CN112795183B - High-strength, low-shrinkage and low-precipitation environment-friendly flame-retardant polyamide composition and preparation method thereof - Google Patents
High-strength, low-shrinkage and low-precipitation environment-friendly flame-retardant polyamide composition and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an environment-friendly flame-retardant polyamide composition with high strength, low shrinkage and low precipitation and a preparation method thereof, wherein the composition comprises the following raw materials in parts by weight: 21-89.96% of environment-friendly flame-retardant polyamide resin; 10-35% of a filler; flame retardant: 0.01-20%; liquid crystal flame retardant: 0.01 to 10 percent; synergistic flame retardant: 0.01 to 5 percent; a compatilizer: 0.01 to 5 percent; antioxidant: 0 to 1 percent; processing aid: 0 to 2 percent; color master batch: 0 to 1 percent. According to the invention, the Liquid Crystal Polymer (LCP) and the traditional flame retardant are compounded to be used as the flame retardant additive in the modification process, the use of the environment-friendly flame retardant polyamide resin and the liquid crystal flame retardant can effectively reduce the addition amount of the traditional flame retardant in the modification process, reduce the precipitation risk of the flame retardant polyamide in a high-temperature high-humidity (85 ℃, 85-RH) environment, the liquid crystal polymer is in fibrous orientation in the polyamide material, the polyamide material is endowed with the characteristics of reinforcement and low shrinkage, and the fibrous distribution can form a space network to further prevent the migration of the flame retardant in the high-temperature high-humidity state.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to an environment-friendly flame-retardant polyamide composition with high strength, low shrinkage and low precipitation and a preparation method thereof.
Background
Polyamide is a general name of thermoplastic resins with molecular chains containing repeated amide groups- (NHCO) -, and polyamide materials have the characteristics of multiple types, large yield and wide application, and are engineering plastics most widely applied at present. Most of polyamide is partially crystallized semitransparent resin, the molecular weight of the polyamide used as engineering plastics is generally 1.5-3 ten thousand, the polyamide material has the characteristics of excellent mechanical property, high softening point, high heat resistance, low friction coefficient, wear resistance, good self-lubricating property, excellent electrical insulation property, good solvent resistance and the like, the excellent performance of the polyamide material determines the wide application field of the polyamide material, but the polyamide resin generally needs to be modified to have application value, and the modification technology comprises an enhancement modification technology, a toughening modification technology, a flame retardation modification technology, a weather resistance modification technology and the like.
The polyamide material has certain flame retardance, but in industries with high requirements for the flame retardance of materials such as new energy automobile battery systems, household appliances and electronic appliances, the flame retardance of the polyamide material cannot meet the existing use requirements, and particularly when the glass fiber reinforced polyamide material is used in the fields, the material is easy to burn due to the wick effect caused by filling glass fibers, so that the flame retardance of the polyamide material needs to be deeply researched.
Chinese patent CN201710009054.8 firstly obtains flame retardant salt through the reaction between DOPO-based reactive phosphorus flame retardant and diamine, then the flame retardant PA66 is prepared by adding additive phosphorus flame retardant, flame retardant salt and other components in the process of polymerizing 66 salt into polyamide 66, the limit oxygen index of the prepared flame retardant polyamide 66 is more than 30%, the flame retardant polyamide can be used as plastic to be applied to products such as gears, bearings and automobile parts, and can also be prepared into fibers and further processed into textiles, military fabrics, equipment and the like. Chinese patent CN201710009053.3 obtains flame retardant salt through the reaction between DOPO-based reactive phosphorus flame retardant and diamine, and then additive phosphorus flame retardant, flame retardant salt and other components are added in the process of polymerizing caprolactam into polyamide 6 to prepare the flame-retardant polyamide 6 with the limiting oxygen index of more than 29 percent. Chinese patent CN201710009055.2 obtains flame retardant salt through the reaction between DPO-based reactive phosphorus flame retardant and diamine, and then adds additive phosphorus flame retardant, flame retardant salt and other components in the process of polymerizing 66 salt into polyamide 66 to prepare the halogen-free flame-retardant polyamide 66 with the limiting oxygen index of more than 30%. The flame-retardant polyamide resin obtained by in-situ polymerization of Chinese patent CN201710707059.8 is added with a small amount of flame retardant or montmorillonite, so that the flame-retardant grade of PA66 UL94 can reach V-0, and the flame-retardant polyamide resin has the characteristics of high CTI and excellent mechanical strength. Most of the published patents obtain flame-retardant polyamide resin through in-situ polymerization, the polyamide resin is rarely directly applied, modification through a filler is generally needed, the modified resin is required to reach the UL 94V-0 flame-retardant grade, a flame retardant is generally needed to be additionally added, the mechanical property of the polyamide material is influenced by the adding amount of the flame retardant, the mechanical property is lower when the adding amount is larger, the risk of precipitation of the flame retardant in a high-temperature and high-humidity state (85 ℃,85 ℃ RH) exists when the flame retardant is additionally added in a blending mode, and the existing patents lack evaluation on related risks and cannot objectively reflect the material property under a real working condition, so the application range of the polyamide composition is limited.
Disclosure of Invention
In order to fill the blank of the prior art, the invention provides the environment-friendly flame-retardant polyamide composition with high strength, low shrinkage and low precipitation and the preparation method thereof, the actual use working condition of the polyamide material is simulated, and the environment-friendly flame-retardant polyamide composition prepared by the method realizes the characteristics of high strength, low precipitation and low shrinkage on the basis of realizing the UL 94V-0 flame-retardant grade.
The invention is realized by the following technical scheme:
the high-strength, low-shrinkage and low-precipitation environment-friendly flame-retardant polyamide composition is prepared from the following raw materials in parts by weight:
the environment-friendly flame-retardant polyamide resin is synthesized by an in-situ polymerization mode, the content of phosphorus in molecular chains is 0.2-1 wt%, 2-10 wt% of additive phosphorus flame retardant is contained between the molecular chains, the oxygen index is more than or equal to 30%, the content of bio-based monomer in the resin is 35-45% (weight ratio), the melting point is 235-270 ℃, and the relative viscosity is 2.2-4.0.
The filler may be fibrous or non-fibrous, the fibrous filler may be one or more of glass fiber, carbon fiber, basalt fiber, aramid fiber, etc., and the non-fibrous filler may be one or more of whisker, wollastonite, mica, kaolin, glass microsphere, and calcium carbonate.
The flame retardant is a halogen-free flame retardant and can be one or more of red phosphorus, phosphate, ammonium polyphosphate (MPP), MCA, aluminum diethylphosphinate, zinc diethylphosphinate, aluminum methyl phenyl phosphinate, aluminum methyl butyl phosphinate, aluminum methyl cyclohexyl phosphinate and metal hydroxide flame retardants. Aluminum diethylphosphinate is preferred as the flame retardant of the present invention.
The liquid crystal flame retardant is a liquid crystal polymer, LCP for short, and has the density: 1.35-1.45g/cm3; melting temperature: 260-350 ℃; UL94 combustion rating V0.
The synergistic flame retardant can be one or more of antimony trioxide, zinc stannate, zinc sulfate, barium sulfate and the like. Zinc stannate is preferably used as the synergistic flame retardant.
The compatilizer is one or more of SEBS, SMA resin, EBA-g-MAH and the like, the compatilizer comprises the substances but is not limited to the substances, and the SMA resin is preferred in the invention.
The antioxidant is a mixture of hindered phenol antioxidant and phosphite antioxidant 1:1 (weight ratio), wherein the hindered phenol antioxidant can be: n, N' -bis- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, 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 tetra [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, CAS No.6683-19-8, etc., the antioxidant of phosphite ester may 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 phenol antioxidant of the present invention is preferably N, N' -bis- (3- (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 a resin lubricant with polar functional groups, can generate intermolecular force among polyamide molecular chains, can quickly break the intermolecular force among the polyamide resin molecular chains under the shearing action, and is beneficial to the dispersion and orientation of the liquid combustion improver among the polyamide molecular chains.
The color master batch contains 10-99% of carbon black, and the carrier is PA6 or a lubricant.
The preparation method of the environment-friendly flame-retardant polyamide composition with high strength, low shrinkage and low precipitation comprises the following steps:
(1) The water content of the environment-friendly flame-retardant polyamide resin is not higher than 2000ppm;
(2) Weighing the dried raw materials according to the formula proportion; uniformly mixing the environment-friendly flame-retardant polyamide resin, the flame retardant, the liquid crystal flame retardant, the synergistic flame retardant, the compatilizer, the antioxidant and the processing aid by using a high-speed mixer for later use, and weighing the filler according to the proportion for later use;
(3) And adding the resin and auxiliary agent mixed raw materials through a main feeding port of a double-screw extruder, adding a filling agent through a side feeding port of the double-screw extruder, and performing melt extrusion, granulation, drying treatment and other processes to obtain the environment-friendly flame-retardant polyamide composition.
The environment-friendly flame-retardant polyamide composition can be applied to the fields of new energy automobiles, household appliances, electronic appliances and the like.
The invention has the beneficial effects that:
1) The polyamide resin synthesized by an in-situ polymerization method is adopted, the pentanediamine in the synthetic resin is prepared by fermenting corn starch, the prepared polyamide resin belongs to bio-based polyamide resin and is an environment-friendly engineering plastic, a flame retardant is introduced in the resin synthesis process, and the prepared filling modified polyamide composition can meet the flame retardant grade of UL 94V0 level in a small amount of flame retardant additive.
2) The flame retardant system selects a liquid crystal flame retardant, utilizes the natural flame retardance of the liquid crystal polymer LCP, reduces the addition amount of the flame retardant polyamide system, and reduces the flame retardant under the high-temperature and high-humidity state (85 ℃.85% RH) has positive significance.
3) The LCP is compounded with the processing aid by combining the liquid crystal characteristics of the LCP, so that the LCP is in fibrous distribution in the polyamide resin, the polyamide is endowed with the performance of reinforcement and low shrinkage, and fibrous network distribution of the LCP in the polyamide resin plays a role in blocking migration of the flame retardant and adsorption of water molecules under the high-temperature and high-humidity states, the water absorption rate is reduced, and the risk of precipitation of the flame retardant under the high-temperature and high-humidity states is further reduced.
4) The environment-friendly flame-retardant polyamide composition simultaneously considers the flame retardant property, the mechanical property and the precipitation property of high temperature and high humidity (85 ℃,85 percent RH), and is more in line with the application working condition of the environment-friendly flame-retardant polyamide composition.
The characteristics of flame retardant property, low shrinkage and high strength of the environment-friendly polyamide composition are realized through the beneficial effects, and the environment-friendly idea and the characteristic of high performance are endowed.
Drawings
FIG. 1 is a photograph of the precipitation resistant appearance of the environmentally friendly flame retardant polyamide compositions of examples 1-10;
FIG. 2 is a photograph showing the appearance of precipitation resistance of the environmentally friendly flame retardant polyamide compositions of comparative examples 1 to 7.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention clearer, the present invention will be further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
The examples and comparative examples of the present invention employ, but are not limited to, the following materials:
the environmental-friendly flame-retardant polyamide resin PA56 is named Ecope E-1273 and is produced by Shanghai Kaiser Biotech Co., ltd;
PA56 salt, commercially available;
the purity of the pentanediamine is more than or equal to 98 percent, and the pentanediamine is sold in the market;
adipic acid with purity of more than or equal to 98 percent is sold in the market;
liquid crystal flame retardant, liquid crystal polymer LCP, trade name LCP KG300, produced by shanghai pril specialty chemicals new materials limited;
flame retardant, reactive DOPO piperazine derivative phosphorus combustion improver, commercially available;
flame retardant, trade name OP1230, from CLARIANT
Zinc stannate, available from Williamblythe corporation;
glass fiber, trade name ECS301HP-3, from international composite of chongqing limited;
a processing aid, trade name TP-P1507, from Bruggemann;
the compatilizer, SMA-800, is produced by chemical industry Limited of Jiaxinghua Wen;
antioxidant 1098, hindered phenolic antioxidants, commercially available;
antioxidant 168, phosphite antioxidant, commercially available;
black masterbatch, PA6-2015, commercially available;
preparation of environment-friendly flame-retardant polyamide resin:
1) Mixing a reactive DOPO piperazine derivative phosphorus combustion improver, pentanediamine and a solvent according to the ratio of 0.9-1.3, stirring for 5-10min at the speed of 50-450rpm, and reacting for 2-8h at the temperature of 60-90 ℃ to prepare a flame retardant salt; the solvent is distilled water or ethanol, and the structural formula of the reactive DOPO piperazine derivative phosphorus combustion improver is as follows:
wherein R1 is a branched or branched C1-C20 alkylidene group, an alkylene group or arylene group having 2 to 15 carbon atoms at the R2 position
2) Mixing the additive phosphorus flame retardant, 56 salt, water, the synergistic flame retardant and adipic acid, and then carrying out heat preservation and pressure maintaining reaction to complete the heat preservation and pressure maintaining reaction and release pressure to normal temperature, wherein the heat preservation and pressure maintaining reaction temperature is as follows: 210-230 ℃, 1.5-2.5MPA pressure, 1-5h time, stirring speed: 50-450rpm, the controlled adding time of 56 salt is 0.5-1.5h, and the additive flame retardant can be: zinc diethylphosphinate, aluminum diethylphosphinate, and the like. The synergistic flame retardant is one or more of antimony trioxide, zinc stannate, zinc sulfate, barium sulfate and the like. The heat-preservation pressure-maintaining reaction raw materials comprise:
3) And (3) post-treatment: and after the polycondensation reaction is finished, vacuumizing the system to-0.05 to-0.1 MPa, adjusting the temperature to 260-280 ℃, keeping the temperature for 0.5-5h, stopping stirring, continuously vacuumizing to realize liquid phase tackifying, standing for 15-30 min, and discharging to obtain the flame-retardant polyamide resin.
The content of phosphorus in molecular chains of the environment-friendly flame-retardant polyamide resin is 0.2-1 wt%, 2-10 wt% of additive phosphorus flame retardant is contained between molecular chains, the oxygen index is more than or equal to 30%, the content of bio-based monomer in the resin is 35-45% (weight ratio), the melting point is 235-270 ℃, and the relative viscosity is 2.2-4.0
Preparation methods of examples 1 to 10 and comparative examples 1 to 7:
preparation of environment-friendly flame-retardant polyamide composition:
weighing the dried raw materials according to the formula proportion; uniformly mixing polyamide resin, a flame retardant, a liquid crystal flame retardant, a synergistic flame retardant, a compatilizer, an antioxidant and a processing aid by a high-speed mixer for later use, and weighing a filling agent according to a ratio for later use; and adding the resin and auxiliary agent mixed raw materials through a main feeding port of a double-screw extruder, adding a filling agent through a side feeding port of the double-screw extruder, and performing melt extrusion, granulation, drying treatment and other processes at 250 ℃ to obtain the environment-friendly flame-retardant polyamide composition.
Preparation of test specimen of environment-friendly flame-retardant polyamide composition:
the materials are dried for 4 hours at 120 ℃ in a forced air drying oven and then injection molded into standard sample strips at the injection molding temperature of 280-300 ℃. The mechanical properties of the injection-molded specimens were tested after conditioning for 24h in a laboratory standard environment (23 ℃ C., 50% RH).
The test method of each performance index comprises the following steps:
tensile property: according to ISO 527 method, spline size: 170 × 10 × 4mm, test speed 5mm/min.
Bending property: according to ISO 178 method, spline size: 80 × 10 × 4mm, test speed 2mm/min.
Notched impact strength: according to ISO 179 method, spline size: 80 x 10 x 4mm.
Flame retardant property: according to UL94 method, spline size: 127 × 12.7 × 1.6mm.
Shrinkage rate: according to ISO 294-4 method, spline size: 60 × 2mm, and is divided into a flow direction shrinkage rate and a perpendicular flow direction shrinkage rate according to the melt flow direction during injection molding.
Precipitation resistance: place 150 x 100 x 3.2mm template in the environmental box, the environmental box regulation set up as: temperature: the state of surface precipitates was visually evaluated at 85 ℃ and a humidity of 85% RH for a time of 1500 h.
Table 1: examples 1-10 environmentally friendly flame retardant polyamide compositions and properties:
table 2: comparative examples 1-7 composition and properties of environmentally friendly flame retardant polyamide compositions:
as can be seen from tables 1 and 2, the environmentally friendly flame retardant polyamide resin can effectively reduce the addition amount of the flame retardant (examples 3 and 4), improve the mechanical properties of the polyamide composition (comparative examples 1, 2, 3 and 4, 5 and 6), improve the risk of easy precipitation of the conventional flame retardant system (comparative examples 1-3 and 4-6), and the prepared polyamide composition has no precipitation in a high-temperature and high-humidity environment (85 ℃, 86%. RH) for a long period of time (examples 1-10), solves the risk of easy precipitation in a high-temperature and high-humidity environment (85 ℃, 86%. RH) for a long period of time (comparative examples 1-3) of the conventional flame retardant system, the addition of the liquid crystal flame retardant effectively reduces the addition amount of the conventional flame retardant (examples 1, 2 and 4), has positive significance for improving the precipitation resistance and the mechanical property (comparative examples 1 to 7), the addition of the compatilizer can improve the compatibility of the liquid flame retardant and the polyamide and improve the mechanical property (examples 3,5 and 6), the processing aid can increase the orientation of the liquid crystal flame retardant in the polyamide composition, the fibrous orientation is favorable for increasing the mechanical property and reducing the shrinkage rate (examples 4, 9 and 10, comparative examples 1 to 3 and comparative examples 4 to 6), and the environment-friendly flame retardant polyamide composition prepared by the invention has the characteristics of environment protection and high performance, can meet the requirements of a new energy automobile battery system, a high energy consumption system and the like, the application requirements in the fields of household appliances, electronic appliances and the like.
Claims (8)
1. The high-strength, low-shrinkage and low-precipitation environment-friendly flame-retardant polyamide composition is characterized in that: the feed is prepared from the following raw materials:
50.2 to 72.2 percent of environment-friendly flame-retardant polyamide resin;
filling agent: 10 to 35 percent;
flame retardant: 3 to 5 percent;
liquid crystal flame retardant: 3 to 10 percent;
synergistic flame retardant: 0.01 to 5 percent;
a compatilizer: 0.01 to 5 percent;
antioxidant: 0.3-1%;
processing aid: 0.5-1%;
color master batch: 1 percent;
the environment-friendly flame-retardant polyamide resin is synthesized by an in-situ polymerization mode, the content of phosphorus in molecular chains is 0.2-1 wt%, 2-10 wt% of additive phosphorus flame retardant is contained between the molecular chains, the oxygen index is more than or equal to 30%, the weight ratio of the content of the bio-based monomer in the resin is 35-45%, the melting point is 235-270 ℃, and the relative viscosity is 2.2-4.0;
the flame retardant is a halogen-free flame retardant;
the liquid crystal flame retardant is a liquid crystal polymer, LCP for short, and has the density: 1.35-1.45g/cm3; melting temperature: 260-350 ℃; UL94 combustion rating V0;
the structural formula of the phosphorus flame retardant is as follows:
the synergistic flame retardant is one or more of antimony trioxide, zinc stannate, zinc sulfate and barium sulfate.
2. The high-strength, low-shrinkage, low-precipitation, environment-friendly and flame-retardant polyamide composition as claimed in claim 1, wherein: the filler is fibrous or non-fibrous according to the form, the fibrous filler is selected from one or more of glass fiber, carbon fiber, basalt fiber and aramid fiber, and the non-fibrous filler is selected from one or more of whisker, wollastonite, mica, kaolin, glass microsphere and calcium carbonate.
3. The high-strength, low-shrinkage, low-precipitation, environment-friendly and flame-retardant polyamide composition as claimed in claim 1, wherein: the flame retardant is selected from one or more of red phosphorus, phosphate, ammonium polyphosphate (MPP), MCA, aluminum diethylphosphinate, zinc diethylphosphinate, aluminum methylphenylphosphinate, aluminum methylbutylphosphinate, aluminum methylcyclohexylphosphinate and metal hydroxide flame retardants.
4. The high-strength, low-shrinkage, low-precipitation, environment-friendly and flame-retardant polyamide composition as claimed in claim 3, wherein: the flame retardant is diethyl aluminum phosphinate.
5. The high-strength, low-shrinkage, low-precipitation, environment-friendly and flame-retardant polyamide composition as claimed in claim 1, wherein: the synergistic flame retardant is zinc stannate.
6. The high-strength, low-shrinkage, low-precipitation, environment-friendly and flame-retardant polyamide composition as claimed in claim 1, wherein:
the compatilizer is one or more of SEBS, SMA resin and EBA-g-MAH;
the antioxidant is a mixture of hindered phenol antioxidant and phosphite ester antioxidant in a weight ratio of 1:1, wherein the hindered phenol antioxidant is: n, N' -bis- (3- (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 tetra [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, CAS No.6683-19-8, the antioxidant of the phosphite ester is 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 color master batch contains 10-99% of carbon black, and the carrier is PA6 or a lubricant.
7. The high-strength, low-shrinkage, low-precipitation, environment-friendly and flame-retardant polyamide composition as claimed in claim 6, wherein:
the compatilizer is selected from SMA resin;
the hindered phenol antioxidant is N, N' -bis- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine; the phosphite ester antioxidant is tris [2, 4-di-tert-butylphenyl ] phosphite.
8. The method for preparing the high-strength, low-shrinkage, low-precipitation, environment-friendly and flame-retardant polyamide composition according to any one of claims 1 to 7, wherein the method comprises the following steps: the method comprises the following steps:
(1) The water content of the environment-friendly flame-retardant polyamide resin is not higher than 2000ppm;
(2) Weighing the dried raw materials according to the formula proportion; uniformly mixing the environment-friendly flame-retardant polyamide resin, the flame retardant, the liquid crystal flame retardant, the synergistic flame retardant, the compatilizer, the antioxidant and the processing aid by using a high-speed mixer for later use, and weighing the filler according to the proportion for later use;
(3) And adding the resin and auxiliary agent mixed raw materials through a main feeding port of a double-screw extruder, adding a filling agent through a side feeding port of the double-screw extruder, and performing melt extrusion, granulation and drying treatment to obtain the environment-friendly flame-retardant polyamide composition.
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| CN114806155B (en) * | 2022-03-31 | 2024-01-23 | 上海化工研究院有限公司 | Double-antibody material and preparation method thereof |
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