CN101838446B - Flame-retardant enhanced polybutylece terephthalate (PBT) material and preparation method thereof - Google Patents
Flame-retardant enhanced polybutylece terephthalate (PBT) material and preparation method thereof Download PDFInfo
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- CN101838446B CN101838446B CN2010101796142A CN201010179614A CN101838446B CN 101838446 B CN101838446 B CN 101838446B CN 2010101796142 A CN2010101796142 A CN 2010101796142A CN 201010179614 A CN201010179614 A CN 201010179614A CN 101838446 B CN101838446 B CN 101838446B
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- polybutylene terephthalate
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 62
- 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 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000463 material Substances 0.000 title abstract description 44
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 title abstract 3
- 239000002131 composite material Substances 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000000314 lubricant Substances 0.000 claims abstract description 10
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 9
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 60
- -1 polybutylene terephthalate Polymers 0.000 claims description 41
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002512 suppressor factor Substances 0.000 claims description 13
- 239000004417 polycarbonate Substances 0.000 claims description 10
- 229920000515 polycarbonate Polymers 0.000 claims description 10
- 239000003365 glass fiber Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- 239000004305 biphenyl Substances 0.000 claims description 5
- 239000011258 core-shell material Substances 0.000 claims description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 4
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004609 Impact Modifier Substances 0.000 claims description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 125000006267 biphenyl group Chemical group 0.000 claims description 3
- 230000031709 bromination Effects 0.000 claims description 3
- 238000005893 bromination reaction Methods 0.000 claims description 3
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- DGZQEAKNZXNTNL-UHFFFAOYSA-N 1-bromo-4-butan-2-ylbenzene Chemical class CCC(C)C1=CC=C(Br)C=C1 DGZQEAKNZXNTNL-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920002379 silicone rubber Polymers 0.000 claims description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 abstract description 6
- 229910052736 halogen Inorganic materials 0.000 abstract description 5
- 150000002367 halogens Chemical class 0.000 abstract description 5
- 239000004033 plastic Substances 0.000 abstract description 3
- 229920003023 plastic Polymers 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000004677 Nylon Substances 0.000 abstract description 2
- 229920001778 nylon Polymers 0.000 abstract description 2
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- BIEHXHIWQHAVFZ-UHFFFAOYSA-M bromoantimony Chemical compound [Sb]Br BIEHXHIWQHAVFZ-UHFFFAOYSA-M 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- GRKDVZMVHOLESV-UHFFFAOYSA-N (2,3,4,5,6-pentabromophenyl)methyl prop-2-enoate Chemical compound BrC1=C(Br)C(Br)=C(COC(=O)C=C)C(Br)=C1Br GRKDVZMVHOLESV-UHFFFAOYSA-N 0.000 description 1
- OWICEWMBIBPFAH-UHFFFAOYSA-N (3-diphenoxyphosphoryloxyphenyl) diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1)(=O)OC1=CC=CC=C1 OWICEWMBIBPFAH-UHFFFAOYSA-N 0.000 description 1
- NDERRIHSWCOMJJ-UHFFFAOYSA-N C(C(=C)C)(=O)OC(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1.P(=O)(O)(O)O Chemical compound C(C(=C)C)(=O)OC(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1.P(=O)(O)(O)O NDERRIHSWCOMJJ-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 206010020843 Hyperthermia Diseases 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000036031 hyperthermia Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003190 poly( p-benzamide) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B29C47/92—
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention discloses a flame-retardant enhanced polybutylece terephthalate (PBT) material and a preparation method thereof. The material comprises the following raw materials in part by weight: 100 parts of polybutylece terephthalate, 40 to 70 parts of composite type fire retardant, 5 to 25 parts of ignition inhibitor, 0 to 15 parts of flexibilizer, 0.5 to 2 parts of lubricant and 50 to 90 parts of enhanced components, wherein the composite type fire retardant is formed by compounding a halogen fire retardant and antimony-containing compounds; and the ignition inhibitor is a composite of a polymer with high-carbon content and phosphate. Compared with those of the common flame-retardant enhanced PBT materials, the GWIT of the flame-retardant enhanced PBT material of the invention reaches 800 DEG C, the mechanical properties are not reduced obviously, and the processability is not changed; and the material has low cost and does not need special equipment. In the field of electronic and electric products, high-cost nylon and special plastics selected for meeting high GWIT requirement can be replaced completely by the material.
Description
Technical field
The present invention relates to polymeric material field, particularly a kind of flame retardant resistance reinforced polybutylene terephthalate and preparation method thereof.
Background technology
Polybutylene terephthalate (be called for short PBT) is a kind of engineering plastics of high comprehensive performance, 36 ℃～49 ℃ of second-order transition temperatures, and 220 ℃～225 ℃ of fusing points have that crystallization velocity is fast, processability good, water-intake rate is low and the stable high characteristics of product size.The PBT material after the modification particularly has excellent more performance, and like glass fibre reinforced modified later PBT material, heat-drawn wire is increased to 210 ℃ (load 1.80MPa), also at double increase of mechanical property.Thereby the PBT material after the modification has a wide range of applications at electronics, electrical apparatus industry, particularly increases sharply in the application aspect connector, the supporting structure.
For the security in use of electronics, electric elements, PBT must have flame retardant resistance and favorable mechanical performance and electrical property as structured material.Because the inflammableness of material is the cause of fire; Thereby the flame retardant resistance quality of material is directly connected to people's the security of the lives and property; American insurance merchant laboratory (Underwriters Laboratories Inc.; Abbreviation UL) the UL94 standard of regulation, the hazard level that the material that causes according to naked light very early catches fire has been formulated the standard of Flame Retardancy.Found in the last few years; The reason of fire of electronic apparatus component product focuses mostly on electric on fire; Mainly be that the localized hyperthermia that causes because of the electrical component current overload causes that parts are on fire on every side; Therefore calendar year 2001 International Electrotechnical Commissio (International Electrotechnical Commission, common name " IEC ") has carried out strengthening significantly revision to resistivity against fire (being flame retardant resistance) standard.New IEC standard is the 4th edition of white domestic appliances safety standards IEC60335-1 standard; According to this standard; In the white domestic appliances the user not occasion action element part, under the condition of operation usually, can take place to surpass the 0.2A electric current component, support the insulating material part of its component and have only the insulating material part below the 3mm should have superior glowing filament characteristic from the distance of junction; The material that is this kind component is asked to have superior glowing filament characteristic; Glowing filament fire burning index (Glow-wire FlammabilityIndex GWFI) should be for more than 850 ℃; And glowing filament ignition temperature (Glow-wire IgnitionTemperature is called for short GWIT) should be for more than 775 ℃.Along with this standard revise, American-European household appliances manufacturer requires to be increased sharply to the glowing filament of electronic apparatus component material.For China numerous electronic apparatus export enterprise; Because the GWIT of a large amount of material modified component of PBT that use is 700 ℃ before this; Can't satisfy the requirement of new standard, convert the high engineering plastics of combustion initiation temperature such as PA66 and special plastic one after another to, material cost also improves much thereupon; Improve the cost of product greatly, thereby pressed for the GWIT problem that solves the tangible PBT material of price advantage.
Publication number is to propose to adopt the composite PBT of the satisfying material of phosphor nitrogen combustion inhibitor GWIT to reach 800 ℃ requirement in the one Chinese patent application of CN101418114A, spells out common flame-retardant reinforced PBT (like the flame-retardant reinforced PBT of halogenated flame retardant) and can not satisfy this requirement.But the mechanical property of materials after its modification can be found out; The mechanical property of this phosphorus nitrogen anti-flaming PBT composite as: it is flame-retardant reinforced PBT that tensile strength, flexural strength, shock strength etc. are starkly lower than common halogen, is restricting this material modified application space to a certain extent.
Summary of the invention
The invention provides a kind of flame retardant resistance and strengthen the polybutylene terephthalate compsn, it has superior glowing filament flame-retarding characteristic, and GWIT reaches 800 ℃, and mechanical property is good.
A kind of flame retardant resistance reinforced polybutylene terephthalate comprises the raw material of following weight part:
100 parts of polybutylene terephthalates
40 parts～70 parts of composite fire retardants
5 parts～25 parts in ignition suppressor factor
0～15 part of toughner
0.5 part～2 parts of lubricants
50 parts～90 parts of enhancement component;
Wherein, described composite fire retardant is by halogenated flame retardant and antimony containing compounds is composite forms;
Described ignition suppressor factor is the polymkeric substance of high-carbon content and the mixture of SULPHOSUCCINIC ACID ESTER.
As preferably:
Described flame retardant resistance reinforced polybutylene terephthalate comprises the raw material of following weight part:
100 parts of polybutylene terephthalates
50 parts～70 parts of composite fire retardants
10 parts～25 parts in ignition suppressor factor
10 parts of toughner
2 parts of lubricants
70 parts～90 parts of enhancement component.
The limiting viscosity of described polybutylene terephthalate is 0.8dl/g～1.3dl/g.
Described halogenated flame retardant is selected bromide fire retardant for use; As can select TDE, brominated Polystyrene (Brominated Polystyrene for use; BPS), brominated polystyrene, brominated epoxy resin oligopolymer (Brominated Epoxy Oligomer; BEO), the brominated polycarbonate oligopolymer (Brominated Carbonated Oligomer, BCO), gather bromination base propenoate (Poly (pentabromobenzyl acrylate), PPBA) one or more in waiting.Wherein, brominated epoxy resin oligomer molecule amount is high, has good consistency with PBT, tool economy.
Described antimony containing compounds is as the synergistic material of halogenated flame retardant, selects in Antimony Trioxide: 99.5Min, stibnate (like sodium antimonate etc.) etc. one or more for use.
In order to play better flame retardant effect, the mass ratio of bromide fire retardant and antimony containing compounds is 1～3: 1 in the composite fire retardant.
The polymkeric substance of described high-carbon content is selected one or more in polycarbonate (PC), ppe (PPO), the polyphenylene sulfide (PPS) etc. for use.Described SULPHOSUCCINIC ACID ESTER select for use Tritolyl Phosphate, triphenylphosphate, tolyl diphenyl phosphoester, tributyl phosphate, tricresyl phosphate (dibromopropyl) ester, tricresyl phosphate (β-chloroethyl) ester, Resorcinol two (hexichol SULPHOSUCCINIC ACID ESTER) (RDP), dihydroxyphenyl propane two (diphenyl phosphoester) one or more in (BDP) etc.Wherein polycarbonate and Resorcinol two (hexichol SULPHOSUCCINIC ACID ESTERs), dihydroxyphenyl propane two (diphenyl phosphoester), Heat stability is good, best with the PBT consistency, can preferably use.
The polymkeric substance of described ignition suppressor factor medium high carbon content and the mass ratio of SULPHOSUCCINIC ACID ESTER are 1～3: 1.
Described toughner is selected one or more in core-shell type multipolymer such as methyl acrylate-divinyl (MBS), all acrylic ester core-shell impact modifiers (being butyl polyacrylate as nuclear, the grafted polymethylmethacrylate core-shell impact modifiers as shell), the silicone elastomer etc. for use.
Described lubricant is selected one or both in ester type waxes class, the silicone etc. for use, as specifically selecting in the commercially available prod such as covering smooth wax, silicone powder, silicone master batch one or more for use.
Described enhancement component is selected alkali free glass fibre for use, comprises continuous long fiber and chopped glass fiber etc., for example can select E type alkali free glass fibre for use.
In order to improve the thermostability of said material; Also need add the few stable agent; Its consumption is generally: in the polybutylene terephthalate weight part is 100 parts; Can also add the stablizer of 0.5 weight part～2 weight parts, also can form the consumption of suitable increase or minimizing stablizer, be advisable to reach suitable thermostability according to the actual raw material of material.
Described stablizer can be selected this area stablizer commonly used for use; Preferably phosphoric acid triphenylmethyl methacrylate (TPP), oxidation inhibitor are like four [β-(3; 5-di-t-butyl 4-hydroxy phenyl) propionic acid] in pentaerythritol ester (antioxidant 1010), three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters (oxidation inhibitor 168) etc. one or more.
The preparation method of described flame retardant resistance reinforced polybutylene terephthalate; Comprise step: send in the twin screw extruder after the stablizer that said polybutylene terephthalate, composite fire retardant, ignition suppressor factor, toughner, lubricant and selectivity are added mixes; Again enhancement component is sent into twin screw extruder; Extrude through twin screw extruder, make the flame retardant resistance reinforced polybutylene terephthalate.
Each section barrel zone temperature is 200 ℃～250 ℃ in the described twin screw extruder, and each section barrel zone temperature can be identical, also can be different.
Described twin screw extruder can be selected this area equipment commonly used for use.
The glowing filament ignition temperature that general flame retardant resistance strengthens the PBT material is 650 ℃～700 ℃, and according to IEC 60695-2-13 standard testing requirement, the GWIT that flame retardant resistance strengthens the PBT material will reach 775 ℃, then when probe temperature is 750 ℃, the ignition phenomenon can not be arranged at least.The combustion initiation temperature that how to improve the PBT material is a core content of the present invention.Inflammable component such as PBT and toughner is at high temperature decomposed, and the spontaneous ignition temperature of decomposed substance is lower, will be on fire at 630 ℃.Halogenated flame retardant such as bromide fire retardant begin to decompose mostly about 300 ℃, and the HBr that discharges is a kind of difficult combustion gas body, covers material surface, play the effect that intercepts surperficial inflammable gas; In the bromo-antimony compound system of composite fire retardant (with the Antimony Trioxide: 99.5Min is example, and stibnide all has this fire retardant mechanism), HBr that bromide fire retardant discharges or bromo element and Antimony Trioxide: 99.5Min reaction produce antimony tribro-(SbBr
3) or bromination stibo (SbOBr), wherein SbBr in the product
3Also can form a kind of rare gas element, reduce combustiblematerials and contact, the charcoal tectum is generated with oxygen; Simultaneously, SbBr under the high temperature
3Can also resolve into various stibnides and Br radical, they can change H radical and OH radical in the flame, with the energy of consumption flame, thereby reach fire-retardant purpose.But only can't make the PBT material be issued to nonflammable effect, therefore need to add the ignition suppressor factor 750 ℃ of hot conditionss through the bromo-sb system.
The polymkeric substance of the ignition suppressor factor medium high carbon content that adopts among the present invention mainly plays the effect of fast rapid-result carbon at high temperature, and is about 24% like the PC carbon forming rate, PPO carbon forming rate about 29%; The polymer molecule of high-carbon content contains a large amount of oxygen elements simultaneously, is fit to form the charcoal layer with the mode of dehydration.SULPHOSUCCINIC ACID ESTER combustion initiation temperature in the ignition suppressor factor is up to 927 ℃, and high temperature decomposes generation phosphoric acid or polyphosphoric acid down, through the oxidation of phosphoric acid to PC or PPO, with H
2The form of O is sloughed H, O element from molecular resin, carbon skeleton and not clean-burning polymer residual on the molecular chain form the charcoal layer jointly, have cut off the contact of inner macromolecular material and extraneous burning things which may cause a fire disaster, oxygen, reach nonflammable purpose.
PBT material of the present invention at high temperature its surface energy forms closely knit carbon-coating fast, plays the effect of crucial raising system combustion initiation temperature.
SULPHOSUCCINIC ACID ESTER and halogenated flame retardant (especially bromide fire retardant) also have flame retardant synergistic effect in the raw material compositional system of the present invention; SULPHOSUCCINIC ACID ESTER has suppressed the further scission reaction under the PBT high temperature at condensed phase; Reduced the generation of inflammable gas; Halogen in the halogenated flame retardant suppresses incendiary in gas phase carries out, the nonflammable effect that finally reaches a high temperature down, and GWIT can reach 800 ℃.
Beneficial effect of the present invention is embodied in:
The present invention mainly adopts composite carbamate additives for low phosphorus acid esters of halogenated flame retardant and carbon forming agent; Adopt enhancement component (like alkali free glass fibre) 20%～35% (weight percent) simultaneously; Make the PBT material after the modification reach 800 ℃ of GWIT; And its mechanical property does not take place obviously to reduce, and processing characteristics does not change, and can substitute the application of common flame-retardant enhanced PBT material fully.In the electric equipment products field, can be replaced by the expensive nylon that satisfies high GWIT and select for use and the application of special plastic fully.Aspect material cost, far below fire retardant PBT with no halogen, being that flame-retardant PBT is identical to production unit and processing requirement with common halogen, is the PBT matrix material of the very high high GWIT of a cost performance.
Embodiment
PBT viscosity is 1.0dl/g, and 130 ℃ of forced air drying 4h make its moisture be no more than 0.02%, and to prevent the meeting water degraded under the PBT high temperature, lower performance is good more more for general moisture.
Composite fire retardant bromo-antimony fire retardant compound scheme: Br-Sb-1 (mass ratio of TDE and Antimony Trioxide: 99.5Min=1: 1); Br-Sb-2 (mass ratio of brominated epoxy resin oligopolymer and Antimony Trioxide: 99.5Min=3: 1), Br-Sb-3 (mass ratio of brominated epoxy resin oligopolymer and sodium antimonate=3: 2).The preparation method is: bromide fire retardant and antimony containing compounds stirring 10min mixed, and subsequent use.
Ignition suppressor factor compound scheme: C-P-1 (polycarbonate powder (melting index MI:20g/10min; Saudi Arabia innovation) with the mass ratio of RDP=1: 1), C-P-2 (mass ratio of ppe powder (blue star LXR 045) and RDP=1: 1), the preparation method is: the SULPHOSUCCINIC ACID ESTER RDP of liquid state is mixed according to aforementioned proportion with powdered resin polycarbonate powder or ppe powder; Stirring at low speed 5min mixes; Place 12h for 90 ℃, liquid is fully absorbed by powder, feeding is convenient when producing like this.
PBT, bromo-antimony fire retardant, ignition suppressor factor, toughner, stablizer and lubricant are added high mixer; (950r/min) stirs 4min at a high speed; Add twin screw extruder by first charging opening; E type alkali free glass fibre adds twin screw extruder from second charging opening continuously to be extruded, and makes flame retardant resistance and strengthens the PBT material.
The temperature distribution of this twin screw extruder is following: be respectively to head by feed zone: 210 ℃, 230 ℃, 240 ℃, 245 ℃, 235 ℃, 225 ℃, 225 ℃, 220 ℃, and die head: 250 ℃, through water-cooled, pelletizing, pack then after material is extruded.
Preparation strengthens PBT material pellet with flame retardant resistance and in 130 ℃ of air dry ovens, placed 4 hours during formed body, is prepared into required formed body by injection moulding machine then or is used for the standard testing batten of test material performance.
According to the method described above, the raw material consumption in the employing table 1 prepares flame retardant resistance enhancing PBT material, formed body and standard testing batten.
The parts by weight of raw materials proportioning of table 1 embodiment 1～13, Comparative Examples 1～2
| Component | Comparative Examples 1 | Comparative Examples 2 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 |
| PBT | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Br-Sb-1 | 40 | 70 | 50 | 55 | 58 | 70 | |||||||||
| Br-Sb-2 | 80 | 70 | 60 | 65 | 70 | ||||||||||
| Br-Sb-3 | 70 | 55 | 65 | 70 | |||||||||||
| C-P-1 | 5 | 14 | 15 | 20 | 25 | 21 | 23 | ||||||||
| C-P-2 | 5 | 5 | 18 | 20 | 15 | 25 | |||||||||
| Toughner | 5 | 12 | 5 | 5 | 0 | 12 | 10 | 15 | |||||||
| Stablizer | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
| Lubricant | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
| E type alkali free glass fibre | 60 | 80 | 75 | 75 | 80 | 72 | 72 | 84 | 83 | 77 | 85 | 90 | 90 | 85 | 90 |
Raw materials used and source is like table 2 in the foregoing description 1～13, the Comparative Examples 1～3:
Raw material manufacturer in table 2 embodiment 1～13 and the Comparative Examples 1～2
| Material category | The producer and the trade mark |
| PBT | Engineering plastics factory of Yihua Group Corporation, L2100 |
| TDE | Jinan safe star Fine Chemical Co., Ltd |
| CR210K (brominated epoxy resin oligopolymer) | Suzhou day novel material ltd, CR-210K |
| Antimony Trioxide: 99.5Min | Yiyang, hunan antimony article factory (0 grade) |
| Sodium antimonate | U.S. big lake |
| Toughner: MBS EXL-2620 | ROHM AND HAAS |
| Polycarbonate | Saudi Arabia's innovation (U.S. GE) |
| The ppe powder | Ruicheng branch office of Lanxing Chemical New Material Co., Ltd. |
| SULPHOSUCCINIC ACID ESTER Fyrolflex RDP | U.S.'s rising sun is auspicious to be reached |
| E type alkali free glass fibre | Zhejiang Jushi Group Co., Ltd. |
| Stablizer: antioxidant 1010, oxidation inhibitor 168 (weight ratio 1: 1) | Jin Haiyabao |
| Lubricant: silicone powder | Ningbo three benefits |
The standard testing batten that the foregoing description 1～13, Comparative Examples 1～2 make carries out performance test by the testing method in the table 4, The performance test results such as table 3:
Flame retardant resistance strengthens PBT material properties test result in table 3 embodiment and the Comparative Examples
| Index | Comparative Examples 1 | Comparative Examples 2 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 |
| Tensile strength | 127 | 120 | 125 | 121 | 118 | 120 | 124 | 110 | 115 | 115 | 108 | 105 | 118 | 112 | 100 |
| Flexural strength | 185 | 190 | 180 | 185 | 180 | 185 | 178 | 170 | 185 | 180 | 176 | 185 | 186 | 175 | 173 |
| Modulus in flexure | 8100 | 8500 | 7800 | 7600 | 7500 | 8200 | 8000 | 7500 | 8300 | 8200 | 8000 | 8500 | 8200 | 7900 | 7800 |
| Notched Izod impact strength | 8 | 6.2 | 7.2 | 7 | 7.5 | 6.5 | 6.7 | 7 | 6.5 | 6.2 | 6.5 | 6.4 | 6.5 | 7.5 | 7.1 |
| Non-notched Izod impact strength | 42 | 35.5 | 38 | 35 | 40 | 32 | 36 | 38 | 35 | 35 | 35 | 33 | 32 | 40 | 39 |
| Vertical combustion | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
| Glowing filament ignition temperature GWI T | 675 | 700 | 750 | 750 | 725 | 775 | 775 | 800 | 800 | 800 | 775 | 800 | 775 | 800 | 775 |
| Heat-drawn wire HDT | 205 | 205 | 200 | 200 | 198 | 200 | 198 | 196 | 195 | 195 | 198 | 190 | 194 | 193 | 192 |
| Relative discharge index CTI | 275 | 225 | 225 | 225 | 225 | 200 | 200 | 200 | 200 | 200 | 200 | 200 | 200 | 200 | 200 |
Table 4: testing method and standard
| Sequence number | Inspection item | Unit | Testing standard |
| 1 | Tensile strength | MPa | GB/T?1040.2-2008 |
| 2 | Flexural strength | MPa | GB/T?9341-2008 |
| 3 | Modulus in flexure | MPa | GB/T?9341-2008 |
| 4 | Simple beam impact strength | Kj/m 2 | GB/T?1043.1-2008 |
| 5 | Heat-drawn wire (A method) | ℃ | GB/T1634.1-2004 |
| 6 | Relative discharge index CTI | V | GB/T?4207-2003 |
| 7 | Glowing filament ignition temperature GWIT | ℃ | GB/T5169.13-2006 (with IEC 60695-2-13 standard) |
| 8 | Vertical combustion | - | UL?94 |
Claims (9)
1. flame retardant resistance reinforced polybutylene terephthalate comprises the raw material of following weight part:
Wherein, described composite fire retardant is by halogenated flame retardant and antimony containing compounds is composite forms;
Described ignition suppressor factor is the polymkeric substance of high-carbon content and the mixture of SULPHOSUCCINIC ACID ESTER;
The polymkeric substance of described high-carbon content is one or more in polycarbonate, ppe, the polyphenylene sulfide;
Described SULPHOSUCCINIC ACID ESTER is one or more in Tritolyl Phosphate, triphenylphosphate, tolyl diphenyl phosphoester, tributyl phosphate, tricresyl phosphate (dibromopropyl) ester, tricresyl phosphate (β-chloroethyl) ester, Resorcinol two (hexichol SULPHOSUCCINIC ACID ESTER), the dihydroxyphenyl propane two (diphenyl phosphoester);
The polymkeric substance of described ignition suppressor factor medium high carbon content and the mass ratio of SULPHOSUCCINIC ACID ESTER are 1～3: 1.
2. flame retardant resistance reinforced polybutylene terephthalate as claimed in claim 1 is characterized in that, comprises the raw material of following weight part:
3. according to claim 1 or claim 2 flame retardant resistance reinforced polybutylene terephthalate is characterized in that the limiting viscosity of described polybutylene terephthalate is 0.8dl/g～1.3dl/g.
4. according to claim 1 or claim 2 flame retardant resistance reinforced polybutylene terephthalate is characterized in that described halogenated flame retardant is selected bromide fire retardant for use.
5. flame retardant resistance reinforced polybutylene terephthalate as claimed in claim 4; It is characterized in that described bromide fire retardant selects TDE, brominated Polystyrene, brominated polystyrene, brominated epoxy resin oligopolymer, brominated polycarbonate oligopolymer for use, gather in the bromination base propenoate one or more.
6. according to claim 1 or claim 2 flame retardant resistance reinforced polybutylene terephthalate is characterized in that described antimony containing compounds is selected one or more in Antimony Trioxide: 99.5Min, the stibnate for use.
7. according to claim 1 or claim 2 flame retardant resistance reinforced polybutylene terephthalate is characterized in that described toughner is selected one or more in core-shell type multipolymer, all acrylic ester core-shell impact modifiers, the silicone elastomer for use;
Perhaps, described lubricant is selected one or both in ester type waxes class, the silicone for use;
Perhaps, described enhancement component is selected alkali free glass fibre for use.
8. according to claim 1 or claim 2 flame retardant resistance reinforced polybutylene terephthalate is characterized in that described raw material comprises stablizer.
9. like the preparation method of each described flame retardant resistance reinforced polybutylene terephthalate of claim 1～8, comprise step:
After mixing, the stablizer that said polybutylene terephthalate, composite fire retardant, ignition suppressor factor, toughner, lubricant and selectivity are added sends in the twin screw extruder; Again enhancement component is sent into twin screw extruder; Extrude through twin screw extruder is mixing, make the flame retardant resistance reinforced polybutylene terephthalate;
Each section barrel zone temperature is 200 ℃～250 ℃ in the described twin screw extruder.
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| US20020111409A1 (en) * | 1999-05-28 | 2002-08-15 | Talibuddin Sapna H. | Polyester compositions having improved color stability |
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