CN109851922A - A kind of V0 flame retardant rating heat discoloration thermoplastic elastomer (TPE) TPE and preparation method thereof - Google Patents
A kind of V0 flame retardant rating heat discoloration thermoplastic elastomer (TPE) TPE and preparation method thereof Download PDFInfo
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Abstract
The present invention provides V0 flame retardant rating heat discoloration thermoplastic elastomer (TPE) TPE and preparation method thereof, V0 flame retardant rating heat discoloration thermoplastic elastomer (TPE) TPE includes following component in parts by weight: 15~40 parts of styrenic elastomer, 5~28 parts of mineral oil, 4~32 parts of polyolefin, 5~15 parts of polyolefin thermoplastic elastomer, graft or 1~10 part of polar copolymer, 25~46 parts of fire retardant, toner 0.1~3,0.1~4 part of lubricant, 0.1~0.5 part of antioxidant.The V0 flame retardant rating heat discoloration thermoplastic elastomer (TPE) TPE have environmental protection, it is soft it is resistance to be precipitated, it is ageing-resistant, superior flame retardant property and can change colour under certain temperature threshold value the advantages that, and do not need carry out vulcanization crosslinking, processing technology is simple, cold tolerance is excellent, have better dimensional accuracy and surface sophistication.
Description
Technical field
The present invention relates to the present invention relates to TPE material fields, more particularly to V0 flame retardant rating heat discoloration thermoplastic elastomehc
Property body TPE and preparation method thereof.
Background technique
The fire-retardant property for referring to obvious postponement propagation of flame that substance has or that material has after processing；This makes in material
It is selected to play directive function with range, it is especially useful in building materials, ship, vehicle, the material requirements anti-flammability on household electrical appliances are high；It comments at present
There are many valence anti-flammability method, such as limiting oxygen index determination method, horizontally or vertically combustion test method；Flame retardant rating, i.e. substance have
Or the property of obvious postponement propagation of flame that material has after processing, and the hierarchy divided with this.Plastic flame grade
It is incremented by step by step by HB, V-2, V-1 to V-0；After V0 grades carry out 10 seconds combustion testings twice to sample, flame is put out in 30 seconds
It goes out；There cannot be comburant to fall down.
With the arrival in intelligent epoch, the life and our daily lifes that each electronic product is just being flooded with us are pasted extremely
Closely；As countries in the world are for the raising of environmental requirement, traditional PVC is since the plasticiser and halogen problem of itself are in electronics
By limitation in the use of the product of electric appliance；And PVC thermal stability is relatively bad, is electrified for a long time and solar radiation in cable
Under, it is easy to ageing failure causes a hidden trouble；And PVC can release toxic chlorine-containing compound in by Heat Ageing,
It is disagreed with Green Sustainable.
Styrenic elastomer is due to environmentally protective, soft comfortable, and hardness range is wide, and the superior advantage of resistance to low temperature is just
Gradually application of the substitution PVC in electronic product；However styrenic elastomer is easier to burn since oxygen index (OI) is low, and itself
Long-term heat resistance be not it is very high, the long-term use temperature that general SBC analog thermoplastic elastomer is just producing generally at 70 DEG C once；And
Mobile phone or electronic equipment are during charging due to the influence in charging time and environment, it is easy to lead to high molecular material temperature
Increase even Fire Overheat.
The wire design of the excessively high early warning of existing temperature is, preparation can excess temperature early warning wire rod when at intermediate structure again
Add with heat discoloration layer；The production process of product is increased, and increases the cost of product.
Based on this, it is necessary to which release is suitable for guaranteeing that it has on the TPE material of electronic device contact product superior fire-retardant
Performance, and material can have colour change function to reach warning function after reaching corresponding temperature, simplify the life of downstream product
It produces.
Summary of the invention
The object of the present invention is to provide a kind of V0 flame retardant rating heat discoloration thermoplastic elastomer (TPE) TPE and preparation method thereof,
The TPE material produced has superior flame retardant property, and material can have colour change function after reaching corresponding temperature
Reach warning function, simplifies the production of downstream product.
In order to achieve the goal above, the technical solution adopted by the present invention are as follows: a kind of V0 flame retardant rating heat discoloration thermoplasticity
Elastomer TPE is made of the raw material of following parts by weight:
Preferably, the styrenic elastomer be styrene-ethylene/butadiene-styrene block copolymer (SEBS) or
One of person's styrene-ethylene/ethylene/propene-styrene block copolymer (SEEPS) or more than one mixture, tool
Figure number such as Kuraray 4055, section, the U.S. rise G1651,1645,1642, TaiWan, China Lee long flourish 7551, TaiWan, China platform
Rubber 6151,6154,6014, Yueyang petrochemical industry YH-503T, YH-511.
Preferably, the mineral oil is that viscosity is higher than 30mm2/ s (40 DEG C) and flash-point are higher than 200 DEG C of saturated straight chain alkane
One of oil, naphthenic oil or more than one mixture；Concrete model for example platform modeling 150N, 380N, Kelamayi KN4010,
Kelamayi KNH4006, Kelamayi KN4006,250SN, 500SN.
Preferably, the polyolefin is one of polypropylene, polyethylene or more than one mixture；Polypropylene is equal
One of poly- polypropylene, copolymer polypropylene or atactic copolymerized polypropene or more than one mixture；Polyethylene is low-density
One of polyethylene, linear low density polyethylene, metallocene PE, medium density polyethylene, high density polyethylene (HDPE) are a kind of
Above mixture；Polypropylene concrete model such as Sinopec PPH-T03, Thailand treasured unicorn PP 1100NK, TaiWan, China Li Changrong
PP7533, TaiWan, China platform mould PP 5090T, Exxon Mobil PP7032, South Korea SK PP R370Y, polyethylene concrete model
Such as Sinopec LLDPE DFDA 7042, Tao Shi DNDB-7147, the graceful MLLDPE SP0540 of Japanese Puri.
Preferably, the polyolefin thermoplastic elastomer is one of POE, EP, EPDM or more than one mixture；
Concrete model such as husky uncle basis C0570D, Exxon Mobil Vistamaxx POE3980, Exxon Mobil
VistamaxxPOE6102, Tao Shi Engage POE8003,39001 Tao Shi, Tao Shi Engage POE8150, Tao Shi Affinity
1880G, three well POE DF810, three well EPDM 3072EM, Tao Shi EPDM 3722P etc..
Preferably, the graft is polypropylene grafted maleic anhydride (PP-g-MAH), POE grafted maleic anhydride (POE-
), g-MAH hydrogenated styrene-butadiene-styrene block copolymers grafted maleic anhydride (SEBS-g-MAH), ethylene-propylene-diene monomer
One of glue grafted maleic anhydride (EPDM-g-MAH) or polar copolymer EVA or more than one mixture；Particular type
Number such as A Kema 18722, Du Pont P353, DOW Chemical GR216,1901,1924 and South Sea Bai Chen PC-8 rises in section, and platform moulds EVA
7350 etc..
Preferably, the fire retardant be melamine polyphosphate, it is melamine cyanurate, alkyl hypophosphites, secondary
One of phosphate, ammonium polyphosphate, piperazine pyrophosphate compound flame retardant or more than one mixture；Concrete model such as gram Lay
Grace OP935, Shandong Shouguang Wei Dong MCA-15, Sichuan fine chemistry industry research institute MPP-A, Japanese Ai Di section FP2200S, Hangzhou are prompt
You think JLS-PNA220, Qingdao Europe Puri NP2536, middle mountain Kang Nuode HF600B etc..
Preferably, the toner is that temperature reaches after a certain specific temperature in thermoplastic elastomer system can be from a certain
Particular color becomes the toner of other particular color；Concrete model such as Clariant PV Fast Yellow HG, PV Fast
Green GNX, thousand discoloration TCR-31, TBB-45 of Dongguan etc..
Preferably, the lubricant is one of silicone powder, silicone master batch, erucyl amide, oleamide, zinc stearate
Or more than one mixture；2418 etc. of MB50-001, MB50-002, Wa Ke company of concrete model such as Dow Corning Corporation.
Preferably, the antioxidant is that four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters are (anti-
Oxygen agent 1010) β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester (antioxidant 1076), three (bis- uncles of 2,4-
Butyl phenyl) phosphite ester (irgasfos 168), one of or more than one mixture.
A kind of another technical solution of the invention are as follows: preparation of V0 flame retardant rating heat discoloration thermoplastic elastomer (TPE) TPE
Method, comprising the following steps:
Step 1: styrenic elastomer, mineral oil, polyolefin, polyolefin thermoplastic elastomer, grafting are weighed according to the proportion
Object or polar copolymer, fire retardant, toner, lubricant and antioxidant；
Step 2: the weighed styrenic elastomer of step 1 and mineral oil are added in agitator and stirred evenly, is placed extremely
Obtain the first mixture within few 2 days；
Step 3: by first mixture and the load weighted polyolefin of step 1, polyolefin elastomer and graft or
Polar copolymer, which is added in agitator, is uniformly mixed to obtain the second mixture；
Step 4: second mixture and the load weighted fire retardant of step 1, toner, lubricant and antioxidant are stirred
It is uniformly mixed and obtains pre-composition；
Step 5: by the pre-composition by twin-screw blending extrusion, be granulated, be dried to obtain V0 flame retardant rating heat discoloration
TPE material.
Preferably, the pre-composition squeezes out, granulation carries out in double screw extruder, the temperature of the double screw extruder
It is 180~210 DEG C, screw speed is 270r/min~450r/min, and screw rod industry ratio is 48:1~58:1.
This TPE material has the advantage that relative to traditional PVC material for electric equipment products environment-protecting and non-poisonous, close
Spend that low, resistance to low temperature is good, soft；The product tool that this TPE material is worked it out relative to traditional fire-retardant class TPE material
Have the advantage that resistance to precipitation, resistance to low temperature are superior, and wherein the feature of this TPE material maximum is exactly with high flame retardant property
Material itself discoloration when temperature reaches certain threshold value, thus reach a high temperature early warning and simplified downstream high temperature discoloration early warning production
The effect of the production technology of product, so being more suitable for doing electronic equipment aftermarket product.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, below to specific reality of the invention
The mode of applying is described in detail.In the following description, numerous specific details are set forth in order to facilitate a full understanding of the present invention.But
The invention can be embodied in many other ways as described herein, and those skilled in the art can be without prejudice to this hair
Similar improvement is done in the case where bright intension, therefore the present invention is not limited to the specific embodiments disclosed below.
Embodiment 1
The SEBS 1654 of 15 parts by weight is put into high-speed mixer, the mineral oil KDN4006 of 5 parts by weight is uniformly added into,
High-speed stirred 3min obtains the first mixture, after mixture packaging, places 4 days.
First required first mixture, 20 parts by weight are put into high-speed mixer, the DOWTM 39001 of 5 parts by weight of addition,
The DOW GR216 of PP 1100NK of 32 parts by weight, 5 parts by weight, high-speed stirred 2min obtain the second mixture.
Japanese Ai Di section FP2200S, the 0.15 parts by weight toner, 0.1 weight of 25 parts by weight are added into the second mixture
Part lubricant oleamide, 0.1 parts by weight antioxidant 1076,0.1 parts by weight irgasfos 168 stir 2.5min, are premixed
Object.
The pre-composition is poured into the hopper of parallel dual-screw extruding machine, is processed and is dispersed by parallel dual-screw, pelletizing,
Up to V0 flame retardant rating heat discoloration thermoplastic elastic material.
Embodiment 2
The SEBS G1645 of SEBS YH-511 of 22 parts by weight, 10.6 parts by weight is put into high-speed mixer, is uniformly added
Enter the mineral oil KDN4006 of 9.7 parts by weight, stir 1.5min, obtain the first mixture, after mixture packaging, places 2
It.
First required first mixture, 42.3 parts by weight are put into high-speed mixer, PP 5090T of 4 parts by weight of addition,
It is mixed to obtain second by graft FG 1901, the high-speed stirred 2min of the Vistamaxx POE 6102 of 6.9 parts by weight, 1 parts by weight
Close object；
9.4 parts by weight O P935,5.2 parts by weight MPP-A, 27.7 parts of MCA-15,0.3 weight are added into the second mixture
The anti-feeding agent 1076 of part toner, 4 parts of silicone MB50-001, the antioxidant 1010 of 0.2 parts by weight, 0.3 parts by weight, stirs 3min, obtains
To pre-composition.
The pre-composition is poured into the hopper of parallel dual-screw extruding machine, is processed and is dispersed by parallel dual-screw, pelletizing,
Up to V0 flame retardant rating heat discoloration thermoplastic elastic material.
Embodiment 3
The SEBS DP6014 of SEBS YH-503T of 15 parts by weight, 6.8 parts by weight is put into high-speed mixer, uniformly
The mineral oil 150N of 13.2 parts by weight is added, stirs 2.5min, obtains the first mixture, after mixture packaging, places 3
It.
First required first mixture, 35 parts by weight are put into high-speed mixer, PP 1100NK of 10 parts by weight of addition,
The Tao Shi 8402 of 5.1 parts by weight, PP the grafted maleic anhydride P353, high-speed stirred 2min of 10 parts by weight obtain the second mixture；
34 parts by weight NP2536,4.2 parts by weight HF600B, 1.5 parts by weight toners, 2.5 parts are added into the second mixture
Silicone MB50-002, the antioxidant 1010 of 0.1 parts by weight, 0.3 parts by weight irgasfos 168 stir 2.5min, obtain pre-composition.
The pre-composition is poured into the hopper of parallel dual-screw extruding machine, is processed and is dispersed by parallel dual-screw, pelletizing,
Up to V0 flame retardant rating heat discoloration thermoplastic elastic material.
Embodiment 4
The SEBS 6154 of 22.3 parts by weight is put into high-speed mixer, the mineral oil of 28 parts by weight is uniformly added into
KN4006 stirs 3min, obtains the first mixture, after mixture packaging, places 2 days.
First required first mixture, 50.3 parts by weight are put into high-speed mixer, PP R370Y of 10 parts by weight of addition,
The A Kema 18722 of the Vistamaxx POE 3980 of 5.6 parts by weight, 3 parts by weight, high-speed stirred 2min obtain the second mixing
Object；
34 parts by weight JLS-PNA220,0.3 parts by weight toner, 2.6 parts of silicone 2418,0.2 are added into the second mixture
The irgasfos 168 of parts by weight, 0.07 parts by weight antioxidant 1010 stir 3min, obtain pre-composition.
The pre-composition is poured into the hopper of parallel dual-screw extruding machine, is processed and is dispersed by parallel dual-screw, pelletizing,
Up to V0 flame retardant rating heat discoloration thermoplastic elastic material.
Embodiment 5
The SEBS G1645 of SEBS DP6014 of 25 parts by weight, 15 parts by weight is put into high-speed mixer, is uniformly added into
The mineral oil 380N of 10.5 parts by weight stirs 3min, obtains the first mixture, after mixture packaging, places 2 days.
First required first mixture, 50.5 parts by weight are put into high-speed mixer, the MLLDPE of 4.8 parts by weight is added
SP0540, the Vistamaxx POE 6202 of 5 parts by weight, 2 parts by weight EVA 7350, high-speed stirred 2min, it is mixed to obtain second
Close object；
Be added into the second mixture 41.3 parts by weight NP2536, the OP935 of 4.7 parts by weight, 3.0 parts by weight toners,
2.6 parts of silicone MB50-001, the antioxidant 1076 of 0.2 parts by weight, 0.07 parts by weight antioxidant 1010 stir 3min, obtain pre-
Mixed object.
The pre-composition is poured into the hopper of parallel dual-screw extruding machine, is processed and is dispersed by parallel dual-screw, pelletizing,
Up to V0 flame retardant rating heat discoloration thermoplastic elastic material.
Embodiment 6
The SEBS 6153 of 17 parts by weight is put into high-speed mixer, the mineral oil 150N of 17.5 parts by weight is uniformly added into,
2.5min is stirred, the first mixture is obtained, after mixture packaging, is placed 2 days.
First required first mixture, 34.5 parts by weight are put into high-speed mixer, PP 5090T of 13 parts by weight of addition,
The Vistamaxx POE 3980 of 10 parts by weight, the Engage 8402 of 5 parts by weight, 4 parts by weight graft PC-8, high-speed stirring
2min is mixed, the second mixture is obtained；
16 parts by weight MCA-15, the HF600B of 14 parts by weight, 0.35 parts by weight toner, 2 parts are added into the second mixture
Silicone 2418, the irgasfos 168 of 0.25 parts by weight, 0.1 parts by weight 1010 stir 3min, obtain pre-composition.
The pre-composition is poured into the hopper of parallel dual-screw extruding machine, is processed and is dispersed by parallel dual-screw, pelletizing,
Up to V0 flame retardant rating heat discoloration thermoplastic elastic material.
The V0 flame retardant rating heat discoloration thermoplastic elastomer (TPE) TPE of above-described embodiment, the test result of main performance is such as
Shown in following table.
As seen from the above table, V0 flame retardant rating heat discoloration thermoplastic elastomer (TPE) TPE of the invention has excellent mechanical property
Can be with high flame retardant rating, resistance to low temperature is good, can change colour under specific temperature range, and can become original again after reducing
Performance of the color come without influencing thermoplastic elastomer (TPE) itself, and V0 flame retardant rating heat discoloration thermoplastic elastomehc of the present invention
Property body TPE process be not necessarily to vulcanization crosslinking, operating procedure is simple, and production is efficient.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of V0 flame retardant rating heat discoloration thermoplastic elastomer (TPE) TPE it is characterised in that it includes it is following in parts by weight
Component:
2. a kind of V0 flame retardant rating heat discoloration thermoplastic elastomer (TPE) TPE according to claim 1, which is characterized in that institute
Stating styrenic elastomer is styrene-ethylene/butadiene-styrene block copolymer (SEBS) or styrene-ethylene/second
One of alkene/propylene-styrene block copolymer (SEEPS) or more than one mixture.
3. a kind of V0 flame retardant rating heat discoloration thermoplastic elastomer (TPE) TPE according to claim 1, which is characterized in that institute
Stating mineral oil is that viscosity is higher than 30mm2The saturated straight chain alkane oil of/s (40 DEG C) and flash-point higher than 200 DEG C, one in naphthenic oil
Kind or more than one mixture.
4. a kind of V0 flame retardant rating heat discoloration thermoplastic elastomer (TPE) TPE according to claim 1, which is characterized in that institute
Stating polyolefin is one of polypropylene, polyethylene or more than one mixture；Polypropylene is homopolypropylene, copolymerization poly- third
One of alkene or atactic copolymerized polypropene or more than one mixture；Polyethylene is low density polyethylene (LDPE), linea low density
One of polyethylene, metallocene PE, medium density polyethylene, high density polyethylene (HDPE) or more than one mixture.
5. a kind of V0 flame retardant rating heat discoloration thermoplastic elastomer (TPE) TPE according to claim 1, which is characterized in that institute
Stating polyolefin thermoplastic elastomer is one of POE, EP, EPDM or more than one mixture.
6. a kind of V0 flame retardant rating heat discoloration thermoplastic elastomer (TPE) TPE according to claim 1, which is characterized in that institute
Stating graft is polypropylene grafted maleic anhydride (PP-g-MAH), POE grafted maleic anhydride (POE-g-MAH), hydrogenated styrene-
Butadiene-styrene block copolymer grafted maleic anhydride (SEBS-g-MAH), grafting maleic anhydride with ethylene propylene terpolymer
(EPDM-g-MAH) or one of polar copolymer EVA or more than one mixture.
7. a kind of V0 flame retardant rating heat discoloration thermoplastic elastomer (TPE) TPE according to claim 1, which is characterized in that institute
Stating toner is that can become in addition from a certain particular color in thermoplastic elastomer system after temperature reaches a certain specific temperature
The toner of particular color.
8. a kind of V0 flame retardant rating heat discoloration thermoplastic elastomer (TPE) TPE according to claim 1, which is characterized in that institute
Stating antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010) β-(3,5- bis-
Tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester (antioxidant 1076), three (2,4- di-tert-butyl-phenyl) phosphite esters
(irgasfos 168), one of or more than one mixture.
9. such as the preparation method of one of any one of claim 1-8 V0 flame retardant rating heat discoloration thermoplastic elastomer (TPE) TPE,
Characterized by comprising the following steps:
Step 1: weigh according to the proportion styrenic elastomer, mineral oil, polyolefin, polyolefin thermoplastic elastomer, graft or
Polar copolymer, fire retardant, toner, lubricant and antioxidant；
Step 2: the weighed styrenic elastomer of step 1 and mineral oil are added in agitator and stirred evenly, is placed at least 2 days
Obtain the first mixture；
Step 3: by first mixture and the load weighted polyolefin of step 1, polyolefin elastomer and graft or polarity
Copolymer, which is added in agitator, is uniformly mixed to obtain the second mixture；
Step 4: second mixture and the load weighted fire retardant of step 1, toner, lubricant and antioxidant are stirred
Uniformly obtain pre-composition；
Step 5: by the pre-composition by twin-screw blending extrusion, be granulated, be dried to obtain V0 flame retardant rating heat discoloration thermoplastic
Property elastomer TPE material.
10. the preparation method of V0 flame retardant rating heat discoloration thermoplastic elastomer (TPE) TPE according to claim 9 a kind of,
It is characterized in that, the pre-composition squeezes out, granulation carries out in double screw extruder, and the temperature of the double screw extruder is 180
~210 DEG C, screw speed is 270r/min~450r/min, and screw rod industry ratio is 48:1~58:1.
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| CN110283414A (en) * | 2019-07-19 | 2019-09-27 | 江苏金陵奥普特高分子材料有限公司 | Gao Dingshen high springs back thermoplastic elastomer (TPE) and preparation method thereof |
| CN110752056A (en) * | 2019-09-10 | 2020-02-04 | 东莞市瀛通电线有限公司 | Temperature sensing color-changing braided cable |
| CN112251032A (en) * | 2020-10-22 | 2021-01-22 | 东莞市汇泽实业有限公司 | TPE (thermoplastic elastomer) foaming material suitable for pillow inner and preparation method thereof |
| WO2022064869A1 (en) | 2020-09-23 | 2022-03-31 | Ｍｃｐｐイノベーション合同会社 | Thermoplastic elastomer composition and composite molded object |
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| CN112251032A (en) * | 2020-10-22 | 2021-01-22 | 东莞市汇泽实业有限公司 | TPE (thermoplastic elastomer) foaming material suitable for pillow inner and preparation method thereof |
| CN116333448A (en) * | 2023-05-30 | 2023-06-27 | 佛山市思特传导科技有限公司 | Oil-proof low-smoke halogen-free material and preparation method thereof |
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