CN1284816C - Method for preparing flame-resisting polyester in phosphorus series - Google Patents
Method for preparing flame-resisting polyester in phosphorus series Download PDFInfo
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- CN1284816C CN1284816C CN 200410022250 CN200410022250A CN1284816C CN 1284816 C CN1284816 C CN 1284816C CN 200410022250 CN200410022250 CN 200410022250 CN 200410022250 A CN200410022250 A CN 200410022250A CN 1284816 C CN1284816 C CN 1284816C
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- ethylene glycol
- flame retardant
- acid
- glycol ester
- benzenephosphonic
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- 238000000034 method Methods 0.000 title claims abstract description 49
- 229920000728 polyester Polymers 0.000 title claims abstract description 42
- 150000003017 phosphorus Chemical class 0.000 title description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 189
- 239000003063 flame retardant Substances 0.000 claims abstract description 111
- 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 53
- 230000032050 esterification Effects 0.000 claims abstract description 45
- 238000005886 esterification reaction Methods 0.000 claims abstract description 45
- -1 propionic acid glycol ester Chemical class 0.000 claims abstract description 34
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 31
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 28
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 14
- 239000011574 phosphorus Substances 0.000 claims abstract description 14
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 claims description 35
- 239000011259 mixed solution Substances 0.000 claims description 25
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000006068 polycondensation reaction Methods 0.000 abstract description 16
- 239000000835 fiber Substances 0.000 abstract description 11
- 239000004744 fabric Substances 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 abstract 2
- DILJSNXGQARQSW-UHFFFAOYSA-N OP(O)(O)C1=CC=CC=C1 Chemical compound OP(O)(O)C1=CC=CC=C1 DILJSNXGQARQSW-UHFFFAOYSA-N 0.000 abstract 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000012757 flame retardant agent Substances 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract 1
- 235000019260 propionic acid Nutrition 0.000 abstract 1
- 239000000047 product Substances 0.000 description 21
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 13
- 238000004043 dyeing Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000004753 textile Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 8
- 239000000178 monomer Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000007670 refining Methods 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 4
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920001634 Copolyester Polymers 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012661 block copolymerization Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- VTTMEWHZJTZMDN-UHFFFAOYSA-N ethane-1,2-diol phenylphosphonic acid Chemical compound C(CO)O.C1(=CC=CC=C1)P(O)(O)=O VTTMEWHZJTZMDN-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 241000909859 Attacus atlas Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 1
- 230000001195 anabolic effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Artificial Filaments (AREA)
- Fireproofing Substances (AREA)
Abstract
The present invention relates to a method for preparing flame retardant phosphorus polyester, which comprises: fine terephthalic acid, ethylene glycol, a catalyst and an auxiliary agent are used for esterifying; after esterification is ended, the mixed liquor of propionic acid glycol ester, radical phosphoric acid glycol ester, 2-propyloic phenyl phosphorous acid and a flame retardant agent of ethylene glycol is added for polycondensation according to a conventional polycondensation technological method to obtain flame retardant polyester slices. Fibers and fabrics made of the flame retardant polyester slices produced by the method have good flame retardant stability, after the flame retardant polyester slices are dyed, the flame retardant performance of the flame retardant polyester slices are basically unchanged, and the flame retardant performance LOI of curtain fabric products can exceed 32%. The present invention also has the advantages of less raw material variety, simple technological process and economic cost reduction.
Description
Technical field:
The present invention relates to a kind of manufacture method of not halogen-containing phosphorus series flame-resisting copolyesters of Polymer Synthesizing Halogenless fire retarded polymer new material technology field, particularly a kind of fire-retardant good stability.
Background technology:
Along with the enhancing of people's fire safety consciousness, the raising of economic and technique level, for the needs of the safety of life and property that ensures people, countries in the world all in various degree textiles is implemented the grade standard of the mandatory rules of law and flame retardant textiles.The flame retardant properties of flame retardant textiles mainly is to differentiate its quality by the limiting oxygen index(LOI) (LOI%) and the damage degree of check product, and for example China's national standard adopts the method for equivalent international standard flame retardant textiles to be divided into " difficult combustion B1 level " (LOI% 〉=32%) and " fire-retardant B2 level " (32%＞LOI% 〉=26%).
The fire-retardant of textiles has two kinds of methods to obtain, and the one, the fire-retardant aftertreatment of textiles, its defective is that flame retardant properties can not be lasting, the obvious variation of the appearance property of textiles, and because of using halogen flame to produce toxic substance; The 2nd, the fibre-forming polymer and the fiber thereof of used for textiles have flame retardant resistance, obtain by copolymerization, the flame retardant textiles that adopts this method to obtain can overcome the defective of fire-retardant post-treating method fully, but, at present the flame retardant properties (LOI) of copolymerization flame retardant products is generally lower, and especially flame retardant properties (LOI) majority of the flame-retardant textile product that is processed into of phosphorous flame-retardant polyester does not reach " difficult combustion B1 level ".According to " synthetic fiber industry " (Vol.No4) among the P41 " various countries manufacturer (company) fire-retardant fibre characteristics comparison sheet both at home and abroad " described, the LOI of the fire-retardant fibre product of producing is all between 27～32% both at home and abroad.About rules and regulations, " difficulty combustion B1 level " (LOI 〉=32%) product is used in most again requirements such as the decoration in high-grade hotel and the transportation means according to both at home and abroad.
Improve fire-retardant stability, the key problem in technology of phosphorus series flame-resisting production of polyester is how to select suitable reactive flame retardant, the reaction active groups of fire retardant is more near the activity of polyester monocase, when polymerization, just can react more, and reaction is just complete, fabric when dyeing fire-retardant stability just can be good more, easy more reaching " difficult combustion B1 level " in addition also should be considered the easiness and the economy of production.
Reported in the past that more was that direct use " 2-propyloic benzenephosphonic acid " is produced flame retardant polyester with monomer copolymerization.As " a kind of preparation method of flame-retarding phosphorus copolymerized terylene chips " of Qilu Chemical Fibre Group Co Ltd, Jinan in January, 2002 application, number of patent application is 02109909.X, its method is: adding phosphorus before esterification finishes post polymerization is reactive flame retardant 2-propyloic benzenephosphonic acid, the content of fire retardant add-on in section is 2～6wt%, fire retardant is prepared by 1: 1 weight ratio by 2-propyloic benzenephosphonic acid and ethylene glycol earlier, be warming up to 140～160 ℃ of ethylene glycol (EG) modulating liquids that obtain fire retardant, again this modulating liquid be added to terephthalic acid and ethylene glycol esterification and finish polycondensation in the preceding system of post polymerization and obtain the flame retardant polyester section.This method is because the active group at its fire retardant two ends active group and ethylene glycol terephthalate monomer two ends is different, when polymerization, be difficult to form block copolymerization, most polyreactions occur in the two ends of molecular chain, and the part fire retardant is still located unpolymerized admixture.Fiber when its fire retardant is aggregated in the end of the chain and fabric run into the effect of painted high temperature, colour additive and medium and fall down from the end of the chain, cause flame retardant properties to descend greatly; Just run away fully when dyeing if be in unpolymerized admixture, the usage quantity that often strengthens fire retardant also is not easy to improve the flame retardant properties of product.
After " 2-propyloic benzenephosphonic acid " or other fire retardant further made derivative, with the polyester monomer polymerization report is arranged also again.Day disclosure special permission communique is disclosed by Sanyo Chemical Industries, Ltd.'s application on December 16th, 1992, and (spy opens flat 4-364196 to the wise husband in gloomy open country for Morino, Tetsuo) " preparation of phosphine ester reactive flame retardant and derivative thereof " that waits the people to invent.Its method is to use (Ph) CH of 2-propyloic benzenephosphonic acid HOP (O)
2CH
2OH and methyl alcohol CH
3The OH reaction generates (Ph) CH of HOP (O)
2CH
2OMe is added dropwise to oxyethane or propylene oxide again, and addition reaction obtains phosphine ester derivative (A-1) formula fire retardant HOCH under vacuum and nitrogen-sealed condition
2CH
2OP (O) is CH (Ph)
2CH
2OMe; Perhaps (A-1) formula fire retardant is added the oxyethane heating and obtain phosphine ester derivative (B-1) formula fire retardant HOCH in the presence of hydration manganese acetate and nitrogen
2CH
2OP (O) is CH (Ph)
2CH
2CO
2CH
2CH
2OH.(A-1) the formula fire retardant or (B-1) formula fire retardant and ethylene glycol terephthalate copolymerization obtain flame-retardant polymer, the oxygen index of this polymkeric substance embodiment is 29～30%, the oxygen index of comparative example is 19%.
And for example disclosedly apply in 3 days Augusts nineteen ninety-five of Patent Cooperation Treaty (PCT) by Sanyo Chemical Industries, Ltd., Tanaka respects time (TANAKA, " organic phosphine is the method for making and the reactive flame retardant of carboxylate " of people's invention such as Keiji), international open designation is WO95/20593.Its method is: with the compound low-grade monobasic alcohol esterification of dichloro phosphine-derivatives and (different) vinylformic acid reaction generation, to react the compound that generates solid alkali metal oxyhydroxide or alkaline earth metal hydroxides or the neutralization of their aqueous solution again, obtain the refining thing that organic phosphine is an alkyl ester compound after making with extra care.The organic phosphine that obtains in the method is that the refining thing and the ethylene glycol of alkyl carboxylate carries out transesterification reaction, and obtaining organic phosphine is the refining thing of alkyl ester cpds, and should refining thing or its ethylene glycol solution anabolic reaction sex flame retardant.Use the alkyl ester, hydroxyalkyl of this refining thing copolymer composition again as polyester.
The phosphine that above-mentioned two kinds of methods are made be the derivative flame retardant two ends active group near the active group at polymerization single polymerization monomer ethylene glycol terephthalate two ends, overcome the shortcoming that is difficult to carry out block copolymerization preferably, can improve the fire-retardant stability of flame retardant polyester, the flame retardant properties height.But these two kinds of methods exist all that operational path is long, reactions steps is more, use raw material type too much, be easy to generate by product and shortcoming such as need make with extra care.
Summary of the invention:
The manufacture method that the purpose of this invention is to provide a kind of phosphorus series flame-resisting copolyesters improves fire-retardant fibre and the fire-retardant stability of fabric product in dyeing course thereof to reach, and simplifies technical process simultaneously, reduces the raw material type that uses, and reduces the purpose of Financial cost.
The method that the present invention adopts is: use pure terephthalic acid, ethylene glycol, catalyzer, auxiliary agent to carry out esterification, before finishing post polymerization, esterification adds propionic acid ethylene glycol ester group benzenephosphonic acid glycol ester and 2-propyloic benzenephosphonic acid and ethylene glycol fire retardant mixed solution, carry out esterification, polymerization, the section of acquisition flame retardant polyester, wherein propionic acid ethylene glycol ester group benzenephosphonic acid glycol ester is to generate by ethylene glycol and the direct esterification of 2-propyloic benzenephosphonic acid, and phosphorus (P) content that fire retardant mixed solution add-on is controlled to be in the section is 5000～10000ppm.
Above-mentioned fire retardant mixed solution is to be mixed by 1: 1～1: 1.8 weight ratio with ethylene glycol by 2-propyloic benzenephosphonic acid, stir, under condition of normal pressure, between 150～200 ℃, carry out esterification, control distillates the water yield, makes esterification yield between 50～96.5%, obtains propionic acid ethylene glycol ester group benzenephosphonic acid glycol ester, and with 2-propyloic benzenephosphonic acid and the formed mixed solution of ethylene glycol, the structural formula of the propionic acid ethylene glycol ester group benzenephosphonic acid glycol ester in the fire retardant mixed solution is:
In the above-mentioned fire retardant mixed solution propionic acid ethylene glycol ester group benzenephosphonic acid glycol ester, 2-propyloic benzenephosphonic acid, the shared ratio of ethylene glycol be respectively 32.5～65.5%, 1.7～23.2%, 32.8～44.3%.
The inventive method is divided two steps, the first step is spent glycol (EG) and commercially available fire retardant 2-propyloic benzenephosphonic acid direct esterification generation propionic acid ethylene glycol ester group benzenephosphonic acid glycol ester, make propionic acid ethylene glycol ester group benzenephosphonic acid glycol ester and 2-propyloic benzenephosphonic acid and ethylene glycol form the fire retardant mixed solution, with the propionic acid ethylene glycol ester group benzenephosphonic acid glycol ester in this fire retardant mixed solution as polymerization single polymerization monomer: second step was to use the pure terephthalic acid, ethylene glycol, auxiliary agent carries out esterification, finish the back in esterification and add the fire retardant mixed solution that the first step of the present invention is made, catalyzer is made the polyester slice of flame retardancy then with conventional polycondensating process method.
Concrete grammar of the present invention is:
The first step, preparation propionic acid ethylene glycol ester group benzenephosphonic acid glycol ester, 2-propyloic benzenephosphonic acid, ethylene glycol fire retardant mixed solution.2-propyloic benzenephosphonic acid and 1: 1 by weight～1: 1.8 ratio of ethylene glycol joined in the esterifying kettle stir, under normal pressure, 150～200 ℃ of conditions, carry out esterification, control distillates the water yield, make esterification yield between 50～96.5%, obtain propionic acid ethylene glycol ester group benzenephosphonic acid glycol ester, and form mixed solution with 2-propyloic benzenephosphonic acid and ethylene glycol, wherein propionic acid ethylene glycol ester group benzenephosphonic acid glycol ester, 2-propyloic benzenephosphonic acid, ethylene glycol proportion are respectively 32.5～65.5%, 1.7～23.2%, 32.8～44.3%.
Second step, the polymerization of flame retardant polyester.Earlier change ethylene glycol (EG), 1: 1.2 in molar ratio～1: 1.3 ratio of pure terephthalic acid (PTA) over to esterifying kettle after being modulated into slurry, carry out esterification under 250～260 ℃ and condition of normal pressure, esterification yield reaches end esterification in back 95% or more.Be in the system before the ratio of 5000～10000ppm propionic acid ethylene glycol ester group benzenephosphonic acid glycol ester that the first step is made and 2-propyloic benzenephosphonic acid and ethylene glycol fire retardant mixed solution join polymerization in phosphorus (P) content in the section then, stir, obtain the needed high flame retardant polyester slice of the object of the invention according to the polycondensating process polymerization of routine.
The present invention compared with prior art has tangible characteristics and effect:
(1) make polymerization single polymerization monomer with propionic acid ethylene glycol ester group benzenephosphonic acid glycol ester, the reactive behavior of the reactive behavior of its two ends group and ethylene glycol terephthalate two ends group is basic identical, can be aggregated in the regular block state of formation on the macromolecular chain when polycondensation.Mainly be propionic acid ethylene glycol ester group benzenephosphonic acid glycol ester in propionic acid ethylene glycol ester group benzenephosphonic acid glycol ester and 2-propyloic benzenephosphonic acid and the ethylene glycol fire retardant mixed solution, small part 2-propyloic benzenephosphonic acid also can be aggregated in the regular block state of formation on the macromolecular chain then because of bringing out with acting in conjunction of propionic acid ethylene glycol ester group benzenephosphonic acid glycol ester.
(2) because the fire retardant monomer forms regular block state in the fire-retardant polyester molecular chain, so:
A. can control the interpolation flame retardant amount and obtain needed flame retardant products, particularly difficult combustion product.
B. the fiber and the fire-retardant stability of fabric product that are processed into of this flame retardant polyester improves greatly, flame retardant properties is unaffected substantially in the time of can making it run into medium such as high temperature, dyestuff and auxiliary agent, soda acid in dyeing and back arrangement process, and dye uptake when boiling dyeing at normal pressure and colour fastness are better than ordinary polyester greatly.
(3) operational path is shorter, uses raw material type few.Except 2-propyloic benzenephosphonic acid the synthetic used raw material of polyester own, so operation steps is simple, the low economy and facility of cost.
Embodiment:
Below the embodiment of the invention is further described.
Embodiment 1:
1, the first step, preparation propionic acid ethylene glycol ester group benzenephosphonic acid glycol ester and 2-propyloic benzenephosphonic acid and ethylene glycol fire retardant mixed solution:
Get commercially available phosphorous 14.5%, moisture 2% 2-propyloic benzenephosphonic acid 45kg, ethylene glycol 55kg, join in the esterifying kettle, under stirring state, progressively be warmed up to 165 ℃, under condition of normal pressure, carry out esterification, suitably improve temperature of reaction to 170 ℃ before esterification finishes, collect distilled water and reach 7.6kg, negate answers product to measure acid number with control with determine required reaction end, esterification yield is 90%, filters standby.This product is propionic acid ethylene glycol ester group benzenephosphonic acid glycol ester and 2-propyloic benzenephosphonic acid and ethylene glycol fire retardant mixed solution, wherein contains propionic acid ethylene glycol ester group benzenephosphonic acid glycol ester 60.6%, 2-propyloic benzenephosphonic acid 4.8%, ethylene glycol 34.4%.
2, second step, the polycondensation of esterification and flame retardant polyester:
Get pure terephthalic acid (PTA) 200kg, after being modulated into slurry, ethylene glycol (EG) 185kg changes esterifying kettle over to, under 255 ℃ of temperature and condition of normal pressure, carry out esterification, finish esterification behind the water 44kg that the collection esterification produces, behind esterification products immigration polymeric kettle, the fire retardant mixed solution 28kg (wherein containing ethylene glycol 9.7kg) that the adding the first step is made is in polymeric kettle, add catalyzer, auxiliary agent, stir, with the method for the polycondensation of polyester of routine in rough vacuum, precondensation under 250～270 ℃ the temperature condition is in the high vacuum of about 50Pa, polycondensation obtains the flame retardancy polyester slice of wanting required for the present invention under 283 ℃ the temperature condition.Phosphorus (P) content is 7650ppm in this fire-retardant polyester section.
Embodiment 2:
1, the first step, preparation propionic acid ethylene glycol ester group benzenephosphonic acid glycol ester and 2-propyloic benzenephosphonic acid and ethylene glycol fire retardant mixed solution: method is identical with embodiment 1.
2, second step, the polymerization of flame retardant polyester:
Get pure terephthalic acid (PTA) 200kg, ethylene glycol (EG) 185kg, esterification technique condition and working method are with embodiment 1, after esterification products moves into polycondensation vessel, the fire retardant mixed solution 20kg (wherein containing EG6.9kg) that the adding the first step is made is in polymeric kettle, catalyzer, promoter addition, polycondensating process condition and working method obtain the flame retardancy polyester slice of wanting required for the present invention with embodiment 1.Phosphorus content is 5560ppm in this fire-retardant polyester section.
Embodiment 3:
1, the first step prepares propionic acid ethylene glycol ester group benzenephosphonic acid glycol ester and 2-propyloic benzenephosphonic acid and ethylene glycol fire retardant mixed solution: get commercially available phosphorous 14.5%, moisture 2% 2-propyloic benzenephosphonic acid 45kg, ethylene glycol 55kg, join in the esterifying kettle, under stirring state, progressively be warming up to 165 ℃, under condition of normal pressure, carry out esterification, before finishing, esterification suitably improves temperature of reaction to 170 ℃, collect distilled water and reach 6.1kg, negate answers product to measure acid number with control and definite required reaction end, esterification yield is 70%, filters standby.This product is propionic acid ethylene glycol ester group benzenephosphonic acid glycol ester and 2-propyloic benzenephosphonic acid and ethylene glycol mixture, wherein contains propionic acid ethylene glycol ester group benzenephosphonic acid glycol ester 46.4%, 2-propyloic benzenephosphonic acid 14.1%, ethylene glycol 39.5%.
2, second step, the polycondensation of esterification and flame retardant polyester:
Get pure terephthalic acid (PTA) 200kg, ethylene glycol (EG) 185kg, esterification technique condition and working method are with embodiment 1, after esterification products moves into polycondensation vessel, the fire retardant mixed solution 20kg (wherein containing EG7.9kg) that the adding present embodiment the first step is made is in polymeric kettle, add catalyzer, auxiliary agent, stir, in rough vacuum, 250～270 ℃ temperature condition precondensation, polycondensation obtains the flame retardancy polyester slice of wanting required for the present invention under the high vacuum of about 50Pa, 283 ℃ temperature condition with the method for the polycondensation of polyester of routine.Phosphorus (P) content is 5560ppm in this fire-retardant polyester section.
Comparative example one:
Get pure terephthalic acid (PTA) 200kg, ethylene glycol (EG) 185kg changes esterifying kettle over to after being modulated into slurry, esterification technique condition and working method are with embodiment one, after esterification products moves into polycondensation vessel, add the 2-propyloic benzenephosphonic acid ethylene glycol solution 27.5kg (wherein containing EG13.75kg) that is mixed with in 2-propyloic benzenephosphonic acid and 1: 1 ratio of ethylene glycol (EG) weight in polycondensation vessel, catalyzer, promoter addition, polycondensating process condition and working method obtain required flame retardant polyester section with embodiment one.Phosphorus content is 7660ppm in this flame retardant polyester section.
Comparative example two:
Get pure terephthalic acid (PTA) 200kg, ethylene glycol (EG) 185kg changes esterifying kettle over to after being modulated into slurry, esterification technique condition and working method are with embodiment one, after esterification products moves into polycondensation vessel, the 2-propyloic benzenephosphonic acid ethylene glycol solution 19.5kg (wherein containing EG9.75kg) that adds comparative example one identical collocation method ratio is in polycondensation vessel, catalyzer, promoter addition, polycondensating process condition and working method obtain required flame retardant polyester section with embodiment 1.Phosphorus content is 5570ppm in this flame retardant polyester section.
Evaluation of result:
Resistance (difficulty) retardant polyester section according to embodiment and comparative example preparation, after further being processed into fiber (long filament and staple), again through weaving, dye the back arrangement, the fiber that obtains is measured its limiting oxygen index(LOI) LOI% with the LOI-1045 limiting oxygen index(LOI) instrument that U.S. ATLAS company produces, fabric is tested its flame retardant properties (LOI%) according to the method for GB8624-1997 and GB/T5454-1997 standard, and its test result sees the following form:
Flame retardant properties comparative evaluation's table of embodiment and comparative example product:
| Sequence number | Fire retardant esterification yield % | Section P (ppm) | Fiber LOI% | Curtain fabric LOI% | LOI changing conditions before and after the dyeing | ||
| Before the dyeing | After the dyeing | Before the dyeing | After the dyeing | ||||
| Embodiment 1 | 90 | 7650 | 32.8 | 32.7 | 36.6 | 36.5 | Substantially constant |
| Embodiment 2 | 90 | 5560 | 31.0 | 31.0 | 33.5 | 33.4 | Substantially constant |
| Embodiment 3 | 70 | 5560 | 31.0 | 30.8 | 33.4 | 33.2 | Substantially constant |
| Comparative example 1 | 7660 | 32.5 | 28.3 | 36.3 | 31.8 | Obviously reduce | |
| Comparative example 2 | 5570 | 30.8 | 27.2 | 32.8 | 27.6 | Obviously reduce | |
Data as can be seen from table: fiber and its fire-retardant good stability of fabric of being processed into the fire-retardant polyester of the inventive method manufacturing, dyeing before and dyeing after limiting oxygen index(LOI) LOI% remain unchanged substantially, the curtain kind fabric product of making can reach the requirement of GB8624B1 (difficult combustion B1 level LOI 〉=32%) standard fully, can satisfy the demand in market.
Claims (1)
1, a kind of manufacture method of phosphorus flame-retardant polyester, comprise and use the pure terephthalic acid, ethylene glycol, catalyzer, auxiliary agent carries out esterification, the fire retardant mixed solution that before esterification finishes post polymerization, adds propionic acid ethylene glycol ester group benzenephosphonic acid glycol ester and 2-propyloic benzenephosphonic acid and ethylene glycol, carry out esterification, polymerization, the section of acquisition flame retardant polyester, wherein propionic acid ethylene glycol ester group benzenephosphonic acid glycol ester is the phosphorus flame retardant that generates by ethylene glycol and the direct esterification of 2-propyloic benzenephosphonic acid, the content that fire retardant mixed solution add-on is controlled to be phosphorus in the section is 5000～10000ppm, described fire retardant mixed solution is mixed by 1: 1～1: 1.8 weight ratio with ethylene glycol by 2-propyloic benzenephosphonic acid, stir, under condition of normal pressure, carry out esterification between 150～200 ℃ of temperature, control distillates the water yield, make esterification yield between 50～96.5%, obtain propionic acid ethylene glycol ester group benzenephosphonic acid glycol ester, and the mixed solution that forms with 2 one propyloic benzenephosphonic acids and ethylene glycol, propionic acid ethylene glycol ester group benzenephosphonic acid glycol ester in the fire retardant mixed solution, 2-propyloic benzenephosphonic acid, the shared ratio of ethylene glycol is respectively 32.5～65.5%, 1.7～23.2%, 32.8～44.3%, wherein the structural formula of propionic acid ethylene glycol ester group benzenephosphonic acid glycol ester is:
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| CN 200410022250 CN1284816C (en) | 2004-04-08 | 2004-04-08 | Method for preparing flame-resisting polyester in phosphorus series |
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| CN 200410022250 CN1284816C (en) | 2004-04-08 | 2004-04-08 | Method for preparing flame-resisting polyester in phosphorus series |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101200820B (en) * | 2006-12-13 | 2010-05-19 | 中国石油天然气集团公司 | Method for preparing flame-proof polyester fiber |
| CN101333287B (en) * | 2007-06-29 | 2011-11-30 | 厦门翔鹭化纤股份有限公司 | Method for preparing fire retardant co-polymerization modified polyester |
| CN101376694B (en) * | 2007-08-30 | 2011-07-20 | 中国石化上海石油化工股份有限公司 | Preparation of flame-retardant polyester for preparing industrial fibre |
| CN101387035B (en) * | 2007-09-10 | 2011-07-20 | 东丽纤维研究所（中国）有限公司 | Bi-component flame-retardant fibre fabric |
| CN101148498B (en) * | 2007-10-18 | 2010-08-18 | 四川大学 | Degradable anti-flaming copolyester, preparation method thereof and mixing material prepared from the same and aliphatic polyester |
| CN101225158B (en) * | 2008-02-03 | 2010-09-29 | 四川大学 | Phosphoric flame-proof copolyester ionomer and preparation method thereof |
| CN101525420B (en) * | 2008-03-04 | 2012-01-18 | 东丽纤维研究所（中国）有限公司 | Fire retardant polyethylene terephthalate |
| TWI664203B (en) | 2017-10-11 | 2019-07-01 | 遠東新世紀股份有限公司 | Flame-retardant polyester and preparation method thereof |
| CN111139548A (en) * | 2018-11-02 | 2020-05-12 | 北京服装学院 | High-flame-retardant polyester PET and fiber thereof |
| CN109438686A (en) * | 2018-11-29 | 2019-03-08 | 上海炼升化工股份有限公司 | A kind of flame retardant polyester containing the liquid flame retardant based on diphenylphosphoryl propionic acid binaryglycol ester |
| CN109537080B (en) * | 2018-11-29 | 2021-05-11 | 上海炼升化工股份有限公司 | Liquid flame retardant based on phenyl phosphoryl propionic acid diethylene glycol ester and preparation method thereof |
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