CN111518391A

CN111518391A - Polyphenylene sulfide resin composition and preparation method and application thereof

Info

Publication number: CN111518391A
Application number: CN202010381680.1A
Authority: CN
Inventors: 曹艳霞; 赖华林; 韦业林; 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: 2020-08-11
Anticipated expiration: 2040-05-08
Also published as: CN111518391B

Abstract

The invention relates to a polyphenylene sulfide resin composition, a preparation method and an application thereof, wherein the polyphenylene sulfide resin composition comprises the following components in percentage by weight: 20-65% of PPS resin, 3.0-20% of PA resin, 20-60% of glass fiber, 0.5-10% of stress release agent, 0.3-3.0% of antioxidant, 0.3-2.0% of ageing resistant agent and 0.5-3.0% of lubricant. The invention prepares the electroplatable material with excellent weather resistance by the synergistic action of the PA resin and the stress release agent, the synergistic action of the PA resin and the anti-aging agent and the optimized proportion of the components, and simultaneously keeps the electrical property, the mechanical property, the heat resistance, the creep resistance, the chemical resistance and the anti-aging property of the PPS engineering plastic, and the material is suitable for the antenna oscillator base material.

Description

Polyphenylene sulfide resin composition and preparation method and application thereof

Technical Field

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

Background

Polyphenylene sulfide resin (PPS) is also known as polyphenylene sulfide or polyparaphenylene sulfide. Linear polyphenylene sulfide resins are crystalline polymers having the chemical formula:

its molecular chain is a rigid structure formed from benzene rings connected by sulfur atoms, so that 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 flame resistance and non-toxic property. The product can be formed by various methods, can be precisely formed, can be electroplated and can be used as a high-temperature resistant structural material, a high-temperature resistant insulating material and the like.

The detailed properties of PPS are as follows:

(1) general properties: PPS is a white to tan colored, highly crystalline, hard and brittle polymer with a relative density of 1.3 for pure PPS. PPS has very low water absorption, which is generally about 0.03%. PPS has good flame retardance, and the oxygen index of the PPS is as high as more than 44 percent; it is a highly flame retardant material in plastics (pure polyvinyl chloride has an oxygen index of 47%, polysulfone of 30%, nylon-66 of 29%, polyphenylene oxide of 28%, polycarbonate of 25%) compared to other plastics.

(2) Mechanical properties: pure PPS has not high mechanical properties, in particular a low impact strength. After the glass fiber is used for reinforcement, the impact strength and the tensile strength can be greatly improved, wherein the tensile strength is more than 170MPa, the bending strength is more than 220MPa, and the notch impact strength is more than 16 MPa. PPS has high rigidity and is rarely used in engineering plastics. The flexural modulus of pure PPS can reach 3.8Gpa, and the flexural modulus of pure PPS can reach 12.6Gpa after inorganic filling modification, which is increased by 5 times. While the polyphenylene oxide (PPO), known for rigidity, is only 2.55GPa, and the PC is only 2.1 GPa. PPS has excellent creep and fatigue resistance, and good creep resistance under load. The surface hardness is high, and the Rockwell hardness is more than 100 HR; the wear resistance is high, the wear loss at 1000 revolutions is only 0.04g, the wear resistance can be greatly improved by filling the lubricating agents such as fluororesin, molybdenum disulfide and the like, and the friction coefficient is 0.01-0.02. PPS also has some self-wetting properties. The mechanical properties of PPS are less sensitive to temperature.

(3) Thermal properties: PPS has excellent thermal properties, has a melting point of over 280 ℃, a heat distortion temperature of over 260 ℃, can resist 260 ℃ in a short period, and can be used for a long time at 200 ℃. Degraded in air at 700 ℃ and the inert gas still maintains 40% by weight at 1000 ℃. The thermal deformation temperature of the product after special modification can reach more than 350 ℃.

(4) Electrical properties: PPS has outstanding electrical properties, and compared with other engineering plastics, the PPS has lower dielectric constant and dielectric loss tangent value and does not change greatly in larger frequency, temperature and temperature ranges; PPS has good arc resistance and can be compared favorably with thermosetting plastics. PPS is commonly used as an electrical insulation material, and the dosage of PPS can be about 30 percent.

(5) Chemical resistance: one of the biggest characteristics of PPS is good chemical resistance, and the chemical stability of PPS is only second to F4; PPS is stable to macroacids, esters, ketones, aldehydes, phenols, aliphatic hydrocarbons, aromatic hydrocarbons, chlorinated hydrocarbons, etc., and no solvent has been found that can dissolve polyphenylene sulfide at temperatures below 200 ℃, and has strong resistance to inorganic acids, bases, and salts. Chlorine-intolerant biphenyl, oxidizing acid, oxidant, concentrated sulfuric acid, concentrated nitric acid, aqua regia, hydrogen peroxide, sodium hypochlorite and the like.

(6) PPS has good radiation resistance, and the radiation resistance reaches 1 × 10⁸Gy is a new material incomparable to other engineering plastics, and is a unique and ideal radiation-resistant excellent material in the fields of electronics, electricity, machinery, instruments, aviation, aerospace, military and the like, particularly atomic bombs and medium bullets.

(7) The dimensional stability is good: the molding shrinkage is very low and is less than 0.0025%, the absorptivity is less than 0.05%, and the linear thermal expansion coefficient is small. The product still shows good dimensional stability under high temperature and high humidity conditions. Therefore, the method has wide application in various aspects such as machinery, chemical engineering, instruments, aviation, aerospace, ships and warships and the like.

(8) The polyphenylene sulfide has excellent electrical property under the conditions of high temperature, high humidity and high frequency, and the volume resistivity of the polyphenylene sulfide is 1 × 10¹⁶Omega cm, surface resistivity of 1 × 10¹⁵Omega, electrical strength>18KV/mm。

(9) Self-flame retardancy: the flame retardance of the polyphenylene sulfide can reach UL94-0 grade, and the oxygen index (LOI) is more than 57%. The chemical structure of polyphenylene sulfide makes the polyphenylene sulfide have good flame-retardant performance without adding flame retardant.

However, due to the molecular structure characteristic of PPS, the glass fiber reinforced PPS engineering plastic has the defects of large internal stress, easy stress cracking in the using process, easy falling of an electroplating circuit bonding layer and the like, and the electromagnetic signal transmission 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 base material is influenced.

CN110655792A discloses a low-dielectric-constant laser direct-molding composite material suitable for 5G communication, which comprises the following components in parts by weight: 52-86 parts of base resin, 0-30 parts of glass fiber, 10-30 parts of filler, 1-9 parts of flame retardant, 4-15 parts of toughening agent, 0.1-1 part of lubricant, 0.2-1 part of antioxidant and 10-30 parts of laser sensitive additive; the preparation method of the composite material comprises the following steps: the double-screw extruder is used for processing, the melt extrusion temperature is 250-380 ℃, and the screw rotating speed is 150-300 rpm/min. The composite material has low dielectric property, and is beneficial to improving the transmission speed of 5G communication millimeter wave signals, reducing signal delay and reducing signal loss; the composite material has LDS processing capacity, small size and large quantity of rapid preparation, and batch laser etching and chemical plating are carried out to form a metal connecting circuit, but the glass fiber reinforced PPS engineering plastic has the defects of large internal stress, easy stress cracking in the using process, easy shedding of an electroplating circuit combining layer, and poor electroplating performance and weather resistance.

CN108264767A discloses a PPS/PPO alloy engineering plastic for NMT technology suitable for high-frequency communication conditions and a preparation method thereof. The PPS/PPO alloy engineering plastic is mainly prepared from the following raw materials in parts by weight: 30-70 parts of PPS resin; 10-50 parts of PPO resin or MPPO resin; 10-50 parts of glass fiber; 3-15 parts of a toughening agent; 0.1-10 parts of a catalyst; 0.5-5 parts of a stabilizer; 0.5-3 parts of a lubricant. The PPS/PPO alloy engineering plastic for the NMT technology has low dielectric constant which is 2.8-3.3 under the 5GHz test condition; PPS/PPO alloy engineering plasticHigh drawing force for metal injection molding, and high drawing force for aluminum alloy exceeding 180kgf/cm²(ii) a The maximum can reach 230kgf/cm²However, the material has large internal stress, is easy to stress crack in the using process, is easy to fall off from the bonding layer of the electroplating circuit, and has poor electroplating property and processability.

Therefore, there is a need in the art to improve the electroplating properties and weather resistance of PPS resin compositions while maintaining the electrical properties, mechanical properties, heat resistance, creep resistance, and chemical resistance of pure PPS engineering plastics.

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 oscillator, which maintains the electrical property, the mechanical property, the heat resistance, the creep resistance, the chemical resistance and the aging resistance of pure PPS engineering plastic to be not changed greatly and simultaneously improves the electroplating performance and the weather resistance of the material.

In order 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 weight:

the invention provides a PPS resin composition, wherein PA resin and a stress release agent are added into a system, and cooperate with each other to destroy the crystallization of PPS, and the mixture ratio of the components is optimized to reduce the internal stress of a material, so that the stability of an electroplating circuit layer caused by the buckling deformation of the material due to the release of the internal stress is improved in the using process, the electroplating performance of the material is improved, the processing performance of the material is better, and the application durability is improved. The addition of the PA is beneficial to improving the processing stability of the material, and further improves the weather resistance of the material when the material is applied in natural environment in a synergistic way with the aging resistant agent.

The invention improves the electroplating performance and the weather resistance, and simultaneously maintains the electrical property, the mechanical property, the heat resistance, the creep resistance, the chemical resistance and the aging resistance of pure PPS engineering plastic. Because each additive in the composition has certain influence on dielectric property, dimensional stability, creep resistance and the like of the material, the content of the added components needs to be strictly controlled, and the technical effect cannot be obtained when the content is beyond the range of the formula.

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

The amount of the PA resin added is 3.0 to 20%, for example, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, etc.

The amount of the glass fiber added is 20 to 60%, for example, 25%, 30%, 35%, 40%, 45%, 50%, 55%, etc.

The stress releasing agent is added in an amount of 0.5 to 10%, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, etc.

The antioxidant is added in an amount of 0.3 to 3.0%, for example, 0.4%, 0.5%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.6%, 2.8%, etc.

The aging resistant agent is added in an amount of 0.3 to 2.0%, for example, 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.

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.

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

preferably, the PPS resin comprises linear PPS.

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

Preferably, the PA resin comprises high temperature nylon. The high-temperature nylon refers to heat-resistant polyamide, and is engineering plastic which can be used in 150 ℃ environment for a long time.

Preferably, the PA resin has a semi-aromatic structure. The semi-aromatic structure in the present invention means: one of the raw materials for preparing the PA resin is aromatic structure, the other one is aliphatic structure, and both the raw materials cannot be aromatic structure at the same time, such as PA6T, PA9T, PA10T, PA12T, MXD6, HPN and the like.

According to the invention, nylon with a semi-aromatic structure is preferably selected, and a flexible hydrocarbon chain is introduced while the high-temperature resistance of the material is maintained, so that the gradual release of the internal stress of the material caused in the processing process is facilitated, and the electroplating performance of the material is further improved.

Preferably, the sum of the weight of the PPS resin and the PA resin is not less than 30%, for example, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 40%, 50%, 51%, 52%, 53%, 54%, 55%, etc., preferably not less than 40%, of the total weight of the polyphenylene sulfide resin composition.

The specific addition amounts of the PPS resin and the PA resin are preferably more than 30%, particularly more than 40%, so that the electroplating performance of the material can be further improved, and the insufficient organic matter coating, the nonuniform coating and the insufficient binding force of an electroplated layer can be caused by the excessively low addition amount.

Preferably, the weight ratio of the PPS resin to the PA resin is (3-10):1, e.g., 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, etc., preferably (4-8): 1.

In the invention, the PPS resin and the PA resin are preferably compounded according to a specific proportion, and within the range, the optimal electroplating performance and weather resistance can be embodied, the excessive PPS resin can cause large internal stress of the material, the stability of an electroplated layer is reduced, the durability of the material is reduced, and the insufficient PPS resin can cause reduction of mechanical property and chemical resistance.

Preferably, the glass fibers comprise continuously wound long fibers and/or chopped glass fibers.

Preferably, the cross section of the glass fiber is round, flat or diamond.

Preferably, the glass fibers have an average diameter of 4 to 15 μm, such as 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 fiber comprises a common glass fiber with a circular section and/or a profiled glass fiber with a flat section.

Preferably, the diameter of the cross section of the ordinary glass fiber is 7-11 μm, such as 8 μm, 9 μm, 10 μm, and the like.

Preferably, the slenderness ratio of the section of the profiled glass fiber is 1.5-4: 1, such as 2:1, 2.5:1, 3:1, 3.5:1, 3.8:1 and the like.

The shaped glass fiber cross section can be exemplarily shown in fig. 1, fig. 2 and fig. 3, wherein a is a long diameter, b is a short diameter, and a/b is an elongation ratio.

Preferably, the stress relief agent comprises a thermoplastic styrenic elastomer and/or a thermoplastic styrenic elastomer grafted maleic anhydride copolymer, preferably a thermoplastic styrenic elastomer grafted maleic anhydride copolymer.

The molecular chain of styrene elastomer is structurally characterized by that it is formed from styrene segment (hard segment) and rubber segment (soft segment) whose chemical compositions are different. The segment-to-segment acting force of the styrene hard segment is enough to form physical cross-linking, and the butadiene, isoprene or hydride soft segment thereof is a high-elasticity segment with larger free rotation capacity to provide flexibility for the material; the soft and soft segments are arranged in a proper order and connected in a proper manner. This physical crosslinking of the hard segment is reversible, i.e., loses the ability to constrain the macromolecular composition at high temperatures, exhibiting plasticity. When the temperature is reduced to room temperature, these "crosslinks" are restored again, acting like the crosslink points of the vulcanized rubber. Benzene ring regions in the styrene thermoplastic elastomer provide compatibility with PPS resin, and a large number of benzene rings toughen the PPS system and simultaneously reduce the influence on the tensile modulus and the bending modulus of the material as little as possible; the butadiene, isoprene or hydride region of the styrene thermoplastic elastomer provides good flexibility, which is beneficial to timely adjusting and releasing the stress in the material processing process.

Preferably, the thermoplastic styrenic elastomer is a hydrogenated thermoplastic styrenic elastomer. The hydrogenated thermoplastic styrene elastomer has more excellent weather resistance.

Preferably, the topology of the thermoplastic styrenic elastomer is a star structure.

The star-shaped block copolymer has much higher Mooney viscosity than that of a linear block copolymer, much higher tensile strength than that of the linear block copolymer, and higher heat resistance than that of a linear structure, and is beneficial to maintaining good mechanical property and heat resistance of the material; in the microstructure, the multi-arm topological structure of the star-shaped thermoplastic styrene elastomer is more beneficial to gradual release of internal stress of the material caused in the processing process, and the electroplating performance is further improved.

Preferably, the thermoplastic styrene-based elastomer includes any one or at least two combinations of a styrene-butadiene-styrene block copolymer (SBS), a styrene-isoprene-styrene block copolymer (SIS), a styrene-ethylene-butylene-styrene block copolymer (SEBS) or a styrene-ethylene-propylene block copolymer (SEPPS) and a maleic anhydride graft copolymer thereof, preferably a styrene-ethylene-butylene-styrene block copolymer (SEBS) and/or a styrene-ethylene-propylene block copolymer (SEPPS) and a maleic anhydride graft copolymer thereof.

Preferably, the thermoplastic styrene-based elastomer grafted maleic anhydride copolymer comprises any one or a combination of 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 (SEPPS) grafted maleic anhydride copolymer, preferably styrene-ethylene-butylene-styrene (SEBS) grafted maleic anhydride copolymer. The anhydride modified styrene elastomer can effectively change a composition system while toughening the PPS resin, has high reactivity, and can increase the binding force between the composition and an electroplating circuit layer.

Preferably, the stress release agent is present in an amount of 20% or less, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, etc., preferably 3-15%, based on the total weight of the PPS resin and the PA resin.

The addition amount of the stress release agent is preferably in a specific range, the electroplating performance can be further improved in the range, the mechanical property, the heat resistance and the electroplated layer binding force are reduced due to the excessively high addition amount of the stress release agent, and the electroplated layer binding force is reduced due to the excessively low addition amount.

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

Preferably, the weight ratio of the hindered phenolic antioxidant to the phosphite antioxidant is 2:1 to 1:4, such as 2:2, 2:3, 2:4, 2:5, 2:6, 2:7, and the like.

Preferably, the hindered phenolic antioxidant comprises any one or at least two of polybasic hindered phenolic antioxidants, thio-hindered phenolic antioxidants or asymmetric hindered phenolic antioxidants. Illustratively, may be selected from basf 1010, 245, 1098, CA, and the like; 3114, 3125, 1790, 330, etc. by Cyanid; sumitomo and ADK one or mixture of at least two of GA-80, BBMC, AO-80 series antioxidants.

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

in formula I, R' is selected from alkyl or aryl, preferably C1-C25 (e.g. C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, etc.) alkyl or C6-C12 (e.g. C8, C10, etc.) aryl.

The phosphite antioxidant includes but is not limited to one or a mixture of at least two of 168, 618, 619, P-EPQ, 626, 627, PEP 36 and 9228.

Preferably, the aging resistor comprises a combination of an ultraviolet light absorber, a light stabilizer and a synergist.

Preferably, the weight ratio of the ultraviolet light absorber to the light stabilizer is from 3:1 to 1:3, such as 3:2, 3:3, 3:4, 3:5, 3:6, 3:7, 3:8, and the like.

Preferably, the synergist is added in an amount of 0.1-2%, such as 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., preferably 0.5-1.2% of the polyphenylene sulfide resin composition.

Preferably, the ultraviolet light absorber comprises any one or a combination of at least two of benzophenones, benzotriazoles or triazines, preferably benzotriazoles and/or triazines.

The ultraviolet light absorbers include benzophenones such as UV531, UV-9, UV214, LA-51, etc.; benzotriazoles such as UV-326, UV-327, UV-328, UV-329, UV-360, UV-234, etc.; triazines such as UV1577, UV-1164 and the like.

Preferably, the light stabilizer is a Hindered Amine Light Stabilizer (HALS).

Preferably, the hindered amine light stabilizer is selected from the group consisting of TINUVIN770, TINUVIN 622, TINUVIN783, Chimassorb2020, Uvinul4050FF, Uvinul5050H, CYASORB UV-3346, and CYASORB UV-3529.

Preferably, the light stabilizer is a low-basic HALS, the molecular structural characteristics of which are N-alkylated (N-R) or N-alkoxylated (NOR), such as Tinuvin123, Tinuvin317, Chimassorb 119, EVERSORB 95, Cyasorb 3529, and the like.

Preferably, the synergist is a radical scavenger, preferably a radical scavenger of the benzofuranone type, such as Irganox HP-136, Revonox 501, etc.

Preferably, the amount of the radical scavenger added is 5% to 30%, for example 6%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, etc., preferably 10% to 20% of the total amount of the ultraviolet absorber and the light stabilizer.

Further, the addition amount of the radical scavenger is preferably controlled within the above range, so that the weather resistance of the material can be further improved, the cost is increased due to the excessive addition of the radical scavenger, the additive is precipitated, and the weather resistance effect is not remarkably improved due to the insufficient content of the radical scavenger.

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

Furthermore, the lubricant with proper type and dosage is beneficial to the uniform dispersion of the glass fiber and the prevention of the exposure of the glass fiber, and the good appearance and surface evenness are beneficial to the formation of an electroplating circuit layer with good bonding force with the base material in the subsequent electroplating process.

Hyperbranched polymers such as Hyper 100, Hyper181, CYD701 series, CYD816, CYD818, and the like; silicone compounds such as TEGOMER E525, TEGOMER H-Si 6440P, RM4-7105, RM4-7051, RM4-7081, etc.; amide compounds such as oleamide, stearamide, erucamide, EBS, TAF series and the like

The second object of the present invention is to provide a method for producing the polyphenylene sulfide resin composition according to the first object, comprising the steps of:

(1) weighing PPS resin and PA resin, adding a dispersant, a stress release agent, an antioxidant, an anti-aging agent and a lubricant in a formula ratio, and uniformly premixing to obtain a premix; adding the premix into a twin-screw extruder according to the specific processing temperature of the premix which is preheated;

(2) and (3) feeding the glass fiber with the formula ratio into a double-screw extruder by side feeding, carrying out melt blending and extrusion granulation, bracing, cooling and detecting performances to obtain the polyphenylene sulfide engineering plastic particles.

The PPS resin is modified by adopting a polymer melt blending means, so that the mechanical property, the electrical property, the electroplating property and the durability of the composition are well balanced, the prepared material is better suitable for a 5G antenna oscillator base material, and the material has strong practicability and wide market prospect in the 5G communication era.

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

The preparation process of the polyphenylene sulfide resin composition of the present invention is shown in FIG. 4.

The third object of the present invention is to provide an application of the polyphenylene sulfide resin composition described in the first object, wherein the polyphenylene sulfide resin composition is applied to an antenna oscillator base material, preferably a 5G antenna oscillator base material.

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

according to the invention, the PA resin and the stress release agent are added into the PPS resin system and cooperate with each other to destroy the crystallization of PPS, and then the ratio of each component is optimized to reduce the internal stress of the material, so that the stability of the plating circuit layer caused by the material buckling deformation due to the release of the internal stress is improved in the using process, the plating performance of the material is improved, the processing performance is better, and the application durability is improved. The addition of the PA resin is beneficial to improving the processing stability of the material, and further improves the weather resistance of the material when the material is applied in natural environment in a synergistic way with the aging resistant agent.

The invention improves the electroplating performance and the weather resistance, simultaneously maintains the electrical property, the mechanical property, the heat resistance, the creep resistance, the chemical resistance and the aging resistance of pure PPS engineering plastic, is used for materials in the communication field, is particularly suitable for being used as a base material of a 5G antenna oscillator, and replaces LCP-LDS materials and sheet metal composite materials used at present.

Drawings

FIG. 1 is a cross-sectional view of a shaped glass fiber according to the present invention.

FIG. 2 is a cross-sectional view of a shaped glass fiber according to the present invention.

FIG. 3 is a cross-sectional view of a shaped glass fiber according to the present invention.

FIG. 4 is a flow chart showing the preparation of the polyphenylene sulfide resin composition of the present invention.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

The following examples and comparative examples respectively provide polyphenylene sulfide resin compositions, the formulations of which are shown in table 1.

TABLE 1

The components in table 1 are as follows:

PPS: purchased from Xinhe Cheng Dynasty;

nylon: semi-aromatic PA, cola PA 9T;

glass fiber: ordinary glass fiber with round section, the 3610 of PPG;

stress release agent: purchased from Yueyang petrochemical in combination with Kraton, YH-602T and 1901GT in a weight ratio of 1: 1;

antioxidant: the combination of antioxidant 1790, antioxidant 300 and antioxidant 9228, the weight ratio of the three is 3:3: 5;

aging resistant agent: the combination of an ultraviolet light absorber (UV328), a light stabilizer (Tinuvin123) and a free radical scavenger (Irganox HP-136), wherein the weight ratio of the ultraviolet light absorber to the light stabilizer is 3:1, and the free radical scavenger accounts for 15% of the total weight of the ultraviolet light absorber and the light stabilizer;

lubricant: a combination of lubricants RM4-7081 and lubricant Hyper C181 in a weight ratio of 1: 1.

The PPS resin compositions of the above examples and comparative examples were prepared as follows:

In the step (2), the heating temperature of the twin-screw extruder is as follows: 200 ℃ in the first zone, 240 ℃ in the second zone, 250 ℃ in the third zone, 240 ℃ in the fourth zone, 260 ℃ in the fifth zone, 270 ℃ in the sixth zone and 260 ℃ in the head.

Example 5

The difference from example 3 is that PPS was added in an amount of 38.3 wt%, PA was added in an amount of 12.8 wt%, the weight ratio of PPS to PA was 3:1, and the preparation method was the same as in example 3.

Example 6

The difference from example 3 is that PPS was added in an amount of 46.2 wt%, PA was added in an amount of 4.9 wt%, the weight ratio of PS to PA was 9.4:1, and the preparation method was the same as in example 3.

Example 7

The difference from example 3 is that PPS was added in an amount of 34.4 wt%, PA was added in an amount of 16.7 wt%, the weight ratio of PS to PA was 2:1, and the preparation method was the same as in example 3.

Example 8

The difference from example 3 is that PPS was added in an amount of 47.2 wt%, PA was added in an amount of 3.9 wt%, the weight ratio of PS to PA was 12:1, and the preparation method was the same as in example 3.

Comparative example 3

The difference from example 3 is that no nylon is added, the addition amount of the stress relieving agent is 14.9 wt%, and the preparation method is different from example 3 only in that no nylon is added.

Comparative example 4

The difference from example 3 is that no stress releasing agent is added, the addition amount of nylon is 14.8 wt%, and the preparation method is different from example 3 only in that no stress releasing agent is added.

Comparative example 5

The difference from example 3 was that no nylon was added, the amount of the aging resistor added was 8.6 wt%, and the preparation method was different from example 3 only in that no nylon was added.

Comparative example 6

The difference from example 3 was that no aging resistor was added, the amount of nylon added was 8.6 wt%, and the preparation method was different from example 3 only in that no aging resistor was added.

And (3) performance testing:

the following property tests were carried out with respect to the PPS resin compositions obtained in examples and comparative examples:

(1) and (3) testing mechanical properties: testing to obtain impact strength (ISO 180) and tensile strength (ISO 527);

(2) and (3) dielectric property test: referring to standard IEC60249-1-2013, taking 5 points of each sample plate under each test condition, removing residual data of obvious abnormal data, and taking an average value;

(3) testing the heat distortion temperature: the test standard was ISO 75/Ae (4mm, 1.80 MPa);

(4) testing the electroplated layer in a hundred-grid mode:

carrying out a Baige experiment according to the standard GBT9286-1998, taking 5 points under each test condition of each sample plate, recording the minimum value and the maximum value, wherein the higher the number is, the lower the adhesion force of the electroplated layer and the base material is;

(5) and (3) weather-resistant gray level test: the test standard is ISO 105-A02:1993, and each sample is tested 5 times, the minimum and maximum values are recorded, and the higher the judgment level is, the lower the discoloration degree of the substrate is, the higher the mechanical property retention degree is, and the higher the weather resistance is.

The results of the performance tests are shown in table 2.

TABLE 2

As is clear from Table 1, the PPS resin composition provided by the invention has excellent electroplating performance and weather resistance, and simultaneously keeps good mechanical property, dielectric property, heat resistance and processability. Wherein, the test result of the galvanized layer is 1-3, the impact strength is 14-16MPa, the tensile strength is 127-138MPa, the dielectric constant is 3.6-4.4GHz, and the thermal deformation temperature is 255-260 ℃.

The electroplating performance of comparative examples 1 and 3, in which no nylon is added, and comparative examples 2 and 4, in which no stress release agent is added, are obviously deteriorated, so that the nylon and the stress release agent can synergistically improve the electroplating performance of the material.

Comparative example 5 and comparative example 6, in which nylon and an aging resistant agent were not added, respectively, the weather resistance was significantly deteriorated, thus demonstrating that nylon and an aging resistant agent can synergistically improve the weather resistance of the material.

The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims

1. The polyphenylene sulfide resin composition is characterized by comprising the following components in percentage by weight:

2. the polyphenylene sulfide resin composition of claim 1, wherein the polyphenylene sulfide resin composition comprises the following components in weight percent:

3. the polyphenylene sulfide resin composition according to claim 1 or 2, wherein the PPS resin comprises linear PPS;

preferably, the PPS resin has a melt flow rate of 20 to 500g/10min, preferably 50 to 350g/10min, at 316 ℃/5 kgf;

preferably, the PA resin comprises high temperature nylon;

preferably, the PA resin has a semi-aromatic structure;

preferably, the sum of the weight of the PPS resin and the weight of the PA resin is not less than 30 percent, preferably not less than 40 percent, of the total weight of the polyphenylene sulfide resin composition;

preferably, the weight ratio of the PPS resin to the PA resin is (3-10):1, preferably (4-8): 1.

4. The polyphenylene sulfide resin composition according to any one of claims 1-3, wherein the glass fiber comprises a continuously wound long fiber and/or a chopped glass fiber;

preferably, the cross section of the glass fiber is round, flat or diamond;

preferably, the glass fibers have an average diameter of 4 to 15 μm, preferably 6 to 11 μm;

preferably, the glass fiber comprises common glass fiber with a circular section and/or profiled glass fiber with a flat section;

preferably, the diameter of the section of the common glass fiber is 7-11 μm;

preferably, the slenderness ratio of the section of the profiled glass fiber is 1.5-4: 1.

5. The polyphenylene sulfide resin composition of any one of claims 1-4, wherein the stress relief agent comprises a thermoplastic styrenic elastomer and/or a thermoplastic styrenic elastomer grafted maleic anhydride copolymer, preferably a thermoplastic styrenic elastomer grafted maleic anhydride copolymer;

preferably, the thermoplastic styrenic elastomer is a hydrogenated thermoplastic styrenic elastomer;

preferably, the topology of the thermoplastic styrenic elastomer is a star structure;

preferably, the thermoplastic styrene-based 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, preferably a styrene-ethylene-butylene-styrene block copolymer and/or a styrene-ethylene-propylene block copolymer, and further preferably a styrene-ethylene-butylene-styrene block copolymer;

preferably, the thermoplastic styrene-based elastomer grafted maleic anhydride copolymer comprises any one or at least two combinations 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, preferably styrene-ethylene-butylene-styrene grafted maleic anhydride copolymer;

preferably, the stress releasing agent accounts for less than or equal to 20 percent of the total weight of the PPS resin and the PA resin, and preferably 3 to 15 percent.

6. The polyphenylene sulfide resin composition of any one of claims 1-5, wherein the antioxidant comprises a complex of a hindered phenolic antioxidant and a phosphite antioxidant;

preferably, the weight ratio of the hindered phenol antioxidant to the phosphite antioxidant is 2:1-1: 4;

preferably, the hindered phenol antioxidant comprises any one or at least two of polybasic hindered phenol antioxidants, thio-hindered phenol antioxidants or asymmetric hindered phenol antioxidants;

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

in the formula I, R' is selected from alkyl or aryl, preferably C1-C25 alkyl or C6-C12 aryl.

7. The polyphenylene sulfide resin composition according to any one of claims 1-6, wherein the aging resistor comprises a combination of an ultraviolet light absorber, a light stabilizer, and a synergist;

preferably, the weight ratio of the ultraviolet light absorber to the light stabilizer is 3:1 to 1: 3;

preferably, the addition amount of the synergist accounts for 0.1-2%, preferably 0.5-1.2% of the polyphenylene sulfide resin composition;

preferably, the ultraviolet light absorber comprises any one or at least two combinations of benzophenones, benzotriazoles or triazines, preferably benzotriazoles and/or triazines;

preferably, the light stabilizer is a hindered amine light stabilizer;

preferably, the synergist is a radical scavenger, preferably a benzofuranone radical scavenger;

preferably, the addition amount of the free radical scavenger is 5 to 30%, preferably 10 to 20% of the total amount of the ultraviolet absorber and the light stabilizer.

8. The polyphenylene sulfide resin composition according to any one of claims 1-7, wherein the lubricant comprises any one or a combination of at least two of a hyperbranched polymer, a silicone-based compound, or an amide compound, preferably a hyperbranched polymer and/or a silicone-based compound.

9. A method for preparing the polyphenylene sulfide resin composition according to any one of claims 1 to 8, comprising the steps of:

(1) after weighing PPS resin and PA resin, adding stress release agent, antioxidant, aging resistant agent and lubricant in a formula amount, premixing uniformly to obtain a premix, and adding the premix into a double-screw extruder;

(2) side feeding, putting the glass fiber with the formula amount into a double-screw extruder, carrying out melt blending and extrusion granulation, bracing, cooling and detecting performances to obtain polyphenylene sulfide engineering plastic particles;

10. Use of the polyphenylene sulfide resin composition according to any one of claims 1-8, wherein the polyphenylene sulfide resin composition is applied to an antenna element substrate, preferably a 5G antenna element substrate.