CN112778745B - Modified polyphenylene ether and thermoplastic elastomer, preparation method and application thereof, and composition for preparing thermoplastic elastomer - Google Patents
Modified polyphenylene ether and thermoplastic elastomer, preparation method and application thereof, and composition for preparing thermoplastic elastomer Download PDFInfo
- Publication number
- CN112778745B CN112778745B CN201911090052.1A CN201911090052A CN112778745B CN 112778745 B CN112778745 B CN 112778745B CN 201911090052 A CN201911090052 A CN 201911090052A CN 112778745 B CN112778745 B CN 112778745B
- Authority
- CN
- China
- Prior art keywords
- thermoplastic elastomer
- amount
- weight
- agent
- content
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/123—Polyphenylene oxides not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
-
- 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
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
Landscapes
- 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
The invention relates to the field of thermoplastic elastomer materials, and discloses modified polyphenyl ether and a thermoplastic elastomer, as well as preparation methods and applications thereof, and a composition for preparing the thermoplastic elastomer, wherein the method for preparing the modified polyphenyl ether comprises the following steps: adding polyphenyl ether, impact-resistant polystyrene, polybutene-1 and linear low-density polyethylene into an extruder for plasticizing, extruding and granulating. The modified polyphenyl ether provided by the invention has high physical and mechanical properties, high heat resistance and good flame retardant property, and the mechanical and flame retardant properties of TPE materials can be improved by adopting the modified polyphenyl ether.
Description
Technical Field
The invention relates to the field of thermoplastic elastomer materials, in particular to a method for preparing modified polyphenyl ether, the modified polyphenyl ether prepared by the method, application of the modified polyphenyl ether in preparing a thermoplastic elastomer, a composition for preparing the thermoplastic elastomer, a method for preparing the thermoplastic elastomer, the thermoplastic elastomer prepared by the method, and application of the thermoplastic elastomer in new energy automobile inner cables and charging pile cables.
Background
The thermoplastic elastomer (TPE) based on hydrogenated styrene-butadiene block copolymer (SEBS) comprises the SEBS, white oil, thermoplastic resin and the like, and is a polymer alloy material with general plastic processing performance and similar cross-linked rubber performance.
Double bonds in the SEBS molecular structure are saturated, so that the SEBS molecular structure has the aging resistance; the composition does not contain halogen, and the PVC material is safe, nontoxic, good in stability, soft in texture, beautiful in appearance, comfortable in hand feeling, good in resilience performance and strong in wet skid resistance, and completely avoids the defects of large specific gravity, stiff and greasy hand feeling, strong toxicity of a stabilizer, dialysis of a plasticizer, obvious change of leather hardness along with environment and the like. Different from common rubber, the rubber can not be recycled after being crosslinked, and the thermoplastic elastomer has recyclability, so the thermoplastic elastomer has the characteristic of environmental protection; furthermore, the SEBS-based TPE has high electrical insulation. Based on these characteristics, TPE material can replace PVC to be used as the insulating material of electric wire and cable.
At present, although more than 20 manufacturers of domestic halogen-free flame-retardant electric wire and cable materials exist, most of low-smoke halogen-free flame-retardant electric wire and cable materials have the problems of low mechanical property, low use temperature, poor processing flow property and the like.
In order to increase the service temperature of the wire and cable material, the material is generally endowed with high temperature resistance by adopting an electron beam radiation crosslinking method, but the electron beam radiation crosslinking method has great influence on both the oxygen index and the elongation at break of the material.
The document (Panyox et al, research on APP/PER flame-retardant SEBS/PP blends; plastic industry, 2008, 2 nd stage: 59-61) reports that an APP/PER (IFR) composite intumescent flame retardant flame-retardant SEBS/PP system is adopted, when the addition amount of the flame retardant is 30 parts, the oxygen index of the SEBS/PP flame-retardant system can reach 27%, the tensile strength of the SEBS/PP flame-retardant system is 12.5MPa, and the elongation at break of the SEBS/PP flame-retardant system reaches 492.6%.
CN102898769A discloses a thermoplastic elastomer composition based on a phosphorus-nitrogen composite flame-retardant system for wires and cables, which comprises the following components in percentage by weight: a) TPE matrix material system: 40-70%; b) phosphorus-nitrogen composite flame-retardant system: 25 to 55 percent; c) other auxiliary agents: 0 to 5 percent. The wire and cable materials with different hardness and different colors are prepared by adjusting the composition proportion, the wire and cable prepared by the composition material can reach the standard of VW-1, but the addition amount of the flame retardant is large, and the heat resistance grade is 105 ℃.
Disclosure of Invention
The invention aims to overcome the defects of large consumption of halogen-free flame retardant, low temperature resistance level or low mechanical property of the prepared TPE material when preparing the halogen-free flame-retardant elastomer material in the prior art.
In order to achieve the above object, a first aspect of the present invention provides a process for producing a modified polyphenylene ether, which comprises: adding polyphenyl ether, impact-resistant polystyrene, polybutene-1 and linear low-density polyethylene into an extruder for plasticizing and extruding granulation, wherein the dosage of the polyphenyl ether is 45-55 wt%, the dosage of the impact-resistant polystyrene is 15-25 wt%, the dosage of the polybutene-1 is 5-15 wt% and the dosage of the linear low-density polyethylene is 15-25 wt% based on the total dosage of the polyphenyl ether, the impact-resistant polystyrene, the polybutene-1 and the linear low-density polyethylene.
A second aspect of the present invention provides a modified polyphenylene ether obtained by the process described in the first aspect.
A third aspect of the present invention provides the use of the modified polyphenylene ether of the second aspect described above for the preparation of a thermoplastic elastomer.
In a fourth aspect of the present invention, there is provided a composition for producing a thermoplastic elastomer, which comprises a hydrogenated styrene-butadiene block copolymer, polypropylene, a softening agent, zinc borate, a reinforcing agent, a nitrogen-phosphorus flame retardant, and a modified polyphenylene ether, and which optionally contains a crosslinking agent, wherein the modified polyphenylene ether is the modified polyphenylene ether according to the second aspect.
A fifth aspect of the present invention provides a method of preparing a thermoplastic elastomer, the method comprising: adding the hydrogenated styrene-butadiene block copolymer, polypropylene, a softening agent, zinc borate, a reinforcing agent, a nitrogen-phosphorus flame retardant and a modified polyphenylene ether, optionally together with a crosslinking agent, into an extruder for micro-crosslinking, blending and extrusion granulation, wherein the modified polyphenylene ether is the modified polyphenylene ether of the second aspect.
A sixth aspect of the present invention provides a thermoplastic elastomer prepared by the method of the fifth aspect described above.
The seventh aspect of the invention provides an application of the thermoplastic elastomer of the sixth aspect in new energy automobile interior cables and charging pile cables.
The modified polyphenyl ether provided by the invention has high physical and mechanical properties, high heat resistance and good flame retardant property, and the mechanical and flame retardant properties of TPE materials can be improved by adopting the modified polyphenyl ether. In addition, the problems of large processing viscosity and poor fluidity of the TPE material can be obviously improved by applying the modified polyphenyl ether.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a process for producing a modified polyphenylene ether, which comprises: adding polyphenylene oxide (PPO), impact-resistant polystyrene (HIPS), polybutylene-1 (PB-1) and linear low-density polyethylene (LLDPE) into an extruder for plasticizing and extruding granulation, wherein the dosage of the polyphenylene oxide is 45-55 wt%, the dosage of the impact-resistant polystyrene is 15-25 wt%, the dosage of the polybutylene-1 is 5-15 wt% and the dosage of the linear low-density polyethylene is 15-25 wt% based on the total dosage of the polyphenylene oxide, the impact-resistant polystyrene, the polybutylene-1 and the linear low-density polyethylene.
According to a preferred embodiment, the temperature of the plasticizing and extrusion granulation is 200-240 ℃. The inventor of the invention finds that when the temperature for plasticizing and extrusion granulation is controlled to be 200-240 ℃, the TPE material formed by the prepared modified polyphenyl ether has larger tensile strength and higher heat-resistant grade.
In the aforementioned method for producing a modified polyphenylene ether, for example, the raw material components for producing the modified polyphenylene ether may be dispersed, plasticized, extruded and pelletized at 200-240 ℃.
The method can prepare high-performance modified polyphenyl ether with good flexibility.
Also, the present invention can prepare the modified polyphenylene ether in, for example, a high-torque twin-screw extruder.
Preferably, the polyphenylene oxide (PPO) is a thermoplastic resin obtained by oxidative coupling polymerization of 2, 6-disubstituted phenol.
Preferably, the impact-resistant polystyrene (HIPS) is prepared by dissolving polybutadiene rubber in styrene monomer before polymerization, and has an impact resistance grade of 1.5-2.5 and a bending strength of 13.8-55.1 MPa; the tensile strength is 13.8-41.4 MPa; the elongation at break is 15-75%; the density is 1.035-1.04 g/ml; vicat softening point 185-.
Preferably, the polybutene-1 (PB-1) is prepared by polymerizing isobutene in B-B (butylene-butane) fractions generated by naphtha cracking as a main monomer under the action of a Friede-Crafts catalyst to obtain isobutene in B-B (butylene-butane) fractions generated by naphtha cracking as a main monomer and polymerizing under the action of a Friede-Crafts catalyst.
Preferably, the Linear Low Density Polyethylene (LLDPE) is prepared by gas phase fluidized bed polymerization of ethylene as main raw material and a small amount of alpha-olefin (such as butene-1, octene-1, etc.) under high pressure or low pressure in the presence of a catalyst.
As described above, the second aspect of the present invention provides a modified polyphenylene ether obtained by the process described in the aforementioned first aspect.
As described above, the third aspect of the present invention provides the use of the modified polyphenylene ether according to the aforementioned second aspect for producing a thermoplastic elastomer.
As described above, the fourth aspect of the present invention provides a composition for producing a thermoplastic elastomer, which contains a hydrogenated styrene-butadiene block copolymer, polypropylene, a softening agent, zinc borate, a reinforcing agent, a nitrogen-phosphorus flame retardant and a modified polyphenylene ether, and optionally contains a crosslinking agent, wherein the modified polyphenylene ether is the modified polyphenylene ether of the second aspect.
According to a preferred embodiment, the hydrogenated styrene-butadiene block copolymer is contained in an amount of 15 to 40 wt%, the polypropylene is contained in an amount of 5 to 30 wt%, the softener is contained in an amount of 10 to 30 wt%, the crosslinking agent is contained in an amount of 0 to 0.1 wt%, the zinc borate is contained in an amount of 0.01 to 3 wt%, the reinforcing agent is contained in an amount of 0.5 to 5 wt%, the nitrogen-phosphorus flame retardant is contained in an amount of 18 to 30 wt%, and the modified polyphenylene ether is contained in an amount of 10 to 25 wt%, based on the total weight of the composition.
In order to further improve the mechanical and heat-resistant boarding of the TPE material obtained by the method of the present invention, the present invention provides another more preferred embodiment, based on the total weight of the composition, the content of the hydrogenated styrene-butadiene block copolymer is 20 to 30 wt%, the content of the polypropylene is 10 to 20 wt%, the content of the softener is 15 to 20 wt%, the content of the crosslinking agent is 0.01 to 0.02 wt%, the content of the zinc borate is 0.5 to 1.5 wt%, the content of the reinforcing agent is 2 to 4 wt%, the content of the nitrogen-phosphorus flame retardant is 20 to 22 wt%, and the content of the modified polyphenylene ether is 15 to 20 wt%.
Preferably, the hydrogenated styrene-butadiene block copolymer has a styrene structural unit content of 13 to 33% by weight and a Shore hardness of 47 to 72A.
Preferably, the polypropylene is homo-or co-polypropylene and has a melt index of 1-20g/10 min.
Preferably, the crosslinking agent is at least one of 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane (i.e., the crosslinking agent bis 25), dicumyl peroxide (DCP), and the crosslinking agent BIBP.
Preferably, the softening agent is at least one of white mineral oil, paraffinic oil (e.g., environmentally friendly paraffinic oil), and naphthenic oil.
Preferably, the reinforcing agent is a vinyl-terminated silicone oil.
Preferably, the nitrogen and phosphorus flame retardant is at least one of Doher-6000-1, Nonoff 320 and EPFR-APP 241.
As previously mentioned, a fifth aspect of the present invention provides a method of preparing a thermoplastic elastomer, the method comprising: adding the hydrogenated styrene-butadiene block copolymer, polypropylene, a softening agent, zinc borate, a reinforcing agent, a nitrogen-phosphorus flame retardant and a modified polyphenylene ether, optionally together with a crosslinking agent, into an extruder for micro-crosslinking, blending and extrusion granulation, wherein the modified polyphenylene ether is the modified polyphenylene ether of the second aspect.
In the fifth aspect of the present invention, the optional kinds of each component are the same as those in the fourth aspect of the present invention, and the present invention will not be described herein again in order to avoid redundancy.
Also, according to a preferred embodiment, the hydrogenated styrene-butadiene block copolymer is used in an amount of 15 to 40 wt%, the polypropylene is used in an amount of 5 to 30 wt%, the softening agent is used in an amount of 10 to 30 wt%, the crosslinking agent is used in an amount of 0 to 0.1 wt%, the zinc borate is used in an amount of 0.01 to 3 wt%, the reinforcing agent is used in an amount of 0.5 to 5 wt%, the nitrogen-phosphorus flame retardant is used in an amount of 18 to 30 wt%, and the polyphenylene ether is modified in an amount of 10 to 25 wt%, based on the total amount of the hydrogenated styrene-butadiene block copolymer, the polypropylene, the softener, the zinc borate, the reinforcing agent, the nitrogen-phosphorus flame retardant, the modified polyphenylene ether, and the crosslinking agent.
According to another preferred embodiment, the hydrogenated styrene-butadiene block copolymer is used in an amount of 20 to 30 wt%, the polypropylene is used in an amount of 10 to 20 wt%, the softening agent is used in an amount of 15 to 20 wt%, the crosslinking agent is used in an amount of 0.01 to 0.02 wt%, the zinc borate is used in an amount of 0.5 to 1.5 wt%, the reinforcing agent is used in an amount of 2 to 4 wt%, the nitrogen-phosphorus flame retardant is used in an amount of 20 to 22 wt%, and the modified polyphenylene ether is used in an amount of 15 to 20 wt%, based on the total amount of the hydrogenated styrene-butadiene block copolymer, the polypropylene, the modified polyphenylene ether and the crosslinking agent.
Preferably, in the fifth aspect of the present invention, the extruder is a twin-screw extruder. The twin-screw extruder is preferably a high-torque twin-screw extruder having a large aspect ratio, for example, 60mm and 45 or more in L/D.
Preferably, the conditions for micro-crosslinking include: the temperature is 180 ℃ and 240 ℃, and the rotating speed is 100 ℃ and 500 rpm.
For example, the micro-crosslinking process can control the temperature of a feeding section in a double-screw extruder to be about 200 ℃; the temperature of the melting section is about 220 ℃ and 230 ℃; the temperature of the discharging section is about 210 ℃, and the rotating speed is about 300 rpm.
As previously mentioned, a sixth aspect of the present invention provides a thermoplastic elastomer produced by the method of the fifth aspect.
The thermoplastic elastomer provided by the invention has the characteristic of high temperature resistance, and has good processability and mechanical properties.
As mentioned above, the seventh aspect of the present invention provides a use of the thermoplastic elastomer according to the sixth aspect in a new energy automobile in-vehicle cable and a charging pile cable.
The present invention will be described in detail below by way of examples. In the following examples, all of them are commercially available unless otherwise specified.
Hereinafter, 10g per part by weight is indicated.
Polyphenylene ether was purchased from Lanzhou under the designation LXR 040.
Impact resistant polystyrene is available from olea petrochemical under the designation QG 7855.
Polybutene-1 was purchased from the eastern macro-industrial chemical industry under the designation 030.
Linear low density polyethylene was purchased from the orthopetrochemical trade mark 7050.
Preparation example 1
The modified polyphenylene ether M1 was prepared by adding polyphenylene ether, impact-resistant polystyrene, polybutene-1, and linear low-density polyethylene to a high-torque twin-screw extruder (available from Nanjing Ke-Toron, model number: STS35), dispersing, plasticizing, extruding, and granulating at 220 deg.C, wherein the amounts of the respective materials are shown in Table 1.
Preparation examples 2, 3 and 1 were prepared in exactly the same manner as in preparation example 1 except that the respective substances were used in different amounts, and the modified polyphenylene ethers obtained in preparation examples 2, 3 and 1 were M2, M3 and DM1, respectively, as shown in Table 1.
Preparation example 4
A process similar to that of preparation example 1 was conducted, except that in this preparation example, dispersion, plasticization, extrusion and pelletization were conducted at 190 ℃ to obtain modified polyphenylene ether M4, wherein the amounts of each substance used were as shown in Table 1.
TABLE 1
Example 1
(1) SEBS (503, ba Ling petrochemical), PP (F401, Yangzi petrochemical), white mineral oil (commercially available), a cross-linking agent bis 25 (commercially available), zinc borate (commercially available), vinyl-terminated silicone oil (commercially available), a nitrogen-phosphorus flame retardant (Doher-6000-1, Doher) and modified polyphenylene oxide (self-made) are added into a double-screw extruder (STS 35, purchased from Beijing Kelong, Nanjing) with high torque and large length-diameter ratio for dynamic micro-crosslinking, blending, extruding and granulating to prepare a thermoplastic elastomer material T1, wherein the dosage of each substance is shown in Table 2;
the dynamic micro-crosslinking process conditions are as follows: the phi of the double-screw extruder is 60mm, and the L/D is 45; the temperature of the feeding section is 200 ℃; the temperature of the melting section is 220-230 ℃; the temperature of the discharging section is 210 ℃; the rotation speed was 300 rpm.
The preparation method of the thermoplastic elastomer materials obtained in the examples 2 to 8 is exactly the same as that of the example 1, except that the amount of each material is different, and the thermoplastic elastomer materials obtained in the examples 2 to 8 are sequentially named as T2 to T8, which is specifically shown in Table 2.
Comparative example 1
Comparative example 1 was prepared in a manner similar to that of example 1, except that in this comparative example, no modified polyphenylene ether was added and the resulting thermoplastic elastomer material was designated DT1, as shown in Table 2.
Comparative example 2
Comparative example 2 was prepared similarly to example 1, except that in this comparative example, no crosslinker bis 25, zinc borate, vinyl terminated silicone oil were added and the resulting thermoplastic elastomer material was designated DT2, as shown in Table 2.
Comparative example 3
Comparative example 3 was prepared in a similar manner to example 1, except that in this comparative example modified polyphenylene ether DM1 was used in place of modified polyphenylene ether M1 in example 1, as shown in Table 2.
TABLE 2
Test example
The thermoplastic elastomer materials prepared in the above examples and comparative examples were subjected to the following tests, and the test results are shown in table 3.
(1) Flame retardant rating
The vertical burning time(s) was measured according to the test method of GB/T2408-1996 and the flame retardant rating was determined based on the measured vertical burning time(s), sample size 125mm x 12.5mm x 1.6 mm.
(2) Oxygen index%
The sample sizes were 85mm by 10mm by 3.2mm, as tested in GB/T2406-1993.
(3) Tensile strength and elongation at break
The tensile rate was 500mm/min, as measured by ASTM D412.
(4) Heat resistance rating
Testing according to GB/T32129-2015.
TABLE 3
The results show that the mechanical and flame retardant properties of the TPE material obtained by the invention are obviously improved.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (8)
1. A composition for preparing a thermoplastic elastomer comprising a hydrogenated styrene-butadiene block copolymer, polypropylene, a softening agent, zinc borate, a strengthening agent, a nitrogen phosphorus flame retardant, and a modified polyphenylene ether, and optionally a crosslinking agent, wherein the modified polyphenylene ether is prepared by a process comprising the steps of:
adding polyphenyl ether, impact-resistant polystyrene, polybutylene-1 and linear low-density polyethylene into an extruder for plasticizing, extruding and granulating, wherein the dosage of the polyphenyl ether is 45-55 wt%, the dosage of the impact-resistant polystyrene is 15-25 wt%, the dosage of the polybutylene-1 is 5-15 wt% and the dosage of the linear low-density polyethylene is 15-25 wt% based on the total dosage of the polyphenyl ether, the impact-resistant polystyrene, the polybutylene-1 and the linear low-density polyethylene; the temperature of the plasticizing and extrusion granulation is 200-240 ℃;
based on the total weight of the composition, the content of the hydrogenated styrene-butadiene block copolymer is 15-40 wt%, the content of the polypropylene is 5-30 wt%, the content of the softening agent is 10-30 wt%, the content of the crosslinking agent is 0-0.1 wt%, the content of the zinc borate is 0.01-3 wt%, the content of the reinforcing agent is 0.5-5 wt%, the content of the nitrogen-phosphorus flame retardant is 18-30 wt%, and the content of the modified polyphenylene ether is 10-25 wt%.
2. The composition as claimed in claim 1, wherein the hydrogenated styrene-butadiene block copolymer is contained in an amount of 20 to 30% by weight, the polypropylene is contained in an amount of 10 to 20% by weight, the softening agent is contained in an amount of 15 to 20% by weight, the crosslinking agent is contained in an amount of 0.01 to 0.02% by weight, the zinc borate is contained in an amount of 0.5 to 1.5% by weight, the reinforcing agent is contained in an amount of 2 to 4% by weight, the nitrogen-phosphorus flame retardant is contained in an amount of 20 to 22% by weight, and the modified polyphenylene ether is contained in an amount of 15 to 20% by weight, based on the total weight of the composition.
3. The composition according to claim 1 or 2, wherein the content of styrene structural units in the hydrogenated styrene-butadiene block copolymer is 13 to 33% by weight, and the shore hardness is 47 to 72A;
the cross-linking agent is at least one of 2, 5-dimethyl-2, 5-bis (tert-butyl peroxide) hexane, dicumyl peroxide and a cross-linking agent BIBP;
the softening agent is at least one of white mineral oil, paraffin oil and naphthenic oil;
the reinforcing agent is vinyl-terminated silicone oil;
the nitrogen and phosphorus flame retardant is at least one of Doher-6000-1, fenofibrate 320 and EPFR-APP 241.
4. A process for preparing a thermoplastic elastomer using the components for preparing a thermoplastic elastomer composition according to any one of claims 1 to 3, comprising: adding hydrogenated styrene-butadiene block copolymer, polypropylene, softener, zinc borate, reinforcing agent, nitrogen-phosphorus flame retardant and modified polyphenyl ether, and optionally crosslinking agent into an extruder to sequentially carry out micro-crosslinking, blending and extrusion granulation.
5. The method of claim 4, wherein the extruder is a twin screw extruder.
6. The method of claim 4 or 5, wherein the conditions of micro-crosslinking comprise: the temperature is 180 ℃ and 240 ℃, and the rotating speed is 100 ℃ and 500 rpm.
7. A thermoplastic elastomer prepared by the process of any one of claims 4 to 6.
8. The use of the thermoplastic elastomer of claim 7 in new energy automobile interior cables and charging post cables.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911090052.1A CN112778745B (en) | 2019-11-08 | 2019-11-08 | Modified polyphenylene ether and thermoplastic elastomer, preparation method and application thereof, and composition for preparing thermoplastic elastomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911090052.1A CN112778745B (en) | 2019-11-08 | 2019-11-08 | Modified polyphenylene ether and thermoplastic elastomer, preparation method and application thereof, and composition for preparing thermoplastic elastomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112778745A CN112778745A (en) | 2021-05-11 |
| CN112778745B true CN112778745B (en) | 2022-09-20 |
Family
ID=75748503
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911090052.1A Active CN112778745B (en) | 2019-11-08 | 2019-11-08 | Modified polyphenylene ether and thermoplastic elastomer, preparation method and application thereof, and composition for preparing thermoplastic elastomer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112778745B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115340741A (en) * | 2022-08-12 | 2022-11-15 | 青岛科技大学 | Thermoplastic elastomer flame-retardant material, preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602887A (en) * | 2009-07-07 | 2009-12-16 | 中国蓝星（集团）股份有限公司 | A kind of polyphenylene ether composition and preparation method thereof |
| CN107936449A (en) * | 2017-12-07 | 2018-04-20 | 江苏德威新材料股份有限公司 | Thermoplastic elastomer (TPE) suitable for automobile charging system actual and its preparation method and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI302548B (en) * | 2004-10-18 | 2008-11-01 | Tsrc Corp | Thermoplastic elastomer and the manufacturing method thereof |
-
2019
- 2019-11-08 CN CN201911090052.1A patent/CN112778745B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602887A (en) * | 2009-07-07 | 2009-12-16 | 中国蓝星（集团）股份有限公司 | A kind of polyphenylene ether composition and preparation method thereof |
| CN107936449A (en) * | 2017-12-07 | 2018-04-20 | 江苏德威新材料股份有限公司 | Thermoplastic elastomer (TPE) suitable for automobile charging system actual and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 聚丁烯在改性聚苯醚中的应用;郭建明等;《塑料工业》;20090630;第7-10页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112778745A (en) | 2021-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5896626B2 (en) | Method for producing electric wire molded body comprising silane crosslinkable flame retardant polyolefin and silanol catalyst resin composition | |
| EP2580258B1 (en) | Halogenated flame retardant systems for use in presence of silane grafting process | |
| CN102030963B (en) | Halogen-free fire-retardant thermoplastic elastomer material and preparation method thereof | |
| EP2226355B1 (en) | Moisture-crosslinked polyolefin compositions | |
| CN105038087A (en) | Halogen-free flame retardant high-tear-resistance wire and cable compound for electric vehicles and wire and cable production method | |
| US6476129B2 (en) | Thermoplastic elastomer composition with superior oil resistance | |
| CN102083894A (en) | Reactively processed, high heat resistant composition of polypropylene and an olefinic interpolymer | |
| KR101990737B1 (en) | Polymer composition and compound therefrom for isotropic film, extruded and molded article | |
| CN110938274B (en) | Silane cross-linked semiconductive shielding material and preparation method and application thereof | |
| CN112778745B (en) | Modified polyphenylene ether and thermoplastic elastomer, preparation method and application thereof, and composition for preparing thermoplastic elastomer | |
| JPH11256004A (en) | Flame-retardant thermoplastic elastomer resin composition and its production | |
| JP2008226850A (en) | Flame-retardant thermoplastic elastomer resin composition and manufacturing method therefor | |
| CN108148336B (en) | Halogen-free conductive TPE cable material and preparation method thereof | |
| CN112745653B (en) | Modified polyphenyl ether, halogen-free flame-retardant TPV, preparation methods and applications of modified polyphenyl ether and halogen-free flame-retardant TPV, and composition for preparing halogen-free flame-retardant TPV | |
| CN112662117A (en) | High-tear-strength high-flame-retardance sheath material and preparation method thereof | |
| US10696835B2 (en) | Polymer composition for insulation layer of power cable, insulation layer including the same and power cable including the same | |
| CN113897044B (en) | PC/EVA composition and preparation method thereof | |
| CN110791012A (en) | Irradiation crosslinking low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof | |
| CN114410053B (en) | Thermoplastic elastomer material and preparation method and application thereof | |
| KR20040048097A (en) | Process for preparing thermoplastic elastomer composition | |
| JP4758588B2 (en) | Cross-linked olefin rubber composition | |
| JP4070472B2 (en) | Thermoplastic resin composition and method for producing the same | |
| JP7157257B2 (en) | Thermoplastic elastomer composition | |
| JP2010272531A (en) | Flame-retardant thermoplastic elastomer resin composition and method for manufacturing the same | |
| CN114437463B (en) | Vulcanized composition, EPDM-based vulcanized rubber composition, vulcanized rubber, preparation method and application thereof |
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 |