C; stirring for 20-100min, preferably 40-60min, allows the polyamide resin to dissolve into a homogeneous solution.
In the present invention, the phosphoric acid solution concentration is 50 to 98wt%, preferably 60 to 80wt%.
In the invention, the weight of the polyamide resin and the volume ratio of the phosphoric acid solution are 1:5-1:20.
In the invention, the metal chloride is one or more of aluminum chloride, lanthanum chloride, cerium chloride and the like.
In the invention, the NaH 2 PO 2 ·H 2 Mass ratio of O to metal chloride 1:2-1:5, preferably 1:3-1:4.
In the step (1) of the present invention, a metal chloride and NaH 2 PO 2 ·H 2 O reacts in phosphoric acid solution to obtain inorganic hypophosphite. The phosphoric acid solution is a solvent of the polyamide resin and is a catalyst for generating a flame retardant, and with the addition of excessive chloridized metal salt, metal ions can be complexed with amide bonds to break original hydrogen bonds, so that the crystallinity of the polyamide resin is reduced and the polyamide resin becomes soft.
In the step (2), the system acidity is reduced after ammonia water is added, and the plasticized polyamide resin is gradually precipitated and separated out on the surface of the flame retardant to form a film, so that the in-situ coating of the plasticized polyamide resin and the inorganic hypophosphite is realized, and the plasticized polyamide resin coated inorganic hypophosphite is obtained. The inorganic hypophosphite obtained by the method has the advantages that on one hand, the thermal stability is improved, the safety in the use process is ensured, and on the other hand, the situation that the appearance of particles is whitened due to the introduction of the inorganic flame retardant can not occur because the surface layer is coated by polyamide.
In addition, with the addition of ammonia water, the original phosphoric acid in the system reacts with the ammonia water to generate ammonium phosphate with condensed phase flame retardant effect, and the ammonium phosphate can be accumulated on the surface with the generation of inorganic hypophosphite, so that the condensed phase of the system is added to form carbon effect. Thereby combining with the gas phase flame retardance of hypophosphite to achieve good synergistic effect.
In the invention, the toughening agent is ethylene propylene segmented copolymer grafted polar group, nylon elastomer, epoxy toughening agent and the like, preferably nylon elastomer.
In the invention, the antioxidant is one or more of copper salt antioxidants, phosphate antioxidants, hindered phenol antioxidants, phosphite antioxidants, thioester antioxidants and macromolecule antioxidants, preferably copper salt antioxidants, more preferably one or more of H1607, H3336, H3376, H3344, S5050, S5070, LXR568, S80 and 608.
In the invention, the lubricant is one or more of fluorine, wax and silicone, preferably PTFE and AC540A.
The preparation method of the halogen-free flame-retardant corrugated pipe material comprises the following steps:
using a twin screw extruder to add components S1, S3 from two main feeding ports, and S2 from a first side feeding port to melt-mix and extrude to obtain a composite material, wherein the extrusion temperature of a melting section is preferably 220-250 ℃, more preferably 230-240 ℃; screw speed is 200-500rpm, preferably 300-400rpm; the feed amount is 40-80kg/h, preferably 45-60kg/h.
The invention skillfully selects the substance of the metal chloride as a reactant for producing the flame retardant by reacting with sodium hypophosphite on one hand, and can complex hydrogen bonds to play a role in plasticizing polyamide on the other hand. Therefore, the plasticized polyamide has lower modulus, and can better wrap the flame retardant, thereby achieving the purposes of improving the temperature resistance of the flame retardant and the compatibility with a matrix.
Halogen-free flame-retardant corrugated pipe material with tensile yield strength more than 30MPa and strong notch impact of normal-temperature simply supported beamDegree of > 7KJ/m 2 And V0 flame retardance is achieved by vertical combustion of 1.6 mm.
The invention has the following main advantages:
(1) The plasticizer is not needed to be added, the crystallization structure of the polyamide is destroyed by utilizing the complexation of the metal chloride to achieve the requirements of plasticizing the polyamide and improving the fluidity of the material. On the one hand, the cost is reduced, on the other hand, the equipment of the available liquid pump is not needed, the universality is stronger, and the method is very beneficial to the environment and the artificial health of the site.
(2) The polyamide-coated hypophosphite metal salt ensures that the flame retardant is tightly coated inside the polyamide, so that on one hand, the heat resistance of the flame retardant is improved, toxic gas is prevented from being generated to harm the human body, and on the other hand, the compatibility of the flame retardant and matrix resin is improved.
Drawings
FIG. 1 refers to the pellets extruded tubing made according to the methods of example 1, comparative example 2, comparative example 3, comparative example 4 from left to right;
fig. 2 refers from left to right to the extruded tubing of pellets produced according to the methods of example 2, example 3, example 4, example 5.
Detailed Description
The technical scheme of the invention is further described through examples, but the scope of the invention is not limited to the examples.
The raw material information used in the examples and comparative examples is shown in table 1 below:
TABLE 1 sources of raw materials
| Raw materials | Material characteristics | Manufacturer' s |
| L2140 | Relative viscosity of 2.05-2.15 | EMS |
| L1940 | Relative viscosity of 1.8-1.9 | EMS |
| EPR24 | Relative viscosity of 2.34-2.40 | Flat-top mountain-horse engineering plastic |
| PA612 | Shandong Guangdong boundary | |
| PA1012 | Shandong Guangdong boundary | |
| Phosphoric acid solution | 98wt％ | Chemical industry of Jinan element |
| NaH 2 PO 2 ·H 2 O | Analytical grade | Tianjin city Miou chemical reagent |
| AlCl 3 ·6H 2 O | Analytical grade | Shanghai Jinshan chemical plant |
| LaCl 3 ·7H 2 O | Analytical grade | TIANJIN KWANGFU FINE CHEMICAL INDUSTRY Research Institute |
| Ammonia water | Analytical grade | Tianjin city Miou chemical reagent |
| BBSA | N-butylbenzenesulfonamide | Wuhan Lanabai pharmaceutical chemical Co., ltd |
| GR216 | POE-g-MAH | Ceramic' s |
| Pebex 5533 | Nylon 12 polyether block copolymer | Axma |
| N493 | Ceramic' s | |
| PTFE | Polytetrafluoroethylene powder | Japanese Dajin |
| AC540A | Ethylene acrylic acid copolymer wax powder | Honiswell |
| Antioxidants, 1010, 1076, 168, 626 | SUNSHOW (YANTAI) SPECIALTY CHEMICAL Co.,Ltd. | |
| LXR568 | Kelaien |
The twin-screw extruder used was a product of Corplon Nanjing mechanical Co., ltd. And the single-screw extruder used was a product of Harnja Co., ltd. And the appearance was visually evaluated by using an extrusion tube at 230 ℃.
The flame retardant rating test in examples and comparative examples was conducted using the UL-94 standard; tensile strength was measured using ISO527 and notched impact strength of a simply supported beam was measured using ISO 179. The apparent morphology of the tube was observed by naked eyes.
Preparation example 1
(1) 100g L2140 and 500g of 95wt% phosphoric acid solution are added into a three-neck flask with a stirrer and a thermometer, and heated to 40 ℃; stirring for 100min causes the polyamide resin to dissolve into a homogeneous solution.
(2) 30g of NaH are added 2 PO 2 ·H 2 O was stirred for an additional 30min. 100g of 60wt% AlCl are then added dropwise 3 The solution was reacted for 30min.
(3) And adding ammonia water to neutralize until the PH=6-7, and separating out the dissolved polyamide resin into a film to obtain the polyamide coated hypophosphite.
Preparation example 2
(1) 100g of EPR24 and 2000g of 50wt% phosphoric acid solution are added into a three-neck flask with a stirrer and a thermometer, and heated to 100 ℃; stirring for 20min to dissolve the polyamide resin into homogeneous solution
(2) 20g of NaH are added 2 PO 2 ·H 2 O was stirred for 80min. 200g of 50wt% AlCl are then added dropwise 3 The solution was reacted for 100min.
(3) And adding ammonia water to neutralize until the PH=6-7, and separating out the dissolved polyamide resin into a film to obtain the polyamide coated hypophosphite.
Preparation example 3
(1) 100g L2140 and 1000g of 80wt% phosphoric acid solution are added into a three-neck flask with a stirrer and a thermometer, and heated to 60 ℃; stirring for 40min to dissolve the polyamide resin into homogeneous solution
(2) 20g of NaH are added 2 PO 2 ·H 2 O was stirred for an additional 40min. 100g of 40wt% LaCl are then added dropwise 3 The solution was reacted for 50min.
(3) And adding ammonia water to neutralize until the PH=6-7, and separating out the dissolved polyamide resin into a film to obtain the polyamide coated hypophosphite.
Preparation example 4
(1) 100g of EPR24 and 1500g of 60wt% phosphoric acid solution are added into a three-neck flask with a stirrer and a thermometer, and heated to 80 ℃; stirring for 60min to dissolve the polyamide resin into homogeneous solution
(2) 20g of NaH are added 2 PO 2 ·H 2 O was stirred for 60min. 100g of 80wt% LaCl are then added dropwise 3 The solution was reacted for 80min.
(3) And adding ammonia water to neutralize until the PH=6-7, and separating out the dissolved polyamide resin into a film to obtain the polyamide coated hypophosphite.
Preparation example 5
(1) 100gPA g of 610 percent by weight phosphoric acid solution 1200g is added into a three-neck flask with a stirrer and a thermometer and heated to 70 ℃; stirring for 50min to dissolve the polyamide resin into homogeneous solution
(2) 20g of NaH are added 2 PO 2 ·H 2 O was stirred for an additional 50min. 100g of 60wt% AlCl are then added dropwise 3 The solution was reacted for 60min.
(3) And adding ammonia water to neutralize until the PH=6-7, and separating out the dissolved polyamide resin into a film to obtain the polyamide coated hypophosphite.
Preparation example 6 (comparative)
(1) 100g L2140 and 500g of 95wt% phosphoric acid solution are added into a three-neck flask with a stirrer and a thermometer, and heated to 40 ℃; stirring for 100min causes the polyamide resin to dissolve into a homogeneous solution.
(2) 40g of NaH was added 2 PO 2 ·H 2 O was stirred for an additional 30min. 100g of 60wt% AlCl are then added dropwise 3 The solution was reacted for 30min.
(3) Adding a small amount of ammonia water to enable the PH of the solution to be=2, and enabling the dissolved polyamide resin to be separated out to form a film, thus obtaining the polyamide coated hypophosphite.
Preparation example 7 (comparative)
(1) 100g L2140 and 500g of 95wt% phosphoric acid solution are added into a three-neck flask with a stirrer and a thermometer, and heated to 40 ℃; stirring for 100min causes the polyamide resin to dissolve into a homogeneous solution.
(2) 40g of NaH was added 2 PO 2 ·H 2 O was stirred for an additional 30min.
(3) And adding ammonia water to neutralize until the PH=6-7, and separating out the dissolved polyamide resin into a film to obtain the polyamide coated hypophosphite.
Preparation example 8 (comparative)
(1) 100g L2140 and 500g of 95wt% phosphoric acid solution are added into a three-neck flask with a stirrer and a thermometer, and heated to 40 ℃; stirring for 100min causes the polyamide resin to dissolve into a homogeneous solution.
(2) 40g of NaH was added 2 PO 2 ·H 2 O was stirred for an additional 30min. 100g of 40wt% AlCl are then added dropwise 3 The solution was reacted for 30min.
(3) And adding ammonia water to neutralize until the PH=6-7, and separating out the dissolved polyamide resin into a film to obtain the polyamide coated hypophosphite.
Example 1
65 parts of L2140, 5 parts of GR216, 0.1 part of 168, 0.1 part of 1098, and 0.01 part of PTFE were cold mixed and then fed from a main feeding port, and 10 parts of the polyamide-coated aluminum hypophosphite of preparation example 1 was fed into a twin screw extruder from a first side feeding port.
The above mixture was melt mixed in a twin screw extruder at the following extrusion temperatures: 86 ℃, 140 ℃, 220 ℃, 240 ℃, 220 ℃, 230 ℃, and the rotation speed of 200rpm, and the feeding amount of 40 kg/h.
Comparative example 1
65 parts L2140, 5 parts GR216, 0.1 part 168, 0.1 part 1098, 0.01 parts PTFE were cold blended and then added from the main feeding port, 10 parts aluminum hypophosphite was added to the twin screw extruder from the first side feeding port, and 7 parts BBSA was added from the liquid injection port.
The above mixture was melt mixed in a twin screw extruder at the following extrusion temperatures: 86 ℃, 140 ℃, 220 ℃, 240 ℃, 220 ℃, 230 ℃, and the rotation speed of 200rpm, and the feeding amount of 40 kg/h.
Comparative example 2
65 parts of L2140, 5 parts of GR216, 0.1 part of 168, 0.1 part of 1098, and 0.01 part of PTFE were cold mixed and then fed from a main feeding port, and 10 parts of the polyamide-coated aluminum hypophosphite of preparation example 6 was fed into a twin screw extruder from a first side feeding port.
The above mixture was melt mixed in a twin screw extruder at the following extrusion temperatures: 86 ℃, 140 ℃, 220 ℃, 240 ℃, 220 ℃, 230 ℃, and the rotation speed of 200rpm, and the feeding amount of 40 kg/h.
Comparative example 3
65 parts of L2140, 5 parts of GR216, 0.1 part of 168, 0.1 part of 1098, and 0.01 part of PTFE were cold mixed and then fed from a main feeding port, and 10 parts of the polyamide-coated aluminum hypophosphite of preparation example 7 was fed into a twin screw extruder from a first side feeding port.
The above mixture was melt mixed in a twin screw extruder at the following extrusion temperatures: 86 ℃, 140 ℃, 220 ℃, 240 ℃, 220 ℃, 230 ℃, and the rotation speed of 200rpm, and the feeding amount of 40 kg/h.
Comparative example 4
65 parts of L2140, 5 parts of GR216, 0.1 part of 168, 0.1 part of 1098, and 0.01 part of PTFE were cold mixed and then fed from a main feeding port, and 10 parts of the polyamide-coated aluminum hypophosphite of preparation example 8 was fed into a twin screw extruder from a first side feeding port.
The above mixture was melt mixed in a twin screw extruder at the following extrusion temperatures: 86 ℃, 140 ℃, 220 ℃, 240 ℃, 220 ℃, 230 ℃, and the rotation speed of 200rpm, and the feeding amount of 40 kg/h.
Example 2
85 parts of PA1012, 10 parts of Pebex 5533, 0.5 part of 168, 0.5 part of LXR568, 0.5 part of 1098, 0.5 part of S80 and 0.05 part of AC540A are cold mixed and then added from a main feeding port, and 35 parts of polyamide-coated aluminum hypophosphite of preparation example 2 are added to a twin screw extruder from a first side feeding port.
The above mixture was melt mixed in a twin screw extruder at the following extrusion temperatures: 86 ℃, 140 ℃, 220 ℃, 250 ℃, 220 ℃, 240 ℃, 220 ℃, 230 ℃, and the rotation speed of 500rpm, and the feeding amount of 60kg/h.
Example 3
35 parts of L2140, 35 parts of L1940, 6 parts of N493, 0.2 part of LXR568, 0.2 part of 1098 and 0.08 part of AC540A were cold mixed and then fed into a main feeding port, and 15 parts of the polyamide-coated lanthanum hypophosphite of preparation example 3 was fed into a twin screw extruder from a first side feeding port.
The above mixture was melt mixed in a twin screw extruder at the following extrusion temperatures: 86 ℃, 140 ℃, 220 ℃, 230 ℃, 220 ℃, 240 ℃, 220 ℃, 230 ℃, and the rotation speed of 300rpm, and the feeding amount of 45 kg/h.
Example 4
80 parts of PA1012, 8 parts of GR216, 0.5 part of LXR568, 0.2 part of 1098, 0.3 part of 1383, 0.05 part of AC540A and 0.05 part of PTFE were cold mixed and fed from a main feeding port, and 25 parts of polyamide-coated lanthanum hypophosphite of preparation example 4 was fed from a first side feeding port into a twin screw extruder.
The above mixture was melt mixed in a twin screw extruder at the following extrusion temperatures: 86 ℃, 140 ℃, 220 ℃, 240 ℃, 220 ℃, 230 ℃, and a rotation speed of 400rpm, and a feeding amount of 80kg/h.
Example 5
75 parts of PA612, 7 parts of GR216, 0.3 part of LXR568, 0.3 part of 1098 and 0.06 part of AC540A were cold mixed and then fed from the main feeding port, and 20 parts of the polyamide-coated aluminum hypophosphite of preparation example 5 was fed into the twin screw extruder from the first side feeding port.
The above mixture was melt mixed in a twin screw extruder at the following extrusion temperatures: 86 ℃, 140 ℃, 220 ℃, 235 ℃, 220 ℃, 240 ℃, 220 ℃, 230 ℃ and the rotation speed of 350rpm, and the feeding amount of 55 kg/h.
The properties of the examples and comparative products are shown in Table 1.
Table 1 properties of the examples and comparative products
As is apparent from comparative examples 1 and 1, untreated aluminum hypophosphite had white spots and holes on the pipe surface due to decomposition products during extrusion and flame retardant did not melt, as shown in FIG. 1. As is clear from comparative example 2, when the amount of ammonia water added to the solution is insufficient to precipitate polyamide at the time of synthesizing polyamide-coated aluminum hypophosphite, the finally formed flame retardant is not coated with polyamide, ammonium phosphate having a char-forming effect is not formed, and the final flame retardant effect is slightly poor and the appearance of the pipeline is poor. As is clear from comparative example 3, the addition of sodium hypophosphite hydrate alone, without the addition of a metal chloride, is inferior in flame retarding effect, and in addition, the toughness of the material is poor because of the non-plasticizing effect. As is clear from comparative example 4, when NaH 2 PO 2 ·H 2 O and AlCl 3 Is not proper in proportion of AlCl 3 The low content of (3) can lead to insufficient aluminum hypophosphite production, insufficient plasticizing effect of chloride ions, and finally no toughening and flame retarding effects are achieved.
As can be seen from examples 2, 3, 4 and 5, the process of the present invention can produce a pipe material having a good appearance and a good low-temperature toughness, as shown in FIG. 2.
Claims (8)
1. The halogen-free flame-retardant corrugated pipe material is prepared from the following raw materials in parts by weight:
s1, 65-85 parts of polyamide;
s2, 10-35 parts of hypophosphite coated by polyamide;
s3, 5-10 parts of a toughening agent;
s4, the auxiliary agent comprises 0.01-0.1 part of lubricant; 0.2-2 parts of an antioxidant;
the parts are mass parts; the preparation method of the S2 polyamide coated hypophosphite comprises the following steps:
(1) Addition of NaH to a phosphoric acid homogeneous solution of a Polyamide resin 2 PO 2 •H 2 O stirring for 30-80min; then dropwise adding a metal chloride solution, and reacting for 30-100min;
(2) Adding ammonia water into the product of the step (1) to neutralize to pH=6-7, so that the dissolved polyamide resin is separated out to form a film, and obtaining polyamide coated hypophosphite;
(3) Filtering, drying and crushing the product obtained in the step (2) to obtain a powdery product, wherein the metal chloride is one or more of aluminum chloride, lanthanum chloride and cerium chloride; the NaH is 2 PO 2 ·H 2 Mass ratio of O to metal chloride 1:2-1:5.
2. The material of claim 1, wherein the polyamide selected for S1 comprises one or more of PA6, PA66, PA610, PA612, PA1012, PA11, and PA 12.
3. The material according to claim 1, characterized in that the preparation method of the phosphoric acid homogeneous solution of polyamide resin comprises the following steps: mixing and heating polyamide resin and phosphoric acid solution to 40-100 ℃; stirring for 20-100min to dissolve the polyamide resin into homogeneous solution.
4. A material according to claim 3, wherein the phosphoric acid solution concentration is 50-98wt%.
5. A material according to claim 3, wherein the polyamide resin weight to phosphoric acid solution volume ratio is 1:5 to 1:20.
6. The material of claim 1, wherein the material does not comprise a plasticizer.
7. The material according to claim 1, wherein the material has a tensile yield strength of > 30MPa and a notched impact strength of > 7KJ/m for a normal temperature simply supported beam 2 The V0 flame retardance is achieved by vertical combustion of 1.6 mm.
8. A method of preparing the material of any one of claims 1-7, comprising the steps of: s1, S3 and S4 are added from a main feeding port of a double-screw extruder after being cold mixed, S2 is added from a feeding port at a first side for melt mixing extrusion to obtain a composite material, and the extrusion temperature of a melting section is 220-250 ℃; the rotating speed of the screw is 200-500rpm; the feeding amount is 40-80kg/h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210391077.0A CN115058116B (en) | 2022-04-14 | 2022-04-14 | Halogen-free flame-retardant corrugated pipe material and preparation method thereof |
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| CN202210391077.0A CN115058116B (en) | 2022-04-14 | 2022-04-14 | Halogen-free flame-retardant corrugated pipe material and preparation method thereof |
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