High-temperature-resistant PPS-based cable sheath material and preparation method thereof
By preparing a blend of temperature-resistant plasticizer and modified filler, the problems of plasticizer migration and degradation of high-temperature resistance of PPS-based cable sheath materials were solved, and high toughness and long life of the material were achieved.
Patent Information
- Application Number
- CN202510850157.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-24
- Publication Date
- 2025-10-03
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
Existing PPS-based cable sheath materials have a short service life due to the use of traditional small molecule plasticizers, which leads to plasticizer migration. In addition, the high-temperature resistance is reduced after the introduction of polymer toughening.
A heat-resistant plasticizer is prepared by substitution reaction of heat-resistant polyol and 5,5-dimethyl-2-chloro-1,3,2-dioxaphosphahexanoyl phosphate, and is melt-blended with flame-retardant modified silica on the surface of modified filler to prepare a high-temperature resistant PPS-based cable sheath material.
It improves the toughness and high temperature resistance of PPS-based cable sheath materials, solves the problem of plasticizer migration, and maintains good service life and heat resistance.
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Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of cable sheath material preparation, and in particular relates to a high-temperature resistant PPS-based cable sheath material and a preparation method thereof. Background Art
[0002] Polyphenylene sulfide (PPS) is a polymer composed of sulfur atoms and phenylene rings in a para-substituted pattern. Its molecular structure contains highly stable chemical bonds, resulting in excellent heat resistance and thermal stability, as well as excellent corrosion and chemical resistance. It also exhibits excellent insulation properties in high-temperature and high-humidity environments, making it a promising material for high-temperature cable sheaths. However, due to its poor toughness, PPS often requires the addition of plasticizers and fillers to improve its toughness when used in cable sheaths. Prior art plasticizers used in PPS are typically traditional small molecule plasticizers, or polymers (typically olefin polymers) are used as plasticizers to improve the toughness of the blend by introducing the polymer's excellent elasticity. Small molecule plasticizers can cause migration and precipitation issues, resulting in a short service life for the resulting cable sheath. Furthermore, when polymers are blended for toughening, the higher the polymer content, the lower the high-temperature resistance of the resulting cable sheath compared to the inherent high-temperature resistance of PPS itself. Summary of the Invention
[0003] In response to the above problems, the present invention provides a high-temperature resistant PPS-based cable sheath material and a preparation method thereof.
[0004] The purpose of the present invention is to provide a high-temperature resistant PPS-based cable sheath material and a preparation method thereof, which has solved the high-temperature resistance problem or the short service life problem of the existing PPS-based cable sheath.
[0005] The purpose of the present invention can be achieved through the following technical solutions: The high-temperature resistant PPS-based cable sheath material comprises the following raw materials in parts by weight: 100-110 parts of polyphenylene sulfide, 10-35 parts of a heat-resistant plasticizer, and 20-55 parts of a modified filler.
[0006] Furthermore, the heat-resistant plasticizer is prepared by a substitution reaction of a heat-resistant polyol and 5,5-dimethyl-2-chloro-1,3,2-dioxaphosphahexanoyl phosphate (hereinafter referred to as PO-Cl); The heat-resistant polyol is prepared by hydrosilylation reaction of 1,1,3,3-tetramethyldisiloxane and an intermediate product; The intermediate product is prepared by esterification reaction of 10-undecenoic acid and alkyl polyol.
[0007] Furthermore, the molar ratio of the 10-undecenoic acid, the alkyl polyol, 1,1,3,3-tetramethyldisiloxane (hereinafter referred to as TMDS), and 5,5-dimethyl-2-chloro-1,3,2-dioxaphosphahexadecanoyl phosphate is 2-2.1:2.2-2.4:1:2-3n; Wherein, n is the number of alcoholic hydroxyl groups in the molecular structure of the alkyl polyol.
[0008] Furthermore, the alkyl polyol is one of glycerol and pentaerythritol.
[0009] Furthermore, the substitution reaction conditions are: in the first organic solvent and alkaline conditions, heating to 80-110° C. and reacting for 6-24 hours.
[0010] Furthermore, the first organic solvent is one of N,N-dimethylformamide, N,N-diethylformamide, tetrahydrofuran, and dichloroethane.
[0011] Furthermore, the alkaline condition is a pH of 10-12.
[0012] Furthermore, the alkaline condition is adjusted by sodium hydroxide and / or pyridine.
[0013] Preferably, the specific operation of the substitution reaction is as follows: After uniformly mixing the heat-resistant polyol, PO-Cl and the first organic solvent, adjusting the pH value of the solution to 10-12 with sodium hydroxide and / or pyridine, heating to 80-110° C., reacting for 6-24 hours, and post-treating to obtain a heat-resistant plasticizer.
[0014] Furthermore, the hydrosilylation reaction conditions are: heating to 70-100° C. in the presence of a second organic solvent and a hydrosilylation catalyst, and reacting for 6-24 hours.
[0015] Furthermore, the second organic solvent is one of N,N-dimethylformamide, N,N-diethylformamide, and tetrahydrofuran.
[0016] The hydrosilylation catalyst may be a hydrosilylation catalyst well known in the art (such as a supported platinum catalyst, a supported palladium catalyst, etc.), and the present invention does not impose any specific limitation thereto.
[0017] Preferably, the hydrosilylation reaction is specifically performed as follows: After uniformly mixing 1,1,3,3-tetramethyldisiloxane, the intermediate product and the second organic solvent, a hydrosilylation catalyst is added, stirred evenly, heated to 70-100°C, reacted for 6-24 hours, and subjected to post-treatment to obtain a temperature-resistant polyol.
[0018] Furthermore, the esterification reaction conditions are: heating to 60-100° C. in the presence of a third organic solvent and an esterification reaction catalyst, and reacting for 6-24 hours.
[0019] Furthermore, the third organic solvent is one of N,N-dimethylformamide, N,N-diethylformamide, tetrahydrofuran, dichloroethane The esterification reaction catalyst is an esterification reaction catalyst well known in the art (such as concentrated sulfuric acid, p-toluenesulfonic acid, etc.), and the present invention does not make any specific limitation thereto.
[0020] Preferably, the esterification reaction is specifically performed as follows: After mixing the alkyl polyol, the third organic solvent and the esterification reaction catalyst, the mixture is heated to 60-100° C., and the third solvent containing 10-undecenoic acid is added dropwise. After the addition is complete, the total reaction time is maintained for 6-24 hours. After post-treatment, an intermediate product is obtained.
[0021] Furthermore, the modified filler is surface flame-retardant modified silica.
[0022] The surface flame-retardant modified silicon dioxide is prepared by a surface modification reaction of a flame-retardant silane coupling agent and silicon dioxide.
[0023] Furthermore, the mass ratio of the flame retardant silane coupling agent to silicon dioxide is 2-4:10; The flame retardant silane coupling agent is generated by the reaction of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphophananthrene-10-oxide (hereinafter referred to as DOPO-OH) and an epoxy silane coupling agent.
[0024] The epoxy silane coupling agent is an epoxy silane coupling agent well known in the art (such as KH560), and the present invention does not make any specific limitation thereto.
[0025] The present invention also provides a method for preparing a high-temperature resistant PPS-based cable sheath material, comprising: Polyphenylene sulfide, a heat-resistant plasticizer, a modified filler and a compatibilizer are melt-blended and extruded into granules to obtain a cable sheath material.
[0026] Furthermore, the temperature during the extrusion granulation is 290-330°C.
[0027] Beneficial effects of the present invention: The high-temperature resistant PPS-based cable sheath material and preparation method thereof of the present invention solve the problems of plasticizer migration and short service life of existing PPS-based cable sheath materials by introducing a temperature-resistant plasticizer and a modified filler, and the problem that the temperature resistance of existing PPS-based cable sheath materials is lower than the high-temperature resistance of PPS itself, while maintaining good toughness.
[0028] The toughening effect of the heat-resistant plasticizer in the present invention is manifested in the synergistic polyester toughening of two flexible chains: a long-chain alkyl group (derived from 10-undecenoic acid) and a heat-resistant elastic chain siloxane chain (derived from TMDS). Compared with traditional aliphatic toughening agents (generally polyesters containing long-chain alkyl groups, such as dioctyl adipate and dioctyl sebacate), the introduction of a heat-resistant elastic chain siloxane chain not only maintains the good cold resistance of the aliphatic toughening agent, but also has good heat resistance. Secondly, the heat-resistant plasticizer also contains a heat-resistant phosphate group (derived from PO-Cl). The introduction of the heat-resistant phosphate group further improves the heat resistance of the plasticizer. At the same time, the anchoring effect of the phosphate group is utilized to give the heat-resistant plasticizer good migration resistance. DETAILED DESCRIPTION
[0029] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.
[0030] Example 1 Preparation of temperature-resistant toughening agent: 1. Mix 0.2 mol of glycerol, 100 mL of DMF, and p-toluenesulfonic acid (2% of the reaction substrate by mass), heat to 70°C, and dropwise add 0.22 mol of 10-undecenoic acid in DMF. After complete addition, continue stirring and reacting for 10 hours. Rotary evaporate, wash, and dry to obtain the intermediate product. 2. After mixing 0.1 mol of 1,1,3,3-tetramethyldisiloxane, the intermediate product prepared in step 1, and 100 mL of DMF, add platinum catalyst (the mass of platinum added is 2% of the reaction substrate), stir evenly, heat to 70°C, react for 8 hours, rotary evaporate, wash, and dry to obtain a temperature-resistant polyol; 3. After uniformly mixing the heat-resistant polyol prepared in step 2, 0.3 mol PO-Cl and 150 mL DMF, adjust the pH value of the solution to 10-12 with sodium hydroxide and pyridine, heat to 110°C, react for 6 hours, rotary evaporate, and dry to obtain a heat-resistant plasticizer.
[0031] Example 2 Preparation of temperature-resistant toughening agent: 1. Mix 0.21 mol of pentaerythritol, 100 mL of DMF, and p-toluenesulfonic acid (3% of the reaction substrate by mass), heat to 90°C, and dropwise add 0.23 mol of 10-undecenoic acid in DMF. After complete addition, continue stirring and reacting for 6 hours. Rotary evaporate, wash, and dry to obtain the intermediate product. 2. After mixing 0.1 mol of 1,1,3,3-tetramethyldisiloxane, the intermediate product prepared in step 1, and 100 mL of DMF, add platinum catalyst (the mass of platinum added is 1% of the reaction substrate), stir evenly, heat to 90°C, react for 7 hours, rotary evaporate, wash, and dry to obtain a temperature-resistant polyol; 3. After uniformly mixing the heat-resistant polyol prepared in step 2, 0.6 mol PO-Cl and 150 mL DMF, adjust the pH value of the solution to 10-12 with sodium hydroxide and pyridine, heat to 80°C, react for 12 hours, rotary evaporate, and dry to obtain a heat-resistant plasticizer.
[0032] The PO-Cl in the above embodiment is prepared by the reaction of neopentyl glycol and POCl3 (a reaction well known in the art), and the specific operation is as follows: After neopentyl glycol and chloroform are evenly mixed, POCl3 is slowly added dropwise under an ice-water bath. After the addition is complete, the temperature is slowly raised to 90°C, and the mixture is stirred and reacted for 12 hours. PO-Cl is obtained by rotary evaporation, wherein the molar ratio of neopentyl glycol to POCl3 is 1:1.
[0033] Example 3 Preparation of surface flame retardant modified silica: 1. Mix 0.1 mol of DOPO-OH (commercially available) and 0.1 mol of epoxy silane coupling agent in 80 mL of DMF, adjust the pH of the solution to 10-12 with sodium hydroxide and pyridine, heat to 55°C, stir and react for 4 hours, rotary evaporate, wash, and dry to obtain a flame-retardant silane coupling agent. 2. Evenly mix 20 g of flame-retardant silane coupling agent (KH560), 100 g of nano-silica, 20 mL of water, and 100 mL of ethanol, heat to 75 ° C, keep warm for 10 hours, stop the reaction, age, filter, wash the filter cake, and dry to obtain surface flame-retardant modified silica.
[0034] Example 4 Preparation of surface flame retardant modified silica: 1. Mix 0.1 mol of DOPO-OH (commercially available) and 0.1 mol of epoxy silane coupling agent (KH560) in 80 mL of DMF, adjust the pH of the solution to 10-12 with sodium hydroxide and pyridine, heat to 60°C, stir and react for 6 hours, rotary evaporate, wash, and dry to obtain a flame-retardant silane coupling agent; 2. Evenly mix 40 g of flame-retardant silane coupling agent, 100 g of nano-silica, 20 mL of water and 100 mL of ethanol, heat to 70 ° C, keep warm for 12 hours, stop the reaction, age, filter, wash the filter cake, and dry to obtain surface flame-retardant modified silica.
[0035] Example 5 Preparation of cable sheath material: The first step comprises the following raw materials in parts by weight: 100 parts of polyphenylene sulfide, 10 parts of the temperature-resistant plasticizer prepared in Example 1, and 55 parts of the modified filler prepared in Example 3; In the second step, polyphenylene sulfide, a heat-resistant plasticizer, a modified filler and a compatibilizer are melt-blended and extruded into granules to obtain a cable sheath material; wherein the temperature during the extrusion granulation is 290-330°C.
[0036] Example 6 Preparation of cable sheath material: The first step includes the following raw materials in parts by weight: 105 parts of polyphenylene sulfide, 20 parts of the temperature-resistant plasticizer prepared in Example 2, and 25 parts of the modified filler prepared in Example 4; In the second step, polyphenylene sulfide, a heat-resistant plasticizer, a modified filler and a compatibilizer are melt-blended and extruded into granules to obtain a cable sheath material; wherein the temperature during the extrusion granulation is 290-330°C.
[0037] Example 7 Preparation of cable sheath material: The first step comprises the following raw materials in parts by weight: 110 parts of polyphenylene sulfide, 35 parts of the temperature-resistant plasticizer prepared in Example 1, and 20 parts of the modified filler prepared in Example 3; In the second step, polyphenylene sulfide, a heat-resistant plasticizer, a modified filler and a compatibilizer are melt-blended and extruded into granules to obtain a cable sheath material; wherein the temperature during the extrusion granulation is 290-330°C.
[0038] Comparative Example 1 Preparation of cable sheath material: Compared with Example 5, the temperature-resistant plasticizer in Example 5 was replaced with an equal amount of dioctyl adipate, and the rest were the same.
[0039] Comparative Example 2 Preparation of cable sheath material: Compared with Example 5, the temperature-resistant plasticizer in Example 5 is replaced by an equal amount of the temperature-resistant polyol prepared in step 2 of Example 1 below, and the rest is the same.
[0040] Comparative Example 3 Preparation of cable sheath material: Compared with Example 5, the modified filler in Example 5 is replaced with an equal amount of nano-silica, and the rest is the same.
[0041] The materials obtained in Examples 5-7 and Comparative Examples 1-3 were subjected to physical property testing, and the test results are shown in Table 1. Tensile strength was measured in accordance with GB / T 1040; notched impact strength was measured in accordance with GB / T 1043.1. Thermogravimetric analysis was performed using a differential scanning calorimeter (DSC) under the following test conditions: nitrogen as the carrier gas, a temperature range of -20-600°C, a heating rate of 10°C / min, and a sample mass of 5-8 mg. The migration loss rate (η1) was calculated using the extraction resistance test method, according to ISO 175-2011, using the polar solvent anhydrous ethanol and the non-polar solvent petroleum ether.
[0042] Table 1
[0043] The data in Table 1 demonstrate that the cable sheath materials obtained in Examples 5-7 exhibit excellent toughness and impact resistance, and the added plasticizer exhibits excellent extraction resistance. Furthermore, the cable sheath materials plasticized with the plasticizers obtained in Examples 1-2 exhibit improved thermal stability, as demonstrated by the thermal weight loss temperature.
[0044] Throughout the specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
[0045] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in similar ways. As long as they do not deviate from the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.
Claims
1. A high temperature resistant PPS based cable sheath material, characterized in that: The invention comprises the following raw materials in parts by weight: 100-110 parts of polyphenylene sulfide, 10-35 parts of a heat-resistant plasticizer, and 20-55 parts of a modified filler.
2. A high temperature resistant PPS based cable sheath material according to claim 1, characterized in that: The heat-resistant plasticizer is prepared by a substitution reaction between a heat-resistant polyol and 5,5-dimethyl-2-chloro-1,3,2-dioxaphosphahexanoyl phosphate; The heat-resistant polyol is prepared by hydrosilylation reaction of 1,1,3,3-tetramethyldisiloxane and an intermediate product; The intermediate product is prepared by esterification reaction of 10-undecenoic acid and alkyl polyol.
3. A high temperature resistant PPS-based cable sheath material according to claim 2, characterized in that: The molar ratio of the 10-undecenoic acid, alkyl polyol, 1,1,3,3-tetramethyldisiloxane, and 5,5-dimethyl-2-chloro-1,3,2-dioxaphosphahexadecanoyl phosphate is 2-2.1:2.2-2.4:1:2-3n; Wherein, n is the number of alcoholic hydroxyl groups in the molecular structure of the alkyl polyol.
4. A high temperature resistant PPS based cable sheath material according to claim 2, characterized in that: The alkyl polyol is one of glycerol and pentaerythritol.
5. A high temperature resistant PPS based cable sheath material according to claim 2, characterized in that: The substitution reaction conditions are: heating to 80-110° C. in a first organic solvent under alkaline conditions and reacting for 6-24 hours.
6. A high temperature resistant PPS based cable sheath material according to claim 2, characterized in that: The hydrosilylation reaction conditions are: heating to 70-100° C. in the presence of a second organic solvent and a hydrosilylation catalyst, and reacting for 6-24 hours.
7. A high temperature resistant PPS based cable sheath material according to claim 2, characterized in that: The esterification reaction conditions are: heating to 60-100° C. in the presence of a third organic solvent and an esterification reaction catalyst, and reacting for 6-24 hours.
8. The high temperature resistant PPS-based cable sheath material according to claim 1, characterized in that: The modified filler is surface flame-retardant modified silicon dioxide. The surface flame-retardant modified silicon dioxide is prepared by a surface modification reaction of a flame-retardant silane coupling agent and silicon dioxide.
9. A high temperature resistant PPS-based cable sheath material according to claim 8, characterized in that: The mass ratio of the flame retardant silane coupling agent to silicon dioxide is 2-4:10; The flame-retardant silane coupling agent is generated by the reaction of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphophananthrene-10-oxide and an epoxy silane coupling agent.
10. The method for preparing a high-temperature resistant PPS-based cable sheath material according to any one of claims 1 to 9, characterized in that: include: Polyphenylene sulfide, a heat-resistant plasticizer and a modified filler are melt-blended and extruded into granules to obtain a cable sheath material.