CN113637322A - Organic phosphorus copolymerized flame-retardant polyamide composition and preparation method thereof - Google Patents
Organic phosphorus copolymerized flame-retardant polyamide composition and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an organic phosphorus copolymerization flame-retardant polyamide composition and a preparation method thereof. The organic phosphorus copolymerized flame-retardant polyamide composition comprises organic phosphorus copolymerized flame-retardant polyamide shown in a formula (1) and 0.1-10 wt% of inorganic nano material relative to the organic phosphorus copolymerized flame-retardant polyamide. The organic phosphorus copolymerization flame-retardant polyamide composition prepared by the invention has the advantages of small addition amount of the reaction flame retardant, controllable viscosity in the preparation process, excellent mechanical property of the obtained product, remarkable molten drop prevention effect and excellent flame retardant property.
Description
The application is a divisional application of patent application with application number 201610933535.3 and invention name 'an organic phosphorus copolymerization flame-retardant polyamide composition and a preparation method thereof'.
Technical Field
The invention belongs to the technical field of flame-retardant polymer synthesis, relates to a copolymerized flame-retardant polyamide composition and a preparation method thereof, and particularly relates to a phosphorus-containing reactive flame retardant copolymerized polyamide molecular chain-embedded polymer material composition and a preparation method thereof.
Background
The polyamide has excellent performances such as high strength, heat resistance, wear resistance, solvent resistance and the like, and is widely applied to the fields of buildings, chemical engineering, traffic, military and the like. However, polyamides are not inherently flame retardant and may cause or exacerbate fire hazards. Therefore, the modification of polyamide to obtain polyamide with good flame-retardant properties has been studied by the industry.
There are generally two ways in which the flame retardant polyamide material can be modified: one is adding reactive flame retardant, introducing functional group with flame retardant activity in the nylon copolymerization process; and the other is that after the polyamide is polymerized, an additive flame retardant and a related synergistic flame retardant are added and blended. The latter physical blending mode is influenced by the factors of dispersibility, compatibility, interfacial property and the like, while the former does not have the problems because of chemical reaction. In addition, to achieve a certain flame retardance, the use amount of the additive flame retardant is large, so that the mechanical property and the electrical property are greatly damaged, and the application of the additive flame retardant is limited. The reactive flame retardant can well solve the problems, the molecular structure of the reactive flame retardant is copolymerized into the main chain of the polyamide molecule, the problems of volatilization, migration, exudation and the like do not exist, and the reactive flame retardant can provide reliable flame retardant performance within the service life of the material.
At present, the commonly used flame retardants mainly include halogen flame retardants, phosphorus flame retardants, nitrogen flame retardants, inorganic filler type flame retardants, and the like. The former can be used as reactive flame retardant. Halogen-containing flame retardants have been widely used as flame retardant materials for high polymers due to their high flame retardancy, but they are gradually limited in use because they generate toxic gases and fumes during combustion, which are harmful to the environment and human body. The phosphorus flame retardant, especially the organic phosphorus flame retardant has a prospect of replacing halogen-containing flame retardants. The phosphorus flame retardant can act in a condensed phase and a gas phase at the same time, and the flame retardant mechanism is that the flame retardant can generate products such as phosphoric acid, polyphosphoric acid and the like in the combustion process, so that the dehydration and carbonization of a polymer are promoted, a glassy protective layer is formed, and the heat and substance transfer between the condensed phase and the gas phase is prevented. The combustion process of the phosphorus-containing flame retardant does not generate toxic and harmful gas, has less smoke generation amount and has better flame retardant effect. Particularly, the reactive phosphorus flame retardant can enter the molecular main chain of a high polymer material needing flame retardance in a polymerization mode, does not migrate and exude, and is effective for a long time.
The patent with publication number CN104231262A discloses a preparation method of organophosphorus copolymerized flame-retardant polyamide, which comprises the following steps: (1) reacting a flame-retardant monomer with a diamine monomer in advance to prepare a prepolymer; (2) and adding a polymerization monomer, a catalyst and the prepolymer into the reaction kettle in a certain sequence. The flame retardant used in this patent is
Or a derivative of a substrate thereof; wherein said R1And R2Alkylene groups each having 1 to 10 carbon atoms; or R1And R2Any of which is H; x1、X2Is H or 1 to 4 halogens which can substitute H on the benzene ring. The flame retardant grade of the copolymerization product obtained in the invention can reach UL94V-0 grade, the limiting oxygen index is greatly improved, the lowest value can reach 32, and the highest value can reach 45.
The patent with the publication number of CN104262619A relates to phosphorus-containing flame-retardant polyamide and a preparation method and application thereof. The preparation method comprises the following steps: (1) carrying out pre-polycondensation reaction on hypophosphite used for flame retardance and diamine to generate an oligomer; (2) carrying out pre-polycondensation reaction on the oligomer and dicarboxylic acid salt in a nitrogen atmosphere to obtain a prepolymer; (3) after two times of pre-polycondensation reaction, raising the temperature and reducing the air pressure to normal pressure; (4) and raising the temperature, pumping air to vacuum, and discharging to obtain the flame-retardant polyamide material. The flame retardant used in this patent is
The patent publication No. JPH09328543 relates to a polyamide copolymer containing phosphorus in the main chain and a method for preparing the same. The preparation method comprises the steps of (1) pre-reacting phosphorus-containing dicarboxylate with diamine to form salt; (2) the salt is condensed with other comonomers (diacid and diamine, or caprolactam) to produce polyamide copolymers. In this patent, the dicarboxylate is
As described above, although the prior art has proposed many phosphorus-containing polyamides with good flame retardant properties, there is still a strong need in the art for flame retardant polyamides with good mechanical properties and flame retardant properties.
Disclosure of Invention
The invention aims to prepare a novel organic phosphorus copolymerization flame-retardant polyamide composition aiming at the situation that the existing market of flame-retardant polyamide mainly adopts blending. The preparation method is characterized in that a flame-retardant monomer with the characteristic of two carboxylic acid groups is salified with diamine, and then is polycondensed with diamine salt of dicarboxylic acid in the presence of an inorganic nano material, so as to prepare the novel organic phosphorus copolymerization flame-retardant polyamide composition, or the flame-retardant polyamide composition is blended with the inorganic nano material after polycondensation to prepare the composition. In the process, the addition amount of the flame retardant is small, no synergistic flame retardant is needed, and the obtained polyamide material composition has excellent mechanical and electrical properties and anti-droplet formation performance.
The technical scheme of the invention is as follows:
an organophosphorus copolymerized flame retardant polyamide composition comprising a flame retardant polyamide represented by the following formula (1) and 0.1 to 10 wt%, preferably 0.5 to 5 wt%, more preferably 1 to 3 wt%, of an inorganic nanomaterial with respect to the organophosphorus copolymerized flame retardant polyamide:
wherein R is selected from H, C1-C5Alkyl radical, C6-C10Aryl radical, C3-C10A heteroaryl group; r is preferably H, C1-C3Alkyl radical, C6-C8Aryl, or C3-C6A heteroaryl group;
R1、R2each independently selected from linear, branched or cyclic C1-C10Alkylene radical, C6-C15Arylene or aralkylene, C3-C10An ester group; r1、R2Each independently preferably being a straight-chain, branched or cyclic C1-C5Alkylene radical, C6-C10Arylene or aralkylene, C3-C8An ester group;
R3、R4、R5each independently selected from C3-C12Linear, branched or cyclic alkylene, C6-C10Arylene radical, C3-C10A heteroaryl group; r3、R4、R5Each independently is preferably C3-C8Linear, branched or cyclic alkylene, C6-C8Arylene radical, C3-C8A heteroaryl group;
x represents 1 to 50, y represents 1 to 50, and n represents 1 to 100; x is preferably from 2 to 30, y is preferably from 2 to 30, and n is preferably from 2 to 80, more preferably from 5 to 50. .
Preferably, the inorganic nano material is selected from one or more of nano layered silicate, nano silicon dioxide, nano zinc oxide and nano titanium dioxide.
The preparation method of the flame-retardant polyamide composition comprises the following steps:
(A) reacting an organic phosphorus flame-retardant monomer or a derivative thereof shown in a formula (2) with a diamine monomer shown in a formula (3);
wherein the content of the first and second substances,
r is selected from H, C1-C5Alkyl radical, C6-C10Aryl radical, C3-C10Heteroaryl, R is preferably H, C1-C3Alkyl radical, C6-C8Aryl, or C3-C6A heteroaryl group;
R1、R2each independently selected from linear, branched or cyclic C1-C10Alkylene radical, C6-C15Arylene or aralkylene, C3-C10An ester group; r1、R2Each independently preferably being H, straight-chain, branched or cyclic C1-C5Alkylene radical, C6-C10Arylene or aralkylene, C3-C8An ester group;
R3is selected from C3-C12Linear, branched or cyclic alkylene, C6-C10Arylene radical, C3-C10Heteroaryl radical, R3Preferably C3-C8Linear, branched or cyclic alkylene, C6-C8Arylene radical, C3-C8A heteroaryl group;
obtaining a compound of the following formula (4):
(B) reacting a compound of formula (4) with a diacid of formula (5) and a diamine of formula (6), or with a diamine salt of formula (7) or a solution thereof, in the presence of 0.1 to 10 wt%, preferably 0.5 to 5 wt%, more preferably 1 to 3 wt% of an inorganic nanomaterial with respect to the total polymerizable monomers comprising (i) the reaction product of step (A), i.e., the compound of formula (4) and (ii) the diacid and the diamine or diamine salt,
wherein R is4And R5Is selected from C3-C12Linear, branched or cyclic alkylene, C6-C10Arylene radical, C3-C10Heteroaryl radical, R4And R5Preferably C3-C8Linear, branched or cyclic alkylene, C6-C8Arylene radical, C3-C8A heteroaryl group;
obtaining a polyamide of formula (1):
wherein, R, R1、R2、R3、R4、R5As defined above;
x represents 1 to 50, y represents 1 to 50, and n represents 1 to 100; preferably, x represents from 2 to 30, y represents from 2 to 30, n represents from 2 to 80, more preferably from 5 to 50;
or, (B') the polyamide of formula (1) is prepared as described above in the absence of inorganic nanomaterial and then the prepared flame-retardant polyamide is blended with 0.1 to 10 wt%, preferably 0.5 to 5 wt%, more preferably 1 to 3 wt% of inorganic nanomaterial with respect to the flame-retardant polyamide. The blending may be carried out by using an extruder, a kneader, a high-speed shear mixer, etc.
Preferably, the flame retardant monomer of formula (2) is reacted with the diamine monomer of formula (3) in a molar ratio of 1:0.1 to 20, preferably 1:0.5 to 10, more preferably 1:1 to 2.
In the step (A), the reaction is usually carried out in the presence of a solvent such as water or an organic solvent such as an alcohol solvent, and preferably, the diamine-based monomer is in excess (e.g., 0.1 to 10%, preferably 0.5 to 5% molar excess) relative to the organophosphorus flame retardant monomer or the derivative thereof so that the pH of the resulting salt solution is 7 to 9. The reaction temperature is increased from room temperature to 40-70 ℃ within 5-20 min.
In the step (B), the molar ratio of the diacid of the formula (5) to the diamine of the formula (6) is not particularly limited, and for example, the molar ratio of the diacid of the formula (5) to the diamine of the formula (6) may be 1:1.01 to 10, preferably 1:1.1 to 2, more preferably about 1: 1.5.
Preferably, in step (A)The diamine monomer is selected from hexamethylenediamine, decamethylenediamine, nonanediamine, undecanediamine, dodecanediamine, and aliphatic C6-C20One or more of imino diamine, aromatic diamine and alicyclic diamine.
In the step (B), preferably, diacid, diamine or diamine salt or solution thereof, the reaction product (salt or salt solution) of the step (A), an antioxidant, a catalyst, a nano inorganic material, and water (including water brought by the diamine salt solution and/or water brought by the reaction product salt solution of the step (A)) are added into a reaction kettle, and the reaction temperature and pressure are regulated and controlled under a nitrogen atmosphere to prepare the required organic phosphorus copolymerized flame-retardant polyamide.
In the step (B), further, the antioxidant is one or more of compounds such as p-phenylenediamine and dihydroquinoline and derivatives thereof, 2, 6-di-tert-butyl-4-methylphenol, bis (3, 5-di-tert-butyl-4-hydroxyphenyl) sulfide, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and the like.
Furthermore, the catalyst is one or more of sodium hypophosphite, methyl benzene sulfonic acid, a new ferrocene chiral polyamide ligand and the like.
Further preferably, the step (B) specifically includes the following steps:
a. adding diacid, diamine or diamine salt or solution thereof, a reaction product (salt solution) obtained in the step (A), a catalyst, an antioxidant and deionized water into a reaction kettle, vacuumizing, and filling nitrogen for several times to ensure that the pressure in the kettle is 0.1-0.5MPa at the initial stage of the reaction;
b. heating the reaction kettle to 200 ℃ and 250 ℃, and maintaining the reaction condition for 30-180min when the pressure is 1.6-2.1 MPa;
c. slowly releasing the pressure to normal pressure at the temperature of 230 ℃ and 280 ℃, then vacuumizing to-0.01 to-0.1 MPa, and copolymerizing for 10-180 min.
d. And finally, filling nitrogen, discharging materials, cooling, granulating, extracting and drying to obtain a final product.
Further, in step a, the addition amount of the polymerized monomer diacid and the diamine or the diamine salt or the solution thereof is 8 to 100 times, more preferably 10 to 40 times, and still more preferably 12 to 30 times of the mass of the flame retardant, and the catalyst and the antioxidant are respectively 0.01 to 1.0 percent, preferably 0.05 to 0.5 percent, more preferably 0.08 to 0.2 percent, and more preferably about 1/1000 percent of the mass of the polymerized monomer (or the diamine salt), and the solution thereof. The addition amount of water in the system is 10-60%, preferably 30-50% of the total mass of reactants.
Further, in step a, the polymerized monomer diacid is one or more of adipic acid, sebacic acid, azelaic acid, undecanedioic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, phthalic acid or their derivatives and other aliphatic and aromatic dicarboxylic acids; diamines are, for example, hexamethylenediamine, nonamethylenediamine, decamethylenediamine, undecanediamine, dodecanediamine, and aliphatic C6-C20One or more of an imino diamine, an aromatic diamine, or an alicyclic diamine; and the diamine salt is one or more of hexamethylene adipamide, pentamethylene adipamide, hexamethylene azelainate, hexamethylene sebacamide, octanedioyl octanediamine, octanedioyl hexamethylene diamine, and octanedioyl octanediamine.
Further, in the step b, the temperature is maintained at 200-250 ℃, the pressure is 1.6-2.1MPa, and the time is 30-180 min; and/or in the step c, the temperature in the reaction kettle is 230-; and/or in the step d, the pressure of the reaction kettle is 0.02-0.5 MPa.
In the present invention, the flame retardant and the diamine-based monomer are preferably mixed in advance in a ratio of, for example, 1: (1-2) salifying, adding the obtained salt into a polymerization monomer, adding an inorganic nano material, and participating in polymerization reaction under the action of a catalyst. The flame retardant property of the obtained polyamide material meets the requirement of flame retardant grade V-0.
To be provided with
Hexamethylenediamine, PA66, for example, the mechanism of the reaction is: firstly, the flame-retardant monomer reacts with hexamethylene diamine to generate salt, and then the salt and nylon 66 salt solution are copolymerized into the flame-retardant polyamide composition in the presence of inorganic nano materials. The reaction process can be written as follows:
the invention further relates to the application of the organic phosphorus copolymerized flame-retardant polyamide composition in preparing engineering plastics, films or fiber materials.
The invention has the beneficial effects that:
as long as the flame-retardant polyamide composition contains phosphorus-containing flame-retardant monomers accounting for about 6 percent of the total mass of reactants, the flame-retardant polyamide composition can basically reach UL-94V-0 level, has a limited oxygen index range of 27 to 32 percent, has good anti-dripping effect, low smoke, low toxicity, high efficiency, stability and controllable viscosity, and solves the problem that a plurality of phosphorus-containing monomers disclosed in the prior art cannot realize higher polymerization degree when the phosphorus content is increased.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
The organic phosphorus based flame retardant polyamide composition of the present invention comprises an organic phosphorus based copolymerized flame retardant polyamide having a molecular structure represented by the following formula 1 and 0.1 to 10 wt%, preferably 0.5 to 5 wt%, more preferably 1 to 3 wt% of an inorganic nanomaterial with respect to the organic phosphorus based copolymerized flame retardant polyamide:
wherein R is selected from H, C1-C5Alkyl radical, C6-C10Aryl radical, C3-C10A heteroaryl group; r is preferably H, C1-C3Alkyl radical, C6-C8Aryl radical, C3-C6A heteroaryl group;
R1、R2each independently selected from linear, branched or cyclic C1-C10Alkylene radical, C6-C15Arylene or aralkylene, C3-C10An ester group; r1、R2Each independently of the others is preferably straight-chain, branched or cyclic C1-C5Alkylene radical，C6-C10Arylene or aralkylene, C3-C8An ester group;
R3、R4、R5each independently selected from C3-C12Linear, branched or cyclic alkylene, C6-C10Arylene radical, C3-C10A heteroaryl group; r3、R4、R5Each independently is preferably C3-C8Linear, branched or cyclic alkylene, C6-C8Arylene radical, C3-C8A heteroaryl group;
x represents 1 to 50, y represents 1 to 50, and n represents 1 to 100; x is preferably from 2 to 30, y is preferably from 2 to 30, and n is preferably from 2 to 80, more preferably from 5 to 50.
The preparation method of the organic phosphorus copolymerized flame-retardant polyamide specifically comprises the following steps: (1) the copolymerized flame-retardant polyamide is prepared by the following steps:
(A) reacting an organic phosphorus flame-retardant monomer with diamine, preferably, leading amino to be excessive to generate a salt solution;
(B) reacting the reaction product of step (a) with a diacid and a diamine or a diamide salt in the presence of an inorganic nanomaterial to produce an organophosphorus copolymeric flame retardant polyamide;
(B') reacting the reaction product of the step (A) with a diacid and a diamine or a diamide salt to produce an organophosphorus copolymerized flame-retardant polyamide, and blending the copolymerized flame-retardant polyamide with an inorganic nanomaterial.
In step (A), the diamine-based monomer is preferably used in a slight excess so that the salt solution has a pH of 7 to 9. The reaction temperature is increased from room temperature to 40-70 ℃ within 5-20 min.
Preferably, the diamine monomer used in step (A) is hexamethylenediamine, decamethylenediamine, nonanediamine, undecanediamine, dodecanediamine, aliphatic C6-C20One or more of imino diamine, aromatic diamine and alicyclic diamine.
In the step (B) or (B'), preferably, diamine, diacid or diamide salt or a solution thereof, the reaction product (salt or salt solution) of the step (A), an antioxidant, a catalyst and deionized water are added into a reaction kettle, and the reaction temperature and pressure are regulated and controlled under the nitrogen atmosphere to prepare the required organic phosphorus copolymerized flame-retardant polyamide material.
In step (B) or (B'), further, the polymerized monomeric dibasic acid is, for example, one or more of adipic acid, sebacic acid, azelaic acid, undecanedioic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, phthalic acid or their derivatives, and other aliphatic and aromatic dicarboxylic acids; the diamine compound is, for example, hexamethylenediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, and aliphatic C6-C20One or more of an imino diamine, an aromatic diamine, or an alicyclic diamine; the diamine salt-type compound is, for example, one or more of polyhexamethylene adipamide, polypentylene adipamide, polyhexamethylene azelamide, polyhexamethylene sebacamide, polyhexamethylene suberoyl, polyhexamethylene dodecanoamide, and polyhexamethylene suberoyl.
In the step (B), further, the antioxidant is one or more of compounds such as p-phenylenediamine and dihydroquinoline and derivatives thereof, 2, 6-di-tert-butyl-4-methylphenol, bis (3, 5-di-tert-butyl-4-hydroxyphenyl) sulfide, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and the like.
Furthermore, the catalyst is one or more of sodium hypophosphite, methyl benzene sulfonic acid, a new ferrocene chiral polyamide ligand and the like.
Further preferably, the step (B) specifically includes the following steps:
a. adding diacid, diamine or diamine salt or solution thereof, the reaction product obtained in the step (A), a catalyst, an antioxidant, an inorganic nano material and deionized water into a reaction kettle, vacuumizing, and filling nitrogen for several times to ensure that the pressure in the kettle is 0.1-0.5MPa at the initial stage of reaction;
b. heating the reaction kettle to 200 ℃ and 250 ℃, and maintaining the reaction condition for 30-180min when the pressure is 1.6-2.1 MPa;
c. slowly releasing the pressure to normal pressure at the temperature of 230 ℃ and 280 ℃, then vacuumizing to-0.01 to-0.1 MPa, and copolymerizing for 10-180 min;
d. and finally, filling nitrogen, discharging materials, cooling, granulating, extracting and drying to obtain a final product.
Further, in step a, the addition amount of the polymerization monomer (or the dibasic amide salt) is preferably 8 to 100 times, more preferably 10 to 40 times, and still more preferably 12 to 30 times the mass of the flame retardant, and the catalyst and the antioxidant are respectively 0.01 to 1.0%, preferably 0.05 to 0.5%, more preferably 0.08 to 0.2%, and more preferably about 1/1000% of the mass of the polymerization monomer (or the dibasic amide salt). The amount of water added in the system is 10-60%, preferably 30-50% of the total mass of the reactants.
Further, in step a, the polymerized monomer diacid is one or more of adipic acid, sebacic acid, azelaic acid, undecanedioic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, phthalic acid or their derivatives and other aliphatic and aromatic dicarboxylic acids; the diamine compound is, for example, hexamethylenediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, and aliphatic C6-C20One or more of an imino diamine, an aromatic diamine, or an alicyclic diamine; the diamine salt-type compound is, for example, one or more of polyhexamethylene adipamide, polypentylene adipamide, polyhexamethylene azelamide, polyhexamethylene sebacamide, polyhexamethylene suberoyl, polyhexamethylene dodecanoamide, and polyhexamethylene suberoyl.
In the blending of step (2), the inorganic nano-material is selected from one or more of nano-layered silicate material, nano-titanium dioxide, nano-zinc oxide, nano-silicon dioxide and the like. The nano layered silicate material comprises one or more clay minerals such as talc, mica, pyrophyllite, kaolin, bentonite (montmorillonite), vermiculite, serpentine and the like.
The examples of the invention are as follows:
the methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified. "%" is by mass fraction unless otherwise specified.
Example 1:
and (2) at 40 ℃, mixing the flame-retardant monomer and hexamethylene diamine in an aqueous solution according to a molar ratio of 1:1.2 stirring and reacting for 0.5h, adjusting the pH value of the solution to 7.2, and drying to form salt. Adding 50% nylon 66 salt (hexamethylene adipamide salt) solution, the salt which is 6.0% of the mass of the nylon 66 salt (excluding solvent, the same below), nano-montmorillonite which is 4 wt% of the mass of the salt, sodium hypophosphite which is a catalyst accounting for 1 wt% of the mass of the nano-montmorillonite, and antioxidant p-phenylenediamine into a reaction kettle, vacuumizing, filling nitrogen for 5 times, and finally keeping the pressure in the reaction kettle at 0.2 MPa. Heating the reaction kettle, keeping high-speed stirring, and keeping constant temperature and pressure for 1.5h when the temperature of the reaction kettle reaches 220 ℃ and the pressure is 1.8 MPa. Then the temperature is raised to 250 ℃, and the pressure is released to the normal pressure within 1 hour. Vacuumizing to-0.05 MPa, introducing nitrogen to 0.2MPa after the stirring speed is reduced for a certain value and is stable, discharging the materials, cooling, granulating, extracting and drying to obtain the final product, namely the organic phosphorus copolymerized flame-retardant polyamide composition, wherein the relative viscosity of the final product is 2.3. The limit oxygen index of the obtained composition is 27.5%, the flame retardant rating reaches UL94V-0 level, no droplet is formed on a combustion product in the flame retardant process, and the droplet-preventing performance is excellent. Wherein the used organic phosphorus flame-retardant monomers are as follows:
example 2:
at 50 ℃, the flame-retardant monomer and hexamethylene diamine are mixed in an aqueous solution according to a molar ratio of 1: the reaction was stirred for 1h, and the pH of the solution was adjusted to 7.8. Mixing adipic acid and hexamethylenediamine according to a molar ratio of 1:1.2, adding the adipic acid and hexamethylenediamine, 7% of the salt solution (calculated by salt) of the adipic acid and hexamethylenediamine, 4 wt% of nano talc of the nano talc, 1 per thousand of catalyst methyl benzenesulfonic acid, 1 per thousand of antioxidant 2, 6-di-tert-butyl-4-methylphenol and 35% of deionized water into a reaction kettle, vacuumizing, filling nitrogen for 3 times, and finally keeping the pressure in the reaction kettle at 0.3 MPa. Heating the reaction kettle, keeping high-speed stirring, and keeping constant temperature and pressure for 1.6h when the temperature of the reaction kettle reaches 215 ℃ and the pressure is 1.7 MPa. Then the temperature is raised to 240 ℃, and the pressure is released to the normal pressure within 1.5 h. Vacuumizing to-0.06 MPa, introducing nitrogen to 0.3MPa after the stirring speed is reduced for a certain value and is stable, discharging the materials, cooling, granulating, extracting and drying to obtain the final product, namely the organic phosphorus copolymerized flame-retardant polyamide composition, wherein the relative viscosity of the final product is 2.1. The limit oxygen index of the obtained composition is 29%, the flame retardant rating reaches UL94V-0 level, no droplet is formed on a combustion product in the flame retardant process, and the droplet-preventing performance is excellent. Wherein the used organic phosphorus flame-retardant monomers are as follows:
example 3:
and (2) mixing the flame-retardant monomer and nonane diamine in an aqueous solution at the temperature of 60 ℃ according to the molar ratio of 1: the reaction was stirred for 1h, and the pH of the solution was adjusted to 7.6. Adding undecanedioic acid, hexamethylene diamine (prepared according to a molar ratio of 1: 1.2), the salt solution (calculated by salt) which accounts for 8% of the total mass of the undecanedioic acid and hexamethylene diamine, nano zinc oxide which accounts for 3 wt% of the total mass of the undecanedioic acid and hexamethylene diamine, sodium hypophosphite which accounts for 1 per mill of the total mass of the undecanedioic acid, antioxidant bis (3, 5-di-tert-butyl-4-hydroxyphenyl) sulfide and deionized water which accounts for 50% of the total mass of the undecanedioic acid and hexamethylene diamine into a reaction kettle, vacuumizing the reaction kettle, filling nitrogen for 4 times, and finally keeping the pressure in the reaction kettle at 0.2 MPa. The reaction kettle is heated and kept stirring at a high speed. When the temperature of the reaction kettle reaches 225 ℃ and the pressure is 1.7MPa, the temperature and the pressure are constant for 2 hours. Then the temperature is raised to 255 ℃, and the pressure is released to the normal pressure within 2 hours. Vacuumizing to-0.09 MPa, introducing nitrogen to 0.3MPa after the stirring speed is reduced for a certain value and is stable, discharging the materials, cooling, granulating, extracting and drying to obtain the final product, namely the organic phosphorus copolymerized flame-retardant polyamide composition, wherein the relative viscosity of the final product is 2.0. The limiting oxygen index of the obtained composition is 32.2%, the flame retardant rating reaches UL94V-0, no droplet is formed on a combustion product in the flame retardant process, and the droplet-preventing performance is excellent. Wherein the used organic phosphorus flame-retardant monomers are as follows:
example 4:
and (2) mixing the flame retardant and hexamethylene diamine in an aqueous solution at a molar ratio of 1:1.2 the reaction was stirred for 50min and the pH of the solution was adjusted to 7.4. Adding undecanedioic acid, octanediamine (prepared according to a molar ratio of 1: 1.25), 8% of the salt solution (calculated by salt), 1 per thousand of catalyst of methyl benzenesulfonic acid, antioxidant of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 40% of deionized water into a reaction kettle, vacuumizing, filling nitrogen for 3 times, and finally keeping the pressure in the reaction kettle at 0.35 MPa. The reaction kettle is heated and kept stirring at a high speed. When the temperature of the reaction kettle reaches 230 ℃ and the pressure is 1.8MPa, the temperature and the pressure are constant for 2 hours. Then the temperature is raised to 260 ℃, and the pressure is released to the normal pressure within 1 hour. Vacuumizing to-0.05 MPa, introducing nitrogen to 0.3MPa after the stirring speed is reduced for a certain value and is stable, discharging the materials, cooling, granulating, extracting and drying to obtain a final product, wherein the relative viscosity of the final product is 2.05.
The polyamide material and 5 wt% of nano-silica relative to the polyamide material are blended by a Banbury mixer to prepare the organophosphorus copolymerized flame-retardant polyamide composition, the limited oxygen index of the obtained composition is 33.5%, the flame-retardant grade reaches UL94V-0, and a comburent does not form droplets in the flame-retardant process, so that the droplet-preventing performance is excellent.
Wherein the used organic phosphorus flame-retardant monomers are as follows:
example 5
At 65 ℃, the flame-retardant monomer and hexamethylene diamine are mixed in an aqueous solution according to a molar ratio of 1:1.2 stirring and reacting for 0.5h, adjusting the pH value of the solution to 7.2, and drying to form salt. Adding 50% nylon 66 salt (hexamethylene adipamide salt) solution, the salt accounting for 10.0% of the mass of the hexamethylene adipamide salt, 2 wt% of nano zinc oxide, 1 per mill of catalyst sodium hypophosphite and antioxidant p-phenylenediamine into a reaction kettle, vacuumizing, filling nitrogen for 3 times, and finally keeping the pressure in the reaction kettle at 0.25 MPa. Heating the reaction kettle, keeping high-speed stirring, and keeping constant temperature and pressure for 1.5h when the temperature of the reaction kettle reaches 240 ℃ and the pressure is 1.95 MPa. Then the temperature is raised to 260 ℃, and the pressure is released to the normal pressure within 1 hour. Vacuumizing to-0.05 MPa, charging nitrogen to 0.4MPa after the stirring speed is reduced for a certain value and is stable, discharging the materials, cooling, granulating, extracting and drying to obtain the final product, namely the organic phosphorus copolymerization flame-retardant polyamide composition, wherein the P content is 0.80-0.84 mass%, the relative viscosity is 2.35, the limited oxygen index is 34.0%, and the flame-retardant grade reaches the UL94V-0 grade. Wherein the organic phosphorus flame-retardant monomer is as follows:
1. preparation of the samples
Test specimens made of polyamide materials to which no flame retardant was added were referred to as "PA", and test specimens made of the organophosphorus flame retardant polyamide compositions obtained in examples 1 to 4 described above were referred to as "FR-A" - "FR-E" in this order.
The test specimen preparation procedure for all the above-mentioned specimens is referred to GB/T9532-.
2. Limiting Oxygen Index (LOI) test
The limit oxygen index test refers to the standard GB/T2406.2-2009 combustion behavior determination by oxygen index method for plastics, and the limit oxygen index is determined by a type limit oxygen index determinator at room temperature. Spline specification: 80mm 10mm 4 mm.
UL-94 testing
The vertical combustion test refers to the standard of GB/T2408-2008 horizontal method and vertical method for testing the combustion performance of plastics, and is carried out at room temperature by adopting a CFZ-5 type vertical combustion tester. Spline specification: 125mm 13.2mm 3.2 mm. The sample strip is vertically fixed on the sample clamp, the part clamped at the upper end is 6mm, the distance between the lower end of the sample strip and absorbent cotton (4mm thick) is 300mm, flame is applied at the position 10mm from the bottom end of the sample strip, and the test data of the sample strip is recorded. After the specimen extinguishes, it is reignited according to the criteria in Table 1 below and the test data recorded.
TABLE 1 comparative standards for assay grade
4. Conclusion of the test
The flame retardant property test results of the examples show that the existence of the organophosphorus flame retardant structure and the nanometer inorganic material improves the flame retardant property and the anti-dripping property of the polyamide composition. When the content of the flame-retardant monomer reaches more than 6 percent, the flame-retardant polyamide composition can pass a V-0 test of UL-94, the LOI value is improved along with the flame-retardant monomer, no molten drop is formed even if the flame-retardant polyamide composition is used for a combustible substance which is easy to form molten drops, and the anti-molten drop performance is particularly excellent. Therefore, the invention proves that the method is feasible and efficient for modifying the polyamide flame retardance by utilizing the reactive organic phosphorus flame retardant. The organic phosphorus copolymerization flame-retardant polyamide composition obtained by the scheme provided by the invention has higher limited oxygen index and higher relative viscosity value. Due to the presence of end groups, conventional solid tackifying processes can be used to obtain a variety of desired viscosity values when higher viscosity materials are to be obtained.
The above description is only a preferred embodiment of the present invention, and does not limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims (10)
1. An organophosphorus copolymerized flame-retardant polyamide composition comprising an organophosphorus copolymerized flame-retardant polyamide represented by the following formula (1) and 0.1 to 10 wt%, preferably 0.5 to 5 wt%, more preferably 1 to 3 wt%, of an inorganic nanomaterial with respect to the organophosphorus copolymerized flame-retardant polyamide:
wherein R is selected from H, C1-C5Alkyl radical, C6-C10Aryl radical, C3-C10A heteroaryl group; r is preferably H, C1-C3Alkyl radical, C6-C8Aryl radical, C3-C6A heteroaryl group;
R1、R2each independently selected from linear, branched or cyclic C1-C10Alkylene radical, C6-C15Arylene or aralkylene, C3-C10An ester group; r1、R2Each independently preferably being a straight-chain, branched or cyclic C1-C5Alkylene radical, C6-C10Arylene or aralkylene, C3-C8An ester group;
R3、R4、R5each independently selected from C3-C12Linear, branched or cyclic alkylene, C6-C10Arylene radical, C3-C10A heteroaryl group; r3、R4、R5Are each independently preferably C3-C8Linear, branched or cyclic alkylene, C6-C8Arylene radical, C3-C8A heteroaryl group;
x represents 2 to 50; y represents 2 to 50; n represents 5 to 100;
preferably, x represents 2 to 30; y represents 2 to 30; n represents 50 to 100 or 50 to 80.
2. The flame retardant polyamide composition according to claim 1, wherein the inorganic nanomaterial is selected from one or more of nano phyllosilicate, nano silica, nano zinc oxide, and nano titanium dioxide.
3. The flame retardant polyamide composition according to claim 1 or 2, prepared by a preparation process comprising the steps of: (A) reacting an organic phosphorus flame-retardant monomer or a derivative thereof shown in a formula (2) with a diamine monomer shown in a formula (3);
wherein R is selected from H, C1-C5Alkyl radical, C6-C10Aryl radical, C3-C10Heteroaryl, R is preferably H, C1-C3Alkyl radical, C6-C8Aryl radical, C3-C6A heteroaryl group;
R1、R2each independently selected from linear, branched or cyclic C1-C10Alkylene radical, C6-C15Arylene or aralkylene, C3-C10Ester group, R1、R2Each independently preferably being a straight-chain, branched or cyclic C1-C5Alkylene radical, C6-C10Arylene or aralkylene, C3-C8An ester group;
R3is selected from C3-C12Linear, branched or cyclic alkylene, C6-C10Arylene radical, C3-C10Heteroaryl radical, R3Preferably C3-C8Linear, branched or cyclic alkylene, C6-C8Arylene radical, C3-C8A heteroaryl group;
obtaining a compound of the following formula (4):
(B) reacting a compound of formula (4) with a diacid of formula (5) and a diamine of formula (6), or with a dibasic amide salt of formula (7) or a solution thereof, in the presence of 0.1-10 wt%, preferably 0.5-5 wt%, more preferably 1-3 wt% of inorganic nanomaterial with respect to the total polymerizable monomers,
wherein R is4And R5Is selected from C3-C12Linear, branched or cyclic alkylene, C6-C10Arylene radical, C3-C10Heteroaryl, preferably selected from C3-C8Linear, branched or cyclic alkylene, C6-C8Arylene radical, C3-C8A heteroaryl group;
obtaining a polyamide of formula (1):
wherein, R, R1、R2、R3、R4、R5X, n are as defined above;
wherein, in the step (A), the flame-retardant monomer shown in the formula (2) and the diamine monomer shown in the formula (3) react according to a molar ratio of 1:1-2, and in the step (A) for preparing the flame-retardant polyamide, the diamine monomer is slightly excessive, so that the pH of the prepared salt solution is 7-9;
the step (B) of preparing the organophosphorus flame-retardant copolymerized nylon specifically comprises the following steps:
a. adding diacid, diamine or diamine salt or solution thereof, the reaction product obtained in the step (A), a catalyst, an antioxidant, an inorganic nano material and water into a reaction kettle, vacuumizing, and filling nitrogen for several times to ensure that the pressure in the kettle is 0.1-0.5MPa at the initial stage of the reaction;
b. heating the reaction kettle to 200 ℃ and 250 ℃, and maintaining the reaction condition for 30-180min when the pressure is 1.6-2.1 MPa;
c. slowly releasing the pressure to normal pressure at the temperature of 230 ℃ and 280 ℃, then vacuumizing to-0.01 to-0.1 MPa, and copolymerizing for 10-180 min.
d. Finally, filling nitrogen, discharging materials, cooling, granulating, extracting and drying to obtain a final product;
in step a, the amount of the diacid and the diamine or the diamine salt or the solution thereof added is 8 to 30 times, preferably 8 to 12 times, more preferably 10 to 12 times the mass of the flame-retardant monomer.
4. Flame retardant polyamide composition according to claim 3Wherein, in the step a, the polymerized monomer diacid is one or more of adipic acid, sebacic acid, azelaic acid, undecanedioic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, phthalic acid or derivatives thereof and other aliphatic and aromatic dicarboxylic acids; the diamine is selected from hexamethylenediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, and aliphatic C6-C20One or more of an imino diamine, an aromatic diamine, or an alicyclic diamine; and the binary amide salt is one or more of hexamethylene adipamide, pentamethylene adipamide, hexamethylene azelainate, hexamethylene sebacamide, octanedioyl diamine, and octanedioyl diamine;
the antioxidant is one or more of p-phenylenediamine, dihydroquinoline and other compounds and derivatives thereof, 2, 6-di-tert-butyl-4-methylphenol, bis (3, 5-di-tert-butyl-4-hydroxyphenyl) thioether and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester;
the catalyst used for preparing the flame-retardant polyamide is one or more of sodium hypophosphite, methyl benzenesulfonic acid and a new ferrocene chiral polyamide ligand.
5. A process for the preparation of a flame retardant polyamide composition according to claim 1 or 2, comprising:
(A) reacting an organic phosphorus flame-retardant monomer or a derivative thereof shown in a formula (2) with a diamine monomer shown in a formula (3);
wherein R is selected from H, C1-C5Alkyl radical, C6-C10Aryl radical, C3-C10Heteroaryl, R is preferably H, C1-C3Alkyl radical, C6-C8Aryl radical, C3-C6A heteroaryl group;
R1、R2each independently selected from linear, branched or cyclic C1-C10Alkylene radical, C6-C15Arylene or aralkylene, C3-C10Ester group, R1、R2Each independently preferably being a straight-chain, branched or cyclic C1-C5Alkylene radical, C6-C10Arylene or aralkylene, C3-C8An ester group;
R3is selected from C3-C12Linear, branched or cyclic alkylene, C6-C10Arylene radical, C3-C10Heteroaryl radical, R3Preferably C3-C8Linear, branched or cyclic alkylene, C6-C8Arylene radical, C3-C8A heteroaryl group;
obtaining a compound of the following formula (4):
(B) reacting a compound of formula (4) with a diacid of formula (5) and a diamine of formula (6), or with a dibasic amide salt of formula (7) or a solution thereof, in the presence of 0.1-10 wt%, preferably 0.5-5 wt%, more preferably 1-3 wt% of inorganic nanomaterial with respect to the total polymerizable monomers,
wherein R is4And R5Is selected from C3-C12Linear, branched or cyclic alkylene, C6-C10Arylene radical, C3-C10Heteroaryl, preferably selected from C3-C8Linear, branched or cyclic alkylene, C6-C8Arylene radical, C3-C8A heteroaryl group;
obtaining a polyamide of formula (1):
wherein, R, R1、R2、R3、R4、R5X and n are as defined above;
or, (B') preparing the polyamide of formula (1) in the absence of inorganic nanomaterial and then blending the prepared flame-retardant polyamide with 0.1 to 10 wt%, preferably 0.5 to 5 wt%, more preferably 1 to 3 wt% of an inorganic nanomaterial with respect to the flame-retardant polyamide;
wherein the flame retardant monomer of formula (2) is reacted with the diamine monomer of formula (3) in a molar ratio of 1:0.5-10, preferably 1:1-2, with a slight excess of diamine monomer to give a salt solution having a pH of 7-9.
6. The production method according to claim 5, wherein, in the step (A) of producing the flame-retardant polyamide, the reaction temperature is raised from room temperature to 40-70 ℃ within 5-20 min; and/or
The diamine monomer used in the step (A) for preparing the flame-retardant polyamide is hexamethylene diamine, decamethylene diamine, nonane diamine, undecane diamine, dodecane diamine, aliphatic C6-C20One or more of imino diamine, aromatic diamine and alicyclic diamine; and/or
In the step (B) of preparing the flame-retardant polyamide, adding diacid, diamine or diamine salt or solution thereof, the reaction product obtained in the step (A), an antioxidant, a catalyst, an inorganic nano material and water into a reaction kettle, and regulating and controlling the reaction temperature and pressure in a nitrogen atmosphere to obtain the required organic phosphorus copolymerized flame-retardant polyamide material.
7. The process according to any one of claims 5 to 6, wherein in the step (B) for producing a flame-retardant polyamide, the antioxidant used is one or more of compounds such as p-phenylenediamine and dihydroquinoline and derivatives thereof, 2, 6-di-t-butyl-4-methylphenol, bis (3, 5-di-t-butyl-4-hydroxyphenyl) sulfide, pentaerythrityl tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate; and/or
The catalyst used for preparing the flame-retardant polyamide is one or more of sodium hypophosphite, methyl benzenesulfonic acid and a new ferrocene chiral polyamide ligand.
8. The production method according to any one of claims 5 to 7, wherein the step (B) of producing the organophosphorus flame-retardant copolymerized nylon specifically comprises the steps of:
a. adding diacid, diamine or diamine salt or solution thereof, the reaction product obtained in the step (A), a catalyst, an antioxidant, an inorganic nano material and water into a reaction kettle, vacuumizing, and filling nitrogen for several times to ensure that the pressure in the kettle is 0.1-0.5MPa at the initial stage of the reaction;
b. heating the reaction kettle to 200 ℃ and 250 ℃, and maintaining the reaction condition for 30-180min when the pressure is 1.6-2.1 MPa;
c. slowly releasing the pressure to normal pressure at the temperature of 230 ℃ and 280 ℃, then vacuumizing to-0.01 to-0.1 MPa, and copolymerizing for 10-180 min.
d. And finally, filling nitrogen, discharging materials, cooling, granulating, extracting and drying to obtain a final product.
9. The process according to claim 8, wherein in step a, the diacid and diamine or diamide salt or solution thereof are added in an amount of 8 to 30 times, preferably 8 to 12 times, more preferably 10 to 12 times the mass of the flame retardant monomer, and the catalyst and antioxidant are 0.01 to 1.0% by mass, preferably 0.05 to 0.5% by mass, more preferably 0.08 to 0.2% by mass, more preferably about 1/1000% by mass, respectively, of the mass of the polymerized monomer (or diamide salt); the addition amount of water in the system is preferably 10-60%, preferably 30-50% of the total mass of reactants; and/or
In step a, the polymerized monomer diacid is one or more of adipic acid, sebacic acid, azelaic acid, undecanedioic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, phthalic acid or derivatives thereof and other aliphatic and aromatic dicarboxylic acids; the diamine is selected from hexamethylenediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, and aliphatic C6-C20One or more of an imino diamine, an aromatic diamine, or an alicyclic diamine; and the dibasic amide salt is hexamethylene adipamide salt or adipoylOne or more of glutaric diamine salt, adipic nonanamide salt, adipic sebacamide salt, suberoyl octanediamine salt, adipic suberoyl diamine salt and suberoyl octanediamine salt.
10. Use of an organophosphorus co-flame retardant polyamide composition according to any one of claims 1-4 for the preparation of engineering plastics, films or fibre materials.
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| CN114989422A (en) * | 2022-06-21 | 2022-09-02 | 浙江理工大学 | Polyamide material for industrial yarn, preparation method thereof and fiber |
| CN114989419A (en) * | 2022-06-21 | 2022-09-02 | 浙江理工大学 | Polyamide for industrial yarn, preparation method thereof and fiber |
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| CN114989421A (en) * | 2022-06-21 | 2022-09-02 | 浙江理工大学 | Modified polyamide material, preparation method thereof and fiber |
| CN115160562A (en) * | 2022-07-22 | 2022-10-11 | 四川轻化工大学 | Phosphorus-containing flame-retardant high-temperature-resistant copolymerized nylon and preparation method thereof |
| CN115160562B (en) * | 2022-07-22 | 2024-05-21 | 濮阳市盛通聚源新材料有限公司 | Phosphorus-containing flame-retardant high-temperature-resistant copolymerized nylon and preparation method thereof |
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