CN116285328A - High-strength low-precipitation halogen-free flame-retardant polyamide composition and preparation method thereof - Google Patents
High-strength low-precipitation halogen-free flame-retardant polyamide composition and preparation method thereof Download PDFInfo
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/22—Halogen free composition
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Abstract
The invention discloses a high-strength low-precipitation halogen-free flame-retardant polyamide composition and a preparation method thereof, wherein the composition comprises the following raw materials in parts by weight: 26-89.98% of polyamide resin; 10-35% of filler; flame retardant: 0.01-25%; modified synergistic flame retardant: 0.01-10%; an antioxidant: 0-1%; processing aid: 0-2%; color master batch: 0-1%. According to the invention, aiming at the 'pain point' of the halogen-free flame-retardant nylon material which is easy to separate out, according to the structural characteristics of the nylon material, in the formula design, the thickness of a carbon layer and the laminar flow of the carbon layer in the combustion process are balanced by introducing the flame retardant with a novel structure, and the flame retardant efficiency is improved. Meanwhile, a modified synergist is introduced, the synergistic effect of the synergist and the flame retardant further improves the flame retardant efficiency, the surface treatment of the synergist increases the compatibility with polyamide resin, and the precipitation risk is avoided.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a high-strength low-precipitation halogen-free flame-retardant polyamide composition and a preparation method thereof.
Background
Polyamide (nylon) has been commercialized by dupont for over 80 years since, and has been used as engineering plastics for over 60 years, and the polyamide has a series of excellent properties such as high strength, wear resistance, heat resistance, solvent resistance, etc., and is widely applied to the fields of automobiles, electronic appliances, civil aircraft, household appliances, etc., and is first to house general engineering plastics (PA, PC, POM, PBT/PET, PPO). The use of polyamides in engineering plastics generally requires modification of the resin according to the requirements of the working conditions.
Flame-retardant polyamide materials are widely applied in the fields of power batteries, high-speed rails, civil aircraft and the like, and the polymer flame-retardant path comprises: in the preparation process of the flame-retardant nylon material, the flame retardance of the nylon material is generally realized by adopting a method of mechanically blending a flame retardant, grafting or bonding a flame retardant group on or on a polymer chain, copolymerizing with a flame retardant monomer and the like in the preparation process of the composite material, and the method of mechanically blending the flame retardant in the preparation process of the composite material is most widely applied.
Chinese patent CN202210816927 provides a halogen-free intumescent flame retardant nylon 66 composition, a nylon 66 composite material and a preparation method thereof, wherein the halogen-free intumescent flame retardant consists of a phosphorus flame retardant, a nitrogen flame retardant and nano montmorillonite, the phosphorus flame retardant and the nitrogen flame retardant react to generate a crosslinked coating containing P-N bonds, and the nano montmorillonite promotes the formation of a carbonized layer during combustion and improves the flame retardance of PA 66. Chinese patent CN202210998254 discloses a flame retardant nylon material and a preparation method thereof, wherein nylon is melted, and the melted nylon is filled into chiral spiral silica nanotubes; mixing and heating the chiral spiral silica nanotube filled with nylon, glass fiber, modified asbestos, compatilizer and anti-aging auxiliary agent, and kneading for at least 10min by using a kneader to obtain a mixture; and (3) melting and extruding the obtained mixture through a double-screw extruder to obtain composite particles, wherein the material has certain flame retardant property. Chinese patent CN202210666576 discloses a halogen-free environment-friendly flame-retardant nylon 66 with high glow wires, and a gas phase and condensed phase flame-retardant mechanism is jointly formed by halogen-free flame retardants of phosphorus and nitrogen components to achieve the aim of flame retardance, and flaky alpha-zirconium phosphate is loaded on the surface of graphene oxide, so that the thermal oxidation stability of the graphene oxide is improved, the alpha-zirconium phosphate can also play a role in catalyzing and carbonizing, the thermal stability and flame retardance of a polymer composite material are improved synergistically, the problems of complex preparation process and high energy consumption of the graphene loaded zirconium phosphate composite material are solved, and large-scale production can be realized. In recent years, published patents focus on research on halogen-free flame-retardant nylon materials composed of phosphorus flame retardants, phosphorus flame retardants and synergists, and compared with halogen flame-retardant systems, the halogen-free flame-retardant nylon materials have the advantage of environmental protection, but are easy to separate out in an injection molding process and a high-temperature and high-humidity environment, so that the application of the halogen-free flame-retardant nylon materials is limited, and most of the published researches focus on mechanical blending modification of the flame retardants, so that the research on the molecular structure design of the flame retardants is relatively less, and the progress of the technology of the halogen-free flame-retardant nylon materials is hindered.
Disclosure of Invention
In order to fill the blank of the prior art, the invention provides the high-strength low-precipitation halogen-free flame-retardant polyamide composition and the preparation method thereof, and the flame retardant with a brand new structure is introduced through the molecular structure design of the flame retardant, so that the flame retardant efficiency is improved, the addition amount of the flame retardant is reduced, the high strength of the flame-retardant polyamide material is realized, the addition amount of the flame retardant is further reduced through the addition of the modified synergistic flame retardant, the precipitation of the synergistic flame retardant is avoided through a pretreatment mode, and the characteristics of high strength and low precipitation of the flame-retardant polyamide material are realized.
The invention is realized by the following technical scheme:
the high-strength low-precipitation halogen-free flame-retardant polyamide composition comprises the following raw materials in parts by weight:
the polyamide resin can be one or more of PA6, PA56, PA66, PA6/66, PA66/6T, PA T/X, PA10T, PA T/X, PA9T, PA46, PA4T, PA5T, PA5T/X, etc.;
the filler can be fibrous or non-fibrous filler according to the form, the fibrous filler can be one or more of glass fiber, aramid fiber, carbon fiber, basalt fiber and the like, and the non-fibrous filler can be one or more of whisker, wollastonite, mica, kaolin, talcum powder, glass microsphere and calcium carbonate.
The preferred filler of the invention is glass fiber, alkali content is less than 0.8%, volume density is 0.6-0.8g/cm3, and monofilament fiber diameter: 7-13 μm, short cut length: 2-5mm, and the water content is less than or equal to 0.05 percent.
The flame retardant is diethyl phosphinated ethyl aluminum diphosphate. Whiteness > 95%, moisture < 0.3%, PH > 4, phosphorus content: 25-28%, aluminum content: 7-8%; the density is 1.34-1.38g/cm3; particle size (D50) 10-20 μm; the structural formula of the flame retardant is as follows:
the synergistic flame retardant is modified zinc aluminum tripolyphosphate, the whiteness is more than 90%, and P 2 O 5 The effective content is 48-52%, al 2 O 3 The effective content is 13-15%, the effective content of ZnO is 18-22%, the pH value is 5-7%, and the particle size (D50) is less than 5 μm.
The modified aluminum tripolyphosphate is prepared by treating the zinc aluminum tripolyphosphate with a surface treating agent and taking foamed nylon as a carrier.
The antioxidant is a mixture of phosphite antioxidants and hindered phenol antioxidants in a weight ratio of 1:1, wherein the phosphite antioxidants can be tris [ 2.4-di-tert-butylphenyl ] phosphite, CAS N0.31570-04-4;3, 9-bis (2, 4-dicumylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane, CAS No.154862-43-8; the hindered phenolic antioxidants may be: n, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, CAS No.23128-74-7; triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, CAS No.36443-68-2; at least one of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], CAS No.6683-19-8, and the like.
The hindered phenol antioxidant is preferably N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, and the phosphite antioxidant is preferably tris [2, 4-di-tert-butylphenyl ] phosphite.
The processing aid is an organic aid which can realize internal and external lubrication and does not influence flame retardant property. Can be one or more of silicone powder, silicone master batch, PETS, montan wax, polyethylene wax, oxidized polyethylene wax, calcium stearate, etc.
The processing aids of the invention are preferably silicone powders, phenylsilicones and silica 1: 1.
The color master batch is characterized in that the content of carbon black is 10-99%, and the carrier is PA6 or the color master batch of the lubricant.
The high-strength low-precipitation halogen-free flame-retardant polyamide composition and the preparation method thereof comprise the following steps:
(1) The water content of the polyamide resin is not higher than 2000ppm;
(2) Weighing the dried raw materials according to the formula proportion; uniformly mixing polyamide resin, a flame retardant, a modified synergistic flame retardant, an antioxidant, a processing aid and color master batches by a high-speed stirrer for standby, and weighing a filler according to a ratio for standby;
(3) The resin and the auxiliary agent mixed raw materials are added through a main feeding port of a double-screw extruder, the filler is added from a side feeding port of the double-screw extruder, and the halogen-free flame retardant polyamide composition is obtained after the procedures of melt extrusion, granulation, drying treatment and the like at 260 ℃.
The halogen-free flame-retardant polyamide composition can be applied to the fields of new energy automobiles, electronic and electric appliances, connectors and the like.
The invention has the beneficial effects that:
1) Aluminum Diethylphosphinate (ADP) has a low carbon residue, which has a certain fluidity at the beginning of combustion to form a carbon film, but the low carbon residue makes the addition amount high enough to form a stable, thick enough carbon film. Aluminum phosphate has a very high carbon residue amount, which is more than 50% even when burned at 800 ℃, but the carbon film is very hard and has no fluidity. The two are added according to a certain proportion to show the most excellent performance, the structure of the two is designed together through molecular structure design, a new molecular structure flame retardant diethyl phosphinated ethyl aluminum diphosphate is introduced, on one hand, the influences of ADP and aluminum phosphate on carbon residue and carbon layer flow are combined, the excellent flame retardant performance is reflected, in addition, compared with the compounding of ADP and aluminum phosphate or aluminum phosphite synergists, the efficiency is higher, the addition amount is low, more beneficial mechanical performance and low precipitation performance can be obtained, and compared with commercial products such as diethyl phosphinated aluminum phosphate and the like, the UL 94V 0 flame retardant effect can be obtained due to the fact that the specific structure of the diethyl phosphinated aluminum diphosphate is not compounded with the synergism and the low addition amount.
2) The modified zinc aluminum tripolyphosphate is used as a synergist, the content of each element of the zinc aluminum tripolyphosphate is limited in order to obtain excellent flame retardance, the zinc aluminum tripolyphosphate is subjected to surface modification in order to achieve the effect of low precipitation, the compatibility of the synergistic flame retardant and nylon is improved by the silane coupling agent in the surface treatment agent, the ethylene maleic anhydride copolymer in the surface treatment agent can be connected with a resin interface through chemical bonds, the dispersibility of the synergistic flame retardant is improved by taking foamed nylon as a carrier, the risk that the synergistic flame retardant is easy to precipitate is solved under the combined action of the three, the flame retardant efficiency is improved, and the addition amount is reduced.
3) The V0 flame retardance of the reinforced nylon under the UL94 standard can be realized only by compounding multiple components of the halogen-free flame retardant, and the diethyl phosphinated ethyl aluminum diphosphate flame retardant adopted by the invention can achieve the V0 flame retardance effect under the state of being singly added in a low addition amount state, and has high flame retardance efficiency.
4) The modified zinc aluminum tripolyphosphate is used as a synergist, so that the addition amount of the flame retardant is reduced on the premise of not affecting flame retardance and precipitation, the comprehensive cost of the material is reduced, and the competition of products is promoted.
The polyamide composition has the advantages of excellent flame retardant property, low cost, low precipitation and high strength, and enhances the market competitiveness of the product.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the invention will be further described in detail with reference to the following examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The examples and comparative examples of the present invention use the following materials, but are not limited to:
polyamide resin, trade name EPR27, produced from god horses;
flame retardant, trade name OP1230, produced by CLARIANT;
flame retardant, trade name HR8900, produced by wehai;
glass fiber, trade name ECS301HP-3, available from Chongqing International composite;
flame retardant: diethyl phosphinated ethyl aluminum diphosphate, commercially available;
synergistic flame retardants, zinc aluminum tripolyphosphate, commercially available;
a synergistic flame retardant, modified zinc aluminum tripolyphosphate, self-made;
processing aids, commercially available under the trade name silicone powder;
antioxidant 1098, a hindered phenolic antioxidant, commercially available;
antioxidant 168, phosphite antioxidant, commercially available;
black master batch, PA6-2015, commercially available;
silane coupling agent: trade name a1100, produced from michaemap;
ethylene maleic anhydride copolymer, trade name
E60P, produced by Vertellus;
adsorbent, trade name Accurel XP700, produced from 3M
Preparation of modified synergistic flame retardant:
1) Will be
E60P and a1100 were added according to 1:15, uniformly mixing the components in proportion, and preparing a surface treating agent;
2) Preheating zinc aluminum tripolyphosphate to 100-110 ℃, adding the zinc aluminum tripolyphosphate into a high-speed stirrer, stirring and drying for 10-15min to ensure that the water content of the filler is lower than 0.2%, and adding a surface treating agent into the zinc aluminum tripolyphosphate for activation and modification for 5min to prepare surface treated zinc aluminum tripolyphosphate;
3) Mixing the surface-treated zinc aluminum tripolyphosphate with Accurel XP700 according to the ratio of 1:1, and mixing for 10min in a high-speed mixer to prepare the modified synergistic flame retardant.
Examples 1-10 and comparative examples 1-7 were prepared by the following procedure:
preparation of a halogen-free flame retardant polyamide composition:
weighing the dried raw materials according to the formula proportion; uniformly mixing polyamide resin, a flame retardant, a modified synergistic flame retardant, an antioxidant, a processing aid and color master batches by a high-speed stirrer for standby, and weighing a filler according to a ratio for standby; the resin and the auxiliary agent mixed raw materials are added through a main feeding port of a double-screw extruder, the filler is added from a side feeding port of the double-screw extruder, and the halogen-free flame retardant polyamide composition is obtained after the procedures of melt extrusion, granulation, drying treatment and the like at 260 ℃.
Preparation of test bars of halogen-free flame retardant polyamide composition:
the above materials were dried in a forced air drying oven at 120 ℃ for 4 hours and then injection molded into standard bars at an injection molding temperature of 280-300 ℃. The injection molded mechanical property sample bars are subjected to state adjustment for 24 hours in a laboratory standard environment (23 ℃ and 50% RH).
The testing method of each performance index comprises the following steps:
tensile properties: spline size according to ISO 527 method: 170 x 10 x 4mm, test speed 5mm/min.
Bending properties: spline size according to ISO 178 method: 80.10.4 mm, test speed 2mm/min.
Notched impact properties: spline size according to ISO 179 method: 80 x 10 x 4mm.
Flame retardant properties: spline size according to UL94 method: 127 x 12.7 x 1.6mm.
Precipitation resistance: a template of 150 x 100 x 3.2mm was placed in an environmental chamber, the conditioning of which was set to: temperature: the state of the surface precipitate was visually evaluated at 85℃with a humidity of 85% RH for 200 hours.
Table 1: examples 1-11 halogen-free flame retardant polyamide composition and Properties:
table 2: comparative examples 1-7 halogen-free flame retardant polyamide composition and properties:
as can be seen from tables 1 and 2, the diethyl phosphinated ethyl aluminum diphosphate can effectively reduce the addition amount of the flame retardant (examples 2-4 and comparative examples 6-7) compared with other similar products commercialized in the market, which shows that the flame retardant has high flame retardant efficiency and small influence on mechanical properties, and the prepared halogen-free flame retardant polyamide has high strength. The modified zinc aluminum tripolyphosphate can still achieve the same flame retardant effect (examples 2-10) by replacing diethyl phosphinated ethyl aluminum diphosphate with the same proportion, the risk that unmodified zinc aluminum tripolyphosphate is easy to separate out and has great influence on mechanical properties (examples 5-7, examples 10-11 and comparative examples 1-5) is solved, the preparation method of the modified zinc aluminum tripolyphosphate is simple, the cost is low, the market competitiveness of halogen-free flame retardant polyamide materials can be improved, and the halogen-free flame retardant polyamide composition prepared by the invention can be applied to the fields of energy automobiles, electronic appliances, connectors and the like.
Claims (12)
1. A high-strength low-precipitation halogen-free flame-retardant polyamide composition is characterized in that: the material comprises the following raw materials in parts by weight:
2. a high strength, low precipitation halogen free flame retardant polyamide composition according to claim 1, wherein: the polyamide resin is one or more of PA6, PA56, PA66, PA6/66, PA66/6T, PA6T/X, PA10T, PA T/X, PA9T, PA46, PA4T, PA5T, PA 5T/X.
3. A high strength, low precipitation halogen free flame retardant polyamide composition according to claim 1, wherein: the filler can be fibrous or non-fibrous filler according to the form, the fibrous filler can be one or more of glass fiber, aramid fiber, carbon fiber and basalt fiber, and the non-fibrous filler can be one or more of whisker, wollastonite, mica, kaolin, talcum powder, glass microsphere and calcium carbonate.
4. A high strength, low precipitation halogen free flame retardant polyamide composition according to claim 1, wherein: the filler is glass fiber, the alkali content is less than 0.8%, the volume density is 0.6-0.8g/cm < 3 >, and the diameter of the monofilament fiber is as follows: 7-13 μm, short cut length: 2-5mm, and the water content is less than or equal to 0.05 percent.
5. A high strength, low precipitation halogen free flame retardant polyamide composition according to claim 1, wherein: the flame retardant is diethyl phosphinated ethyl aluminum diphosphate. Whiteness > 95%, moisture < 0.3%, PH > 4, phosphorus content: 25-28%, aluminum content: 7-8%; density of 1.34-1.38g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Particle size (D50) 10-20 μm; the structural formula of the flame retardant is as follows:
6. a high strength, low precipitation halogen free flame retardant polyamide composition according to claim 1, wherein: the synergistic flame retardant is modified zinc aluminum tripolyphosphate, the whiteness is more than 90%, and P 2 O 5 The effective content is 48-52%, al 2 O 3 The effective content is 13-15%, the effective content of ZnO is 18-22%, the pH value is 5-7%, and the particle size (D50) is less than 5 μm; the modified aluminum tripolyphosphate is prepared by treating the zinc aluminum tripolyphosphate with a surface treating agent and taking foamed nylon as a carrier.
7. A high strength, low precipitation halogen free flame retardant polyamide composition according to claim 1, wherein: the antioxidant is a mixture of phosphite antioxidants and hindered phenol antioxidants in a weight ratio of 1:1, wherein the phosphite antioxidants can be tris [2, 4-di-tert-butylphenyl ] phosphite, CAS N0.31570-04-4;3, 9-bis (2, 4-dicumylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane, CAS No.154862-43-8; the hindered phenolic antioxidants may be: n, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, CAS No.23128-74-7; triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, CAS No.36443-68-2; at least one of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, CAS No. 6683-19-8.
8. A high strength, low precipitation halogen free flame retardant polyamide composition according to claim 1, wherein: the hindered phenol antioxidant is selected from N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, and the phosphite antioxidant is selected from tris [2, 4-di-tert-butylphenyl ] phosphite.
9. A high strength, low precipitation halogen free flame retardant polyamide composition according to claim 1, wherein: the processing aid is an organic aid which can realize internal and external lubrication and does not influence the flame retardant property; one or more selected from silicone powder, silicone masterbatch, PETS, montan wax, polyethylene wax, oxidized polyethylene wax, and calcium stearate.
10. A high strength, low precipitation halogen free flame retardant polyamide composition according to claim 1, wherein: the processing aid is silicone powder, phenyl silicone and silicon dioxide 1: 1.
11. A high strength, low precipitation halogen free flame retardant polyamide composition according to claim 1, wherein: the color master batch is characterized in that the content of carbon black is 10-99%, and the carrier is PA6 or the color master batch of the lubricant.
12. The high strength, low precipitation halogen free flame retardant polyamide composition according to any of claims 1-11, comprising the steps of:
(1) The water content of the polyamide resin is not higher than 2000ppm;
(2) Weighing the dried raw materials according to the formula proportion; uniformly mixing polyamide resin, a flame retardant, a modified synergistic flame retardant, an antioxidant, a processing aid and color master batches by a high-speed stirrer for standby, and weighing a filler according to a ratio for standby;
(3) The resin and the auxiliary agent mixed raw materials are added through a main feeding port of a double-screw extruder, the filler is added from a side feeding port of the double-screw extruder, and the halogen-free flame retardant polyamide composition is obtained after the procedures of melt extrusion, granulation, drying treatment and the like at 260 ℃.
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