A kind of durable polyphenylene sulfide and preparation method thereof

Abstract

The present invention discloses a durable polyphenylene sulfide and a preparation method thereof. The durable polyphenylene sulfide comprises the following components in parts by weight: 100 parts of polyphenylene sulfide and 30 to 50 parts of modified inorganic fibers, wherein the modified inorganic fibers are obtained by grafting a first coupling agent onto the surface of the inorganic fibers; the durable polyphenylene sulfide is obtained by the following steps: (1) polyphenylene sulfide and the modified inorganic fibers are melt blended and extruded to obtain a primary treated polyphenylene sulfide; (2) the primary treated polyphenylene sulfide is subjected to corona treatment or oxidation treatment and then grafted with a second coupling agent to obtain the durable polyphenylene sulfide. The preparation method of the durable polyphenylene sulfide in the present invention comprises the steps of inorganic fiber treatment, extrusion molding, and re-treatment. The durable polyphenylene sulfide provided by the present invention has an antioxidant effect.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a durable polyphenylene sulfide and a preparation method thereof. Background Art

[0002] Polyphenylene sulfide (PPS) is a high-performance thermoplastic resin with excellent heat resistance, chemical corrosion resistance, flame retardancy, radiation resistance, excellent electrical properties and dimensional stability. It has high strength and hardness, can be processed by a variety of molding methods, and can be precisely molded. PPS is widely used in high-tech fields such as petrochemicals, automobiles, machinery, electronics, aerospace, and military due to its excellent performance.

[0003] Although PPS has excellent thermal stability, the sulfur in the PPS molecular structure exists in a divalent form and is easily lost electrons and combined with oxygen. It is easily oxidized in harsh environments, causing PPS to undergo oxidative cross-linking, macromolecular chain breakage, degradation and other reactions. The apparent appearance is that PPS turns yellow, becomes brittle, and cracks, which limits the service life of PPS. Summary of the invention

[0004] In view of the deficiencies in the prior art, the object of the present invention is to provide a durable polyphenylene sulfide and a preparation method thereof.

[0005] In order to achieve the above-mentioned invention object, the technical solution adopted by the present invention includes:

[0006] In one aspect, a durable polyphenylene sulfide comprises the following components in parts by weight:

[0007] 100 parts of polyphenylene sulfide,

[0008] 30-50 parts of modified inorganic fiber,

[0009] The modified inorganic fiber is obtained by grafting a first coupling agent onto the surface of the inorganic fiber;

[0010] Durable polyphenylene sulfide is obtained by the following steps:

[0011] (1) melt-blending and extruding the polyphenylene sulfide and the modified inorganic fiber to obtain pre-treated polyphenylene sulfide;

[0012] (2) The primary treated polyphenylene sulfide is subjected to corona treatment or oxidation treatment and then grafted with a second coupling agent to obtain a durable polyphenylene sulfide.

[0013] Preferably, the second coupling agent forms a film structure on the surface of the pre-treated polyphenylene sulfide.

[0014] In the present invention, the second coupling agent can isolate the contact between polyphenylene sulfide and oxygen after forming a film structure, thereby improving the antioxidant capacity of the polyphenylene sulfide system.

[0015] In the present invention, the first coupling agent and the second coupling agent are both selected from one or more of amino coupling agents, silicon coupling agents, phosphoric acid coupling agents, carboxylic acid coupling agents, polyurethane coupling agents, titanate coupling agents, aluminate coupling agents, bimetallic coupling agents, and borate coupling agents.

[0016] Specifically, in the present invention, the first coupling agent and the second coupling agent are both silane coupling agent KH550.

[0017] Silane coupling agent KH550 contains Si atoms. The introduction of silicon elements can improve the thermal stability of PPS, improve the mechanical properties of PPS, and make PPS have better performance in a wider range of chemical environments.

[0018] Preferably, the film structure comprises an organic film-forming agent.

[0019] In the present invention, the film-forming agent helps the second silane coupling agent to form a smoother and denser film, thereby better blocking oxygen and being beneficial to improving the antioxidant capacity of the polyphenylene sulfide system.

[0020] Preferably, the organic film-forming agent is selected from one or more of acrylic resin, alkyd resin, polyurethane and epoxy resin.

[0021] In the present invention, the organic film-forming agent is specifically selected from polyurethane-35.

[0022] Preferably, in the step (1), the polyphenylene sulfide is immersed in an organic solvent for swelling and then melt-blended and extruded with the modified inorganic fiber.

[0023] In the present invention, polyphenylene sulfide can reduce entanglement after swelling, so as to be more evenly compatible with the modified inorganic fiber, which is beneficial to improving the mechanical strength and durability of the durable polyphenylene sulfide.

[0024] Preferably, the inorganic fiber is selected from one or more of glass fiber, carbon fiber, alumina fiber and silicon carbide fiber.

[0025] Preferably, part of the first coupling agent is connected with an organic antioxidant.

[0026] On the other hand, a method for preparing durable polyphenylene sulfide comprises the following steps:

[0027] Inorganic fiber treatment: the inorganic fiber is treated with acid and then reacted with the first coupling agent to obtain modified inorganic fiber;

[0028] Extrusion molding: melt-blending and extruding the polyphenylene sulfide and the modified inorganic fiber to obtain the initially treated polyphenylene sulfide;

[0029] Re-treatment: subjecting the initially treated polyphenylene sulfide to corona treatment or oxidation treatment to make oxygen-containing groups appear on the surface, and then immersing it in a second coupling agent so that the second coupling agent reacts with the oxygen-containing groups, and then separating and cleaning to obtain durable polyphenylene sulfide.

[0030] The main raw materials of the present invention are introduced as follows:

[0031] Acrylic resin: The film formed by acrylic resin has many significant advantages:

[0032] ①Good transparency and gloss: Acrylic resin has excellent transparency and gloss, which makes the film formed by it have excellent visual performance. This property makes acrylic resin film an ideal choice for making advanced coatings and electroplating coatings.

[0033] ②Good stability: The chemical properties of acrylic resin are stable and not easily affected by environmental factors. Therefore, the film formed by it has good weather resistance and corrosion resistance, and can maintain stable performance under various environmental conditions.

[0034] ③Excellent adhesion: Acrylic resin film-forming agent has good adhesion and can firmly bond with the surface of the coated object. This characteristic makes acrylic resin film have a wide range of application prospects in the fields of coatings, adhesives, etc.

[0035] ④Excellent mechanical properties: Acrylic resin film has the characteristics of high hardness and good ductility, which enables it to withstand certain mechanical pressure and deformation without being easily broken or deformed.

[0036] ⑤ Light resistance and aging resistance: Acrylic resin film has excellent light resistance and aging resistance, and can maintain stable performance under long-term light and oxidation. This makes the acrylic resin film have a long service life in outdoor use environments.

[0037] ⑥ Strong adjustability: Acrylic resin can change its properties by copolymerizing with different monomers and adding different additives. This allows the properties of acrylic resin films to be customized and adjusted according to specific needs.

[0038] Alkyd resins: The films formed by alkyd resins have several significant advantages:

[0039] ① Weather resistance and aging performance: After drying, the alkyd resin paint film forms a highly reticular structure, which is not easy to age, has good weather resistance, and has a long-lasting gloss. After baking, the water resistance, oil resistance, insulation, weather resistance, hardness, and flexibility of the coating film are significantly improved.

[0040] ②Physical properties: The paint film is flexible, strong, friction-resistant, and has good mechanical properties. It has good resistance to mineral oil and alcohol solvents and has good chemical stability.

[0041] ③ Construction and performance adjustability: Alkyd resin raw materials are widely available and inexpensive. The paint film produced has high gloss, good fullness, excellent adhesion, and easy construction and maintenance. It can be combined with other materials (such as amino resins, isocyanate curing agents, etc.) to prepare coatings with different properties, such as alkyd polyurethane acid-resistant anticorrosive paints.

[0042] ④ Environmental protection: Water-based alkyd resin can be made from bio-based sources and has a low VOC content, which is in line with the trend of environmental protection and green development.

[0043] Polyurethane: The film formed by polyurethane has many significant advantages:

[0044] ①Excellent wear resistance: Polyurethane film has extremely high wear resistance, good flexibility, and especially high tear resistance, which enables it to maintain a long service life in various application scenarios.

[0045] ②Excellent chemical resistance: oil resistance, low temperature resistance, heat aging resistance, ozone resistance, radiation resistance, and electrical insulation properties enable the polyurethane film to maintain stable performance in a variety of complex environments.

[0046] ③Good biocompatibility: Polyurethane materials have good biocompatibility, so they are increasingly used in the medical field, such as wound dressings, medical gloves, etc.

[0047] ④ Unique molecular structure and adjustability: Polyurethane elastic materials are synthesized from polyols and diisocyanates as raw materials, and have a unique block molecular structure. The elasticity, hardness, hydrophilicity, etc. can be changed by adjusting the ratio of soft and hard segment components of polyurethane to meet different application requirements.

[0048] ⑤ Waterproof and breathable performance: There are two types of polyurethane films: microporous and hydrophilic. The diameter of the pores in microporous films is very small, between water vapor and water droplets, thus achieving the purpose of waterproof and breathable. Hydrophilic films achieve waterproof and breathable properties through a complex molecular diffusion mechanism, while blocking dust and bacteria.

[0049] ⑥High strength and high toughness: Polyurethane film has high strength and high toughness, which makes it have good heat resistance, tear resistance, and tensile resistance, and is not easy to break or deform.

[0050] ⑦ Corrosion resistance and oxidation resistance: Polyurethane film can withstand acidic and alkaline media, and at the same time has good antioxidant properties, is not easy to age, and has a long service life.

[0051] ⑧Good softness and comfortable touch: Polyurethane film has good softness and comfortable touch, strong plasticity and is not easy to harden.

[0052] Epoxy resin: The film formed by epoxy resin has the following significant advantages:

[0053] ①Good adhesion: Epoxy resin film has excellent adhesion to concrete, metal, wood and other substrates. Usually the adhesion of concrete is above 4MPa.

[0054] ②High hardness and wear resistance: The cured epoxy resin film has high hardness and wear resistance, and is suitable for use in situations where wear resistance is required.

[0055] ③Excellent corrosion resistance: Epoxy resin film can resist the erosion of various chemical substances such as acid, alkali, salt, etc., and shows good corrosion resistance.

[0056] ④ Anti-chemical corrosion: Epoxy resin film has good corrosion resistance in chemical media such as acid, salt, alkali, and water.

[0057] ⑤ Anti-ultraviolet aging: It can resist ultraviolet radiation for a long time without aging, maintaining the stability and beauty of the film layer.

[0058] ⑥Excellent electrical insulation performance: Epoxy resin film has a small dielectric constant and high dielectric strength, and can maintain stable electrical insulation performance within a wide frequency band. Therefore, it is widely used in electronics, electrical and other fields.

[0059] ⑦Good volume stability: The volume shrinkage of epoxy resin is low, usually only about 2%, which helps to reduce internal stress during the coating process and prevent paint film cracking. It is suitable for large-area coating and thick coating.

[0060] The beneficial effects of glass fiber on polyphenylene sulfide are mainly reflected in the following aspects:

[0061] ① Reinforcement: Glass fiber acts as a nucleating agent in the polyphenylene sulfide matrix, allowing polyphenylene sulfide molecules to crystallize around the glass fiber. This structure can enhance the strength and modulus of the composite material. For example, the most common PPS is reinforced with 40% glass fiber, which gives PPS multiple properties such as high fluidity, high wear resistance, high strength, high CTI (comparative tracking index), and low dielectric.

[0062] ② Improve the interface bonding: Adding a coupling agent to the composite material of polyphenylene sulfide and glass fiber can further improve the interface bonding between the two. When the composite material is subjected to external impact, this enhanced interface bonding can play a better reinforcing role.

[0063] ③ Improve heat resistance: The addition of glass fiber can significantly improve the heat resistance of polyphenylene sulfide. Polyphenylene sulfide itself has good high temperature resistance, and the reinforcement of glass fiber can make it more stable under high temperature conditions.

[0064] ④ Improved mechanical properties: The reinforcement of glass fiber significantly improves the mechanical properties of polyphenylene sulfide, such as rigidity, dimensional stability, and hardness. This enables polyphenylene sulfide composite materials to meet a wider range of industrial application needs.

[0065] Antioxidant Antioxidant 1010: Antioxidant 1010, scientifically known as tetrakis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, is a high-performance phenolic antioxidant with the following significant advantages:

[0066] Highly effective antioxidant performance: It has excellent antioxidant effect on olefin resins such as polypropylene, polyethylene, polyphenylene sulfide, etc. It can effectively inhibit free radical chain reactions, delay the aging process of materials, and extend the service life of products.

[0067] Thermal stability and durability: It has high thermal stability and can maintain good antioxidant properties even in high-temperature processing or use environments, with long-lasting effectiveness.

[0068] Low volatility and low migration: Antioxidant 1010 has low volatility and is not easy to migrate or be extracted from the product, which is particularly important for applications that require long-term stability and prevention of contamination.

[0069] Non-toxic and pollution-free: It is a non-toxic additive. It will not pollute the environment or have a negative impact on human health during use. It meets food safety and environmental protection requirements and is suitable for sensitive applications such as food packaging materials.

[0070] Color stability: It will not cause the base material to discolor or change color during use, and is suitable for products with strict color requirements.

[0071] Compared with the prior art, the advantages of the present invention include:

[0072] (1) The present invention provides a durable polyphenylene sulfide, wherein a first coupling agent is grafted onto the surface of an inorganic fiber, and the first coupling agent can be entangled with the polyphenylene sulfide system to improve the compatibility between the inorganic fiber and the polyphenylene sulfide; at the same time, the first coupling agent can increase the content of the coupling agent in the polyphenylene sulfide system, thereby improving the stability of the polyphenylene sulfide system, which is beneficial to maintaining the mechanical strength of the polyphenylene sulfide;

[0073] (2) The durable polyphenylene sulfide provided by the present invention can form oxygen-containing groups on the surface of the initially treated polyphenylene sulfide after corona treatment or oxidation treatment, which is convenient for the second coupling agent to be grafted on the surface of the polyphenylene sulfide; at the same time, the second coupling agent can be combined with the inorganic fiber located on the surface of the polyphenylene sulfide, thereby improving the stability of the surface layer of the polyphenylene sulfide system, which is beneficial to improving the ability of the polyphenylene sulfide surface to resist cracking;

[0074] (3) The durable polyphenylene sulfide provided by the present invention forms oxygen-containing groups on the surface of the polyphenylene sulfide system through corona treatment or oxidation treatment, and combines with the oxygen-containing groups through a second coupling agent, so that the points on the surface of the polyphenylene sulfide system that can be oxidized are controllably oxidized in advance without destroying the polyphenylene sulfide system, thereby reducing the points on the surface of the polyphenylene sulfide system that can be oxidized under harsh environments, thereby improving the antioxidant capacity of the polyphenylene sulfide system;

[0075] (4) In the durable polyphenylene sulfide provided by the present invention, the second coupling agent can cover the surface of the polyphenylene sulfide system to form a protection, play a role in isolating oxygen, reduce the contact between polyphenylene sulfide and oxygen, and thus improve the antioxidant capacity of the polyphenylene sulfide system. DETAILED DESCRIPTION

[0076] In order to enable those skilled in the art to understand the characteristics and effects of the present application, the following is a general description and definition of the terms and expressions mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used herein have the common meanings understood by those skilled in the art for the present application. In case of conflict, the definitions in this specification shall prevail.

[0077] The theories or mechanisms described and disclosed herein, whether correct or incorrect, should not limit the scope of the present application in any way, that is, the content of the present application can be implemented without being limited by any specific theory or mechanism.

[0078] As used herein, "this application" means "the present invention" or "the present disclosure".

[0079] The use of "one", "an", "a kind" or similar expressions to describe the components and technical features described in this application is merely for the convenience of expression and to provide a general meaning to the scope of this application. Therefore, such description should be understood to include one or at least one, and the singular also includes the plural, unless it is obvious that it refers to another meaning.

[0080] In this document, "or its combination" means "or any combination thereof", and "any one", "any one" means "any one", "any one" or "any one".

[0081] As used herein, the terms "comprises," "including," "having," "containing," or any other similar terms are open-ended transitional phrases that are intended to cover non-exclusive inclusions. For example, a composition or article containing multiple elements is not limited to the elements listed herein, but may also include other elements that are not explicitly listed but are generally inherent to the composition or article. In addition, unless otherwise expressly stated, the term "or" refers to an inclusive "or" rather than an exclusive "or." For example, any of the following situations satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist). In addition, in this article, the terms "comprising", "including", "having", and "containing" should be interpreted as being specifically disclosed and simultaneously covering closed conjunctions such as "consisting of", "consisting of", and "the remainder is", as well as conjunctions such as "consisting essentially of", "mainly consisting of", "mainly consisting of", "basically containing", "essentially consisting of", "essentially consisting of", and "essentially containing".

[0082] In this article, all features or conditions such as numerical values, quantities, contents and concentrations defined in the form of numerical ranges or percentage ranges are only for simplicity and convenience. Accordingly, the description of numerical ranges or percentage ranges should be deemed to have covered and specifically disclosed all possible sub-ranges and individual values ​​within the range (including integers and fractions), especially integer values. For example, the range description of "1.0 to 8.0" or "between 1.0 and 8.0" or "between 1.0 and 8.0" should be deemed to have specifically disclosed all sub-ranges such as 1.0 to 8.0, 1.0 to 7.0, 2.0 to 8.0, 2.0 to 6.0, 3.0 to 6.0, 4.0 to 8.0, 3.0 to 8.0, etc., and should be deemed to cover endpoint values, especially sub-ranges defined by integer values, and should be deemed to have specifically disclosed individual values ​​such as 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, etc. Unless otherwise indicated, the foregoing method of interpretation applies to all contents of the entire application, regardless of whether the scope is broad or not.

[0083] If the quantity, concentration or other numerical value or parameter is expressed as a range, a preferred range (or a better range) or a series of upper and lower limits, it should be understood that all ranges consisting of any pair of the upper limit or preferred value (or a better value) of the range and the lower limit or preferred value (or a better value) of the range have been specifically disclosed herein, regardless of whether these ranges are disclosed separately. In addition, if a numerical range is mentioned herein, unless otherwise specified, the range should include its endpoints and all integers and fractions within the range.

[0084] In this document, numerical values ​​should be understood to have the accuracy of the number of significant digits of the numerical value, provided that the purpose of the invention can be achieved. For example, the number 40.0 should be understood to cover the range of 39.50 to 40.49.

[0085] In this article, for the use of Markush groups or optional terms to describe the features or examples of the present application, those skilled in the art should understand that all subgroups or any individual elements in the Markush group or option list can also be used to describe the present application. For example, if X is described as "selected from the group consisting of X1, X2 and X3", it also means that the claim that X is X1 and the claim that X is X1 and / or X2 and / or X3 have been fully described. Furthermore, for the use of Markush groups or optional terms to describe the features or examples of the present application, those skilled in the art should understand that any combination of subgroups or individual members of all elements in the Markush group or option list can also be used to describe the present application. Accordingly, for example, if X is described as "selected from the group consisting of X1, X2 and X3", and Y is described as "selected from the group consisting of Y1, Y2 and Y3", it means that the claim that X is X1 and / or X2 and / or X3 and Y is Y1 and / or Y2 and / or Y3 has been fully described.

[0086] Unless otherwise specified, in this application, a compound refers to a chemical substance formed by two or more elements connected by chemical bonds, including small molecule compounds and polymer compounds, but not limited thereto. The interpretation of a compound in this article is not limited to a single chemical substance, but can also be interpreted as the same type of chemical substances with the same composition or the same properties.

[0087] If not otherwise specified, in this application, polymer refers to the product formed by monomer through polymerization reaction, often including many polymer aggregates, each polymer is formed by many simple structural units repeatedly connected by covalent bonds, and monomer is a compound of synthetic polymer. Polymer can include homopolymer, copolymer, prepolymer, etc., and is not limited to this. Homopolymer refers to a polymer polymerized by a monomer. Copolymer includes random copolymer (structure is such as -AABABBBAAABBA-), alternating copolymer (structure is such as -ABABABAB-), graft copolymer (structure is such as -AA(A-BBBB)AA(A-BBBB)AAA-) and block copolymer (structure is such as -AAA AA-BBBBBB-AAAAA-) etc. Prepolymer refers to a polymer with a lower molecular weight between the monomer and the final polymer, and the prepolymer contains reactive functional groups that can further undergo polymerization reaction to obtain a product with a higher molecular weight that is fully cross-linked or hardened. Polymer certainly includes oligomers, and is not limited to this. Oligomers, also known as low polymers, are polymers composed of 2 to 20 repeating units, usually 2 to 5 repeating units.

[0088] Unless otherwise specified, the "resin" in this application is a customary name for a synthetic polymer, which may include monomers, polymers thereof, combinations of monomers, combinations of polymers thereof, or combinations of monomers and polymers thereof, etc., and is not limited thereto.

[0089] If not otherwise specified, in the present application, modified products include products after modification of reactive functional groups of each resin, products after prepolymerization of each resin with other resins, products after crosslinking of each resin with other resins, products after copolymerization of each resin with other resins, and the like.

[0090] If not otherwise specified, the unsaturated bonds described in the present application refer to reactive unsaturated bonds, such as but not limited to unsaturated double bonds that can undergo cross-linking reactions with other functional groups, such as but not limited to unsaturated carbon-carbon double bonds that can undergo cross-linking reactions with other functional groups.

[0091] The unsaturated carbon-carbon double bonds described in the present application preferably include, but are not limited to, vinyl, vinylbenzyl, (meth)acryloyl, allyl or a combination thereof. Vinyl should be interpreted to include vinyl and vinylidene. (Meth)acryloyl should be interpreted to include acryloyl and methacryloyl.

[0092] Unless otherwise specified, the hydrocarbon groups described in this application include, but are not limited to, alkyl, alkenyl or alkynyl, and include their various isomers when interpreted. For example, a C1-C6 divalent hydrocarbon group is interpreted to include a C1-C6 divalent straight-chain hydrocarbon group, a C2-C6 divalent branched hydrocarbon group or a C3-C6 divalent cyclic hydrocarbon group. For another example, a propyl group should be interpreted to include n-propyl and isopropyl.

[0093] Unless otherwise specified, in this application, parts by weight represent relative parts by weight in a composition, which may be any weight unit, such as but not limited to kilograms, kilograms, grams, pounds, etc. For example, 100 parts by weight of polyphenylene ether resin may represent 100 kilograms of polyphenylene ether resin or 100 pounds of polyphenylene ether resin.

[0094] It should be understood that the features disclosed in the various embodiments herein may be arbitrarily combined to form the technical solution of the present application, as long as there is no contradiction in the combination of these features.

[0095] The present application will be described below with specific implementations and examples. It should be understood that these specific implementations and examples are merely illustrative and are not intended to limit the scope of the present application and its use.

[0096] Unless otherwise stated, the methods, reagents and conditions used in the following preparation examples, comparative examples and examples are conventional methods, reagents and conditions in the art.

[0097] In the following descriptions:

[0098] Polyurethane-35: Active ingredient content ≥99%, solid content 40±2%, curing temperature 54°C,

[0099] Cyclohexanone: purity ≥99.9%,

[0100] Glass fiber: diameter is 10-20 μm, length is 2-4 mm,

[0101] Antioxidant 1010: Active ingredient content ≥ 99.8%, loss on drying ≤ 0.2%,

[0102] Silane coupling agent kh550: effective substance ≥99%, density 0.947g / ml.

[0103] Preparation Example

[0104] Preparation Example 1

[0105] The raw materials used in this preparation example include: glass fiber and silane coupling agent KH550.

[0106] The preparation method of this preparation example includes:

[0107] Z1. At 25°C, immerse the glass fiber in a hydrochloric acid solution with a pH of 2.0 for 0.5 h, and then dilute to a pH of 6.0 to obtain a mixture A;

[0108] Z2. At 25°C, silane coupling agent KH550 was mixed into mixture A, the mass ratio of silane coupling agent KH550 to mixture A was 6:100, and the mixture was treated at 25kHz for 4h, and then filtered to obtain mixture B;

[0109] Z3. At 25°C, the mixture B was first washed with deionized water for 3 times, then washed with anhydrous ethanol for 3 times, and then dried at 45°C to obtain modified inorganic fibers.

[0110] Preparation Example 2

[0111] The raw materials used in this preparation example include: glass fiber, silane coupling agent KH550, and antioxidant 1010.

[0112] The preparation method of this preparation example includes:

[0113] Z1. At 25°C, immerse the glass fiber in a hydrochloric acid solution with a pH of 2.0 for 0.5 h, and then dilute to a pH of 6.0 to obtain a mixture A;

[0114] Z2. At 25°C, silane coupling agent KH550 was mixed into mixture A, the mass ratio of silane coupling agent KH550 to mixture A was 6:100, the mass ratio of antioxidant 1010 to silane coupling agent KH550 was 6:1, and the mixture was treated at 25kHz for 4h, and then filtered to obtain mixture B;

[0115] Z3. At 25°C, the mixture B was first washed with deionized water for 3 times, then washed with anhydrous ethanol for 3 times, and then dried at 45°C to obtain a solid C;

[0116] Z4. At 60°C, mix solid C and antioxidant 1010 into anhydrous ethanol and treat at 25kHz for 1h. After filtering, wash with anhydrous ethanol for 3 times and then dry at 45°C to obtain modified inorganic fiber.

[0117] Comparative Example

[0118] Comparative Example 1

[0119] The raw materials used in this comparative example include: 1 kg of polyphenylene sulfide, 300 g of the modified inorganic fiber obtained in Example 1, and silane coupling agent KH550.

[0120] The preparation method of this comparative example comprises: mixing polyphenylene sulfide and modified inorganic fiber uniformly, extruding the mixture through an extruder, and cooling and molding the mixture to obtain durable polyphenylene sulfide.

[0121] Example

[0122] Example 1

[0123] The raw materials used in this example include: 1 kg of phenylene sulfide, 300 g of the modified inorganic fiber obtained in Preparation Example 1, and silane coupling agent KH550.

[0124] The preparation method of this embodiment includes:

[0125] S1, mixing polyphenylene sulfide and modified inorganic fiber uniformly, extruding through an extruder, and cooling and molding to obtain initially treated polyphenylene sulfide;

[0126] S2, immersing the initially treated polyphenylene sulfide obtained in step S1 in a 10% nitric acid solution at 25° C. for 10 min, filtering, washing with deionized water for 3 times, and drying to obtain a solid D;

[0127] S3. Mix solid D and silane coupling agent KH550 into cyclohexanone in a mass ratio of 1:10, and treat at 25kHz for 4h, then filter to obtain a mixture E; wash solid E with anhydrous ethanol for 3 times and dry at 45°C to obtain durable polyphenylene sulfide.

[0128] Example 2

[0129] The difference between this embodiment and embodiment 1 is that in step S3 of this embodiment, the mass ratio of silane coupling agent kh550 to cyclohexanone is 1:20.

[0130] Example 3

[0131] The difference between this embodiment and embodiment 1 is that the modified inorganic fiber in this embodiment comes from preparation example 2.

[0132] Example 4

[0133] The difference between this embodiment and embodiment 1 is that step S1 of this embodiment includes: immersing polyphenylene sulfide in cyclohexanone and treating it at 20kHz for 1h, then filtering, washing it with deionized water for 3 times, then washing it with anhydrous ethanol for 3 times, and then drying it at 45°C to obtain the swollen polyphenylene sulfide; then the swollen polyphenylene sulfide and modified inorganic fiber are evenly stirred and extruded through an extruder, and cooled and formed to obtain the initially treated polyphenylene sulfide.

[0134] Example 5

[0135] The difference between this embodiment and embodiment 1 is that the amount of modified inorganic fiber used is 500g.

[0136] Example 6

[0137] The raw materials used in this example include: 1 kg of phenylene sulfide, 300 g of the modified inorganic fiber obtained in Preparation Example 1, silane coupling agent KH550, and polyurethane-35.

[0138] The preparation method of this embodiment includes:

[0139] S1, mixing polyphenylene sulfide and modified inorganic fiber uniformly, extruding through an extruder, and cooling and molding to obtain initially treated polyphenylene sulfide;

[0140] S2, immersing the initially treated polyphenylene sulfide obtained in step S1 in a 10% nitric acid solution at 25° C. for 10 min, filtering, washing with deionized water for 3 times, and drying to obtain a solid D;

[0141] S3. Mix solid D, silane coupling agent KH550 and polyurethane-35 into cyclohexanone, the mass ratio of silane coupling agent KH550 to cyclohexanone is 1:10, and the mass ratio of silane coupling agent KH550 to polyurethane-35 is 5:1, and treat at 25 kHz for 4 hours, and then filter to obtain a mixture E; wash solid E with anhydrous ethanol for 3 times and dry it at 70°C to obtain durable polyphenylene sulfide.

[0142] Performance Testing

[0143] The durable polyphenylene sulfide prepared in Examples 1 to 6 and Comparative Example 1 was tested according to the following test items:

[0144] The thermal oxidation stability was tested in accordance with the provisions of GB / T 19466.6-2009. The test conditions were an oxygen atmosphere with an atmosphere flow rate of 60 ml / min and a heating rate of 5°C / min.

[0145] Test Results

[0146] Table 1 Thermal oxidation stability of durable polyphenylene sulfide obtained in Examples 1 to 6 and Comparative Example 1

[0147] Test example Oxidation induction temperature / ℃ Example 1 471.3 Example 2 470.4 Example 3 476.7 Example 4 471.6 Example 5 473.3 Example 6 475.9 Comparative Example 1 466.2

[0148] According to Table 1 above, by comparing Example 1 with Comparative Example 1, it can be seen that the antioxidant capacity of the durable polyphenylene sulfide obtained in Example 1 is better than that in Comparative Example 1. The possible reason is that the silane coupling agent KH550 allows the points on the surface of the polyphenylene sulfide system that can be oxidized to be controllably oxidized in advance, reducing the points on the surface of the polyphenylene sulfide system that can be oxidized under harsh conditions, thereby improving the antioxidant capacity of the polyphenylene sulfide system. In addition, the silane coupling agent KH550 can cover the surface of the polyphenylene sulfide system to form protection, isolate oxygen, reduce the contact between polyphenylene sulfide and oxygen, thereby improving the antioxidant capacity of the polyphenylene sulfide system.

[0149] By comparing Example 1 and Example 4, it can be obviously found that the antioxidant capacity of the durable polyphenylene sulfide obtained in Example 4 is better than that in Example 1. This may be because the polyphenylene sulfide is more compatible with the modified inorganic fiber after swelling, so that the polyphenylene sulfide system is denser and more uniform, making the protective layer formed by the silane coupling agent KH550 on the surface of the polyphenylene sulfide system more uniform.

[0150] It should be understood that the above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with this technology to understand the content of the present invention and implement it accordingly. It cannot be determined that the specific implementation of the present invention is limited to these descriptions. For ordinary technicians in the technical field to which the present invention belongs, some simple deductions or substitutions can be made without departing from the concept of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims

1. A durable polyphenylene sulfide, characterized in that: The composition comprises the following components in parts by weight: 100 parts of polyphenylene sulfide, 30-50 parts of modified inorganic fiber, The modified inorganic fiber is obtained by grafting a first coupling agent onto the surface of the inorganic fiber; The first coupling agent and the second coupling agent are both silane coupling agent KH550; The preparation method of durable polyphenylene sulfide comprises the following steps: Inorganic fiber treatment: the inorganic fiber is treated with acid and then reacted with the first coupling agent to obtain modified inorganic fiber; Extrusion molding: melt-blending and extruding the polyphenylene sulfide and the modified inorganic fiber to obtain the initially treated polyphenylene sulfide; Re-treatment: subjecting the initially treated polyphenylene sulfide to corona treatment or oxidation treatment to make oxygen-containing groups appear on the surface, and then immersing it in a second coupling agent so that the second coupling agent reacts with the oxygen-containing groups, and then separating and cleaning to obtain durable polyphenylene sulfide.

2. A durable polyphenylene sulfide according to claim 1, characterized in that: The second coupling agent forms a film structure on the surface of the pre-treated polyphenylene sulfide.

3. A durable polyphenylene sulfide according to claim 1, characterized in that: The film structure includes an organic film former.

4. A durable polyphenylene sulfide according to claim 3, characterized in that: The organic film-forming agent is selected from one or more of acrylic resin, alkyd resin, polyurethane and epoxy resin.

5. The durable polyphenylene sulfide according to claim 1, characterized in that: In the step (1), the polyphenylene sulfide is immersed in an organic solvent for swelling and then melt-blended and extruded with the modified inorganic fiber.

6. The durable polyphenylene sulfide according to claim 1, characterized in that: The inorganic fiber is selected from one or more of glass fiber, carbon fiber, alumina fiber and silicon carbide fiber.

7. The durable polyphenylene sulfide according to claim 1, characterized in that: Part of the first coupling agent is connected with an organic antioxidant.