CN113354867A - Flame-retardant thermoplastic polyamide, flame retardant and application - Google Patents
Flame-retardant thermoplastic polyamide, flame retardant and application Download PDFInfo
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- CN113354867A CN113354867A CN202010150587.XA CN202010150587A CN113354867A CN 113354867 A CN113354867 A CN 113354867A CN 202010150587 A CN202010150587 A CN 202010150587A CN 113354867 A CN113354867 A CN 113354867A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/5205—Salts of P-acids with N-bases
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/50—Phosphorus bound to carbon only
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention discloses a composition, preparation and application of a novel flame-retardant polyamide polymer (flame-retardant nylon). Specifically, the disclosed flame retardant polyamide polymers include thermoplastic polyamides and novel flame retardants. The novel flame retardant comprises an ionic liquid component, wherein the ionic liquid can be a single ionic liquid component, can also be shared by several ionic liquids, and can also be used by mixing the ionic liquid with the traditional flame retardant. The flame retardant may be added in the polymerization stage of the polyamide or may be added by mixing in an extruder in the modification stage of the polymer. The flame-retardant polyamide polymer disclosed by the invention can be used in the fields of plastics, fibers and the like.
Description
Technical Field
The present invention relates to a novel flame retardant polyamide polymer. Specifically, the invention discloses a thermoplastic polyamide composition containing a novel flame retardant with an ionic liquid structure, and preparation and application thereof, belonging to the technical field of high molecular polymers and flame retardants.
Background
The Polyamide (PA) is a polymer having a polar amide group (-CO-NH-) in the main chain. The fiber can be used as a raw material for manufacturing fibers, can also be used as engineering plastics to be widely applied to industrial production and living products, and has the characteristics of toughness, wear resistance, self lubrication and wide use temperature range.
The polyamide materials are widely classified into aliphatic polyamides, semi-aromatic polyamides, wholly aromatic polyamides, and copolyamides. The aliphatic polyamide accounts for more than 90% of the market amount, although the price is relatively low, the aliphatic polyamide can be continuously combusted in the air due to the oxygen index of 23-25, and the application of the aliphatic polyamide is limited.
At present, common traditional flame retardants for polyamides comprise melamine salts (such as melamine cyanurate), organic phosphonates, aluminum tris (diethylphosphinate), ammonium polyphosphate, metal oxides and hydroxides, inorganic fillers and the like, and the single or composite addition amount of the flame retardants is generally 20-35%. The addition amount of the flame retardant is high, so that the processing performance of the polyamide is reduced, the dispersion difficulty is improved, and the physical and mechanical properties of the polyamide are reduced, so that the application of the flame-retardant polyamide is influenced. Aluminum tris (diethylphosphinate) products (commercial OP series flame retardants) developed by the Corey company have been used widely in polyamide polymers for flame retardancy over the past few years, but OP series products are highly corrosive to plastic processing equipment.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a novel flame retardant based on an ionic liquid structure, which can be used for flame retardance of thermoplastic polyamide and can overcome the defects of the traditional flame retardant.
The technical scheme is as follows: a novel polyamide composition is prepared from ionic liquid flame retardant through extruding out, mixing, and injection moulding.
Further, the ionic liquid flame retardant is composed of an organic cation and an inorganic or organic anion.
Further, the cation includes quaternary ammonium salt ion, quaternary phosphonium salt ion, imidazolium salt ion and pyrrole salt ion.
Further, the anion includes halogen ion, hydroxyl, mercapto, cyanide inorganic ion, acetate ion, trifluoroacetate ion, dicyanamide ion, sulfonate ion, tetrafluoroborate ion, hexafluorophosphate ion, phosphate anion, sulfonate anion, bis (trifluoromethylsulfonyl) imide ion, and the like.
Further, the ionic liquid flame retardant is tributyl methyl dibutyl ammonium phosphate.
Further, the ionic liquid flame retardant is a 1-ethyl-3-methylimidazole diethyl phosphate compound.
The specific advantages of the invention are as follows:
(1) the ionic liquid flame retardant of the invention can not volatilize and mainly stays in a solid phase during combustion to play a role in flame retardance. Conventional phosphates are semi-volatile compounds that volatilize to the gas phase upon combustion. Although studies have revealed that phosphates may also have a flame-retarding effect in the gas phase, the effect is not significant. Therefore, the ionic liquid flame retardant has better flame retardant effect than the traditional phosphate ester flame retardant.
(2) The "designability" of the structure of the ionic liquid in the present invention provides a flame retardant design that provides optimal compatibility for different plastic products. The excellent compatibility enables the flame retardant to be uniformly dispersed and even dissolved in the plastic, thereby having minimal impact on the physical and mechanical properties of the plastic.
(3) In the invention, different molecular forces are introduced between the flame retardant and the plastic polymer chain due to the special structure of ions, so that the plasticizing side effect of the flame retardant is weakened, and the glass transition temperature or the thermal deformation temperature of the plastic is not reduced or is not reduced a lot.
(4) The ionic liquid has good solubility to organic matters, inorganic matters and high polymer materials, so that the ionic liquid flame retardant can be compounded with the traditional flame retardant for use, the compatibility and the dispersibility of the traditional flame retardant in plastics can be improved, and the influence on the physical and mechanical properties of the plastics is reduced.
(5) The ionic liquid flame retardant is simple to use and can be used for general polyamide processing and modifying equipment.
In particular, the use of ionic liquid flame retardants in thermoplastic polyamides has the advantage that: the addition amount is low; the influence on the physical properties of the plastic is small; has little effect on thermal stability.
Drawings
FIG. 1 is a schematic view of the structure of cations in the flame retardant of the present invention; FIG. 2 is a schematic view of the structure of anions in the flame retardant of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below so that those skilled in the art can better understand the advantages and features of the present invention, and thus the scope of the present invention will be more clearly defined. The described embodiments of the present invention are only a part of the present invention, and not all embodiments, and all other embodiments obtained by those skilled in the art without any inventive work based on the embodiments of the present invention belong to the protection scope of the present invention.
EXAMPLE 1 tributyl methyl dibutylphosphonium salt
3% tributyl methyl dibutylphosphonium phosphate and nylon 6 pellets were melt blended with an extruder at 265 ℃. Then, a sample strip is prepared by an injection molding machine, and the flame retardant property is tested.
EXAMPLE 2.1-Ethyl-3-methylimidazolium diethyl phosphate
The processing and testing processes of embodiment 2 are similar to those of embodiment 1 and will not be repeated. Wherein the compound is 1-ethyl-3-methylimidazole diethyl phosphate compound.
Example 3 was carried out.
The processing test process of embodiment 3 is similar to that of embodiment 1.
Example 4 was carried out.
The processing test process of embodiment 4 is similar to that of embodiment 1.
Example 5 was carried out.
The flame retardant of embodiment 5 is a flame retardant (tributyl methyl dibutyl ammonium phosphate) in embodiment 1 and MPP (ammonium polyphosphate) compounded according to a certain ratio, and the processing and testing processes are similar to those of embodiment 1.
Example 6 was carried out.
The flame retardant of embodiment 6 is the flame retardant of embodiment 2 (1-ethyl-3-methylimidazolium diethylphosphate) compounded with the Crainen OP series products according to a certain proportion, and the processing and testing processes are similar to those of embodiment 1.
Results of Performance testing
Take BASF nylon 6 (BASF Ultramid B3S) or nylon 66 (A3W) as examples:
flame retardancy (as measured by UL-94 standard): the B3S pure resin sample is easy to be ignited, releases dense smoke during burning, is accompanied by serious dripping phenomenon, and is easy to cause fire accidents.
And (3) testing results:
Claims (8)
1. a novel flame retardant polyamide polymer comprising an ionic liquid flame retardant.
2. The composition of claim 1, wherein the ionic liquid flame retardant is of the formula: a. the+B-Wherein the structure of the cation may be one of the following structures:
wherein R is（0-5）Can be selected from the following groups: hydrogen, C (1-20) alkyl, aryl, C (3-10) heterocycle, C (3-10) cycloalkyl, (C3-ClO) heterocycle (C1-C8) alkyl, aryl (Cl-C8) alkyl, heterocyclic aryl, and heterocyclic aryl (Cl-C8) alkyl, which may have no substituent or the following substituents: one or two halogens, nitro, trifluoromethyl, trifluoromethoxy, methoxy, carboxyl, -NH2， -OH，-SH，-NHCH3，-N(CH3)2Cyano radicals, -SO3H，-P(O)(OC(1-5))2 (ii) a Wherein the anionic structure may be one of the following structures:
wherein R is selected from the group consisting of: hydrogen, C (1-20) alkyl, aryl, C (3-10) heterocycle, C (3-10) cycloalkyl, (C3-ClO) heterocycle (C1-C8) alkyl, aryl (Cl-C8) alkyl, heterocyclic aryl, and heterocyclic aryl (Cl-C8) alkyl, which may have no substituent(s) or the following substituent(s): one or two halogens, nitro, trifluoromethyl, trifluoromethoxy, methoxy, carboxyl, -NH2，-OH，-SH，-NHCH3，-N(CH3)2Cyano radicals, -SO3H， -P(O)(OC(1-5))2。
3. The flame retardant of claim 1, which may be a single ionic liquid, a mixture of several ionic liquids, or a mixture of conventional flame retardants, comprising: inorganic flame retardants, halogen-based flame retardants, phosphorus and phosphine-based flame retardants, nitrogen-based flame retardants, and the like.
4. The flame retardant of claims 1 to 3 can be used in combination with other polyamide auxiliaries to improve the processability and mechanical properties of the compositions, including modifiers, stabilizers, antioxidants, mold release agents, nucleating agents, coloring dyes and other organic and inorganic fillers.
5. The flame retardant of claim 1, added in an amount of from 0.1% to 40%, more reasonable in the interval of from 0.2% to 30%, more reasonable in the interval of from 0.5% to 20%, more reasonable in the interval of from 1% to 15%.
6. The flame retardant polyamide composition of claim 1, which is useful in the fields of plastics and fibers.
7. The use of ionic liquids as flame retardants in thermoplastic polyamides.
8. The flame retardant of claim 7 comprising an ionic liquid component of the formula: a + B-, wherein the structure of the cation may be one of the following structures,
wherein R is(0-5)Can be selected from the following groups: hydrogen, C (1-20) alkyl, aryl, C (3-10) heterocycle, C (3-10) cycloalkyl, (C3-ClO) heterocycle (C1-C8) alkyl, aryl (Cl-C8) alkyl, heterocyclic aryl, and heterocyclic aryl (Cl-C8) alkyl, which may have no substituent(s) or the following substituent(s): one or two halogens, nitro, trifluoromethyl, methoxy, carboxyl, -NH2, -OH, -SH, -NHCH3，-N(CH3)2Cyano radicals, -SO3H，-P(O)(OC(1-5))2，
The structure of the anion can be selected from the following structures,
wherein R is selected from the group consisting of: hydrogen, C (1-20) alkyl, aryl, C (3-10) heterocycle, C (3-10) cycloalkyl,(C3-ClO) heterocyclic (C1-C8) alkyl, aryl (Cl-C8) alkyl, heterocyclic aryl and heterocyclic aryl (Cl-C8) alkyl, which may have no substituents or the following substituents: one or two halogens, nitro, trifluoromethyl, trifluoromethoxy, methoxy, carboxyl, -NH2，-OH，-SH，-NHCH3，-N(CH3)2Cyano radicals, -SO3H，-P(O)(OC(1-5))2。
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| CN202010150587.XA CN113354867A (en) | 2020-03-06 | 2020-03-06 | Flame-retardant thermoplastic polyamide, flame retardant and application |
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| CN202010150587.XA CN113354867A (en) | 2020-03-06 | 2020-03-06 | Flame-retardant thermoplastic polyamide, flame retardant and application |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113881178A (en) * | 2021-09-28 | 2022-01-04 | 江苏金发科技新材料有限公司 | Weather-resistant flame-retardant polymethyl methacrylate composite material and preparation method and application thereof |
| CN114213845A (en) * | 2021-12-10 | 2022-03-22 | 中化学科学技术研究有限公司 | Spinnable polyamide and preparation method and product thereof |
| CN115044100A (en) * | 2022-07-20 | 2022-09-13 | 广东粤港澳大湾区黄埔材料研究院 | Ionic liquid flame retardant, preparation method thereof and polyamide material |
| CN115536909A (en) * | 2022-06-17 | 2022-12-30 | 上海力道新材料科技股份有限公司 | Halogen-free flame retardant composition, and preparation method and application thereof |
-
2020
- 2020-03-06 CN CN202010150587.XA patent/CN113354867A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113881178A (en) * | 2021-09-28 | 2022-01-04 | 江苏金发科技新材料有限公司 | Weather-resistant flame-retardant polymethyl methacrylate composite material and preparation method and application thereof |
| CN114213845A (en) * | 2021-12-10 | 2022-03-22 | 中化学科学技术研究有限公司 | Spinnable polyamide and preparation method and product thereof |
| CN115536909A (en) * | 2022-06-17 | 2022-12-30 | 上海力道新材料科技股份有限公司 | Halogen-free flame retardant composition, and preparation method and application thereof |
| CN115536909B (en) * | 2022-06-17 | 2023-11-17 | 上海力道新材料科技股份有限公司 | Halogen-free flame retardant composition and preparation method and application thereof |
| CN115044100A (en) * | 2022-07-20 | 2022-09-13 | 广东粤港澳大湾区黄埔材料研究院 | Ionic liquid flame retardant, preparation method thereof and polyamide material |
| CN115044100B (en) * | 2022-07-20 | 2023-05-02 | 广东粤港澳大湾区黄埔材料研究院 | Ionic liquid flame retardant, preparation method thereof and polyamide material |
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