CN104262909B - Low-smoke low-toxicity copolymerized polyester elastomer composition and preparation method thereof - Google Patents
Low-smoke low-toxicity copolymerized polyester elastomer composition and preparation method thereof Download PDFInfo
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- CN104262909B CN104262909B CN201410478029.0A CN201410478029A CN104262909B CN 104262909 B CN104262909 B CN 104262909B CN 201410478029 A CN201410478029 A CN 201410478029A CN 104262909 B CN104262909 B CN 104262909B
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 58
- 239000000806 elastomer Substances 0.000 title claims abstract description 58
- 229920000728 polyester Polymers 0.000 title claims abstract description 49
- 231100000053 low toxicity Toxicity 0.000 title claims abstract description 45
- 239000000779 smoke Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000203 mixture Substances 0.000 title abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 45
- 239000002184 metal Substances 0.000 claims abstract description 45
- 239000003063 flame retardant Substances 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 40
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 35
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 33
- 239000010703 silicon Substances 0.000 claims abstract description 33
- 239000002270 dispersing agent Substances 0.000 claims abstract description 23
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000010452 phosphate Substances 0.000 claims abstract description 8
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 5
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 5
- 229920006344 thermoplastic copolyester Polymers 0.000 claims description 95
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 58
- 150000002148 esters Chemical class 0.000 claims description 32
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 13
- -1 phosphate ester Chemical class 0.000 claims description 8
- 235000021317 phosphate Nutrition 0.000 claims description 6
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 239000008188 pellet Substances 0.000 claims description 4
- 238000005453 pelletization Methods 0.000 claims description 4
- TVAJJUOMNRUGQA-UHFFFAOYSA-N 2-butoxyethyl dihydrogen phosphate Chemical class CCCCOCCOP(O)(O)=O TVAJJUOMNRUGQA-UHFFFAOYSA-N 0.000 claims description 3
- RREGISFBPQOLTM-UHFFFAOYSA-N alumane;trihydrate Chemical group O.O.O.[AlH3] RREGISFBPQOLTM-UHFFFAOYSA-N 0.000 claims description 3
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 3
- 125000005340 bisphosphate group Chemical group 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 239000011863 silicon-based powder Substances 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims 1
- 239000004576 sand Substances 0.000 claims 1
- 239000012747 synergistic agent Substances 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 3
- 150000004677 hydrates Chemical class 0.000 abstract 2
- 239000003607 modifier Substances 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- LAUIXFSZFKWUCT-UHFFFAOYSA-N [4-[2-(4-phosphonooxyphenyl)propan-2-yl]phenyl] dihydrogen phosphate Chemical compound C=1C=C(OP(O)(O)=O)C=CC=1C(C)(C)C1=CC=C(OP(O)(O)=O)C=C1 LAUIXFSZFKWUCT-UHFFFAOYSA-N 0.000 description 14
- 239000013500 performance material Substances 0.000 description 11
- 235000019504 cigarettes Nutrition 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 229920001634 Copolyester Polymers 0.000 description 3
- 229920002725 thermoplastic elastomer Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 description 2
- NUOYJPPISCCYDH-BYPYZUCNSA-N (2s)-1-(2,2,2-trifluoroacetyl)pyrrolidine-2-carbonyl chloride Chemical compound FC(F)(F)C(=O)N1CCC[C@H]1C(Cl)=O NUOYJPPISCCYDH-BYPYZUCNSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000004595 color masterbatch Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002036 drum drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229920005684 linear copolymer Polymers 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a low-smoke low-toxicity copolymerized polyester elastomer composition and a preparation method thereof. The low-smoke low-toxicity copolymerized polyester elastomer composition comprises the following components in percentage by weight: 20-80 percent of thermoplastic copolymerized polyester elastomer TPC, 30-70 percent of metal hydrates, 2-30 percent of a liquid phosphate modifier and 1-10 percent of an organic silicon flame retardant synergist. The preparation method comprises the following steps: pre-drying; feeding at a first twin-screw feeding hole through a loss-in-weight feeder; pumping liquid phosphate through a loss-in-weight liquid feeder; mixing the metal hydrates with a hyper-dispersant, extruding, slicing and drying. The low-smoke low-toxicity copolymerized polyester elastomer composition disclosed by the invention has high flame retardant characteristics; and compared with a conventional flame retardant copolymerized polyester elastomer in the market, the low-smoke low-toxicity copolymerized polyester elastomer composition has obvious characteristics of low smoke and low toxicity.
Description
【Technical field】
The present invention relates to one includes copolyester thermoplastic elastomers compositionss, and in particular to one kind shows low in burning
Halogen-free flame-proof copolymerized polyester elastomer composition of cigarette low toxicity characteristic and preparation method thereof.
【Background technology】
Thermoplastic copolyester elastomer (TPC) is that a class contains PBT polyester hard section and soft section is aliphatic polyester or gathers
The linear copolymer elastomer of ether soft section.Typically be subdivided into polyester-type copolymerized polyester elastic body and polyether-type copolymerized polyester elastic body or
Copolymerized polyester elastic body of person's polyester polyether mixed type etc..It is due to the relatively light weight of copolyester thermoplastic elastomer (TPE), excellent
Different tensile strength and tearing strength, flex life, relative high temperature resistant and superior anti-wear performance, are used for many application necks
Domain, the application include electric wire, household electrical appliances, vehicle, instrument, electronic device etc..
In the application of such as motor vehicles and electric/electronic devices component etc, also it is desirable to be made up of thermoplastic elastomer (TPE)
Product there is anti-flammability, so as to promote product safety, prevent fire spread and reduction be exposed to fire product breaking-up and people
Life security.
The fire retardant for being conventionally used for TPC compositionss is that based on halogen, i.e., they include chlorine, bromine etc..But due to continuous
Exist to environment and the concern of safety, more advantageously halogen-free flame retardants now.It is conventionally used for the resistance of TPEE halogen-free flameproofs
Combustion agent includes, based on phosphoric acid ester such as RDP, BDP, the such as MPP of the fire retardant based on P-N type, APP etc., and hypophosphorous acid salt
Fire retardant, the cigarette of variable concentrations still can be discharged when so the fire proofing of the Halogen system of system burns, however it remains to ring
Protect and safe hidden danger.Low-smoke low-toxicity environmental protection is not solved the problems, such as, existing market does not show good low-smoke low-toxicity yet
Flame-proofed thermoplastic copolymerized polyester elastic body TPC (TPC/TPEE) compositionss.And low cigarette materials some other on market is not
Possess TPC others combination properties, such as high resiliency, high temperature resistant, insulating properties etc..So TPC industry exigences have
The TPC compositionss for showing good low-smoke low-toxicity and halogen-free flameproof performance occur.
【The content of the invention】
In order to solve technical problem present in prior art, the invention provides a kind of low-smoke low-toxicity copolyester is elastic
Body compositionss.
Present invention also offers the preparation method of this low-smoke low-toxicity copolymerized polyester elastic body compositionss.
The technical scheme adopted by present invention solution prior art problem has been to provide a kind of low-smoke low-toxicity copolyester bullet
Elastomeric composition, the low-smoke low-toxicity copolymerized polyester elastic body compositionss include：Thermoplastic copolyester elastomer TPC, metal
Ester modified dose of hydrate, liquid phosphoric acid and organic silicon flame-retardant synergist, weight accounting is：
Thermoplastic copolyester elastomer TPC20% is to 80%；
Metal hydrate 30% to 70%；
Ester modified dose 2% to 30% of liquid phosphoric acid；
Organic silicon flame-retardant synergist 1% to 10%.
Optimal technical scheme of the invention：The weight of each composition of the low-smoke low-toxicity copolymerized polyester elastic body compositionss
Accounting is：
Thermoplastic copolyester elastomer TPC 40% to 50%；
Metal hydrate 35% to 55%；
Ester modified dose 7% to 13% of liquid phosphoric acid；
Organic silicon flame-retardant synergist 4% to 7%；
Hyper-dispersant 0.2% to 1.5%；
Hydrolysis-resisting agent 0.2% to 1%.
Optimal technical scheme of the invention：Thermoplastic copolyester elastomer TPC is common for polyether thermoplastic
Poly- polyester elastomer TPC, shore hardness are 25D～75D.
Optimal technical scheme of the invention：The metal hydrate is aluminum trihydrate.
Optimal technical scheme of the invention：Ester modified dose of the liquid phosphoric acid is bisphenol-A, bisphosphate, trisphenol
One kind or several in phosphate ester, resorcinol biphenol phosphate ester, three butoxyethyl phosphates and/or xylenols phosphate ester
Kind.
Optimal technical scheme of the invention：The organic silicon flame-retardant synergist is silicone polymer and/or organosilicon
Micropowder.
Present invention also offers a kind of preparation method of low-smoke low-toxicity copolymerized polyester elastic body compositionss, the low-smoke low-toxicity
The preparation method of copolymerized polyester elastic body compositionss includes：Will be thermoplastic copolyester elastomer TPC and metal hydrate advance
It is dried, makes the water content in thermoplastic copolyester elastomer TPC less than 800ppm, the moisture content in the metal hydrate contains
Amount is less than 600ppm；
Dried thermoplastic copolyester elastomer TPC material passes through weightless feeding in the first segment spout of twin screw
Device feeds；
Liquid phosphoric acid ester is pumped into by weightless liquid feeder by the 5th section of upper end of double screw extruder；
After metal hydrate is mixed 2 to 5 minutes in high-speed mixer with hyper-dispersant, add hydrolysis stabilizer and have
Machine silicon fire retarding synergist mixes mixed at high speed 3-7 minute by high-speed mixer, at the 7th section of double screw extruder, by losing
Weight feeder and forced feed screw rod are added；
The a diameter of 35mm to 90mm of the twin screw, draw ratio L/D are 35：1 to 55:1, the extruder temperature is arranged and is divided into 12
Area, from main feed opening to the temperature setting of die head be：170℃-185℃-195℃-200℃-195℃-190℃-185℃-180
℃-180℃-185℃-185℃-190℃；
Temperature allow for above-mentioned numerical value or it is upper or or lower 1.5 DEG C of the temperature difference,
After weightless feeder presses formula addition, the extruded velocity of screw rod is 150RPM to 500RPM to various components, is melted
Body is cooled down into tank by die head, then through pelleter pelletizing, finally by the pellet of gained dry 3 at 100 DEG C to 110 DEG C
To 5 hours.
Optimal technical scheme of the invention：Thermoplastic copolyester elastomer TPC is placed on dehumidifier to do
In dry hopper, temperature setting is 80 DEG C to 125 DEG C, is dried 3 to 4 hours；
The metal hydrate is placed in drying oven and is dried, temperature setting is 60 DEG C to 130 DEG C, dry 4 to 6 little
When.
Low-smoke low-toxicity copolymerized polyester elastic body compositionss of the present invention have good flame-retarding characteristic, existing with market fire-retardant
Copolymerized polyester elastic body compares the characteristic with significant low cigarette, low toxicity.
【Specific embodiment】
With reference to embodiments technical solution of the present invention is described in detail：
The invention provides a kind of low-smoke low-toxicity copolymerized polyester elastic body compositionss, the low-smoke low-toxicity copolyester elasticity
Body compositionss include：Ester modified dose of thermoplastic copolyester elastomer TPC, metal hydrate, liquid phosphoric acid and organic silicon flame-retardant
Synergist, weight accounting is：Thermoplastic copolyester elastomer TPC10% is to 80%；Metal hydrate 30% to 70%；Liquid
Phosphate modified dose 2% to 30%；Organic silicon flame-retardant synergist 1% to 10%.
In the preferred version of the present invention, thermoplastic copolyester elastomer TPC 40% to 50%；Metal hydrate
35% to 55%；Ester modified dose 7% to 13% of liquid phosphoric acid；Organic silicon flame-retardant synergist 4% to 7%；Hyper-dispersant 0.2% to
1.5%；Hydrolysis-resisting agent 0.2% to 1%, using the ratio outfit will cause made by low-smoke low-toxicity copolymerized polyester elastic body group
Compound has more preferable stability and overall characteristic.
In the inventive solutions, described thermoplastic copolyester elastomer (TPC) is poly- including polyester-type copolymerization
Ester elastomer and polyether-type copolymerized polyester elastic body, preferred, polyethers type copolymerized polyester elastic body TPC, thermoplastic co-polymer used gather
It is 25D～75D that the hardness range of ester elastomer TPC is shore hardness.
In the inventive solutions, described metal hydrate includes aluminium hydroxide (ATH) and magnesium hydroxide (MDH)
One or more, preferred aluminum trihydrate.
In the inventive solutions, described liquid phosphoric acid ester be bis-phenol A diphosphate (BDP), trisphenol phosphoric acid
Ester (TPP), resorcinol biphenol phosphate ester (RDP), two (dimethylbenzene of three butoxyethyl phosphates (TBEP) and resorcinol
Phenol phosphate ester) (XDP) one or more.
In the inventive solutions, the organic silicon flame-retardant synergist is silicone polymer, for example, step figure SFR-
6600 or organic silicon powders, such as Dow4-7105,DowOne or more of 4-7081.
In the inventive solutions, described hyper-dispersant be polycaprolactone-polyamine dispersant, such as Lubrizol
'sLubrizolOne or more.
In technical scheme kind, described hydrolysis-resisting agent is single second carbide imine, one kind of polycarbodiimide
Or it is several, preferably gather carbonization diamidogen Stabaxol_P200 (Rhein chemistry).
Illustrate with reference to embodiments：
Embodiment 1：
The low-smoke low-toxicity copolymerized polyester elastic body compositionss include that weight accounting is：Thermoplastic copolyester elastomer
TPC20%；Metal hydrate 70%；Ester modified dose 9% of liquid phosphoric acid；Organic silicon flame-retardant synergist 1%.
Wherein, thermoplastic copolyester elastomer TPC selects Riteflex 640, and metal hydrate selects Martinal
OL-104LEO, ester modified dose of liquid phosphoric acid select BDP FP600 (Adeka), organic silicon flame-retardant synergist to select SFR6600
(Movementive Performance materials)。
The performance parameter obtained using embodiment 1 and performance parameter deck watch of the prior art such as table 1：
Table 1：
Embodiment 2：
The low-smoke low-toxicity copolymerized polyester elastic body compositionss include that weight accounting is：Thermoplastic copolyester elastomer
TPC30%；Metal hydrate 58%；Ester modified dose 10% of liquid phosphoric acid；Organic silicon flame-retardant synergist 2%.
Wherein, thermoplastic copolyester elastomer TPC selects Riteflex 640, and metal hydrate selects Martinal
OL-104LEO, ester modified dose of liquid phosphoric acid select BDP FP600 (Adeka), organic silicon flame-retardant synergist to select SFR6600
(Movementive Performance materials)。
The performance parameter obtained using embodiment 2 and performance parameter deck watch of the prior art such as table 2：
Table 2：
Embodiment 3：
The low-smoke low-toxicity copolymerized polyester elastic body compositionss include that weight accounting is：Thermoplastic copolyester elastomer
TPC35%；Metal hydrate 50%；Ester modified dose 10% of liquid phosphoric acid；Organic silicon flame-retardant synergist 5%.
Wherein, thermoplastic copolyester elastomer TPC selects Riteflex 640, and metal hydrate selects Martinal
OL-104LEO, ester modified dose of liquid phosphoric acid select BDP FP600 (Adeka), organic silicon flame-retardant synergist to select SFR6600
(Movementive Performance materials)。
The performance parameter obtained using embodiment 3 and performance parameter deck watch of the prior art such as table 2：
Table 3：
Embodiment 4：
The low-smoke low-toxicity copolymerized polyester elastic body compositionss include that weight accounting is：Thermoplastic copolyester elastomer
TPC40%；Metal hydrate 55%；Ester modified dose 2% of liquid phosphoric acid；Organic silicon flame-retardant synergist 3%.
Wherein, thermoplastic copolyester elastomer TPC selects Riteflex 640, and metal hydrate selects Martinal
OL-104LEO, ester modified dose of liquid phosphoric acid select BDP FP600 (Adeka), organic silicon flame-retardant synergist to select SFR6600
(Movementive Performance materials)。
The performance parameter obtained using embodiment 4 and performance parameter deck watch of the prior art such as table 4：
Table 4：
Embodiment 5：
The low-smoke low-toxicity copolymerized polyester elastic body compositionss include that weight accounting is：Thermoplastic copolyester elastomer
TPC36%；Metal hydrate 30%；Ester modified dose 30% of liquid phosphoric acid；Organic silicon flame-retardant synergist 4%.
Wherein, thermoplastic copolyester elastomer TPC selects Riteflex 640, and metal hydrate selects Martinal
OL-104LEO, ester modified dose of liquid phosphoric acid select BDP FP600 (Adeka), organic silicon flame-retardant synergist to select SFR6600
(Movementive Performance materials)。
The performance parameter obtained using embodiment 5 and performance parameter deck watch of the prior art such as table 5：
Table 5：
Embodiment 6：
The low-smoke low-toxicity copolymerized polyester elastic body compositionss include that weight accounting is：Thermoplastic copolyester elastomer
TPC40%；Metal hydrate 30%；Ester modified dose 20% of liquid phosphoric acid；Organic silicon flame-retardant synergist 10%.
Wherein, thermoplastic copolyester elastomer TPC selects Riteflex 640, and metal hydrate selects Martinal
OL-104LEO, ester modified dose of liquid phosphoric acid select BDP FP600 (Adeka), organic silicon flame-retardant synergist to select SFR6600
(Movementive Performance materials)。
The performance parameter obtained using embodiment 6 and performance parameter deck watch of the prior art such as table 6：
Table 6：
Preferably, for these embodiments thermoplastic copolyester elastomer TPC (TPC) is from Celanese640, a kind of conjugated polyether ester elastomer.Done under 105C in advance in dehumidifying heat pump using the front TPC samples
Dry at least 4 hours.BDP FP600 are obtained and are directly used by Adeka.Aluminum trihydrate Martinal OL-104LEO are purchased from U.S.
The refined treasured of state, is dried 4 hours in vacuum drum drying machine using front.Silicone master batch SFR6600 is purchased from Movementive
Performance materials are simultaneously directly used.Described hyper-dispersant is that Solplus DP310g are purchased from Lubrizol, and
Directly use.Described hydrolysis-resisting agent is Stabaxol_P200, purchased from Rhein chemistry, and is directly used.
As everybody understands, hyper-dispersant helps disperse toner in being widely used in color masterbatch manufacture.In the present invention, Wo Menfa
Hyper-dispersant and hydrolysis-resisting agent are added in existing formula, the flame-retarding characteristic of final products is not only increased：Guarantee that product passes through VW-
1 tests and to further reducing smoke density and flue gas toxity, and improves the processing characteristics of product.
Embodiment 7：
The low-smoke low-toxicity copolymerized polyester elastic body compositionss include that weight accounting is：Thermoplastic copolyester elastomer
TPC 40%；Metal hydrate 47%；Ester modified dose 7% of liquid phosphoric acid；Organic silicon flame-retardant synergist 4.5%；Hyper-dispersant
1%；Hydrolysis-resisting agent 0.5%.
Wherein, thermoplastic copolyester elastomer TPC selects Riteflex 640, and metal hydrate selects Martinal
OL-104LEO, ester modified dose of liquid phosphoric acid select BDP FP600 (Adeka), organic silicon flame-retardant synergist to select SFR6600
(Movementive Performance materials)；Hyper-dispersant selects 310 (the advanced materials of Lu Borun of SOLPLUS DP
Material), hydrolysis-resisting agent is from STABAXOLP200 (Rhein chemistry).
The performance parameter obtained using embodiment 7 and performance parameter deck watch of the prior art such as table 7：
Table 7：
Embodiment 8：
The low-smoke low-toxicity copolymerized polyester elastic body compositionss include that weight accounting is：Thermoplastic copolyester elastomer
TPC 48%；Metal hydrate 35%；Ester modified dose 10% of liquid phosphoric acid；Organic silicon flame-retardant synergist 5.8%；Hyper-dispersant
0.2%；Hydrolysis-resisting agent 1%.
Wherein, thermoplastic copolyester elastomer TPC selects Riteflex 640, and metal hydrate selects Martinal
OL-104LEO, ester modified dose of liquid phosphoric acid select BDP FP600 (Adeka), organic silicon flame-retardant synergist to select SFR6600
(Movementive Performance materials)；Hyper-dispersant selects 310 (the advanced materials of Lu Borun of SOLPLUS DP
Material), hydrolysis-resisting agent is from STABAXOL (Rhein chemistry).
The performance parameter obtained using embodiment 8 and performance parameter deck watch of the prior art such as table 8：
Table 8：
Embodiment 9：
The low-smoke low-toxicity copolymerized polyester elastic body compositionss include that weight accounting is：Thermoplastic copolyester elastomer
TPC 45%；Metal hydrate 40.5%；Ester modified dose 8% of liquid phosphoric acid；Organic silicon flame-retardant synergist 4%；Hyper-dispersant
1.5%；Hydrolysis-resisting agent 1%.
Wherein, thermoplastic copolyester elastomer TPC selects Riteflex 640, and metal hydrate selects Martinal
OL-104LEO, ester modified dose of liquid phosphoric acid select BDP FP600 (Adeka), organic silicon flame-retardant synergist to select SFR6600
(Movementive Performance materials)；Hyper-dispersant selects 310 (the advanced materials of Lu Borun of SOLPLUS DP
Material), hydrolysis-resisting agent is from STABAXOL P-200 (Rhein chemistry).
The performance parameter obtained using embodiment 9 and performance parameter deck watch of the prior art such as table 9：
Table 9：
Embodiment 10：
The low-smoke low-toxicity copolymerized polyester elastic body compositionss include that weight accounting is：Thermoplastic copolyester elastomer
TPC 43%；Metal hydrate 40%；Ester modified dose 10% of liquid phosphoric acid；Organic silicon flame-retardant synergist 5%；Hyper-dispersant 1%；
Hydrolysis-resisting agent 1%.
Wherein, thermoplastic copolyester elastomer TPC selects Riteflex 640, and metal hydrate selects Martinal
OL-104LEO, ester modified dose of liquid phosphoric acid select BDP FP600 (Adeka), organic silicon flame-retardant synergist to select SFR6600
(Movementive Performance materials)；Hyper-dispersant selects 310 (the advanced materials of Lu Borun of SOLPLUS DP
Material), hydrolysis-resisting agent is from STABAXOLP-200 (Rhein chemistry).
The performance parameter obtained using embodiment 10 and performance parameter deck watch such as table of the prior art：
Table 10：
Present invention also offers a kind of preparation method of low-smoke low-toxicity copolymerized polyester elastic body compositionss, the low-smoke low-toxicity
The preparation method of copolymerized polyester elastic body compositionss includes：
Thermoplastic copolyester elastomer TPC and metal hydrate are pre-dried, thermoplastic copolyester elastomer is made
Water content in TPC is less than 800ppm, and the water content in the metal hydrate is less than 600ppm；
Dried thermoplastic copolyester elastomer TPC material passes through weightless feeding in the first segment spout of twin screw
Device feeds；
Liquid phosphoric acid ester is pumped into by weightless liquid feeder by the 5th section of upper end of double screw extruder；
Metal hydrate is mixed after 3 minutes in high-speed mixer with hyper-dispersant, adds hydrolysis stabilizer and organosilicon
Fire retarding synergist mixes mixed at high speed 5 minutes by high-speed mixer, at the 7th section of double screw extruder, by weightless feeding
Device and forced feed screw rod are added
The a diameter of 35mm to 90mm of the twin screw, draw ratio L/D are 35：1 to 55:1, the extruder temperature is arranged and is divided into 12
Area, from main feed opening to the temperature setting of die head be：170-185-195-200-195-190-185-180-180-185-185-
190；
After weightless feeder presses formula addition, the extruded velocity of screw rod is 150RPM to 500RPM to various components, is melted
Body is cooled down into tank by die head, then through pelleter pelletizing, finally by the pellet of gained dry 3 at 100 DEG C to 110 DEG C
To 5 hours.
Specifically, thermoplastic copolyester elastomer TPC is placed in dehumidifier drying hopper, temperature setting is
80 DEG C to 125 DEG C, it is dried 3 to 4 hours；
The metal hydrate is placed in drying oven and is dried, temperature setting is 60 DEG C to 130 DEG C, dry 4 to 6 little
When.
Preferred version, a diameter of 52mm of the twin screw, draw ratio L/D are 44：1, the extruder temperature is arranged and is divided into 12nd area,
From main feed opening to the temperature setting of die head it is：170-185-195-200-195-190-185-180-180-185-185-190.
After weightless feeder presses formula addition, the extruded velocity of screw rod is 150RPM to various components, and melt body is by mould
Head enters tank cooling, then through pelleter pelletizing, finally by the pellet of gained at 105 DEG C 4 hours of drying.
65mm diameters are used on wire rod Extrusion Coating machine, L/D is 25：Cable is extruded on 1 single screw extrusion machine.TPC hinders
Used as sheathing, its thickness is that 1.2mm. insulated wire cores are three cores, the copper cash of PP materials to fuel.The linear velocity of cable extruding is
25 ms/min.
The invention provides a kind of low-smoke low-toxicity copolymerized polyester elastic body compositionss, said composition has good fire-retardant spy
Property (by UL1581VW-1 cable flame retardant tests), while having the characteristic of low-smoke low-toxicity concurrently.
Above content is with reference to specific optimal technical scheme further description made for the present invention, it is impossible to assert
The present invention be embodied as be confined to these explanations.For general technical staff of the technical field of the invention,
On the premise of without departing from present inventive concept, some simple deduction or replace can also be made, should all be considered as belonging to the present invention's
Protection domain.
Claims (6)
1. a kind of low-smoke low-toxicity copolymerized polyester elastic body compositionss, it is characterised in that：The low-smoke low-toxicity copolymerized polyester elastic body
Compositionss include：Ester modified dose of thermoplastic copolyester elastomer TPC, metal hydrate, liquid phosphoric acid, organic silicon flame-retardant synergistic
Agent, hyper-dispersant and hydrolysis-resisting agent, each component ratio sum are 100%, and each Ingredients Weight accounting is：
Thermoplastic copolyester elastomer TPC40% is to 50%；
Metal hydrate 35% to 55%；The metal hydrate is aluminum trihydrate；
Ester modified dose 7% to 13% of liquid phosphoric acid；
Organic silicon flame-retardant synergist 4% to 7%；
Hyper-dispersant 0.2% to 1.5%；The hyper-dispersant is selected from Lubrizol'sAnd/or LubrizolPolycaprolactone-polyamine dispersant；
Hydrolysis-resisting agent 0.2% to 1%, during the hydrolysis-resisting agent is single second carbide imine and/or polycarbodiimide.
2. low-smoke low-toxicity copolymerized polyester elastic body compositionss according to claim 1, it is characterised in that：
Thermoplastic copolyester elastomer TPC is polyether thermoplastic copolymerized polyester elastic body TPC, and shore hardness is 25D
To 75D.
3. low-smoke low-toxicity copolymerized polyester elastic body compositionss according to claim 1, it is characterised in that：
Ester modified dose of the liquid phosphoric acid is bisphosphate, trisphenol phosphate ester, three butoxyethyl phosphates and/or dimethylbenzene
One or more in phenol phosphate ester.
4. low-smoke low-toxicity copolymerized polyester elastic body compositionss according to claim 1, it is characterised in that：
The organic silicon flame-retardant synergist is silicone polymer and/or organic silicon powder.
5. a kind of preparation method of the low-smoke low-toxicity copolymerized polyester elastic body compositionss as described in one of Claims 1-4, its
It is characterised by：The preparation method of the low-smoke low-toxicity copolymerized polyester elastic body compositionss includes：
Thermoplastic copolyester elastomer TPC and metal hydrate are pre-dried, in making thermoplastic copolyester elastomer TPC
Moisture be less than 800ppm, the moisture in the metal hydrate be less than 600ppm；
Dried thermoplastic copolyester elastomer TPC material is fed by weightless feeder in the first segment spout of twin screw
Enter；
Liquid phosphoric acid ester is pumped into by weightless liquid feeder by the 5th section of upper end of double screw extruder；
After metal hydrate is mixed 2 to 5 minutes in high-speed mixer with hyper-dispersant, hydrolysis-resisting agent and organosilicon resistance are added
Combustion synergist mixes mixed at high speed 3-7 minute by high-speed mixer, at the 7th section of double screw extruder, by weightless feeding
Device and forced feed screw rod are added；
The a diameter of 35mm to 90mm of the twin screw, draw ratio L/D are 35：1 to 55:1, the extruder temperature is arranged and is divided into 12nd area,
From main feed opening to the temperature setting of die head it is：170℃-185℃-195℃-200℃-195℃-190℃-185℃-180℃-
180℃-185℃-185℃-190℃；
Temperature has the temperature difference of 1.5 DEG C of up or down,
Various components press after formula adds by weightless feeder, and the extruded velocity of screw rod is 150RPM to 500RPM, and melt body is logical
Cross die head to cool down into tank, then through pelleter pelletizing, finally by the pellet of gained dry 3 to 5 at 100 DEG C to 110 DEG C
Hour.
6. the preparation method of low-smoke low-toxicity copolymerized polyester elastic body compositionss according to claim 5, it is characterised in that：
Thermoplastic copolyester elastomer TPC is placed in dehumidifier drying hopper, temperature setting is 80 DEG C to 125
DEG C, it is dried 3 to 4 hours；
The metal hydrate is placed in drying oven and is dried, temperature setting is 60 DEG C to 130 DEG C, is dried 4 to 6 hours.
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