CN100587006C - Copolyester flame-retardant material containing Lewis acid and preparation method thereof - Google Patents
Copolyester flame-retardant material containing Lewis acid and preparation method thereof Download PDFInfo
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- CN100587006C CN100587006C CN200610086238A CN200610086238A CN100587006C CN 100587006 C CN100587006 C CN 100587006C CN 200610086238 A CN200610086238 A CN 200610086238A CN 200610086238 A CN200610086238 A CN 200610086238A CN 100587006 C CN100587006 C CN 100587006C
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 61
- 239000000463 material Substances 0.000 title claims abstract description 44
- 239000002841 Lewis acid Substances 0.000 title claims abstract description 33
- 229920001634 Copolyester Polymers 0.000 title claims abstract description 31
- 150000007517 lewis acids Chemical class 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 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 abstract description 19
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 50
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 21
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 21
- 229920001707 polybutylene terephthalate Polymers 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 26
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 24
- 230000002378 acidificating effect Effects 0.000 claims description 24
- 150000008065 acid anhydrides Chemical class 0.000 claims description 19
- 239000011592 zinc chloride Substances 0.000 claims description 15
- 235000005074 zinc chloride Nutrition 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 235000011187 glycerol Nutrition 0.000 claims description 14
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 12
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 12
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 claims description 11
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 10
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 10
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 9
- 229940059574 pentaerithrityl Drugs 0.000 claims description 8
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 8
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229960003280 cupric chloride Drugs 0.000 claims description 6
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 claims description 5
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 claims description 5
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 5
- 229940091181 aconitic acid Drugs 0.000 claims description 5
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 claims description 5
- 229940074391 gallic acid Drugs 0.000 claims description 5
- 235000004515 gallic acid Nutrition 0.000 claims description 5
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 claims description 5
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 5
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 claims description 5
- 239000000811 xylitol Substances 0.000 claims description 5
- 235000010447 xylitol Nutrition 0.000 claims description 5
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 5
- 229960002675 xylitol Drugs 0.000 claims description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 229960005150 glycerol Drugs 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 30
- 239000000203 mixture Substances 0.000 abstract description 28
- 238000005886 esterification reaction Methods 0.000 abstract description 24
- 230000032050 esterification Effects 0.000 abstract description 22
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 21
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 abstract description 18
- 239000012752 auxiliary agent Substances 0.000 abstract description 18
- 239000003054 catalyst Substances 0.000 abstract description 17
- 238000006068 polycondensation reaction Methods 0.000 abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- 238000003756 stirring Methods 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 7
- 229920001577 copolymer Polymers 0.000 abstract description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 abstract 1
- 239000003610 charcoal Substances 0.000 description 20
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 17
- 238000013019 agitation Methods 0.000 description 12
- 229920000728 polyester Polymers 0.000 description 12
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 8
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 8
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 8
- 239000006224 matting agent Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000003712 anti-aging effect Effects 0.000 description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 229940071125 manganese acetate Drugs 0.000 description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 3
- GLDQAMYCGOIJDV-UHFFFAOYSA-N 2,3-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1O GLDQAMYCGOIJDV-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- UIAFKZKHHVMJGS-UHFFFAOYSA-N beta-resorcylic acid Natural products OC(=O)C1=CC=C(O)C=C1O UIAFKZKHHVMJGS-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000138 intercalating agent Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 240000004859 Gamochaeta purpurea Species 0.000 description 1
- 206010053615 Thermal burn Diseases 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a copolyester flame-retardant material containing Lewis acid and a preparation method thereof. The material is one or more Lewis acids are uniformly distributed in a copolymer generated after a reaction monomer of polyethylene terephthalate or polybutylene terephthalate and one or more comonomers are copolymerized; the method comprises the steps of uniformly stirring a terephthalic acid monomer and an ethylene glycol or butanediol monomer, adding a comonomer, Lewis acid, a corresponding esterification and polycondensation catalyst and an auxiliary agent to obtain a uniform mixture, and stirring the uniform mixture under the pressure of 2-3 kg/cm2The esterification reaction is carried out for 2-3 h at 250-260 ℃ under nitrogen atmosphere, then excessive water is discharged under normal pressure, and then the esterification reaction is carried out for 0.5-1.5 h at 265-275 ℃ under nitrogen atmosphere with the vacuum degree of less than or equal to 700Pa and for 2-3 h at 265-275 ℃ under nitrogen atmosphere with the vacuum degree of less than or equal to 70Pa under stirring, and the stirring is carried out until the viscosity reaches the standard, so as to prepare the copolyester flame retardant material containing Lewis acid. It can be widely used in the flame retardant field.
Description
Technical field
The present invention relates to a kind of fire retardant material and method for making, especially contain copolyester fire retardant material of Louis (Lewis) acid and preparation method thereof.
Background technology
Polyester with advantages such as high-modulus, high strength, snappiness, conformality and thermotolerances has become a kind of broad-spectrum thermoplastic macromolecule material, yet, the same with most of organic polymer materials, because of it is flammable high, limited the scope of using.In order to change this present situation, people are everlasting to add in the polyester when fire retardant tries hard to it burn and hide, the one-tenth charcoal when burning to utilize stop oxygen and heat to internal diffusion and low molecular breakdown product to external diffusion, thereby reach fire-retardant purpose.As a kind of " the phosphor-containing flame-proof polyethylene terephthalate/laminated nm-silicate composite material and its production and use " that discloses among the disclosed Chinese invention patent ublic specification of application CN 1396206A on February 12nd, 2003.It is intended to provide, and a kind of mechanical property is significantly improved, flame retardant properties satisfies phosphor-containing flame-proof polyethylene terephthalate/laminated nm-silicate composite material and this preparation methods and the purposes that practicality requires, slows down the fusion drippage significantly.Wherein, laminated nm-silicate composite material is made up of dimethyl terephthalate (DMT) or terephthalic acid, ethylene glycol, layered silicate, response type phosphonium flame retardant, intercalator, dispersion medium and catalyzer; The preparation method is after aforesaid raw material is pressed the weighing of recipe ingredient difference, earlier layered silicate being added the dispersion medium high speed stirs, form stable suspensoid, again intercalator or intercalator and protonating agent are added and be warming up to 60~80 ℃ and fully stir, after the filtration throw out is washed 2~3 centrifuge drippings, add dimethyl terephthalate (DMT) and ethylene glycol afterwards, fully mix once more, be warming up to 160~230 ℃ and carry out transesterification reaction 2.5~4h, add the response type phosphonium flame retardant then, catalyst mix is even, at 245~275 ℃, below the pressure 60pa, polymerization 2~3h makes laminated nm-silicate composite material; This laminated nm-silicate composite material can be used for preparing the raw material of flame retardant plastics goods and fire-retardant fibre.But, no matter this laminated nm-silicate composite material, or its preparation method, the shortcoming part is all arranged, at first, though matrix material can increase into charcoal when burning, be to reach fire-retardant purpose by added a large amount of inorganic anti-flaming material rears in polyester, this can reduce the original over-all properties of polyester self unavoidably; Secondly, raw material that uses among the preparation method and processing step are all more, cause the process of preparation more numerous and diverse, are difficult to reduce production costs.
Summary of the invention
The technical problem to be solved in the present invention is for overcoming weak point of the prior art, provide a kind of and have certain side chain and become charcoal with degree of crosslinking and in combustion processes voluntarily in a large number and do not have molten drop, the lewis acidic copolyester fire retardant material and preparation method thereof that contains easy to prepare.
Contain lewis acidic copolyester fire retardant material and comprise polyethylene terephthalate or polybutylene terephthalate, particularly the multipolymer that produces after the reaction monomers of (a) said polyethylene terephthalate or polybutylene terephthalate and one or more comonomer copolymerization; (b) be evenly distributed with one or more Lewis acids in the said multipolymer.
As the further improvement that contains lewis acidic copolyester fire retardant material, described comonomer is the above polyvalent alcohol of ternary and ternary or ternary and above polyprotonic acid or its acid anhydrides or hydroxyl diprotic acid or the carboxyl dibasic alcohol of ternary; The above polyvalent alcohol of described ternary and ternary is glycerine or tetramethylolmethane or Xylitol or sorbyl alcohol; The polyprotonic acid that described ternary and ternary are above or its acid anhydrides are fourth four alkane tetracarboxylic acids or the third three acid or aconitic acid or mellic acid or pentamethylene tetracarboxylic acid or trimellitic acid list acid anhydride or pyromellitic acid anhydrides; Described hydroxyl diprotic acid or carboxyl dibasic alcohol are citric acid or gallic acid or equal resorcylic acid; Described Lewis acid is zinc chloride or aluminum chloride or germanium chloride or tin chloride or iron(ic) chloride or nickelous chloride or magnesium chloride or cupric chloride.
The preparation method who contains lewis acidic copolyester fire retardant material comprises the polyester synthesis method, particularly it is finished according to the following steps: (a) terephthalic acid monomers and ethylene glycol monomer or butyleneglycol monomer are mixed mixture, mol ratio between the two is 1: 1.05~1.7; (b) in mixture, add one or more comonomers and one or more Lewis acids and corresponding esterification and polycondensation catalyst and auxiliary agent, and stir to such an extent that mix thing, wherein, the add-on of comonomer is that to make the mol ratio between carboxyl and hydroxyl be 1: 1.05~1.7, and lewis acidic add-on is 0.01~30% of the copolyester mass percent that makes; (c) will mix thing earlier is 2~3kg/cm in pressure under agitation
2Nitrogen atmosphere under in 250~260 ℃ esterification 2~3h, again it is discharged unnecessary water down in normal pressure, afterwards it is under agitation placed successively vacuum tightness be≤react under 0.5~1.5h, vacuum tightness the nitrogen atmosphere at 265~275 ℃ under the nitrogen atmosphere of 700Pa and react 2~3h at 265~275 ℃ for≤70Pa, it is up to standard to be stirred to viscosity, makes to contain lewis acidic copolyester fire retardant material.
Further improvement as the preparation method who contains lewis acidic copolyester fire retardant material, described comonomer is the above polyvalent alcohol of ternary and ternary or ternary and above polyprotonic acid or its acid anhydrides or hydroxyl diprotic acid or the carboxyl dibasic alcohol of ternary, wherein, the above polyvalent alcohol of ternary and ternary is glycerine or tetramethylolmethane or Xylitol or sorbyl alcohol, the polyprotonic acid that ternary and ternary are above or its acid anhydrides are fourth four alkane tetracarboxylic acids or the third three acid or aconitic acid or mellic acid or pentamethylene tetracarboxylic acid or trimellitic acid list acid anhydride or pyromellitic acid anhydrides, and hydroxyl diprotic acid or carboxyl dibasic alcohol are citric acid or gallic acid or equal resorcylic acids; Described Lewis acid is zinc chloride or aluminum chloride or germanium chloride or tin chloride or iron(ic) chloride or nickelous chloride or magnesium chloride or cupric chloride, and its addition is 0.01~10% of the copolyester mass percent that makes; Described esterification and polycondensation catalyst are antimony acetate or antimonous oxide or manganese acetate or Cobaltous diacetate, and its add-on is a constant, and auxiliary agent is matting agent or oxidation inhibitor or anti-aging agent, and its add-on is a constant; The value that described normal pressure is discharged unnecessary water down is its corresponding theory aquifer yield; Described viscosity value up to standard is a constant.
Beneficial effect with respect to prior art is, one, one or more Lewis acids that distribute equably in the multipolymer that is produced after the reaction monomers of polyethylene terephthalate (PET) or polybutylene terephthalate (PBT) and one or more comonomer copolymerization have greatly improved the flame retardant properties of fire retardant material; Wherein, after one or more Lewis acids are distributed among PET or the PBT equably, under its catalysis, occur in the Friedel-Crafts substitution reaction on the phenyl ring, the a large amount of phenyl ring that contain in the polyester construction are bound up, change into charcoal by the conjugation aromatization, make under lower temperature, to make polyester generate a large amount of charcoals, realize that catalysis is fire-retardant.After the reaction monomers copolymerization of one or more comonomers and PET or PBT, the side chain number of the molecular chain of the multipolymer that is produced and degree of crosslinking are all greatly promoted, under lewis acidic effect, further suppress the thermolysis of superpolymer, reduce or stoped the generation of combustible volatile, and then slowed down incendiary widely and spread and propagate, the utmost point is beneficial to its one-tenth charcoal under combustion position, realizes cross-linking flame-retardant.Combination of them and synergistic combinations are fire-retardant, having overcome pure polyester becomes the charcoal layer quality of charcoal bad when burning, shielding effect is not high, there is not excellent shielding effect, heat can penetrate the charcoal layer when burning away, can not play the defective of good solid phase fire retardation, it has been had on the basis of certain side chain and degree of crosslinking at the molecular chain through copolyester after the polymerization, add the performance of one or more lewis acidic further catalytic crosslinking effects wherein, promoted copolyester in combustion processes, promptly to be become charcoal in a large number more, need keep continuous decomposing copolymer when both having broken off the polyester burning and produce the condition of organic molecule, stoped organic molecule to the outside diffusion of polyester again, oxygen and heat are to the process of polyester internal divergence, even slowing down, the process of these two diffusions interrupts stopping, bring into play the solid phase fire retardation of charcoal layer itself fully, thereby obtained the fire retardant material of no molten drop; They are two years old, respectively with PET or PBT and the fire retardant material that makes after molded or injection molding, carry out the test of tensile property and bending property according to standard GB/T 1040-92 and GB/T 9341-2000, testing tool is that China Shenzhen is newly thought carefully CMT4204 type microcomputer control electronics universal testing machine, and bend specimen is of a size of 10 * 4 * 80mm
3, tension specimen is the sample of I type described in the GB/T 1040-92, test result is as shown in table 1:
Table 1
01# in the table 1 and 02# sample be not for adding the PET and the PBT of any auxiliary agent, and 6~10# sample is one or more comonomers and one or more the lewis acidic fire retardant materials that are added with different ratios.As seen from Table 1, the performance of fire retardant material has kept the performance of PET and PBT substantially, and as Young's modulus, modulus in flexure, flexural strength etc., tensile strength keeps substantially and slightly improves.Hence one can see that, and performance index between the two are more or less the same, and do not influence its normal use in former Application Areas at all; They are three years old, use thermogravimetric analyzer and field emission scanning electron microscope to characterize PET or PBT with the fire retardant material that makes respectively, from the thermogravimetric curve figure that obtains and electromicroscopic photograph as can be known, after in PET or PBT, adding one or more comonomers and one or more Lewis acids, the one-tenth charcoal situation of fire retardant material is obviously improved, and neat coal amout is enhanced.Do not add one or more comonomers and one or more lewis acidic PET or the formed charcoal layer of PBT more cavity is arranged, and the cavity of adding one or more comonomers and the formed charcoal layer of one or more lewis acidic fire retardant materials obviously dwindles, and the charcoal layer is fine and close and hard; Its four, the fire retardant material that makes after molded or injection molding, is carried out the mensuration of oxygen index according to GB/T 2406-93, sample is of a size of 6.5 * 3 * 80mm
3, testing tool is the JF-1 type oxygen index instrument of Chinese Jiangning analytical instrument factory, test result is as shown in table 2:
Table 2
As shown in Table 2, the oxygen index of fire retardant material is all more than 29, and what obtain is the fire retardant material of molten drop not, and this not only makes fire retardant material have higher flame retardant properties, the scald that the molten drop when also having overcome because of material combustion simultaneously very easily causes and the defective that spreads of fire; They are five years old, the preparation method is simple and easy to do, and required equipment is universalization equipment, is easy to the commercial applications of suitability for industrialized production and product, product can be widely used in flame retardant textiles, fire-resistant engineering plastics, and fire-retardant film, mechanical component, the Electrical and Electronic part, auto parts, the shell and the part of other office auto-plants, household electric appliances part etc.
Further embodiment as beneficial effect, the one, comonomer is the above polyvalent alcohol of ternary and ternary or ternary and above polyprotonic acid or its acid anhydrides or hydroxyl diprotic acid or the carboxyl dibasic alcohol of ternary, make the source of the raw material for preparing fire retardant material extensive more, be easy to get, also more flexible during preparation; The 2nd, Lewis acid is zinc chloride or aluminum chloride or germanium chloride or tin chloride or iron(ic) chloride or nickelous chloride or magnesium chloride or cupric chloride, its addition is 0.01~10% of the copolyester mass percent that makes, also make the source of raw material wide, technology is flexible, and is littler to original Effect on Performance of PET or PBT; The 3rd, esterification and polycondensation catalyst are antimony acetate or antimonous oxide or manganese acetate or Cobaltous diacetate, and its add-on is a constant, and auxiliary agent is matting agent or oxidation inhibitor or anti-aging agent, and its add-on is a constant, both made wide as the source of the catalyzer of auxiliary material and auxiliary agent, be easy to get, be convenient to operation again; The 4th, the value that normal pressure is discharged unnecessary water down is that its corresponding theory aquifer yield and viscosity value up to standard are constant, all makes the process of preparation simpler, and is easy to the raising of automatization.
Description of drawings
Below in conjunction with accompanying drawing optimal way of the present invention is described in further detail.
Fig. 1 is to use Perkin-Elmer Pyris Diamond-I type thermogravimetric analyzer to record, contain different comonomer add-ons and Lewis acid add-on fire retardant material become the charcoal graphic representation, wherein, ordinate zou is that mass percent, X-coordinate are temperature.Intensification condition during test is 10 ℃/min, and flow of nitrogen gas speed is 80ml/min, and temperature rises to 750 ℃ from 50 ℃;
Fig. 2 is after polyethylene terephthalate (PET) or polybutylene terephthalate (PBT) are carried out thermo-cracking, use Sirion 200FESEM type field emission scanning electron microscope that the photo that the back is taken is observed in the cross section of sample charcoal layer, the formed charcoal layer of PET (PBT too) has more cavity as can be seen from photo;
Fig. 3 is after the fire retardant material that makes is carried out thermo-cracking, use Sirion 200FESEM type field emission scanning electron microscope that the photo that the back is taken is observed in the cross section of sample charcoal layer, the formed charcoal layer of the fire retardant material cavity of adding as can be seen from photo behind comonomer and the Lewis acid obviously dwindles, and the charcoal layer is fine and close and hard.
Embodiment
At first make or buy terephthalic acid monomers from market with ordinary method, ethylene glycol monomer and butyleneglycol monomer, and as the ternary of comonomer and the polyvalent alcohol more than the ternary, polyprotonic acid or its acid anhydrides that ternary and ternary are above, hydroxyl diprotic acid or carboxyl dibasic alcohol, wherein, the above polyvalent alcohol of ternary and ternary is glycerine or tetramethylolmethane or Xylitol or sorbyl alcohol, the polyprotonic acid that ternary and ternary are above or its acid anhydrides are fourth four alkane tetracarboxylic acids or the third three acid or aconitic acid or mellic acid or pentamethylene tetracarboxylic acid or trimellitic acid list acid anhydride or pyromellitic acid anhydrides, hydroxyl diprotic acid or carboxyl dibasic alcohol are citric acid or gallic acid or equal resorcylic acid, as lewis acidic zinc chloride or aluminum chloride or germanium chloride or tin chloride or iron(ic) chloride or nickelous chloride or magnesium chloride or cupric chloride, antimony acetate or antimonous oxide or manganese acetate or Cobaltous diacetate as esterification and polycondensation catalyst, matting agent or oxidation inhibitor or anti-aging agent as auxiliary agent, then
Embodiment 1: finish preparation according to the following steps successively: a) terephthalic acid monomers and ethylene glycol monomer are mixed mixture, mol ratio between the two is 1: 1.05.B) in mixture, add a kind of comonomer and five kinds of Lewis acids and corresponding esterification and polycondensation catalyst and auxiliary agent, and stir to such an extent that mix thing, now selecting the glycerine in the above polyvalent alcohol of ternary and ternary is that comonomer, zinc chloride, aluminum chloride, germanium chloride, tin chloride and iron(ic) chloride are Lewis acid; Wherein, the add-on of comonomer glycerine is that to make the mol ratio between carboxyl and hydroxyl be 1: 1.05, the add-on of Lewis acid zinc chloride, aluminum chloride, germanium chloride, tin chloride and iron(ic) chloride is 30% of the copolyester mass percent that makes, esterification and polycondensation catalyst are antimony acetate, auxiliary agent is a matting agent, and its add-on is constant.C) will mix thing earlier is 3kg/cm in pressure under agitation
2Nitrogen atmosphere under in 250 ℃ esterification 3h, again it is discharged down unnecessary water in normal pressure; Wherein, the following value of discharging unnecessary water of normal pressure is its corresponding theory aquifer yield.Afterwards, it is under agitation placed vacuum tightness successively is to react under the nitrogen atmosphere that 1.5h, vacuum tightness are 50Pa at 265 ℃ under the nitrogen atmosphere of 500Pa to react 3h at 265 ℃, and it is up to standard to be stirred to viscosity; Wherein, viscosity value up to standard is a constant, make as 10# curve among Fig. 1, Fig. 3 with and mechanical property and flame retardant properties shown in 10# sample in table 1, the table 2, contain lewis acidic copolyester fire retardant material.
Embodiment 2: finish preparation according to the following steps successively: a) terephthalic acid monomers and ethylene glycol monomer are mixed mixture, mol ratio between the two is 1: 1.2.B) in mixture, add two kinds of comonomers and four kinds of Lewis acids and corresponding esterification and polycondensation catalyst and auxiliary agent, and stir to such an extent that mix thing, now selecting above polyprotonic acid or the four alkane tetracarboxylic acids of the fourth in its acid anhydrides of glycerine, ternary and ternary in the above polyvalent alcohol of ternary and ternary is that comonomer, zinc chloride, aluminum chloride, germanium chloride and tin chloride are Lewis acid; Wherein, the add-on of comonomer glycerine and fourth four alkane tetracarboxylic acids is that to make the mol ratio between carboxyl and hydroxyl be 1: 1.2, the add-on of Lewis acid zinc chloride, aluminum chloride, germanium chloride and tin chloride is 24% of the copolyester mass percent that makes, esterification and polycondensation catalyst are that antimony acetate, auxiliary agent are matting agent, and its add-on is constant.C) will mix thing earlier is 2.8kg/cm in pressure under agitation
2Nitrogen atmosphere under in 253 ℃ esterification 2.8h, again it is discharged down unnecessary water in normal pressure; Wherein, the following value of discharging unnecessary water of normal pressure is its corresponding theory aquifer yield.Afterwards, it is under agitation placed vacuum tightness successively is to react under the nitrogen atmosphere that 1.3h, vacuum tightness are 55Pa at 268 ℃ under the nitrogen atmosphere of 550Pa to react 2.8h at 268 ℃, and it is up to standard to be stirred to viscosity; Wherein, viscosity value up to standard is a constant, make as 9# curve among Fig. 1, Fig. 3 with and mechanical property and flame retardant properties shown in 9# sample in table 1, the table 2, contain lewis acidic copolyester fire retardant material.
Embodiment 3: finish preparation according to the following steps successively: a) terephthalic acid monomers and ethylene glycol monomer are mixed mixture, mol ratio between the two is 1: 1.4.B) in mixture, add three kinds of comonomers and three kinds of Lewis acids and corresponding esterification and polycondensation catalyst and auxiliary agent, and stir to such an extent that mix thing, now selecting above polyprotonic acid or the citric acid in the four alkane tetracarboxylic acids of the fourth in its acid anhydrides, hydroxyl diprotic acid or the carboxyl dibasic alcohol of glycerine, ternary and ternary in the above polyvalent alcohol of ternary and ternary is that comonomer, zinc chloride, aluminum chloride and germanium chloride are Lewis acid; Wherein, the add-on of comonomer glycerine, fourth four alkane tetracarboxylic acids and citric acid is that to make the mol ratio between carboxyl and hydroxyl be 1: 1.4, the add-on of Lewis acid zinc chloride, aluminum chloride and germanium chloride is 16% of the copolyester mass percent that makes, esterification and polycondensation catalyst are that antimony acetate, auxiliary agent are matting agent, and its add-on is constant.C) will mix thing earlier is 2.5kg/cm in pressure under agitation
2Nitrogen atmosphere under in 255 ℃ esterification 2.5h, again it is discharged down unnecessary water in normal pressure; Wherein, the following value of discharging unnecessary water of normal pressure is its corresponding theory aquifer yield.Afterwards, it is under agitation placed vacuum tightness successively is to react under the nitrogen atmosphere that 1h, vacuum tightness are 60Pa at 270 ℃ under the nitrogen atmosphere of 600Pa to react 2.5h at 270 ℃, and it is up to standard to be stirred to viscosity; Wherein, viscosity value up to standard is a constant, make as 8# curve among Fig. 1, Fig. 3 with and mechanical property and flame retardant properties shown in 8# sample in table 1, the table 2, contain lewis acidic copolyester fire retardant material.
Embodiment 4: finish preparation according to the following steps successively: a) terephthalic acid monomers and ethylene glycol monomer are mixed mixture, mol ratio between the two is 1: 1.5.B) in mixture, add four kinds of comonomers and two kinds of Lewis acids and corresponding esterification and polycondensation catalyst and auxiliary agent, and stir to such an extent that mix thing, now selecting glycerine and above polyprotonic acid or the citric acid in the four alkane tetracarboxylic acids of the fourth in its acid anhydrides, hydroxyl diprotic acid or the carboxyl dibasic alcohol of tetramethylolmethane, ternary and ternary in the above polyvalent alcohol of ternary and ternary is that comonomer, zinc chloride and aluminum chloride are Lewis acid; Wherein, the add-on of comonomer glycerine, tetramethylolmethane, fourth four alkane tetracarboxylic acids and citric acid is that to make the mol ratio between carboxyl and hydroxyl be 1: 1.5, the add-on of Lewis acid zinc chloride and aluminum chloride is 8% of the copolyester mass percent that makes, esterification and polycondensation catalyst are that antimony acetate, auxiliary agent are matting agent, and its add-on is constant.C) will mix thing earlier is 2.3kg/cm in pressure under agitation
2Nitrogen atmosphere under in 258 ℃ esterification 2.3h, again it is discharged down unnecessary water in normal pressure; Wherein, the following value of discharging unnecessary water of normal pressure is its corresponding theory aquifer yield.Afterwards, it is under agitation placed vacuum tightness successively is to react under the nitrogen atmosphere that 0.8h, vacuum tightness are 65Pa at 273 ℃ under the nitrogen atmosphere of 650Pa to react 2.3h at 273 ℃, and it is up to standard to be stirred to viscosity; Wherein, viscosity value up to standard is a constant, make as 7# curve among Fig. 1, Fig. 3 with and mechanical property and flame retardant properties shown in 7# sample in table 1, the table 2, contain lewis acidic copolyester fire retardant material.
Embodiment 5: finish preparation according to the following steps successively: a) terephthalic acid monomers and ethylene glycol monomer are mixed mixture, mol ratio between the two is 1: 1.7.B) in mixture, add five kinds of comonomers and a kind of Lewis acid and corresponding esterification and polycondensation catalyst and auxiliary agent, and stir to such an extent that mix thing, now selecting the citric acid in above polyprotonic acid of glycerine in the above polyvalent alcohol of ternary and ternary and tetramethylolmethane, ternary and ternary or the four alkane tetracarboxylic acids of the fourth in its acid anhydrides and the third three acid, hydroxyl diprotic acid or the carboxyl dibasic alcohol is that comonomer, zinc chloride are Lewis acid; Wherein, the add-on of comonomer glycerine, tetramethylolmethane, fourth four alkane tetracarboxylic acids, the third three acid and citric acid is that to make the mol ratio between carboxyl and hydroxyl be 1: 1.7, the add-on of Lewis acid zinc chloride is 0.01% of the copolyester mass percent that makes, esterification and polycondensation catalyst are that antimony acetate, auxiliary agent are matting agent, and its add-on is constant.C) will mix thing earlier is 2kg/cm in pressure under agitation
2Nitrogen atmosphere under in 260 ℃ esterification 2h, again it is discharged down unnecessary water in normal pressure; Wherein, the following value of discharging unnecessary water of normal pressure is its corresponding theory aquifer yield.Afterwards, it is under agitation placed vacuum tightness successively is to react under the nitrogen atmosphere that 0.5h, vacuum tightness are 70Pa at 275 ℃ under the nitrogen atmosphere of 700Pa to react 2h at 275 ℃, and it is up to standard to be stirred to viscosity; Wherein, viscosity value up to standard is a constant, make as 6# curve among Fig. 1, Fig. 3 with and mechanical property and flame retardant properties shown in 6# sample in table 1, the table 2, contain lewis acidic copolyester fire retardant material.
Select the butyleneglycol monomer more respectively for use, as Xylitol or the sorbyl alcohol in the ternary of comonomer and the polyvalent alcohol more than the ternary, polyprotonic acid or the aconitic acid in its acid anhydrides or mellic acid or pentamethylene tetracarboxylic acid or trimellitic acid list acid anhydride or pyromellitic acid anhydride that ternary and ternary are above, gallic acid in hydroxyl diprotic acid or the carboxyl dibasic alcohol or equal resorcylic acid, nickelous chloride in the Lewis acid or magnesium chloride or cupric chloride, antimonous oxide in esterification and the polycondensation catalyst or manganese acetate or Cobaltous diacetate, oxidation inhibitor in the auxiliary agent or anti-aging agent, repeat the foregoing description 1~5, make equally as 6~10# curve among Fig. 1, Fig. 3 with and mechanical property and flame retardant properties such as table 1, polyester inorganic nano composite material in the table 2 shown in 6~10# sample with flame retardant resistance.
Obviously, those skilled in the art can carry out various changes and modification and not break away from the spirit and scope of the present invention the lewis acidic copolyester fire retardant material and preparation method thereof that contains of the present invention.Like this, if of the present invention these are revised and modification belongs within the scope of claim of the present invention and equivalent technologies thereof, then the present invention also is intended to comprise these changes and modification interior.
Claims (4)
1, a kind ofly contain lewis acidic copolyester fire retardant material, comprise polyethylene terephthalate or polybutylene terephthalate, it is characterized in that:
Also comprise the multipolymer that produces after the reaction monomers of described polyethylene terephthalate or polybutylene terephthalate and one or more comonomer copolymerization, described comonomer is the above polyprotonic acid of above polyvalent alcohol of ternary or ternary or its acid anhydrides or equal resorcylic acids;
Be evenly distributed with one or more Lewis acids in the described multipolymer, described Lewis acid adds before copolyreaction takes place, and it is zinc chloride or aluminum chloride or germanium chloride or tin chloride or iron(ic) chloride or nickelous chloride or magnesium chloride or cupric chloride.
2, according to claim 1ly contain lewis acidic copolyester fire retardant material, it is characterized in that the above polyvalent alcohol of ternary is glycerine or tetramethylolmethane or Xylitol or sorbyl alcohol or gallic acid.
3, according to claim 1ly contain lewis acidic copolyester fire retardant material, it is characterized in that polyprotonic acid that ternary is above or its acid anhydrides are fourth four alkane tetracarboxylic acids or the third three acid or aconitic acid or mellic acid or pentamethylene tetracarboxylic acid or trimellitic acid list acid anhydride or pyromellitic acid anhydrides.
4, according to claim 1ly contain lewis acidic copolyester fire retardant material, it is characterized in that the above polyprotonic acid of ternary is a citric acid.
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CN1101356A (en) * | 1992-11-23 | 1995-04-12 | 阿克奥化学技术有限合伙 | Preparation of polyesters from polyethers by an ester-insertion process |
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CN1396206A (en) * | 2002-08-12 | 2003-02-12 | 四川大学 | Phosphorus-contained flame-retarding nano-class ethanediol polyterephthalate/laminated silicate composition and its preparing process and application |
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CN1101356A (en) * | 1992-11-23 | 1995-04-12 | 阿克奥化学技术有限合伙 | Preparation of polyesters from polyethers by an ester-insertion process |
WO1999064515A1 (en) * | 1998-06-05 | 1999-12-16 | Basf Aktiengesellschaft | Thermoplastic polyester molding materials with enhanced stability |
JP2001207041A (en) * | 2000-01-26 | 2001-07-31 | Mitsubishi Engineering Plastics Corp | Thermoplastic resin composition |
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