CN113755010A - Organic phosphorus flame-retardant copolymerized nylon composition and preparation method thereof - Google Patents
Organic phosphorus flame-retardant copolymerized nylon composition and preparation method thereof Download PDFInfo
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- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
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Abstract
The invention discloses an organic phosphorus flame-retardant copolymerized nylon 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 organophosphorus flame-retardant nylon composition prepared by the invention needs fewer reaction flame retardants, has controllable viscosity in the preparation process, excellent anti-dripping effect and excellent flame retardant property.
Description
The application is a divisional application of patent application with application number 201610933669.5 and invention name 'an organic phosphorus flame-retardant copolymerized nylon composition and a preparation method thereof'.
Technical Field
The invention relates to an organic phosphorus flame-retardant copolymerized nylon composition and a preparation method thereof, belongs to the field of high-molecular flame-retardant materials, and particularly relates to a flame-retardant copolymerized nylon composition for textile, packaging materials, automobile parts, motor parts, engineering plastics and the like and a preparation method thereof.
Background
Nylon is widely used in the fields of building, chemical engineering, traffic, military and the like due to the excellent performances of high strength, heat resistance, wear resistance, solvent resistance and the like. But the amido bond and the water molecule can form hydrogen bond, so that the product has poor dimensional stability and electrical property reduction due to larger water absorption, and simultaneously, the product has the defects of low impact strength in a dry state or at low temperature, opacity, poor solubility and the like, thereby limiting the wider application of the product. In addition, the non-flame retardancy of nylon itself limits its applications. Therefore, the modification of nylon with good flame retardant property has been studied by the industry personnel.
There are generally two ways in which the flame retardant nylon material can be modified: one is adding reactive flame retardant, introducing functional group with flame retardant activity in the nylon copolymerization process; the other is to blend an additive flame retardant and a related synergistic flame retardant into nylon. The latter is susceptible to factors such as dispersibility, compatibility, interfacial properties, etc.; to achieve a certain flame retardancy, the use of a larger amount of additive flame retardant can cause great damage to mechanical properties and electrical properties, thereby limiting the application thereof. 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 nylon molecule, the problems of volatilization, migration, seepage 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. Halogen-containing flame retardants have been widely used as flame retardant materials for high polymers due to their high flame retardancy, but they are harmful to the environment and human body because of the generation of toxic gases and fumes during combustion, and have been restricted by the European Union. Therefore, the development of a novel flame retardant which is efficient, durable and environmentally friendly has been the subject of intense research in this field. The phosphorus flame retardant, especially the organic phosphorus flame retardant has a prospect of replacing halogen-containing flame retardants. The phosphorus flame retardant can simultaneously act in a condensed phase and a gas phase, and the flame retardant mechanism is that the flame retardant generates 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.
The prepared organic phosphorus flame-retardant copolymerized nylon has great academic research and industrial market value. The copolymerization modification can change the main chain, branched chain and molecular chain structure of the polymer, improve the heat resistance, crystallinity, transparency, flexibility, solubility and the like of the nylon polymer, and hopefully obtain a nylon product with low cost and excellent comprehensive performance.
The patent with publication number CN104744690A discloses a preparation method of flame-retardant nylon 6, which comprises the following steps: (1) heating aminomethyl phenyl phosphinic acid, thionyl chloride and ether according to a certain molar ratio in a reaction kettle for reaction to prepare chloromethyl phenyl phosphinic acid; (2) introducing ammonia gas into the chloromethyl phenyl phosphinic acid in a sodium hydroxide solution to carry out ammoniation reaction to prepare aminomethyl phenyl phosphinic acid; (3) the flame-retardant nylon 6 is prepared by polymerizing nylon polymerization monomer caprolactam, aminomethyl phenyl phosphinic acid and a catalyst. The flame retardant used in the patent not only does not have negative influence on the mechanical properties of nylon 6, but also can enable the nylon 6 to have good flame retardant effect under the condition of small addition amount of the flame retardant.
Patent publication No. CN103694468A discloses a preparation method of nylon resin: mixing a polymerization monomer, a catalyst, a reactive flame retardant (DOPO derivative) and a char forming agent, and carrying out high-temperature polycondensation to prepare the nylon resin. Wherein the polymerized monomer is one or more of a compound containing carboxyl of amino and lactam; or a diacid and a diamine. The flame retardant is one or more of five DOPO derivatives. The phosphorus-containing flame retardants used in this patent are stable within the polymer and are not easily lost after copolymerization with the monomers. The finally prepared flame-retardant nylon has excellent mechanical properties and can pass a UL-94V-0 test.
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
The patent publication No. 104262169 relates to a 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
As described above, although the prior art has proposed a lot of nylon materials with good flame retardant properties, there is still a strong need in the art for flame retardant nylon with good mechanical properties and flame retardant properties.
Disclosure of Invention
The invention aims to prepare a novel organic phosphorus flame-retardant copolymerized nylon composition aiming at the scene that the flame-retardant nylon in the market mainly takes blending. The method is characterized in that the characteristics of flame-retardant monomer with two carboxylic acid groups are utilized to carry out pre-polycondensation with diamine, and then the flame-retardant monomer is subjected to polycondensation with lactam monomer in the presence of inorganic nano materials to prepare a novel organic phosphorus flame-retardant nylon composition through copolymerization, or the flame-retardant nylon composition is blended with the inorganic nano materials after polycondensation to prepare the nylon composition. In the process, the addition amount of the flame retardant is small, no synergistic flame retardant is needed, and the obtained nylon material has excellent mechanical property, flame retardant property and anti-droplet formation property.
The technical scheme of the invention is as follows:
an organophosphorus based flame-retardant copolymerized nylon composition comprising organophosphorus based flame-retardant copolymerized nylon 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 organophosphorus 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;
R3is selected from C3-C12Linear, branched or cyclic alkylene, C6-C10Arylene radical, C3-C10A heteroaryl group; r3Preferably C3-C8Linear, branched or cyclic alkylene, C6-C8Arylene radical, C3-C8A heteroaryl group;
R4is selected from C3-C12Linear or branched alkylene; r4Preferably C3-C8Linear or branched alkylene;
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 organic phosphorus flame-retardant copolymerized nylon 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 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-C10Heteroarylene radical, R3Preferably C3-C8Linear, branched or cyclic alkylene, C6-C8Arylene radical, C3-C8A heteroaryl group;
obtaining a compound of the following formula (4):
wherein R is4Is selected from C3-C12Linear or branched alkylene, R4Preferably C3-C8Linear or branched alkylene;
(B) reacting a compound of formula (4) with a lactam of formula (5) 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 to obtain a nylon of formula (1):
wherein, R, R1、R2、R3、R4As defined above;
x represents 1 to 50; y represents 1 to 50; n represents 1 to 100; preferably x represents 2 to 30; y represents 2 to 30; n represents 2 to 80, more preferably 5 to 50;
or (B') preparing the nylon of formula (1) in the absence of the inorganic nanomaterial, and then blending the prepared organophosphorus flame-retardant copolymerized nylon composition with the inorganic nanomaterial. 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) of preparing the organophosphorus flame-retardant copolymerized nylon, the diamine monomer is preferably in excess (for example, 0.1 to 10%, preferably 0.5 to 5% molar excess) relative to the organophosphorus flame-retardant monomer or its derivative so that the pH of the prepared salt solution is 7 to 9. The reaction temperature is increased from room temperature to 40-70 ℃ within 5-20 min. It is preferred to strictly control the amount of water to be used to be not more than 10%, preferably not more than 5% by mass of the total mass of the reaction system.
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) of preparing the organic phosphorus flame-retardant copolymerized nylon, preferably, the lactam monomer, the reaction product of the step (A), the antioxidant, the catalyst, the molecular weight regulator, the inorganic nano material and a proper amount of water are added into a reaction kettle, and the reaction temperature and the reaction pressure are regulated and controlled under the nitrogen atmosphere to prepare the required organic phosphorus flame-retardant copolymerized nylon.
In the step (B) of preparing the organophosphorus flame-retardant copolymerized nylon, the antioxidant used 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) thioether, 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, new ferrocene chiral nylon ligand and the like.
Further, the molecular weight regulator is one or more of benzoic acid, adipic acid, acetic acid and the like.
Further, the step (B) of preparing the organophosphorus flame-retardant copolymerized nylon specifically comprises the following steps:
a. adding a lactam monomer, the reaction product obtained in the step (A), a catalyst, an antioxidant, a molecular weight regulator, an inorganic nano material and a proper amount of 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 the step a, the total amount of the lactam monomer added is 8-100 times, preferably 10-40 times, more preferably 12-30 times of the mass of the flame retardant; the catalyst and the antioxidant are 0.01 to 1.0 percent of the mass of the lactam polymerization monomer or the lactam polymer, preferably 0.05 to 0.5 percent of the mass of the lactam polymerization monomer or the lactam polymer, more preferably 0.08 to 0.2 percent of the mass of the lactam polymerization monomer or the lactam polymer, and more preferably about 1/1000.
Further, in step a, the lactam monomer is caprolactam, capryllactam, undecanolactam, dodecanolactam, and various lactam monomers with lactam characteristics.
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, 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.
To be provided with
And hexamethylenediamine and caprolactam, the mechanism of the reaction is: firstly, the flame-retardant monomer reacts with hexamethylene diamine to generate salt, and then the salt and caprolactam are copolymerized into the flame-retardant nylon in the presence of inorganic nano materials. The reaction equation is:
the invention further relates to application of the organic phosphorus flame-retardant copolymerized nylon composition in preparation of engineering plastics, films or fiber materials.
The invention has the beneficial effects that:
as long as the flame-retardant nylon composition comprises 6 percent of flame-retardant monomer based on the mass of the polymer, the flame-retardant nylon composition can basically reach UL-94V-0 level, the limit oxygen index range is 27-32 percent, the drip-proof effect is good, the smoke is low, the toxicity is low, the efficiency is stable, the viscosity is controllable, and 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 is solved.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
The organic phosphorus flame-retardant nylon composition comprises organic phosphorus flame-retardant copolymerized nylon with a molecular structure shown in the following formula 1 and 0.1-10 wt%, preferably 0.5-5 wt%, more preferably 1-3 wt% of inorganic nano-material relative to the organic phosphorus 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;
R3is selected from C3-C12Linear, branched or cyclic alkylene, C6-C10Arylene radical, C3-C10A heteroaryl group; r3Preferably C3-C8Linear, branched or cyclic alkylene, C6-C8Arylene radical, C3-C8A heteroaryl group;
R4is selected from C3-C12Linear or branched alkylene; r4Preferably C3-C8Linear or branched alkylene;
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 flame-retardant nylon composition comprises the following steps:
(A) reacting an organic phosphorus flame-retardant monomer or a derivative thereof with a diamine monomer to make amino excessive and prepare a salt solution;
(B) reacting the reaction product of step (a) with a lactam in the presence of an inorganic nanomaterial to produce a flame retardant nylon composition; or
(B') generating the organic phosphorus flame-retardant copolymerized nylon in the absence of the inorganic nano material, and blending the organic phosphorus flame-retardant copolymerized nylon and the inorganic nano material.
In step (A), preferably, the flame retardant is reacted with the diamine-based monomer in a molar ratio of 1:0.1 to 20, preferably 1:0.5 to 10, more preferably 1:1 to 2.
In step (A), the diamine-based monomer is preferably used in a slight excess so that a salt solution having a pH of 7 to 9 is prepared. The reaction temperature is increased from room temperature to 40-70 ℃ within 5-20 min. The amount of water used must be strictly controlled.
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), preferably, the lactam monomer, the reaction product (salt solution) obtained in the step (A), the antioxidant, the molecular weight regulator and the catalyst are added into a reaction kettle, and the reaction temperature and the reaction pressure are regulated and controlled under the nitrogen atmosphere to obtain the required organophosphorus flame-retardant copolymerized nylon.
In the step (B), 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.
Further, the lactam monomer is caprolactam, decanolactam, undecanolactam, dodecanolactam, and various lactam monomers having lactam characteristics.
Furthermore, the catalyst is one or more of sodium hypophosphite, methyl benzene sulfonic acid, new ferrocene chiral nylon ligand and the like.
Further, the molecular weight regulator is one or more of benzoic acid, adipic acid, acetic acid and the like.
Further, the step (B) specifically includes the steps of:
a. adding a lactam monomer, the salt solution obtained in the step (A), a catalyst, a molecular weight regulator, an antioxidant and a proper amount of 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 the step a, the total amount of the lactam monomer added is 8-100 times, preferably 10-40 times and more preferably about 12-30 times of the mass of the flame retardant; the catalyst and the antioxidant are 0.01 to 1.0 percent of the mass of the lactam polymerization monomer or the lactam polymer, preferably 0.05 to 0.5 percent of the mass of the lactam polymerization monomer or the lactam polymer, more preferably 0.08 to 0.2 percent of the mass of the lactam polymerization monomer or the lactam polymer, and more preferably about 1/1000.
Further, in step a, the lactam monomer is caprolactam, capryllactam, undecanolactam, dodecanolactam, and various lactam monomers with lactam characteristics.
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.
Example 1:
at 50 ℃, a flame-retardant monomer and hexamethylene diamine are mixed in a small amount of water according to a molar ratio of 1: 1.3 stirring to react for 0.5h, adjusting the pH value of the solution to 7.5, and drying to form salt. Adding caprolactam monomer, the obtained salt (6 percent of the total mass of the caprolactam monomer, the same below), nano montmorillonite accounting for 4 percent of the weight of the caprolactam monomer, sodium hypophosphite serving as a catalyst accounting for 1 percent of the weight of the caprolactam monomer, antioxidant p-phenylenediamine, benzoic acid serving as a molecular weight regulator and water accounting for 3 percent of the weight of the caprolactam monomer into a reaction kettle, vacuumizing, filling nitrogen for three 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 2h when the temperature of the reaction kettle reaches 215 ℃ and the pressure is 1.75 MPa. Then the temperature is raised to 260 ℃ and the pressure is released to the normal pressure within 1.5 h. Vacuumizing to-0.05 MPa, filling nitrogen to 0.2MPa after the stirring speed is reduced by a certain value and is stable, discharging materials, cooling, granulating, extracting and drying to obtain the final product, namely the organic phosphorus flame-retardant nylon composition, wherein the relative viscosity of the organic phosphorus flame-retardant nylon composition is 2.5, the limited oxygen index of the obtained composition is 27.9 percent, the flame-retardant grade reaches UL-94V-0, and a combustion substance is not formed in the flame-retardant process, so that the anti-dripping performance is excellent. Wherein the used organic phosphorus flame-retardant monomers are as follows:
example 2:
and (2) at the temperature of 55 ℃, mixing the flame-retardant monomer and hexamethylene diamine in a small amount of water according to the molar ratio of 1: 1.1 stirring and reacting for 40min, adjusting the pH value of the solution to 7.3, and drying to form salt. Adding a decanolactam monomer, the obtained salt (accounting for 7 percent of the total mass of the decanolactam monomer), nano talc accounting for 4 percent by weight, a catalyst of methyl benzenesulfonic acid accounting for 1 per thousand of the total mass of the decanolactam monomer, an antioxidant of 2, 6-di-tert-butyl-4-methylphenol and a molecular weight regulator of adipic acid into a reaction kettle, vacuumizing, filling nitrogen for three 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 2h when the temperature of the reaction kettle reaches 220 ℃ and the pressure is 1.9 MPa. Then the temperature is increased to 270 ℃, and the pressure is released to the normal pressure within 2 hours. Vacuumizing to-0.08 MPa, filling nitrogen to 0.3MPa after the stirring speed is reduced by a certain value and is stable, discharging materials, cooling, granulating, extracting and drying to obtain the final product, namely the organic phosphorus flame-retardant nylon composition, wherein the relative viscosity of the organic phosphorus flame-retardant nylon composition is 2.5, the limited oxygen index of the obtained composition is 28.5 percent, the flame-retardant grade reaches UL-94V-0, no liquid drops are formed in a combustion product in the flame-retardant process, and the anti-dripping performance is excellent. Wherein the used organic phosphorus flame-retardant monomers are as follows:
example 3:
and (2) at the temperature of 55 ℃, mixing the flame-retardant monomer and decamethylene diamine in a small amount of water according to the molar ratio of 1: 1.1 stirring and reacting for 1h, adjusting the pH value of the solution to 7.8, and drying to form salt. Preparing caprolactam and laurolactam according to the mass ratio of 7:3, adding the obtained salt (accounting for 8 percent of the total mass of lactam monomers), 3 percent by weight of nano zinc oxide, 1 per thousand of catalyst sodium hypophosphite, an antioxidant dihydroquinoline and a molecular weight control agent benzoic acid into a reaction kettle, vacuumizing, filling nitrogen for three times, finally keeping the pressure in the reaction kettle at 0.3MPa, heating the reaction kettle, keeping high-speed stirring, and keeping constant temperature and pressure for 1.7 hours when the temperature of the reaction kettle reaches 210 ℃ and the pressure is 1.8 MPa. Then the temperature is raised to 250 ℃ and the pressure is released to the normal pressure within 1.5 h. Vacuumizing to-0.06 MPa, after the stirring speed is reduced by a certain value and is stable, filling nitrogen to 0.3MPa, discharging materials, cooling, granulating, extracting and drying to obtain the final product, namely the organic phosphorus flame-retardant nylon composition, wherein the relative viscosity of the organic phosphorus flame-retardant nylon composition is 2.1, the limited oxygen index of the obtained composition is 31.6 percent, the flame-retardant grade reaches UL-94V-0, no liquid drops are formed in a combustion product in the flame-retardant process, and the molten drop resistance is excellent. Wherein the used organic phosphorus flame-retardant monomers are as follows:
example 4:
flame-retardant monomer and nonane diamine are mixed in a small amount of water at a molar ratio of 1: 1.3 stirring and reacting for 1h, adjusting the pH value of the solution to 7.3, and drying to form salt. Adding an undecanolactam monomer, the salt (accounting for 6.5 percent of the total mass of the undecanolactam monomer), nano silicon dioxide accounting for 5 percent by weight, sodium hypophosphite serving as a catalyst accounting for 1 per thousand of the total mass of the undecanolactam monomer, an antioxidant 2, 6-di-tert-butyl-4-methylphenol and acetic acid serving as a molecular weight control agent into a reaction kettle, vacuumizing, filling nitrogen for three 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, filling nitrogen to 0.3MPa after the stirring speed is reduced by a certain value and is stable, discharging materials, cooling, granulating, extracting and drying to obtain the final product, namely the organic phosphorus flame-retardant nylon composition, wherein the relative viscosity of the organic phosphorus flame-retardant nylon composition is 2.85, the limited oxygen index of the obtained composition is 28.8, the flame-retardant grade reaches UL-94V-0, no liquid drops are formed in a combustion product in the flame-retardant process, and the molten drop resistance is excellent. Wherein the used organic phosphorus flame-retardant monomers are as follows:
example 5:
and (2) mixing the flame-retardant monomer and hexamethylene diamine in a small amount of water at the temperature of 48 ℃ according to the molar ratio of 1: 1.2 stirring to react for 30min, adjusting the pH value of the solution to 7.4, and drying to form salt. Adding the obtained salt (accounting for 8 percent of the total mass of the caprolactam monomer), caprolactam, nano titanium dioxide accounting for 4 percent by weight, catalyst methyl benzenesulfonic acid accounting for 1 percent by weight, antioxidant p-phenylenediamine and molecular weight regulator adipic acid into a reaction kettle, vacuumizing, filling nitrogen for three 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 MP, after the stirring speed is reduced by a certain value and is stable, filling nitrogen to 0.3MPa, discharging materials, cooling, granulating, extracting and drying to obtain the final product, namely the organic phosphorus flame-retardant nylon composition, wherein the relative viscosity of the organic phosphorus flame-retardant nylon composition is 2.74, the limited oxygen index of the obtained composition is 29.2 percent, the flame-retardant grade reaches UL-94V-0, no liquid drops are formed in a combustion product in the flame-retardant process, and the molten drop resistance is excellent. Wherein the used organic phosphorus flame-retardant monomer:
example 6:
and (2) at 65 ℃, mixing a flame retardant monomer and decamethylene diamine in an aqueous solution according to a molar ratio of 1: the reaction was stirred for 1h, decamethylenediamine was added dropwise, and the pH of the solution was adjusted to 7.7. Adding a decanolactam monomer, the salt solution (accounting for 8 percent of the total mass of the decanolactam monomer) obtained by the previous step, 1 per thousand of catalysts of methyl benzenesulfonic acid, antioxidant p-phenylenediamine and molecular weight control agent benzoic acid into a reaction kettle, vacuumizing, filling nitrogen for three 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 2h when the temperature of the reaction kettle reaches 215 ℃ and the pressure is 1.8 MPa. Then the temperature is increased to 270 ℃, and the pressure is released to the normal pressure within 2 hours. Vacuumizing to-0.1 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 2.15.
The flame-retardant copolymerized nylon and 4 wt% of nano kaolin relative to the flame-retardant copolymerized nylon are blended by an extruder to prepare the organic phosphorus flame-retardant nylon composition, the limited oxygen index of the obtained composition is 31.6, the flame-retardant grade reaches UL-94V-0, no droplets are formed in a combustion product in the flame-retardant process, and the anti-droplet performance is excellent. Wherein the used organic phosphorus flame-retardant monomers are as follows:
example 7:
and (2) at the temperature of 55 ℃, mixing the flame-retardant monomer and hexamethylene diamine in a small amount of water according to the molar ratio of 1: 1.3 stirring to react for 0.5h, adjusting the pH value of the solution to 7.5, and drying to form salt. Adding caprolactam monomer, the obtained salt (accounting for 10 percent of the total mass of the caprolactam monomer), nano montmorillonite accounting for 4 percent of the weight of the caprolactam monomer, sodium hypophosphite serving as a catalyst accounting for 1 percent of the weight of the caprolactam monomer, p-phenylenediamine serving as an antioxidant, benzoic acid serving as a molecular weight regulator and water accounting for 3 percent of the weight of the caprolactam monomer into a reaction kettle, vacuumizing, filling nitrogen for three 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 2h when the temperature of the reaction kettle reaches 215 ℃ and the pressure is 1.75 MPa. Then the temperature is raised to 260 ℃ and the pressure is released to the normal pressure within 1.5 h. Vacuumizing to-0.05 MPa, after the stirring speed is reduced by a certain value and is stable, filling nitrogen to 0.2MPa, discharging materials, cooling, granulating, extracting and drying to obtain the final product, namely the organic phosphorus flame-retardant nylon composition, wherein the P content is 8.3-8.6%, the relative viscosity is 2.5, the limited oxygen index of the obtained composition is 31.5%, the flame-retardant grade reaches UL-94V-0, and a combustion object does not form molten drops in the flame-retardant process, so that the molten drop resistance is excellent. Wherein the used organic phosphorus flame-retardant monomers are as follows:
test samples made of nylon materials to which no flame retardant was added were referred to as "PA", and test samples made of the organophosphorus flame retardant nylon materials obtained in the above examples 1 to 7 were referred to as "FR-A" - "FR-G" in this order.
The test specimen preparation procedure for all the above-mentioned specimens is referred to GB/T9532-.
1. 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
3. Conclusion of the test
The flame retardant property test results 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 nylon composition. When the content of the flame-retardant monomer reaches more than 6 percent, the flame-retardant grade of the copolymerized nylon composition is UL-94V-0 grade, the LOI value is improved, and the anti-dripping performance is obviously improved. It can be proved that the invention utilizes the reactive organophosphorus flame-retardant monomer to modify the flame-retardant property of the nylon composition, which is feasible and efficient. The organophosphorus flame-retardant copolymerized nylon composition obtained by the scheme provided by the invention has higher LOI 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 flame-retardant copolymerized nylon composition comprising organophosphorus flame-retardant copolymerized nylon 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 flame-retardant copolymerized nylon:
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;
R3is selected from C3-C12Linear, branched or cyclic alkylene, C6-C10Arylene radical, C3-C10A heteroaryl group; r3Preferably C3-C8Linear, branched or cyclic alkylene, C6-C8Arylene radical, C3-C8A heteroaryl group;
R4is selected from C3-C12Linear or branched alkylene; r4Preferably C3-C8Linear or branched alkylene;
x represents 2 to 50, y represents 2 to 50, and n represents 5 to 100;
preferably, x is from 2 to 30, y is from 2 to 30, and n is from 50 to 80.
2. The organophosphorus flame retardant copolymerized nylon composition of claim 1, wherein the inorganic nanomaterial is selected from one or more of nano layered silicate, nano silica, nano zinc oxide, and nano titanium dioxide.
3. The organophosphorus based flame retardant copolymerized nylon composition according to claim 1 or 2, which is prepared by a method 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 H, 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-C10Heteroarylene radical, R3Preferably C3-C8Linear, branched or cyclic alkylene, C6-C8Arylene radical, C3-C8A heteroaryl group;
obtaining a compound of the following formula (4):
wherein R is4Is selected from C3-C12Linear or branched alkylene, preferably C3-C8Linear or branched alkylene;
(B) reacting a compound of formula (4) with a lactam of formula (5) 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 to obtain a nylon of formula (1):
wherein, R, R1、R2、R3、R4X, y and n are as defined above;
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 the diamine monomer is excessive relative to the organic phosphorus flame-retardant monomer or the derivative thereof, so that the pH value of the prepared salt solution is 7-9;
the step (B) of preparing the organophosphorus flame-retardant copolymerized nylon comprises the following steps:
a. adding a lactam monomer, the reaction product obtained in the step (A), a catalyst, a molecular weight regulator, an antioxidant, an inorganic nano material and a proper amount of 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. finally, filling nitrogen, discharging materials, cooling, granulating, extracting and drying to obtain a final product;
in the step a, the total amount of the lactam monomer is 8-30 times, preferably 8-12 times, and more preferably 10-12 times of the mass of the flame retardant monomer.
4. The organophosphorus flame retardant copolymerized nylon composition of claim 3, wherein, in the step (B) of preparing the organophosphorus flame retardant copolymerized nylon, the lactam monomer is one or more of caprolactam, decanolactam, undecanolactam, dodecanolactam, and various lactam monomers having lactam characteristics;
the antioxidant is one or more of compounds such as p-phenylenediamine, dihydroquinoline and the like 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 is one or more of sodium hypophosphite, methyl benzenesulfonic acid, a new ferrocene chiral nylon ligand and the like;
the molecular weight regulator is one or more of benzoic acid, adipic acid and acetic acid.
5. The method for preparing an organophosphorus flame retardant copolymerized nylon 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 H, 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-C10Heteroarylene radical, R3Preferably C3-C8Linear, branched or cyclic alkylene, C6-C8Arylene radical, C3-C8A heteroaryl group;
obtaining a compound of the following formula (4):
wherein R is4Is selected from C3-C12Linear or branched alkylene, preferably C3-C8Linear or branched alkylene;
(B) reacting a compound of formula (4) with a lactam of formula (5) 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 to obtain a nylon of formula (1):
wherein, R, R1、R2、R3、R4As defined above;
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 80;
or (B') preparing the nylon of formula (1) in the absence of inorganic nanomaterial and then blending the prepared organophosphorus flame-retardant copolymerized nylon 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 copolymerized nylon;
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 to 10, more preferably 1:1 to 2, and in the step (A) of preparing the organophosphorus flame retardant copolymerized nylon, the diamine monomer is in excess relative to the organophosphorus flame retardant monomer or derivative thereof so that the pH of the prepared salt solution is 7 to 9.
6. The preparation method according to claim 5, wherein the reaction temperature is increased from room temperature to 40-70 ℃ within 5-20 min; and/or controlling the using amount of water not to exceed 10 percent of the total mass of the reaction system, preferably not to exceed 5 percent; and/or
Di used in the step (A) for preparing the organophosphorus flame-retardant copolymerized nylonThe amine monomer is hexamethylenediamine, decamethylenediamine, nonanediamine, undecanediamine, dodecanediamine, or aliphatic C6-C20One or more of imino diamine, aromatic diamine and alicyclic diamine; and/or
In the step (B) of preparing the organophosphorus flame-retardant copolymerized nylon, a lactam monomer, a reaction product obtained in the step (A), an antioxidant, a molecular weight regulator, a catalyst, an inorganic nano material and a proper amount of water are added into a reaction kettle, and the reaction temperature and the reaction pressure are regulated and controlled under the nitrogen atmosphere to prepare the required organophosphorus flame-retardant copolymerized nylon material.
7. The preparation method according to claim 5 or 6, wherein, in the step (B) of preparing the organophosphorus flame-retardant copolymerized nylon, the lactam monomer is one or more of caprolactam, decanolactam, undecanolactam, dodecanolactam and various lactam monomers having lactam characteristics; and/or
The antioxidant is one or more of compounds such as p-phenylenediamine, dihydroquinoline and the like 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; and/or
The catalyst is one or more of sodium hypophosphite, methyl benzenesulfonic acid, a new ferrocene chiral nylon ligand and the like; and/or
The molecular weight regulator is one or more of benzoic acid, adipic acid and acetic acid.
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 a lactam monomer, the reaction product obtained in the step (A), a catalyst, a molecular weight regulator, an antioxidant, an inorganic nano material and a proper amount of 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.
9. The preparation method according to claim 8, wherein in step a, the total amount of the lactam monomer added is 8 to 30 times, preferably 8 to 12 times, more preferably 10 to 12 times the mass of the flame retardant monomer; the catalyst and the antioxidant are 0.01 to 1.0 percent of the mass of the lactam polymerization monomer or the lactam polymer, preferably 0.05 to 0.5 percent, more preferably 0.08 to 0.2 percent, and more preferably about 1/1000 for example; and/or
In the step a, the lactam monomer is one or more of caprolactam, decanolactam, undecanolactam, dodecanolactam and various lactam monomers with lactam characteristics.
10. Use of the organophosphorus based flame retardant copolymerized nylon composition according to any one of claims 1 to 4 for producing engineering plastics, films or fiber 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 |
| CN114989420A (en) * | 2022-06-21 | 2022-09-02 | 浙江理工大学 | Modified polyamide, 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 |
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