WO2022068139A1 - Pps composite material and preparation method therefor, and application - Google Patents
Pps composite material and preparation method therefor, and application Download PDFInfo
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- WO2022068139A1 WO2022068139A1 PCT/CN2021/077421 CN2021077421W WO2022068139A1 WO 2022068139 A1 WO2022068139 A1 WO 2022068139A1 CN 2021077421 W CN2021077421 W CN 2021077421W WO 2022068139 A1 WO2022068139 A1 WO 2022068139A1
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- phosphite
- composite material
- pps
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- pps composite
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- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 18
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 239000011256 inorganic filler Substances 0.000 claims description 8
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000002667 nucleating agent Substances 0.000 claims description 7
- AUTOISGCBLBLBA-UHFFFAOYSA-N trizinc;diphosphite Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])[O-].[O-]P([O-])[O-] AUTOISGCBLBLBA-UHFFFAOYSA-N 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- VMFOHNMEJNFJAE-UHFFFAOYSA-N trimagnesium;diphosphite Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])[O-].[O-]P([O-])[O-] VMFOHNMEJNFJAE-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- LXXDUCAGSSICDI-UHFFFAOYSA-N iron(3+);phosphite Chemical group [Fe+3].[O-]P([O-])[O-] LXXDUCAGSSICDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011325 microbead Substances 0.000 claims description 4
- 239000005819 Potassium phosphonate Substances 0.000 claims description 3
- YXXXKCDYKKSZHL-UHFFFAOYSA-M dipotassium;dioxido(oxo)phosphanium Chemical compound [K+].[K+].[O-][P+]([O-])=O YXXXKCDYKKSZHL-UHFFFAOYSA-M 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- XWKBMOUUGHARTI-UHFFFAOYSA-N tricalcium;diphosphite Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])[O-].[O-]P([O-])[O-] XWKBMOUUGHARTI-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- HJJOHHHEKFECQI-UHFFFAOYSA-N aluminum;phosphite Chemical compound [Al+3].[O-]P([O-])[O-] HJJOHHHEKFECQI-UHFFFAOYSA-N 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- XBMOWLAOINHDLR-UHFFFAOYSA-N dipotassium;hydrogen phosphite Chemical compound [K+].[K+].OP([O-])[O-] XBMOWLAOINHDLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- -1 whisker Substances 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims 1
- 239000001488 sodium phosphate Substances 0.000 claims 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims 1
- 230000008025 crystallization Effects 0.000 abstract description 18
- 238000002425 crystallisation Methods 0.000 abstract description 17
- 239000000155 melt Substances 0.000 abstract description 11
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 abstract 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 35
- 229920000069 polyphenylene sulfide Polymers 0.000 description 35
- 230000007423 decrease Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000007547 defect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 2
- ZNEMGFATAVGQSF-UHFFFAOYSA-N 1-(2-amino-6,7-dihydro-4H-[1,3]thiazolo[4,5-c]pyridin-5-yl)-2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound NC=1SC2=C(CN(CC2)C(CC=2OC(=NN=2)C=2C=NC(=NC=2)NC2CC3=CC=CC=C3C2)=O)N=1 ZNEMGFATAVGQSF-UHFFFAOYSA-N 0.000 description 1
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- BZWGENDDUSTHIR-UHFFFAOYSA-N iron phosphorous acid Chemical compound [Fe].P(O)(O)O BZWGENDDUSTHIR-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- 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
- C08K3/32—Phosphorus-containing compounds
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
Definitions
- the invention relates to the technical field of polymer materials, in particular to a PPS composite material and a preparation method thereof.
- Polyphenylene sulfide has excellent heat resistance, solvent resistance, high dimensional stability, and also has excellent dielectric properties, excellent flame retardancy and mechanical properties, and is widely used in electrical and electronic, automotive, machinery, chemical and other fields.
- PPS Polyphenylene sulfide
- the crystallization speed of PPS is relatively slow, which leads to a longer molding cycle and reduced production efficiency, and due to excessive crystallization time, it is easy to lead to insufficient strength during mold release, resulting in mold top cracking, top white, top convex and other problems. Therefore, how to improve the crystallization speed of PPS and shorten the molding cycle is an important topic in the research of PPS modification.
- the nucleating agents used in thermoplastic resins such as PP, PE, and LCP in the prior art cannot be used in PPS composite materials.
- thermoplastic resins such as PP, PE, and LCP in the prior art
- common ultrafine talc, metal carboxylates, etc. because the main chain of the PPS molecule contains a large number of benzene rings, which are rigid and difficult to form microcrystalline nuclei around the nucleating agent, so the common nucleating agent does not promote the crystallization of PPS. effect.
- the purpose of the present invention is to overcome the above technical defects and provide a PPS composite material with a high crystallization rate.
- Another object of the present invention is to provide a method for preparing the above-mentioned PPS composite material.
- a PPS composite material by weight, comprises the following components:
- the improvement of the melt fluidity of the PPS composite material is better.
- the principle that the metal phosphite can nucleate in the PPS resin matrix is that the metal phosphite reacts with PPS to form a crystal nucleus with a tiny size, and the crystal nucleus acts as a crystallization center, thereby promoting the crystallization speed of PPS.
- the metal phosphite is selected from at least one of iron phosphite, potassium phosphite, zinc phosphite, aluminum phosphite, magnesium phosphite, potassium hydrogen phosphite, sodium phosphite and calcium phosphite.
- the metal phosphite is selected from at least one of iron phosphite, zinc phosphite and magnesium phosphite.
- the present invention can improve the technical defect that the melt flow rate decreases to a certain extent by adding a certain amount of phosphite metal salt.
- it also includes 0-100 parts of inorganic fillers; the inorganic fillers are selected from calcium carbonate, talc, mica, barium sulfate, wollastonite, silica, kaolin, montmorillonite, whiskers, glass At least one of microbeads and ceramic microbeads.
- the melting index of the PPS resin is between 10-250g/10min (ISO 1133-2011 standard, 300°C, 1.2kg).
- the preparation method of the above-mentioned PPS composite material is characterized in that, according to the proportioning, the components are mixed uniformly and then added to extrude and granulate through a twin-screw extruder.
- the twin-screw extrusion process is as follows, and the extrusion temperature is 180 in 1 zone -200°C, 260-290°C in zone 2-9, screw speed 300-500 rpm.
- metal phosphite as a nucleating agent for PPS composite materials, in parts by weight, includes the following components: 100 parts of PPS resin; 0.1-10 parts of metal phosphite.
- the present invention overcomes the application defect that the existing nucleating agent cannot effectively function and the PPS composite material, and provides metal phosphite as a nucleating agent, which can effectively improve the crystallization performance of the PPS composite material (reduce the crystallization peak half of the material). height and width, increase the crystallization temperature).
- the addition of metal phosphite can improve the melt flow rate decrease after the addition of inorganic fillers to a certain extent.
- the raw materials used in the present invention are derived from commercially available products:
- PPS resin PPS 1150C, melting index 60g/10min (ISO 1133-2011 standard, 300°C, 1.2kg);
- Magnesium phosphite commercially available
- Zinc phosphite commercially available
- Ferric phosphite commercially available
- Potassium phosphite commercially available
- Aluminum hypophosphite commercially available.
- the preparation method of the PPS composite material of the examples and comparative examples the components are mixed uniformly and then added to the twin-screw extruder for extrusion and granulation.
- the twin-screw extrusion process is as follows. °C, three zones 280°C, four zones 285°C, five zones 285°C, six zones 285°C, seven zones 280°C, eight zones 280°C, nine zones 280°C, the screw speed is 400 rpm.
- FWHM of crystallization peak FWHM of crystallization peak ( ⁇ T 1/2 ):
- the test is carried out with reference to ASTM D3418-2003, Standard Test Method for Transition Temperatures of Polymers By Differential Scanning Calorimetry.
- Table 1 The distribution ratio (parts by weight) of each component of the PPS composite material of Example 1-5 and the test results of various properties
- Table 2 The distribution ratio (parts by weight) of each component of the PPS composite material of Example 6-11 and the test results of various properties
- Example 11 It can be seen from Example 11 that the addition of 50 parts of calcium carbonate filler will lead to a decrease in the melt flow rate of the PPS composite material. Combining with Comparative Example 2, it can be seen that the presence of magnesium phosphite can to a certain extent improve the defect that the melt flow rate decreases after the addition of inorganic fillers.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Disclosed is a PPS composite material, comprising the following components in parts by weight: 100 parts of a PPS resin, and 0.1-10 parts of a phosphorous acid metal salt. By adding the phosphorous acid metal salt, the crystallization rate of the PPS composite material can be increased. The PPS composite material can have the advantage of rapid crystallization, and the melt flow rate of the PPS composite material can be increased.
Description
本发明涉及高分子材料技术领域，特别是涉及一种PPS复合材料及其制备方法。The invention relates to the technical field of polymer materials, in particular to a PPS composite material and a preparation method thereof.
聚苯硫醚(PPS)具有优异的耐热性、耐溶剂、高尺寸稳定性，还具有优良的介电性能、优良的阻燃性及力学性能，广泛应用于电子电气、汽车、机械、化工等领域。但是PPS的结晶速度比较慢，导致其成型周期变长、降低了生产效率，并且由于过长的结晶时间，容易导致出模时强度不够，使得产生出模顶裂、顶白、顶凸等问题，因此，如何提高PPS的结晶速度，缩短成型周期，是PPS改性研究中的重要课题。Polyphenylene sulfide (PPS) has excellent heat resistance, solvent resistance, high dimensional stability, and also has excellent dielectric properties, excellent flame retardancy and mechanical properties, and is widely used in electrical and electronic, automotive, machinery, chemical and other fields. However, the crystallization speed of PPS is relatively slow, which leads to a longer molding cycle and reduced production efficiency, and due to excessive crystallization time, it is easy to lead to insufficient strength during mold release, resulting in mold top cracking, top white, top convex and other problems. Therefore, how to improve the crystallization speed of PPS and shorten the molding cycle is an important topic in the research of PPS modification.
但是，由于各种聚合物的成核方式与成核机理并不完全相同，现有技术中应用于PP、PE、LCP等热塑性树脂的成核剂并不能应用于PPS复合材料中。如常见的超细滑石粉、金属羧酸盐等，由于PPS分子中主链含有大量苯环，刚性大，难以围绕成核剂形成微晶核，因此普通成核剂对PPS的结晶并无促进作用。However, since the nucleation methods and nucleation mechanisms of various polymers are not exactly the same, the nucleating agents used in thermoplastic resins such as PP, PE, and LCP in the prior art cannot be used in PPS composite materials. For example, common ultrafine talc, metal carboxylates, etc., because the main chain of the PPS molecule contains a large number of benzene rings, which are rigid and difficult to form microcrystalline nuclei around the nucleating agent, so the common nucleating agent does not promote the crystallization of PPS. effect.
进一步的，PPS复合材料在加入填料后会导致熔体流动速率的下降，在提升了PPS复合材料结晶速率的前提下，如果PPS复合材料的熔体流动性下降，可能会导致制件中充填不完整、孔洞、表面不完整等缺陷。Further, the addition of fillers to PPS composites will lead to a decrease in the melt flow rate. On the premise of increasing the crystallization rate of PPS composites, if the melt flowability of PPS composites decreases, it may lead to poor filling in the parts. Defects such as completeness, holes, and incomplete surfaces.
发明内容SUMMARY OF THE INVENTION
本发明目的在于，克服上述技术缺陷，提供一种具有高结晶速率的PPS复合材料。The purpose of the present invention is to overcome the above technical defects and provide a PPS composite material with a high crystallization rate.
本发明的另一目的在于，提供上述PPS复合材料的制备方法。Another object of the present invention is to provide a method for preparing the above-mentioned PPS composite material.
本发明是通过以下技术方案实现的：The present invention is achieved through the following technical solutions:
一种PPS复合材料，按重量份计，包括以下组分：A PPS composite material, by weight, comprises the following components:
PPS树脂 100份；100 parts of PPS resin;
亚磷酸金属盐 0.1-10份。Phosphite metal salt 0.1-10 parts.
优选的，按重量份计，亚磷酸金属盐2.5-7份。在本优选的用量范围下，对于PPS复合材料熔体流动性的提升更好。Preferably, in parts by weight, 2.5-7 parts of metal phosphite. Under the preferred dosage range, the improvement of the melt fluidity of the PPS composite material is better.
亚磷酸金属盐能够在PPS树脂基体中成核的原理是亚磷酸金属盐与PPS反应，形成具有微小尺寸的晶核，晶核作为结晶中心，从而促进PPS的结晶速度。The principle that the metal phosphite can nucleate in the PPS resin matrix is that the metal phosphite reacts with PPS to form a crystal nucleus with a tiny size, and the crystal nucleus acts as a crystallization center, thereby promoting the crystallization speed of PPS.
所述的亚磷酸金属盐选自亚磷酸铁、亚磷酸钾、亚磷酸锌、亚磷酸铝、亚磷酸镁、亚磷酸氢钾、亚磷酸钠、亚磷酸钙中的至少一种。The metal phosphite is selected from at least one of iron phosphite, potassium phosphite, zinc phosphite, aluminum phosphite, magnesium phosphite, potassium hydrogen phosphite, sodium phosphite and calcium phosphite.
优选的，所述的亚磷酸金属盐选自亚磷酸铁、亚磷酸锌、亚磷酸镁中的至少一种。Preferably, the metal phosphite is selected from at least one of iron phosphite, zinc phosphite and magnesium phosphite.
为了提升PPS复合材料的机械性能，可以加入一定量的无机填料。但是无机填料的加入量越大，PPS复合材料的熔体流动速率下降越多。本发明通过加入一定量的亚磷酸金属盐能够在一定程度上改善熔体流动速率下降的技术缺陷。按重量份计，还包括0-100份无机填料；所述的无机填料选自碳酸钙、滑石粉、云母、硫酸钡、硅灰石、二氧化硅、高岭土、蒙脱土、晶须、玻璃微珠、陶瓷微珠中的至少一种。所述的PPS树脂的熔指在10-250g/10min之间(ISO 1133-2011标准，300℃，1.2kg)。In order to improve the mechanical properties of PPS composites, a certain amount of inorganic fillers can be added. However, the greater the amount of inorganic filler added, the more the melt flow rate of the PPS composite decreased. The present invention can improve the technical defect that the melt flow rate decreases to a certain extent by adding a certain amount of phosphite metal salt. In parts by weight, it also includes 0-100 parts of inorganic fillers; the inorganic fillers are selected from calcium carbonate, talc, mica, barium sulfate, wollastonite, silica, kaolin, montmorillonite, whiskers, glass At least one of microbeads and ceramic microbeads. The melting index of the PPS resin is between 10-250g/10min (ISO 1133-2011 standard, 300°C, 1.2kg).
上述的PPS复合材料的制备方法，其特征在于，按照配比，将各组分混合均匀后加入通过双螺杆挤出机挤出造粒，双螺杆挤出工艺如下，挤出温度：1区180-200℃，2-9区260-290℃，螺杆转速为300-500转/分钟。The preparation method of the above-mentioned PPS composite material is characterized in that, according to the proportioning, the components are mixed uniformly and then added to extrude and granulate through a twin-screw extruder. The twin-screw extrusion process is as follows, and the extrusion temperature is 180 in 1 zone -200°C, 260-290°C in zone 2-9, screw speed 300-500 rpm.
亚磷酸金属盐作为PPS复合材料成核剂的应用，按重量份计，包括以下组分：PPS树脂100份；亚磷酸金属盐0.1-10份。The application of metal phosphite as a nucleating agent for PPS composite materials, in parts by weight, includes the following components: 100 parts of PPS resin; 0.1-10 parts of metal phosphite.
本发明具有如下有益效果The present invention has the following beneficial effects
一方面，本发明克服了现有的成核剂无法有效作用与PPS复合材料中的应用缺陷，提供了亚磷酸金属盐作为成核剂，能够有效提升PPS复合材料的结晶性能(降低结晶峰半高宽、提升结晶温度)。另一方面，亚磷酸金属盐的加入，能够在一定程度上改善无机填料加入后导致熔体流动速率下降。On the one hand, the present invention overcomes the application defect that the existing nucleating agent cannot effectively function and the PPS composite material, and provides metal phosphite as a nucleating agent, which can effectively improve the crystallization performance of the PPS composite material (reduce the crystallization peak half of the material). height and width, increase the crystallization temperature). On the other hand, the addition of metal phosphite can improve the melt flow rate decrease after the addition of inorganic fillers to a certain extent.
本发明是通过以下实施例进行更详细描述，但是本发明不受以下实施例的限制。The present invention is described in more detail by the following examples, but the present invention is not limited by the following examples.
本发明所使用的原料来源于市售产品：The raw materials used in the present invention are derived from commercially available products:
PPS树脂：PPS 1150C，熔指60g/10min(ISO 1133-2011标准，300℃，1.2kg)；PPS resin: PPS 1150C, melting index 60g/10min (ISO 1133-2011 standard, 300℃, 1.2kg);
亚磷酸镁：市售；Magnesium phosphite: commercially available;
亚磷酸锌：市售；Zinc phosphite: commercially available;
亚磷酸铁：市售；Ferric phosphite: commercially available;
亚磷酸钙：市售；Calcium phosphite: commercially available;
亚磷酸钠：市售；Sodium phosphite: commercially available;
亚磷酸钾：市售；Potassium phosphite: commercially available;
碳酸钙：800目；Calcium carbonate: 800 mesh;
次磷酸铝：市售。Aluminum hypophosphite: commercially available.
实施例和对比例PPS复合材料的制备方法：将各组分混合均匀后加入通过双螺杆挤出机 挤出造粒，双螺杆挤出工艺如下，挤出温度：一区190℃，二区270℃，三区280℃，四区285℃，五区285℃，六区285℃，七区280℃，八区280℃，九区280℃，螺杆转速为400转/分钟。The preparation method of the PPS composite material of the examples and comparative examples: the components are mixed uniformly and then added to the twin-screw extruder for extrusion and granulation. The twin-screw extrusion process is as follows. ℃, three zones 280°C, four zones 285°C, five zones 285°C, six zones 285°C, seven zones 280°C, eight zones 280°C, nine zones 280°C, the screw speed is 400 rpm.
各项性能测试方法：Various performance test methods:
(1)结晶温度：采用DSC测试。(1) Crystallization temperature: DSC test was used.
(2)结晶峰半高宽：结晶峰半高宽(ΔT
1/2)：参照ASTM D3418-2003，Standard Test Method for Transition Temperatures of PolymersBy Differential Scanning Calorimetry进行测试。具体的测试方法为采用Perkin Elmer Dimond DSC分析仪测试样品的熔点；氮气气氛，流速为40mL/min；测试时先以10℃/min升温至350℃，在350℃保持5min，然后以10℃/min冷却到50℃，将放热峰起始温度设为熔点T
1，放热峰终点温度设为熔点T
2，ΔT
1/2＝(T
1-T
2)/2。。
(2) FWHM of crystallization peak: FWHM of crystallization peak (ΔT 1/2 ): The test is carried out with reference to ASTM D3418-2003, Standard Test Method for Transition Temperatures of Polymers By Differential Scanning Calorimetry. The specific test method is to use Perkin Elmer Dimond DSC analyzer to test the melting point of the sample; nitrogen atmosphere, the flow rate is 40mL/min; during the test, the temperature is first heated to 350°C at 10°C/min, kept at 350°C for 5min, and then at 10°C/min. Min cooled to 50°C, the exothermic peak starting temperature was set to melting point T 1 , the exothermic peak ending temperature was set to melting point T 2 , ΔT 1/2 =(T 1 −T 2 )/2. .
(3)熔体流动速率：按照ISO1133表针，测试条件300℃，1.2kg(3) Melt flow rate: according to ISO1133 needle, test condition 300℃, 1.2kg
表1：实施例1-5PPS复合材料各组分配比(重量份)及各项性能测试结果Table 1: The distribution ratio (parts by weight) of each component of the PPS composite material of Example 1-5 and the test results of various properties
由实施例1-5可知，亚磷酸锌的含量在2.5-7份时结晶峰半高宽较低，并且熔体流动速率较高。当亚磷酸锌含量10份时，熔体流动速率下降，而结晶峰半高宽也会开始上升。It can be seen from Examples 1-5 that when the content of zinc phosphite is 2.5-7 parts, the full width at half maximum of the crystallization peak is lower, and the melt flow rate is higher. When the content of zinc phosphite is 10 parts, the melt flow rate decreases, and the FWHM of the crystallization peak also begins to increase.
表2：实施例6-11PPS复合材料各组分配比(重量份)及各项性能测试结果Table 2: The distribution ratio (parts by weight) of each component of the PPS composite material of Example 6-11 and the test results of various properties
由实施例11可知，50份碳酸钙填料的加入会导致PPS复合材料熔体流动速率的下降。结合对比例2可知，亚磷酸镁的存在能够在一定程度上改善无机填料加入后熔体流动速率下降的缺陷。It can be seen from Example 11 that the addition of 50 parts of calcium carbonate filler will lead to a decrease in the melt flow rate of the PPS composite material. Combining with Comparative Example 2, it can be seen that the presence of magnesium phosphite can to a certain extent improve the defect that the melt flow rate decreases after the addition of inorganic fillers.
表3：对比例-PPS复合材料各组分配比(重量份)及各项性能测试结果Table 3: Comparative example-PPS composite material distribution ratio (parts by weight) and various performance test results
Claims (8)
- 一种PPS复合材料，其特征在于，按重量份计，包括以下组分：A kind of PPS composite material is characterized in that, by weight, comprises the following components:PPS树脂 100份；100 copies of PPS resin;亚磷酸金属盐 0.1-10份。0.1-10 parts of metal phosphite.
- 根据权利要求1所述的PPS复合材料，其特征在于，按重量份计，亚磷酸金属盐2.5-7份。The PPS composite material according to claim 1, wherein, in parts by weight, 2.5-7 parts of metal phosphite.
- 根据权利要求1所述的PPS复合材料，其特征在于，所述的亚磷酸金属盐选自亚磷酸铁、亚磷酸钾、亚磷酸锌、亚磷酸铝、亚磷酸镁、亚磷酸氢钾、亚磷酸钠、亚磷酸钙中的至少一种。PPS composite material according to claim 1, is characterized in that, described phosphite metal salt is selected from iron phosphite, potassium phosphite, zinc phosphite, aluminum phosphite, magnesium phosphite, potassium hydrogen phosphite, phosphite At least one of sodium phosphate and calcium phosphite.
- 根据权利要求3所述的PPS复合材料，其特征在于，所述的亚磷酸金属盐选自亚磷酸铁、亚磷酸锌、亚磷酸镁中的至少一种。The PPS composite material according to claim 3, wherein the metal phosphite is selected from at least one of iron phosphite, zinc phosphite and magnesium phosphite.
- 根据权利要求1所述的PPS复合材料，其特征在于，按重量份计，还包括0-100份无机填料；所述的无机填料选自碳酸钙、滑石粉、云母、硫酸钡、硅灰石、二氧化硅、高岭土、蒙脱土、晶须、玻璃微珠、陶瓷微珠中的至少一种。The PPS composite material according to claim 1, further comprising 0-100 parts by weight of inorganic filler; the inorganic filler is selected from calcium carbonate, talc, mica, barium sulfate, wollastonite , at least one of silica, kaolin, montmorillonite, whisker, glass microbeads and ceramic microbeads.
- 根据权利要求1所述的PPS复合材料，其特征在于，所述的PPS树脂的熔指在10-250g/10min之间(ISO 1133-2011标准，300℃，1.2kg)。The PPS composite material according to claim 1, wherein the melting finger of the PPS resin is between 10-250g/10min (ISO 1133-2011 standard, 300°C, 1.2kg).
- 权利要求1-6任一项所述PPS复合材料的制备方法，其特征在于，按照配比，将各组分混合均匀后加入通过双螺杆挤出机挤出造粒，双螺杆挤出工艺如下，挤出温度：1区180-200℃，2-9区260-290℃，螺杆转速为300-500转/分钟。The preparation method of the PPS composite material described in any one of claims 1-6, it is characterized in that, according to proportioning, after each component is mixed uniformly, add and extrude and granulate by twin-screw extruder, and the twin-screw extrusion process is as follows , Extrusion temperature: 180-200 ℃ in zone 1, 260-290 ℃ in zone 2-9, screw speed of 300-500 rpm.
- 亚磷酸金属盐作为PPS复合材料成核剂的应用，其特征在于，按重量份计，包括以下组分：PPS树脂100份；亚磷酸金属盐0.1-10份。The application of a phosphite metal salt as a nucleating agent for a PPS composite material is characterized in that, in parts by weight, the following components are included: 100 parts of PPS resin; and 0.1-10 parts of a phosphite metal salt.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1205020A (en) * | 1996-07-22 | 1999-01-13 | 东丽株式会社 | Polyphenylene sulfide resin composition |
| CN1513914A (en) * | 2002-12-27 | 2004-07-21 | ������������ʽ���� | Polyphenyl thioether resin composition |
| CN108219460A (en) * | 2018-02-07 | 2018-06-29 | 深圳华力兴新材料股份有限公司 | A kind of NMT technologies PPS/SPS engineering plastics and preparation method |
| CN108250751A (en) * | 2018-02-07 | 2018-07-06 | 深圳华力兴新材料股份有限公司 | The NMT technologies polyphenyl thioether resin composition and preparation method of a kind of low-k |
| CN109385091A (en) * | 2017-08-03 | 2019-02-26 | 吕素慧 | A kind of fiberglass reinforced polyphenyl thioether composite material and preparation method thereof |
| CN112341816A (en) * | 2020-09-30 | 2021-02-09 | 金发科技股份有限公司 | PPS composite material, preparation method and application thereof |
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| CN109082115A (en) * | 2018-08-09 | 2018-12-25 | 江苏利思德新材料有限公司 | Thermoplastic polymer or the high-temperature thermal stability method of its compound are improved using inorganic phosphorous acid metal salt |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1205020A (en) * | 1996-07-22 | 1999-01-13 | 东丽株式会社 | Polyphenylene sulfide resin composition |
| CN1513914A (en) * | 2002-12-27 | 2004-07-21 | ������������ʽ���� | Polyphenyl thioether resin composition |
| CN109385091A (en) * | 2017-08-03 | 2019-02-26 | 吕素慧 | A kind of fiberglass reinforced polyphenyl thioether composite material and preparation method thereof |
| CN108219460A (en) * | 2018-02-07 | 2018-06-29 | 深圳华力兴新材料股份有限公司 | A kind of NMT technologies PPS/SPS engineering plastics and preparation method |
| CN108250751A (en) * | 2018-02-07 | 2018-07-06 | 深圳华力兴新材料股份有限公司 | The NMT technologies polyphenyl thioether resin composition and preparation method of a kind of low-k |
| CN112341816A (en) * | 2020-09-30 | 2021-02-09 | 金发科技股份有限公司 | PPS composite material, preparation method and application thereof |
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