CN1057472A - The manufacture method of reactive flame-retardant copolyester - Google Patents
The manufacture method of reactive flame-retardant copolyester Download PDFInfo
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- CN1057472A CN1057472A CN 91101260 CN91101260A CN1057472A CN 1057472 A CN1057472 A CN 1057472A CN 91101260 CN91101260 CN 91101260 CN 91101260 A CN91101260 A CN 91101260A CN 1057472 A CN1057472 A CN 1057472A
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- flame
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- tbs
- dmt
- transesterification reaction
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Abstract
The present invention makes flame retardant resistance, the method for the reactive flame-retardant copolyester that resistance toheat is good.This invention is with two [3.5-two bromo-4-(2-hydroxy ethoxy) phenyl] sulfones of a kind of BACN (being called for short TBS-2EO).Before transesterification reaction began, with TBS-2EO, DMT after EG mixes, added in the transesterification reactor, adds the mixture of composite catalyst calcium acetate and Cobaltous diacetate simultaneously, carries out transesterification reaction contains fire retardant with formation performed polymer.According to the different requirements to flame retardant properties, the fire retardant addition can change in 10-4% scope, is preferably in 8-6% (to DMT weight), and this moment, its limiting oxygen index(LOI) LOI value was 31.5-28.5.
Description
(1) carry out adding in the ester-exchange reaction fire retardant 10-4%(of the represented brominated and element sulphur of molecule formula I to DMT weight at dimethyl terephthalate (DMT) (DMT) and ethylene glycol (EG)) to make the reactive flame-retardant copolyester of flame retardant resistance and good thermal stability.
(X in the formula: elements such as expression Br or CL)
(2) in order to improve DMT and EG, TBS-2EO transesterification reaction speed, reduce the residence time of reactant in ester interchange vessel, the whiteness that improves copolyesters is the transesterification catalyst except that adding acetate, also add the represented compound of molecule formula II, addition is that 0.01-0.03%(is to DMT weight)
MeO （Ⅱ）
(Me in the formula: expression Zn, Mg, elements such as Pb)
The objective of the invention is to make the method for the good reaction-type flame-retarding co-polymeric acids of flame retardant resistance and thermotolerance.
As everyone knows, by DMT, EG or by PTA, EG can make fiber, film through the polyester of transesterify or the manufacturing of direct esterification method, or other forming composition, industry and civilian in be widely used.But because of polyester is combustible, its application is restricted.For this reason, require polyester is carried out fire-retardantization research.
Polyester carried out fire-retardantization research is known three kinds of methods.The one, in the polyester building-up process, add reactive flame retardant and make flame-proof copolyester by polycondensation.The 2nd, in the later stage of polyester building-up process, non-reactive flame retardant mixed in polyester fondant, carry out melt blending, this kind method equipment complexity, difficulty is big, and is difficult for mixing, and application is restricted.The 3rd, in the polyester spinning process,, sneak into by screw injector and to spin fire-retardant polyester fibre in the melt fire retardant or fire-retardant master granule.
The two kinds of methods in back, when fire-retardant fibre or fire-retardant fibre finished product or other forming composition were subjected to ambient conditions and influences, fire retardant oozed out from the surface of these finished product easily, and decompose and come off, the flame retardant properties reduction, use is restricted.Its flame retardant effect of the flame retardant polyester of Zhi Zaoing belongs to semi-permanent in this way.
The flame retardant polyester of first method manufacturing has permanent flame retardant effect.But addition hour, flame retardant effect is not obvious, and addition is easy to generate limiting viscosity and descends more for a long time, and fusing point reduces, and shortcomings such as thermostability variation bring difficulty for the processing of spinning processing or other forming composition, and its use also is restricted.Therefore it then is very important selecting the few high reactive flame retardant of flame retardant properties of a kind of addition.
Set forth among the United States Patent (USP) 3.794.617 with 2.2 a pair ofs [3.5-two bromo-4-(2-hydroxy ethoxies) phenyl] propane (being called for short TBA-EO) for fire retardant and DMT, EG under 210 ℃, after carrying out transesterification reaction, carry out polycondensation manufacturing flame-proof copolyester at 270-300 ℃ again and make fire-retardant polyester fibre with melt spinning method again.
Fraud point of this patent is that fire retardant TBA-EO fusing point is low for 117-120 ℃, decomposition temperature is 250 ℃, therefore when polycondensation, must make TBA-EO all participate in transesterification reaction in the past and enter and become heat-staple polymer fire retardant in the macromolecular chain of copolyesters at 245 ℃, further polycondensation becomes the high-molecular weight flame retardant polyester again.TBA-EO easily decomposes when surpassing 250 ℃, the copolyesters color and luster jaundice that obtains, and the thermostability variation, flame retardant properties reduces.Even begin fire retardant TBA-EO preceding and DMT in transesterify, carry out transesterification reaction behind the EG mixed melting again, because the TBA-EO molecular volume is bigger than EG, the activity performance is littler than EG, few with DMT collision probability, although EG is that the reactive behavior of excessive TBA-EO hydroxy ethoxy is identical with EG in reaction system in addition, but also inevitable some TBA-EO fails to form the polymer performed polymer of Heat stability is good and is free in the reaction system in ester-exchange reaction, cause in the reaction process of aftercondensated temperature to surpass 250 ℃ and decompose, give that manufacturing property is good to bring difficulty with the good flame-proof copolyester of whiteness.The flame-proof copolyester fusing point that obtains therefrom is also lower.When fire retardant TBA-EO content was 20-5%, the fusing point of its copolyesters was 230-254 ℃, and the decomposition temperature of this copolyesters is 355 ℃; Limiting oxygen index(LOI) LOI value is 28-22.5.This flame-proof copolyester only is to play fire retardation by bromo element when burning, only when large usage quantity, tangible flame retardant effect is arranged, and the fire retardant consumption increases, and damages polyester inherent premium properties again.Therefore it is not a kind of good fire retardant.
The present invention selects the represented BACN of a kind of molecule formula I two [3.5-two bromo-4-(2-hydroxy ethoxies) phenyl] sulfone (being called for short TBS-2EO) for use, and it is a kind ofly promptly to contain the ignition-proof element bromine at same intramolecularly, contains the compound of ignition-proof element sulphur again.Sulphur atom in molecule is a sexavalence, all is in the high oxidation state, and sulfuryl and adjacent two phenyl ring form conjugated system.Therefore, has very strong antioxidant property.Burning itself is exactly a kind of oxidizing reaction of fierceness.This compound with high antioxygenic property be present in copolyesters greater than just having excellent flame-retardant in the molecular chain.And the bromine radical that decomposites in burning can be caught and made the ongoing high-octane hydrogen radical of combustion reactions that combustion reactions is stopped.Therefore, TBS-2EO be a kind of can be in gas phase fire-retardant also can be in condensed phase the fire retardant of fire-retardant excellent property, under the less situation of consumption, just can demonstrate tangible flame retardant effect, and not damage polyester inherent premium properties.
The fusing point 234-237 of fire retardant TBS-2EO ℃, 311 ℃ of initial decomposition temperatures, higher because of the fire retardant decomposition temperature, even have a spot of TBS-2EO to be free in to have neither part nor lot in the system transesterification reaction also can therefore not decompose, polycondensation is with regard to easy handling like this.When the TBS-2EO addition was 10-4%, the fusing point of its copolyesters was 250-256 ℃, and decomposition temperature is 376-380 ℃, and limiting oxygen index(LOI) LOI value is 32.5-28.5.The thermostability height of flame-proof copolyester, spinning is easy, finished silk yield height.If when the addition of TBS-2EO is identical with amount among the United States Patent (USP) 3.794.617 in the polyester manufacturing processed, or the consumption that is lower than in the United States Patent (USP) all can obtain the LOI value more much higher than United States Patent (USP).Its result is shown in the I table.
The fire retardant TBS-2EO that the present invention uses adds when transesterification reaction begins, and the catalyzer that uses is the mixture of calcium acetate and Cobaltous diacetate.Because add after the TBS-2EO fire retardant in the transesterify process, transesterify speed is slack-off, so this patent adds a kind of promotor ZnO again, accelerates transesterification reaction speed.Make fire retardant TBS-2EO become integral part in the performed polymer by transesterification reaction, become the fire retardant of polymer, when carrying out polycondensation, more help improving the thermostability of flame retardant polyester like this, fire retardant is not come off, be easy to carry out the processing of spinning and other forming composition and then improve its flame retardant properties.
Use Sb during polycondensation
2O3 is a catalyzer, and triphenyl phosphite is a thermo-stabilizer, and sodium monophosphate is a metal chelating agent.In reaction system the adding of sodium monophosphate can with the acetate catalyst Ca that exists in the reaction system
Lv, Co
LvForm complex compound Deng metal ion, can eliminate the heat-degradation that metal ion at high temperature produces copolyesters.General addition is that 0.01-0.03%(is to DMT weight)
Transesterification reaction temperature when the present invention uses TBS-2EO to make flame-proof copolyester as fire retardant is 210 ℃, when the methyl alcohol discharge reaches 95% when above of theoretical amount, transesterification reaction end.Under 240-250 ℃, carry out 40-60 minute normal pressure polycondensation then, steam the ethylene glycol that produces in excessive ethylene glycol and the reaction process.Afterwards, carry out rough vacuum polycondensation in 90 minutes at 260-270 ℃, resulting pressure is controlled at 133Pa, steams after a large amount of ethylene glycol of initial stage polycondensation generation, carries out the high vacuum polycondensation again, and temperature is controlled at 270-280 ℃, and time 3-4 hour, resulting pressure≤40Pa.When melt viscosity reached set(ting)value, blowing was annotated bar, enters dicing machine by cooling trough, was cut into the flame retardant polyester section of 5 * 5 * 2mm, and screening back packing is finished product.So far finished the present invention.
Flame-retardant textile with manufacturing of the present invention is carrying out measuring its vertical combustion performance by the standard method of GB5455-85 vertical combustion behind 50 washing and dryings more repeatedly under the similarity condition after 80-90 ℃ of washing taking-up in 30 minutes is clean with flushing with clean water in the aqueous solution that contains 4 grams per liter washing powder.Measure its limiting oxygen index(LOI) value by the GB5455-85 method, test result is shown in the 2nd table and the 3rd table.By test result as can be seen, under alkaline condition, after 80-90 ℃ of relatively harsher high temperature washing of process, basic identical even also slightly reduction before after flame time and char length and the washing, this explanation has permanent flame retardant effect with this flame-proof copolyester woven fabric after spinning.The slurry of fabric face is washed off behind the fabric washing, and by the 2nd table as can be known, its after flame time and char length do not change, but the LOI value has raising shown in the 3rd table.This explanation fabric slurry has combustion-supporting effect, and the LOI value of washing off behind the slurry just really characterizes flame-resistant terylene inherent flame-retarding characteristic.
At DMT and EG, in the TBS-2EO ester-exchange reaction as metal ion in the acetate of catalyst for ester exchange reaction such as calcium, cobalts etc. form metal complex with the hydroxyl or the hydroxyl among the TBS-2EO of ethylene glycol, this metal complex and dimethyl terephthalate (DMT) form a kind of cyclic intermediate, this ring-type intermediate progressively decomposes with certain speed and discharges methyl alcohol and form ethylene glycol terephthalate, the present invention adds the represented metal oxide of molecule formula II it can accelerate the formation of ethylene glycol metal complex and hydroxy ethoxy metal complex in the transesterify process, thereby can improve transesterification reaction speed, test-results is shown in the 4th table.
The manufacture method system of the fire retardant that the present invention uses adopts four mistake bisphenol Ss and simple substance bromine to carry out substitution reaction and generates tetrabromo-bisphenol s, carries out addition reaction with oxyethane in solvent again.Temperature of reaction can be carried out in 40-80 ℃ of scope.Used flux can be that the halides of hydro carbons also can be the mixture of alcohols or alcohol and water.Burn the agent fusing point through its resistance behind the recrystallization and can reach 234-237 ℃.
Sour composition used in the present invention is identical with conventional polyester with pure composition.As dicarboxylic acid component can be terephthalic acid, dimethyl terephthalate (DMT), m-phthalic acid or dimethyl isophthalate.What the present invention was used is dimethyl terephthalate (DMT).As pure composition can be ethylene glycol, propylene glycol, 1.4-butyleneglycol.What the present invention was used is ethylene glycol.
The polycondensation catalyst that the present invention uses is an antimonous oxide.To 0.04% of DMT consumption.Transesterification catalyst can be a kind of in the acetate of zinc, magnesium, calcium, cobalt, manganese etc. or their two kinds of mixtures.The present invention uses is that the mixture of the Cobaltous diacetate (all to DMT weight) of 0.06% calcium acetate and 0.01% is transesterification catalyst.
The present invention uses the fire retardant shown in the molecule formula I to begin preceding adding in transesterify, also can begin preceding adding in polycondensation.The present invention be before transesterification reaction begins with fire retardant and DMT, EG mixes the back and adds in the transesterification reactor and carries out transesterification reaction.The fire retardant addition can be preferably in the scope interior (to DMT weight) of 8-6% at 10-4% according to the requirement to flame retardant resistance.
Explanation the present invention below gives an actual example.
[η] in the example measures down at 25 ℃ with phenol-four oxidative ethane, and the part in the example is an expression weight.Fusing point is to measure with melting point detector.Carboxyl-content is to measure with ordinary method, and the LOI value is measured with the limited oxygen index instrument.
The example I
With DMT600 part, EG420 part, fire retardant TBS-2EO36 part, 0.36 part of calcium acetate, 0.06 part of Cobaltous diacetate joins after the mixing in 2.5 liters of stainless steel transesterification reactors together, carries out transesterification reaction; Temperature is controlled at below 210 ℃, and when the methyl alcohol quantity of distillate reaches 95% when following of theoretical amount, transesterification reaction finishes.Import again in 2.5 liters of stainless steel batch condensation polymerization reactors, add 0.36 part of The catalytic antimony trioxide, begin to carry out the normal pressure polycondensation and steam the ethylene glycol that generates in excessive ethylene glycol and the reaction, temperature is controlled at below 250 ℃, the normal pressure polycondensation adds 0.12 part of one package stabilizer triphenyl phosphite after 60 minutes, sodium monophosphate begins to change over to rough vacuum polycondensation temperature for 0.06 part and is controlled at 250-265 ℃, resulting pressure is 133Pa, begin to change over to the high vacuum polycondensation after 90 minutes, temperature is controlled at 270-282 ℃, and resulting pressure is controlled at below the 55Pa, melt viscosity can reach set(ting)value after 340 minutes, the beginning blowing, casting, pelletizing are the finished product.Measure flame-proof copolyester fusing point Tm=256 ℃, [η] value 0.56, the LOI value is 31.5.Test-results is listed in the 5th table.
Example 2
Prescription is fully identical with the example I, just at DMT and EG, adds transesterify promotor ZnO 0.12 in the ester-exchange reaction of TBS-2EO.Methyl alcohol quantity of distillate 230mL, ester exchange rate 94.65%, 105 minutes total transesterify time, the condition of normal pressure polycondensation, rough vacuum polycondensation, high vacuum polycondensation is with routine I.300 minutes polycondensation time, experimental result is listed in the 5th table.
The comparative example I
Material proportion is with the example I, and fire retardant changes TBA-EO into, and 60 parts of additions, the addition of catalyzer and stable composition are also with the example I.The high vacuum condensation temperature is controlled at 275 ℃, contracts 350 minutes time, and its experiment the results are shown in the 5th table.
The 1st table
| Embodiment | United States Patent (USP) 3.719.617 | ||
| The TBS-2EO consumption | The LOI value | The TBA-EO consumption | The LOI value |
| 4 6 8 10 | 28.5 31.5 32.0 32.5 | 5 10 15 20 | 22.5 23.0 24.0 28.0 |
The 4th table
| Embodiment | Calcium acetate (%) | Calcium acetate (%) | Zinc oxide (%) | Transesterify total time (branch) | Ester exchange rate (%) |
| 1 2 3 4 | 0.06 0.06 0.06 0.06 | 0.01 0.01 0.01 0.01 | 0 0.01 0.015 0.020 | 165 150 120 105 | 95.05 94.24 94.65 94.65 |
Annotate: catalyzer and promotor addition are all to DMT weight %
Claims (4)
1, a kind of flame retardant resistance of preparation and the good reactive flame-retardant copolyester of thermotolerance is characterized in that adding a kind of BACN TBS-2EO, and structural formula is
,
(x∶Br.cl)
When transesterification reaction, (ZnO, MgO PbO) improve transesterification reaction speed for promotor to add a kind of metal oxide.
When polycondensation, add by sodium monophosphate (NaH
2Po
4) and the compound stablizer formed of triphenyl phosphite, improve the flame retardant polyester thermostability.
2, newly state the preparation flame-proof copolyester by right 1, the add-on that it is characterized in that BACN TBS-2EO is that 10-4%(is to DMT weight) wherein be best with 8-6%.Its limiting oxygen index(LOI) LOI value is 31.5-28.5.
3, by the flame-proof copolyester of right 1 described preparation, it is characterized in that the metal oxide addition is 0.01-0.03%, wherein is best with 0.015%-0.020%.
4, by the flame-proof copolyester of right 1 described preparation, it is characterized in that the add-on of sodium monophosphate is 0.01-0.03%, be preferably in 0.02%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91101260 CN1057472A (en) | 1991-02-26 | 1991-02-26 | The manufacture method of reactive flame-retardant copolyester |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91101260 CN1057472A (en) | 1991-02-26 | 1991-02-26 | The manufacture method of reactive flame-retardant copolyester |
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| CN1057472A true CN1057472A (en) | 1992-01-01 |
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| CN 91101260 Pending CN1057472A (en) | 1991-02-26 | 1991-02-26 | The manufacture method of reactive flame-retardant copolyester |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101121776B (en) * | 2006-08-08 | 2010-10-06 | 远东新世纪股份有限公司 | Method for preparing polyester using non-antimony catalyst |
| CN101200834B (en) * | 2006-12-12 | 2010-12-08 | 东丽纤维研究所（中国）有限公司 | Flame-proof textile |
| CN101309995B (en) * | 2005-09-16 | 2011-08-03 | 沙伯基础创新塑料知识产权有限公司 | Flame retardant polysulfone blends |
| CN101440156B (en) * | 2008-12-18 | 2011-08-31 | 四川大学 | Phosphor-containing halogen-free flame-retardant polylactic acid, preparation thereof and flame-retardant material blended therewith |
-
1991
- 1991-02-26 CN CN 91101260 patent/CN1057472A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101309995B (en) * | 2005-09-16 | 2011-08-03 | 沙伯基础创新塑料知识产权有限公司 | Flame retardant polysulfone blends |
| CN101121776B (en) * | 2006-08-08 | 2010-10-06 | 远东新世纪股份有限公司 | Method for preparing polyester using non-antimony catalyst |
| CN101200834B (en) * | 2006-12-12 | 2010-12-08 | 东丽纤维研究所（中国）有限公司 | Flame-proof textile |
| CN101440156B (en) * | 2008-12-18 | 2011-08-31 | 四川大学 | Phosphor-containing halogen-free flame-retardant polylactic acid, preparation thereof and flame-retardant material blended therewith |
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