CN114410108B - Halogen-free flame-retardant semi-aromatic polyamide composition, and preparation method and application thereof - Google Patents

Halogen-free flame-retardant semi-aromatic polyamide composition, and preparation method and application thereof Download PDF

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CN114410108B
CN114410108B CN202210095161.8A CN202210095161A CN114410108B CN 114410108 B CN114410108 B CN 114410108B CN 202210095161 A CN202210095161 A CN 202210095161A CN 114410108 B CN114410108 B CN 114410108B
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semi
halogen
aromatic
free flame
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CN114410108A (en
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陈跃民
陈原振
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Jiangsu Ginar Plastic Technology Co ltd
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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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

The invention discloses a halogen-free flame-retardant semi-aromatic polyamide composition, a preparation method and application thereof, wherein the composition comprises 35.0-65.0wt% of semi-aromatic polyamide, 10.0-25.0wt% of halogen-free flame retardant, 10.0-50.0wt% of reinforcing agent, 0.1-1.0wt% of calcium-based compound, 0.5-2.5wt% of phosphorus-containing epoxy resin, less than or equal to 5.0wt% of auxiliary agent, and the sum of components is 100wt%; wherein the semi-aromatic polyamide is a semi-crystalline polymer, the melting temperature is 280-340 ℃, and the halogen-free flame retardant is selected from dialkyl phosphinate or a mixture of dialkyl phosphinate and phosphite with the mass ratio of 9-99:1. The polyamide composition provided by the invention simultaneously meets the performance advantages of not lower than 280 ℃, good color stability, no degradation of mechanical properties, low corrosiveness and the like, and the product can be used as an electronic device for assembling a circuit board by using a surface-bonding lead-free welding technology.

Description

Halogen-free flame-retardant semi-aromatic polyamide composition, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a halogen-free flame-retardant semi-aromatic polyamide composition, and a preparation method and application thereof.
Background
The semi-aromatic polyamide is a polyamide polymer with an aromatic ring and an aliphatic chain in a molecular main chain, has excellent performance of the aromatic polyamide and good molding processability of the aliphatic polyamide, and can provide more excellent mechanical performance, electronic performance and high temperature resistance compared with the aliphatic polyamide, and the water absorption rate and the moisture absorption rate can be reduced by more than 50%. Therefore, the semi-aromatic polyamide is very suitable for electronic devices, especially in the field of electronic products requiring surface mounting technology under severe conditions of lead-free soldering.
In the field of electronic and electric products, a semi-aromatic polyamide material is required to have a flame retardant requirement of UL 94V-0 grade. Based on the promise of improving the environment and health of flame retardant products, halogen-free products that are completely free of halogen and red phosphorus have become increasingly popular. At present, the halogen-free flame retardant suitable for the semi-aromatic polyamide is mainly organic aluminum phosphinate, but the organic aluminum phosphinate has poor processing stability, is easy to degrade and discolor the polyamide composition during processing, and releases phosphorus-containing compound gas during degradation to corrode processing equipment and dies. The organic aluminum phosphinate composition can slowly release trace phosphorus compound gas in the later use process, and the high-temperature and high-humidity environment accelerates the release rate of the gas, so that the phosphorus compound can cause corrosion of metal elements contacted with the product to cause electrical performance failure. This problem is particularly pronounced with semi-aromatic polyamide compositions, because semi-aromatic polyamides have a higher melting point than other aliphatic polyamides.
In order to solve the problems of the organic aluminum phosphinate flame retardant, the adding proportion of the organic aluminum phosphinate is mainly reduced by adding a synergist, so that the negative influence degree caused by the flame retardant is reduced, but the improvement degree is limited. And most of the flame retardant synergists are inorganic matters such as zinc borate, boehmite, montmorillonite and the like, the inorganic matters have poor compatibility with semi-crystalline organic polymers, and excessive addition can obviously deteriorate the mechanical properties of the composition, and white fog precipitation is caused by being repelled to the surface of the product when molecular chains move and are recrystallized after the later moisture absorption of the polyamide. Patent publication number CN105745281B discloses a polyamide composition synergistically flame-retarded by melamine mono-amide and/or melamine di-amide, and an organophosphorus halogen-free flame retardant, the melting temperature of the polyamide resin of which is higher than 265 ℃, but the synthesis cost of melamine mono-amide and/or melamine di-amide is high and difficult to obtain; the publication CN102378784a discloses a flame retardant semiaromatic polyamide resin composition and especially manufactured articles comprising a semi-crystalline polyamide, an amorphous polyamide, at least one aluminium diethylphosphinate and/or aluminium methylethylphosphinate flame retardant, zinc borate and glass fibers of non-circular cross section, the composition having a high stiffness and hardness, low warpage, good appearance and reduced corrosive effects on melt processing equipment, but the disadvantage is that the addition of the amorphous polyamide results in a composition with a significantly reduced heat resistance, and in addition zinc borate in the composition, although having the effect of stabilizing the organophosphorus flame retardant, is also an additive which precipitates easily, which precipitates may affect the aesthetics and performance of the product. The patent application with publication number of CN101735609A discloses a halogen-free flame-retardant reinforced polyamide composition, which uses inorganic fillers such as zinc borate, zinc sulfide or aluminum oxide as flame-retardant synergist, can reduce the addition amount of organic phosphinate flame retardant, and additionally adds nano molecular sieve to absorb acidic substances released by halogen-free flame-retardant materials in the processing process, thereby improving the color stability of a finished product.
In the prior art, there is a lack of organic phosphinate-containing polyamide compositions which simultaneously meet the requirements of, for example, having a melting point of not less than 280 ℃, good color stability, no deterioration of the mechanical properties of the compositions, and low corrosiveness to melting equipment, molds and electronic metal parts.
Disclosure of Invention
The invention mainly aims to provide a halogen-free flame-retardant semi-aromatic polyamide composition.
Another object of the present invention is to provide a method for preparing the halogen-free flame retardant semiaromatic polyamide composition.
It is a further object of the present invention to provide the use of the halogen-free flame retardant semiaromatic polyamide composition and its articles in electronic devices.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a halogen-free flame-retardant semi-aromatic polyamide composition, which comprises the following components:
wherein the sum of the components (A) to (F) is 100% by weight.
Component (A) is a semiaromatic polyamide, which is a semi-crystalline polymer, and has a melting temperature of 280-340 ℃, preferably 300-330 ℃, characterized by Differential Scanning Calorimetry (DSC), and a heating and cooling rate of 10 ℃/min.
The semi-aromatic polyamide is selected from one or more than two of semi-aromatic polyamide homopolymers and/or semi-aromatic polyamide copolymers according to the structure; wherein:
when the semiaromatic polyamide is selected as a semiaromatic polyamide copolymer, the aromatic repeating unit ratio is not less than 55mol%;
when the semiaromatic polyamide is selected from a semiaromatic polyamide homopolymer and/or a semiaromatic polyamide copolymer blended in two or more, one of the semiaromatic polyamide homopolymer or semiaromatic polyamide copolymer is used as a main component and the content is not less than 70% of the total mass of the semiaromatic polyamide.
The aromatic repeating units in the semi-aromatic polyamide are selected from one or more monomers of aromatic diamine and aromatic dicarboxylic acid; wherein the aromatic diamine is selected from the group consisting of: m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 1, 4-bis (aminomethyl) naphthalene, 1, 5-bis (aminomethyl) naphthalene, 2, 6-bis (aminomethyl) naphthalene, 2, 7-bis (aminomethyl) naphthalene, 4' -diaminodiphenylmethane, 2-bis (4-aminophenyl) propane, 4' -diaminodiphenylsulfone, 4' -diaminodiphenylether;
the aromatic dicarboxylic acid is selected from the group consisting of: terephthalic acid, isophthalic acid, 1, 4-naphthalene dicarboxylic acid, 1, 5-naphthalene dicarboxylic acid, 2, 6-naphthalene dicarboxylic acid, 2, 7-naphthalene dicarboxylic acid, 1, 3-phenylene dioxydiacetic acid, 1, 4-phenylene dioxydiacetic acid, 4 '-oxydibenzoic acid, diphenylmethane-4, 4' -dicarboxylic acid, diphenylethane-4, 4 '-dicarboxylic acid, diphenylpropane-4, 4' -dicarboxylic acid, diphenylether-4, 4 '-dicarboxylic acid, diphenylsulfone-4, 4' -dicarboxylic acid, 4 '-biphenyl dicarboxylic acid, 4' -triphenyldicarboxylic acid.
The aliphatic repeating unit in the semi-aromatic polyamide is selected from one or more monomers of aliphatic dicarboxylic acid and aliphatic diamine, alicyclic diamine and lactam with no less than four carbon atoms, wherein the aliphatic dicarboxylic acid is selected from the group consisting of: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, preferably adipic acid;
the aliphatic diamine having not less than four carbon atoms is selected from the group consisting of: butanediamine, pentanediamine, ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecylenediamine, dodecamethylenediamine, tridecyldiamine, tetradecylenediamine, pentadecylenediamine, hexadecylenediamine, heptadecylenediamine, octadecanediamine, nonadecylenediamine, icosanediamine, 2-methyl-1, 8-octanediamine, 2, 4-trimethylhexamethylenediamine, 2, 4-trimethylhexamethylenediamine, preferably ethylenediamine;
the cycloaliphatic diamine is selected from the group consisting of: 1, 3-cyclohexyldiamine, 1, 4-cyclohexyldiamine, bis (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane, bis (3-methyl-4-aminocyclohexyl) methane, (3-methyl-4-aminocyclohexyl) propane, 1, 3-diaminomethylcyclohexane, 1, 4-diaminomethylcyclohexane, 5-amino-2, 4-trimethyl-1-cyclopentanemethylamine, 5-amino-1, 3-trimethylcyclohexanemethylamine, bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, norbornane dimethylamine;
the lactam is selected from the group consisting of: epsilon-caprolactam, enantholactam, undecanolactam, dodecanolactam, alpha pyrrolidone, alpha piperidone, preferably epsilon-caprolactam.
In an embodiment of the present invention, the semiaromatic polyamide includes, but is not limited to, semiaromatic polyamide and monomers, wherein the semiaromatic polyamide homopolymer includes, but is not limited to:
semi-aromatic polyamide homopolymers Monomer(s)
PA 4T Butanediamine and terephthalic acid
PA 6T Hexamethylenediamine and terephthalic acid
PA 9T Nonylenediamine and terephthalic acid
PA 10T Decanediamine and terephthalic acid
PA 12T Dodecadiamine and terephthalic acid
The semiaromatic polyamide copolymers include, but are not limited to:
semi-aromatic polyamide copolymer Monomer(s)
PA 4T/6T/66 Butanediamine, hexanediamine, adipic acid and terephthalic acid
PA 6T/66 Hexamethylenediamine, adipic acid terephthalic acid
PA 6T/6 Hexamethylenediamine, adipic acid and epsilon-caprolactam
PA 6T/6I Hexamethylenediamine, terephthalic acid and isophthalic acid
PA 6T/6I/66 Hexamethylenediamine, adipic acid, terephthalic acid and isophthalic acid
PA 6T/DT Hexamethylenediamine, 2-methylpentanediamine and terephthalic acid
PA 6T/10T Hexamethylenediamine, decamethylenediamine and terephthalic acid
It should be noted that, since the blending of different semiaromatic polyamides is liable to undergo an amide exchange reaction, resulting in a change in thermal properties, exhibiting a remarkable decrease in melting temperature and heat distortion temperature, the component (a) is preferably a single polymer from the viewpoint of application, and if two or more polymers are used for blending, the content of one polymer is 70% by weight or more based on the total content of the mixture, and the maximum melting temperature of the mixture is ensured to be not lower than 280 ℃.
The component (B) is a halogen-free flame retardant, and is selected from dialkyl phosphinate shown in the formula (I) or a mixture of dialkyl phosphinate shown in the formula (I) and phosphite shown in the formula (II) according to the mass ratio of 9-99:1;
in the formula (I), R 1 And R is 2 The same or different are respectively selected from linear or branched C1-C6 alkyl; m is selected from Mg, ca, al, sb, sn, ge, ti, zn, fe, zr, ce, bi, sr, mn, li, na, K and/or protonated nitrogen base; m is selected from integers from 1 to 4;
[HP(＝O)O2] 2- M m+ (II)
in formula (II), M is selected from Mg, ca, al, sb, sn, ge, ti, zn, fe, zr, ce, bi, sr, mn, li, na and/or K, and M is selected from integers from 1 to 4.
In the examples of the present invention, the halogen-free flame retardants of the above formulas (I) and (II) are described in patent CN103154110B, which are commercially available.
Component (C) is a reinforcing agent for improving the mechanical properties of the halogen-free flame retardant semiaromatic polyamide composition, which may be selected from glass fibers, or a mixture of glass fibers and glass microspheres.
The component (D) is a calcium-based compound, is selected from one or more than two of calcium oxide, calcium stearate, calcium carbonate and calcium hydroxide, can efficiently stabilize the halogen-free flame-retardant semi-aromatic polyamide composition, and is easy to obtain and low in cost, and raw materials are common substances.
Component (E) is a phosphorus-containing epoxy resin. The phosphorus content of the phosphorus-containing epoxy resin is 2.0 to 4.0wt%, and the phosphorus-containing epoxy resin is obtained by reacting 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) shown in a formula (III) or 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ) shown in a formula (IV) with epoxy resin, preferably DOPO-HQ phosphorus-containing epoxy resin, and the phosphorus-containing epoxy resin can be obtained by commercial purchase:
the component (F) is an auxiliary agent and can be one or a mixture of more than two of a colorant, a release agent, a heat stabilizer, a flow improver, a crystallization accelerator and a toughening agent.
The halogen-free flame-retardant semi-aromatic polyamide composition is obtained by melt blending processing through a double-screw extruder, wherein:
the twin-screw extruder has an L/D of 36 to 48, preferably an L/D of 40 to 44;
the processing temperature of the twin-screw extruder is 280-340 ℃, the screw rotating speed is 200-500rpm, and the temperature of the polymer melt is ensured to be within +/-10 ℃ of the melting temperature of the semi-aromatic polyamide at the die head position.
In the embodiment of the invention, the halogen-free flame retardant semi-aromatic polyamide composition is processed by referring to the process route shown in fig. 1, and specifically comprises the following steps: premixing the component (A), the component (D) and the component (F) by a mixer, metering the premixed material at a position (1), metering the component (E) at a position (2), and adding the component (B) and the component (C) at a position (3), wherein the position (1) represents a feed port interval, the position (2) represents a heating and melting interval, and the position (3) represents a heating and melting end interval.
In a preferred embodiment of the invention, adjusting the extruder screw combination controls the plasticizing speed of the composition, increasing/decreasing the plasticizing speed of the processed polymer by increasing/decreasing the number of shear elements in the combination, suitable for representative screw design requirements are given in: twin screw extruder and its use, geng Xiaozheng, editorial: chinese light industry press, 2003.1; plastic mixing Process and apparatus, [ Maillard (Todd, D.B.); zhan Maocheng, beijing: chemical industry Press 2002.8.
In the preferred embodiment of the invention, the plasticizing condition of the materials in the equipment is sampled and analyzed through an opening area of the double-screw extruder, the sampling is performed to perform cold pressing sample within 30 seconds, then the plasticizing degree of the materials is analyzed by statistically analyzing the proportion of the melted materials and the unmelted granular materials, the higher the proportion of the melted materials is, the higher the plasticizing degree is, the plasticizing degree of the materials in the corresponding area is particularly important for processing the polymer, the plasticizing degree of the materials in the corresponding area is not good for the performance of the composition, the plasticizing degree of the polymer in the position (2) is ensured to be 50% -70%, and the plasticizing degree of the polymer in the position (3) is ensured to be more than 80%; venting the extruder barrel openings at normal pressure between the position (2) and the position (3); and (3) pressurizing and exhausting the extruder charging barrel opening between the position (3) and the die, wherein the pressure range is 30-70cm-Hg.
In the embodiment of the invention, the melt of the double-screw extruder is extruded through a die, cooled through a water tank, cut into particles by a granulator, and the collected particles are dried to a water content of below 0.1% and packaged.
The invention also provides application of the halogen-free flame-retardant semi-aromatic polyamide composition and the product thereof in electronic devices, in particular application in electronic devices adopting a surface bonding technology to assemble circuit boards.
Compared with the prior art, the invention has the following beneficial effects:
(1) The phosphorus-containing epoxy resin is added in the invention, firstly, the added phosphorus-containing epoxy resin is an organic matter with a double-base structure, DOPO or DOPO-HQ structure of the phosphorus-containing epoxy resin has compatibility with flame retardants (diethyl aluminum phosphinate and aluminum phosphinate), and the epoxy resin has compatibility with semi-aromatic polyamide and a coupling agent coated by glass fibers, so that the compatibility of a system can be obviously improved after the phosphorus-containing epoxy resin is added. And secondly, the added phosphorus-containing epoxy resin has excellent flame retardant property and can play a role in flame retardant synergism. And thirdly, the epoxy resin is an excellent polyamide viscosity reducer, the processing characteristic of the composition is improved after the epoxy resin component is added, and the risk of degradation of the organic aluminum hypophosphite flame retardant is reduced due to the improvement of the processing characteristic.
(2) The invention introduces the stabilizer calcium-based compound, can efficiently stabilize the color and processing stability of the halogen-free flame-retardant semi-aromatic polyamide composition, and has the effect of optimizing the appearance characteristics, which is obviously superior to similar compounds of other elements (such as zinc, magnesium, sodium and the like), and antioxidants such as hindered phenol, hindered amine, phosphite and the like.
(3) The halogen-free flame-retardant semi-aromatic polyamide composition provided by the invention simultaneously meets the performance advantages of not lower than 280 ℃ of melting point, good color stability, no degradation of mechanical properties of the composition, low corrosiveness to metal elements of melting equipment, dies and electronic products and the like.
Drawings
FIG. 1 is a schematic view of a process for preparing a halogen-free flame retardant semi-aromatic polyamide composition in examples.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention are clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by a person skilled in the art without creative efforts, based on the described embodiments of the present invention fall within the protection scope of the present invention.
The following materials were used in the examples and comparative examples:
PA 9T refers to a homopolymer of monomers nonanediamine and terephthalic acid, with a melt temperature of 305 ℃.
PA10T refers to a homopolymer of monomers decanediamine and terephthalic acid, with a melting temperature of 316 ℃.
PA 6T/66 means a copolyamide of 6T/66 in a mass ratio of 65/35, with a melting temperature of 330 ℃.
PA 6T/6I/66 means a copolyamide of 6T/6I/66 in a mass ratio of 65/25/10, with a melting temperature of 310 ℃.
PA 6T/DT means a copolyamide of 6T/DT in a mass ratio of 50/50 and a melting temperature of 300 ℃.
PPA-MIX refers to a mixture of PA 9T, PA10T, PA T/66, PA 6T/6I/66 and PA 6T/DT according to the mass ratio of 20:20:20:20:20, and the mixture is mixed by Jiangsu Jin Lun plastic technology Co., ltd.
EXOLIT OP1230 refers to aluminum diethylphosphinate, manufactured by clariant corporation.
EXOLIT OP1400 refers to aluminum diethylphosphinate and aluminum hypophosphite Al 2 (HPO 3 ) 3 The mixture was produced by the company clariant at a mass ratio of 90:10.
GF means glass fibers, chopped, with a monofilament diameter of 10 μm.
GB refers to hollow glass beads and is a commercially available product.
CaO refers to calcium oxide, analytically pure grade.
CaSt refers to calcium stearate, analytically pure grade.
Ca(OH) 2 Refers to calcium hydroxide, analytical grade.
CaCO 3 Refers to calcium carbonate, analytically pure.
Ca-MIX is CaO, caSt, ca (OH) 2 And Ca 2 CO 3 The mixture was mixed in a ratio of 25:25:25:25 by Jiangsu Jin Lun plastics technologies Co.
ZnO refers to zinc oxide, analytically pure.
MgO refers to magnesium oxide, analytically pure.
Ma(OH) 2 Refers to magnesium hydroxide, analytically pure.
AlOOH refers to boehmite, a lamellar structure.
SEN-300A75 is DOPO-epoxy resin having a phosphorus content of 3.0% and produced by SHIN-A T & C company.
SEN-600M60 is DOPO-HQ-epoxy resin, having a phosphorus content of 3.8%, produced by SHIN-A T & C company.
SEN-250MPM80 is DOPO-HQ-epoxy resin, having a phosphorus content of 2.0%, manufactured by SHIN-A T & C company.
EPOXY DER 671 is bisphenol a EPOXY resin, manufactured by dow corporation.
BLACK PEARLS 880 refers to carbon BLACK, manufactured by cabot corporation.
RUGGOLEN H10 is a phosphorus antioxidant, available from Bulgerman.
Preparation method
The components were weighed according to the compositions shown in tables 1, 2 and 3, and then subjected to process settings according to the preparation process schematic shown in fig. 1.
Extruder screw nominal diameter: 35mm
Extruder screw aspect ratio: 44
The processing temperature range is as follows: 280-330 DEG C
Host rotation speed range: 300rpm
Feeding sequence: the semi-aromatic polyamide resin, the calcium-based compound, the auxiliary agent, the carbon black and other components are premixed by a mixer, then the premixed material is metered in a position (1), the phosphorus-containing epoxy resin is metered in a position (2), and the halogen-free flame retardant and the reinforcing agent are metered in a position (3).
Plasticizing control: and controlling the material processing plasticizing state according to the shearing elements in the adjusting screw combination.
And (3) exhausting: and (3) between the position (2) and the position (3), venting the extruder charging barrel opening at normal pressure, and between the position (3) and the die, pressurizing and venting the extruder charging barrel opening, wherein the pressure range is 30-70cm-Hg.
The melt of the double-screw extruder is extruded through a die, cooled through a water tank, cut into particles by a granulator, and the collected particles are dried to a water content of below 0.1% and packaged.
Plasticizing degree analysis
The plasticizing condition of the materials in the equipment is sampled through the opening area of the double-screw extruder, the sampling quantity is about 100g, the samples are subjected to cold pressing by a tablet press within 30 seconds, the tablet thickness is 3.0mm, then the proportion of the melted materials and the unmelted granular materials is analyzed by statistics, and the plasticizing degree of the materials is obtained by analysis.
Sample molding and conditioning
Sample molding and conditioning were performed as specified in ISO 16396-2, mold melt temperature 300-340 ℃, mold temperature 100-140 ℃, mechanical property testing placed the test pieces in an environment at 23 ℃ for conditioning for more than 16 hours, and ensuring that the test pieces had a moisture content of less than 0.2%, flammability testing performed the test pieces at two preconditioning conditions of 23 ℃/50% rh/48 hours and 70 ℃/168 hours, respectively.
Injection molding salivation test
The test equipment is a sea-sky MA2000II/700 type injection molding machine, a test sample is added into the injection molding machine, the temperature of the melt is heated to 340 ℃, the injection molding machine is operated to store the material to the maximum, then the material is loosened and stopped for 1min, and the melt flowing out of a nozzle is collected and weighed.
Mechanical property test
The tensile property test is carried out according to the method specified in ISO 527-2, the traction speed of a Type 1A test piece is 5mm/min, and the testing instrument is a ZWICK Z010 Type universal testing machine; the notched impact test was performed according to the method prescribed in ISO 179-1, with sample dimensions 80mm 10mm 4.0mm, notched A (machining), pendulum energy 2J, and the test instrument being an INSTRON 9050 type pendulum impact tester.
Flammability test
The V-stage vertical burning test was carried out according to the method prescribed in UL94, the test piece size was 125 mm. Times.13.0 mm. Times.0.8 mm, the burner burning power was 50W, the flame height was 20mm, and the test instrument was an ATLAS HVUL2 burning box.
Color difference value test
The color difference value test was carried out according to the method specified in ASTM D2244, the test piece size was 60 mm. Times.60 mm. Times.2.0 mm, a D65℃light source was used, and the test instrument was a type KONICA MINOLTA CM-5 spectrocolorimeter.
Thermal performance testing
The melting temperature is carried out according to the method specified in ISO 11357-3, the heating and cooling rate is 10 ℃/min, and the testing instrument is a TA Q10 differential scanning calorimeter.
The heat distortion temperature is carried out according to the method specified in ISO 75-2, the heating rate is 2 ℃/min, the load is 1.8MPa, and the testing instrument is an MST ZWK1302-B type heat distortion Vicat softening point tester.
The thermal weight loss is carried out according to the method specified in ISO 11358, the heating and cooling rate is 20 ℃/min, and the testing instrument is a TA Q50 thermal weight analyzer.
Accelerated corrosiveness test
A200 ml small-mouth conical flask is taken as a container, 100g of halogen-free flame-retardant semi-aromatic composition particles are added into the flask, 5ml of distilled water is added, silver/nickel 20 alloy strips with the cutting length of about 50mm are put into the conical flask to be paved on the surface of the particles, a bottle cap is covered and sealed, and the conical flask in the steps is put into an oven at 80 ℃ for 28 days and taken out. The appearance of the silver/nickel 20 alloy strips was then assessed by comparison.
Examples and comparative examples
Tables 1 to 3 list the composition behavior of each example.
Table 1 shows the composition and preparation method of the halogen-free flame retardant polyamide composition, and different processes are designed for the example 1, and the specific steps are as follows:
the screw combination shearing elements of the process 1 and the process 2 are fewer in number, the polymer plasticizing degree is lower, the mechanical property is lower, and the V-0 cannot be realized in the flame retardant grade; the screw combination shearing elements in the process 3 are the most, the polymer is basically completely plasticized in the middle section of the extruder, and the polymer has ideal flame retardant property under the process condition, but the mechanical property is deteriorated; process 4 controls the plasticization of the polymer at different locations of the extruder to a more reasonable level, and the final composition has the best combination of flame retardant and mechanical properties. Since the semi-crystalline semiaromatic has a melting point generally up to 300 ℃ or higher, it has been difficult to achieve good melt plasticization by virtue of the heating function of the extruder, mainly by virtue of the shearing elements providing suitable shear strength to achieve the plasticization function. The number of the shearing elements in the process 1 and the process 2 is smaller, the shearing strength of the screw combination is lower, and the polymer combination cannot be provided with enough distribution and dispersion mixing, so that the flame retardant effect of the composition is poor; meanwhile, the semi-aromatic polyamide is still in a particle state with a high proportion, so that the infiltration effect of the polymer and the glass fiber is poor, and the glass fiber is excessively sheared by particle/processing equipment, so that the mechanical property of the composition is deteriorated. Process 3 exhibits an excessive plasticizing effect, while the distribution and dispersion mixing effect of the flame retardant and the glass fibers is ensured, the semi-aromatic polyamide undergoes excessive shearing and heating in the extruder with a tendency to degrade, and the mechanical properties of the final composition are also consumed.
Table 2 shows the stability of the calcium-based compound in the composition with respect to color and processing stability, as follows:
after the calcium-based compound is added, the color fluctuation change of the injection molding test piece is small, and the casting quantity of the nozzle is low. In contrast, the Mg element compound, which is the same alkaline earth metal element, does not exhibit a similar effect, and the deterioration of mechanical properties of magnesium oxide to the polymer is remarkable, and the Zn element compound is known to stabilize red phosphorus better, but tests have found that the stabilizing effect on organic phosphorus is poor. Boehmite also contributes to improving the color and processing stability of the composition, but has drawbacks affecting the mechanical properties of the composition, in particular resulting in a significant decrease in impact strength. DOPO epoxy resins also improved the color and processing stability of the compositions to some extent with little impact on mechanical properties, impact strength being highest in the comparative examples.
Table 3 is a composition of the halogen-free flame retardant polyamide composition and its flammability, mechanical, thermal and corrosiveness tests, and the results of the evaluation of the flammability, mechanical, thermal and corrosiveness of the halogen-free flame retardant semiaromatic polyamide compositions of different combinations are as follows:
example 1, comparative example 1 and comparative example 10 are compared, example 1 is added with 0.2% analytically pure grade calcium oxide and 1.5% DOPO-HQ epoxy resin SEN-600M60, 15% flame retardant OP1230 is added; comparative example 1, with 16% flame retardant OP1230, was added without calcium oxide and phosphorous epoxy resin; as a result of the fact that 0.2% of analytically pure calcium oxide was added in comparative example 10 as in example 1, but the phosphorus-containing epoxy resin was changed to a normal bisphenol A epoxy resin, it was found that 16% of flame retardant was required in comparative example 1, whereas 15% of flame retardant was required in example 1, and that the flame retardant rating was only V-1 in comparative example 10, in which 15% of phosphorus-containing epoxy resin was added but no phosphorus-containing epoxy resin was compounded. According to the comparison results of the examples, 1 and the comparative examples 1 and 10, the phosphorus-containing epoxy resin can play a role in the synergistic halogen-free flame retardant of diethyl aluminum phosphinate, and the addition amount of the diethyl aluminum phosphinate can be reduced by partially replacing the diethyl aluminum phosphinate. In addition, according to the comparison result of the thermal weight loss temperature and the corrosiveness acceleration test, the addition of the calcium oxide and the DOPO-HQ epoxy resin SEN-600M60 obviously improves the thermal weight loss temperature of the composition and reduces the corrosiveness to metal elements.
In comparison with comparative example 11, comparative example 11 increased the proportion of DOPO-HQ epoxy resin SEN-600M60 from 1.5% to 5.0%. The comparison of the composition properties revealed that the mechanical properties of comparative example 11 were degraded by 10% or more and the heat distortion temperature was reduced by 19 ℃. From the comparison, it was confirmed that the excessive addition of the phosphorus-containing epoxy resin adversely affects the mechanical properties and thermal properties of the composition, and the ratio thereof was controlled at a reasonable level.
Examples 1 to 4 demonstrate typical combinations and performance properties of halogen-free flame retardant semiaromatic polyamide compositions at different filler contents.
The effect of the transamidation effect after blending a plurality of semi-aromatic polyamides was verified by comparing example 5 with comparative example 12. The polyamide in example 5 was about 70% based on PA 6T/66 and the semi-aromatic polyamide in comparative example 12 was a mixture of PA 9T, PA10T, PA T/66, PA 6T/6I/66& PA 6T/DT in a ratio of 20:20:20:20:20:20. As compared with the case of only adding a single semi-aromatic polyamide amine, the melting temperature is reduced by 10 ℃, the thermal deformation temperature is reduced by about 20 ℃, the thermal performance is still in an acceptable range, and the requirements of an application end can be met (the peak temperature of surface mounting lead-free welding is 255-280 ℃); in comparative example 12, the melting temperature and heat distortion temperature were significantly reduced compared to either of the individual components in the mixture, with heat distortion temperatures of only 138℃and quality which was not satisfactory for high temperature applications.
TABLE 1
Remarks: position (1) represents a feed port section, position (2) represents a section before heating and melting, and position (3) represents a heating and melting end section.
TABLE 2
TABLE 3 Table 3
Remarks: appearance evaluation: o=no significant change occurred; x = slight change; ×=significant change.
The foregoing is illustrative of a preferred embodiment of the present invention, but the present invention should not be limited to the disclosure of this embodiment. So that equivalents and modifications will fall within the scope of the invention, all within the spirit and scope of the invention as disclosed.

Claims (7)

1. The halogen-free flame-retardant semi-aromatic polyamide composition is characterized by comprising the following components:
wherein the sum of components (A) to (F) is 100wt%;
the semi-aromatic polyamide is a semi-crystalline polymer, the melting temperature is 280-340 ℃, and the semi-aromatic polyamide is selected from one or more than two of semi-aromatic polyamide homopolymers and/or semi-aromatic polyamide copolymers; wherein:
when the semiaromatic polyamide is selected as a semiaromatic polyamide copolymer, the aromatic repeating unit ratio is not less than 55mol%;
when the semiaromatic polyamide is selected from a semiaromatic polyamide homopolymer and/or a semiaromatic polyamide copolymer blended with two or more thereof, one of the semiaromatic polyamide homopolymer or semiaromatic polyamide copolymer is used as a main component and the content thereof is not less than 70% of the total mass of the semiaromatic polyamide;
the halogen-free flame retardant is selected from dialkyl phosphinate or a mixture of dialkyl phosphinate and phosphite according to the mass ratio of 9-99:1;
the phosphorus content of the phosphorus-containing epoxy resin is 2.0-4.0wt% and the phosphorus-containing epoxy resin is obtained by reacting 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or 10- (2, 5-dihydroxyphenyl) -10-hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide with epoxy resin.
2. The halogen-free flame retardant semiaromatic polyamide composition according to claim 1, characterized in that,
the aromatic repeating units of the semi-aromatic polyamide are selected from one or more monomers of aromatic diamines and aromatic dicarboxylic acids, the aromatic diamines being selected from the group consisting of: m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 1, 4-bis (aminomethyl) naphthalene, 1, 5-bis (aminomethyl) naphthalene, 2, 6-bis (aminomethyl) naphthalene, 2, 7-bis (aminomethyl) naphthalene, 4' -diaminodiphenylmethane, 2-bis (4-aminophenyl) propane, 4' -diaminodiphenylsulfone, 4' -diaminodiphenylether;
the aromatic dicarboxylic acid is selected from the group consisting of: terephthalic acid, isophthalic acid, 1, 4-naphthalene dicarboxylic acid, 1, 5-naphthalene dicarboxylic acid, 2, 6-naphthalene dicarboxylic acid, 2, 7-naphthalene dicarboxylic acid, 1, 3-phenylene dioxydiacetic acid, 1, 4-phenylene dioxydiacetic acid, 4 '-oxydibenzoic acid, diphenylmethane-4, 4' -dicarboxylic acid, diphenylethane-4, 4 '-dicarboxylic acid, diphenylpropane-4, 4' -dicarboxylic acid, diphenylether-4, 4 '-dicarboxylic acid, diphenylsulfone-4, 4' -dicarboxylic acid, 4 '-biphenyl dicarboxylic acid, 4' -triphenyldicarboxylic acid;
and/or the aliphatic repeating units of the semi-aromatic polyamide are selected from one or more monomers of aliphatic dicarboxylic acids and aliphatic diamines having not less than four carbon atoms, alicyclic diamines, lactams, the aliphatic dicarboxylic acids being selected from the group consisting of: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid;
the aliphatic diamine having not less than four carbon atoms is selected from the group consisting of: butanediamine, pentanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecylenediamine, dodecamethylenediamine, tridecyldiamine, tetradecanediamine, pentadecylenediamine, hexadecanediamine, heptadecylenediamine, octadecanediamine, nonadecylenediamine, icosanediamine, 2-methyl-1, 8-octanediamine, 2, 4-trimethylhexamethylenediamine, 2, 4-trimethylhexamethylenediamine;
the cycloaliphatic diamine is selected from the group consisting of 1, 3-cyclohexyldiamine, 1, 4-cyclohexyldiamine, bis (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane, bis (3-methyl-4-aminocyclohexyl) methane, (3-methyl-4-aminocyclohexyl) propane, 1, 3-diaminomethylcyclohexane, 1, 4-diaminomethylcyclohexane, 5-amino-2, 4-trimethyl-1-cyclopentanemethylamine, 5-amino-1, 3-trimethylcyclohexanemethylamine, bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, norbornane dimethylamine;
the lactam is selected from the group consisting of: epsilon-caprolactam, enantholactam, undecanolactam, dodecanolactam, alpha pyrrolidone, alpha piperidone.
3. The halogen-free flame retardant semiaromatic polyamide composition according to claim 1, characterized in that the semiaromatic polyamide homopolymer and monomer are selected from the compositions shown in the following table:
semi-aromatic polyamide homopolymers Monomer(s) PA 4T Butanediamine and terephthalic acid PA 6T Hexamethylenediamine and terephthalic acid PA 9T Nonylenediamine and terephthalic acid PA 10T Decanediamine and terephthalic acid PA 12T Dodecadiamine and terephthalic acid
The semiaromatic polyamide copolymer and monomer are selected from the compositions shown in the following table:
4. the halogen-free flame retardant semiaromatic polyamide composition according to claim 1, characterized in that,
the reinforcing agent is selected from glass fiber or a mixture of glass fiber and glass microsphere;
and/or the calcium-based compound is selected from one or more than two of calcium oxide, calcium stearate, calcium carbonate and calcium hydroxide;
and/or the auxiliary agent is selected from one or a mixture of more than two of coloring agent, release agent, heat stabilizer, flow improver, crystallization accelerator and toughening agent.
5. The method for producing a halogen-free flame retardant semiaromatic polyamide composition according to any of claims 1 to 4, characterized in that it is obtained by melt blending processing in a twin-screw extruder, wherein:
the L/D of the twin-screw extruder is 36-48;
the processing temperature of the twin-screw extruder is 280-340 ℃, the screw rotating speed is 200-500rpm, and the polymer melt temperature is within + -10 ℃ of the melt temperature of the semi-aromatic polyamide at the die position.
6. The process for producing a halogen-free flame retardant semiaromatic polyamide composition according to claim 5, characterized in that the component (A), the component (D) and the component (F) are premixed by a mixer, then the premixed material is metered in the inlet section of the twin-screw extruder, the component (E) is metered in the section before the heating and melting, the component (B) and the component (C) are metered in the section at the end of the heating and melting, the melt is extruded through a die, cooled by a water tank and cut into particles by a granulator, and the collected particles are dried to a water content of 0.1% or less.
7. Use of the halogen-free flame retardant semiaromatic polyamide composition according to any of claims 1 to 4 for assembling electronic devices of circuit boards by means of surface-mount lead-free soldering technique.
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