CN102604336B - Low-smoke, halogen-free and flame-retardant polyester elastomer thin-wall insulating material and preparation method thereof - Google Patents

Low-smoke, halogen-free and flame-retardant polyester elastomer thin-wall insulating material and preparation method thereof Download PDF

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CN102604336B
CN102604336B CN201210070032.XA CN201210070032A CN102604336B CN 102604336 B CN102604336 B CN 102604336B CN 201210070032 A CN201210070032 A CN 201210070032A CN 102604336 B CN102604336 B CN 102604336B
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polyester elastomer
low
retardant polyester
insulation material
flame
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CN102604336A (en
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董景茹
汪全信
董文博
汪全伟
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TIANJIN POLYTECH POLYMER TECHNOLOGY Co Ltd
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TIANJIN POLYTECH POLYMER TECHNOLOGY Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B29C2948/9259—Angular velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92885—Screw or gear
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The invention discloses a low-smoke, halogen-free and flame-retardant polyester elastomer thin-wall insulating material and a preparation method thereof. The insulating material mainly comprises the following components in parts by weight: 60-80 parts of polyester elastomer, 20-30 parts of nanocomposite flame retardant, 2-5 parts of anti-hydrolysis stabilizer, 1-2 parts of main antioxidant, 0.3-0.5 part of auxiliary antioxidant and 2-5 parts of lubricant. The method comprises the following steps of: uniformly mixing each component of the low-smoke, halogen-free and flame-retardant polyester elastomer thin-wall insulating material in a mixer at the temperature of 125 DEG C; and extruding and pelletizing in a double screw extruder. According to the insulating material, degradation and carbonization of acids are prevented, degradation and brittleness of the polyester elastomer in a high-heat and moist heat environment are eliminated by using the amine anti-hydrolysis stabilizer, long-term aging performance is ensured by using the special high-temperature-resistant antioxidant, the insulating performance is improved by blending polyolefin resin, and smooth and fine product appearance are ensured by using the special lubricant.

Description

Low-smoke non-halogen flame-retardant polyester elastomer thin-walled insulation material and preparation method thereof
One, technical field
The present invention relates to a kind of wire cable material and preparation method thereof, particularly a kind of low-smoke non-halogen flame-retardant polyester elastomer thin-walled insulation material for rail transit rolling stock cable and automotive line and preparation method thereof.
Two, background technology
Current developing rapidly and appearance and the security needs of the ROHS of European Union and REACH environmental regulation along with high-speed railway, urban track traffic and automobile industry, more and more higher with cable and line for cars beam request to track traffic (bullet train, subway), require to meet the automotive line standards such as the rolling stock specifications of cables such as GB/T12528, TB/T1484, BS EN50306 and QC/T730, ISO6722, Japanese JASC3406 and JASO D611, U.S. SAE1678, German DIN72551, French NF R13414.
Above standard not only requires cable safety, environmental protection, energy-conservation, the resistance to 125 ℃ of high temperature of specific requirement, wear-resisting, oil resistant, Halogen, cold-resistant, high strength, fire-retardant, and need to be to lightweight future development, be thin-walled, ultra-thin-wall (0.25mm), and traditional polyvinyl chloride (PVC), flame retardant polyolefine material, fluorine material cannot meet the demands, only have low-smoke non-halogen flame-retardant polyester elastomer Insulation Material can meet above requirement.
Low-smoke non-halogen flame-retardant polyester elastomer thin-walled insulation material has the following disadvantages at present: 1. 158 ℃, 168 hours aging resistance of high temperature ageing are defective; 2. processing safety is poor, easily degraded; 3. insulating property are poor, and volume specific resistance is low; 4. flame retardant properties is difficult to reach UL94V-O level level.According to existing market, use kind sampling and testing test result performance as following table 1.
Table 1
Figure GDA0000432645530000011
Three, summary of the invention
For solving the deficiencies in the prior art, the object of the present invention is to provide a kind of low-smoke non-halogen flame-retardant polyester elastomer thin-walled insulation material that comprehensively meets above standard-required and preparation method thereof, polyester elastomer (ester-ester) multipolymer of concrete employing special molecular structure is that basic raw material is to substitute the poor traditional polyester-ether type multipolymer of high-temperature behavior, add the efficient halogen-free combustion inhibitor special that does not contain acids group, prevent degraded and charing that acids produces, the degraded embrittlement producing under Gao Re and hygrothermal environment to solve polyester elastomer with amine resistant to hydrolysis stablizer, special fire-resistant oxidation resistant agent is to guarantee long-term ageing property, with polyolefin blend, improve insulating property, special lubricant is to guarantee the smooth exquisiteness of product appearance.
For realizing above object, technical scheme of the present invention is:
A low-smoke non-halogen flame-retardant polyester elastomer thin-walled insulation material, described Insulation Material chief component and content are: (following component is in parts by weight)
Figure GDA0000432645530000022
Figure GDA0000432645530000031
It is the ester-ester multipolymer of 50～70D that wherein said polyester elastomer resin is preferentially selected hardness.
Described polyolefin resin is 4-methylpentene multipolymer.
Described composite nanometer flame retardant preferentially adopts decomposition temperature to be greater than 280 ℃, the composite nitrogen phosphorus fire retardant that contains nano-dispersed agent that pH value is 5～7.
Described resistant to hydrolysis stablizer preferentially adopts aggretion type carbonization diamines.
Described primary antioxidant preferentially adopts N, N '-hexamethylene-bis-[3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid amide].
Described auxiliary antioxidant preferentially adopts Tyox B.
Described lubricant preferentially adopts high molecular silicone resin.
The preparation method of low-smoke non-halogen flame-retardant polyester elastomer thin-walled insulation material of the present invention is:
Material in described composition of raw materials is sent in mixing machine and mixed after preparing according to parts by weight separately, extruding pelletization in the twin screw extruder that is then 65mm at diameter, wherein extrusion temperature is 160～240 ℃, extruded velocity is 300～400 revs/min.
Adopt electric wire main performance requirements that low-smoke non-halogen flame-retardant polyester elastomer thin-walled insulation material of the present invention and preparation method thereof extrudes as following table 2:
Table 2
Figure GDA0000432645530000032
Figure GDA0000432645530000041
Four, accompanying drawing explanation
Below in conjunction with drawings and Examples, invention is further illustrated.
Fig. 1 is process flow sheet of the present invention
Five, embodiment
The low-smoke non-halogen flame-retardant polyester elastomer thin-walled insulation material and preparation method thereof of take is embodiment, in conjunction with Fig. 1, the present invention is done to further specific descriptions, but is not limited to this.In following example, raw materials is commercially available industrial goods.
Embodiment prepares according to weight part shown in each component in table 3:
Table 3
Project Implement formula
Polyester elastomer 70
Polyolefine 10
Composite nanometer flame retardant 20
Resistant to hydrolysis stablizer 2
Oxidation inhibitor A 0.5
Oxidation inhibitor B 0.3
Lubricant 3
Preparation method:
Step of preparation process of the present invention is as follows, by measuring raw materials 1, according to the parts by weight in table, starting material are joined after mixing machine mixing 2 evenly, wherein mixing machine capacity is 200L, then extrudes 3 in the twin screw extruder that is 65mm with diameter, then water cooling bracing pelletizing 4, extrusion temperature is 170～240 ℃, and extruded velocity is 300～400 revs/min, and then dehydrates 5, last cooling packing 6, completes whole manufacturing process.
Adopt the CABLE MATERIALS performance obtaining of the present invention as shown in table 4: forcing machine is the mono-screw rod cable extruding machine of 65mm, and extrusion temperature is 180～240 ℃, and extruded velocity is 100m/min, and core cross section is 1.5mm 2.
Table 4
Figure GDA0000432645530000051
As can be seen from Table 4, the complete conformance with standard requirement of the electric wire of making.
The above, it is only preferred embodiment of the present invention, not the present invention is done to any pro forma restriction, any simple modification, equivalent variations and modification that every foundation technical spirit of the present invention is done above embodiment, all still belong in the scope of technical solution of the present invention.

Claims (6)

1. a low-smoke non-halogen flame-retardant polyester elastomer thin-walled insulation material, is characterized in that, described Insulation Material chief component and content are counted by weight:
Described polyester elastomer resin is that hardness is 50 to 70D ester-ester multipolymer, described polyolefin resin is 4-methylpentene multipolymer, described composite nanometer flame retardant is that decomposition temperature is greater than 280 ℃, and pH value is 5 to 7 the composite nitrogen phosphorus fire retardant that contains nano-dispersed agent.
2. low-smoke non-halogen flame-retardant polyester elastomer thin-walled insulation material according to claim 1, is characterized in that, described resistant to hydrolysis stablizer is aggretion type carbonization diamines.
3. low-smoke non-halogen flame-retardant polyester elastomer thin-walled insulation material according to claim 1, is characterized in that, described primary antioxidant is aromatic amine oxidation inhibitor.
4. low-smoke non-halogen flame-retardant polyester elastomer thin-walled insulation material according to claim 1, is characterized in that the sulphur ester antioxidant that described auxiliary antioxidant is high molecular.
5. low-smoke non-halogen flame-retardant polyester elastomer thin-walled insulation material according to claim 1, is characterized in that, described lubricant is high molecular silicone resin.
6. the preparation method of a low-smoke non-halogen flame-retardant polyester elastomer thin-walled insulation material as claimed in claim 1, it is characterized in that, material in described composition of raw materials is sent in mixing machine and mixed after preparing according to parts by weight separately, then extruding pelletization in the twin screw extruder that is 65mm at diameter, wherein extrusion temperature is 160 to 240 ℃, and extruded velocity is 300 to 400 revs/min.
CN201210070032.XA 2012-03-16 2012-03-16 Low-smoke, halogen-free and flame-retardant polyester elastomer thin-wall insulating material and preparation method thereof Active CN102604336B (en)

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CN101707069A (en) * 2009-11-23 2010-05-12 常州市利多合金材料有限公司 Strand
CN102146193A (en) * 2011-04-11 2011-08-10 广东聚石化学股份有限公司 Non-halogen flame-retardant thermoplastic elastomer composite with SEBS (Styrene-Ethylene/Butylene-Styrene) as base material and preparation method thereof

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JP2000302851A (en) * 1999-04-23 2000-10-31 Toyobo Co Ltd Preparation of flame-retardant polyester elastomer and polyester elastomer composition

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CN101707069A (en) * 2009-11-23 2010-05-12 常州市利多合金材料有限公司 Strand
CN102146193A (en) * 2011-04-11 2011-08-10 广东聚石化学股份有限公司 Non-halogen flame-retardant thermoplastic elastomer composite with SEBS (Styrene-Ethylene/Butylene-Styrene) as base material and preparation method thereof

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JP特开2000-302851A 2000.10.31

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