CN110922518B - Water-resistant intumescent flame retardant and preparation method and application thereof - Google Patents
Water-resistant intumescent flame retardant and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a water-resistant intumescent flame retardant and a preparation method and application thereof. The waterproof intumescent flame retardant is prepared by a melamine derivative and a hydrophobic polymer through a melt reaction, wherein the molar ratio of the melamine derivative to the hydrophobic polymer is 1:1 to 5. The intumescent flame retardant prepared by the invention is a nitrogen-phosphorus integrated high molecular flame retardant, can improve the compatibility with matrix resin by adjusting the addition amount of a hydrophobic polymer and reserving part of active groups, forms a compact intumescent carbon layer on the surface of the polymer through the synergistic effect of nitrogen and phosphorus in the combustion process of the material, and has low smoke, no toxicity and no corrosion in the combustion process. The flame retardant can be used independently, can also be compounded with inorganic filler, can be applied to flame retardance of nylon materials, and can be compounded with flaky inorganic powder to effectively solve the problem of a candlewick effect generated by combustion of glass fiber reinforced nylon materials and obtain a good flame retardant effect.
Description
Technical Field
The invention relates to a flame retardant, in particular to a waterproof intumescent flame retardant and a preparation method and application thereof.
Background
The flame retardant is a functional assistant for imparting flame retardancy to a polymer, is designed mainly for flame retardancy modification of a high molecular material, and can be classified into halogen, nitrogen, phosphorus, silicon, inorganic and the like according to the type of a flame retardant element. At present, most of the flame retardants used at home and abroad are halogen flame retardants, and have the characteristics of small addition amount, high flame retardant efficiency and the like, but a large amount of toxic dense smoke and corrosive gas can be generated in the combustion process, so that the environment is polluted, and the health of human beings is harmed. Therefore, the use of halogen flame retardants is being prohibited gradually, and hazardous substances such as polybromodiphenyl ether, polybromobiphenyl, and the like have been all prohibited. The inorganic flame retardant has the advantages of good thermal stability, non-volatility, no toxicity and the like, but has large addition amount, and the mechanical property of the filled material is greatly deteriorated. The nitrogen flame retardant has low volatility and low toxicity of the nitrogen flame retardant and decomposition products, so that the nitrogen flame retardant accords with the trend of the current flame retardant developing towards high efficiency and low toxicity, the nitrogen flame retardant has poor single use effect and is best in effect when compounded with a phosphorus flame retardant and a char forming agent, and the existing intumescent flame retardant has the defects of easiness in moisture absorption, poor water resistance and the like. The nylon as an engineering plastic has good mechanical property, electrical property, heat resistance and processability. The addition of the glass fiber overcomes the defects in the aspect of mechanical property, but simultaneously, the nylon is easier to burn due to the candle wick effect. Therefore, the development of the water-resistant intumescent flame retardant which has low volatility, high efficiency, no toxicity, low smoke and good compatibility with the base material and the application of the flame retardant to nylon have great social and economic benefits.
Patent ZL201610156718.9 discloses a preparation method of a halogen-free flame-retardant glass fiber reinforced nylon 6 material, wherein piperazine pyrophosphate and hypophosphite are compounded to have a good flame-retardant effect, and the main purpose is to reduce the PH value in a single hypophosphite system3The amount of (a) released. Patent ZL201410087920.1 discloses a preparation method of high heat-resistant halogen-free flame-retardant nylon 6, which is characterized in that flame retardant red phosphorus or melamine cyanurate, nylon 6, a toughening agent and a compatilizer are blended to prepare a halogen-free flame-retardant nylon 6 material. Although the prepared nylon material has excellent flame retardant effect, the problem of the candle wick effect caused by the glass fiber reinforced nylon is still not solved. Patent CN 106479165 a discloses a preparation method of a halogen-free flame-retardant long glass fiber reinforced PA6 composite material. The PA6 is blended with powder such as flame retardant DOPO, charring agent, synergist, nucleating agent, tackifier and the like, so that the processing performance and the overall strength of the PA6 material are enhanced, and the problem of flame retardance of the glass fiber reinforced material is not solved.
Disclosure of Invention
The invention aims to provide a water-resistant intumescent flame retardant and a preparation method and application thereof, and aims to solve the problems that the existing intumescent flame retardant is poor in water resistance and the effective flame-retardant components are lost after long-term soaking.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a water-resistant intumescent flame retardant which is prepared by copolymerizing a melamine derivative and a hydrophobic polymer through a melt reaction, wherein the molar ratio of the melamine derivative to the hydrophobic polymer is 1: 1-5.
In one embodiment of the present invention, the melamine derivative has a structure represented by the following formula:
wherein R is
In one embodiment of the present invention, the melamine derivative may specifically be aminotrimethylene phosphonic acid melamine (relative molecular mass 551 Da).
In one embodiment of the invention, the hydrophobic polymer is selected from one or more of the following:
an epoxy resin with two epoxy groups,
copolymers of styrene and glycidyl methacrylate with four to six epoxy groups,
copolymers of styrene and maleic anhydride with four to five anhydride groups, polypropylene glycol diglycidyl ether,
polymers with one or two isocyanate groups.
In one embodiment of the present invention, a copolymer of styrene and glycidyl methacrylate with four to six epoxy groups can be prepared by referring to yellow glow in the synthesis study of styrene-glycidyl methacrylate block copolymer [ D ].2008 ].
In one embodiment of the invention, the copolymers of styrene and maleic anhydride with four or five anhydride groups can be referred to: such as the preparation method described in Lixiuqing et al, "Studies on Synthesis and Properties of styrene-maleic anhydride copolymer" [ J ] university of inner Mongolia Industrial Association ", 2006(3) Liaozhenfu et al," Studies on Synthesis and Properties of styrene/maleic anhydride copolymer "[ J ] elastomer, 2004,14(6):19-21.
In one embodiment of the present invention, the number average molecular weight of the hydrophobic polymer is between 3000 and 15000.
The invention also provides a preparation method of the water-resistant intumescent flame retardant, which comprises the following steps:
adding a melamine derivative and a hydrophobic polymer into an internal mixer or a screw extruder according to a molar ratio of 1: 1-5, blending for 0.1-1 h at a temperature above the melting temperature, and after the reaction is finished, cooling and drying the polymer to obtain the waterproof intumescent flame retardant. The water-resistant intumescent flame retardant is a novel nitrogen-phosphorus flame retardant.
In one embodiment of the present invention, the melting temperature is 150-.
In one embodiment of the present invention, the preparation method of the melamine derivative comprises:
mixing aminotrimethylene phosphonic acid and a solvent, adding the mixture into a reactor, stirring, introducing nitrogen, heating to 90-150 ℃, preserving heat, dissolving melamine with the solvent, dropwise adding the melamine into the reactor, keeping the temperature for reaction for 2-6 hours, stopping stirring after the reaction is finished, stopping heating, stopping introducing nitrogen, distilling under reduced pressure to remove the solvent, and finally drying to obtain the melamine derivative.
In one embodiment of the present invention, the solvent is selected from one or more of water, methanol or ethanol.
The invention also provides the application of the water-resistant intumescent flame retardant, the flaky inorganic powder and the processing aid are compounded and blended and added into the glass fiber reinforced nylon resin, the problem of the candlewick effect in the glass fiber reinforced nylon is solved through the synergistic effect of nitrogen and phosphorus and the barrier effect of the flaky powder, and the glass fiber reinforced flame retardant nylon product with good comprehensive performance is prepared.
The invention also provides a halogen-free flame-retardant glass fiber reinforced nylon material which comprises the following components in percentage by weight:
in one embodiment of the present invention, the nylon resin is selected from one or more of nylon 6, nylon 66, nylon 610, and the like.
In one embodiment of the present invention, the flaky inorganic powder is one or more selected from flaky kaolin, graphene oxide, graphite oxide, and organic montmorillonite.
In one embodiment of the invention, the antioxidant is selected from one or more of antioxidant 168, antioxidant 1010, antioxidant B215 or hindered phenol 1098.
In one embodiment of the invention, the anti-drip agent is selected from polytetrafluoroethylene anti-drip agents.
The invention has the innovativeness that the flame retardant integrates nitrogen and phosphorus, an expanded carbon layer is formed during combustion, and the problems of poor water resistance and loss of effective flame-retardant components after long-term soaking of the conventional expanded flame retardant are solved due to the excellent water resistance of the flame retardant.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts the melamine derivative and the hydrophobic compound as raw materials to synthesize the nitrogen-phosphorus integrated intumescent flame retardant, has high phosphorus content, is a high molecular polymer, is compounded with the flaky inorganic powder, can effectively solve the problem of the candlewick effect of the glass fiber reinforced nylon, and is a high-efficiency flame retardant of polymer materials such as nylon resin and the like.
The intumescent flame retardant disclosed by the invention belongs to a high-molecular flame retardant, a compact intumescent carbon layer is generated on the surface of a material by combustion, and the generated product is low in smoke, non-toxic, safe and environment-friendly, excellent in flame retardant property and high in thermal stability, and meets the requirements of the flame retardant at present. The addition amount of the hydrophobic compound is adjusted, part of active groups are reserved, the compatibility and the dispersibility of the halogen-free flame retardant in the material are improved, and the optimal flame retardant effect is achieved.
The intumescent flame retardant and the preparation method thereof have the advantages of simple processing technology, easily obtained raw materials and suitability for industrial production. The flame-retardant nylon material is widely applied to most flame-retardant high polymer materials, and is particularly suitable for glass fiber reinforced nylon materials.
Detailed Description
The following examples are given by way of illustration only and are not to be construed as limiting the scope of the invention, which is to be construed as providing the skilled person in the art with a few insubstantial modifications and adaptations of the invention in light of the above teachings.
Preparation of aminotrimethylene phosphonic acid melamine applied in the following examples: mixing aminotrimethylene phosphonic acid and water, adding the mixture into a reactor, stirring, introducing nitrogen, heating to 100 ℃, keeping the temperature, dissolving melamine in water, and then dropwise adding the dissolved melamine into the reactor, wherein the reaction molar ratio of aminotrimethylene phosphonic acid to melamine is 1: 2. And (3) keeping the temperature for reacting for 4 hours, stopping stirring after the reaction is finished, stopping heating, stopping introducing nitrogen, removing the solvent by reduced pressure distillation, and finally drying to obtain the amino trimethylene phosphonic acid melamine (relative molecular mass 551 Da).
Example 1:
15 g (0.018 mol) of aminotrimethylene phosphonic acid melamine (relative molecular mass 551Da) is added into an internal mixer at the temperature of 180 ℃, after the mixture is melted, 41.4 g (epoxy value: 0.14 unit) of a styrene-GMA copolymer is added, and the mixture reacts for 20 minutes under the condition of the rotating speed of 60 revolutions per minute to obtain an aminotrimethylene phosphonic acid melamine-styrene-GMA block copolymer marked as A.
Example 2:
20g (0.036 mol) of aminotrimethylene phosphonic acid melamine (relative molecular mass 551Da) was put into a Haake rheometer at 150 ℃, after melting, 40.36 g (epoxy value 0.52) of bisphenol A epoxy resin was added, and the mixture was reacted for 40 minutes at a rotation speed of 60 rpm to obtain an aminotrimethylene phosphonic acid melamine-epoxy resin block copolymer, which was labeled B.
Example 3:
20g (0.036 mol) of amino trimethylene phosphonic acid melamine (relative molecular mass 551Da) is added into a Haake rheometer at the temperature of 200 ℃, after melting, 50.8 g (number average molecular weight 700Da, 0.072 mol) of polypropylene glycol diisocyanate is added, and reaction is carried out for 30 minutes under the condition of the rotating speed of 60r/min, so as to obtain the amino trimethylene phosphonic acid melamine-polypropylene glycol diisocyanate block copolymer marked as C.
Example 4:
17 g (0.03 mol) of aminotrimethylene phosphonic acid melamine (relative molecular mass 551Da) is added into a Haake rheometer at 240 ℃, after melting, 39.5 g (number average molecular weight 640Da, 0.06 mol) of polypropylene glycol diglycidyl ether is added, and reaction is carried out for 50 minutes at the rotation speed of 60r/min, so as to obtain the aminotrimethylene phosphonic acid melamine-polypropylene glycol diglycidyl ether block copolymer which is marked with D.
Example 5:
14 g (0.025 mol) of amino trimethylene phosphonic acid melamine (relative molecular mass 551Da) is added into a Haake rheometer at 220 ℃, after melting, 41 g (number average molecular weight 3200Da) of maleic anhydride grafted polyethylene wax is added, and reaction is carried out for 15 minutes under the condition of 60 revolutions per minute, so as to obtain the amino trimethylene phosphonic acid melamine-maleic anhydride grafted polyethylene wax block copolymer marked as E.
Example 6:
25 g of amino trimethylene melamine phosphonate (relative molecular mass 551Da) is added into a Haake rheometer at 160 ℃, 34.1 g of diphenylmethane-4, 4' -diisocyanate (MDI) is added after melting, and the reaction is carried out for 60 minutes under the condition of 60 revolutions per minute to obtain the amino trimethylene melamine phosphonate-MDI block copolymer, which is marked as: F.
the intumescent flame retardants (A-F) obtained in examples 1 to 6 were subjected to a water resistance test: 20g of the sample was placed in 100g of deionized water and stirred at the set temperature (25 ℃, 40 ℃, 60 ℃) for 60 min. The solution was rapidly filtered at this temperature, the filtrate was placed in a 250mL beaker (empty beaker mass W0) and dried in an oven at 100 ℃ to constant weight (total mass W1), and the solubility of the sample at a certain temperature was calculated as Ws ═ W1-W0 (g), and each sample was measured 5 times and averaged. The results obtained are compared with the intumescent flame retardant ammonium polyphosphate (APP) in table 1.
TABLE 1 results of water resistance test of examples 1 to 6 flame retardants
The raw materials used in the following application examples are as follows:
nylon 6: spinning stage
Glass fiber: alkali-free chopped glass fiber (chopped length 3-12mm)
Flaky inorganic powder: graphene oxide (plate diameter: 0.5-5 μm, thickness: 0.8-1.2nm), graphite oxide (plate diameter: 0.5-5 μm, thickness: 1-3nm), kaolin (average particle diameter: 0.5-5 μm), graphene (average thickness: 1-3nm, diameter: 3-5 μm)
Antioxidant: antioxidant 168 tris (2, 4-di-tert-butylphenyl) phosphite, antioxidant 1010 tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, antioxidant B215, hindered phenol 1098(N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine)
Anti-dripping agent: polytetrafluoroethylene micropowder (average particle size 1.6 micron)
Comparative example 1:
(1) weighing 654.4 g of PA, 24 g of glass fiber, 2150.4 g of antioxidant B and 1.2 g of anti-dripping agent polytetrafluoroethylene micro powder
(2) The raw materials are sequentially added into a Haake rheometer, the temperature is 240 ℃, the rotating speed is 60r/min, the mixture is blended for 10min, and the performance detection of the obtained glass fiber reinforced nylon 6 is shown in Table 2.
Application example 1:
(1) weighing 634.56 g of PA, 24 g of glass fiber, 20g of aminotrimethylene phosphonic acid melamine-styrene-GMA A serving as a halogen-free flame retardant, 0.4 g of graphene oxide, 2150.4 g of antioxidant B and 0.64 g of polytetrafluoroethylene micropowder serving as an anti-dripping agent.
(2) The raw materials are sequentially added into a Haake rheometer, the temperature is 250 ℃, the rotating speed is 60r/min, the blending is carried out for 10min, and the performance detection of the obtained halogen-free flame-retardant glass fiber nylon 6 is shown in Table 2.
Application example 2:
(1) weighing 637.92 g of PA, 24 g of glass fiber, 16 g of block copolymer B of amino trimethylene phosphonic acid melamine-epoxy resin as a halogen-free flame retardant, 0.8 g of graphite oxide, 1680.48 g of antioxidant and 0.8 g of polytetrafluoroethylene micropowder as an anti-dripping agent.
(2) The raw materials are sequentially added into a Haake rheometer, the temperature is 260 ℃, the rotating speed is 60r/min, the blending is carried out for 8min, and the performance detection of the obtained halogen-free flame-retardant glass fiber nylon 6 is shown in Table 2.
Application example 3:
(1) weighing 632.96 g of PA, 24 g of glass fiber, 20g of segmented copolymer C of amino trimethylene phosphonic acid melamine-polypropylene glycol diisocyanate serving as a halogen-free flame retardant, 1.6 g of kaolin, 10100.24 g of antioxidant and 1.2 g of polytetrafluoroethylene micropowder serving as an anti-dripping agent.
(2) The raw materials are sequentially added into a Haake rheometer, the temperature is 240 ℃, the rotating speed is 45r/min, the blending is carried out for 10min, and the performance detection of the obtained halogen-free flame-retardant glass fiber nylon 6 is shown in Table 2.
Application example 4:
(1) weighing 633.68 g of PA, 24 g of glass fiber, 17.6 g of halogen-free flame retardant amino trimethylene phosphonic acid melamine-polypropylene glycol diglycidyl ether segmented copolymer D, 2.4 g of graphene, 10100.72 g of antioxidant and 1.6 g of anti-dripping agent polytetrafluoroethylene micro powder.
(2) The raw materials are sequentially added into a Haake rheometer, the temperature is 250 ℃, the rotating speed is 30r/min, the blending is 15min, and the performance detection of the obtained halogen-free flame-retardant glass fiber nylon 6 is shown in Table 2.
The halogen-free flame-retardant glass fiber reinforced nylon material prepared in application examples 1-4 is subjected to injection molding according to the standard to form a test sample strip, vertical combustion is performed according to UL94-2009 to test, tensile property is performed according to ASTM D-638, bending property is performed according to ASTM D-790, and notched impact strength is performed according to ASTM D-256.
Table 2 comparative example 1 application examples 1 to 4 performance test results
The embodiment shows that the intumescent flame retardant prepared by the invention is a nitrogen-phosphorus-integrated macromolecular flame retardant, the compatibility between the intumescent flame retardant and matrix resin can be improved by adjusting the addition amount of the hydrophobic polymer and reserving part of active groups, a compact intumescent carbon layer is formed on the surface of the polymer through the synergistic effect of nitrogen and phosphorus in the combustion process of the material, and the combustion process is low in smoke, non-toxic and non-corrosive. The flame retardant can be used independently, can also be compounded with inorganic filler, can be applied to flame retardance of nylon materials, and can be compounded with flaky inorganic powder to effectively solve the problem of a candlewick effect generated by combustion of glass fiber reinforced nylon materials and obtain a good flame retardant effect.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (6)
1. The application of the water-resistant intumescent flame retardant is characterized in that the water-resistant intumescent flame retardant, flaky inorganic powder and processing aid are compounded and blended into a nylon material to prepare a glass fiber reinforced flame retardant nylon product, so that the problem of the candlewick effect of glass fiber reinforced nylon is solved;
the waterproof intumescent flame retardant is prepared by copolymerizing melamine derivatives and hydrophobic polymers through a melting reaction, wherein the molar ratio of the melamine derivatives to the hydrophobic polymers is 1: 1-5;
the melamine derivative is specifically amino trimethylene phosphonic acid melamine;
the hydrophobic polymer is selected from one or more of the following substances:
an epoxy resin with two epoxy groups,
copolymers of styrene and glycidyl methacrylate with four to six epoxy groups,
copolymers of styrene and maleic anhydride with four to five anhydride groups, polypropylene glycol diglycidyl ether,
polymers with one or two isocyanate groups.
2. The halogen-free flame-retardant glass fiber reinforced nylon material is characterized by comprising the following components in percentage by weight:
the waterproof intumescent flame retardant is prepared by copolymerizing melamine derivatives and hydrophobic polymers through a melting reaction, wherein the molar ratio of the melamine derivatives to the hydrophobic polymers is 1: 1-5;
the melamine derivative is specifically amino trimethylene phosphonic acid melamine;
the hydrophobic polymer is selected from one or more of the following substances:
an epoxy resin with two epoxy groups,
copolymers of styrene and glycidyl methacrylate with four to six epoxy groups,
copolymers of styrene and maleic anhydride with four to five anhydride groups, polypropylene glycol diglycidyl ether,
polymers with one or two isocyanate groups.
3. The halogen-free flame-retardant glass fiber reinforced nylon material as claimed in claim 2, wherein the preparation method of the water-resistant intumescent flame retardant comprises the following steps:
adding a melamine derivative and a hydrophobic polymer into an internal mixer or a screw extruder according to a molar ratio of 1: 1-5, blending for 0.1-1 h at a temperature above the melting temperature, and after the reaction is finished, cooling and drying the polymer to obtain the waterproof intumescent flame retardant.
4. The halogen-free flame-retardant glass fiber reinforced nylon material as claimed in claim 3, wherein the preparation method of the melamine derivative comprises the following steps:
mixing aminotrimethylene phosphonic acid and a solvent, adding the mixture into a reactor, stirring, heating to 90-150 ℃, dissolving melamine with the solvent, dropwise adding the mixture into the reactor, reacting for 2-6 hours with the molar ratio of the aminotrimethylene phosphonic acid to the melamine being 1: 1-6, removing the solvent after the reaction is finished, and finally drying to obtain the melamine derivative.
5. The halogen-free flame-retardant glass fiber reinforced nylon material as claimed in claim 4, wherein the solvent is selected from one or more of water, methanol and ethanol.
6. The halogen-free flame-retardant glass fiber reinforced nylon material as claimed in claim 1,
the nylon resin is selected from nylon 6, nylon 66 or nylon 610;
the flaky inorganic powder is selected from one or more of flaky kaolin, graphene oxide, graphite oxide and organic montmorillonite;
the antioxidant is selected from one or more of antioxidant 168, antioxidant 1010, antioxidant B215 or hindered phenol 1098;
the anti-dripping agent is selected from polytetrafluoroethylene anti-dripping agents.
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