CN117510835A - Bulk flame-retardant nylon polymer and preparation method thereof - Google Patents
Bulk flame-retardant nylon polymer and preparation method thereof Download PDFInfo
- Publication number
- CN117510835A CN117510835A CN202210909669.7A CN202210909669A CN117510835A CN 117510835 A CN117510835 A CN 117510835A CN 202210909669 A CN202210909669 A CN 202210909669A CN 117510835 A CN117510835 A CN 117510835A
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- Prior art keywords
- flame retardant
- nylon polymer
- diamine
- bulk
- retardant nylon
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 52
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229920001778 nylon Polymers 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title description 12
- 239000000178 monomer Substances 0.000 claims abstract description 35
- 150000004985 diamines Chemical class 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 20
- 125000003118 aryl group Chemical group 0.000 claims abstract description 18
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 8
- 150000002367 halogens Chemical class 0.000 claims abstract description 8
- 239000004952 Polyamide Substances 0.000 claims description 19
- 229920002647 polyamide Polymers 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- -1 aliphatic diamines Chemical class 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 238000010998 test method Methods 0.000 claims description 4
- 238000012662 bulk polymerization Methods 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 150000003504 terephthalic acids Chemical class 0.000 claims description 2
- 239000004677 Nylon Substances 0.000 abstract description 22
- 229920000642 polymer Polymers 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 6
- 239000011347 resin Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 description 13
- 238000002844 melting Methods 0.000 description 12
- 230000008018 melting Effects 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 150000003503 terephthalic acid derivatives Chemical class 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 229920003233 aromatic nylon Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- KZCBXHSWMMIEQU-UHFFFAOYSA-N Chlorthal Chemical compound OC(=O)C1=C(Cl)C(Cl)=C(C(O)=O)C(Cl)=C1Cl KZCBXHSWMMIEQU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000003097 mucus Anatomy 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
Abstract
The invention provides a nylon polymer with flame retardant body, wherein polymerization monomers comprise dibasic acid and diamine, the dibasic acid contains halogenated aromatic dibasic acid with molar ratio not less than 5%, and the diamine comprises at least two diamine monomers. The polymer is of a nylon structure containing halogen monomers, can realize flame retardance of a nylon resin body, has stable CTI, and can be used for high-voltage electrical equipment.
Description
Technical Field
The invention relates to the technical field of engineering plastics, in particular to a nylon polymer with flame retardant body.
Background
Nylon is the most widely used engineering plastic and has excellent mechanical strength, thermal stability and electrical property. However, the mass-produced nylon can not achieve flame retardance of the body except for the wholly aromatic aramid fiber, which is one of the defects that the nylon is limited in electrical application and the like, and the processing and difficulty of the wholly aromatic nylon are caused by the insoluble and infusible characteristics of the wholly aromatic nylon. The added flame retardant, whether the halogen flame retardant or the halogen-free phosphorus flame retardant, can seriously affect the performance of the material, so that the strength is reduced, the thermal stability is reduced and the ageing performance is reduced.
The existing common flame-retardant materials such as PPS, LCP and the like have better performance, but due to the molecular structure, the CTI of the flame-retardant materials is generally not high and is below 400V, so that the flame-retardant materials are limited to be applied to high-voltage electricity. The introduction of the monomer containing halogen can improve the flame retardant property of the nylon polymer and realize the flame retardance of the nylon body.
The literature "synthesis of polyamides and polyesters from halogenated terephthalic acid" ("foreign textile technology", 1981 (10): 10-13) uses halogenated terephthalic acid as the starting material for the synthesis of polyamides and polyesters, flame retardant polyamides and polyesters are obtained. The polyamide products produced in this document have a relatively high melting point, close to the decomposition temperature, and are difficult to melt process.
Patent 201410156622.3 discloses a preparation method of self-flame-retardant semi-aromatic polyamide with high sulfur content, which comprises the steps of stirring sulfide-containing semi-aromatic diamine, a catalyst and diformyl chloride for reaction, and pouring reaction mucus into water to obtain a crude polymer product; the polymer is washed, dried and crushed by water, purified by deionized water and acetone respectively, and dried for 12 hours at the temperature of 100 ℃ to obtain the high-sulfur self-flame-retardant semi-aromatic polyamide pure resin. The main raw material of the method is diamine monomer containing thioether, which is difficult to obtain and has high cost.
Disclosure of Invention
Aiming at the technical problems, the invention provides a nylon polymer with flame retardant body. The polymer is of a nylon structure containing halogen monomers, can realize flame retardance of a nylon resin body, has stable CTI, and can be used for high-voltage electrical equipment.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a bulk flame retardant nylon polymer, wherein the polymeric monomer comprises a diacid and a diamine, the diacid comprises a halogenated aromatic diacid in a molar ratio of not less than 5%, and the diamine comprises at least two diamine monomers.
The diamine is selected from aliphatic diamines containing 2-15 carbon atoms.
Because the nylon prepared by the aromatic dibasic acid has a higher melting point, at least two diamine monomers are adopted, so that the regularity of molecules is destroyed, the melting point of a polymeric material is reduced, and the product processing is more convenient. The diamine content with the highest proportion is controlled to be not more than 99 percent of the total mole number of diamine monomers.
The halogenated aromatic dibasic acid contains 1-6 halogen atoms. The monocyclic halogenated aromatic dibasic acid generally contains 1 to 4 halogen atoms, and the condensed ring halogenated aromatic dibasic acid may contain more halogen atoms, but is generally not more than 6 in the present invention.
Preferably, the halogenated aromatic diacid is selected from halogenated terephthalic acids.
Further preferably, the halogenated aromatic dibasic acid contains tetrachloroterephthalic acid.
Preferably, the halogen element is selected from at least one of chlorine and bromine. Chlorine and bromine are better in stability, fluorine can affect the stability of materials due to strong electronegativity of fluorine, and iodine is also widely different from chlorine and bromine in stability.
Under the condition that no flame retardant is added, the flame retardant grade of the nylon polymer reaches V0 and above according to the UL94 flame retardant test method, and CTI is more than or equal to 500V.
The nylon polymer is prepared by a melt bulk polymerization process. This is due to the poor water solubility of halogenated dibasic acids, which is achieved by the present invention using a melt bulk polymerization process.
The preparation method of the nylon polymer comprises the following steps: the method comprises the steps of firstly, melting and dispersing the dibasic acid and the polyamide in a continuous mixing and conveying device to form a continuously conveyed melt, then adding diamine into the conveying device, uniformly mixing, and then, entering a polymerization device, and polymerizing in the polymerization device to reach the required molecular weight.
The polyamide is added into the raw materials as a reactive dispersion medium to carry out melt polymerization reaction with the dibasic acid or ester and diamine monomers in the screw extrusion equipment, the raw materials continuously enter the screw extrusion equipment, and the polymerization reaction is completed in the flowing process of material transmission, so that the continuity of feeding, reaction and discharging is realized. The polyamide raw material can have the same structure as the nylon monomer, so that a homopolymer product is obtained, and if the polyamide raw material and the nylon monomer have different structures, a copolymer product is obtained, and the proportion of the polyamide raw material can be adjusted according to the requirement.
Preferably, the polyamide has the same composition as the monomer feed in the reaction, and is more compatible with nylon products.
In addition to the halogenated aromatic diacid, the nylon monomer of the present invention may also include an aliphatic diacid, allowing for a wider range of tuning of the properties of the nylon polymer. And the halogenated dibasic acid production process can generate different halogenated amounts without special purification of the monomer. Therefore, the nylon monomer diacid can comprise more than two types of diacid, so that the adjustment of the material performance in a wider range is realized, the difficulty of raw material purification can be reduced, and the proper raw materials can be conveniently obtained.
The nylon polymer can be used as a flame retardant, added into other polymers, especially nylon, and used as the flame retardant to improve the flame retardant property of the whole material system. Because the invention can select wide sources of the monomers, the polymer performance can be adjusted in a wide range, and the compatibility with other polymers is realized. The high molecular flame retardant has small influence on physical properties, is difficult to migrate and separate out, and is an excellent external flame retardant.
The invention has the beneficial effects that:
1. the invention selects the halogenated aromatic dibasic acid as the halogen monomer, and the halogen atom is directly connected on the aromatic ring, thereby ensuring the stability of the material. At least two diamine monomers are adopted, so that the regularity of molecules is destroyed, the melting point of a material product is reduced, and the processing is more convenient. According to the UL94 flame-retardant test method, the flame retardant rating reaches V0 or above, and the CTI of the resin is stable to or exceeds 500V, which is far higher than the CTI performance of the prior commonly used bulk flame-retardant resin PPS, LCP and the like, and the resin can be used for high-voltage electrical equipment.
2. The nylon with high halogen content can be used as a flame retardant to improve the overall flame retardant level, and is a high-molecular flame retardant, so that the nylon has small influence on physical properties of materials, does not migrate, has a similar structure with nylon, and has particularly excellent compatibility.
3. The polyamide which is the same as the monomer raw material is used as a dispersion medium for the melting reaction instead of water, so that the problem that the aromatic dibasic acid is difficult to react is solved, the polyamide can be continuously produced in a rod extrusion device, and the mass production of the nylon flame retardant is realized.
Detailed Description
The invention will be further described by the following examples for the purpose of more clearly and specifically describing the object of the invention. The following examples are only for specific illustration of the implementation method of the present invention and do not limit the protection scope of the present invention.
A bulk flame retardant nylon polymer, wherein the polymerization monomers comprise dibasic acid and diamine, the dibasic acid contains halogenated aromatic dibasic acid with a molar ratio of not less than 5%, and the diamine comprises at least two diamine monomers;
the diamine is selected from aliphatic diamines containing 2 to 15 carbon atoms.
The diamine content with the highest proportion is controlled to be not more than 99 percent of the total mole number of diamine monomers.
The halogenated aromatic diacid is selected from halogenated terephthalic acid.
The halogenated aromatic dibasic acid contains 1-6 halogen atoms.
The preparation method of the nylon polymer comprises the following steps: the method comprises the steps of firstly, melting and dispersing the dibasic acid and the polyamide in a continuous mixing and conveying device to form a continuously conveyed melt, then adding diamine into the conveying device, uniformly mixing, and then, entering a polymerization device, and polymerizing in the polymerization device to reach the required molecular weight.
Example 1
The polyamide and the monomer diacid which are the same as the monomer raw materials are mixed according to the weight ratio of 1:5, continuously adding the mixture into a double-screw extruder through a weightless scale, continuously adding diamine according to the molar ratio of total diamine to diacid of 1.01:1 after uniformly melting and mixing, and then feeding the mixture into a subsequent continuous polymerization device, and performing devolatilization granulation through the double-screw extruder to obtain the flame-retardant nylon product. The residence time of the material in the polymerization apparatus was about 30 minutes.
Example 2
The preparation method is the same as in example 1.
Example 3
The preparation method is the same as in example 1, and the weight ratio of polyamide to monomer diacid is 1:6.
example 4
The preparation method is the same as in example 1, and the weight ratio of polyamide to monomer diacid is 1:6.
example 5
The preparation method is the same as in example 1.
Example 6
The preparation method is the same as in example 1.
Example 7
The preparation method is the same as in example 1, and the weight ratio of polyamide to monomer diacid is 1:7.
example 8
The preparation method is the same as in example 1.
The specific raw material and product properties of examples 1-8 are shown in the following table, and the flame retardant rating of the above products was tested according to the UL94 flame retardant test method:
as can be seen from the table, the CTI value of the flame-retardant nylon product reaches 600, which is far higher than that of flame-retardant plastics PPS and LCP in the market, and the flame-retardant nylon product can be used for high-voltage electrical equipment. The monomer raw materials of the embodiment 3 and the embodiment 5 only contain one diamine monomer, the melting point of the prepared product is close to the decomposition temperature, the product is difficult to process, the flame retardant index after melting cannot be measured, and the embodiment 4 and the embodiment 6 destroy the regularity of molecules, the flame retardant performance is unchanged, the melting point of the product is reduced, the product can be processed in a melting way under the same reaction condition, and the practicability is improved.
The foregoing examples merely illustrate specific embodiments of the invention, which are described in greater detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention.
Claims (10)
1. A bulk flame retardant nylon polymer, wherein the polymeric monomer comprises a diacid and a diamine, the diacid comprises a halogenated aromatic diacid in a molar ratio of not less than 5%, and the diamine comprises at least two diamine monomers.
2. The bulk flame retardant nylon polymer of claim 1, wherein the halogenated aromatic diacid contains 1 to 6 halogen atoms.
3. The bulk flame retardant nylon polymer of claim 2, wherein said halogenated aromatic diacid is selected from the group consisting of halogenated terephthalic acids.
4. The bulk flame retardant nylon polymer of claim 2, wherein the halogen element is selected from at least one of chlorine and bromine.
5. The bulk flame retardant nylon polymer of claim 1, wherein the diamine is selected from aliphatic diamines containing 2 to 15 carbon atoms.
6. The bulk flame retardant nylon polymer of claim 1, wherein the highest diamine content is no more than 99% of the total moles of diamine monomer.
7. The bulk flame retardant nylon polymer of claim 1, wherein the nylon polymer has a flame retardant rating of V0 and above, and a CTI greater than or equal to 500V according to UL94 flame retardant test method without the addition of flame retardant.
8. The bulk flame retardant nylon polymer of claim 1, wherein the nylon polymer is prepared by a melt bulk polymerization process.
9. The method for preparing the nylon polymer with flame retardation according to claim 1, wherein the dibasic acid and the polyamide are melted and dispersed in a continuous mixing and conveying device to form a continuous conveying melt, diamine is added into the conveying device, and the mixture is uniformly mixed and enters a polymerization device, and the polymerization device is used for polymerizing the mixture to reach the required molecular weight.
10. The method of preparing a bulk flame retardant nylon polymer of claim 9, wherein the polyamide has the same composition as the monomer feed in the reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210909669.7A CN117510835A (en) | 2022-07-29 | 2022-07-29 | Bulk flame-retardant nylon polymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210909669.7A CN117510835A (en) | 2022-07-29 | 2022-07-29 | Bulk flame-retardant nylon polymer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117510835A true CN117510835A (en) | 2024-02-06 |
Family
ID=89740634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210909669.7A Pending CN117510835A (en) | 2022-07-29 | 2022-07-29 | Bulk flame-retardant nylon polymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117510835A (en) |
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2022
- 2022-07-29 CN CN202210909669.7A patent/CN117510835A/en active Pending
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