CN102477212A - Thermoplastic polyester elastomer composition and preparation method thereof - Google Patents
Thermoplastic polyester elastomer composition and preparation method thereof Download PDFInfo
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- CN102477212A CN102477212A CN201010565529XA CN201010565529A CN102477212A CN 102477212 A CN102477212 A CN 102477212A CN 201010565529X A CN201010565529X A CN 201010565529XA CN 201010565529 A CN201010565529 A CN 201010565529A CN 102477212 A CN102477212 A CN 102477212A
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- 229920006346 thermoplastic polyester elastomer Polymers 0.000 title claims abstract description 51
- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003063 flame retardant Substances 0.000 claims abstract description 43
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- 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 21
- 239000004593 Epoxy Substances 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 239000000314 lubricant Substances 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 10
- -1 butanediol ester Chemical class 0.000 claims description 23
- 239000003112 inhibitor Substances 0.000 claims description 19
- 230000003647 oxidation Effects 0.000 claims description 19
- 238000007254 oxidation reaction Methods 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 17
- 238000009775 high-speed stirring Methods 0.000 claims description 14
- 229920000728 polyester Polymers 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000001993 wax Substances 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 6
- 229920000052 poly(p-xylylene) Polymers 0.000 claims description 6
- 229920001610 polycaprolactone Polymers 0.000 claims description 6
- 239000004632 polycaprolactone Substances 0.000 claims description 6
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical compound C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920000151 polyglycol Polymers 0.000 claims description 3
- 239000010695 polyglycol Substances 0.000 claims description 3
- 239000002689 soil Substances 0.000 claims description 3
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 claims description 3
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- MKYLOMHWHWEFCT-UHFFFAOYSA-N Manthidine Natural products C1C2=CC=3OCOC=3C=C2C2C3=CC(OC)C(O)CC3N1C2 MKYLOMHWHWEFCT-UHFFFAOYSA-N 0.000 claims description 2
- SNFRINMTRPQQLE-JQWAAABSSA-N Montanin Chemical compound O[C@H]([C@@]1(CO)O[C@H]1[C@H]1[C@H]2O3)[C@]4(O)C(=O)C(C)=C[C@H]4[C@]11OC3(CCCCCCCCCCC)O[C@@]2(C(C)=C)C[C@H]1C SNFRINMTRPQQLE-JQWAAABSSA-N 0.000 claims description 2
- SNFRINMTRPQQLE-OFGNMXNXSA-N Montanin Natural products O=C1[C@@]2(O)[C@@H](O)[C@@]3(CO)O[C@H]3[C@@H]3[C@H]4[C@@]5(C(=C)C)O[C@](CCCCCCCCCCC)(O4)O[C@@]3([C@H](C)C5)[C@@H]2C=C1C SNFRINMTRPQQLE-OFGNMXNXSA-N 0.000 claims description 2
- QTZPBQMTXNEKRX-UHFFFAOYSA-N Voacristine pseudoindoxyl Natural products N1C2=CC=C(OC)C=C2C(=O)C21CCN(C1)C3C(C(C)O)CC1CC32C(=O)OC QTZPBQMTXNEKRX-UHFFFAOYSA-N 0.000 claims description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
- 229940075507 glyceryl monostearate Drugs 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims description 2
- 239000004200 microcrystalline wax Substances 0.000 claims description 2
- 235000019808 microcrystalline wax Nutrition 0.000 claims description 2
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 claims description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 229960003742 phenol Drugs 0.000 claims description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 150000003918 triazines Chemical class 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 abstract description 12
- 238000002156 mixing Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000003963 antioxidant agent Substances 0.000 abstract 2
- 230000003078 antioxidant effect Effects 0.000 abstract 2
- 238000003756 stirring Methods 0.000 abstract 2
- 238000000465 moulding Methods 0.000 abstract 1
- 239000002861 polymer material Substances 0.000 abstract 1
- 238000002347 injection Methods 0.000 description 16
- 239000007924 injection Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 10
- 239000008188 pellet Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000007664 blowing Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 1
- 229920006465 Styrenic thermoplastic elastomer Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000003197 gene knockdown Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002643 polyglutamic acid Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the field of high polymer materials and molding processing thereof, and particularly relates to a thermoplastic polyester elastomer composition and a preparation method thereof. The composition comprises the following components in parts by weight: 100 parts of thermoplastic polyester elastomer, 10-40 parts of flame retardant, 0.5-8 parts of epoxy polymer, 0.1-2 parts of anti-dripping agent, 0.1-2 parts of antioxidant and 0.1-2 parts of lubricant. The preparation method of the composition comprises the following steps: firstly, placing a flame retardant and an anti-dripping agent in a high-speed stirrer, stirring at a high speed for 2-10 min, then adding a thermoplastic polyester elastomer, an epoxy polymer, an antioxidant and a lubricant, stirring at a high speed for 2-10 min, finally placing the mixed components in an extruder, mixing at a temperature for keeping the mixture in a molten state to obtain a polymer, extruding the obtained polymer in a strip shape, and cutting the polymer into segments to form particles. The composition has the advantages of higher tensile strength, better heat resistance, lower mass flow rate and excellent flame retardance, and is suitable for extrusion molding of pipes.
Description
Technical field
The invention belongs to macromolecular material and forming process field thereof, be specifically related to a kind of thermoplastic polyester elastomer composition and preparation method thereof.
Background technology
Thermoplastic polyester elastomer (TPEE) is the segmented copolymer that contains hard section of polyester and polyester soft segment; Has the elasticity of rubber and the intensity of engineering plastics; Also have characteristics such as oil resistant, acid and alkali-resistance, high temperature resistant, radiation hardness and anti-creep simultaneously; The use temperature scope is very wide, is-55 ℃～+ 150 ℃, durometer level 30-75D.Being mainly used in car safety air bag at present launches at the bottom of door, industrial wheel, fire(fighting)hose hose lining, vehicle dust protector, the ski boots and field such as electronic cables.
TPEE can be divided into injection grade, extrusion grade, blowing level and modification level according to the difference of flowability.This is the grade of dividing to the TPEE raw material, the injection grade good fluidity, and promptly mass flow rate is big, is applicable to injection moulding and blending and modifying; Extrusion grade is mainly used in extruding pipe material or other products, and mass flow rate is less; The blowing level not only requires mass flow rate little, also requires melt strength high; The modification level is meant TPEE is joined in other resins to increase toughness as elastomer modifier.
Along with constantly widening of Application Areas, also increasingly high to the requirement of TPEE material property.At present a lot of motor car engine peripheral conduits require to use have flame retardant resistance, high, the good heat resistance of intensity, and TPEE material that can extrusion moulding.Its mass flow rate of the material requirements of extrusion moulding otherwise can't be regulated the thickness of pipe between 2～5g/10min.And TPEE need add the more fire retardant of deal when flame-retardant modified, directly adopts the extrusion grade raw material that fire retardant is disperseed not open, the flame retardant effect that does not reach, and add after the fire retardant, the mass flow rate of TPEE can increase.It is flame-retardant modified to use the TPEE of injection grade to carry out as raw material, can reach flame retardant effect preferably, but the mass flow rate of product is bigger, can't satisfy the extrusion moulding needs.And the common flame-retardant modified mechanical propertys such as tensile strength that make TPEE descend a lot, can't satisfy request for utilization.The tensile strength of general requirement TPEE material will be more than 30MPa at present.
Patent USP4124653, EP0506409, the development (plastics industry of USP4303106 and USP40134624 and paper blowing grade thermoplastic polyester elastomer (TPEE); 28 (2); 2000,3) all be in polymerization process, to introduce special segment the melt strength of TPEE is increased; The mobile reduction, these all are the research that belongs to blowing level TPEE preparation.Do not see also at present that useful injection grade TPEE prepares the report of flame retardant extruded level TPEE.
Summary of the invention
It is good to the purpose of this invention is to provide a kind of flame retardant properties; Tensile strength is high; The extrusion grade thermoplastic polyester elastomer composition of good heat resistance, said composition are to be prepared through flame-retardant modified by the injection grade thermoplastic polyester elastomer, and said composition is fit to do the motor car engine peripheral conduits.
Another object of the present invention provides the preparation method of the extrusion grade thermoplastic polyester elastomer composition that a kind of above-mentioned flame retardant properties is good, tensile strength is high.
Technical scheme of the present invention is following:
The invention provides a kind of thermoplastic polyester elastomer composition, said composition comprises following component and weight part:
Thermoplastic polyester elastomer 100,
Fire retardant 10～40,
Epoxy polymer 0.5～8,
Anti-dripping agent 0.1～2,
Oxidation inhibitor 0.1～2,
Lubricant 0.1～2.
Among the present invention comparatively preferred compositions comprise following component and weight part:
Thermoplastic polyester elastomer 100,
Fire retardant 15～35,
Epoxy polymer 1～6,
Anti-dripping agent 0.2～1,
Oxidation inhibitor 0.2～1,
Lubricant 0.2～1.
Described thermoplastic polyester elastomer is made up of the segmented copolymer of hard section of polyester and polyester soft segment, injection grade; Wherein, the hard section of polyester be selected from high firmness crystallinity parylene butanediol ester Poly (butylene terephthalate) (PBT), a kind of among parylene's glycol ester Polyethylene terephthalat (PET) or the parylene's propylene glycol ester Polytrimethylene terephthalate (PTT) etc.; Described polyester soft segment is selected from polyglycol ether Polyethylene glycol (PEG), polypropylene glycol ether Polypropylene glycol (PPG) or polytetramethylene glycol ether Poly butylene ether polyethers such as (PTMG) or polylactide Polylactide (PLLA), gather a kind of in NSC 403079 Polyglycolide (PGA) or the polycaprolactone Polycaprolactone polyester such as (PCL).
Described fire retardant is selected from a kind of in nitrogen phosphorus flame retardant or the triazines fire retardant; A kind of as in melamine cyanurate or the melamine pyrophosphate etc.
Described epoxy polymer is the polymkeric substance that contains the epoxy active end group, is selected from a kind of in elastomerics, polyester-triglycidyl isocyanurate or the brominated epoxy resin etc. of styrenic thermoplastic elastomer and epoxy-functional copolymerization; Epoxy polymer EP802 that produces like the inferior rubber and plastic of Shanghai huge rock ltd or Shanghai is a kind of among the epoxy polymer LP2500 that produces of dimerization worker etc. still.
Described anti-dripping agent is selected from a kind of in clay, polynite, kaolin or the nanometer soil etc.
Described oxidation inhibitor is selected from four [methyl-β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic ester] in pentaerythritol ester (CAS No.:6683-19-8), three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters (CAS No.:31570-04-4) or the organic phosphites thermo-stabilizer (CAS No:38613-77-3) one or more; The mixture of one or more in oxidation inhibitor 1098, the oxidation inhibitor 168 of Ciba or the oxidation inhibitor 626 of Ciba etc. of preferred Ciba.
Described lubricant is selected from one or several the mixture in the two amine hydroxybenzenes of Triple Pressed Stearic Acid, calcium stearate, Zinic stearas, Magnesium Stearate, glyceryl monostearate, Tristearoylglycerol, amine hydroxybenzene, stearic amide, ethylene bis stearic acid amide, ethylene, paraffin, microcrystalline wax, whiteruss, polyethylene wax, silicone oil, montanin wax or the beautiful section wax.
The present invention also provides a kind of preparation method of above-mentioned thermoplastic polyester elastomer composition, and this method may further comprise the steps:
At first, 10～40 parts of fire retardants and 0.1-2 part anti-dripping agent are placed in the impeller high-speed stirring 2～10min; Add 100 parts of thermoplastic polyester elastomers, 0.5-8 part epoxy polymer, 0.1-2 part oxidation inhibitor and 0.1-2 part lubricant then; High-speed stirring 2～10min will mix the back component at last and put into forcing machine again, and said mixture is kept under the temperature of melted state; Mix and obtain polymkeric substance; The polymkeric substance that is obtained is extruded with strip, and the section of being cut to forms particle then.
Described forcing machine is selected from a kind of in single screw rod or the twin screw extruder.
The temperature of described maintenance melted state is meant 180～250 ℃.
One of principle of the present invention is, selects for use injection grade TPEE as raw material, can reach better dispersion effect.Add anti-dripping agent, the one-tenth carbon amount in the material combustion process is increased, these carbon have intercepted contacting of material and air, help knock down the flame and stop the material drippage.
Two of principle of the present invention is, adds the polymkeric substance that has epoxy group, in extruding the process of modification; The ring opening copolymer reaction takes place in epoxy group, and the TPEE molecular chain is coupled together, and the molecular weight of TPEE can improve thereupon like this; The mobile reduction, promptly mass flow rate reduces.The raising of molecular weight helps the raising of mechanical propertys such as tensile strength equally.
The present invention compares with prior art, has following advantage and beneficial effect:
1, compsn of the present invention not only has excellent flame-retardant, and its tensile strength is high, good heat resistance, and flowing property satisfies the demand of extrusion grade material.
2, to adopt the TPEE of injection grade be raw material in the present invention, is easy to obtain, and on the preparation method, earlier fire retardant and anti-dripping agent mixed, and can make the anti-better effects if of dripping in the composition burn process.Present method is simple, and remarkably productive.
Embodiment
Below in conjunction with embodiment the present invention is further described.
In following examples,
TPEE1 representes: the segmented copolymer that crystallinity PBT and polylactide PLLA form, and fusing point is 206 ℃, hardness is 63D, injection grade.
TPEE2 representes: the segmented copolymer that crystallinity PET and polyglycol ether PEG form, and fusing point is 204 ℃, hardness is 55D, injection grade.
TPEE3 representes: the segmented copolymer that crystallinity PTT and polycaprolactone (PCL) are formed, fusing point are 196 degree, and hardness is 40D, injection grade.
Fire retardant 1 expression: melamine cyanurate, commercially available.
Fire retardant 2 expressions: melamine pyrophosphate, commercially available.
Epoxy polymer 1:EP802, the inferior rubber and plastic of Shanghai huge rock ltd.
Epoxy polymer 2:LP2500, Shanghai is the dimerization worker still.
Anti-dripping agent 1: polynite, particle diameter＜20 μ, commercially available.
Anti-dripping agent 2: nanometer soil, particle diameter＜200nm, commercially available.
Oxidation inhibitor: the mixture of oxidation inhibitor 1098 and oxidation inhibitor 168, blending ratio is 1: 1, Ciba.Lubricant 1: polyethylene wax and ethylene bis stearic acid amide were according to 1: 1 mixture.
Lubricant 2: Tristearoylglycerol and Li Ke wax were according to 1: 1 mixture.
According to ISO 527 canonical measure tensile strengths:
Flame retardant resistance according to the fire-retardant batten of UL94 canonical measure 1.6mm.
According to ISO1133 canonical measure mass flow rate.
Embodiment 1
Be 10 fire retardant 1 at first and weight part is that 0.1 anti-dripping agent 1 is placed in the impeller with weight part; High-speed stirring 2min; Adding weight part then and be 100 TPEE1, weight part and be 0.5 epoxy polymer 1, weight part and be 0.1 oxidation inhibitor and weight part and be 0.1 lubricant 1 adds in the high-speed mixer; High-speed stirring 2 minutes will be mixed the back component at last and put into single screw extrusion machine at 190～250 ℃ of mixing acquisition polymkeric substance, and the polymkeric substance that is obtained is extruded with strip; The section of being cut to forms 2～5mm particle then.The gained pellet is injection molded into corresponding batten according to the dependence test standard, tests after 24 hours at 23 ± 2 ℃, the environment held of 50 ± 5% relative humidity then.The tensile strength that test obtains is 36MPa, and flame retardant resistance is UL94V-2, and melt flow rate is 3.2g/10min.
Embodiment 2
Be 40 fire retardant 1 at first and weight part is that 2 anti-dripping agent 1 is placed in the impeller with weight part; High-speed stirring 10min; Adding weight part then and be 100 TPEE2, weight part and be 8 epoxy polymer 1, weight part and be 2 oxidation inhibitor and weight part and be 2 lubricant 1 adds in the high-speed mixer; High-speed stirring 10 minutes will be mixed the back component at last and put into single screw extrusion machine at 180～250 ℃ of mixing acquisition polymkeric substance, and the polymkeric substance that is obtained is extruded with strip; The section of being cut to forms 2～5mm particle then.The gained pellet is injection molded into corresponding batten according to the dependence test standard, tests after 24 hours at 23 ± 2 ℃, the environment held of 50 ± 5% relative humidity then.The tensile strength that test obtains is 32MPa, and flame retardant resistance is UL94 V-2, and melt flow rate is 2.0g/10min.
Embodiment 3
Be 15 fire retardant 2 at first and weight part is that 0.2 anti-dripping agent 2 is placed in the impeller with weight part; High-speed stirring 3min; Adding weight part then and be 100 TPEE3, weight part and be 1 epoxy polymer 2, weight part and be 0.2 oxidation inhibitor and weight part and be 0.2 lubricant 2 adds in the high-speed mixers; High-speed stirring 5 minutes will be mixed the back component at last and put into twin screw extruder at 180～250 ℃ of mixing acquisition polymkeric substance, and the polymkeric substance that is obtained is extruded with strip; The section of being cut to forms 2～5mm particle then.The gained pellet is injection molded into corresponding batten according to the dependence test standard, tests after 24 hours at 23 ± 2 ℃, the environment held of 50 ± 5% relative humidity then.The tensile strength that test obtains is 33MPa, and flame retardant resistance is UL94V-2, and melt flow rate is 2.3g/10min.
Embodiment 4
Be 35 fire retardant 2 at first and weight part is that 1 anti-dripping agent 2 is placed in the impeller with weight part; High-speed stirring 5min; Adding weight part then and be 100 TPEE1, weight part and be 6 epoxy polymer 2, weight part and be 1 oxidation inhibitor and weight part and be 1 lubricant 2 adds in the high-speed mixers; High-speed stirring 5 minutes will be mixed the back component at last and put into twin screw extruder at 180～250 ℃ of mixing acquisition polymkeric substance, and the polymkeric substance that is obtained is extruded with strip; The section of being cut to forms 2～5mm particle then.The gained pellet is injection molded into corresponding batten according to the dependence test standard, tests after 24 hours at 23 ± 2 ℃, the environment held of 50 ± 5% relative humidity then.The tensile strength that test obtains is 35MPa, and flame retardant resistance is UL94 V-2, and melt flow rate is 2.5g/10min.
Embodiment 5
Be 20 fire retardant 1 at first and weight part is that 0.5 anti-dripping agent 2 is placed in the impeller with weight part; High-speed stirring 5min; Adding weight part then and be 100 TPEE1, weight part and be 3 epoxy polymer 2, weight part and be 0.5 oxidation inhibitor and weight part and be 0.5 lubricant 1 adds in the high-speed mixer; High-speed stirring 3min will mix the back component at last and put into twin screw extruder at 180～250 ℃ of mixing acquisition polymkeric substance, and the polymkeric substance that is obtained is extruded with strip; The section of being cut to forms 2～5mm particle then.The gained pellet is injection molded into corresponding batten according to the dependence test standard, tests after 24 hours at 23 ± 2 ℃, the environment held of 50 ± 5% relative humidity then.The tensile strength that test obtains is 37MPa, and flame retardant resistance is UL94 V-2, and melt flow rate is 3.0g/10min.
The above-mentioned description to embodiment is can understand and use the present invention for ease of the those of ordinary skill of this technical field.The personnel of skilled obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not breaking away from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (10)
1. thermoplastic polyester elastomer composition, it is characterized in that: said composition comprises following component and weight part,
Thermoplastic polyester elastomer 100,
Fire retardant 10～40,
Epoxy polymer 0.5～8,
Anti-dripping agent 0.1～2,
Oxidation inhibitor 0.1～2,
Lubricant 0.1～2.
2. thermoplastic polyester elastomer composition according to claim 1 is characterized in that: described compsn comprises following component and weight part,
Thermoplastic polyester elastomer 100,
Fire retardant 15～35,
Epoxy polymer 1～6,
Anti-dripping agent 0.2～1,
Oxidation inhibitor 0.2～1,
Lubricant 0.2～1.
3. thermoplastic polyester elastomer composition according to claim 1 is characterized in that: described thermoplastic polyester elastomer is made up of the segmented copolymer of hard section of polyester and polyester soft segment.
4. thermoplastic polyester elastomer composition according to claim 3 is characterized in that: the hard section of described polyester is selected from a kind of in high firmness crystallinity parylene butanediol ester, parylene's glycol ester or the parylene's propylene glycol ester; Described polyester soft segment is selected from polyglycol ether, polypropylene glycol ether, polytetramethylene glycol ether, polylactide, gather a kind of in NSC 403079 or the polycaprolactone.
5. thermoplastic polyester elastomer composition according to claim 1 is characterized in that: described fire retardant is selected from a kind of in nitrogen phosphorus flame retardant or the triazines fire retardant.
6. thermoplastic polyester elastomer composition according to claim 1 is characterized in that: described epoxy polymer is the polymkeric substance that contains the epoxy active end group; Described anti-dripping agent is selected from a kind of in clay, polynite, kaolin or the nanometer soil.
7. thermoplastic polyester elastomer composition according to claim 1; It is characterized in that: described oxidation inhibitor is selected from four [methyl-β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic ester] one or more mixture in pentaerythritol ester, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester or the organic phosphites thermo-stabilizer.
8. thermoplastic polyester elastomer composition according to claim 1 is characterized in that: described lubricant is selected from one or several the mixture in the two amine hydroxybenzenes of Triple Pressed Stearic Acid, calcium stearate, Zinic stearas, Magnesium Stearate, glyceryl monostearate, Tristearoylglycerol, amine hydroxybenzene, stearic amide, ethylene bis stearic acid amide, ethylene, paraffin, microcrystalline wax, whiteruss, polyethylene wax, silicone oil, montanin wax or the beautiful section wax.
9. the preparation method of arbitrary described thermoplastic polyester elastomer composition in the claim 1 to 8, it is characterized in that: this method may further comprise the steps, and at first 10～40 parts of fire retardants and 0.1-2 part anti-dripping agent is placed in the impeller; High-speed stirring 2～10min adds 100 parts of thermoplastic polyester elastomers, 0.5-8 part epoxy polymer, 0.1-2 part oxidation inhibitor and 0.1-2 part lubricant, high-speed stirring 2～10min more then; To mix the back component at last and put into forcing machine; In that said mixture is kept under the temperature of melted state, mix obtaining polymkeric substance, the polymkeric substance that is obtained is extruded with strip; The section of being cut to forms particle then.
10. the preparation method of thermoplastic polyester elastomer composition according to claim 9 is characterized in that: described forcing machine is selected from a kind of in single screw rod or the twin screw extruder; The temperature of described maintenance melted state is meant 180～250 ℃.
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| CN102775740A (en) * | 2012-07-24 | 2012-11-14 | 金发科技股份有限公司 | Halogen-free flame-retardant elastomer composition |
| CN103788585A (en) * | 2013-12-31 | 2014-05-14 | 金发科技股份有限公司 | Thermoplastic polyether ester elastomer composition as well as preparation method and application thereof |
| CN103788584A (en) * | 2013-12-31 | 2014-05-14 | 金发科技股份有限公司 | Thermoplastic polyether ester elastomer composition as well as preparation method and application thereof |
| CN103951845A (en) * | 2014-04-02 | 2014-07-30 | 合肥杰事杰新材料股份有限公司 | Application of fullerene as composition flame retardation anti-drip agent |
| CN105754079A (en) * | 2014-11-10 | 2016-07-13 | 财团法人工业技术研究院 | Thermoplastic polyester elastomer and method for forming same |
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| CN102775740A (en) * | 2012-07-24 | 2012-11-14 | 金发科技股份有限公司 | Halogen-free flame-retardant elastomer composition |
| CN102775740B (en) * | 2012-07-24 | 2014-02-19 | 金发科技股份有限公司 | Halogen-free flame-retardant elastomer composition |
| CN103788584B (en) * | 2013-12-31 | 2016-08-17 | 金发科技股份有限公司 | A kind of thermoplastic polyether ester elastomer compositions and its preparation method and application |
| CN103788584A (en) * | 2013-12-31 | 2014-05-14 | 金发科技股份有限公司 | Thermoplastic polyether ester elastomer composition as well as preparation method and application thereof |
| CN103788585A (en) * | 2013-12-31 | 2014-05-14 | 金发科技股份有限公司 | Thermoplastic polyether ester elastomer composition as well as preparation method and application thereof |
| CN103788585B (en) * | 2013-12-31 | 2016-08-17 | 金发科技股份有限公司 | A kind of thermoplastic polyether ester elastomer compositions and its preparation method and application |
| CN103951845A (en) * | 2014-04-02 | 2014-07-30 | 合肥杰事杰新材料股份有限公司 | Application of fullerene as composition flame retardation anti-drip agent |
| CN103951845B (en) * | 2014-04-02 | 2017-08-01 | 合肥杰事杰新材料股份有限公司 | A kind of fullerene as composition flame-retardant anti-dropping agent purposes |
| CN105754079A (en) * | 2014-11-10 | 2016-07-13 | 财团法人工业技术研究院 | Thermoplastic polyester elastomer and method for forming same |
| US9688813B2 (en) | 2014-11-10 | 2017-06-27 | Industrial Technology Research Institute | Thermoplastic polyester elastomer and method for manufacturing the same |
| CN107868645A (en) * | 2017-11-02 | 2018-04-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Thermal-induced deformation plastic sheeting and preparation of sections method and products thereof and application |
| CN109912938A (en) * | 2019-02-28 | 2019-06-21 | 深圳市新华安包装制品有限公司 | A kind of degradable optical protection layer and preparation method thereof |
| CN115873379A (en) * | 2021-09-26 | 2023-03-31 | 常熟市三恒建材有限责任公司 | Halogen-free flame-retardant high-molecular waterproof composite material and preparation method thereof |
| CN115873379B (en) * | 2021-09-26 | 2024-11-22 | 常熟市三恒建材有限责任公司 | A halogen-free flame-retardant polymer waterproof composite material and preparation method thereof |
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Application publication date: 20120530 |