CN115058116A - 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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Abstract
The invention discloses a halogen-free flame-retardant corrugated pipe material and a preparation method thereof. Prepared from the following raw materials: s1 polyamide, S2 polyamide-coated hypophosphite, an S3 toughening agent, and an auxiliary agent package of S4 containing a lubricant and an antioxidant. The polyamide-coated hypophosphorous acid metal salt enables the flame retardant to be tightly coated in the polyamide, so that on one hand, the heat resistance of the flame retardant is improved, the toxic gas is prevented from being generated to harm human bodies, and on the other hand, the compatibility of the flame retardant and the matrix resin is improved. The method does not need to add a plasticizer, and utilizes the complexation of the chlorinated metal salt to destroy the crystal structure of the polyamide so as to plasticize the polyamide and improve the requirement of material fluidity. The composite material prepared by the invention can achieve V0 level flame retardance, no smoke is generated in the pipeline extrusion process, the environment is friendly, the surface of the extruded corrugated pipe material is smooth, the toughness and the forming are excellent, and the use requirement can be met.
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 a bright surface and high toughness and a preparation method thereof.
Background
Nylon is a widely used engineering plastic, and has a plurality of excellent performances such as high strength, good toughness, high temperature resistance and the like. However, when the nylon material is used as a pipeline material for extrusion, a large amount of plasticizer and flame retardant are often required to be added due to too high hardness, high modulus, flammability and the like. The plasticizer which is common in the market at present 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 partially volatilize in the extrusion process to cause slightly large smoke of a machine head, and the plasticizer has great influence on the health of workers on the site.
Hypophosphite is a flame retardant with low cost and extremely high phosphorus content (about 40 percent), and is widely applied to resins such as PET, PBT, PA, TPU, ABS and the like. There are several disadvantages in use: (1) when the temperature is slightly higher than 130 ℃, the pH is easy to decompose to generate highly toxic pH 3 Gas, it is extremely harmful to human body and environment. The gas generated by the decomposition reduces the surface gloss of the particles and causes pores to appear. (2) When hypophosphite is directly added into polyamide resin, the flame retardant has a large particle size and is formed of inorganic substances, and white pockmarks are formed on the appearance of the particles. (3) Hypophosphite is mainly gas-phase flame retardant, the condensed phase flame retardant capability is slightly poor, and a synergist needs to be matched for use in the using process.
At present, few documents and patents are reported in the aspect of the technology. Chinese patent CN112457663A reports a modified material of flame-retardant nylon corrugated pipe and a preparation method thereof, wherein PA and a flame retardant are directly selected for blending and extrusion, so that the prepared pipe is too hard on one hand, and in addition, the flame retardant is easy to have the conditions of more pores and more pits on the surface of particles without treatment. Chinese patent CN110079021A reports a high-temperature aging resistant flame-retardant polypropylene material for corrugated pipes and a preparation method thereof, and the halogen flame retardant is used, which has great harm to the 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 material prepared by the method uses a halogen flame retardant, so that toxic gas generated by fire disasters greatly harm human bodies. Chinese patent CN1696120A reports that melamine cyanuric acid is synthesized by using a polyamide resin solution as a reaction medium and a preparation method thereof, the problem of overlarge particle size of a flame retardant is solved by adopting MCA generated by the reaction of melamine and cyanuric acid, but the material prepared by the method cannot be used for V0 flame retardance, 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 and is poorly dispersed in a polyamide matrix, and pores and pockmarks are caused on the appearance of particles 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 a bright surface and high toughness and a preparation method thereof. Solves the problems of dispersion of inorganic hypophosphite in a 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 purpose, the technical scheme of the invention is as follows:
a 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 of polyamide-coated hypophosphite, preferably 15-25 parts;
s3, and toughening agent 5-10 parts, preferably 6-8 parts
S4 and an auxiliary agent, wherein the auxiliary agent comprises 0.01-0.1 part of lubricant, preferably 0.05-0.08 part; 0.2-2 parts of antioxidant, preferably 0.4-1 part;
the above-mentioned parts are parts by mass.
As a preferable scheme, the halogen-free flame retardant corrugated pipe material does not contain a plasticizer.
In the invention, the S1 selects polyamide comprising one or more of PA6, PA66, PA610, PA612, PA1012, PA11 and PA12, 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 homogeneous solution of polyamide resin in phosphoric acid 2 PO 2 ·H 2 O stirring for 30-80min, preferably 40-60 min; then dropwise adding a chlorinated metal salt solution, and reacting for 30-100min, preferably 50-80 min;
(2) adding ammonia water into the product obtained in the step (1) to neutralize until the pH value is 6-7, so that dissolved polyamide resin is precipitated and formed into a film, and obtaining a polyamide-coated hypophosphite;
(3) and (3) filtering, drying and crushing the product 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 polyamide resin and phosphoric acid solution, and heating to 40-100 deg.C, preferably 60-80 deg.C; stirring for 20-100min, preferably 40-60min to dissolve the polyamide resin into a homogeneous solution.
In the present invention, the concentration of the phosphoric acid solution is 50 to 98 wt%, preferably 60 to 80 wt%.
In the invention, the weight ratio of the polyamide resin to the volume ratio of the phosphoric acid solution is 1:5-1: 20.
In the invention, the metal chloride salt is one or more of aluminum chloride, lanthanum chloride, cerium chloride and the like.
In the present invention, the NaH is used 2 PO 2 ·H 2 The mass ratio of O to the metal chloride salt is 1: 2-1:5, preferably 1:3-1: 4.
In the step (1) of the present invention, a metal salt and NaH are chlorinated 2 PO 2 ·H 2 And reacting O in the phosphoric acid solution to obtain the inorganic hypophosphite. The phosphoric acid solution is a solvent of the polyamide resin and is also a catalyst for generating the flame retardant, and with the addition of excessive metal chloride salt, metal ions can be complexed with amide bonds to destroy original hydrogen bonds, so that the crystallinity of the polyamide resin is reduced and the polyamide resin becomes soft.
In the step (2), after ammonia water is added, the acidity of the system is reduced, 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 flame retardant is realized, and the plasticized polyamide resin coated inorganic hypophosphite is obtained. The inorganic hypophosphite obtained in the way has the advantages that on one hand, the thermal stability is improved, the safety in the using process is guaranteed, and on the other hand, the condition that the particle appearance is whitish due to the introduction of the inorganic flame retardant can not occur because the surface layer is coated by the 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 is also gathered on the surface with the generation of inorganic hypophosphite, so that the condensed phase added into the system has carbon forming effect. Thereby combining the gas-phase flame retardance of hypophosphite and achieving good synergistic effect.
In the invention, the toughening agent is an ethylene-propylene block copolymer grafted polar group, a nylon elastomer, an epoxy toughening agent and the like, and the nylon elastomer is preferred.
In the invention, the antioxidant is one or more of copper salt antioxidant, phosphate antioxidant, hindered phenol antioxidant, phosphite antioxidant, thioester antioxidant and polymer antioxidant, preferably copper salt antioxidant, more preferably one or more of H1607, H3336, H3376, H3344, S5050, S5070, LXR568, S80 and 608.
In the present invention, the lubricant is one or more of fluorine, wax and silicone, and PTFE and AC540A are preferred.
The preparation method of the halogen-free flame-retardant corrugated pipe material comprises the following steps:
adding the components S1 and S3 from two main feeding ports by using a double-screw extruder, adding S2 from a first side feeding port, and carrying out melt mixing extrusion to obtain the composite material, wherein the extrusion temperature of a melting section is preferably 220-; the rotation speed of the screw is 200-500rpm, preferably 300-400 rpm; the feeding amount is 40-80kg/h, preferably 45-60 kg/h.
The invention skillfully selects the substance of the metal chloride salt, on one hand, the substance is used as a reactant for producing the flame retardant by reacting with sodium hypophosphite, and on the other hand, the substance can play a role of plasticizing polyamide by complexing hydrogen bonds. Therefore, the plasticized polyamide is low in modulus, relatively soft and capable of wrapping the flame retardant better, and the aims of improving the temperature resistance and the compatibility with a matrix of the flame retardant are fulfilled.
Halogen-free flame-retardant corrugated pipe material with tensile yield strength of more than 30MPa and normal-temperature simple supported beam notch impact strength of more than 7KJ/m 2 And 1.6mm vertical combustion reaches V0 flame retardance.
The invention has the following advantages:
(1) the method does not need to add a plasticizer, and utilizes the complexation of the chlorinated metal salt to destroy the crystal structure of the polyamide so as to plasticize the polyamide and improve the requirement of material fluidity. On one hand, the cost is reduced, on the other hand, equipment of an available liquid pump is not required to be selected, the universality is stronger, and the method is very favorable for the on-site environment and the artificial health.
(2) The phosphinate metal salt coated by the polyamide ensures that the flame retardant is tightly coated in the polyamide, thereby improving the heat resistance of the flame retardant, preventing toxic gas from generating to harm human bodies and improving the compatibility of the flame retardant and matrix resin.
Drawings
FIG. 1 shows, from left to right, extruded pipes of pellets produced according to the process of example 1, comparative example 2, comparative example 3 and comparative example 4;
FIG. 2 shows, from left to right, extruded pipes of pellets produced according to the methods of examples 2, 3, 4 and 5.
Detailed Description
The technical solutions of the present invention are further illustrated by examples, but the scope of the present invention is not limited to the described scope of the examples.
The raw material information used in the examples and comparative examples is as follows in table 1:
TABLE 1 sources of raw materials
| Raw material | Characteristics of the material | Manufacturer of the product |
| 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 | Engineering plastic for flat-topped mountain horse |
| PA612 | Wide range of Shandong | |
| PA1012 | Wide range of Shandong | |
| Phosphoric acid solution | 98wt％ | Chemical engineering of Jinan elements |
| NaH 2 PO 2 ·H 2 O | Analytical purity | Tianjin chemical reagent for Kemiou |
| AlCl 3 ·6H 2 O | Analytical purity | Shanghai Jinshan chemical plant |
| LaCl 3 ·7H 2 O | Analytical purity | TIANJIN KWANGFU FINE CHEMICAL INDUSTRY Research Institute |
| Aqueous ammonia | Analytical purity | Tianjin City Koimei chemical reagent |
| BBSA | N-butylbenzenesulphonamide | Wuhan La Na Bai pharmaceutical chemical Co Ltd |
| GR216 | POE-g-MAH | Dow's disease |
| Pebex 5533 | Nylon 12 polyether block copolymer | Hadama |
| N493 | Dow's disease | |
| PTFE | Polytetrafluoroethylene powder | Japan Dajin |
| AC540A | Ethylene acrylic acid copolymer wax powder | Honeywell |
| Antioxidants, 1010, 1076, 168, 626 | SUNSHOW (YANTAI) SPECIALTY CHEMICAL Co.,Ltd. | |
| LXR568 | Kelaien |
The twin-screw extruder used was a product of kyron Nanjing machinery, Inc., and the single-screw extruder used was a product of Hairyka, and the appearance was evaluated by visual observation using an extruded tube at 230 ℃.
The flame retardant rating tests in the examples and comparative examples were conducted using the UL-94 standard; tensile strength was tested using ISO527, and simple beam notched impact strength was tested using ISO 179. The apparent morphology of the tubes was observed by eye.
Preparation of example 1
(1) 100g L2140 g of 95 wt% phosphoric acid solution was put into a three-necked flask with a stirrer and a thermometer and heated to 40 ℃; stirring for 100min allowed the polyamide resin to dissolve into a homogeneous solution.
(2) 30g of NaH was added 2 PO 2 ·H 2 Stirring is continued for 30 min. Then 100g of 60 wt% AlCl was added dropwise 3 And (5) reacting for 30 min.
(3) Adding ammonia water to neutralize until the pH value is 6-7, so that the dissolved polyamide resin is precipitated to form a film, and obtaining the polyamide-coated hypophosphite.
Preparation of example 2
(1) 100g of EPR24 and 2000g of a 50 wt% phosphoric acid solution were put into a three-necked flask equipped 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 was added 2 PO 2 ·H 2 Stirring is continued for 80 min. Then 200g of 50 wt% AlCl were added dropwise 3 And (5) solution reaction for 100 min.
(3) Adding ammonia water to neutralize until the pH value is 6-7, so that the dissolved polyamide resin is precipitated to form a film, and obtaining the polyamide-coated hypophosphite.
Preparation of example 3
(1) 100g of 2140 g of 80 wt% phosphoric acid solution was put into a three-necked flask equipped 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 was added 2 PO 2 ·H 2 Stirring is continued for 40 min. Then 100g of 40 wt% LaCl were added dropwise 3 Solution and reaction for 50 min.
(3) Adding ammonia water to neutralize until the pH value is 6-7, so that the dissolved polyamide resin is precipitated to form a film, and obtaining the polyamide-coated hypophosphite.
Preparation of example 4
(1) 100g of EPR24 and 1500g of a 60 wt% phosphoric acid solution were put into a three-necked flask equipped 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 was added 2 PO 2 ·H 2 Stirring is continued for 60 min. Then 100g of 80 wt% LaCl were added dropwise 3 And (5) reacting for 80 min.
(3) Adding ammonia water to neutralize until the pH value is 6-7, so that the dissolved polyamide resin is precipitated to form a film, and obtaining the polyamide-coated hypophosphite.
Preparation of example 5
(1) 100gPA610, 1200g of 70 wt% phosphoric acid solution was put into a three-necked 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 was added 2 PO 2 ·H 2 O is continuously stirred for 50min. Then 100g of 60 wt% AlCl was added dropwise 3 And (5) reacting for 60 min.
(3) Adding ammonia water to neutralize until the pH value is 6-7, so that the dissolved polyamide resin is precipitated to form a film, and obtaining the polyamide-coated hypophosphite.
Preparation of example 6 (comparative)
(1) 100g L2140 g of 95 wt% phosphoric acid solution was added to a three-necked flask with a stirrer and a thermometer, and heated to 40 ℃; stirring for 100min allowed the polyamide resin to dissolve into a homogeneous solution.
(2) 40g of NaH was added 2 PO 2 ·H 2 Stirring is continued for 30 min. Then 100g of 60 wt% AlCl was added dropwise 3 And (5) reacting for 30 min.
(3) And adding a small amount of ammonia water to enable the pH of the solution to be 2, so that the dissolved polyamide resin is precipitated to form a film, and thus obtaining the polyamide-coated hypophosphite.
Preparation of example 7 (comparative)
(1) 100g L2140 g of 95 wt% phosphoric acid solution was put into a three-necked flask with a stirrer and a thermometer and heated to 40 ℃; stirring for 100min allowed the polyamide resin to dissolve into a homogeneous solution.
(2) 40g of NaH was added 2 PO 2 ·H 2 Stirring is continued for 30 min.
(3) Adding ammonia water to neutralize until the pH value is 6-7, so that the dissolved polyamide resin is precipitated to form a film, and obtaining the polyamide-coated hypophosphite.
Preparation of example 8 (comparative)
(1) 100g L2140 g of 95 wt% phosphoric acid solution was put into a three-necked flask with a stirrer and a thermometer and heated to 40 ℃; stirring for 100min allowed the polyamide resin to dissolve into a homogeneous solution.
(2) 40g of NaH was added 2 PO 2 ·H 2 Stirring is continued for 30 min. Then 100g of 40 wt% AlCl was added dropwise 3 And (5) reacting for 30 min.
(3) Adding ammonia water to neutralize until the pH value is 6-7, so that the dissolved polyamide resin is precipitated to form a film, and obtaining 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 fed from a main feed port, and 10 parts of the polyamide-coated aluminum hypophosphite prepared in example 1 were fed from a first side feed port into a twin-screw extruder.
The mixture is melted and mixed in a double-screw extruder, and the extrusion temperature of each section is as follows: 86 deg.C, 140 deg.C, 220 deg.C, 230 deg.C, 220 deg.C, 240 deg.C, 220 deg.C, 230 deg.C, 200rpm, and 40kg/h feeding amount.
Comparative 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 are cold mixed and then added from a main feeding port, 10 parts of aluminum hypophosphite is added into a double-screw extruder from a first side feeding port, and 7 parts of BBSA is added from an injection port.
The mixture is melted and mixed in a double-screw extruder, and the extrusion temperature of each section is as follows: 86 deg.C, 140 deg.C, 220 deg.C, 230 deg.C, 220 deg.C, 240 deg.C, 220 deg.C, 230 deg.C, 200rpm, and 40kg/h feeding amount.
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 fed from a main feed port, and 10 parts of the polyamide-coated aluminum hypophosphite of preparative example 6 were fed from a first side feed port into a twin-screw extruder.
The mixture is melted and mixed in a double-screw extruder, and the extrusion temperature of each section is as follows: 86 deg.C, 140 deg.C, 220 deg.C, 230 deg.C, 220 deg.C, 240 deg.C, 220 deg.C, 230 deg.C, 200rpm, and 40kg/h feeding amount.
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 fed from a main feed port, and 10 parts of the polyamide-coated aluminum hypophosphite of preparative example 7 were fed from a first side feed port into a twin-screw extruder.
The mixture is melted and mixed in a double-screw extruder, and the extrusion temperature of each section is as follows: 86 ℃, 140 ℃, 220 ℃, 240 ℃, 220 ℃, 230 ℃ and a rotation speed of 200rpm, and a feeding amount of 40kg/h to obtain the mixture.
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 fed from a main feed port, and 10 parts of the polyamide-coated aluminum hypophosphite of preparative example 8 were fed from a first side feed port into a twin-screw extruder.
The mixture is melted and mixed in a double-screw extruder, and the extrusion temperature of each section is as follows: 86 ℃, 140 ℃, 220 ℃, 240 ℃, 220 ℃, 230 ℃ and a rotation speed of 200rpm, and a feeding amount of 40kg/h to obtain the mixture.
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 were cold-mixed and fed from the main feed port, and 35 parts of the polyamide-coated aluminum hypophosphite prepared in example 2 were fed from the first side feed port into the twin-screw extruder.
The mixture is melted and mixed in a double-screw extruder, and the extrusion temperature of each section is as follows: 86 deg.C, 140 deg.C, 220 deg.C, 250 deg.C, 220 deg.C, 230 deg.C, 220 deg.C, 240 deg.C, 220 deg.C, 230 deg.C, 500rpm, and 60kg/h of feed amount.
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 fed from the main feeding port, and 15 parts of the polyamide-coated lanthanum hypophosphite of preparation example 3 was fed from the first side feeding port to the twin-screw extruder.
The mixture is melted and mixed in a double-screw extruder, and the extrusion temperature of each section is as follows: 86 deg.C, 140 deg.C, 220 deg.C, 230 deg.C, 220 deg.C, 240 deg.C, 220 deg.C, 230 deg.C, 300rpm, and a 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 introduced from the main feed port, and 25 parts of the polyamide-coated lanthanum hypophosphite of preparatory example 4 were introduced from the first side feed port into the twin-screw extruder.
The mixture is melted and mixed in a double-screw extruder, and the extrusion temperature of each section is as follows: 86 deg.C, 140 deg.C, 220 deg.C, 240 deg.C, 220 deg.C, 230 deg.C, 400rpm, and 80kg/h of feed amount.
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 fed from the main feed port, and 20 parts of the polyamide-coated aluminum hypophosphite of preparative example 5 were fed from the first side feed port into the twin-screw extruder.
The mixture is melted and mixed in a double-screw extruder, and the extrusion temperature of each section is as follows: 86 deg.C, 140 deg.C, 220 deg.C, 235 deg.C, 220 deg.C, 230 deg.C, 350rpm, and 55kg/h of feed amount.
The properties of the examples and comparative products are shown in Table 1.
TABLE 1 Properties of the examples and comparative examples
It can be seen from comparative example 1 and comparative example 1 that untreated aluminum hypophosphite had white spots and holes on the surface of the pipe due to decomposition during extrusion and the non-melting of the flame retardant, as shown in fig. 1. As can be seen from comparative example 2, if the amount of ammonia added in the solution during the synthesis of the polyamide-coated aluminum hypophosphite was insufficient, resulting in insufficient precipitation of polyamide, the finally formed flame retardant was not coated with polyamide, and ammonium phosphate having a char-forming effect could not be formed, resulting in a slightly poor flame retardant effect and poor appearance of the pipe. It can be seen from the comparison example 3 that if the chlorinated metal salt is not added, the flame retardant effect is poor if only the hydrated sodium hypophosphite is added, and in addition, the toughness of the material is poor because no plasticizing effect exists. As can be seen from comparative example 4, if NaH is used 2 PO 2 ·H 2 O and AlCl 3 In an inappropriate ratio of AlCl 3 Too low content of (b) results in insufficient generation of aluminum hypophosphite and insufficient plasticizing effect of chloride ions, and finally, the toughening and flame retarding effects are not achieved.
It can be seen from examples 2, 3, 4 and 5 that the pipe material with good appearance and good low-temperature toughness can be obtained by the method of the present invention, as shown in FIG. 2.
Claims (10)
1. A halogen-free flame-retardant corrugated pipe material is prepared from the following raw materials:
s1, 65-85 parts of polyamide, preferably 70-80 parts;
s2, 10-35 parts of polyamide-coated hypophosphite, preferably 15-25 parts;
s3, and toughening agent 5-10 parts, preferably 6-8 parts
S4 and an auxiliary agent, wherein the auxiliary agent comprises 0.01-0.1 part of lubricant, preferably 0.05-0.08 part; 0.2-2 parts of antioxidant, preferably 0.4-1 part;
the above-mentioned portions are mass portions.
2. The material of claim 1, wherein S1 is selected from polyamide comprising one or more of PA6, PA66, PA610, PA612, PA1012, PA11, and PA 12.
3. A material according to claim 1 or 2, characterized in that said S2 polyamide-coated hypophosphite is prepared by a process comprising the following steps:
(1) addition of NaH to a homogeneous solution of polyamide resin in phosphoric acid 2 PO 2 ·H 2 O stirring for 30-80min, preferably 40-60 min; then dropwise adding a chlorinated metal salt solution, and reacting for 30-100min, preferably 50-80 min;
(2) adding ammonia water into the product obtained in the step (1) to neutralize until the pH value is 6-7, so that dissolved polyamide resin is precipitated and formed into a film, and obtaining a polyamide-coated hypophosphite;
(3) and (3) filtering, drying and crushing the product obtained in the step (2) to obtain a powdery product.
4. The material of claim 3, wherein the chlorinated metal salt is one or more of aluminum chloride, lanthanum chloride, and cerium chloride.
5. A material according to claim 3, characterized in that said process for the preparation of a homogeneous solution of polyamide resin in phosphoric acid comprises the following steps: mixing polyamide resin and phosphoric acid solution, and heating to 40-100 deg.C, preferably 60-80 deg.C; stirring for 20-100min, preferably 40-60min to dissolve the polyamide resin into a homogeneous solution.
6. A material according to claim 5, characterized in that the phosphoric acid solution has a concentration of 50-98 wt.%, preferably 60-80 wt.%.
7. The material of claim 5, wherein the weight to volume ratio of polyamide resin to phosphoric acid solution is from 1:5 to 1: 20.
8. The material of claim 1, wherein the material does not contain a plasticizer.
9. The material of claim 1, wherein the material has a tensile yield strength of greater than 30MPa and a room temperature simple beam notched impact strength of greater than 7KJ/m 2 And the 1.6mm vertical burning reaches V0 flame retardance.
10. A method of making a material according to any one of claims 1 to 9, comprising the steps of: adding the components S1 and S3 from two main feeding ports by using a double-screw extruder, adding S2 from a first side feeding port, and carrying out melt mixing extrusion to obtain the composite material, wherein the extrusion temperature of a melting section is preferably 220-; the rotation speed of the screw is 200-500rpm, preferably 300-400 rpm; the feeding amount is 40-80kg/h, preferably 45-60 kg/h.
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