CN107936245B - Permanent halogen-free flame-retardant PA10T polyamide resin and preparation method thereof - Google Patents
Permanent halogen-free flame-retardant PA10T polyamide resin and preparation method thereof Download PDFInfo
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- CN107936245B CN107936245B CN201711229995.9A CN201711229995A CN107936245B CN 107936245 B CN107936245 B CN 107936245B CN 201711229995 A CN201711229995 A CN 201711229995A CN 107936245 B CN107936245 B CN 107936245B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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 relates to the field of halogen-free environment-friendly polyamide resin, in particular to permanent halogen-free flame-retardant PA10T polyamide resin and a synthetic method thereof. The polyamide resin is a polymer formed by embedding 1,1,3, 5-tetraanilino cyclotriphosphazene serving as a monomer into a PA10T polyamide macromolecular chain. The preparation method of the polyamide resin comprises the following steps: hexamethylenediamine, terephthalic acid and 1,1,3, 5-tetraanilino cyclotriphosphazene are directly added into a high-pressure reaction kettle as reaction monomers, and the 1,1,3, 5-tetraanilino cyclotriphosphazene is embedded into the PA10T polyamide macromolecular chain as the monomer by adopting a three-step method of salt formation, prepolymerization and solid phase polymerization to form a polymer. The modified PA10T polyamide resin is halogen-free and more environment-friendly, has excellent flame retardant property and higher processability.
Description
Technical Field
The invention relates to the field of halogen-free environment-friendly polyamide resin, in particular to permanent halogen-free flame-retardant PA10T polyamide resin and a preparation method thereof.
Background
Poly (decamethylene terephthalamide) (PA10T) is a novel semi-aromatic polyamide, has good rigidity, heat resistance, dimensional stability, processability and low water absorption rate, and has wide application prospect in the fields of electronics, electricity, automobiles and the like. Decamethylene diamine as the raw material of PA10T is derived from castor oil, and meets the requirements of environmental protection and sustainable development. However, the flame retardant property of PA10T is poor and cannot meet the requirements of various environments, which greatly limits the application development of the PA10 in various aspects. Therefore, there is a certain urgency and necessity to improve the flame retardant performance of PA 10T.
The main chain of the polyphosphazene and the derivative material thereof is a nitrogen-phosphorus alternating system, the special structure determines that the polyphosphazene and the derivative material thereof have excellent flame retardant effect, and toxic gas is not released in the combustion process, so that the polyphosphazene and the derivative material thereof can be used as an environment-friendly flame retardant material.
Disclosure of Invention
In order to solve the problem that the flame retardant property of PA10T in the prior art is different from the actual requirement, the polyphosphazene derivative serving as a reactive flame retardant is directly bonded to the molecular main chain of PA10T to obtain the PA10T polyamide resin with excellent flame retardant property.
A permanent halogen-free flame-retardant PA10T polyamide resin is characterized in that: 1,1,3, 5-tetraanilino cyclotriphosphazene is used as a monomer to be embedded into a PA10T polyamide macromolecular chain to form a polymer, and the structural formula of the polymer is as follows:
a preparation method of permanent halogen-free flame-retardant PA10T polyamide resin is characterized by comprising the following steps: the method comprises the following steps: hexamethylenediamine, terephthalic acid and 1,1,3, 5-tetraanilino cyclotriphosphazene are directly added into a high-pressure reaction kettle as reaction monomers, and the 1,1,3, 5-tetraanilino cyclotriphosphazene is embedded into the PA10T polyamide macromolecular chain as the monomer by adopting a three-step method of salt formation, prepolymerization and solid phase polymerization to form a polymer.
In a preferred embodiment of the present invention, the salt formation step comprises: adding 30-80% of decamethylenediamine, terephthalic acid and 1,1,3, 5-tetraanilino cyclotriphosphazene which are used as reaction monomers into a reaction kettle filled with an N-methylpyrrolidone solution, wherein the molar ratio of carboxyl to amino is 0.9-1.1, the temperature is 100-150 ℃, and the reaction lasts for 1-8 hours, so as to obtain the PA10T salt.
In a preferred embodiment of the present invention, the prepolymerization step comprises: adding 1500-5000 g of PA10T salt and 50-600 g of deionized water into a high-pressure reaction kettle, replacing air in the reaction kettle with nitrogen atmosphere, gradually heating to 200-260 ℃, pressurizing, continuously reacting for 3-20 h, and cooling to normal temperature to obtain the PA10T prepolymer.
In a preferable embodiment of the present invention, the pressure of the reaction kettle in the prepolymerization step is 1.5 to 3 kPa.
In a preferred embodiment of the present invention, the solid-phase polymerization step comprises: the PA10T prepolymer is crushed into particles of 1-5 microns, then the particles are placed in a high-pressure reaction kettle, air in the reaction kettle is replaced by nitrogen atmosphere, the temperature is gradually increased to 180-240 ℃, and the modified PA10T is prepared by continuous reaction for 3-12 hours under the pressure of-0.05-0.5 MPa.
In a preferred embodiment of the present invention, the synthesis of 1,1,3, 5-tetraanilinocyclotriphosphazene comprises the following steps:
(1) under the protection of nitrogen, dissolving hexachlorocyclotriphosphazene in a solvent, adding calcium hydride with the mass fraction of the total solution of 0.2-10 and triethylamine with the mass fraction of the total solution of 0.1-5%, and refluxing for 0.1-2 h;
(2) then dropwise adding a solvent solution of phenol with the total solution mass fraction of 5-35%, and continuously reacting for 1-5 h at 20-80 ℃;
(3) then removing the solvent, washing by a large amount of deionized water, and drying to obtain the 1,1,3, 5-tetraanilino cyclotriphosphazene.
According to the invention, hexachlorocyclotriphosphazene is phenoxylated and then prepolymerized to obtain 1,1,3, 5-tetraanilino cyclotriphosphazene, so that halogen-chlorine on hexachlorocyclotriphosphazene is removed, the influence of halogen on human body and environment is reduced, and the subsequently synthesized polyamide resin is more environment-friendly; 2. the obtained 1,1,3, 5-tetraanilino cyclotriphosphazene has a better flame retardant effect compared with hexachlorocyclotriphosphazene, and the 1,1,3, 5-tetraanilino cyclotriphosphazene is used as a monomer to be added into a PA10T polyamide macromolecular chain, so that the synthesized polymer has a better flame retardant property.
In a preferred embodiment of the present invention, the solvent for dissolving hexachlorocyclotriphosphazene is: cyclohexane, toluene, xylene, dimethyl sulfoxide, N-dimethylformamide, petroleum ether and octane.
Has the advantages that: 1.1, 1,3, 5-tetraanilino cyclotriphosphazene serving as a reactive flame retardant is directly bonded to a molecular main chain of PA10T to obtain PA10T polyamide resin with excellent flame retardant property; 2. due to the introduction of the polyphosphazene derivative as a flame retardant group, the dipole force between PA10T molecules is greatly weakened, and the modified PA10T also has higher processability. 3. The modified PA10T does not contain halogen, thereby avoiding the influence of halogen on human body and environment, and keeping the advantages of environmental protection while having excellent performance.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. The following is a more detailed description of specific embodiments, and the formulations of the examples are shown in the following table:
(1) synthesis of reactive flame retardant 1,1,3, 5-tetraanilino cyclotriphosphazene:
(2) synthesis of PA10T salt
(3) Synthesis of PA10T prepolymer
(4) Synthesis of modified PA10T according to the invention
| Example 16 | Example 17 | Example 18 | Example 19 | Example 20 | |
| Particle size of prepolymer | 1um | 2um | 3um | 4um | 5um |
| Reaction temperature | 180℃ | 200℃ | 220℃ | 230℃ | 240℃ |
| Reaction time | 3h | 5h | 7h | 9h | 12h |
(5) Performance testing
The flame retardant grades of the PA10T polymers of the invention all reach V0And (4) grading, and having excellent flame retardant effect. Meanwhile, the PA10T polymer provided by the invention has the characteristics of small smoke generation amount during combustion, lasting flame retardant effect, high efficiency and the like. The strength test result shows that the PA10T polymer holding resin has excellent mechanical property, high temperature resistance and processing performance, and the PA10T polymer has better application value on the premise of meeting the environmental protection, and can be widely applied to the fields of electronics, electricity, automobiles, aerospace and the like.
The above-mentioned embodiments are only specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive various equivalent modifications, substitutions and improvements within the technical scope of the present invention, and these modifications, substitutions and improvements should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (8)
1. A permanent halogen-free flame-retardant PA10T polyamide resin is characterized in that: 1,1,3, 5-tetraanilino cyclotriphosphazene is used as a monomer to be embedded into a PA10T polyamide macromolecular chain to form a polymer, and the structural formula of the polymer is as follows:
2. a preparation method of permanent halogen-free flame-retardant PA10T polyamide resin is characterized by comprising the following steps: the method comprises the following steps: decamethylenediamine, terephthalic acid and 1,1,3, 5-tetraanilino cyclotriphosphazene are directly added into a high-pressure reaction kettle as reaction monomers, and the 1,1,3, 5-tetraanilino cyclotriphosphazene is embedded into the PA10T polyamide macromolecular chain as a monomer by adopting a three-step method of salt formation, prepolymerization and solid phase polymerization to form a polymer.
3. The preparation method of the permanent halogen-free flame retardant PA10T polyamide resin as claimed in claim 2, wherein: the salifying step comprises the following steps: adding 30-80% of decamethylenediamine, terephthalic acid and 1,1,3, 5-tetraanilino cyclotriphosphazene which are used as reaction monomers into a reaction kettle filled with an N-methylpyrrolidone solution, wherein the molar ratio of carboxyl to amino is 0.9-1.1, the temperature is 100-150 ℃, and the reaction lasts for 1-8 hours, so as to obtain the PA10T salt.
4. The preparation method of the permanent halogen-free flame retardant PA10T polyamide resin as claimed in claim 3, wherein: the pre-polymerization step comprises: adding 1500-5000 g of PA10T salt and 50-600 g of deionized water into a high-pressure reaction kettle, replacing air in the reaction kettle with nitrogen atmosphere, gradually heating to 200-260 ℃, pressurizing, continuously reacting for 3-20 h, and cooling to normal temperature to obtain the PA10T prepolymer.
5. The method for preparing the permanent halogen-free flame retardant PA10T polyamide resin according to claim 4, wherein the method comprises the following steps: the pressure of the reaction kettle in the prepolymerization step is 1.5-3 kPa.
6. The method for preparing the permanent halogen-free flame retardant PA10T polyamide resin according to claim 4, wherein the method comprises the following steps: the solid phase polymerization step comprises: the PA10T prepolymer is crushed into particles of 1-5 microns, then the particles are placed in a high-pressure reaction kettle, air in the reaction kettle is replaced by nitrogen atmosphere, the temperature is gradually increased to 180-240 ℃, and the modified PA10T is prepared by continuous reaction for 3-12 hours under the pressure of-0.05-0.5 MPa.
7. The method for preparing the permanent halogen-free flame retardant PA10T polyamide resin according to any one of claims 2-6, wherein the method comprises the following steps: the synthesis of the 1,1,3, 5-tetraanilino cyclotriphosphazene comprises the following steps:
(1) under the protection of nitrogen, dissolving hexachlorocyclotriphosphazene in a solvent, adding calcium hydride with the mass fraction of 0.2-10% of total solution and triethylamine with the mass fraction of 0.1-5% of total solution, and refluxing for 0.1-2 h;
(2) then dropwise adding a solvent solution of aniline with the total solution mass fraction of 5-35%, and continuously reacting for 1-5 h at 20-80 ℃;
(3) then removing the solvent, washing by a large amount of deionized water, and drying to obtain the 1,1,3, 5-tetraanilino cyclotriphosphazene.
8. The preparation method of the permanent halogen-free flame retardant PA10T polyamide resin as claimed in claim 7, wherein: the solvent for dissolving the hexachlorocyclotriphosphazene is as follows: cyclohexane, toluene, xylene, dimethyl sulfoxide, N-dimethylformamide, petroleum ether and octane.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456949A (en) * | 2007-12-14 | 2009-06-17 | 金发科技股份有限公司 | Semi-aromatic polyamide and preparation method thereof |
| CN102286149A (en) * | 2011-06-29 | 2011-12-21 | 上海大学 | Polyphosphazene-semi-aromatic amide material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB921034A (en) * | 1959-09-14 | 1963-03-13 | Ici Ltd | New phosphorus nitrilo compounds |
| CN104140559A (en) * | 2013-05-10 | 2014-11-12 | 信汇科技有限公司 | Application of cyclophosphazene compound in preparation of resin as fire retardant |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456949A (en) * | 2007-12-14 | 2009-06-17 | 金发科技股份有限公司 | Semi-aromatic polyamide and preparation method thereof |
| CN102286149A (en) * | 2011-06-29 | 2011-12-21 | 上海大学 | Polyphosphazene-semi-aromatic amide material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "环三磷腈类阻燃剂的合成及应用研究进展";游歌云等;《应用化学》;20140930;第31卷(第9期);第993-1009页 * |
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Effective date of registration: 20201225 Address after: No.18, no.1513, hi tech Industrial Development Zone, Tian'an City, Guangdong Province Patentee after: GUANGDONG JUHANG INSTITUTE FOR ADVANCED MATERIALS Co.,Ltd. Patentee after: GUANGDONG GUNAKAI MATERIAL TECHNOLOGY Co.,Ltd. Address before: 511500 No.19, Tianan Zhigu Exhibition Center, No.18, Chuangxing Avenue, science and Technology Innovation Park, Qingyuan high tech Industrial Development Zone, Guangdong Province Patentee before: GUANGDONG JUHANG INSTITUTE FOR ADVANCED MATERIALS Co.,Ltd. Patentee before: GUANGDONG NANFANG ZHIQUAN PLASTIC TECHNOLOGY Co.,Ltd. |