CN110283386A - Take into account the thermoplastic elastomer (TPE) and preparation method thereof of low-k and anti-flammability - Google Patents
Take into account the thermoplastic elastomer (TPE) and preparation method thereof of low-k and anti-flammability Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
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- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
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- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
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- C08L2201/02—Flame or fire retardant/resistant
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C—CHEMISTRY; METALLURGY
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- 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
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- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/10—Peculiar tacticity
- C08L2207/14—Amorphous or atactic polypropylene
Abstract
The invention discloses a kind of thermoplastic elastomer (TPE)s and preparation method thereof for taking into account low-k and anti-flammability, belong to thermoplastic elastic material technical field, component are as follows: styrene block copolymer, polyolefin resin, fire retardant, coupling agent, white oil, processability auxiliary agent.This method are as follows: fire retardant is subjected to surface active pretreatment first, it is dry；Then by styrene block copolymer and white oil pre-oiling, melt blending is carried out after mixing again with polyolefin resin, processability auxiliary agent high-speed stirred, fire retardant is additionally added after preparing the intermediate of specific low-k and processability auxiliary agent carries out secondary blending, obtained low-k has both the thermoplastic elastomer (TPE) of anti-flammability.The present invention takes into account flame retardant property under the premise of guaranteeing has the advantages that lower dielectric constant, while having preferable weatherability and resistance to ag(e)ing, is of great significance to the application field for widening thermoplastic elastomer (TPE).
Description
Technical field:
The present invention relates to thermoplastic elastic material technical fields more particularly to one kind to take into account low-k and anti-flammability
Thermoplastic elastomer (TPE) and preparation method thereof.
Background technique:
It between rubber and plastics is a kind of composite structured high-performance material that thermoplastic elastomer (TPE), which is physical property,
Material, it had not only had the elasticity of rubber, but also the workability with plastics.One new " raw material of industry system " is constituted, by people
Referred to as " third generation rubber ".It is known as TPE (Thermoplastic by elastomer prepared by substrate of styrene block copolymers
Elastome), can be machined with general thermoplastic plastics shaping, high production efficiency, processing performance is superior, can without vulcanization
Cost is reduced to be recycled, soft-touch has preferable weatherability, fatigue resistance and temperature tolerance.Such as application No. is
Disclose a kind of thermoplastic elastomer (TPE) and preparation method thereof in the Chinese patent of CN 101983990, the component of the composition and
Proportion are as follows: 20-70 parts of oil-filled hydrogenated styrene resinoid, 20-80 parts of fluoropolymer resin, 6-25 parts of compatilizer, processing aid 1-
19 parts, 1-4 parts of weather resisting agent.The elastomer that the invention this method produces has more cladding purposes, physical mechanical property and weather-proof
The good feature of property, and on the basis of meeting TPE material service performance, obtaining ideal processing fluidity in technique.
Existing market thermoplastic elastomer (TPE) be widely used to auto industry, Communication Equipment, building materials, electronic apparatus,
The fields such as health care and consumer appliance.When it is applied to communications industry, in order to avoid communication component not by extraneous electricity as far as possible
Magnetic destroys or radiation interference, it usually needs can have the elastic protecting envelope body of protection electromagnetic interference.It is logical in order to realize simultaneously
News device reduces loss of signal as far as possible during transmitting signal, realizes maximum effect, needs outsourcing elastomer to electromagnetism
The transmitting influence of wave is as small as possible, therefore needs to reach certain index value in the selection of dielectric properties, wherein mainly investigating elastomer
Dielectric constant, tangent angle loss value.When elastomer outsourcing material relative dielectric constant is bigger, then signal is transmitted in air and day
Reflections affect on line shell interface is bigger, this plays negative effect for electromagnetic transmission efficiency, simultaneously as signal needs
It initially passes through shell protective layer and enters back into signal receiving/transmission device, losstangenttanδ is bigger, and wherein electromagnetic wave is penetrating outside antenna
The energy for being converted into heat during shell and being lost is more, and in addition, many materials that communicate all are applied to open air, needs certain
Resistance to ag(e)ing, and heat distributes relatively slow in the system, combustion phenomena easily occurs, at the same market is also badly in need of having preferable weatherability with
The outsourcing of anti-flammability communicates material, therefore there is also corresponding requirements for the anti-flammability of product.
Currently, the outsourcing material of the communication apparatus is predominantly based on plastics, wherein being divided into thermoplastic and thermosetting property again
Plastics two major classes, thermoplastic is mainly with high polymer polypropylene (PP), polyvinyl chloride (PVC), impact resistance polystyrene
(HIPS), based on acrylonitrile-butadiene-styrene copolymer (ABS).Wherein it is its dielectric constant using polyacrylic advantage
It is low, it is 2.2 or so, while density is low, processing fluidity is adjustable；The advantage of polyvinyl chloride is that cheap, hardness is adjustable model
It encloses extensively, with preferable anti-flammability, chemical corrosion resistance；The advantage of impact resistance polystyrene is that impact resistance is strong, heat is steady
Qualitative and good weatherability；For acrylonitrile-butadiene-styrene copolymer as engineering plastics, comprehensive performance is strong, and use scope is wide.
But the above material itself also has its disadvantage, for example, PP intensity is lower, PVC poor heat resistance and contain halogen, HIPS processability
Poor, ABS acid-alkali-corrosive-resisting is poor.Thermosetting plastics is mainly with epoxy resin, phenolic resin, unsaturated polyester resin
Main, although thermosetting material mechanical strength is higher, weather resistance is preferable, and dimensional stability is preferable, and global density is higher, dielectric
Constant is higher (3.8-6.5), and complex manufacturing technology, can not be recycled.Between the above material, lightweight, weather-proof resistance to old is selected
Change, fire-retardant, low-dielectric, easy processing thermoplastic elastomer (TPE) become inevitable.
Low-dielectric material used at present is mainly in the majority with plastics, is divided into thermosetting material and thermoplastic material, heat
Thermoset material mainly use unsaturated polyester resin, epoxy resin, phenolic resin, vinylite etc. compound with glass fibre and
At the advantages that thermosetting material mechanical strength is higher, and weather resistance is preferable, and dimensional stability is preferable；But thermosetting material one
As density it is higher, heavier (the density 1.7-2.0g/cm of shell overall weight3), dielectric constant is higher (4.0-5.5), can not recycle
It recycles, the outer casing forming of this thermoset class is complicated, and overall cost is higher and forming process pollution is larger, to human health
The defects of being affected.Also most common antenna casing thermoplastic material is mainly polyvinyl chloride (PVC) class, PVC to dosage maximum
Material is one of current the most widely used plastic material, it have it is cheap, soft or hard it is adjustable, flame retardant property is good, resistance toization
The advantages that corrode, excellent electric properties, applies on antenna casing weight relatively gently (density 1.4-1.65g/cm3),
The advantages that weatherability is preferable, and overall cost is lower.Although PVC material has many advantages, such as, there is also heat-resisting poor (thermal changes
Shape temperature 60 C or so), the defects of dielectric constant is relatively high (3-4.8), and intensity is relatively low, and true qualities contain halogen.In addition,
The common thermoplastic material of antenna casing material also includes acrylonitrile-butadiene-styrene copolymer (ABS), esters of acrylic acid
The graft copolymer (ASA) of rubber bodies and acrylonitrile, styrene, impact resistance polystyrene (HIPS), high polymer polypropylene
(PP) etc. materials, ABS, PS material dielectric constant are 2.8-3.0, cheap, due to containing unsaturation in molecular structure itself
Double bond, therefore be not suitable for using outdoors.ASA has excellent weather resistance, and is the preferred material of outdoor application, but ASA dielectric constant
Between 2.8-3.3, and higher cost, which limits its large-scale uses.PP material dielectric constant is 2.2 or so, close
Spend low, low in cost, but intensity is lower, aging is poor, also limits its use.
Have Related product for low-k thermoplastic elastomer (TPE) currently on the market to come into the market, such as in application number
A kind of low-k dynamic vulcanization thermoplastic elastomer and its preparation side are disclosed in Chinese patent for CN 103627091
Method, the component and proportion of the composition are as follows: 10-100 parts of polyolefin resin, 10-100 parts of elastomer, 0.5-2 parts of crosslinking agent,
0.5-20 parts of cross-linking aid, 10-120 parts of oil of filling, 1-30 parts of filler, 0.2-2 parts of antioxidant, 2-15 parts of processing aid.The hair
The elastomer that bright this method produces is guaranteeing it by the way that special cross-linking aid, cooperation crosslinking agent and other raw materials are added
There is relatively low dielectric constant again while good physical property.Application No. is CN 106700302 and CN
106700302 Chinese patent discloses the thermoplastic elastomer alloy material of a kind of antibiotic property and antistatic property, low possessing
With certain antibiotic property and antistatic property while dielectricity, but it is based only upon in product antibiotic property and antistatic elaboration
Antibacterial agent and antistatic agent are added, is played the role of only temporary, is not done simultaneously for the anti-flammability of outdoor products
Consider out.
Summary of the invention:
Based on the elaboration above for existing low-dielectric elastomer, low-dielectric and resistance are taken into account for thermoplastic elastomer (TPE)
Combustion property becomes inevitable, and the invention discloses a kind of thermoplastic elastomer (TPE) for taking into account low-k and anti-flammability and its preparation sides
Method, elastomer obtained have not only taken into account preferable low-k and dielectric loss, also possess permanent anti-flammability, and have
Good processability and mechanical strength have very big market potential in communication device package, industry security protection.Its specific skill
Art scheme is as follows:
A kind of thermoplastic elastomer (TPE) for taking into account low-k and anti-flammability, in parts by weight, including following components:
15-35 parts of styrene block copolymer,
20-40 parts of polyolefin resin,
10-20 parts of fire retardant,
0-40 parts of white oil,
0-10 parts of inorganic filler,
0-0.5 parts of antioxidant,
0-5 parts of dispersing agent,
0-0.5 parts of light stabilizer,
0-5 parts of coupling agent,
0-1 parts of release agent.
Further, the styrene block copolymer is that Styrene-Butadiene-Styrene Block Copolymer or hydrogenation produce
Object, styrene-isoprene-styrene block copolymer or hydrogenated products, styrene-ethylene-butylene-styrene block copolymerization
One or two kinds of combinations of object or hydrogenated products, styrene ethylene-propylene-styrene type block copolymer or hydrogenated products.
Further, the polyolefin resin is polyethylene, polypropylene, polyphenylene oxide, polystyrene or polyethylene and gathers
One of mixture of propylene or any number of combination.
Further, the styrene block copolymers is styrene-fourth two of number-average molecular weight 50000-300000
Alkene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene
Block copolymer, styrene ethylene-propylene-styrene type block copolymer or its above-mentioned hydrogenated products.
Further, the fire retardant be inorganic fire retardants, phosphorus flame retardant, nitrogenated flame retardant or phosphorus flame retardant and
One of nitrogenated flame retardant or any number of combination.
Further, the coupling agent is that titanate coupling agent, silane coupling agent or titanate coupling agent and silane are even
Join one of agent or any number of combination.
Further, the above-mentioned process for preparation of thermoplastic elastomer for taking into account low-k and anti-flammability, including it is following
Step:
A), fire retardant is added in coupling agent solution and is infiltrated, adjust pH value to being in alkalescent, heating water bath stirs, dry
After obtain activation fire retardant；
B), styrene block copolymer and white oil are uniformly mixed pre-oiling in proportion, polyolefin resin, processability is added
Auxiliary agent obtains low-k thermoplastic elastomer (TPE) after melting mixing equipment melt blending；
C), low-k thermoplastic elastomer (TPE), fire retardant obtained by step B), processability auxiliary agent are uniformly mixed, it is secondary
It is kneaded, the thermoplastic elastomer (TPE) for taking into account low-k and anti-flammability is made.
Further, the melting mixing equipment be double screw extruder, process conditions be temperature 160~
220 DEG C, 200~320rpm of revolving speed.By above-mentioned antistatic thermoplastic elastic material using vertical injection molding machine 180
The print of thickness 3mm is molded under the conditions of DEG C, using dielectric constant and the dielectric constant and damage of dielectric loss tester measurement sample
Angle tangent value is consumed, using the combustibility of oxygen index (OI) tester measurement sample, tensile bars, measurement are prepared using universal sampling machine
The processing flowability of the tensile strength and elongation at break of material, material passes through 230 DEG C of measuring temperature, load 5/10kg condition
Under melt flow index (MFR) characterize.
The working principle of the invention is:
It, need to be for material in addition to impressed frequency, temperature, humidity factor from the good low-dielectric of elastomer is realized
Selection has corresponding requirement, it may be assumed that (1) the lower resin of dielectric constant is selected in the selection of plastics；(2) selection of rubber, except choosing
It is lower with elastomeric dielectric constant, it is also necessary to guarantee that molecular weight rubber is unsuitable excessively high, guarantee that density of material is lower, present loose porous
Structure；(3) selection of filler selects the filler compared with low-k and additive amount is smaller as far as possible；(4) selection of auxiliary agent, choosing
With the auxiliary agent compared with low-k；(5) processing technology of material is guaranteeing that it is outer that all material is dried, by using pre- place
Reason mode changes the microscopic topology and form of material.Thereby it is ensured that all the selection of material dielectric constants of product are lower, produce
Between product with good compatibility and dispersibility, do the pretreatment before good material preparation be realize integral material low-dielectric must
Standby factor.
From realize elastomer good flame-retardance, need to be associated with the fire-retardant mode of action, it may be assumed that (1) coating effect,
(2) drop effect, (5) condensed phase fire retardation are melted in gas dilution effect, (3) heat-absorbing action, (4).For inorganic fire retardants,
Protection coating, starvation, while internal heat absorption are formed after fire retardant melting on the surface of the material, reduces ignition temperature；For
It is main to occur that condensed phase is fire-retardant, and fire retardant is decomposed thermally to form the oxyacid of phosphorus for phosphorus flame retardant, make material dehydration at charcoal,
Combustible production quantity is reduced, while there are diluting effects to oxygen for the volatile gas generated；For nitrogenated flame retardant, nitrogen
Compound and combustible effect, promote interlinkage at charcoal, reduce the decomposition temperature of combustible, the non-flammable compressive gas of generation plays dilute
Release the effect of fuel gas.Respective mechanism based on the above fire retardant can will be respective by will both wherein or more persons are compound
Fire retarding effect synergistic effect, and each stage when being directed to material combustion generates corresponding fire retardation, guarantees to contain same
When measuring even lower, the flame retarding efficiency of composite flame-retardant agent is significantly greater than single fire retardant.In addition, in order to further decrease fire retardant
Itself dielectricity is also additionally activated fire retardant, is cleaned by ethyl alcohol in addition to selecting dielectric materials when selecting
The surface potential energy between compatilizer or coupling agent reduction and macromolecule is added afterwards, promotes, guarantee dispersibility compatible between macromolecule
And low-dielectric.
When adding more filler in system, easily there is decline phenomenon and removes to reduce fall in product mechanical property
Outside being pre-processed in advance to fire-retardant medium, is taken in processing and first prepare the mode that low dielectric elastomer adds fire-retardant medium
Implement, on the one hand investment can increase material mixing number increase elastomeric component and form preferable continuous phase and dispersion several times
On the other hand phase is directed to fire retardant nature, selects different technological parameters to can guarantee each filler in system in different phase
Interior better dispersion, avoiding reuniting influences mechanical strength.
In order to realize that low-dielectric, anti-flammability, mechanical property are taken into account, the present invention first by being activated to fire retardant,
By wrapping amphiphilic active group chain on surface, one side fire retardant autohemagglutination ensures to have good dispersibility in system,
And active group chain possesses longer living chain and can be more conducive to form preferably fire-retardant network structure between particle, it is on the other hand living
Possess bigger specific surface after change and reduces the surface potential energy between macromolecule, it can be more effectively compatible with macromolecule.Then
The ratio for controlling polypropylene and styrene block copolymer, so that system both can reflect the lower polypropylene of dielectric constant in benzene
Low-dielectric under ethylene block copolymer promotion, and can reflect the preferable styrene block copolymer of mechanical property in polypropylene
Preferable processability under promoting, guarantees preferably to disperse, and makes to form preferable microscopic topology in system.Then in bullet
Property body in the composite flame-retardant agent that has been pre-dried is added, the technological parameter that adjustment adapts to fire retardant addition is kneaded again, is made
Obtaining fire retardant, preferably dispersion and the dielectricity as small as possible for influencing entirety, realization reach reasonable economy, system in elastomer
Make easy mode to guarantee to the simultaneous of the comprehensive performance of thermoplastic elastomer (TPE) dielectricity, anti-flammability, mechanical property and product processability
It cares for.
The beneficial effects of the present invention are:
The thermoplastic elastomer (TPE) provided by the present invention for taking into account low-k and anti-flammability, it is total using polystyrene block
Polymers/polyolefin resin compound system is substrate, after preparing low dielectric elastomer, then launches the composite flame-proof of high fire-retardance efficiency
Agent by adjusting polystyrene block copolymer, the ratio of polyolefin resin, fire retardant, and selects suitable white oil and auxiliary agent
Hardness, mobility are controlled, finally prepares simple process, easy processing has both the complex function of dielectricity, anti-flammability, mechanical property
Material.The compound system is multiple dispersion island structure, in the island structure based on rubber phase and resin phase, fire-retardant medium benefit
Dispersion is easier to completely with existing interface phase network structure, therefore there is preferable mechanical strength and have both stronger dielectric stability
With highly effective flame-retardant, while guaranteeing there is preferable weatherability and resistance to ag(e)ing under product operates outdoors.Overcome communication at present normal
See the defect that dielectric material performance, weatherability, anti-flammability, mechanical property, environmental requirement etc. can not combine, and preparation process
Simplicity, it is easily controllable, it can satisfy the demand of different processing methods, therefore, in Communication Equipment package, industry security protection, doctor
Treat the composite functional material that the similar fields such as analysis are a kind of great application prospects.
Specific embodiment:
With reference to embodiment, the present invention is furture elucidated.It should be understood that following specific embodiments are only used for
It is bright the present invention rather than limit the scope of the invention.
Embodiment 1
The process for preparation of thermoplastic elastomer of low-k and anti-flammability is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh 1 part of coupling agent, be put into ethanol solution and be stirred, and adjust PH
For alkalescent, make its hydrolysis, then weighs and 15 parts of melamines and 5 parts of aluminum diethylphosphinates are added.The melamine partial size
For 2.5-3.5um, pH value 5-7, the aluminum diethylphosphinate partial size is 15-20um, phosphorus content 20-24%, is stirred, then water
Bath heating makes ethyl alcohol volatilize, and pretreatment fire retardant 1 is obtained after dry.
B), measured according to weight ratio, first weigh the hydrogenated styrene-butadiene block copolymer of 25 parts of preliminary fillings, 18 parts of white oils
It is added in high-speed mixer, the number-average molecular weight 260000 of the hydrogenated styrene-butadiene block copolymer, styrene
Content 35%.Then 28 parts of random polypropylenes are added, the polypropylene melt flow rate is 16 ± 3.Then 5 parts are added to gather
Phenylate, the polyphenylene oxide anti-flammability are V-1 grades, tensile strength 58Mpa.0.3 part of stabilization is added after mixing one minute in blender
Agent, 0.3 part of antioxidant, 1.1 parts of lubricants are processed in double screw extruder after mediating one minute and are granulated, double screw extruder
The temperature of heating zone is set are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185
DEG C, 180 DEG C (sequentially for from feed opening to head), a kind of low-dielectric thermoplastic elastomer (TPE) 1 is finally made in revolving speed 260rpm.
C), pretreatment fire retardant 1 is added in low dielectric thermoplastic elastomer (TPE) 1, then 0.2 part of stabilizer of addition, 0.2 part
Antioxidant, 0.8 part of lubricant stir one minute, 0.1 part of release agent are eventually adding, after mediating one minute in double screw extruder
Processing is granulated, the setting of the temperature of double screw extruder heating zone are as follows: 100 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, 210 DEG C,
215 DEG C, 215 DEG C, 215 DEG C, 210 DEG C, 200 DEG C (sequentially for from feed opening to head), fire-retardant low dielectric is made in revolving speed 260rpm
Property thermoplastic elastomer (TPE) 1.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm using vertical injection molding machine, and V1 grades of flame retardant rating is drawn
Stretch that intensity is 10.4MPa, elongation at break 571%, losstangenttanδ value 0.0025, dielectric constant 2.6, MFR are
10.2g/10min(10kg)。
Embodiment 2
The process for preparation of thermoplastic elastomer of low-k and anti-flammability is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh 1 part of coupling agent, be put into ethanol solution and be stirred, and adjust PH
For alkalescent, make its hydrolysis, then weighs and 15 parts of melamines and 5 parts of aluminum diethylphosphinates are added.The melamine partial size
For 2.5-3.5um, pH value 5-7, the aluminum diethylphosphinate partial size is 15-20um, phosphorus content 20-24%, is stirred, then water
Bath heating makes ethyl alcohol volatilize, and pretreatment fire retardant 2 is obtained after dry.
B), measured according to weight ratio, first weigh the hydrogenated styrene-butadiene block copolymer of 15 parts of preliminary fillings, 16 parts of white oils
It is added in high-speed mixer, the number-average molecular weight 260000 of the hydrogenated styrene-butadiene block copolymer, styrene
Content 35%.Then it is 16 ± 3 that polypropylene melt flow rate described in 40 parts of random polypropylenes, which is added,.Then 5 parts are added to gather
Phenylate, the polyphenylene oxide anti-flammability are V-1 grades, tensile strength 58Mpa.0.3 part of stabilization is added after mixing one minute in blender
Agent, 0.3 part of antioxidant, 1.1 parts of lubricants are processed in double screw extruder after mediating one minute and are granulated, double screw extruder
The temperature of heating zone is set are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185
DEG C, 180 DEG C (sequentially for from feed opening to head), a kind of low-dielectric thermoplastic elastomer (TPE) 2 is finally made in revolving speed 260rpm.
C), pretreatment fire retardant 2 is added in low dielectric thermoplastic elastomer (TPE) 2, then 0.2 part of stabilizer of addition, 0.2 part
Antioxidant, 0.8 part of lubricant stir one minute, 0.1 part of release agent are eventually adding, after mediating one minute in double screw extruder
Processing is granulated, the setting of the temperature of double screw extruder heating zone are as follows: 100 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, 210 DEG C,
215 DEG C, 215 DEG C, 215 DEG C, 210 DEG C, 200 DEG C (sequentially for from feed opening to head), fire-retardant low dielectric is made in revolving speed 260rpm
Property thermoplastic elastomer (TPE) 2.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm using vertical injection molding machine, and V1 grades of flame retardant rating is drawn
Stretch that intensity is 15.9MPa, elongation at break 253%, losstangenttanδ value 0.0021, dielectric constant 2.4, MFR are
12.1g/10min(10kg)。
Embodiment 2 mainly has adjusted styrene block copolymer, white oil, the ratio between polypropylene three based on embodiment 1
Example, compared to embodiment 1, the tensile strength of system increases, and elongation at break decline, melt index slightly rises；Flame retardant rating maintains an equal level,
Dielectric constant and dielectric loss decline show that the increase of polypropylene content is conducive to that lower dielectric constant and dielectric damage is presented
Consumption, but whole flexibility is also sacrificed, so that bulk property is tended to plastics.
Embodiment 3
The process for preparation of thermoplastic elastomer of low-k and anti-flammability is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh 1 part of coupling agent, be put into ethanol solution and be stirred, and adjust PH
For alkalescent, make its hydrolysis, then weighs and 15 parts of melamines and 5 parts of aluminum diethylphosphinates are added.The melamine partial size
For 2.5-3.5um, pH value 5-7, the aluminum diethylphosphinate partial size is 15-20um, phosphorus content 20-24%, is stirred, then water
Bath heating makes ethyl alcohol volatilize, and pretreatment fire retardant 3 is obtained after dry.
B), measured according to weight ratio, first weigh the hydrogenated styrene-butadiene block copolymer of 35 parts of preliminary fillings, 25 parts of white oils
It is added in high-speed mixer, the number-average molecular weight 260000 of the hydrogenated styrene-butadiene block copolymer, styrene
Content 35%.Then it is 16 ± 3 that polypropylene melt flow rate described in 11 parts of random polypropylenes, which is added,.Then 5 parts are added to gather
Phenylate, the polyphenylene oxide anti-flammability are V-1 grades, tensile strength 58Mpa.0.3 part of stabilization is added after mixing one minute in blender
Agent, 0.3 part of antioxidant, 1.1 parts of lubricants are processed in double screw extruder after mediating one minute and are granulated, double screw extruder
The temperature of heating zone is set are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185
DEG C, 180 DEG C (sequentially for from feed opening to head), a kind of low-dielectric thermoplastic elastomer (TPE) 3 is finally made in revolving speed 260rpm.
C), pretreatment fire retardant 3 is added in low dielectric thermoplastic elastomer (TPE) 3, then 0.2 part of stabilizer of addition, 0.2 part
Antioxidant, 0.8 part of lubricant stir one minute, 0.1 part of release agent are eventually adding, after mediating one minute in double screw extruder
Processing is granulated, the setting of the temperature of double screw extruder heating zone are as follows: 100 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, 210 DEG C,
215 DEG C, 215 DEG C, 215 DEG C, 210 DEG C, 200 DEG C (sequentially for from feed opening to head), fire-retardant low dielectric is made in revolving speed 260rpm
Property thermoplastic elastomer (TPE) 3.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm using vertical injection molding machine, and V2 grades of flame retardant rating is drawn
Stretch that intensity is 8.1MPa, elongation at break 611%, losstangenttanδ value 0.0035, dielectric constant 2.9, MFR are
6.3g/10min(10kg)。
Embodiment 3 mainly has adjusted styrene block copolymer, white oil, the ratio between polypropylene three based on embodiment 1
Example, compared to embodiment 1, the tensile strength of system declines, and elongation at break increases, melt index decline；Flame retardant rating reduces,
Dielectric constant and dielectric loss rise, show the increase of styrene block copolymer so that dielectric constant and dielectric loss mention
Height is unfavorable for whole dielectric properties, while the increase of white oil, affects the fire-retardant quality of product, although improving whole
Flexibility, but sacrifice excessive other properties.
Embodiment 4
The process for preparation of thermoplastic elastomer of low-k and anti-flammability is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh 1 part of coupling agent, be put into ethanol solution and be stirred, and adjust PH
For alkalescent, make its hydrolysis, then weighs and 15 parts of melamines and 5 parts of aluminum diethylphosphinates are added.The melamine partial size
For 2.5-3.5um, pH value 5-7, the aluminum diethylphosphinate partial size is 15-20um, phosphorus content 20-24%, is stirred, then water
Bath heating makes ethyl alcohol volatilize, and pretreatment fire retardant 4 is obtained after dry.
B), measured according to weight ratio, first weigh the hydrogenated styrene-butadiene block copolymer of 25 parts of preliminary fillings, 18 parts of white oils
It is added in high-speed mixer, the number-average molecular weight 360000 of the hydrogenated styrene-butadiene block copolymer, styrene
Content 33%.Then it is 16 ± 3 that polypropylene melt flow rate described in 28 parts of random polypropylenes, which is added,.Then 5 parts are added to gather
Phenylate, the polyphenylene oxide anti-flammability are V-1 grades, tensile strength 58Mpa.0.3 part of stabilization is added after mixing one minute in blender
Agent, 0.3 part of antioxidant, 1.1 parts of lubricants are processed in double screw extruder after mediating one minute and are granulated, double screw extruder
The temperature of heating zone is set are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185
DEG C, 180 DEG C (sequentially for from feed opening to head), a kind of low-dielectric thermoplastic elastomer (TPE) 4 is finally made in revolving speed 260rpm.
C), pretreatment fire retardant 4 is added in low dielectric thermoplastic elastomer (TPE) 4, then 0.2 part of stabilizer of addition, 0.2 part
Antioxidant, 0.8 part of lubricant stir one minute, 0.1 part of release agent are eventually adding, after mediating one minute in double screw extruder
Processing is granulated, the setting of the temperature of double screw extruder heating zone are as follows: 100 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, 210 DEG C,
215 DEG C, 215 DEG C, 215 DEG C, 210 DEG C, 200 DEG C (sequentially for from feed opening to head), fire-retardant low dielectric is made in revolving speed 260rpm
Property thermoplastic elastomer (TPE) 4.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm using vertical injection molding machine, and V1 grades of flame retardant rating is drawn
Stretch that intensity is 11.6MPa, elongation at break 613%, losstangenttanδ value 0.0029, dielectric constant 2.9, MFR are
8.2g/10min(10kg)。
Embodiment 4 is based on embodiment 1 and mainly has adjusted styrene block copolymer molecular weight and styrene-content ratio, phase
Than increasing in the tensile strength of embodiment 1, system, elongation at break increases, melt index decline；Flame retardant rating maintains an equal level, dielectric
Constant and dielectric loss rise, and show that the raising of styrene block copolymer molecular weight can slightly improve the mechanical strength of arrangement, but
It differs larger with polypropylene viscosity, is unfavorable for that preferable micropore topological structure is integrally formed, whole dielectric properties is caused to decline,
Simultaneously because the raising of molecular weight, whole processability is influenced there is also certain.
Embodiment 5
The process for preparation of thermoplastic elastomer of low-k and anti-flammability is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh the hydrogenated styrene-butadiene block copolymer of 25 parts of preliminary fillings, 18 parts of white oils
It is added in high-speed mixer, the number-average molecular weight 260000 of the hydrogenated styrene-butadiene block copolymer, styrene
Content 35%.Then it is 16 ± 3 that polypropylene melt flow rate described in 28 parts of random polypropylenes, which is added,.Then 5 parts are added to gather
Phenylate, the polyphenylene oxide anti-flammability are V-1 grades, tensile strength 58Mpa.0.3 part of stabilization is added after mixing one minute in blender
Agent, 0.3 part of antioxidant, 1.1 parts of lubricants are processed in double screw extruder after mediating one minute and are granulated, double screw extruder
The temperature of heating zone is set are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185
DEG C, 180 DEG C (sequentially for from feed opening to head), a kind of low-dielectric thermoplastic elastomer (TPE) 5 is finally made in revolving speed 260rpm.
B), 15 parts of melamines and 5 parts of aluminum diethylphosphinates are added in low dielectric thermoplastic elastomer (TPE) 5.Described three
Poly cyanamid partial size be 2.5-3.5um, pH value 5-7, the aluminum diethylphosphinate partial size be 15-20um, phosphorus content 20-24%,
Then 0.2 part of stabilizer, 0.2 part of antioxidant is added, 0.8 part of lubricant stirs one minute, is eventually adding 0.1 part of release agent, pinches
Granulation, the temperature setting of double screw extruder heating zone are as follows: 100 DEG C, 190 are processed in double screw extruder after unifying minute
DEG C, 200 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 215 DEG C, 215 DEG C, 215 DEG C, 210 DEG C, 200 DEG C (sequentially for from feed opening to machine
Head), fire-retardant low-dielectric thermoplastic elastomer (TPE) 5 is made in revolving speed 260rpm.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm using vertical injection molding machine, and V1 grades of flame retardant rating is drawn
Stretch that intensity is 8.9MPa, elongation at break 541%, losstangenttanδ value 0.0033, dielectric constant 3.1, MFR are
9.2g/10min(10kg)。
Embodiment 5 eliminates the pretreatment stage for being previously with regard to fire retardant based on embodiment 1, compared to embodiment 1, system
Tensile strength decline, elongation at break decline, melt index decline；Flame retardant rating maintains an equal level, on dielectric constant and dielectric loss
It rises, shows not carry out fire retardant pretreatment, so that the compatibility between fire retardant and other components reduces, and then affect fire-retardant
Dispersion of the agent in system also causes whole microcosmos network structure to be formed poor, eventually leads to the decline of whole properties.
Embodiment 6
The process for preparation of thermoplastic elastomer of low-k and anti-flammability is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh 1 part of coupling agent, be put into ethanol solution and be stirred, and adjust PH
For alkalescent, make its hydrolysis, then weigh be added 20 parts of melamines, the melamine partial size be 2.5-3.5um, pH value 5-7,
Stirring, then heating water bath makes ethyl alcohol volatilize, and pretreatment fire retardant 6 is obtained after dry.
B), measured according to weight ratio, first weigh the hydrogenated styrene-butadiene block copolymer of 25 parts of preliminary fillings, 18 parts of white oils
It is added in high-speed mixer, the number-average molecular weight 260000 of the hydrogenated styrene-butadiene block copolymer, styrene
Content 35%.Then it is 16 ± 3 that polypropylene melt flow rate described in 28 parts of random polypropylenes, which is added,.Then 5 parts are added to gather
Phenylate, the polyphenylene oxide anti-flammability are V-1 grades, tensile strength 58Mpa.0.3 part of stabilization is added after mixing one minute in blender
Agent, 0.3 part of antioxidant, 1.1 parts of lubricants are processed in double screw extruder after mediating one minute and are granulated, double screw extruder
The temperature of heating zone is set are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185
DEG C, 180 DEG C (sequentially for from feed opening to head), a kind of low-dielectric thermoplastic elastomer (TPE) 6 is finally made in revolving speed 260rpm.
C), pretreatment fire retardant 6 is added in low dielectric thermoplastic elastomer (TPE) 6, then 0.2 part of stabilizer of addition, 0.2 part
Antioxidant, 0.8 part of lubricant stir one minute, 0.1 part of release agent are eventually adding, after mediating one minute in double screw extruder
Processing is granulated, the setting of the temperature of double screw extruder heating zone are as follows: 100 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, 210 DEG C,
215 DEG C, 215 DEG C, 215 DEG C, 210 DEG C, 200 DEG C (sequentially for from feed opening to head), fire-retardant low dielectric is made in revolving speed 260rpm
Property thermoplastic elastomer (TPE) 6.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm using vertical injection molding machine, and V2 grades of flame retardant rating is drawn
Stretch that intensity is 10.1MPa, elongation at break 564%, losstangenttanδ value 0.0026, dielectric constant 2.6, MFR are
9.8g/10min(10kg)。
Embodiment 7
The process for preparation of thermoplastic elastomer of low-k and anti-flammability is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh 1 part of coupling agent, be put into ethanol solution and be stirred, and adjust PH
For alkalescent, make its hydrolysis, then weigh and 20 parts of aluminum diethylphosphinates are added, the aluminum diethylphosphinate partial size is 15-
20um, phosphorus content 20-24%, stirring, then heating water bath makes ethyl alcohol volatilize, and pretreatment fire retardant 6 is obtained after dry.
B), measured according to weight ratio, first weigh the hydrogenated styrene-butadiene block copolymer of 25 parts of preliminary fillings, 18 parts of white oils
It is added in high-speed mixer, the number-average molecular weight 260000 of the hydrogenated styrene-butadiene block copolymer, styrene
Content 35%.Then it is 16 ± 3 that polypropylene melt flow rate described in 28 parts of random polypropylenes, which is added,.Then 5 parts are added to gather
Phenylate, the polyphenylene oxide anti-flammability are V-1 grades, tensile strength 58Mpa.0.3 part of stabilization is added after mixing one minute in blender
Agent, 0.3 part of antioxidant, 1.1 parts of lubricants are processed in double screw extruder after mediating one minute and are granulated, double screw extruder
The temperature of heating zone is set are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185
DEG C, 180 DEG C (sequentially for from feed opening to head), a kind of low-dielectric thermoplastic elastomer (TPE) 6 is finally made in revolving speed 260rpm.
C), pretreatment fire retardant 6 is added in low dielectric thermoplastic elastomer (TPE) 6, then 0.2 part of stabilizer of addition, 0.2 part
Antioxidant, 0.8 part of lubricant stir one minute, 0.1 part of release agent are eventually adding, after mediating one minute in double screw extruder
Processing is granulated, the setting of the temperature of double screw extruder heating zone are as follows: 100 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, 210 DEG C,
215 DEG C, 215 DEG C, 215 DEG C, 210 DEG C, 200 DEG C (sequentially for from feed opening to head), fire-retardant low dielectric is made in revolving speed 260rpm
Property thermoplastic elastomer (TPE) 6.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm using vertical injection molding machine, and V2 grades of flame retardant rating is drawn
Stretch that intensity is 9.8MPa, elongation at break 551%, losstangenttanδ value 0.0027, dielectric constant 2.7, MFR are
10.2g/10min(10kg)。
Embodiment 6/7 eliminates the pretreatment stage for being previously with regard to fire retardant based on embodiment 1, compared to embodiment 1, body
The tensile strength and elongation at break of system all slightly decline, and melt index maintains an equal level；Flame retardant rating decline, dielectric constant and dielectric damage
Consumption slightly rises, and shows compared to composite flame-retardant agent, single fire retardant can not play and composite flame-retardant agent phase under same amount
Matched flame retardant effect, so that anti-flammability declines.
Embodiment 8
The process for preparation of thermoplastic elastomer of low-k and anti-flammability is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh 1 part of coupling agent, be put into ethanol solution and be stirred, and adjust PH
For alkalescent, make its hydrolysis, then weighs and 5 parts of melamines and 5 parts of aluminum diethylphosphinates are added.The melamine partial size is
2.5-3.5um, pH value 5-7, the aluminum diethylphosphinate partial size are 15-20um, phosphorus content 20-24%, stirring, then water-bath
Heating makes ethyl alcohol volatilize, and pretreatment fire retardant 7 is obtained after dry.
B), measured according to weight ratio, first weigh the hydrogenated styrene-butadiene block copolymer of 30 parts of preliminary fillings, 18 parts of white oils
It is added in high-speed mixer, the number-average molecular weight 260000 of the hydrogenated styrene-butadiene block copolymer, styrene
Content 35%.Then it is 16 ± 3 that polypropylene melt flow rate described in 33 parts of random polypropylenes, which is added,.Then 5 parts are added to gather
Phenylate, the polyphenylene oxide anti-flammability are V-1 grades, tensile strength 58Mpa.0.3 part of stabilization is added after mixing one minute in blender
Agent, 0.3 part of antioxidant, 1.1 parts of lubricants are processed in double screw extruder after mediating one minute and are granulated, double screw extruder
The temperature of heating zone is set are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185
DEG C, 180 DEG C (sequentially for from feed opening to head), a kind of low-dielectric thermoplastic elastomer (TPE) 7 is finally made in revolving speed 260rpm.
C), pretreatment fire retardant 7 is added in low dielectric thermoplastic elastomer (TPE) 7, then 0.2 part of stabilizer of addition, 0.2 part
Antioxidant, 0.8 part of lubricant stir one minute, 0.1 part of release agent are eventually adding, after mediating one minute in double screw extruder
Processing is granulated, the setting of the temperature of double screw extruder heating zone are as follows: 100 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, 210 DEG C,
215 DEG C, 215 DEG C, 215 DEG C, 210 DEG C, 200 DEG C (sequentially for from feed opening to head), fire-retardant low dielectric is made in revolving speed 260rpm
Property thermoplastic elastomer (TPE) 7.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm using vertical injection molding machine, and HB grades of flame retardant rating is drawn
Stretch that intensity is 13.4MPa, elongation at break 681%, losstangenttanδ value 0.0023, dielectric constant 2.4, MFR are
14.1g/10min(10kg)。
Embodiment 8 reduces ratio of the fire retardant in system based on embodiment 1, compared to embodiment 1, the stretching of system
Intensity and elongation at break all obviously rise, and melt index increases；Flame retardant rating is decreased obviously, dielectric constant and dielectric loss drop
It is low, show that fire retardant is to influence one of dielectricity and the principal element of mechanical property, but excessively reduce group of the fire retardant in system
Point, the flame retardant effect of system can be lost.
Embodiment 9
The process for preparation of thermoplastic elastomer of low-k and anti-flammability is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh 1 part of coupling agent, be put into ethanol solution and be stirred, and adjust PH
For alkalescent, make its hydrolysis, then weighs and 15 parts of melamines and 5 parts of aluminum diethylphosphinates are added.The melamine partial size
For 2.5-3.5um, pH value 5-7, the aluminum diethylphosphinate partial size is 15-20um, phosphorus content 20-24%, is stirred, then water
Bath heating makes ethyl alcohol volatilize, and pretreatment fire retardant 9 is obtained after dry.
B), measured according to weight ratio, first weigh the hydrogenated styrene-butadiene block copolymer of 25 parts of preliminary fillings, 18 parts of white oils
It is added in high-speed mixer, the number-average molecular weight 260000 of the hydrogenated styrene-butadiene block copolymer, styrene
Content 35%.Then it is 4 ± 1 that polypropylene melt flow rate described in 28 parts of random polypropylenes, which is added,.Then 5 parts of polyphenyl are added
Ether, the polyphenylene oxide anti-flammability are V-1 grades, tensile strength 58Mpa.Blender mix one minute after be added 0.3 part of stabilizer,
0.3 part of antioxidant, 1.1 parts of lubricants are processed in double screw extruder after mediating one minute and are granulated, double screw extruder heating
The temperature in area is set are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180
A kind of low-dielectric thermoplastic elastomer (TPE) 9 is finally made in DEG C (sequentially for from feed opening to head), revolving speed 260rpm.
C), pretreatment fire retardant 9 is added in low dielectric thermoplastic elastomer (TPE) 9, then 0.2 part of stabilizer of addition, 0.2 part
Antioxidant, 0.8 part of lubricant stir one minute, 0.1 part of release agent are eventually adding, after mediating one minute in double screw extruder
Processing is granulated, the setting of the temperature of double screw extruder heating zone are as follows: 100 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, 210 DEG C,
215 DEG C, 215 DEG C, 215 DEG C, 210 DEG C, 200 DEG C (sequentially for from feed opening to head), fire-retardant low dielectric is made in revolving speed 260rpm
Property thermoplastic elastomer (TPE) 9.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm using vertical injection molding machine, and V1 grades of flame retardant rating is drawn
Stretch that intensity is 8.9MPa, elongation at break 527%, losstangenttanδ value 0.0027, dielectric constant 2.8, MFR are
6.1g/10min(10kg)。
Embodiment 9 is based on embodiment 1 and mainly changes wherein polyacrylic mobility, compared to embodiment 1, the drawing of system
Stretch intensity decline, elongation at break decline, processability decline；Flame retardant rating maintains an equal level, and dielectric constant and dielectric loss increase, and shows
Lower polypropylene mobility easily leads to the decline of the compatibility between other components, and is easy dispersion unevenness, leads to body force
Learn the reduction of performance and dielectric properties.
Embodiment 10
The process for preparation of thermoplastic elastomer of low-k and anti-flammability is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh 1 part of coupling agent, be put into ethanol solution and be stirred, and adjust PH
For alkalescent, make its hydrolysis, then weighs and 15 parts of melamines and 5 parts of aluminum diethylphosphinates are added.The melamine partial size
For 2.5-3.5um, pH value 5-7, the aluminum diethylphosphinate partial size is 15-20um, phosphorus content 20-24%, is stirred, then water
Bath heating makes ethyl alcohol volatilize, and pretreatment fire retardant 10 is obtained after dry.
B), measured according to weight ratio, first weigh the hydrogenated styrene-butadiene block copolymer of 25 parts of preliminary fillings, 18 parts of white oils
It is added in high-speed mixer, the number-average molecular weight 260000 of the hydrogenated styrene-butadiene block copolymer, styrene
Content 35%.Then it is 14 ± 2 that polypropylene melt flow rate described in 28 parts of shock resistance type polystyrene, which is added,.Then it is added
5 parts of polyphenylene oxide, the polyphenylene oxide anti-flammability are V-1 grades, tensile strength 58Mpa.Blender is added 0.3 part after mixing one minute
Stabilizer, 0.3 part of antioxidant, 1.1 parts of lubricants are processed in double screw extruder after mediating one minute and are granulated, and twin-screw squeezes
Out machine heating zone temperature setting are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C,
185 DEG C, 180 DEG C (sequentially for from feed opening to head), a kind of low-dielectric thermoplastic elastomer (TPE) is finally made in revolving speed 260rpm
10。
C), pretreatment fire retardant 10 is added in low dielectric thermoplastic elastomer (TPE) 10, then 0.2 part of stabilizer of addition, 0.2
Part antioxidant, 0.8 part of lubricant stir one minute, 0.1 part of release agent are eventually adding, in double screw extruder after mediating one minute
Middle processing is granulated, the temperature setting of double screw extruder heating zone are as follows: 100 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, 210
DEG C, 215 DEG C, 215 DEG C, 215 DEG C, 210 DEG C, 200 DEG C (sequentially for from feed opening to head), revolving speed 260rpm is made fire-retardant low
Dielectricity thermoplastic elastomer (TPE) 10.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm using vertical injection molding machine, and V1 grades of flame retardant rating is drawn
Stretch that intensity is 11.6MPa, elongation at break 521%, losstangenttanδ value 0.0033, dielectric constant 2.9, MFR are
9.3g/10min(10kg)。
Embodiment 10 is based on embodiment 1 and polypropylene is mainly replaced by high impact polystyrene, compared to embodiment 1, body
The tensile strength of system rises, and elongation at break decline, melt index slightly declines；Flame retardant rating maintains an equal level, dielectric constant and dielectric
Loss increases, and shows that high impact polystyrene is poor compared to compatibility between polypropylene and other components, with mentioning to a certain degree
High tensile, but whole mechanical property and processability decline, and high impact polystyrene itself dielectric constant compares polypropylene number
The main reason for value is bigger, this is also dielectric constant and dielectric loss increase.
Embodiment 11
The process for preparation of thermoplastic elastomer of low-k and anti-flammability is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh 1 part of coupling agent, be put into ethanol solution and be stirred, and adjust PH
For alkalescent, make its hydrolysis, then weighs and 15 parts of melamines and 5 parts of aluminum diethylphosphinates are added.The melamine partial size
For 2.5-3.5um, pH value 5-7, the aluminum diethylphosphinate partial size is 15-20um, phosphorus content 20-24%, is stirred, then water
Bath heating makes ethyl alcohol volatilize, and pretreatment fire retardant 11 is obtained after dry.
B), measured according to weight ratio, the styrene-butadiene block copolymer for first weighing 25 parts of preliminary fillings, 18 parts of white oils is added
In high-speed mixer, the number-average molecular weight 280000 of the hydrogenated styrene-butadiene block copolymer, styrene-content
40%.Then it is 16 ± 3 that polypropylene melt flow rate described in 28 parts of random polypropylenes, which is added,.Then 5 parts of polyphenylene oxide are added,
The polyphenylene oxide anti-flammability is V-1 grades, tensile strength 58Mpa.0.3 part of stabilizer, 0.3 is added after mixing one minute in blender
Part antioxidant, 1.1 parts of lubricants, process in double screw extruder after mediating one minute and are granulated, double screw extruder heating zone
Temperature setting are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C
A kind of low-dielectric thermoplastic elastomer (TPE) 11 is finally made in (sequentially for from feed opening to head), revolving speed 260rpm.
C), pretreatment fire retardant 11 is added in low dielectric thermoplastic elastomer (TPE) 11, then 0.2 part of stabilizer of addition, 0.2
Part antioxidant, 0.8 part of lubricant stir one minute, 0.1 part of release agent are eventually adding, in double screw extruder after mediating one minute
Middle processing is granulated, the temperature setting of double screw extruder heating zone are as follows: 100 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, 210
DEG C, 215 DEG C, 215 DEG C, 215 DEG C, 210 DEG C, 200 DEG C (sequentially for from feed opening to head), revolving speed 260rpm is made fire-retardant low
Dielectricity thermoplastic elastomer (TPE) 11.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm using vertical injection molding machine, and V1 grades of flame retardant rating is drawn
Stretch that intensity is 9.4MPa, elongation at break 546%, losstangenttanδ value 0.0026, dielectric constant 2.7, MFR are
9.1g/10min(10kg)。
Embodiment 11 is based on embodiment 1 and hydrogenated styrene-butadiene block copolymer (SEBS) is mainly replaced with benzene second
Alkene-butadiene block copolymer (SBS), compared to embodiment 1, the tensile strength of system declines, elongation at break decline, processing
Property decline；Flame retardant rating maintains an equal level, and dielectric constant and dielectric loss increase, and show compared to SEBS, and oil-filled property ratio SEBS is poor, with
Compatibility between other components is not so good as SEBS, consequently leads to overall performance and is generally not so good as SEBS.
Comparative example 1
Common thermoplastic's elasticity preparation, comprising the following steps:
A), measured according to weight ratio, first weigh the hydrogenated styrene-butadiene block copolymer of 25 parts of preliminary fillings, 18 parts of white oils
It is added in high-speed mixer, the number-average molecular weight 260000 of the hydrogenated styrene-butadiene block copolymer, styrene
Content 35%.Then it is 16 ± 3 that polypropylene melt flow rate described in 33 parts of random polypropylenes, which is added,.Then 5 parts are added to gather
Phenylate, the polyphenylene oxide anti-flammability are V-1 grades, tensile strength 58Mpa.After blender mixes one minute, it is eventually adding 20 parts
Kaolin, 0.3 part of stabilizer, 0.3 part of antioxidant, 1.2 parts of lubricants, are eventually adding 0.1 part of release agent, after mediating one minute
Process and be granulated in double screw extruder, the setting of the temperature of double screw extruder heating zone are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C,
180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to head), revolving speed 260rpm, most
A kind of common thermoplastic's elastomer is made eventually.
Low dielectric flame-proof elastomer 1 obtained and comparative example 1 are subjected to performance comparison, as a result as shown in table 1 below, additionally
It is as shown in table 2 below to list the performance comparison of elastomer Examples 1 after weathering:
1 elastomer performance contrast test result of table
The performance test results after 2 elastomer degradation of table
As can be seen from the table, low dielectric flame-proof elastomer is compared with conventional elastomers: low dielectric flame-proof elastomer due to
Pre-processing is taken to fire retardant, guarantees to can be good at compatible dispersion between filler and other components, therefore in mechanical property
On show as better than conventional elastomers, on dielectricity, though the fire retardant of selection low-k and low-dielectric loss, but phase
Than influencing in conventional elastomers there are still certain, but influence less, simultaneously because being added to fire retardant, to possess compared to ball
The property more preferably resistance to fire-retardant advantage of body, therefore low dielectric flame-proof elastomer has taken into account mechanical property, anti-flammability and low-dielectric；Meanwhile
Low dielectric flame-proof elastomer in 7 days and 15 days heat ageings the result shows that product is not much different after heat ageing with unaged, table
Reveal good resistance to ag(e)ing and weatherability.
Finally, it should be noted that above embodiments are only to illustrate the present invention and not limit technology described in the invention
Scheme；Therefore, although this specification is referring to above-mentioned each embodiment, the present invention has been described in detail, this
Field it is to be appreciated by one skilled in the art that still can modify to the present invention or equivalent replacement；And all do not depart from this
The technical solution and its improvement of the spirit and scope of invention, should all cover within the scope of the claims of the present invention.
Claims (8)
1. a kind of thermoplastic elastomer (TPE) for taking into account low-k and anti-flammability, which is characterized in that by the raw material of following parts by weight
It is made:
15-35 parts of styrene block copolymer,
20-40 parts of polyolefin resin,
10-20 parts of fire retardant,
0-40 parts of white oil,
0-10 parts of inorganic filler,
0-0.5 parts of antioxidant,
0-5 parts of dispersing agent,
0-0.5 parts of light stabilizer,
0-5 parts of coupling agent,
0-1 parts of release agent.
2. the thermoplastic elastomer (TPE) according to claim 1 for taking into account low-k and anti-flammability, which is characterized in that described
Styrene block copolymer is Styrene-Butadiene-Styrene Block Copolymer or hydrogenated products, styrene-isoprene-benzene
Ethylene block copolymer or hydrogenated products, styrene-ethylene-butylene-styrene block copolymer or hydrogenated products, styrene-
One or two kinds of combinations of ethylene-propylene, Styrene type block copolymer or hydrogenated products.
3. the thermoplastic elastomer (TPE) according to claim 2 for taking into account low-k and anti-flammability, which is characterized in that described
Styrene block copolymers is the Styrene-Butadiene-Styrene Block Copolymer of number-average molecular weight 50000-300000, benzene
Ethylene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, styrene-ethylene-
One or two kinds of combinations of propylene-styrene type block copolymer or its above-mentioned hydrogenated products.
4. the thermoplastic elastomer (TPE) according to claim 1 for taking into account low-k and anti-flammability, which is characterized in that described
Polyolefin resin be one of polyethylene, polypropylene, polyphenylene oxide, polystyrene or polyethylene and polyacrylic mixture or
Any number of combination.
5. the thermoplastic elastomer (TPE) according to claim 1 for taking into account low-k and anti-flammability, which is characterized in that described
Fire retardant be inorganic fire retardants, phosphorus flame retardant, nitrogenated flame retardant or one of phosphorus flame retardant and nitrogenated flame retardant or
Any number of combination.
6. the thermoplastic elastomer (TPE) according to claim 1 for taking into account low-k and anti-flammability, which is characterized in that described
Coupling agent is titanate coupling agent, silane coupling agent or one of titanate coupling agent and silane coupling agent or any number of group
It closes.
7. a kind of preparation of the thermoplastic elastomer (TPE) as claimed in any one of claims 1 to 6 for taking into account low-k and anti-flammability
Method, which comprises the steps of:
A), fire retardant is added in coupling agent solution and be infiltrated, adjust pH value to being in alkalescent, heating water bath stirring, it is dry after
To activation fire retardant；
B), styrene block copolymer and white oil are uniformly mixed pre-oiling in proportion, polyolefin resin are added, processability helps
Agent obtains low-k thermoplastic elastomer (TPE) after melting mixing equipment melt blending；
C), low-k thermoplastic elastomer (TPE), spark fire retardant obtained by step B), processability auxiliary agent are uniformly mixed, it is secondary
It is kneaded, the thermoplastic elastomer (TPE) for taking into account low-k and anti-flammability is made.
8. the process for preparation of thermoplastic elastomer according to claim 7 for taking into account low-k and anti-flammability, special
Sign is, the melting mixing equipment is double screw extruder, process conditions be 160~220 DEG C of temperature, revolving speed 200~
320rpm.Above-mentioned antistatic thermoplastic elastic material is molded under the conditions of 180 DEG C to the sample of thickness 3mm using vertical injection molding machine
Piece is surveyed using dielectric constant and the dielectric constant and loss tangent of dielectric loss tester measurement sample using oxygen index (OI)
The combustibility for trying instrument measurement sample prepares tensile bars using universal sampling machine, and the tensile strength and fracture for measuring material are stretched
The processing flowability of long rate, material passes through the melt flow index (MFR) under the conditions of 230 DEG C of measuring temperature, load 5/10kg
To characterize.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112194854A (en) * | 2020-09-22 | 2021-01-08 | 江苏金陵奥普特高分子材料有限公司 | Low-dielectric-property composite thermoplastic elastomer and preparation method thereof |
| CN112812440A (en) * | 2021-02-05 | 2021-05-18 | 牡丹江医学院 | Polypropylene insulation cable material and preparation method thereof |
| CN112852095A (en) * | 2021-02-25 | 2021-05-28 | 宁波中聚新材料有限公司 | Thermoplastic elastomer and preparation method thereof |
| CN116333426A (en) * | 2022-12-22 | 2023-06-27 | 广州敬信高聚物科技有限公司 | Waterproof low-dielectric thermoplastic elastomer insulating material for charging pile cable and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102477204A (en) * | 2010-11-23 | 2012-05-30 | 上海方田弹性体有限公司 | Thermoplastic elastomer, preparation method thereof, application thereof and cable sheathing tube made therefrom |
| CN103435955A (en) * | 2013-08-13 | 2013-12-11 | 东莞市安拓普塑胶聚合物科技有限公司 | Halogen-free flame retardant thermoplastic elastomer composite material and preparation method thereof |
| CN106009465A (en) * | 2016-06-30 | 2016-10-12 | 中广核高新核材集团（东莞）祈富新材料有限公司 | High-fluidity toughening type thermoplastic elastomer material and preparation method thereof |
| CN107033523A (en) * | 2017-05-16 | 2017-08-11 | 浙江大学 | Electric wire halogen-free flame-retardant thermoplastic elastomer composition of anti-UV discolorations 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 |
-
2019
- 2019-07-19 CN CN201910655677.1A patent/CN110283386A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102477204A (en) * | 2010-11-23 | 2012-05-30 | 上海方田弹性体有限公司 | Thermoplastic elastomer, preparation method thereof, application thereof and cable sheathing tube made therefrom |
| CN103435955A (en) * | 2013-08-13 | 2013-12-11 | 东莞市安拓普塑胶聚合物科技有限公司 | Halogen-free flame retardant thermoplastic elastomer composite material and preparation method thereof |
| CN106009465A (en) * | 2016-06-30 | 2016-10-12 | 中广核高新核材集团（东莞）祈富新材料有限公司 | High-fluidity toughening type thermoplastic elastomer material and preparation method thereof |
| CN107033523A (en) * | 2017-05-16 | 2017-08-11 | 浙江大学 | Electric wire halogen-free flame-retardant thermoplastic elastomer composition of anti-UV discolorations 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 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112194854A (en) * | 2020-09-22 | 2021-01-08 | 江苏金陵奥普特高分子材料有限公司 | Low-dielectric-property composite thermoplastic elastomer and preparation method thereof |
| CN112812440A (en) * | 2021-02-05 | 2021-05-18 | 牡丹江医学院 | Polypropylene insulation cable material and preparation method thereof |
| CN112852095A (en) * | 2021-02-25 | 2021-05-28 | 宁波中聚新材料有限公司 | Thermoplastic elastomer and preparation method thereof |
| CN116333426A (en) * | 2022-12-22 | 2023-06-27 | 广州敬信高聚物科技有限公司 | Waterproof low-dielectric thermoplastic elastomer insulating material for charging pile cable and preparation method thereof |
| CN116333426B (en) * | 2022-12-22 | 2024-01-09 | 广州敬信高聚物科技有限公司 | Waterproof low-dielectric thermoplastic elastomer insulating material for charging pile cable and preparation method thereof |
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Application publication date: 20190927 |