CN114350149A - Polyphenylene sulfide resin composition and preparation method and application thereof - Google Patents
Polyphenylene sulfide resin composition and preparation method and application thereof Download PDFInfo
- Publication number
- CN114350149A CN114350149A CN202111454012.8A CN202111454012A CN114350149A CN 114350149 A CN114350149 A CN 114350149A CN 202111454012 A CN202111454012 A CN 202111454012A CN 114350149 A CN114350149 A CN 114350149A
- Authority
- CN
- China
- Prior art keywords
- polyphenylene sulfide
- resin composition
- sulfide resin
- ethylene
- zinc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention relates to a polyphenylene sulfide resin composition, a preparation method and application thereof. The composition comprises the following components in parts by weight: 70-98 parts of PPS resin; 1-20 parts of ethylene copolymer; 0.1-3 parts of siloxane compound; 0.1-5 parts of nano flaky filler; 0.1-5 parts of divalent metal ion compound. The composition has good modulus and elongation at break.
Description
Technical Field
The invention belongs to the technical field of engineering plastics, and particularly relates to a polyphenylene sulfide resin composition, and a preparation method and application thereof.
Background
The polyphenylene sulfide composition has the advantages of excellent flame retardant property, high rigidity, good fluidity, excellent chemical reagent resistance and the like. However, the elongation at break of PPS is low, and the requirement of partial application scenes on the elongation of the material cannot be met.
Generally, the toughness of PPS may be increased by means of a toughening agent such as an ethylene copolymer, but most toughening agents such as ethylene copolymers are incompatible or less compatible with PPS. The effect of increasing the elongation at break by using a toughening agent such as an ethylene copolymer is not obvious, and a good effect can be obtained only by using a high addition amount. When the amount of the flame retardant is large, the rigidity of the material is greatly lowered, and the flame retardant property of the material cannot be maintained. There are some studies to improve the compatibility of the toughening agent with PPS or directly improve the elongation at break of PPS by adding additional components, for example, chinese patent CN106062076A discloses improving the compatibility of PPS and ethylene copolymers by adding a disulfide, but the disulfide usually causes the melt viscosity to become uncontrollable, affecting the use of the back end. Chinese patent CN102224202A discloses improving the toughness of PPS by adding metal particles, but the metal particles have conductivity, which is unacceptable in many scenarios, so that the application is limited. Chinese patent CN103013118A discloses that the high-toughness filling reinforced PPS/PPO alloy comprises components such as polyphenylene sulfide, polyphenylene oxide, glass fiber, filler, compatilizer, toughening agent and the like, and the alloy has the advantages of high toughness, excellent rigidity and the like, but the properties such as elongation at break, modulus and the like need to be further improved. Therefore, it is required to find a polyphenylene sulfide resin composition having a high elongation at break and having other excellent characteristics such as modulus.
Disclosure of Invention
The invention aims to solve the technical problem of providing a polyphenylene sulfide resin composition, a preparation method and application thereof, so as to overcome the defects of low elongation at break and poor modulus of the polyphenylene sulfide resin composition in the prior art.
The invention provides a polyphenylene sulfide resin composition, which comprises the following components in parts by weight:
the melt flow rate of the PPS resin is 20-500g/10min under the conditions of 316 ℃ and 5Kg of load. The melt flow rate was tested according to ISO 1133-1: 2011.
Preferably, the PPS resin at 316 degrees C, 5Kg load conditions under the melt flow rate of 50-300g/10 min. PPS, which has a low melt flow rate, will also generally have better elongation by itself.
The silicone compound is preferably present in an amount of 0.5 to 2 parts by weight.
The siloxane compound is not particularly limited, and is preferably one or more selected from ethoxysilane, vinylsilane, aminosilane oligomer, and polysiloxane, and more preferably cage-type polyhedral oligomeric silsesquioxane. The substance is an inorganic inner core consisting of a silicon-oxygen framework alternately connected by Si-O, groups R connected by Si atoms on eight vertex angles can be reactive or inert groups, and the molecular structural formula is as follows:
when the amount of the siloxane compound added is too low, the effect of enhancing modulus and elongation at break cannot be exerted; if the amount is too high, the modulus and elongation at break properties of the material are impaired.
The aminosilane oligomer has a molecular weight of 400-4000.
The ethylene copolymer contains 1-10 mass percent of glycidyl methacrylateAn oil ester segment. The glycidyl methacrylate chain segment can react with the end group of PPS to improve compatibility, if the proportion is too low, the effect is not obvious, if the proportion is too high, the reaction is too violent in the processing process, a gel compound is easily formed, and the performance of the material is not facilitated. The method for testing the glycidyl methacrylate chain segment is an infrared spectrum absorption method, and specifically comprises the following steps: first, an infrared spectrum of A910cm was prepared using a series of standards of known epoxy content-1/A1610 cm－1Baseline, then make A910cm-1/A1610 cm-1When the epoxy content of a certain sample is measured, the epoxy content can be determined only by knowing the ratio of A910/M1610 of the sample.
The ethylene copolymer comprises one or more of glycidyl methacrylate-ethylene propylene copolymer, glycidyl methacrylate-ethylene butylene copolymer, glycidyl methacrylate-ethylene octene copolymer, ethylene-glycidyl methacrylate copolymer and ethylene-methyl acrylate-glycidyl methacrylate terpolymer.
The weight portion of the nano flaky filler is preferably 0.4-3.
The thickness of the nano flaky filler is 0.8-5nm, and the diameter of the nano flaky filler is 0.6-5 mu m. When the sheet size is too large, the elongation of the material is adversely affected. When the addition amount is too low, the effect of improving modulus and elongation at break cannot be achieved; when the amount is too high, the elongation is adversely affected. The lamellar structure enables to increase the area of interaction between the resin and the filler without negatively affecting the elongation of the material, which is not possible with spherical or rod-shaped structures.
The nano flaky filler comprises one or more of montmorillonite, kaolin, graphene, boron nitride and talc.
The weight portion of the divalent metal ionic compound is preferably 1-2 portions.
The divalent metal ion compound comprises one or more of zinc ion inorganic salt, zinc ion organic salt, copper ion inorganic salt and copper ion organic salt.
The zinc ion inorganic salt comprises one or more of zinc chloride, zinc sulfate and zinc nitrate.
The zinc ion organic salt comprises one or more of zinc stearate and ethylene-acrylic acid zinc salt copolymer.
The copper ion inorganic salt comprises one or more of copper sulfate and copper nitrate.
The copper ion organic salt comprises one or more of copper stearate and copper acetate.
The composition also comprises 0-3 parts of an auxiliary agent.
The auxiliary agent comprises one or more of a lubricant, an antioxidant and a colorant.
The weight portion of the lubricant is 0.1-3.
The lubricant comprises one or more of polyethylene wax, oxidized polyethylene wax and erucamide.
The weight portion of the antioxidant is 0.1-3.
The antioxidant comprises one or more of ester antioxidant, phosphite antioxidant and thioether antioxidant.
The colorant accounts for 0.1-3 parts by weight.
The colorant comprises one or more of carbon black and titanium dioxide.
The invention also provides a preparation method of the polyphenylene sulfide resin composition, which comprises the following steps;
the components are mixed and added into a double-screw extruder for extrusion granulation to obtain the polyphenylene sulfide resin composition, wherein the extrusion temperature is 280-330 ℃, and the rotation speed is 300-500 revolutions per minute.
0-3 parts of an auxiliary agent is added when all the components are mixed.
The invention also provides application of the polyphenylene sulfide resin composition in electronic and electrical parts, such as battery separators.
Advantageous effects
In the invention, siloxane can interact with molecular chains of PPS to reduce the crystallinity of PPS, so that the modulus of the polyphenylene sulfide resin composition is reduced, but the modulus of the polyphenylene sulfide resin composition can be improved by adding the siloxane and the nano flaky filler at the same time. In addition, the divalent metal ion compound and the nano flaky filler have a synergistic effect, so that the elongation at break of the composition is improved, and the addition of the siloxane can further improve the elongation at break of the polyphenylene sulfide resin composition.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The raw material sources are as follows:
PPS resin: PPS 21150C, with a melt flow rate (316 ℃, 5Kg) of 500g/10min, Xinjiang Xinhe specialty materials Co., Ltd; PPS 1130C having a melt flow rate (316 ℃ C., 5Kg) of 300g/10min, New Zhejiang province specialty materials, Inc.; PPS 3508 having a melt flow rate (316 ℃ C., 5Kg) of 80g/10min was newly blended.
Ethylene copolymer: ethylene-methyl acrylate-glycidyl methacrylate terpolymer, LOTADER AX8840 (mass fraction of glycidyl methacrylate segment 7%), Arkema; the copolymer of glycidyl methacrylate and ethylene octene is preferably easy to prepare, namely SOG-03 (the mass fraction of glycidyl methacrylate chain segments is 3%); BF-E (mass fraction of glycidyl methacrylate chain segment of 12%), Sumitomo.
Siloxane compound: cage-type polyhedral oligomeric silsesquioxane: HSi 1160, national center for research on flame retardant materials engineering technology;
AP1030, aminosilane oligomer, mw 636, new material of han, north of lake, inc.
Nano flaky filler:
montmorillonite (thickness 1nm, diameter 2 μm), FCM-41, Shanghai Maitai Industrial development Co., Ltd;
kaolin (5 nm thick, 5 μm diameter), TRANSLINK 445, 89445, basf;
talc powder: TYT-777A (thickness of 2 μm, diameter of 6 μm), Haicheng addition chemical company, Inc.
Divalent metal ion compound:
zinc stearate, BS-2818, wamitai science and technology, ltd;
copper sulfate, denna bloo chemical ltd;
cuprous chloride, commercially available.
Lubricant: GLYCOLUBE P, commercially available.
Antioxidant: irganox 1076, commercially available.
Colorant: PE2718, commercially available.
The preparation method comprises the following steps:
the components are mixed according to the proportion in the table 1 or the table 2, and the mixture is added into a double-screw extruder to be extruded and granulated to obtain the polyphenylene sulfide resin composition, wherein the temperature of each section of the extruder is set to be 280-330 ℃, and the rotating speed is 300-500 revolutions per minute.
And (3) performance testing:
(1) tensile modulus: ISO 527-2: 2012.
(2) Elongation at break: ISO 527-2: 2012.
TABLE 1 example proportions (parts by weight)
TABLE 2 comparative example proportions (parts by weight)
As is apparent from tables 1 and 2, comparative example 1 in which kaolin was not added and comparative example 2 in which zinc stearate was not added, the elongation at break of the polyphenylene sulfide resin compositions in comparative example 1 and comparative example 2 was significantly lower than that of example 1. Therefore, the divalent metal ion compound and the nano flaky filler have a synergistic effect, and the elongation at break of the polyphenylene sulfide resin composition is improved. Comparative example 3, in which no siloxane was added, the elongation at break of the polyphenylene sulfide resin composition was lower than that of example 1, indicating that the addition of siloxane further increased the elongation at break of the polyphenylene sulfide resin composition. Meanwhile, comparative example 4, in which no silicone and no nano-platelet filler were added, comparative example 1, in which only silicone and no nano-platelet filler were added, and the polyphenylene sulfide resin composition of comparative example 1, having a lower modulus than comparative example 4 and example 1, showed that adding only silicone decreased the modulus of the composition, and comparative example 3, in which only nano-platelet filler and no silicone were added, showed that the polyphenylene sulfide resin composition had a higher modulus than comparative example 4, but less than example 1, showed that adding both nano-platelet filler and silicone increased the modulus of the composition. Also, comparative examples 5 and 6, in which the amount of silicone added is out of the range of the present invention, had compositions with lower elongation at break and lower modulus than example 1. Comparative example 7, in which the amount of the nano flaky filler added was less than the range of the present invention, had a composition modulus and elongation at break lower than those of example 1, and comparative example 8, in which the amount of the nano flaky filler added was more than the range of the present invention, had a composition elongation at break lower than that of example 1. Comparative example 9 using a monovalent metal ion compound, the elongation at break of the composition was significantly lower than that of example 1. The polyphenylene sulfide resin composition has the tensile modulus of more than 2000MPa and the elongation at break of more than 20 percent, and can meet the production requirements in the fields of electronic and electric parts and the like.
Claims (10)
1. The polyphenylene sulfide resin composition is characterized by comprising the following components in parts by weight:
2. the polyphenylene sulfide resin composition according to claim 1, wherein the PPS resin has a melt flow rate of 20 to 500g/10min at 316 ℃ under a 5Kg load; the siloxane compound comprises one or more of ethoxysilane, vinyl silane, aminosilane oligomer and polysiloxane.
3. The polyphenylene sulfide resin composition according to claim 1, wherein the ethylene copolymer comprises 1 to 10 mass% of a glycidyl methacrylate segment; the ethylene copolymer comprises one or more of glycidyl methacrylate-ethylene propylene copolymer, glycidyl methacrylate-ethylene butylene copolymer, glycidyl methacrylate-ethylene octene copolymer, ethylene-glycidyl methacrylate copolymer and ethylene-methyl acrylate-glycidyl methacrylate terpolymer.
4. The polyphenylene sulfide resin composition according to claim 1, wherein the siloxane compound is present in an amount of 0.5 to 2 parts by weight; 0.4-3 parts of nano flaky filler; the weight portion of the divalent metal ionic compound is 1-2 portions.
5. The polyphenylene sulfide resin composition according to claim 1, wherein the nano plate-like filler has a thickness of 0.8 to 5nm and a diameter of 0.6 to 5 μm; the nano flaky filler comprises one or more of montmorillonite, kaolin, graphene, boron nitride and talc.
6. The polyphenylene sulfide resin composition of claim 1, wherein the divalent metal ion compound comprises one or more of zinc ion inorganic salt, zinc ion organic salt, copper ion inorganic salt, and copper ion organic salt.
7. The polyphenylene sulfide resin composition of claim 6, wherein the inorganic salt of zinc ions comprises one or more of zinc chloride, zinc sulfate, and zinc nitrate; the zinc ion organic salt comprises one or more of zinc stearate and ethylene-zinc acrylate copolymer; the copper ion inorganic salt comprises one or more of copper sulfate and copper nitrate; the copper ion organic salt comprises one or more of copper stearate and copper acetate.
8. The polyphenylene sulfide resin composition according to claim 1, further comprising 0-3 parts of an auxiliary; the auxiliary agent comprises one or more of a lubricant, an antioxidant and a colorant.
9. A method for producing the polyphenylene sulfide resin composition according to any one of claims 1 to 8, comprising the steps of;
the components are mixed and added into a double-screw extruder for extrusion granulation to obtain the polyphenylene sulfide resin composition, wherein the extrusion temperature is 280-330 ℃, and the rotation speed is 300-500 revolutions per minute.
10. Use of the polyphenylene sulfide resin composition according to any one of claims 1 to 8 in electronic and electric parts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111454012.8A CN114350149B (en) | 2021-12-01 | 2021-12-01 | Polyphenylene sulfide resin composition and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111454012.8A CN114350149B (en) | 2021-12-01 | 2021-12-01 | Polyphenylene sulfide resin composition and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114350149A true CN114350149A (en) | 2022-04-15 |
| CN114350149B CN114350149B (en) | 2023-07-21 |
Family
ID=81096864
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111454012.8A Active CN114350149B (en) | 2021-12-01 | 2021-12-01 | Polyphenylene sulfide resin composition and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114350149B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1464008A (en) * | 2002-06-07 | 2003-12-31 | 四川大学 | Nano particle polyarylthio-ether composite and method for making same |
| CN101225231A (en) * | 2008-01-29 | 2008-07-23 | 银禧工程塑料（东莞）有限公司 | Insulating heat-conductive glass-fiber reinforced PPS composite material and preparation method thereof |
| CN101275015A (en) * | 2007-03-28 | 2008-10-01 | 四川得阳化学有限公司 | Preparation for fiberglass-containing polyphenyl thioether composite granulates |
| CN107698973A (en) * | 2017-09-14 | 2018-02-16 | 芜湖林电子科技有限公司 | A kind of heat-resisting 3D printing material of automobile high-strength |
-
2021
- 2021-12-01 CN CN202111454012.8A patent/CN114350149B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1464008A (en) * | 2002-06-07 | 2003-12-31 | 四川大学 | Nano particle polyarylthio-ether composite and method for making same |
| CN101275015A (en) * | 2007-03-28 | 2008-10-01 | 四川得阳化学有限公司 | Preparation for fiberglass-containing polyphenyl thioether composite granulates |
| CN101225231A (en) * | 2008-01-29 | 2008-07-23 | 银禧工程塑料（东莞）有限公司 | Insulating heat-conductive glass-fiber reinforced PPS composite material and preparation method thereof |
| CN107698973A (en) * | 2017-09-14 | 2018-02-16 | 芜湖林电子科技有限公司 | A kind of heat-resisting 3D printing material of automobile high-strength |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114350149B (en) | 2023-07-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107629314B (en) | Polypropylene composition and preparation method thereof | |
| CN104788917B (en) | A kind of high-antiwear self-lubricating polyethylene terephthalate and preparation method thereof | |
| CN110204879B (en) | Polycarbonate composition and preparation method thereof | |
| CN104371162A (en) | Flame-retardant wear-resisting modified polypropylene material and preparation method thereof | |
| CN106905674B (en) | A kind of Flame-retardant PET and PC composite material and preparation method | |
| CN109503954A (en) | A kind of PP composite material and its preparation method and application | |
| CN105419294A (en) | Wide angle bending-resistant low-fiber emergency reinforced PC/PBT alloy material and preparation method thereof | |
| CN104194337B (en) | A kind of polyphenyl thioether composite material | |
| CN108727697A (en) | A kind of high flow flame-proof masterbatch | |
| CN115093670B (en) | Multifunctional composite auxiliary agent for PC (personal computer) | |
| US4739001A (en) | Rubber-modified styrene resin composition | |
| CN114350149B (en) | Polyphenylene sulfide resin composition and preparation method and application thereof | |
| CN113308042A (en) | Halogen-free flame-retardant sheath rubber material and preparation method thereof | |
| CN110229441B (en) | Permanent antistatic PVC resin composition and antistatic pipe fitting prepared from same | |
| CN103396643A (en) | Modifier-containing polyacrylate grafted vinyl chloride composite resin composition | |
| CN109486152B (en) | PC/ASA alloy material and preparation method and application thereof | |
| CN113969048B (en) | Bio-based flame-retardant wear-resistant polycarbonate composite material and preparation method and application thereof | |
| CN114163746B (en) | Glass fiber reinforced AS composition and application thereof | |
| CN105885200A (en) | Mildew-proof anti-corrosion flame-retardant cable material and preparation method thereof | |
| CN110183839A (en) | High filled polycarbonate material with excellent surface performance and preparation method thereof | |
| CN114276639B (en) | Weather-resistant high-temperature-resistant high-humidity-resistant ABS (acrylonitrile butadiene styrene) composition and preparation method thereof | |
| CN114149671A (en) | PC/ABS composition and preparation method thereof | |
| CN114274639A (en) | Multilayer co-extrusion transparent high-impact-resistance antistatic polycarbonate composite material and preparation method thereof | |
| CN109135235B (en) | Polycarbonate composition and preparation method and application thereof | |
| JPH0735476B2 (en) | Polyamide resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |