CN114196196B - Flame-retardant polyamide resin composition - Google Patents
Flame-retardant polyamide resin composition Download PDFInfo
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- CN114196196B CN114196196B CN202111616670.2A CN202111616670A CN114196196B CN 114196196 B CN114196196 B CN 114196196B CN 202111616670 A CN202111616670 A CN 202111616670A CN 114196196 B CN114196196 B CN 114196196B
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- antimony trioxide
- polyamide resin
- resin composition
- brominated
- flame retardant
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 38
- 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 37
- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 23
- 239000011342 resin composition Substances 0.000 title claims abstract description 13
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 11
- 239000000314 lubricant Substances 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- OCKWAZCWKSMKNC-UHFFFAOYSA-N [3-octadecanoyloxy-2,2-bis(octadecanoyloxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(COC(=O)CCCCCCCCCCCCCCCCC)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC OCKWAZCWKSMKNC-UHFFFAOYSA-N 0.000 claims description 8
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 6
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 4
- -1 polyethylene Polymers 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 14
- 239000002904 solvent Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 238000002485 combustion reaction Methods 0.000 description 8
- 239000004952 Polyamide Substances 0.000 description 7
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 7
- 229920002647 polyamide Polymers 0.000 description 7
- JVPKLOPETWVKQD-UHFFFAOYSA-N 1,2,2-tribromoethenylbenzene Chemical compound BrC(Br)=C(Br)C1=CC=CC=C1 JVPKLOPETWVKQD-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000004342 Benzoyl peroxide Substances 0.000 description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- XRXMNWGCKISMOH-UHFFFAOYSA-N 2-bromobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1Br XRXMNWGCKISMOH-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- LSCYTCMNCWMCQE-UHFFFAOYSA-N n-methylpyridin-4-amine Chemical compound CNC1=CC=NC=C1 LSCYTCMNCWMCQE-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- HQLOEBRPCVIFCT-UHFFFAOYSA-N 2,6-dibromobenzoic acid Chemical compound OC(=O)C1=C(Br)C=CC=C1Br HQLOEBRPCVIFCT-UHFFFAOYSA-N 0.000 description 1
- VOIZNVUXCQLQHS-UHFFFAOYSA-N 3-bromobenzoic acid Chemical compound OC(=O)C1=CC=CC(Br)=C1 VOIZNVUXCQLQHS-UHFFFAOYSA-N 0.000 description 1
- TUXYZHVUPGXXQG-UHFFFAOYSA-N 4-bromobenzoic acid Chemical compound OC(=O)C1=CC=C(Br)C=C1 TUXYZHVUPGXXQG-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000001462 antimony Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
Abstract
The invention discloses a flame-retardant polyamide resin composition, which comprises the following components in parts by weight: 75-90 parts of polyamide resin, 5-10 parts of antimony trioxide master batch, 5-15 parts of brominated macromolecular polymer strong flame retardant, 0.1-0.5 part of antioxidant and 0.1-0.5 part of lubricant. The invention self-prepares the brominated macromolecular polymer flame retardant, and matches with the antimonous oxide master batch, thereby improving the compatibility of the flame retardant and the polyamide resin and further improving the flame retardance of the polyamide resin.
Description
Technical Field
The invention relates to the field of polyamide resin, in particular to a flame-retardant polyamide resin composition containing brominated macromolecules and an antimony trioxide composite flame retardant.
Background
Polyamide (PA, commonly known as nylon) was the first resin developed for fibers by DuPont in the united states and was commercialized in 1939. Injection molded products are developed and produced in the 50 s of the 20 th century to replace metals to meet the requirements of light weight and cost reduction of downstream industrial products. The polyamide contains many repeated amide groups on the main chain, and the polyamide can be prepared from diamine and diacid, and can also be synthesized by omega-amino acid or cyclic lactam. According to the difference of carbon atom number contained in diamine and dibasic acid or amino acid, several different polyamides can be prepared, and the number of polyamide varieties is up to tens.
The polyamide has good comprehensive properties including mechanical properties, heat resistance, abrasion resistance, chemical resistance and self-lubricating property, low friction coefficient and certain flame retardance. However, the above-mentioned flame retardancy does not meet the current demand, and thus an additional flame retardant is required to obtain a good effect.
The main stream flame retardant in the current research field is bromoalkane or antimony series. However, small molecule bromides tend to phase separate from the bulk during the molding process and greatly limit the overall flame retardant properties of the polyamide.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a flame-retardant polyamide resin composition containing brominated macromolecules and an antimony trioxide composite flame retardant, which solves the problem that the flame retardant and the polyamide resin are subjected to integral phase separation in the molding process, and further improves the flame retardant property of the polyamide resin.
The invention provides the following technical scheme:
the flame-retardant polyamide resin composition comprises the following components in parts by weight:
75-90 parts of polyamide resin, 5-10 parts of antimony trioxide master batch, 5-15 parts of brominated macromolecular polymer strong flame retardant, 0.1-0.5 part of antioxidant and 0.1-0.5 part of lubricant.
As a preferable embodiment of the present invention, the polyamide resin is at least one of PA6, PA66 or PA6/PA66 copolymer.
As a preferable technical scheme of the invention, the antimony trioxide master batch comprises base resin and antimony trioxide particles.
As a preferable technical scheme of the invention, the base resin in the antimony trioxide master batch is at least one of PA6, PA66 or PA6/PA66 copolymer.
As a preferable technical scheme of the invention, the particle size of the antimony trioxide particles in the antimony trioxide master batch is 0.1-0.3 mu m, and the mass of the antimony trioxide particles accounts for 80-90% of the total mass of the antimony trioxide master batch.
As a preferable technical scheme of the invention, the brominated macromolecular polymer flame retardant has the following structure:
wherein n is 0, 1, 2 or 3.
As a preferred embodiment of the present invention, a: (a+b+c) =0.65-0.9.
As a preferred embodiment of the present invention, b: c= (1-4): 1
As a preferable technical scheme of the invention, the antioxidant is at least one of an antioxidant 1098 and an antioxidant 1171.
As a preferable technical scheme of the invention, the lubricant is at least one of pentaerythritol tetrastearate, ethylene bis-stearamide, modified ethylene bis-stearamide and polyethylene wax.
As a preferable technical scheme, the synthetic method of the brominated macromolecular polymer is as follows:
(1) And dissolving the tribromostyrene and the glycidyl methacrylate in ethyl acetate to obtain a pre-prepared solution 1, wherein the total mass fraction of the tribromostyrene and the glycidyl methacrylate in the pre-prepared solution 1 is 45-55%.
(2) And (2) pre-dissolving benzoyl peroxide accounting for 0.5-2% of the total mass fraction of the tribromostyrene and the glycidyl methacrylate in the step (1) by using ethyl acetate to obtain a pre-prepared solution 2, wherein the mass fraction of the benzoyl peroxide in the pre-prepared solution 2 is 30-40%.
(3) Dripping the prepared solution 1 into the prepared solution 2 at 65-85deg.C, maintaining the temperature and aging for 2-4 hr, and observing 1640cm by infrared -1 And judging the progress of the reaction by the infrared peak until the infrared peak completely disappears, and judging the end of the reaction.
(4) And adding bromobenzoic acid into the system, continuously reacting at 75-95 ℃, judging the reaction progress according to the titration acid value and the epoxy value until the acid value is less than 0.5mgKOH/g, and treating the reaction to be complete.
(5) Removing most of the solvent by reduced pressure distillation, crushing the solid obtained after concentration into powder, and then placing the powder in a vacuum oven at 60-80 ℃ for drying to remove the residual solvent until the content of the GC test solvent is less than 1%.
As a further scheme of the high-flame-retardance polyamide resin, the antioxidant is one or more of an antioxidant 1098 and an antioxidant 1171.
As a further scheme of the high flame retardant polyamide resin, the lubricant is pentaerythritol tetrastearate.
The technical scheme provided by the invention has the beneficial effects that:
according to the invention, the antimony trioxide is prepared into the master batch containing the components similar to the matrix resin, and the master batch is added into the polyamide resin, so that the dispersibility of antimony trioxide particles in the polyamide resin can be effectively improved.
The self-made brominated macromolecular polymer flame retardant uses brominated styrene monomers and glycidyl methacrylate monomers for copolymerization, and then uses bromobenzoic acid to react to remove part of epoxy groups, so as to retain part of epoxy groups. On one hand, the epoxy groups react with trace amounts of primary amino groups, secondary amino groups and amide groups remained in the polyamide resin under high-temperature molding, so that the self-made brominated macromolecular polymer flame retardant can be grafted in the polyamide resin through chemical grafting, and on the other hand, hydroxyl generated after the reaction of carboxylic acid and the epoxy groups can further increase the hydrogen bonding effect with the matrix resin, so that the compatibility among the macromolecular flame retardant, antimony trioxide and the matrix resin is improved.
In addition, the invention can play a better role in flame retardance through the interaction of the two flame retardants of the antimony trioxide master batch with high antimony trioxide content and the self-made brominated macromolecular polymer flame retardant.
Drawings
FIG. 1 is a final GPC chart of Synthesis example 1
FIG. 2 is a final GPC chart of Synthesis example 2
FIG. 3 is a final GPC chart of Synthesis example 3
Detailed description of the preferred embodiments
The invention will be further described by means of specific examples.
In the following specific examples, the operations involved were performed under conventional conditions or conditions recommended by the manufacturer, without specifying the conditions.
Synthesis example 1
686g of tribromostyrene and 14.2g of glycidyl methacrylate were dissolved in 700g of ethyl acetate to obtain a solution to be pre-prepared 1, and 7g of benzoyl peroxide was also dissolved in 100g of ethyl acetate to obtain a pre-prepared solution 2.
Dripping the prepared solution 1 into the prepared solution 2 at 70deg.C, maintaining the temperature and aging for 3 hr, and observing 1640cm by infrared -1 At this point, the reaction was deemed to be completed until the infrared peak completely disappeared.
10.06g of 3-bromobenzoic acid is added into the system, 0.2g of triphenylphosphine is added as a catalyst, the reaction is continued at 70 ℃, the reaction progress is judged according to the titration acid value until the acid value is less than 0.5mgKOH/g, and the reaction is considered complete.
Most of the solvent was removed by rotary evaporation, then the solid was crushed into powder and placed in a vacuum oven at 80 ℃ and dried for 24 hours to remove the remaining solvent until the GC test solvent content was < 1%. Thus obtaining the brominated macromolecular polymer flame retardant 1.
Synthesis example 2
343g of tribromostyrene and 85.2g of glycidyl methacrylate were dissolved in 400g of ethyl acetate to obtain a pre-prepared liquid 1, and 5g of benzoyl peroxide was also dissolved in 100g of ethyl acetate to obtain a pre-prepared liquid 2.
Dripping the prepared solution 1 into the prepared solution 2 at 70deg.C, maintaining the temperature and aging for 3 hr, and observing 1640cm by infrared -1 At this point, the reaction was deemed to be completed until the infrared peak completely disappeared.
55.98g of 2, 6-dibromobenzoic acid is added into the system, 1g of 4-methylaminopyridine is added as a catalyst, the reaction is continued at 70 ℃, the reaction progress is judged according to the titration acid value until the acid value is less than 0.5mgKOH/g, and the reaction is considered complete.
Most of the solvent was removed by rotary evaporation, then the solid was crushed into powder and placed in a vacuum oven at 80 ℃ and dried for 24 hours to remove the remaining solvent until the GC test solvent content was < 1%. Thus obtaining the brominated macromolecular polymer flame retardant 2.
Synthesis example 3
343g of tribromostyrene and 47.3g of glycidyl methacrylate were dissolved in 700g of ethyl acetate to obtain a pre-prepared liquid 1, and 5g of benzoyl peroxide was also dissolved in 100g of ethyl acetate to obtain a pre-prepared liquid 2.
Dripping the prepared solution 1 into the prepared solution 2 at 70deg.C, maintaining the temperature and aging for 3 hr, and observing 1640cm by infrared -1 At this point, the reaction was deemed to be completed until the infrared peak completely disappeared.
26.95g of 4-bromobenzoic acid is added into the system, 1g of 4-methylaminopyridine is added as a catalyst, the reaction is continued at 70 ℃, and the reaction progress is judged according to the titration acid value until the acid value is <
The reaction was considered complete after 0.5 mgKOH/g.
Most of the solvent was removed by rotary evaporation, then the solid was crushed into powder and placed in a vacuum oven at 80 ℃ and dried for 24 hours to remove the remaining solvent until the GC test solvent content was < 1%. Thus obtaining the brominated macromolecular polymer flame retardant 3.
Example 1
820g of PA6 base material, 70g of antimony trioxide master batch (the particle size of the antimony trioxide is 0.1um, the mass fraction is 80 percent, PA6 resin base material), 100g of brominated macromolecular flame retardant 1, 5g of antioxidant 1098 and 5g of lubricant pentaerythritol tetrastearate are uniformly mixed by a high-speed mixer, and then extruded and molded at 260 ℃ by a double-screw extruder.
Example 2
840g of PA66 base material, 100g of antimony trioxide master batch (the particle size of the antimony trioxide is 0.3um, the mass fraction is 85 percent, PA66 resin base material), 50g of brominated macromolecular flame retardant 2, 5g of antioxidant 1171 and 5g of lubricant pentaerythritol tetrastearate are uniformly mixed by a high-speed mixer, and then extruded and molded at 260 ℃ by a double-screw extruder.
Example 3
840g of PA66 base material, 50g of antimony trioxide master batch (the particle size of the antimony trioxide is 0.3um, the mass fraction is 85 percent, PA66 resin base material), 100g of brominated macromolecular flame retardant 2, 5g of antioxidant 1098 and 5g of lubricant pentaerythritol tetrastearate are uniformly mixed by a high-speed mixer, and then extruded and molded at 260 ℃ by a double-screw extruder.
Example 4
870g of PA6 base material, 50g of antimony trioxide master batch (the particle size of the antimony trioxide is 0.3um, the mass fraction is 85 percent, the PA66 resin base material), 70g of brominated macromolecular flame retardant 3, 5g of antioxidant 1098 and 5g of lubricant pentaerythritol tetrastearate are uniformly mixed by a high-speed mixer, and then extruded and molded at 260 ℃ by a double-screw extruder.
Example 5
840g of PA66 base material, 100g of antimony trioxide master batch (the particle size of the antimony trioxide is 0.1um, the mass fraction is 85 percent, PA66 resin base material), 50g of brominated macromolecular flame retardant 2, 5g of antioxidant 1171 and 5g of lubricant pentaerythritol tetrastearate are uniformly mixed by a high-speed mixer, and then extruded and molded at 260 ℃ by a double-screw extruder.
Comparative example 1
Brominated macromolecular flame retardant 1 in the formulation of example 1 was replaced with brominated polystyrene.
Comparative example 2
Antimony trioxide master batches were not added to the formulation of example 1.
Comparative example 3
The antimony trioxide master batch in the formulation of example 1 was replaced with an equivalent amount of antimony trioxide particles as in the master batch.
To illustrate the technical effect of the present invention, the limiting oxygen index and the flame retardant effect of each example were tested, wherein the limiting oxygen index was tested as GB/T2406 and the flame retardant effect was tested as UL-94.
Preparing a spline: the respective examples were prepared as follows: a spline 127mm long, 12.7mm wide and 12.7mm high.
| Limiting oxygen index LOI/% | Flame retardancy | |
| Example 1 | 36.3 | V-0, no combustion products drip |
| Example 2 | 35.7 | V-0, no combustion products drip |
| Example 3 | 36.9 | V-0, no combustion products drip |
| Example 4 | 35.3 | V-0, no combustion products drip |
| Example 5 | 37.9 | V-0, no combustion products drip |
| Comparative example 1 | 29.1 | V-1, no combustion products drip |
| Comparative example 2 | 26.8 | V-2, with combustion products dripping |
| Comparative example3 | 32.5 | V-1, no combustion products drip |
The foregoing embodiment numbers of the present invention are merely for the purpose of description, and do not represent the advantages or disadvantages of the embodiments.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (7)
1. The flame-retardant polyamide resin composition is characterized by comprising the following components in parts by weight:
75-90 parts of polyamide resin, 5-10 parts of antimony trioxide master batch, 5-15 parts of brominated macromolecular polymer strong flame retardant, 0.1-0.5 part of antioxidant and 0.1-0.5 part of lubricant;
the brominated macromolecular polymer strong flame retardant has the structure shown as follows:
，
wherein n is 1, 2 or 3;
the brominated macromolecular polymer structure of a: (a+b+c) =0.65-0.95, b: c= (1-4): 1.
2. The resin composition of claim 1, wherein the polyamide resin is at least one of PA6, PA66 or PA6/PA66 copolymer.
3. The resin composition of claim 1, wherein the antimony trioxide master batch comprises a base resin and antimony trioxide particles.
4. A resin composition according to claim 3, wherein the binder resin is at least one of PA6, PA66 or PA6/PA66 copolymer.
5. A resin composition according to claim 3, wherein the particle size of the antimony trioxide particles is 0.1 to 0.3 μm, and the mass of the antimony trioxide particles is 80 to 90% of the total mass of the antimony trioxide master batch.
6. The resin composition according to claim 1, wherein the antioxidant is at least one of an antioxidant 1098 and an antioxidant 1171.
7. The resin composition according to claim 1, wherein the lubricant is at least one of pentaerythritol tetrastearate, ethylene bisstearamide, modified ethylene bisstearamide, and polyethylene wax.
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| JPH01131274A (en) * | 1987-11-16 | 1989-05-24 | Unitika Ltd | Flame-retardant resin composition |
| CN104231622A (en) * | 2014-10-09 | 2014-12-24 | 晋德塑料科技(东莞)有限公司 | Low-precipitate flame-retarded polyamide composition and preparation method thereof |
| CN105754327A (en) * | 2016-03-04 | 2016-07-13 | 广西华锑科技有限公司 | Antimony trioxide compound flame retardant masterbatch for polycaprolactam and preparation method thereof |
| CN113773554A (en) * | 2021-10-22 | 2021-12-10 | 北京普利宏斌化工材料有限责任公司 | Efficient flame retardant and preparation method thereof |
| CN113789002A (en) * | 2021-10-26 | 2021-12-14 | 北京普利宏斌化工材料有限责任公司 | High-flame-retardant antimony trioxide master batch |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080303006A1 (en) * | 2007-06-08 | 2008-12-11 | Frank Huijs | Flame retardant thermoplastic resinous compostion |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01131274A (en) * | 1987-11-16 | 1989-05-24 | Unitika Ltd | Flame-retardant resin composition |
| CN104231622A (en) * | 2014-10-09 | 2014-12-24 | 晋德塑料科技(东莞)有限公司 | Low-precipitate flame-retarded polyamide composition and preparation method thereof |
| CN105754327A (en) * | 2016-03-04 | 2016-07-13 | 广西华锑科技有限公司 | Antimony trioxide compound flame retardant masterbatch for polycaprolactam and preparation method thereof |
| CN113773554A (en) * | 2021-10-22 | 2021-12-10 | 北京普利宏斌化工材料有限责任公司 | Efficient flame retardant and preparation method thereof |
| CN113789002A (en) * | 2021-10-26 | 2021-12-14 | 北京普利宏斌化工材料有限责任公司 | High-flame-retardant antimony trioxide master batch |
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