CN111393849B

CN111393849B - Polyphenylene sulfide resin composition and application thereof

Info

Publication number: CN111393849B
Application number: CN202010382117.6A
Authority: CN
Inventors: 曹艳霞; 韦业林; 赖华林; 邓冬颜
Original assignee: Shenzhen Halcyon New Materials Co ltd
Current assignee: Shenzhen Halcyon New Materials Co ltd
Priority date: 2020-05-08
Filing date: 2020-05-08
Publication date: 2023-07-04
Anticipated expiration: 2040-05-08
Also published as: CN111393849A

Abstract

The invention relates to a polyphenylene sulfide resin composition and application thereof, wherein the polyphenylene sulfide resin composition comprises the following components in percentage by mass: 20-65% of PPS resin, 20-60% of glass fiber, 0.1-3% of dispersing agent, 0.5-10% of stress releasing agent, 0.3-2.0% of antioxidant, 0.5-3.0% of lubricant and 0.5-10% of filling agent. According to the invention, the stress release agent is added into the PPS-glass fiber composite system, so that not only is the partial crystallization regularity of PPS destroyed, but also the free space volume among PPS molecules is increased, and the thermal stress and mechanical stress generated in the material processing process are released in time; further, the components of the resin composition are compounded according to a specific proportion, so that the problem of large internal stress of the glass fiber reinforced PPS engineering plastic is effectively solved, the stability of an electroplating line is improved, and good mechanical property, dielectric property and processing property are maintained.

Description

Polyphenylene sulfide resin composition and application thereof

Technical Field

The invention relates to the technical field of engineering plastics, in particular to a polyphenylene sulfide resin composition and application thereof.

Background

The antenna element is an element and a functional component in the communication base station, and has the main functions of guiding and amplifying electromagnetic waves, so that electromagnetic signals received by the antenna are stronger, the antenna element is an important element of the antenna, the consumption of the antenna is large, and the general structural design is complex. The traditional production and manufacturing process of the antenna oscillator adopts metal materials (aluminum alloy or zinc alloy) for die casting molding, however, as the antenna oscillator is often complicated in structure, the machining and molding processes of the metal materials are more, the difficulty is high, the precision is difficult to ensure, and the production cost of the product is high; and the metal material density is big, and the antenna quality is big in the antenna that gathers numerous antenna element, brings inconvenience for installation, transportation, and high accuracy, low weight and low cost's plastic antenna element is expected to become market mainstream gradually.

The integrated plastic vibrator has the advantages of high precision, high integration, low weight, low cost and the like, but how to realize an antenna circuit on a common plastic substrate with high reliability is a core technical difficulty. The integrated plastic vibrator needs to take the dielectric property, mechanical property, processing property and electroplating property of the material into consideration

At present, the plastic vibrator in the antenna industry is introduced into mass production by an LDS technology (laser direct structuring technology), and the main technology comprises the following steps: injection molding, laser etching, ultrasonic cleaning, rapid copper, chemical copper, acid cleaning, chemical nickel, chemical gold and the like. However, this process has the following disadvantages:

the LDS technology adopts LDS-LCP (laser direct structuring-thermoplastic liquid crystal polymer) material with the density of 1.81g/cm at present ³ The weight is larger, the material cost is high, the source of the raw materials of the LCP is less, the processing technology requirement is high, and the equipment requirement is high. The LDS-LCP material has very high requirements on the mold temperature, the barrel temperature, the injection speed, the molding cycle and the like of the injection molding process, the yield is generally 85%, and the injection molding process cost is high.

The intrinsic defect of the antenna element combining LDS functional plastic and metal material seriously hinders the large-scale application market demand of the antenna element in the 5G communication era, and related markets and researchers rapidly develop the second research and development direction and the direction of the antenna element of the integrated selective plating plastic antenna. Polyphenylene Sulfide (PPS) is the highest-calling-for-market integrated selective plating plastic antenna element substrate of the most market potential at present. The PPS resin has low molding shrinkage, good creep resistance and good dimensional stability; is the material base material with the most market potential of the integrated antenna element. PPS is chemically named polyphenylene sulfide or poly-p-phenylene sulfide. The linear polyphenylene sulfide resin is a crystalline polymer, and has a chemical structural formula:

because its molecular chain is a rigid structure formed from benzene rings connected by sulfur atom, it possesses some unique properties, not only possesses the properties of general engineering plastics, but also possesses high thermal stability, excellent chemical corrosion resistance, good fire resistance and non-toxic property. The product can be formed by various methods, can be precisely formed, and can be electroplated to be used as a high-temperature resistant structural material, a high-temperature resistant insulating material and the like.

However, due to the molecular structure characteristics of PPS, the glass fiber reinforced PPS engineering plastic has the defects of poor processing performance, flash of injection molding, obvious flash, large internal stress, easy stress cracking in the use process, easy falling of an electroplating circuit bonding layer and the like, and the electromagnetic signal emission and transmission can be influenced after the electroplating circuit layer falls off, so that the application performance of the PPS engineering plastic as an antenna oscillator substrate is influenced.

CN102904010a discloses an antenna oscillator and a manufacturing method thereof, which are an antenna oscillator using plastic as a main material and a manufacturing method thereof, wherein the main body of the antenna oscillator is an injection molded plastic body with an antenna oscillator structure and a size, the plastic is one of ABS, PP, PA, PC, POM, PPS, a copper plating layer with the thickness of 3-25 μm is electroplated on the outer surface of the plastic body, and a silver plating layer or a tin plating layer with the thickness of 2-20 μm is electroplated on the copper plating layer. The manufacturing method comprises injection molding, electroplating and welding. The invention uses plastic to replace steel plastic vibrator, and through electroplating and low temperature welding, all tests installed in the antenna can reach the original aluminum vibrator standard, and the antenna manufacturing cost and the antenna overall quality are greatly reduced. However, PPS has the disadvantages of large internal stress, easy cracking, easy falling of the plating line bonding layer, and poor plating performance and workability.

CN108425113a discloses a vibrator and a manufacturing method thereof, the manufacturing method comprises the following steps: s1, preparing a vibrator body with a preset structure by injection molding, wherein raw materials of the vibrator body comprise glass fiber reinforced polyphenylene sulfide or liquid crystal polymer; s2, performing mechanical roughening treatment on the surface of the vibrator body, and performing ultrasonic cleaning; s3, carrying out chemical nickel plating on the vibrator body, and forming a chemical nickel layer on the surface of the vibrator body; s4, forming a barrier line on the chemical nickel layer by laser etching so as to separate an electroplating area and a non-electroplating area on the surface of the vibrator body; s5, electroplating copper to form a copper plating layer on the electroplating area of the vibrator body; s6, degrading chemical nickel treatment, namely removing a chemical nickel layer on an electroless plating area of the vibrator body; s7, electroplating tin, namely forming an electroplating tin layer on the copper plating layer and carrying out tin protection treatment. The invention discloses a vibrator body which takes PPS as a vibrator body, an electroplating circuit bonding layer is easy to fall off, and electromagnetic signal emission and transmission can be influenced after the electroplating circuit layer falls off, so that the performance of the vibrator is influenced.

Therefore, there is a need in the art to develop a PPS resin composition having plating properties, mechanical properties, dielectric properties, and processability.

Disclosure of Invention

The invention aims to provide a polyphenylene sulfide resin composition, in particular to a polyphenylene sulfide resin composition for a 5G antenna element substrate, which can improve the binding force between a plating layer of a plating circuit and the substrate, is used for the 5G antenna element substrate, can improve the stability of the plating circuit and has good mechanical property, dielectric property and processing property.

To achieve the purpose, the invention adopts the following technical scheme:

the invention provides a polyphenylene sulfide resin composition, which comprises the following components in percentage by mass:

the invention provides a PPS resin composition, wherein a stress release agent is added into a PPS-glass fiber system, the addition of the stress release agent damages the crystallization of PPS, and meanwhile, the PPS resin composition is compounded with other components according to a specific proportion, so that the problem of large internal stress of glass fiber reinforced PPS engineering plastics is effectively solved, the stability of an electroplating line is improved, and meanwhile, good mechanical property, dielectric property and processability are maintained, and the PPS resin composition has a very high application value.

The PPS resin is added in an amount of 20 to 65%, for example, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 63%, etc.;

the addition amount of the glass fiber is 20-60%, such as 25%, 30%, 35%, 40%, 45%, 50%, 55%, 58%, etc.;

the dispersant is added in an amount of 0.1 to 3%, for example, 0.2%, 0.4%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.6%, 2.8%, etc.;

the stress releasing agent is added in an amount of 0.5 to 10%, for example, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, etc.;

the antioxidant is added in an amount of 0.3-2.0%, for example, 0.4%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, etc.;

the amount of the lubricant added is 0.5 to 3.0%, for example, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.6%, 2.8%, etc.;

the filler is added in an amount of 0.5 to 10%, for example, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, etc.

The PPS characteristics are as follows:

(1) General performance: PPS is a white to tan-looking, high crystallinity, hard, brittle polymer with a relative density of 1.3 for pure PPS. PPS has very small water absorption, generally about 0.03%. PPS has good flame retardance, and the oxygen index of the PPS is as high as more than 44%; compared with other plastics, the flame-retardant plastic belongs to high flame-retardant materials in plastics (the oxygen index of pure polyvinyl chloride is 47%, polysulfone is 30%, nylon-66 is 29%, polyphenyl ether is 28%, and polycarbonate is 25%).

(2) Mechanical properties: the mechanical properties of pure PPS are not high, in particular the impact strength is relatively low. The glass fiber can greatly improve the impact strength and the tensile strength, the tensile strength is more than 170MPa, the bending strength is more than 220MPa, and the notch impact strength is more than 16MPa after being reinforced. PPS has very high rigidity and is rarely used in engineering plastics. The flexural modulus of pure PPS can reach 3.8Gpa, and the flexural modulus of the modified PPS can reach 12.6Gpa after inorganic filling modification, and the flexural modulus is increased by more than 5 times. Whereas polyphenylene oxide (PPO), which is known as rigid, is only 2.55Gpa and pc is only 2.1Gpa. PPS has excellent creep and fatigue resistance, with good creep resistance under load. The surface hardness is high, and the Rockwell hardness is more than 100HR; the wear resistance is high, the wear amount is only 0.04g when the wear resistance is 1000 revolutions, and the wear resistance can be greatly improved by filling the lubricating agent such as fluorine resin, molybdenum disulfide and the like, and the friction coefficient is 0.01-0.02.PPS also has some self-wettability. The mechanical properties of PPS are less sensitive to temperature.

(3) Thermal properties: PPS has excellent thermal properties, with a melting point exceeding 280 ℃, a heat distortion temperature exceeding 260 ℃, short-term tolerance to 260 ℃, and long-term use at 200 ℃. Degradation in air at 700 c and inert gas at 1000 c still maintains 40% by weight. The heat distortion temperature of the special modified variety can reach more than 350 ℃.

(4) Electrical properties: the electrical performance of PPS is very outstanding, and compared with other engineering plastics, the PPS has lower dielectric constant and dielectric loss tangent value and little change in larger frequency, temperature and temperature range; PPS is arc resistant, comparable to thermosets. PPS is commonly used in electrical insulation materials, and can be used in amounts of about 30%.

(5) Chemical resistance: one of the biggest characteristics of PPS is that the PPS has good chemical resistance, and the chemical stability is inferior to F4; PPS is stable to large polyacids, esters, ketones, aldehydes, phenols, aliphatic hydrocarbons, aromatic hydrocarbons, chlorinated hydrocarbons, and the like, and no solvent capable of dissolving polyphenylene sulfide at 200 ℃ or below has been found yet, and is extremely resistant to inorganic acids, bases, and salts. Not resistant to chlorinated biphenyl, oxidizing acid, oxidizing agent, concentrated sulfuric acid, concentrated nitric acid, aqua regia, hydrogen peroxide, sodium hypochlorite, etc.

(6) PPS has good radiation resistance, and the radiation resistance reaches 1 multiplied by 10 ⁸ Gy is an incomparable new material for other engineering plastics, and is the only ideal excellent material for resisting radiation in the fields of electronics, electricity, machinery, instruments, aviation, aerospace, military and the like, in particular atomic bullets and middle bullets.

(7) The dimensional stability is good: the molding shrinkage is very low, less than 0.0025%, the absorptivity is less than 0.05%, and the linear thermal expansion coefficient is also small. And still exhibit good dimensional stability under high temperature, high humidity conditions. Therefore, the method has wide application in various aspects of machinery, chemical industry, instruments, meters, aviation, spaceflight, ships and the like.

(8) The electrical properties are excellent: polyphenylene sulfide has excellent electrical properties under high temperature, high humidity and high frequency conditions, and has volume resistivity of 1×10 ¹⁶ Omega cm, surface resistivity of 1X 10 ¹⁵ Omega, electrical strength>18KV/mm。

(9) The flame retardant has flame retardance: the flame retardance of the polyphenylene sulfide can reach UL94-0 grade, and the oxygen index (LOI) is more than 57 percent. The chemical structure of the polyphenylene sulfide itself makes the polyphenylene sulfide have good difficult-to-burn performance, and no flame retardant is needed to be added.

Preferably, the polyphenylene sulfide resin composition comprises the following components in percentage by mass:

the amount of the heat stabilizer added is 0.1 to 2.0%, for example, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, etc.

According to the invention, the heat stabilizer is preferably added into the PPS composition, so that the processability of the material is improved, the application stability of the performance is improved, the processability of the material is excellent, and the material has better durability.

preferably, the stress release agent comprises any one or at least two of polyolefin thermoplastic elastomer, polyolefin thermoplastic elastomer grafted glycerol methacrylate copolymer, ethylene-acrylate-glycerol methacrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-acrylic acid copolymer, ABS resin and high rubber powder thereof, ASA resin and high rubber powder thereof, styrene thermoplastic elastomer or styrene thermoplastic elastomer grafted maleic anhydride copolymer, preferably any one or at least two of ABS resin and high rubber powder thereof, ASA resin and high rubber powder thereof, styrene thermoplastic elastomer or styrene thermoplastic elastomer grafted maleic anhydride copolymer.

The ABS resin is acrylonitrile-butadiene-styrene copolymer, and the ASA resin is an impact modified resin formed by copolymerizing styrene, acrylonitrile, acrylic rubber and other ternary polymers.

Preferably, the styrenic thermoplastic elastomer is a hydrogenated styrenic thermoplastic elastomer.

Preferably, the styrenic thermoplastic elastomer comprises any one or a combination of at least two of styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS) or styrene-ethylene-propylene block copolymer (seps), preferably styrene-ethylene-butylene-styrene block copolymer (SEBS) and/or styrene-ethylene-propylene block copolymer (seps).

The styrene thermoplastic elastomer is preferably used as a stress release agent, particularly SEBS and SEPPS, and compared with ABS, ASA and the like, the comprehensive performance of electroplating stability, mechanical property, dielectric property and processability can be further improved.

Preferably, the styrenic thermoplastic elastomer grafted maleic anhydride copolymer comprises any one or at least two of styrene-butadiene-styrene (SBS) grafted maleic anhydride copolymer, styrene-isoprene-styrene (SIS) grafted maleic anhydride copolymer, styrene-ethylene-butylene-styrene (SEBS) grafted maleic anhydride copolymer, or styrene-ethylene-propylene (seps) grafted maleic anhydride copolymer, preferably styrene-ethylene-butylene-styrene (SEBS) grafted maleic anhydride copolymer.

The invention further preferably takes the SEBS grafted maleic anhydride copolymer as a stress release agent, introduces partial polar functional groups (maleic anhydride), and is beneficial to improving the binding force between the plating layer of the electroplating circuit and the substrate and improving the electroplating stability.

Preferably, the topology of the styrenic thermoplastic elastomer comprises a linear structure or a star structure.

Preferably, the stress releasing agent accounts for 15% or less, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or the like, preferably 3 to 10% by mass of the PPS resin.

The invention preferably selects the addition amount (especially 3-10%) of the specific stress release agent, in the range, the comprehensive performance of electroplating stability, mechanical property, dielectric property and processing property can be improved to the greatest extent, the addition amount of the internal stress release agent is too large to easily reduce the rigidity of the material, and the stress release is too small to be insufficient.

Preferably, the filler comprises any one or a combination of at least two of a sheet filler, a lamellar filler or a microfibrous filler, preferably a microfibrous filler.

Preferably, the microfibrous filler comprises whisker-like filler.

The filler with the whisker structure is preferably selected, and the addition of the filler with the special form further improves the dielectric property of the material, reduces the warpage of the material and is beneficial to the release and stability of the internal stress of the material on the premise of not obviously reducing the mechanical property, the processing property and the heat resistance of the material. The amount of filler added should not be excessive, and the particle size should be controlled within a certain range.

Preferably, the filler comprises any one or a combination of at least two of talc, kaolin, calcium carbonate whiskers, calcium sulfate whiskers, magnesium sulfate whiskers or wollastonite fibers, preferably any one or a combination of at least two of calcium carbonate whiskers, calcium sulfate whiskers or magnesium sulfate whiskers.

Preferably, the particle size of the sheet-like filler or lamellar filler is each independently 800 to 10000 mesh, for example 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, etc., preferably 1250 to 7000 mesh.

Preferably, the whiskers have an aspect ratio of (10-100): 1, e.g., 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, etc., preferably (30-70): 1.

Preferably, the whiskers have a diameter of 0.5-5 μm, e.g., 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, etc.

Preferably, the PPS resin includes linear PPS.

Preferably, the PPS resin has a Melt Flow Rate (MFR) of 20 to 500g/10min at 316℃under 5kgf, for example 50g/10min, 100g/10min, 150g/10min, 200g/10min, 250g/10min, 300g/10min, 350g/10min, 400g/10min, 450g/10min, etc., preferably 50 to 350g/10min. The above MFR values are measured according to ASTM D1238-86.

Preferably, the glass fibers comprise continuous wound long fibers and/or chopped glass fibers. Among them, continuous winding of long fibers is a concept well known to those skilled in the art, as opposed to the concept of chopped fibers.

Preferably, the glass fiber has a circular, flat or diamond-shaped cross section.

Preferably, the glass fibers have an average diameter of 4 to 15 μm, for example 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, etc., preferably 6 to 11 μm.

Preferably, the glass fibers comprise round section glass fibers having an average diameter of 7-11 μm.

Preferably, the dispersing agent comprises any one or at least two of silicone, cage-like silsesquioxane (POSS) and a carrier thereof, long carbon chain amide compound (with C8-C40 carbon number) or ionomer, preferably cage-like silsesquioxane and a carrier thereof. POSS supports refer to substances such as silica, titania, silicates having POSS compounds on their surface.

Preferably, the antioxidant comprises a complex of a hindered phenolic antioxidant and a phosphite antioxidant.

Preferably, the mass ratio of hindered phenolic antioxidant to phosphite antioxidant is from 2:1 to 1:4, such as 2:2, 2:3, 2:4, 2:5, 2:6, 2:7, etc.

Preferably, the hindered phenol antioxidant comprises any one or at least two of a polyhydric hindered phenol antioxidant, a thio hindered phenol antioxidant or an asymmetric hindered phenol antioxidant.

Specifically, the hindered phenol antioxidant may be selected from basf 1010, 245, 1098, CA, etc.; 3114, 3125, 1790, 330, etc. from cyante company; GA-80, BBMC, AO-80 series antioxidant of Sumitomo and ADK company; and combinations of at least two of these antioxidants.

Preferably, the phosphite antioxidant has a structure shown in a formula I;

in formula I, R' is selected from alkyl or aryl, preferably C1-C25 (e.g., C2, C5, C6, C8, C10, C12, C14, C16, C18, C20, C22, C24, etc.) alkyl or C6-C12 (e.g., C8, C10, etc.) aryl.

Specifically, the phosphite antioxidant includes, but is not limited to, one or a combination of at least two of 168, 618, 619, P-EPQ, 626, 627, PEP36, 9228.

Preferably, the heat stabilizer comprises any one or at least two of long carbon chain fatty acid salt (the carbon number is C12-C40), organic tin compound, epoxy compound or hydrotalcite.

Preferably, the long carbon chain fatty acid salt comprises any one or at least two of calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, barium stearate, calcium laurate, barium laurate or zinc laurate.

Preferably, the organotin compound comprises any one or a combination of at least two of laurate organotin, maleate organotin or thiol organotin, preferably any one or a combination of at least two of dibutyltin dilaurate, methyltin mercaptide, dioctyl dimaleate, dioctyl tin dilaurate or dioctyl dimaleate.

Preferably, the epoxy compound includes any one or a combination of at least two of epoxidized soybean oil, epoxidized fatty acid ester, bisphenol a diglycidyl ether, bisphenol F diglycidyl ether, glycidyl ether of phenolic resin, glycidyl ether of tetraphenylethane, alicyclic epoxy resin, triglycidyl trimellitate, or diglycidyl terephthalate.

Preferably, the lubricant comprises any one or a combination of at least two of a hyperbranched polymer, a silicone-based lubricant or an amide compound, preferably a combination of a hyperbranched polymer and a silicone-based lubricant.

The hyperbranched polymer includes, but is not limited to, any one or a combination of at least two of Hyper 100, hyper181, CYD701 series, CYD816, CYD 818.

The silicone-based lubricant includes, but is not limited to, any one or a combination of at least two of TEGOMER E525, TEGOMER H-Si 6440P, RM-7105, RM4-7051, RM 4-7081.

The amide compound may be selected from any one or a combination of at least two of oleamide, stearic acid amide, erucamide, EBS and TAF series.

The preparation method of the polyphenylene sulfide resin composition provided by the invention comprises the following steps:

(1) Weighing PPS resin, adding a formula amount of dispersing agent, stress release agent, antioxidant and lubricant, and uniformly premixing to obtain a premix; the premix is fed into a twin-screw extruder which has been preheated to a specific processing temperature;

(2) And (3) feeding glass fiber and microfibrous filler with the formula amount into an extruder by side feeding, carrying out melt blending, extrusion granulation, bracing, cooling and performance detection to obtain the polyphenylene sulfide engineering plastic particles.

In one embodiment of the present invention, the preparation flow of the polyphenylene sulfide resin composition is shown in FIG. 1.

Preferably, in step (2), the heating temperature of the extruder is as follows: first 160-220 ℃, second 210-240 ℃, third 230-280 ℃, fourth 230-280 ℃, fifth 230-280 ℃, sixth 230-280 ℃ and head 240-270 ℃.

Another object of the present invention is to provide an application of the polyphenylene sulfide resin composition according to one of the objects, wherein the polyphenylene sulfide resin composition is used for a 5G antenna element substrate.

Compared with the prior art, the invention has the following beneficial effects:

The PPS resin composition provided by the invention has the hundred-lattice test results of 1-3 and the impact strength of 14-18KJ/m ² Tensile strength of 94-135MPa, flexural modulus of 7610-10300MPa, vicat softening point of 253-263 ℃, dielectric strength of 13-15kV/mm, dielectric constant of 3.8-4.1GHz, and low-temperature notch impact strength of 12-16KJ/m ² Is close to notch impact at normal temperature.

Drawings

Fig. 1 is a flowchart of the preparation of a polyphenylene sulfide resin composition according to an embodiment of the present invention.

Detailed Description

The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.

PPS resins used in the following examples and comparative examples were purchased from new products.

Example 1

The present example provides a PPS resin composition, the formulation of which is as follows:

the preparation method comprises the following steps:

(2) The side feeding is to put glass fiber and filler with the formula amount into an extruder for melt blending, extrusion granulation, bracing, cooling and performance detection to obtain polyphenylene sulfide engineering plastic particles;

in the step (2), the heating temperature of the extruder is as follows: one zone 200 ℃, two zones 220 ℃, three zones 250 ℃, four zones 250 ℃, five zones 250 ℃, six zones 250 ℃ and a machine head 260 ℃.

Example 2

the preparation method is the same as in example 1.

Example 3

the preparation method is the same as in example 1.

Example 4

the preparation method is the same as in example 1.

Example 5

The difference from example 2 is that the amount of the PPS resin added was 62% without adding a heat stabilizer.

Example 6

The difference from example 2 was that the amount of YH-503 added was 1%, the amount of YH-602T added was 1%, the amount of PPS resin added was 61.7%, and the weight percentage of the stress releasing agent to the PPS resin was 3.2%.

Example 7

The difference from example 2 was that the amount of YH-503 added was 3%, the amount of YH-602T added was 3%, the amount of PPS resin added was 57.7%, and the weight percentage of the stress releasing agent to the PPS resin was 10.4%.

Example 8

The difference from example 2 was that the amount of YH-503 added was 4%, the amount of YH-602T added was 4.3%, the amount of PPS resin added was 55.4%, and the weight percentage of the stress releasing agent to the PPS resin was 15.0%.

Comparative example 1

The difference from example 1 is that no heat stabilizer, no stress releasing agent and no filler are added.

Comparative example 2

The difference from example 2 is that the stress releasing agent was not added and the added amount of PPS resin was 63.7%.

Comparative example 3

The difference from example 2 was that the amount of YH-503 added was 0.1%, the amount of YH-602T added was 0.2% and the amount of PPS resin added was 63.4%.

Comparative example 4

The difference from example 2 was that the amount of YH-503 added was 5%, the amount of YH-602T added was 5%, the amount of PPS resin added was 53.7%, and the weight percentage of the stress releasing agent to the PPS resin was 18.6%.

Performance test:

the PPS resin compositions obtained in the above examples and comparative examples were tested as follows:

(1) According to the standard, the impact strength (ISO 180), tensile strength (ISO 527), flexural modulus (ISO 178), vicat softening point (ISO 306), dielectric strength (taking at least 5 points under each test condition of each sample plate, taking the average value of the rest of the obvious abnormal data, and referring to the standard IEC 60249-1-2013) and dielectric constant (taking at least 5 points under each test condition of each sample plate, taking the average value of the rest of the obvious abnormal data);

(2) Performing a hundred-cell experiment according to standard GBT9286-1998, performing (taking at least 5 points under each test condition of each sample plate) test on each sample, recording a minimum value and a maximum value, wherein the higher the number is, the lower the adhesion of a plating layer to a substrate is;

(3) The bars were first frozen at-30 ℃ for 24 hours and immediately after removal tested for notched impact strength, and tested according to standard (ISO 180) to obtain low temperature notched impact strength.

The results of the performance test are shown in Table 1.

TABLE 1

The range values in table 1 were obtained by multiple measurements.

As is clear from Table 1, the PPS resin composition of the present invention has excellent plating stability, and also has good mechanical properties, dielectric properties and processability, wherein the plating stability is 1-3, and the impact strength is 14-18KJ/m ² The tensile strength is 94-135MPa, the flexural modulus is 7610-10300MPa, the Vicat softening point is 253-263 ℃, the dielectric strength is 13-15kV/mm, the dielectric constant is 3.8-4.1GHz, and the low-temperature notch impact strength is 12-16KJ/m ² 。

The heat stabilizer, the stress release agent and the filler are not added in comparative example 1, the stress release agent is not added in comparative example 2, the addition amount of the stress release agent in comparative example 3 is not in the range of 0.5-10%, the mass percentage of the stress release agent in comparative example 4 is higher than 15% of that of the PPS resin, and the stability of the electroplated layer in comparative examples 1-4 is poorer than that of the electroplated layer in the examples, so that the problem of large internal stress of the PPS resin is effectively solved and the stability of the electroplated layer is improved by adding the stress release agent with specific content and compounding with other components.

As is clear from comparative examples 2 and examples 6 to 8, when the weight percentage of the stress releasing agent to the PPS resin is in the range of 3 to 10%, the plating properties of the material can be further improved (examples 2, 6 and 7).

The applicant states that the detailed method of the present invention is illustrated by the above examples, but the present invention is not limited to the detailed method described above, i.e. it does not mean that the present invention must be practiced in dependence upon the detailed method described above. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims

1. The application of the polyphenylene sulfide resin composition in the 5G antenna element base material is characterized by comprising the following components in percentage by mass:

PPS resin 30-60%

30-50% of glass fiber

0.3 to 1.5 percent of dispersing agent

Stress releasing agent 1-5%

Antioxidant 0.5-2.0%

0.5 to 2.0 percent of heat stabilizer

1-3% of lubricant

1-5% of filler;

the stress release agent accounts for 3-5% of the PPS resin by mass;

the stress release agent is any one or at least two of polyolefin thermoplastic elastomer, polyolefin thermoplastic elastomer grafted glycidyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-acrylic ester-methyl acrylate copolymer, ethylene-methyl acrylic acid copolymer, ethylene-acrylic acid copolymer, ABS resin and high rubber powder thereof, ASA resin and high rubber powder thereof, styrene thermoplastic elastomer or styrene thermoplastic elastomer grafted maleic anhydride copolymer;

the filler is whisker filler.

2. The use according to claim 1, wherein the stress releasing agent is selected from any one or at least two of ABS resin and its high rubber powder, ASA resin and its high rubber powder, styrene thermoplastic elastomer or styrene thermoplastic elastomer grafted maleic anhydride copolymer.

3. Use according to claim 1, wherein the styrenic thermoplastic elastomer is a hydrogenated styrenic thermoplastic elastomer.

4. The use according to claim 1, wherein the styrenic thermoplastic elastomer comprises any one or a combination of at least two of a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a styrene-ethylene-butylene-styrene block copolymer or a styrene-ethylene-propylene block copolymer.

5. Use according to claim 4, characterized in that the styrenic thermoplastic elastomer is selected from styrene-ethylene-butylene-styrene block copolymers and/or styrene-ethylene-propylene block copolymers.

6. The use according to claim 1, wherein the styrenic thermoplastic elastomer grafted maleic anhydride copolymer comprises any one or a combination of at least two of styrene-butadiene-styrene grafted maleic anhydride copolymer, styrene-isoprene-styrene grafted maleic anhydride copolymer, styrene-ethylene-butylene-styrene grafted maleic anhydride copolymer, or styrene-ethylene-propylene grafted maleic anhydride copolymer.

7. Use according to claim 6, characterized in that the styrenic thermoplastic elastomer grafted maleic anhydride copolymer is selected from styrene-ethylene-butylene-styrene grafted maleic anhydride copolymers.

8. The use according to claim 1, wherein the topology of the styrenic thermoplastic elastomer comprises a linear structure or a star structure.

9. The use according to claim 1, wherein the filler is selected from any one or a combination of at least two of calcium carbonate whiskers, calcium sulfate whiskers, or magnesium sulfate whiskers.

10. The use according to claim 1, wherein the whisker has an aspect ratio of (10-100): 1.

11. The use according to claim 10, wherein the whisker has an aspect ratio of (30-70): 1.

12. The use according to claim 1, characterized in that the whisker has a diameter of 0.5-5 μm.

13. The use according to claim 1, wherein the PPS resin comprises linear PPS.

14. The use according to claim 1, wherein the PPS resin has a melt flow rate of 20 to 500g/10min at 316 ℃/5 kgf.

15. The use according to claim 14, wherein the PPS resin has a melt flow rate of 50-350g/10min at 316 ℃/5 kgf.

16. Use according to claim 1, characterized in that the glass fibres comprise continuous wound long fibres and/or chopped glass fibres.

17. The use according to claim 1, wherein the glass fiber has a circular, flat or diamond-shaped cross section.

18. Use according to claim 1, characterized in that the glass fibres have an average diameter of 4-15 μm.

19. Use according to claim 18, characterized in that the glass fibres have an average diameter of 6-11 μm.

20. The use according to claim 19, wherein the glass fibers comprise round section glass fibers having an average diameter of 7-11 μm.

21. The use according to claim 1, wherein the dispersant comprises any one or a combination of at least two of silicone, cage silsesquioxane and its carrier, long carbon chain amide compound or ionomer.

22. The use according to claim 21, wherein the dispersant is a cage silsesquioxane and its carrier.

23. The use according to claim 1, wherein the antioxidant comprises a complex of a hindered phenolic antioxidant and a phosphite antioxidant.

24. The use according to claim 23, wherein the mass ratio of hindered phenolic antioxidant to phosphite antioxidant is from 2:1 to 1:4.

25. The use of claim 23, wherein the hindered phenolic antioxidant comprises any one or a combination of at least two of a polyhydric hindered phenolic antioxidant, a thio hindered phenolic antioxidant, or an asymmetric hindered phenolic antioxidant.

26. The use according to claim 23, wherein the phosphite antioxidant has the structure of formula I;

；

i is a kind of

In formula I, R' is selected from alkyl or aryl.

27. The use according to claim 26, wherein in formula I, R' is selected from C1-C25 alkyl or C6-C12 aryl.

28. The use according to claim 1, wherein the heat stabilizer comprises any one or a combination of at least two of a long carbon chain fatty acid salt, an organotin compound, an epoxy compound or hydrotalcite.

29. The use according to claim 28, wherein the long carbon chain fatty acid salt comprises any one or a combination of at least two of calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, barium stearate, calcium laurate, barium laurate or zinc laurate.

30. The use according to claim 28, wherein the organotin compound comprises any one or a combination of at least two of laurate organotin, maleate organotin, or thiol organotin.

31. Use according to claim 30, characterized in that the organotin compound is selected from any one or a combination of at least two of dibutyltin dilaurate, methyltin mercaptide, dioctyl tin dimaleate, dioctyl tin dilaurate or dioctyl tin dimaleate.

32. The use according to claim 28, wherein the epoxy compound comprises any one or a combination of at least two of epoxidized soybean oil, epoxidized fatty acid ester, bisphenol a diglycidyl ether, bisphenol F diglycidyl ether, glycidyl ether of phenolic resin, glycidyl ether of tetraphenylethane, cycloaliphatic epoxy resin, triglycidyl trimellitate or diglycidyl terephthalate.

33. The use according to claim 1, wherein the lubricant comprises any one or a combination of at least two of hyperbranched polymers, silicone-based lubricants or amide compounds.

34. The use according to claim 33, wherein the lubricant is selected from the group consisting of hyperbranched polymers and silicone-based lubricants.