CN116217921A - Phosphorus-containing in-situ flame-retardant polyamide - Google Patents
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Abstract
The invention belongs to the field of novel high polymer materials, and particularly relates to phosphorus-containing in-situ flame-retardant polyamide. The phosphorus-containing in-situ flame-retardant polyamide is formed by polycondensing phosphorus-containing organic amine salt and nylon salt; the phosphorus-containing organic amine salt is obtained by condensing a reactive phosphorus-containing flame retardant with carboxyl and diamine. The phosphorus-containing functional groups in the phosphorus-containing in-situ flame-retardant polyamide are positioned on branched chains, so that the main performance of a main chain is not affected; the phosphorus-containing functional group has a simple structure, does not contain a rigid structure, and has little influence on the secondary structure of the molecular chain; the phosphorus content of the phosphorus-containing dibasic acid used in the preparation method is up to 13.68%, which is favorable for improving the flame retardant property; the phosphorus-containing in-situ flame-retardant polyamide provided by the invention avoids the problem of uneven distribution such as agglomeration, precipitation or migration of inorganic micromolecular phosphorus flame retardant to the surface of a material in a flame-retardant modified compound.
Description
Technical Field
The invention belongs to the field of novel high polymer materials, and particularly relates to phosphorus-containing in-situ flame-retardant polyamide.
Background
The polyamide is the engineering plastic with the most extensive application, and has important application in the fields of electronic appliances and the like, but most of the polyamide has an oxygen index of 24-27, belongs to inflammable materials, and the flame retardant modification of most of the polyamide at present achieves the aim of flame retardance by a blending and adding method. Flame retardant modification of polyamide is mostly realized by means of compounds of elements such as halogen elements, phosphorus elements, nitrogen elements, silicon elements and the like as flame retardants, but the halogen-containing flame retardant material generates a large amount of halogen-containing toxic corrosive gases during combustion to cause secondary harm, so that the in-situ flame retardant polyamide synthesized by the monomer containing phosphorus elements has more application value.
In general, most of phosphorus-based flame retardants are used as phosphorus-containing inorganic salts, for example, patent CN1771292a (application number of cn200480009662. X) discloses a flame-retardant polyamide molding material; the material consists of 30-80 wt% of partially aromatic and partially crystalline polyamide and 1-30 wt% of flame retardant containing phosphinate and/or diphosphinate, and has good flame retardant effect; however, the flame retardant is a small molecular inorganic salt, has poor compatibility with a high molecular resin matrix, is easy to cause the problems of agglomeration, precipitation or migration to the surface of a material and the like, and affects the performance of the material.
US5859147a synthesizes an alkyl compound containing a phosphate structure, which can solve the problem of precipitation on the surface of the flame retardant to a certain extent. Chinese patents CN106433103A, CN106497027a and CN106496549a disclose copolyamide polymers with a backbone containing phosphorus. The gold technology (CN 110204708A) also develops a series of modified materials with DOPO derivatives as flame-retardant monomers by the principle, and the Kaiser organism (CN 114836031A) discloses a method for synthesizing flame-retardant biological polyamide. Early research into flame retardant monomers abroad has been initiated by Monsanto Company (US 4070336A) which developed a phosphorus containing structure that reacted with an amino group to form an amide bond. William Giroldini (US 5338787A) developed a phosphorus-containing monomer of double helix structure for polymer copolymerization and issued related patents, EMS company (US 5859147A) developed a transparent nylon with flame retardant properties, but no corresponding products are currently publicly sold, and J.K.Kalitsis synthesizes phosphorus-containing copolymer polymer by phosphorus-containing dibasic acid with aniline and dibenzoyl chloride and studied its thermal stability. The Donghua university also improves the flame retardant properties of PA66 fibers by adding DOPO-based flame retardants, and oxygen index can be mentioned to be above 30%. However, the above disclosed patents and the prior art still have many disadvantages, such as that the phosphorus content in the main chain affects the properties of polyamide, that the oligomer or in-situ flame retardant prepared by relying on DOPO derivatives contains more rigid functional groups, that the phosphorus content is relatively low, and that the obtained product is not truly in-situ flame retardant polyamide.
Therefore, it is imperative to develop an in-situ flame retardant polyamide which maintains the original properties of the polyamide main chain and has excellent flame retardant properties.
Disclosure of Invention
Aiming at the problems, the invention provides the phosphorus-containing in-situ flame-retardant polyamide which has the advantages of no precipitation, excellent flame retardant property and no influence on the main chain property of the polyamide copolymer.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a phosphorus-containing in-situ flame-retardant polyamide, which has a structure shown in a formula I:
wherein A is a phosphorus-containing flame-retardant structural unit, and B is a main chain structural unit;
the phosphorus-containing flame retardant structural unit comprises the following components: r is R 1 And R is 2 Each independently is C 1 -C 10 Straight-chain, branched or cyclic alkylene, or no R 1 Or no R 2 ；R 3 Is C 1 -C 10 Straight-chain, branched or cyclic alkylene, or no R 3 ；R 4 And R is 5 Each independently is C 1 -C 10 Straight, branched, cyclic alkyl groups; r is R 6 Is C 1 -C 10 Linear, branched, cyclic alkylene groups;
the main chain structural unit comprises: r is R 7 And R is 8 Each independently is C 1 -C 12 Straight-chain, branched, cyclic alkylene, C 6 -C 12 Arylene or aralkylene;
x is any integer from 1 to 20; y is any integer from 1 to 50; n is any integer from 10 to 100.
Preferably, in the phosphorus-containing flame retardant structural unit: no R 1 And R is 2 Is methylene, or R 1 Is methylene and is free of R 2 The method comprises the steps of carrying out a first treatment on the surface of the No R 3 ；R 4 And R is 5 Is methyl; r is R 6 Is a hexylene group or a decylene group.
Preferably, in the main chain structural unit: r is R 7 、R 8 Is a hexylene group or a decylene group.
The invention also provides a preparation method of the phosphorus-containing in-situ flame-retardant polyamide, which comprises the following steps:
(1) Reacting a reactive phosphorus-containing flame retardant with diamine with an equal molar weight at 35-45 ℃ to obtain phosphorus-containing organic ammonium salt; the structural formula of the reactive phosphorus-containing flame retardant is shown as a formula II:
wherein R is 1 And R is 2 Each independently is C 1 -C 10 Straight-chain, branched or cyclic alkylene, or no R 1 Or no R 2 ；R 3 Is C 1 -C 10 Straight-chain, branched or cyclic alkylene, or no R 3 ；R 4 And R is 5 Each independently is C 1 -C 10 Straight, branched, cyclic alkyl groups;
the diamine is shown in a formula III:
H 2 N-R 6 -NH 2
III
Wherein R is 6 Is C 1 -C 10 Linear, branched, cyclic alkylene groups;
the structural formula of the phosphorus-containing organic amine salt is shown in a formula IV:
(2) Preparing nylon salt solution with the mass fraction of 40-70% by using nylon salt and deionized water, and adjusting the pH value of the nylon salt solution to 7.5-8.0;
the nylon salt has the specific structure as follows:
- OOC-R 7 -COO -+ H 3 N-R 8 -NH 3 +
v (V)
Wherein R is 7 And R is 8 Each independently is C 1 -C 18 Straight-chain, branched, cyclic alkylene, C 6 -C 12 Arylene or aralkylene;
(3) The nylon salt in the step (2) is dehydrated at 180-230 ℃ in the presence of a catalyst and nitrogen; then carrying out prepolymerization reaction at 240-260 ℃ and 16-18bar, gradually decompressing, and discharging water vapor generated in the polymerization process.
(4) Continuously adding the phosphorus-containing organic amine salt in the step (1) into a system after the pre-polymerization reaction in the step (3), keeping the reaction temperature and the pressure condition unchanged, performing polymerization reaction, gradually increasing the temperature to 270-290 ℃ for secondary reaction, and then reducing the pressure to 0.55-0.8bar within 0.1-0.3h for devolatilization; and (3) raising the pressure to normal pressure, then discharging, granulating and drying to obtain a white cylindrical phosphorus-containing in-situ flame-retardant polyamide particle finished product.
Preferably, the step (1) is: and respectively dissolving the reactive phosphorus-containing flame retardant and diamine with equal molar weight in an organic solvent to obtain a first solution and a second solution, dropwise adding the first solution into the second solution, stirring, cooling, filtering after dropwise adding, leaching by ethanol, and drying to obtain a finished product of the phosphorus-containing organic amine salt. The condensation reaction of carboxylic acid and diamine can raise the temperature, and the dripping can ensure slow temperature raising and avoid the bumping of the reaction system. Further preferably, the organic solvent is ethanol.
Preferably, the mass fraction of the nylon salt solution in the step (2) is 50-60%; the pH value of the nylon salt solution is 7.8-7.9.
Preferably, R in the nylon salt structure of step (2) 7 And R is 8 Each independently is C 6 -C 10 Straight chain alkylene of (a).
Preferably, the catalyst in step (3) is sodium hypophosphite; the catalyst is used in an amount of 0.05 to 0.15wt% of the nylon salt.
Preferably, the temperature of the dehydration in step (3) is 205-215 ℃.
Preferably, the temperature of the reaction in step (3) is 245-255 ℃; the pressure of the reaction is 16.5-17.5bar; the reaction time is 1-3h.
Preferably, the polymerization time in step (4) is from 0.1 to 1 hour; the secondary reaction time is 0.5-2h.
Preferably, the secondary reaction temperature in the step (4) is 275-285 ℃; preferably, the devolatilization pressure is 0.7-0.75bar; the devolatilization time was 1h.
Compared with the prior art, the invention has the following advantages:
(1) The phosphorus-containing functional group in the phosphorus-containing in-situ flame-retardant polyamide is positioned on the branched chain, so that the main performance of the main chain is not affected;
(2) The phosphorus-containing functional group in the phosphorus-containing in-situ flame-retardant polyamide has a simple structure, does not contain a rigid structure, and has little influence on the secondary structure of a molecular chain;
(3) The phosphorus content of the phosphorus-containing dibasic acid used in the preparation method of the phosphorus-containing in-situ flame-retardant polyamide is up to 13.68%, which is beneficial to improving the flame retardant property;
(4) The phosphorus-containing in-situ flame-retardant polyamide provided by the invention avoids the problem of uneven distribution such as agglomeration, precipitation or migration of inorganic micromolecular phosphorus flame retardant to the surface of a material in a flame-retardant modified compound.
Detailed Description
The invention will be further described with reference to specific embodiments, and advantages and features of the invention will become apparent from the description. The embodiments are merely exemplary and do not limit the scope of the invention in any way. It will be understood by those skilled in the art that various changes and substitutions of details and forms of the technical solution of the present invention may be made without departing from the spirit and scope of the present invention, but these changes and substitutions fall within the scope of the present invention.
The raw materials used in the examples and comparative examples of the present invention were derived from commercial products except for the phosphorus-containing monomers involved in the phosphorus-containing structural units. The method for synthesizing the phosphorus-containing monomer related to the phosphorus-containing structural unit in the embodiment of the invention is as follows:
adding dialkyl phosphite into a reactor provided with a nitrogen inlet and outlet, a thermometer socket and a mechanical stirrer, adding a certain amount of ethanol as a solvent, adding a catalytic amount of benzoyl peroxide, and introducing nitrogen for protection; heating and stirring until the mixture is dissolved;
and then dripping ethanol solution of dibasic acid with double bonds, controlling the dripping temperature at 40-50 ℃, generating a large amount of white precipitates in the system during the dripping process, centrifuging, leaching, washing with water, and drying to obtain the phosphorus-containing monomer.
Example 1
The preparation method of the phosphorus-containing in-situ flame-retardant polyamide comprises the following steps:
(1) Preparation of organic amine salt containing phosphorus
Accurately weighing 22.6g (0.1 mol) O, O' -dimethyl- (2-succinic acid) phosphonate, preparing a solution with a certain concentration with 100ml ethanol, then dripping the solution into a three-mouth bottle containing 11.6g (0.1 mol) hexamethylenediamine and 100ml ethanol, wherein the dripping temperature is ensured to be 40+/-5 ℃, stirring for 0.5 hour after the dripping is finished, cooling to 20 ℃, filtering, eluting with ethanol, and drying to obtain about 34g of phosphorus-containing organic amine salt finished product.
(2) Preparation of Nylon 66 salt solution
Accurately weighing 131g (0.5 mol) of nylon 66 salt and 87.4g of deionized water, mixing to prepare a nylon 66 salt solution with the mass fraction of 60%, and regulating the pH value of the salt solution to be between 7.85 and 7.9.
(3) Pre-polymerization of backbone building blocks
Firstly, transferring the nylon 66 salt solution prepared in the step (2) into a 0.5 liter stainless steel polymerization reaction kettle; simultaneously adding 0.165g of sodium hypophosphite; high-purity nitrogen is introduced into the reaction kettle for 5 times of replacement; then gradually raising the temperature to 210+/-5 ℃ and removing the water in the system; then, the reaction is carried out for 2.5 hours at the temperature of 250+/-3 ℃ and the pressure of 17.5bar, and then, the pressure is gradually released, and the vapor generated in the polymerization process is discharged.
(4) Copolymerization of flame-retardant structural units
After the step (3) is completed, continuously adding the phosphorus-containing organic amine salt prepared in the step (1) into the 0.5 liter stainless steel polymerization reaction kettle, keeping the temperature at 250+/-3 ℃ and the pressure at 17.5bar for reaction for 0.5h, gradually heating to 280 ℃, after reaction for 1h, reducing the pressure to 0.71bar within 15min, and keeping for 1h to discharge water vapor and other small molecular substances generated by the polymerization reaction.
(5) Discharging material
And (3) raising the pressure in the kettle to normal pressure, discharging, granulating, and drying for 6 hours under the pressure of 0.95bar at 110 ℃ under nitrogen atmosphere to obtain about 140g of white cylindrical particle finished product, wherein the phosphorus content is about 2.10% after testing, and the product is marked as the in-situ flame-retardant polyamide-1.
Example 2
This example synthesis method was performed as in example 1, except that the nylon 66 salt was replaced with 187g (0.5 mol) nylon 1010 salt, resulting in approximately 197g of white cylindrical particles, with a phosphorus content of approximately 1.54% tested. Is denoted as in-situ flame retardant polyamide-2.
Example 3
This example synthesis method was carried out with reference to example 1, under otherwise unchanged conditions, the hexamethylenediamine in the step of synthesizing the organic amine salt containing phosphorus was changed to 17.2g (0.1 mol) of 1, 10-decanediamine, and finally about 148g of white cylindrical particles were obtained, and the phosphorus content was measured to be about 2.02%. Is denoted as in situ flame retardant polyamide-3.
Example 4
This example synthesis method was performed under otherwise unchanged conditions with reference to example 1, increasing the nylon 66 salt usage to 196.5g (0.75 mol) and increasing the deionized water usage to 131.1g for the nylon 66 salt solution, resulting in about 198g of white cylindrical particles, with a phosphorus content of about 1.50% tested. Is denoted as in situ flame retardant polyamide-4.
Example 5
This example synthesis with reference to example 1, with the other conditions unchanged, the amount of O, O' -dimethyl- (2-succinic) phosphonate was increased to 33.9g (0.15 mol) and the corresponding hexamethylenediamine used was increased to 17.4g (0.15 mol), resulting in approximately 157g of white cylindrical particles, the phosphorus content being approximately 2.90% as tested. Is denoted as in situ flame retardant polyamide-5.
Example 6
This example synthesis with reference to example 1, the other conditions were unchanged, and O, O '-dimethyl- (2-succinic acid) phosphonate was converted to O, O' -diethyl- (2-succinic acid) phosphonate (0.1 mol,25.4 g) to finally yield about 140g of white cylindrical particles, which were tested for phosphorus content of about 2.0%. Is denoted as in situ flame retardant polyamide-6.
Example 7
This example synthesis with reference to example 1, the other conditions were unchanged, and O, O '-dimethyl- (2-succinic acid) phosphonate was converted to O, O' -dioctyl- (2-succinic acid) phosphonate (0.1 mol,42.2 g) to finally yield about 170g of white cylindrical particles, which were tested for phosphorus content of about 1.8%. Is denoted as in situ flame retardant polyamide-7.
Example 8
This example synthesis with reference to example 1, the other conditions were unchanged, and O, O '-dimethyl- (2-succinic acid) phosphonate was converted to O, O' -didecyl- (2-succinic acid) phosphonate (0.1 mol,47.8 g) to finally yield about 175g of white cylindrical particles, which were tested for phosphorus content of about 1.74%. Is denoted as in situ flame retardant polyamide-8.
Example 9
This example synthesis was carried out with reference to example 5, under otherwise unchanged conditions, by converting O, O '-dimethyl- (2-succinic acid) phosphonate to O, O' -didecyl- (2-succinic acid) phosphonate (0.15 mol,71.7 g), the corresponding hexamethylenediamine used was added to 17.4g (0.15 mol) and finally to about 203g of white cylindrical granules, the phosphorus content being tested to about 2.23%. Is denoted as in situ flame retardant polyamide-9.
To better illustrate the properties of the phosphorus-containing in-situ flame retardant polyamide copolymer of the present invention, the phosphorus-containing in-situ flame retardant polyamide obtained in examples 1-9 was now subjected to the following comparative tests:
(1) The performance testing method comprises the following steps:
(1) relative viscosity: with reference to standard GB/T12006.1-1989, the relative viscosity of a product at a concentration of 0.25g/dL was measured in 98% concentrated sulfuric acid at (25.+ -. 0.01) ℃ using an Ubbelohde viscometer.
(2) Tensile strength: the tensile strength of the resin material was measured with reference to standard ISO 527.
(3) UL94 flame retardant rating: the measurement was carried out with reference to GB/T2408-1996, and the sample size was 13 cm. Times.1.3 cm. Times.0.3 cm.
(4) Limiting Oxygen Index (LOI): the measurement was carried out with reference to the standard GB/T5454-1997, and the dimensions of the sample were 12 cm. Times.1 cm. Times.0.4 cm.
(5) Melting process: determination with reference to standard GB/T19466.3-2004
(6) Molecular weight calculation method: the method adopts a chemical method to calculate, specifically a terminal group analysis method, and the calculation formula is as follows:
M＝mx/n t
wherein M is the molecular weight; m is the weight of the sample, x is the number of end groups analyzed in the polymer chain, n t The total number of moles of end groups analyzed, i.e., the total number of moles of end amino groups and end carboxyl groups.
i. Terminal carboxyl group (n) COOH ) And (3) measuring: the polymer was sheared into sesame-sized particles, dried at 105℃for 15 minutes, 0.0500g of the sample was accurately weighed and placed into a10 ml Erlenmeyer flask, and 5ml of purified benzyl alcohol was removed. Heating and dissolving the conical flask in a glycol steam bath at 180 ℃ until the polymer is completely dissolved; maintaining the temperature at 180deg.C, adding a stirrer, starting a magnetic stirrer, adding microphenol phthalein reagent, titrating to reddish color with 0.02mol/L potassium hydroxide-ethylene glycol-methanol solution by a microtitrator, and counting the number of degrees. Blank tests were performed in the same manner. The carboxyl content was determined by the following formula:
wherein N is the molar concentration of the potassium hydroxide solution, and V is the ml of the potassium hydroxide solution consumed by the sample; v (V) 0 The ml of potassium hydroxide solution consumed for the blank test was measured, and W was the weight (g) of the sample.
Amino-terminated (n) NH2 ) Measurement
The polymer was sheared into sesame-sized particles, dried at 105℃for 15 minutes, accurately weighed 0.0250g of the sample into a 20ml Erlenmeyer flask, and removed 10ml of the phenol-ethanol solution. Put on a magnetic stirrer and stir for 45min until complete dissolution, add 2 drops of thymol blue indicator, titrate to mauve with 0.02mol/L hydrochloric acid by a microtitrator and record the number of degrees. Blank tests were performed in the same manner. The amino group content was determined by the following formula:
wherein N is hydrochloric acid solution moleThe molar concentration, V, is the ml of hydrochloric acid solution consumed by the sample; v (V) 0 The ml of hydrochloric acid solution consumed for the blank test was measured, and W was the weight (g) of the sample.
(2) PA66 slice (china god Ma Nilong) with the trademark EPR27 and PA1010 slice (EMS) with the trademark Grilamid 1SXE4224 were respectively selected as comparison samples for testing, and specific test results are shown in table 1:
table 1 comparison of the Properties of the polyamides prepared in the examples with commercially available nylons
By analyzing the above table, the following results were obtained:
1. under the same polymerization conditions, the comparison of examples 1/4/5/9 shows that: the more the number of the phosphorus-containing flame-retardant structural units is, the better the flame-retardant effect is, but the negative effect on the improvement of the polymerization degree is realized, the certain effect on the intermolecular structure is realized, the corresponding melting range is reduced, and the tensile strength is also reduced.
2. Under the same polymerization conditions, as can be seen from example 1/2/3/4/5/6/7/8/9, the flame retardant effect is best when the phosphorus content in the copolymer reaches about 2%; the phosphorus content of about 1.5% can only reach V1 grade.
3. As can be seen from examples 1/2/3, the preferred monomers O, O' -dimethyl- (2-succinic acid) phosphonate containing phosphorus flame retardant structural units form salts with 1, 6-hexamethylenediamine and 1, 10-decamethylenediamine, and the resulting salts can be copolymerized with PA66 salt and PA1010 salt to form polymers.
4. As can be seen from examples 6/7/8/9, the number of alkyl C atoms of the side group of the phosphorus-containing flame retardant structural unit is increased, and the influence on the polymerization process and the polymerization degree is small; however, the corresponding phosphorus content decreases due to the increased number of alkyl C atoms; in addition to having a slight effect on the oxygen index, other aspects have little effect.
5. The copolymer synthesized in example 1/2/3/4/5/6/7/8/9, compared with commercial PA66 and PA1010, shows that the presence of the phosphorus-containing flame retardant structural unit has a slight influence on the mechanical properties, melting range and polymerization degree without adding a molecular weight regulator, and has an increasing trend along with the increase of the phosphorus-containing flame retardant structural unit, but the influence on the overall properties is not great; the flame retardant property is greatly improved.
Claims (10)
1. The phosphorus-containing in-situ flame-retardant polyamide is characterized by having a structure shown in a formula I:
wherein A is a phosphorus-containing flame-retardant structural unit, and B is a main chain structural unit;
the phosphorus-containing flame retardant structural unit comprises the following components: r is R 1 And R is 2 Each independently is C 1 -C 10 Straight-chain, branched or cyclic alkylene, or no R 1 Or no R 2 ；R 3 Is C 1 -C 10 Straight-chain, branched or cyclic alkylene, or no R 3 ；R 4 And R is 5 Each independently is C 1 -C 10 Straight, branched, cyclic alkyl groups; r is R 6 Is C 1 -C 10 Linear, branched, cyclic alkylene groups;
the main chain structural unit comprises: r is R 7 And R is 8 Each independently is C 1 -C 12 Straight-chain, branched, cyclic alkylene, C 6 -C 12 Arylene or aralkylene;
x is any integer from 1 to 20; y is any integer from 1 to 50; n is any integer from 10 to 100.
2. The phosphorus-containing, in-situ flame retardant polyamide of claim 1, wherein the phosphorus-containing, flame retardant polyamide comprises a polyamideThe structural unit comprises: no R 1 And R is 2 Is methylene, or R 1 Is methylene and is free of R 2 The method comprises the steps of carrying out a first treatment on the surface of the No R 3 ；R 4 And R is 5 Is methyl; r is R 6 Is a hexylene group or a decylene group.
3. The phosphorus-containing in-situ flame retardant polyamide of claim 1, wherein in the backbone structural unit: r is R 7 、R 8 Is a hexylene group or a decylene group.
4. The process for preparing a phosphorus-containing in-situ flame retardant polyamide as claimed in any one of claims 1 to 3, wherein (1) reacting a reactive phosphorus-containing flame retardant with an equimolar amount of diamine at 35 to 45 ℃ to obtain a phosphorus-containing organoammonium salt; the structural formula of the reactive phosphorus-containing flame retardant is shown as a formula II:
wherein R is 1 And R is 2 Each independently is C 1 -C 10 Straight-chain, branched or cyclic alkylene, or no R 1 Or no R 2 ；R 3 Is C 1 -C 10 Straight-chain, branched or cyclic alkylene, or no R 3 ；R 4 And R is 5 Each independently is C 1 -C 10 Straight, branched, cyclic alkyl groups;
the diamine is shown in a formula III:
H 2 N-R 6 -NH 2
III
Wherein R is 6 Is C 1 -C 10 Linear, branched, cyclic alkylene groups;
the structural formula of the phosphorus-containing organic amine salt is shown in a formula IV:
(2) Preparing nylon salt solution with the mass fraction of 40-70% by using nylon salt and deionized water, and adjusting the pH value of the nylon salt solution to 7.5-8.0;
the specific structure of the nylon salt is shown as formula V:
- OOC-R 7 -COO -+ H 3 N-R 8 -NH 3 +
v (V)
Wherein R is 7 And R is 8 Each independently is C 1 -C 18 Straight-chain, branched, cyclic alkylene, C 6 -C 12 Arylene or aralkylene;
(3) The nylon salt in the step (2) is dehydrated at 180-230 ℃ in the presence of a catalyst and nitrogen; then carrying out prepolymerization reaction under the conditions of 240-260 ℃ and 16-18bar pressure, gradually decompressing, and discharging water vapor generated in the polymerization process;
(4) Continuously adding the phosphorus-containing organic amine salt in the step (1) into a system after the pre-polymerization reaction in the step (3), and carrying out polymerization reaction while keeping the reaction temperature and the pressure condition unchanged; gradually raising the temperature to 270-290 ℃ to carry out secondary reaction; then the pressure is reduced to 0.55 to 0.8bar within 0.1 to 0.3h for devolatilization; and (3) raising the pressure to normal pressure, then discharging, granulating and drying to obtain a white cylindrical phosphorus-containing in-situ flame-retardant polyamide particle finished product.
5. The method for preparing a phosphorus-containing in-situ flame retardant polyamide as claimed in claim 4, wherein the step (1) is: respectively dissolving a reactive phosphorus-containing flame retardant and diamine with equal molar weight in an organic solvent to respectively obtain a first solution and a second solution, dropwise adding the first solution into the second solution, stirring, cooling, filtering after dropwise adding, leaching with ethanol, and drying to obtain a phosphorus-containing organic amine salt finished product;
preferably, the organic solvent is ethanol; stirring time is 0.5h; cooling to 20 ℃.
6. The method for preparing phosphorus-containing in-situ flame retardant polyamide according to claim 4, wherein the mass fraction of the nylon salt solution in the step (2) is 50-60%; the pH value of the nylon salt solution is 7.8-7.9;
preferably, R in the nylon salt structure of step (2) 7 And R is 8 Each independently is C 6 -C 10 Straight chain alkylene of (a).
7. The method for preparing a phosphorus-containing in-situ flame retardant polyamide as claimed in claim 4, wherein the catalyst in the step (3) is sodium hypophosphite; the catalyst is used in an amount of 0.05 to 0.15wt% of the nylon salt.
8. The method for preparing a phosphorus-containing in-situ flame retardant polyamide according to claim 4, wherein the temperature of dehydration in step (3) is 205-215 ℃; preferably, the temperature of the prepolymerization reaction in step (3) is 245-255 ℃, the pressure is 16.5-17.5bar, and the time is 1-3h.
9. The method for preparing a phosphorus-containing in-situ flame retardant polyamide according to claim 4, wherein the polymerization time in the step (4) is 0.1 to 1h; the secondary reaction time is 0.5-2h.
10. The method for preparing a phosphorus-containing in-situ flame retardant polyamide as claimed in claim 4, wherein the secondary reaction temperature in the step (4) is 275-285 ℃; preferably, the devolatilization pressure is 0.7-0.75bar; the devolatilization time was 1h.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5998491A (en) * | 1998-01-27 | 1999-12-07 | Donlar Corporation | Super-absorbing polymeric networks |
| CN104262619A (en) * | 2014-09-15 | 2015-01-07 | 浙江理工大学 | Phosphorus-containing flame-retardant polyamide and preparation method and application thereof |
| CN106496548A (en) * | 2016-10-25 | 2017-03-15 | 成都拓利科技股份有限公司 | A kind of organophosphor system copolymerization Flameproof polyamide and preparation method thereof |
| CN106633828A (en) * | 2017-01-06 | 2017-05-10 | 东华大学 | Halogen-free flame-retardant polyamide 66 and preparation method thereof |
| CN113527669A (en) * | 2016-10-25 | 2021-10-22 | 成都拓利科技股份有限公司 | Organic phosphorus copolymerized flame-retardant polyamide and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5998491A (en) * | 1998-01-27 | 1999-12-07 | Donlar Corporation | Super-absorbing polymeric networks |
| CN104262619A (en) * | 2014-09-15 | 2015-01-07 | 浙江理工大学 | Phosphorus-containing flame-retardant polyamide and preparation method and application thereof |
| CN106496548A (en) * | 2016-10-25 | 2017-03-15 | 成都拓利科技股份有限公司 | A kind of organophosphor system copolymerization Flameproof polyamide and preparation method thereof |
| CN113527669A (en) * | 2016-10-25 | 2021-10-22 | 成都拓利科技股份有限公司 | Organic phosphorus copolymerized flame-retardant polyamide and preparation method thereof |
| CN106633828A (en) * | 2017-01-06 | 2017-05-10 | 东华大学 | Halogen-free flame-retardant polyamide 66 and preparation method thereof |
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