CN109942946A - A kind of wire and cable thermoplastic elastic material - Google Patents
A kind of wire and cable thermoplastic elastic material Download PDFInfo
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Abstract
The present invention provides a kind of wire and cable flame retardant thermoplastic elastomer materials, are related to thermoplastic elastomer (TPE) technical field.In order to which the flame-retardant thermoplastic elastomer fire block articles performance of existing P-N intumescent flame retardant preparation is poor, fire retardant is easy to migrate to material surface and the problem of influence its mechanical property when using under high temperature and humidity.The present invention is provided using low density polyethylene (LDPE), high density polyethylene (HDPE), rubber powder as major ingredient, compound flame retardant forms again, with good with fire line, smoke is few, low precipitation, anti-drip, the characteristics of high electrical property and excellent heat resistance, smoke amount can be greatly controlled in elastomer open fire combustion process, fire-retardant rank can achieve UL94-V0 grades.
Description
Technical field
The present invention relates to thermoplastic elastomer (TPE) technical fields, particularly, are related to a kind of wire and cable thermoplastic elastomer (TPE)
Material.
Background technique
The development of modern society has increasingly shown the importance of the energy and information, wire and cable, optical fiber cable conduct
The carrier of the energy and information just develops towards the direction of high-performance, high density, large capacity.Polyethylene is due to excellent electricity
(ε is about δ<4 2.3, tan × 10-4, v>10 ρ to gas performance16Ψ .cm) and excellent mechanical performance；Good chemical corrosion resistance
The advantages that energy and resistance to low temperature, raw material sources are extensive, cheap, thus polyethylene is in the row such as wire & cable and optical fiber cable
Industry is widely used.However thermoplastic polyethylene's oxygen index (OI) is 18, is combustible material, is there is external fire source or electricity
Cable is particularly easy to ignition in the case where heating up due to ontology failure.Especially in the modern life, wire and cable and light
Cable is distributed widely in each corner such as power plant, underground installation, building, once occur fire and to spread rapidly, to people's life with
Property brings massive losses.The Developing direction of cable-flame retardant is " secondary danger caused by reducing noxious gas emission
Evil ", thus develop non-halogen flame-retardant cable and have important practical significance.
Currently, halogen-free flame-retardant thermoplastic elastomer product in the market mostly uses the P-N intumescent of ammonium polyphosphate system
Fire retardant (hereinafter referred to as IFR) etc., and with ammonium polyphosphate (APP) although the P-N intumescent flame retardant flame retarding efficiency of system is high,
But the poor water resistance of ammonium polyphosphate, the flame-retardant thermoplastic elastomer product poor electrical performance of preparation, when using under high temperature and humidity
Fire retardant is easy to migrate to affect the mechanical properties to material surface.
Summary of the invention
Present invention aims at disadvantage of the existing technology is directed to, a kind of wire and cable thermoplastic elastomer (TPE) is provided
Preparation method.
In order to achieve the object of the present invention, The technical solution adopted by the invention is as follows:
A kind of wire and cable thermoplastic elastic material, is made of: low density polyethylene (LDPE) the raw material of following parts by weight
30-50 parts, 30-50 parts of high density polyethylene (HDPE), 10-15 parts of rubber powder, 0.1-0.5 parts of cumyl peroxide, pinus massoniana
1-2 parts of quality, 15-20 parts of fire retardant, 18.00-28.00 parts of white oil.
Further, the fire retardant is made of the raw material of following parts by weight: 1-3 parts of zinc borate, polytetrafluoroethylene (PTFE) 2-
5 parts, 0.5-2 parts of nano silica, 5-8 parts of ammonium polyphosphate, 7-15 parts of pentaerythrite, 0.1-1 parts of nickelous carbonate, lanthana 0.2-
0.8 part.
Further, the rubber powder is ultra-fine rubber powder.
Further, wire and cable thermoplastic elastic material preparation method, specifically includes the following steps:
1. prepared by fire retardant: by zinc borate, polytetrafluoroethylene (PTFE), nano silica, ammonium polyphosphate, pentaerythrite, carbonic acid
Drying to constant weight at 60 DEG C in nickel, lanthana placement vacuum oven, spare；Then by zinc borate, polytetrafluoroethylene (PTFE), nanometer
Silica, ammonium polyphosphate, pentaerythrite mix in high-speed mixer, and stirring 10min is placed on 160-200 DEG C of rheometer
In after its completely melting after, be slowly added to nickelous carbonate, lanthana be blended 10min up to fire retardant；
2. the preparation of thermoplastic elastomer (TPE)
Low density polyethylene (LDPE), high density polyethylene (HDPE), rubber powder, cumyl peroxide are uniformly mixed to be placed in and mixed at a high speed
It is kneaded 5-10min in mill, then puts into screw extruder and is squeezed out and be granulated, the revolving speed of screw extruder is 220-
430r/min, temperature are 160-175 DEG C to get masterbatch；Masterbatch, pinus massoniana quality, fire retardant and white oil are uniformly mixed again
It is kneaded uniformly under conditions of on plastics processing mill in 60-80 DEG C to get thermoplastic elastomer (TPE).
The beneficial effects of the invention are that:
1, the present invention solves the flame-retardant thermoplastic elastomer fire block articles performance of existing P-N intumescent flame retardant preparation
Poor, fire retardant is easy to migrate to material surface and the problem of influence its mechanical property when using under high temperature and humidity.Present invention preparation
Thermoplastic elastomer (TPE) good flame retardation effect, smoke amount can be greatly controlled in elastomer open fire combustion process, fire-retardant rank can
To reach UL94-V0 grades, have fire line good, smoke is few, low precipitation, anti-drip, the spy of high electrical property and excellent heat resistance
Point.
2, the thermoplastic elastomer (TPE) of wire and cable prepared by the present invention be with low density polyethylene (LDPE), high density polyethylene (HDPE),
Rubber powder is major ingredient, then compound flame retardant forms, and the rubber powder present invention therein selects ultra-fine rubber powder preferably right
Fire retardant plays the role of dispersion, improves the flame retardant property of thermoplastic elastomer (TPE) of the present invention.
3, compared with traditional P-N intumescent flame retardant, nickelous carbonate and lanthana are added in fire retardant prepared by the present invention
Play the role of cooperative flame retardant in P-N intumescent system, it is compound after flame-retardant system combustion residue to be formed by Char Residues Structure steady
Determine, keep flame retardant mechanism to stablize under the condition of high temperature and high humidity, hard and compact, so that fire retardant is not easy to move to elastic body surface
Face has played heat-insulated, oxygen barrier effect well.After nickelous carbonate and lanthana is added, thermoplastic elastomer (TPE) passes through high-temp combustion
The hole in material surface layer of charcoal tails off afterwards, and carbon layer increases, and Char Residues Structure becomes continuous and closely knit, and closure and intensity are all
Very well, so that system is effectively isolated with flame, the generation of imflammable gas can be slowed down during thermal polymer degradation and released
It puts；Since nickelous carbonate is unstable compound, it can be heated under high temperature action when being excessively added and be decomposed into nickel oxide, water and two
Carbonoxide, wherein the vapor and carbon dioxide that generate can form many tiny Bubble Regions, inorganic matter oxidation in material internal
Nickel and thermoplastic elastomer (TPE) matrix are also incompatible, and serious stress concentration phenomenon occurs when will cause hot plastomer's material stress,
So that the mechanical properties decrease of material；When lanthana excess, so that entire reaction system viscosity increases and nickelous carbonate is heated and divides
Solving ammonia promotes the rate-matched for being esterified layer foaming to be deteriorated, so that the intensity of the layer of charcoal generated and closure decline, are caused
The reduction of neat coal amout finally makes the flame retardant property decline of the thermoplastic elastic material of preparation, therefore, nickelous carbonate and lanthana
When weight ratio is 1:1, the thermoplastic elastomer (TPE) mechanical property and flame retardant property of preparation reach best simultaneously.
4, the present invention also added pinus massoniana quality, on the one hand the masson pine of addition when preparing thermoplastic elastomer (TPE)
Lignin improves the antioxygenic property of thermoplastic elastic material, and service life extends in hot and humid environment, saves life
At cost；On the other hand it since structure is complicated for pinus massoniana quality, is increased after being added in reaction system in vulcanization crosslinking knot
Microcosmic multiphase node in structure makes elastomer chain be easy to orient and improve thermoplastic elastomer (TPE) prepared by the present invention when stretching
Intensity, and then improve its mechanical property.
Other than objects, features and advantages described above, there are also other objects, features and advantages by the present invention.
The present invention is further detailed explanation below.
Specific embodiment
The embodiment of the present invention is described in detail below, but the present invention can be limited and be covered according to claim
Multitude of different ways implement.
Embodiment 1
A kind of wire and cable thermoplastic elastic material, is made of: low density polyethylene (LDPE) the raw material of following parts by weight
30 parts, 30 parts of high density polyethylene (HDPE), 10 parts of ultra-fine rubber powder, 0.1 part of cumyl peroxide, 1 part of pinus massoniana quality, resistance
Fire 15 parts of agent, 18.00 parts of white oil；The fire retardant is made of the raw material of following parts by weight: 1 part of zinc borate, polytetrafluoroethyl-ne
2 parts of alkene, 0.5 part of nano silica, 5 parts of ammonium polyphosphate, 7 parts of pentaerythrite, 0.1 part of nickelous carbonate, 0.2 part of lanthana.
Wire and cable thermoplastic elastic material preparation method, specifically includes the following steps:
1. prepared by fire retardant: by zinc borate, polytetrafluoroethylene (PTFE), nano silica, ammonium polyphosphate, pentaerythrite, carbonic acid
Drying to constant weight at 60 DEG C in nickel, lanthana placement vacuum oven, spare；Then by zinc borate, polytetrafluoroethylene (PTFE), nanometer
Silica, ammonium polyphosphate, pentaerythrite mix in high-speed mixer, stirring 10min be placed in 160 DEG C of rheometer to
After it is melted completely, it is slowly added to nickelous carbonate, 10min is blended up to fire retardant in lanthana；
2. the preparation of thermoplastic elastomer (TPE)
Low density polyethylene (LDPE), high density polyethylene (HDPE), rubber powder, cumyl peroxide are uniformly mixed to be placed in and mixed at a high speed
It is kneaded 5min in mill, then puts into screw extruder and is squeezed out and be granulated, the revolving speed of screw extruder is 220r/min,
Temperature is 160 DEG C to get masterbatch；Masterbatch, pinus massoniana quality, fire retardant and white oil are uniformly mixed on plastics processing mill in 60 again
It is kneaded under conditions of DEG C uniformly to get thermoplastic elastomer (TPE).
Embodiment 2
A kind of wire and cable thermoplastic elastic material, is made of: low density polyethylene (LDPE) the raw material of following parts by weight
50 parts, 45 parts of high density polyethylene (HDPE), 15 parts of ultra-fine rubber powder, 0.5 part of cumyl peroxide, 2 parts of pinus massoniana quality, resistance
Fire 20 parts of agent, 28.00 parts of white oil；The fire retardant is made of the raw material of following parts by weight: 3 parts of zinc borate, polytetrafluoroethyl-ne
5 parts of alkene, 2 parts of nanometer titanium dioxide, 8 parts of ammonium polyphosphate, 15 parts of pentaerythrite, 1 part of nickelous carbonate, 0.8 part of lanthana；
Wire and cable thermoplastic elastic material preparation method, specifically includes the following steps:
1. prepared by fire retardant: by zinc borate, polytetrafluoroethylene (PTFE), nano silica, ammonium polyphosphate, pentaerythrite, carbonic acid
Drying to constant weight at 60 DEG C in nickel, lanthana placement vacuum oven, spare；Then by zinc borate, polytetrafluoroethylene (PTFE), nanometer
Silica, ammonium polyphosphate, pentaerythrite mix in high-speed mixer, stirring 10min be placed in 200 DEG C of rheometer to
After it is melted completely, it is slowly added to nickelous carbonate, 10min is blended up to fire retardant in lanthana；
2. the preparation of thermoplastic elastomer (TPE)
Low density polyethylene (LDPE), high density polyethylene (HDPE), rubber powder, cumyl peroxide are uniformly mixed to be placed in and mixed at a high speed
It is kneaded 10min in mill, then puts into screw extruder and is squeezed out and be granulated, the revolving speed of screw extruder is 430r/
Min, temperature are 175 DEG C to get masterbatch；Masterbatch, pinus massoniana quality, fire retardant and white oil are uniformly mixed on plastics processing mill again
It is kneaded under conditions of 80 DEG C uniformly to get thermoplastic elastomer (TPE).
Embodiment 3
A kind of wire and cable thermoplastic elastic material, is made of: low density polyethylene (LDPE) the raw material of following parts by weight
40 parts, 50 parts of high density polyethylene (HDPE), 13 parts of ultra-fine rubber powder, 0.3 part of cumyl peroxide, 1.5 parts of pinus massoniana quality,
17 parts of fire retardant, 23 parts of white oil；The fire retardant is made of the raw material of following parts by weight: 2 parts of zinc borate, polytetrafluoroethyl-ne
3.5 parts of alkene, 1.5 parts of nano silica, 6.5 parts of ammonium polyphosphate, 10 parts of pentaerythrite, 0.5 part of nickelous carbonate, 0.5 part of lanthana.
Wire and cable thermoplastic elastic material preparation method, specifically includes the following steps:
1. prepared by fire retardant: by zinc borate, polytetrafluoroethylene (PTFE), nano silica, ammonium polyphosphate, pentaerythrite, carbonic acid
Drying to constant weight at 60 DEG C in nickel, lanthana placement vacuum oven, spare；Then by zinc borate, polytetrafluoroethylene (PTFE), nanometer
Silica, ammonium polyphosphate, pentaerythrite mix in high-speed mixer, stirring 10min be placed in 180 DEG C of rheometer to
After it is melted completely, it is slowly added to nickelous carbonate, 10min is blended up to fire retardant in lanthana；
2. the preparation of flame-retardant thermoplastic elastomer
Low density polyethylene (LDPE), high density polyethylene (HDPE), rubber powder, cumyl peroxide are uniformly mixed to be placed in and mixed at a high speed
It is kneaded 7min in mill, then puts into screw extruder and is squeezed out and be granulated, the revolving speed of screw extruder is 350r/min,
Temperature is 170 DEG C to get masterbatch；Masterbatch, pinus massoniana quality, fire retardant and white oil are uniformly mixed on plastics processing mill in 70 again
It is kneaded under conditions of DEG C uniformly to get thermoplastic elastomer (TPE).
Test example 1
The test of thermoplastic elastomer (TPE) flame retardant property
Using
The embodiment of the present invention 1, embodiment 2, embodiment 3 and the thermoplastic elastomer (TPE) of reference examples preparation burn respectively, survey
Determine limit oxygen index, limit oxygen index (LOI) is measured according to GB/T2406-1993.Concrete outcome is shown in Table 1 (remarks: control
Elastomer phase ratio prepared by thermoplastic elastomer (TPE) prepared by example and embodiment 3, is not added with fire retardant.)
Table 1
| Subjects | LOI/% | Combustion phenomena |
| Embodiment 1 | 32.6 | It is put out from fire, no smoke, no molten drop |
| Embodiment 2 | 32.1 | It is put out from fire, no smoke, no molten drop |
| Embodiment 3 | 33.6 | It is put out from fire, no smoke, no molten drop |
| Reference examples | 27.1 | It is put out from fire, has black smoke, there is molten drop drippage |
By table 1, it will be apparent that, the flame retardant property for being not added with the thermoplastic elastomer (TPE) of fire retardant preparation is poor, and is added to resistance
The embodiment 1 for firing agent arrives thermoplastic elastomer (TPE) prepared by embodiment 3, and flame-retardant smoke inhibition effect is obvious.
Test example 2
Thermoplastic elastomer (TPE) Mechanics Performance Testing
(1) tensile strength: tested according to GB/T1040-92.
(6) elongation rate of tensile failure is tested: being tested according to GB/T528-1998
2, subjects: thermoplasticity prepared by the embodiment of the present invention 1, embodiment 2, embodiment 3 and reference examples is (standby
Note: elastomer phase ratio prepared by thermoplastic elastomer (TPE) prepared by reference examples and embodiment 3 is not added with fire retardant.) specifically tie
Fruit is shown in Table 2
Table 2
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Reference examples | |
| Tensile strength (MPa) | 2.59 | 2.60 | 2.61 | 2.61 |
| Elongation rate of tensile failure (%) | 322 | 320 | 323 | 324 |
By table 2 it will be apparent that, the power of thermoplastic elastomer (TPE) prepared by the embodiment of the present invention 1, embodiment 2 and embodiment 3
It learns performance and the mechanical property for the thermoplastic elastomer (TPE) for being not added with fire retardant preparation is preferable, illustrate fire retardant prepared by the present invention
Do not have an impact the mechanical property of thermoplastic elastomer (TPE) obtained.
Test example 3
Thermoplastic elastomer (TPE) resistance to migration can measure
Thermoplastic elastomer (TPE) prepared by embodiment 1, embodiment 2, embodiment 3 and reference examples is carried out acceleration analysis by the present invention
Comparative experiments out, experimental condition are as follows: 85 DEG C at a temperature of and 85%RH climatic chamber in place 168h.(remarks: right
Prepared thermoplastic elastomer (TPE) and elastomer phase ratio prepared by embodiment 3 as usual, are not added with fire retardant.)
By measurement, many white precipitates of the thermoplastic elastomer article surface appearance of reference examples preparation, and embodiment
1,3 any surface finish of embodiment 2 and embodiment, does not find precipitate.
Test example 4
The measurement of thermoplastic elastomer (TPE) water resistance
The thermoplastic elastomer (TPE) that the present invention prepares embodiment 1, embodiment 2, embodiment 3 and reference examples carries out water resistance
Test.Long 130mm, wide 13mm is made in the thermoplastic elastomer (TPE) of the embodiment of the present invention 1, embodiment 2, embodiment 3 and reference examples,
The sample of thick 1.6mm is placed respectively to be dried in 70 DEG C of vacuum ovens to constant weight, is placed after cooling and is soaked in 70 DEG C of distilled water
168h is steeped, takes out in 70 DEG C of vacuum ovens of juxtaposition and dries to constant weight, and the sample after immersion is subjected to limit oxygen index (LOI)
With UL-94 vertical burn test, according to standard ASTM D2863, limit oxygen index is according to standard ASTM D2863, operating limit
Oxygen index instrument is tested；According to standard ASTM D635, tested using Vertical combustion instrument.Concrete outcome is shown in Table 3
Table 3
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Reference examples | |
| UL-94 grade | V0 | V0 | V0 | V2 |
| LOI/% | 27.6 | 27.9 | 28.1 | 26.1 |
It can be seen that compared with the thermoplastic elastomer (TPE) for being not added with fire retardant from the test result of table 3, be added to fire retardant
Thermoplastic elastomer (TPE) have significant flame-retarding characteristic, UL-94 grade is 0；
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (4)
1. a kind of wire and cable flame retardant thermoplastic elastomer material, it is characterised in that: be made of the raw material of following parts by weight:
30-50 parts of low density polyethylene (LDPE), 30-50 parts of high density polyethylene (HDPE), 10-15 parts of rubber powder, cumyl peroxide 0.1-0.5
Part, 1-2 parts of pinus massoniana quality, 15-20 parts of fire retardant, 18.00-28.00 parts of white oil；
The fire retardant is made of the raw material of following parts by weight: 1-3 parts of zinc borate, 2-5 parts of polytetrafluoroethylene (PTFE), nanometer two
0.5-2 parts of silica, 5-8 parts of ammonium polyphosphate, 7-15 parts of pentaerythrite, 0.1-1 parts of nickelous carbonate, 0.2-0.8 parts of lanthana.
2. a kind of wire and cable flame retardant thermoplastic elastomer material according to claim 1, it is characterised in that: described
The preparation method of wire and cable flame retardant thermoplastic elastomer material, specifically includes the following steps:
1. prepared by fire retardant: by zinc borate, polytetrafluoroethylene (PTFE), nano silica, ammonium polyphosphate, pentaerythrite, nickelous carbonate, oxygen
Drying to constant weight at 60 DEG C in change lanthanum placement vacuum oven, spare；Then by zinc borate, polytetrafluoroethylene (PTFE), nano-silica
SiClx, ammonium polyphosphate, pentaerythrite mix in high-speed mixer, stirring 10min be placed in 160-200 DEG C of rheometer to
After it is melted completely, it is slowly added to nickelous carbonate, 10min is blended up to fire retardant in lanthana；
2. the preparation of flame-retardant thermoplastic elastomer
Low density polyethylene (LDPE), high density polyethylene (HDPE), rubber powder, cumyl peroxide are uniformly mixed and are placed in high speed mixing smelting machine
Then upper mixing 5-10min puts into screw extruder and is squeezed out and be granulated, the revolving speed of screw extruder is 220-430r/
Min, temperature are 160-175 DEG C to get masterbatch；Masterbatch, pinus massoniana quality, fire retardant and white oil are uniformly mixed again and moulded in refining
It is kneaded under conditions of 60-80 DEG C uniformly on machine to get flame-retardant thermoplastic elastomer.
3. a kind of wire and cable flame retardant thermoplastic elastomer material according to claim 1, it is characterised in that: described
Rubber powder is ultra-fine rubber powder.
4. a kind of wire and cable flame retardant thermoplastic elastomer material according to claim 1, it is characterised in that: the resistance
The weight ratio for firing nickelous carbonate and lanthana in agent is 1:1.
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| CN201910309411.1A CN109942946A (en) | 2019-04-17 | 2019-04-17 | A kind of wire and cable thermoplastic elastic material |
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| CN201910309411.1A CN109942946A (en) | 2019-04-17 | 2019-04-17 | A kind of wire and cable thermoplastic elastic material |
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Application publication date: 20190628 |