CN115011122A - Preparation method and application of high-heat-resistant polyphenylene sulfide/polyamide flame-retardant reinforced alloy material - Google Patents
Preparation method and application of high-heat-resistant polyphenylene sulfide/polyamide flame-retardant reinforced alloy material Download PDFInfo
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Abstract
The invention adopts PPS and polyamide as the matrix resin of the alloy, the fiber is enhanced and modified, the strength and the thermal deformation temperature of the material are improved, the thermal deformation temperature of the product keeps the higher level of the enhanced alloy material after irradiation crosslinking, simultaneously the infusibility characteristic of the thermosetting material is embodied, and the product can not deform and melt under the condition of local high temperature (exceeding the melting point of the resin). The invention adopts the high-concentration crosslinking master batch and the flame-retardant reinforced PPS/PA alloy modified composite material to be directly mixed in the preparation process, the crosslinking agent does not need to experience longer high-temperature thermal history, the loss of components is reduced, the content of the components of the crosslinking agent in a product directly injected or extruded from the mixed material is stable and controllable, the irradiation crosslinking condition selectivity is wide, and the polyphenylene sulfide and the nylon resin can be subjected to composite crosslinking to form an interpenetrating network structure. The formed product is applied to electric appliances, automobiles and the like in scenes with local instantaneous high temperature or chemical corrosion resistance, the reliability of the product is improved, and the service life of the product is prolonged.
Description
Technical Field
The invention relates to a preparation method and application of a high-heat-resistant polyphenylene sulfide/polyamide flame-retardant reinforced alloy material, and particularly belongs to the field of processing of high-molecular composite materials.
Background
Polyphenylene Sulfide (PPS) is a special engineering plastic with excellent performance, has high heat resistance, low water absorption and high self-oxygen index, can reach UL V-0 grade without adding a flame retardant, but has poor toughness and lower comparative tracking index, and limits the application of the PPS in certain fields. The PPS/PA alloy material combines the outstanding toughness, wear resistance and electrical properties of the nylon material, and the application scene of the PPS material is enlarged. Although PPS has a higher melting point, the thermal deformation temperature can reach more than 260 ℃ after enhancement and modification, in some practical application scenes, particularly electrical appliances and automobile parts, an instant ultrahigh-temperature working condition can be generated, the local temperature is far higher than the melting point of the plastic, PPS and PA materials are instantly melted, the product function is invalid, and even safety accidents are caused. In order to reduce the use risk, special engineering plastics or ceramic materials with higher melting points are mostly selected, so that the cost of the finished piece is greatly increased. PPS and nylon alloy material system can carry out later-stage crosslinking modification on polyphenylene sulfide and polyamide components, so that the high mechanical property and electrical property of the alloy material can be kept, and the instant local high-temperature resistance of the product can be improved. Such as: under a certain load, the local temperature is 400 ℃, the product can not generate melting collapse, and the product keeps higher dimensional stability and is safer and more reliable in application.
The invention with publication number CN111875963A adopts polyphenylene sulfide resin, nylon 6 resin, mica powder, flat glass fiber, calcium sulfate whisker, titanate coupling agent, ethylene-maleic anhydride-glycidyl methacrylate copolymer, 2'- (1, 3-phenylene) -bisoxazoline, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate to prepare the polyphenylene sulfide/nylon 6 composite material, through the inhibition of the molecular activity of the amorphous region by mineral and glass fiber fillers and the combination of the low linear expansion coefficient of the inorganic filler, the PPS/PA6 alloy material has low linear expansion coefficient and low warping characteristic. The invention discloses a preparation method of a polyphenylene sulfide and high-temperature nylon composite material with publication number CN110746777A, the polyphenylene sulfide, high-temperature nylon, a compatilizer and a processing aid are mixed in a rotary mixer, and then are put in from a main feed opening of a double-screw extruder, conductive potassium titanate whisker fiber is put in from a side feed opening of the double-screw extruder, and then are melted, mixed, extruded and granulated, so that the high-strength, high-wear-resistance, antistatic flame-retardant polyphenylene sulfide/high-temperature nylon composite material is prepared. Compared with a reinforced nylon material modified by a common laser marking agent, the nylon/polyphenylene sulfide alloy material prepared by adding a certain proportion of polyphenylene sulfide resin into nylon resin and then reinforcing the polyphenylene sulfide resin by glass fibers has good mechanical properties and excellent laser marking performance, is not easy to fade in a high-temperature and high-humidity environment, still has a good laser marking effect, and has a wider application range. The publication No. CN109651814A discloses a highly reinforced and toughened polyphenylene sulfide composite material, which adopts polyphenylene sulfide resin as a matrix, nylon as a toughening agent, a composite compatilizer and other additives; the surface of the glass fiber is subjected to silane coupling agent impregnation treatment, and is subjected to twin-screw extrusion granulation to prepare the polyphenylene sulfide composite material, which has high rigidity, high toughness and high flame retardant, is particularly suitable for preparing small parts and ultrathin parts with higher requirements on impact performance, and widens the application range of the polyphenylene sulfide material. The invention utilizes the characteristics of the alloy to exert the basic advantages of the respective resin, does not help the heat-resistant characteristics of the material too much, and even introduces the nylon resin to cause the negative effects of the reduction of the heat-resistant temperature and the increase of the water absorption rate of the product.
The invention patent of publication No. CN112079967A discloses that nylon 6 or nylon 66 is added with a polyfunctional monomer crosslinking agent, a heat stabilizer and an ethylene-vinyl acetate copolymer, and then is blended and extruded, and then is irradiated by a cobalt source and an electron accelerator, so that the heat resistance, glow wire resistance, chemical resistance, environmental stress cracking resistance and flame retardance of the material are improved, and the nylon can replace thermoplastic engineering plastics with higher cost to be applied to the fields of automobiles, aerospace and the like. In the invention patent of publication No. CN112126224A, nylon 6 or nylon 66, a cross-linking agent, a heat stabilizer, a flame retardant and EVA particles are blended according to the above proportion, melt extrusion granulation is carried out by a co-rotating twin-screw extruder at 250-270 ℃, and the obtained flame retardant can reach UL 94V-0 grade after irradiation crosslinking, can resist continuous high temperature of 280 ℃ and has good stability and ductility. The material prepared by the method has the performance of reflecting the basic characteristics of the irradiation crosslinking nylon, the material presents the characteristics of a thermosetting material after crosslinking, and the melt index is reduced after irradiation, which shows that the material is only partially crosslinked, so that the crosslinking degree of the nylon prepared by the method is lower. The practical applicable temperature of the material is related to the Heat Distortion Temperature (HDT) of the material, the heat distortion temperature after non-reinforced nylon is crosslinked is determined by the self characteristics of nylon, the HDT is generally 60-100 ℃, the HDT is not obviously improved, but the heat distortion temperature of the material can be obviously improved by reinforced nylon.
The invention adopts PPS and nylon as alloy matrix resin, fiber reinforcement modification is carried out, the material strength and the thermal deformation temperature are improved, after irradiation crosslinking, the thermal deformation temperature of a product keeps a higher level of a reinforced alloy material, meanwhile, the infusibility characteristic of a thermosetting material is embodied, and a workpiece cannot deform and melt under the condition of local high temperature (exceeding the melting point of the resin). The invention adopts the high-concentration crosslinking master batch and the flame-retardant reinforced PPS/PA alloy modified composite material to be directly mixed in the preparation process, the crosslinking agent does not need to experience longer high-temperature thermal history, the loss of components is reduced, the content of the components of the crosslinking agent in a product directly injected or extruded from the mixed material is stable and controllable, the irradiation crosslinking condition selectivity is wide, and the polyphenylene sulfide and the nylon resin can be subjected to composite crosslinking to form an interpenetrating network crosslinking structure. The formed product is applied to electric appliances, automobiles and the like with local instantaneous high temperature or chemical corrosion resistant scenes, the reliability of the product is improved, and the service life of the product is prolonged.
Disclosure of Invention
In order to solve the problem that the thermoplastic plastic parts are instantaneously melted and failed in the local high-temperature scene of the existing electric appliance and automobile product parts, the invention provides a high-temperature-resistant polyphenylene sulfide/polyamide flame-retardant reinforced alloy material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high-heat-resistant polyphenylene sulfide/polyamide flame-retardant reinforced alloy material is composed of the following raw materials in parts by mass:
polyphenylene sulfide resin: 10 to 60 portions of
Polyamide resin: 10 to 50 parts of
Crosslinking master batch: 3 to 20 portions of
Flame retardant: 5 to 15 parts of
The reinforcing component: 10 to 50 parts of
A compatilizer: 0 to 10 parts of
Antioxidant: 0.1 to 2 portions
Coupling agent: 0.1 to 2 portions
Lubricant: 0.1-2 parts.
Preferably, the high-heat-resistant polyphenylene sulfide/polyamide flame-retardant reinforced alloy material is prepared from the following raw materials in parts by mass:
polyphenylene sulfide resin: 20 to 40 portions of
Polyamide resin: 10 to 30 portions of
Crosslinking master batch: 5 to 15 parts of
Flame retardant: 5 to 15 parts of
The reinforcing component: 30 to 50 portions of
A compatilizer: 1 to 5 portions of
Antioxidant: 0.2 to 1.5 portions
Coupling agent: 0.1 to 1.5 portions
Lubricant: 0.2 to 1.5 portions.
According to the invention, the high-heat-resistant polyphenylene sulfide/polyamide flame-retardant reinforced alloy material is characterized in that the polyphenylene sulfide resin can be in a cross-linking type or a linear type, a melt index is 20-3000 g/10min, and the polyamide resin can be aliphatic polyamide resin such as: PA6, PA66, PA11, PA12, PA46, PA610, PA1010, PA1212 and the like or one or more of semi-aromatic nylon PPA, PA9T, PA10T, PA12T and other nylon varieties.
According to the invention, the high-heat-resistant polyphenylene sulfide/polyamide flame-retardant reinforced alloy material is characterized in that the cross-linking agent master batch is a product of Jun Rlinker series in China, and the high-temperature-resistant polyphenylene sulfide/polyamide flame-retardant reinforced alloy material is a high-concentration master batch which takes various nylons as a carrier and contains one or more unsaturated monomers containing multiple carbon-carbon double bonds. Wherein the crosslinking agent is one or more of triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), trimethallyl allyl isocyanurate (TMAIC) and trimethylolpropane trimethacrylate (TMPTMA), and the content of the crosslinking agent in the master batch is 5-35%.
According to the invention, the high-heat-resistant polyphenylene sulfide/polyamide flame-retardant reinforced alloy material is characterized in that the flame retardant is a halogen-containing flame retardant such as: polybrominated styrenes, decabromodiphenylethane, and the like; halogen-free flame retardants such as: red phosphorus, ammonium polyphosphate APP, organic hypophosphite and the like, nitrogen system (MCA, MPP) and the like, wherein the red phosphorus flame retardant is used in the form of red phosphorus master batch, and one or more flame retardants are selected for compounding.
According to the invention, the high-heat-resistant polyphenylene sulfide/polyamide flame-retardant reinforced alloy material is characterized in that the reinforcing component is one or more of glass fiber, basalt fiber, carbon fiber, whisker and inorganic mineral such as talcum powder, calcium carbonate and barium sulfate.
According to the invention, the high-heat-resistant polyphenylene sulfide/polyamide flame-retardant reinforced alloy material is characterized in that the compatilizer is selected from one or more of maleic anhydride graft, and grafted or copolymerized olefin elastomer containing epoxy functional groups.
According to the invention, the high-heat-resistant polyphenylene sulfide/polyamide flame-retardant reinforced alloy material is characterized in that the antioxidant is selected from one or more of hindered phenol antioxidants and phosphite antioxidants.
According to the invention, the high-heat-resistant polyphenylene sulfide/polyamide flame-retardant reinforced alloy material is characterized in that the lubricant is selected from any one or more of organic siloxane, mesoacid amide, ester wax and alkane wax.
The invention also provides a preparation method of the high-heat-resistant polyphenylene sulfide/polyamide flame-retardant reinforced alloy material, which comprises the following steps:
the preparation method comprises the steps of premixing polyphenylene sulfide and polyamide resin with a flame retardant, a compatilizer, an antioxidant and a coupling agent in a high-speed mixer according to a certain proportion, adding the premix from a main feed inlet of a double-screw extruder, adding a reinforcing component into a side feed inlet according to the proportion, and carrying out melt plasticizing, extrusion, cooling, grain cutting and drying on the materials by the double-screw extruder so as to obtain the high-heat-resistant polyphenylene sulfide/polyamide flame-retardant reinforced alloy material matrix. The polyphenylene sulfide/polyamide alloy matrix and the cross-linking agent master batch are mixed according to a certain proportion, and then the polyphenylene sulfide/polyamide flame-retardant reinforced alloy material product with high heat resistance is obtained after injection molding and gamma-ray or electron beam irradiation processing. The irradiation processing is gamma ray or electron beam irradiation, and the irradiation dose is 50-200 kGy.
Compared with the prior art, the invention has the beneficial effects that:
through the design of the flame-retardant reinforced polyphenylene sulfide/polyamide alloy formula, the screening of the cross-linking agent master batch and the matching verification, the cross-linking agent and the alloy components are in a specific proportion range, and the alloy system can be fully cross-linked. The product parts are obtained through the forming modes of injection molding, extrusion and the like, and then the crosslinked polyphenylene sulfide/polyamide parts are obtained through irradiation of gamma rays or electron beams, so that the material has high mechanical property, flame retardant property and electrical property, and meanwhile, the parts can bear local high temperature of 400 ℃ and keep non-deformation and non-melting. The conventional method for directly adding the cross-linking agent and the high-temperature resin matrix through double-screw shearing plasticization causes self-polymerization and high-temperature volatilization of the cross-linking agent, so that the effective ingredients of the cross-linking agent in the product are difficult to control.
Detailed Description
The reinforced flame-retardant PPS/PA66 alloy system is taken as an example, and the essence of the invention is further illustrated by specific examples and comparative examples.
The raw materials and the auxiliary agent information used in the examples and comparative examples are as follows:
polyphenylene Sulfide (PPS), new sum 1150C;
polyamide (PA 66), samara EPR 27;
semi-aromatic polyamide (PA 10T), guangdong longjie HT 8000;
crosslinking agent master batch: juner Rlinker-002;
glass fiber: international ECS 309A for Chongqing;
a compatilizer: photo-active MAH-g-EPDM N428;
halogen-containing flame retardant: decabromodiphenylethane, goddess of longevity RDT-3;
flame retardant synergist: antimony trioxide, grade 0 in southern Hunan Yiyang Huachang;
hindered phenol antioxidant: tianjin Lianlong RIANOX 1098;
phosphite antioxidants, Tianjin Lianlong RIANOX 168;
thioester antioxidant: tianjin Lianlong RIANOX 412S
Silane coupling agent, south beijing KH 560;
lubricant: jiahua SG-200A, Kelain WARADUR E wax
The preparation methods of the high-heat-resistant polyphenylene sulfide/polyamide flame-retardant reinforced alloy materials in the embodiments 1-4 and the comparative examples 1-3 comprise the following steps:
mixing the polyphenylene sulfide, the dried polyamide resin, a flame retardant, a compatilizer, an antioxidant, a coupling agent and a lubricant in a certain proportion for 3min in a high-speed mixer according to the mass parts in the table 1, then adding a premix from a main feeding port of a double-screw extruder, adding a reinforcing component glass fiber from a side feeding port of the extruder, and carrying out melt mixing, extrusion cooling and grain cutting on the materials in the double-screw extruder to obtain the polyphenylene sulfide/polyamide alloy material. Wherein the length-diameter ratio of a screw of the double-screw extruder is 40:1, the temperature of a machine barrel is 230-280 ℃, and the rotating speed of the screw is 300-500 rpm. And drying the polyamide modified material matrix, mixing with the cross-linking agent master batch, performing injection molding on the product, and performing irradiation treatment and test. The comparative example was tested directly without addition of a crosslinking agent and without irradiation.
Irradiation processing conditions: electron beam irradiation dose 120 kGy;
pretreatment of a sample strip test: all the sample bars were annealed at 150 ℃ for 2hr before testing, and subjected to performance testing after standing for 24 hr.
Test items
Table 1 examples 1-4 polyphenylene sulfide/polyamide modified material matrix and crosslinking master batch stirring mode and comparative examples 1-3 formula without adding crosslinking agent
Table 2 shows the properties of the polyphenylene sulfide/polyamide modified material matrix and the crosslinking master batch in the examples 1-4 and the material without the crosslinking agent in the comparative examples 1-3.
Examples 1 to 4 are data of performance test after irradiation crosslinking.
The matrix resins of comparative examples 1, 2, 3 were identical to those of the examples, with no crosslinker component added. The comparative example 1 is a PPS matrix, and compared with a low Comparative Tracking Index (CTI), the comparative example 2 is a PPS/PA resin matrix, the toughness and the CTI value of the material are improved, the comparative example 3 is a PPS/PA10T resin matrix, the heat resistance and the CTI of the material are improved, but the instant heat resistance characteristic of the comparative example, namely, the rapid melting in an electric soldering iron test is realized. Compared with the embodiment 1-4, after the cross-linking component is introduced, irradiation cross-linking is carried out, so that the mechanical property of the material is maintained, the instant heat-resistant property of the material is rapidly improved, the experimental melting depth of the electric soldering iron is extremely small, and the function of a workpiece cannot be damaged. In examples 1 to 3, the more the PA content, the better the instantaneous heat-resistant effect of the alloy material, because the PPS molecular chains are partially cross-linked under the electron beam irradiation, the PA molecular chains are more likely to undergo a cross-linking reaction, and as the PA resin content increases, the cross-linking density of the alloy material increases, and when the alloy material is locally heated, the resin in the cross-linking structure forms a three-dimensional network structure due to the cross-linking of the molecular chains, and the molecular chains are restricted from moving and cannot move, so that melting is not generated any more, thereby maintaining a higher strength. In addition, the polymer has lower heat conductivity coefficient, slower heat conduction and smaller temperature rise of plastic cement at the periphery of a heat source, so that the influence on the mechanical property attenuation of the material is smaller, and the heated surface of the thermal contact point is carbonized, thereby further improving the heat-resisting property. Embodiment 4 adopts the long carbon chain high temperature nylon alloy component, on one hand improves the self thermal deformation temperature of the material, on the other hand also has certain promotion to the high temperature resistant characteristic in the twinkling of an eye.
The above examples are only preferred embodiments of the present invention, and are not intended to limit the embodiments of the present invention, it should be noted that, for those skilled in the art, various changes or modifications can be made without departing from the method of the present invention, and these changes or modifications should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A high-heat-resistant polyphenylene sulfide/polyamide flame-retardant reinforced alloy material is composed of the following raw materials in parts by mass:
polyphenylene sulfide resin: 10-60 parts
Polyamide resin: 10 to 50 parts of
Crosslinking master batch: 3 to 20 portions of
Flame retardant: 5-15 parts of
The reinforcing component: 10-50 parts of
A compatilizer: 0 to 10 portions of
Antioxidant: 0.1 to 2 portions
Coupling agent: 0.1 to 2 portions
Lubricant: 0.1-2 parts.
2. A high-heat-resistant polyphenylene sulfide/polyamide flame-retardant reinforced alloy material is composed of the following raw materials in parts by mass:
polyphenylene sulfide resin: 20-40 parts of
Polyamide resin: 10 to 30 parts of
Crosslinking master batch: 5 to 15 parts of
Flame retardant: 5-15 parts of
The reinforcing component: 30-50 parts of
A compatilizer: 1-5 parts of
Antioxidant: 0.2 to 1.5 portions
Coupling agent: 0.1 to 1.5 portions
Lubricant: 0.2-1.5 parts.
3. The high heat resistant polyphenylene sulfide/polyamide flame retardant reinforced alloy material as claimed in claim 1, wherein the polyphenylene sulfide resin is cross-linked or linear, the melt index is 20-3000 g/10min, and the polyamide resin is aliphatic polyamide resin such as: PA6, PA66, PA11, PA12, PA46, PA610, PA1010 and PA1212 or one or more of semi-aromatic nylon PPA, PA9T, PA10T, PA12T and other nylon varieties.
4. The high-heat-resistant polyphenylene sulfide/polyamide flame-retardant reinforced alloy material as claimed in claim 1, wherein the cross-linking agent master batch is a product of Jun Rlinker series, which is a high-concentration master batch containing one or more unsaturated monomers containing multiple carbon-carbon double bonds and using various nylons as carriers; wherein the crosslinking agent is one or more of triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), trimethallyl allyl isocyanurate (TMAIC) and trimethylolpropane trimethacrylate (TMPTMA), and the content of the crosslinking agent in the master batch is 5-35%.
5. The high heat resistant polyphenylene sulfide/polyamide flame retardant reinforced alloy material as claimed in claim 1, wherein the flame retardant is a halogen-containing flame retardant or a halogen-free flame retardant.
6. The high-heat-resistant polyphenylene sulfide/polyamide flame-retardant reinforced alloy material as claimed in claim 1, wherein the reinforcing component is one or more of glass fiber, basalt fiber, carbon fiber, whisker and inorganic mineral such as talc powder, calcium carbonate and barium sulfate.
7. The high heat resistant polyphenylene sulfide/polyamide flame retardant reinforced alloy material as recited in claim 1, wherein the compatibilizer is one or more selected from the group consisting of maleic anhydride graft, grafted or copolymerized olefin elastomer containing epoxy functional groups.
8. The high heat resistant polyphenylene sulfide/polyamide flame retardant reinforced alloy material as claimed in claim 1, wherein the antioxidant is selected from one or more of hindered phenol antioxidants and phosphite antioxidants.
9. The high heat resistant polyphenylene sulfide/polyamide flame retardant reinforced alloy material of claim 1, wherein the lubricant is selected from any one or more of organic siloxane, mesoacid amide, ester wax, and alkane wax.
10. The preparation method of the high-heat-resistant polyphenylene sulfide/polyamide flame-retardant reinforced alloy material according to the claims 1-9 specifically comprises the following steps:
premixing polyphenyl ether thioether, polyamide resin and a flame retardant, a compatilizer, an antioxidant and a coupling agent in a high-speed stirrer according to a certain proportion, adding the premix from a main feed inlet of a double-screw extruder, adding a reinforcing component into a side feed inlet according to the proportion, and carrying out melt plasticizing, extrusion, cooling, grain cutting and drying on the materials by the double-screw extruder so as to obtain a high-heat-resistant polyphenyl thioether/polyamide flame-retardant reinforced alloy material matrix;
the polyphenylene sulfide/polyamide alloy matrix and the cross-linking agent master batch are mixed according to a certain proportion, injection molding is carried out, and then gamma-ray or electron beam irradiation processing is carried out, so that the high-heat-resistant polyphenylene sulfide/polyamide flame-retardant reinforced alloy material product is obtained, wherein the irradiation processing is gamma-ray or electron beam irradiation, and the irradiation dose is 50-200 kGy.
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