CN102691133A - Flame-retardant polyester fiber and production method thereof - Google Patents
Flame-retardant polyester fiber and production method thereof Download PDFInfo
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- CN102691133A CN102691133A CN2011100735112A CN201110073511A CN102691133A CN 102691133 A CN102691133 A CN 102691133A CN 2011100735112 A CN2011100735112 A CN 2011100735112A CN 201110073511 A CN201110073511 A CN 201110073511A CN 102691133 A CN102691133 A CN 102691133A
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Abstract
The invention discloses a flame-retardant polyester fiber and a production method thereof; the flame-retardant polyester fiber is obtained by mixing and spinning flame-retardant copolymerization master batch and common polyester; the flame-retardant polyester fiber has a phosphorus content of 5000-7500 ppm, has excellent flame retardancy, a good color, a high melting point, superior heat resistance, and low cost, and is widely applicable to decoration material fields such as curtains, carpets, and materials and equipment in vehicles.
Description
Technical field
The present invention relates to a kind of fire-retardant polyester fibre and production method thereof.
Background technology
PETG (PET) has characteristics such as high-modulus, high strength, tensile elasticity be good, and in polyester, its output is the biggest in the world, and purposes is also extensive.Pet fiber; Be called for short terylene; Also be the kind that output is maximum in the synthetic fiber, purposes is the widest, polyster fibre has excellent mechanical intensity and tensile property, is widely used in fields such as clothes, industry, communications and transportation, ornament materials.
But because pet fiber belongs to flammable article; Limited it greatly in the application that requires fire-retardant field, such as the ornament materials in military affairs, aviation, communications and transportation, hotel, public place of entertainment, hospital, cinema, supermarket etc., fire-fighting etc.The whole world is annual because the inflammable fire that causes of fibrous material has caused enormous economic loss.
Recently functionalization, the special typeization research along with polyester fiber becomes increasingly active; People have also carried out going deep into extensive studies to the anti-flammability of polyester fiber; Developed multiple fire retardant; Invented multiple flame-proof treatment method, such as fire retardant surface modification, blend interpolation, copolymerization interpolation etc., various fire-retardant polyester fibres also constantly emerge thereupon.
Halogen-containing; Such as fire retardant chloride, bromo element; In fire retardant, be widely used; But the fire-retardant polyester fibre of halogen-containing flame retardant has discharged excitant and corrosive toxic hydrogen halide and cigarette easily when burning, environment and personal safety are threatened, thereby its application is restricted.
Some inorganic material also can be used for fire retardant, such as isocyanates etc., use flame retardant polyester but this based flame retardant is mainly used in the preparation plastics.
At present most popular is that phosphorus is the copoly type fire retardant, and copolyreaction type phosphorus fire retardant has hydroxyl, two kinds of functional groups of carboxylic acid, can join in the strand of polyester with alcohol, acid reaction, reaches the good flame effect.Phosphorus is that reactive flame retardant is distributed with phosphorus in main chain and phosphorus two kinds of forms on side chain in the polyester molecule chain, and using more at present is the backbone chain type phosphorus fire retardant.
But because the increase of P elements content in polyester, make the color and luster variation of polyester slice and polyster fibre, the reduction of product flavescence L value, the tone of fiber is also bad.The quality of fiber tone can influence the tone of source textile, and the source textile hue difference makes its brightness and lightness all not obvious, thereby the effect after the influence dyeing makes the lightness and the color and luster variation of yarn-dyed fabric, influences attractive in appearancely, is difficult to meet consumers' demand.
Patent CN200480038764.4 discloses a kind of fire retardant with good tone; This patent is thought the hue difference of fire retardant own; In the preparation fire retardant, add the tone that anti-oxidant can improve fire retardant; But this method can not finally be improved the tone of polyester slice, and the b value of the polyester that is obtained by this method is still relatively poor.
Summary of the invention
The object of the present invention is to provide a kind of good spinnability, Product Safety good, save low fire-retardant polyester fibre of the energy and cost and preparation method thereof.
The technical scheme that the present invention adopts is:
A kind of fire-retardant polyester fibre, with respect to this fire-retardant polyester fibre total amount, wherein phosphorus element content is 5000~7500ppm, and cobalt element content is 3~20ppm, and DEG content is below 2.5wt%, and the fire-retardant polyester fibre fusing point is 240 ℃~255 ℃.
Said P elements is from the response type phosphorus fire retardant shown in the following structural formula one or more:
R wherein
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8Be H, CH
3, (CH
2)
nOH, (CH
2)
nCOOH, or (CH
2)
nCH
3, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8Identical or inequality, n is between 1~5.
Described response type phosphorus fire retardant comprises methyl phosphorus, side chain phosphorus and phenyl phosphorus, as: 2-hydroxyethylbenzene phosphoric acid, 2-ethoxy methyl phosphorodithioate, 2-ethoxy methyl acid phosphate etc.
The production method of above-mentioned fire resistance fibre polyester comprises the steps:
(1) carry out copolymerization by aromatic acid, dihydroxylic alcohols and response type phosphorus fire retardant, and add cobalt compound in polycondensation phase, obtain the flame-proof copolyester master batch, wherein phosphorus element content is 10000~50000ppm, and cobalt element content is 5~120ppm;
(2) normal polyester section and flame-proof copolyester master batch are being carried out spinning after with the mixed of 1: 1~9: 1 weight under the molten condition; Obtain fire-retardant polyester fibre; Wherein phosphorus element content is 5000~7500ppm, and the fire-retardant polyester fibre fusing point is 240 ℃~255 ℃.
In the phosphorus fire retardant that said response type phosphorus fire retardant is following structure one or more:
nOH, (CH
2)
nCOOH, or (CH
2)
nCH
3, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8Identical or inequality, n is between 1~5.
This mixing preparation method of the present invention can reduce production costs widely, according to fire-retardant master granule and polyester mixed proportion, can reduce cost 10%~35%, and can effectively improve the tone of fire-retardant polyester fibre, obviously reduces the b value, improves the L value; Also improved simultaneously the quality and the fusing point (Tm) of fire-retardant polyester fibre, made it reach at 240 ℃~255 ℃ Δ H
TmBe higher than the fire-retardant polyester fibre that common combined polymerization obtains, heat resistance has been enhanced.
In the production process of fire-resistant copolyesters master batch; At first with terephthalic acid (TPA) and ethylene glycol esterification reaction or carry out ester exchange with the derivative of terephthalic acid (TPA) and ethylene glycol and make ethylene glycol terephthalate; In this engineering, use known catalyst, as: in butyl titanate, isopropyl titanate, n-butylstannoic acid, manganese acetate, cobalt acetate, the magnesium acetate one or more.When the reactivity of esterification or ester exchange reach 95% or its shift when above and carry out polycondensation reaction.In polycondensation process, add fire retardant, soluble catalyst, cobalt compound and phosphonium stabilizer.
The above-mentioned fire retardant that in polycondensation process, adds is meant one or several EG solution of above-named four kinds of fire retardants, makes that middle phosphorus element content is 10000~50000ppm, preferred 10000~30000ppm with respect to the fire-resistant copolyesters master batch.The content of P elements need be controlled within certain scope in the fire-resistant copolyesters master batch; Hang down less than 10000ppm if the content of P is crossed, then can not embody this preparation method's superiority, do not have the effect on reducing cost; And can not effectively improve the b value and improve fusing point; If but P content is too much, then polymerisation reactivity is poor, in addition can't polymerization or fire-resistant copolyesters master batch polyester performance too poor and can't use.
Above-mentioned soluble catalyst is meant the catalyst of soluble antimony class catalyst or titanium class, like antimony oxide, antimony acetate, the metatitanic acid tetrabutyl etc., adds proper catalyst, makes that the content of antimony in the fire-resistant copolyesters master batch or titanium elements is 5~800ppm.
Above-mentioned cobalt compound adds the amounts of cobalt compound as toner, makes that cobalt element content is 5~120ppm with respect to the fire-resistant copolyesters master batch.Cobalt compound can effectively improve the tone of difficult combustion master batch polyester, the Co catalysts amount very little, tone b value height; Do not have the effect of improvement, and if the Co catalysts amount is too much, then can cause the tone deepening of fire-resistant copolyesters master batch; The L value is serious to descend, and can reduce the heat resistance of fire-resistant copolyesters master batch.The present invention passes through the self-criticism to hot three aspects of color harmony fire-resistant copolyesters master batch resistant polyester of cobalt compound amount, fire-resistant copolyesters master batch, selects the cobalt element content in this scope.When to for the fire-resistant copolyesters master batch, cobalt element content is in 5~120ppm the time, and cobalt compound can effectively improve tone b value, and don't can reduce L value and heat resistance.
Said phosphonium stabilizer can effectively improve the color harmony heat resistance of difficult fire-resistant copolyesters master batch; The phosphonium stabilizer amount does not have the effect of improving tone very little, and the phosphonium stabilizer amount is too much; Then can cause the polymerisation reactivity of fire-resistant copolyesters master batch to descend; Even can't polymerization, the present invention confirms that through the self-criticism to both the P elements addition is with respect to 5~150ppm of fire-resistant copolyesters master batch amount in the phosphonium stabilizer; Add phosphonium stabilizer in this scope and can effectively improve the color harmony heat resistance, do not influence polymerisation reactivity again.Phosphonium stabilizer is trivalent or pentavalent phosphorous compound, like commercially available PEP36, AP1500, AX-71.
In the polycondensation reaction of fire-resistant copolyesters master batch, also adding antioxidant, to improve fire-resistant copolyesters master batch resistant polyester hot, like antioxidant IR1010, antioxidant 1078, antioxidant 168 and antioxidant PW9225 etc.
The temperature of polycondensation reaction is controlled at 250~300 ℃; Vacuum reaches below 200 Pascals slowly, deviates from the micromolecule glycol, in polycondensation process; FBT is at 270~290 ℃ in control; When the viscosity of polymer is in 0.60~0.95 scope, can finish reaction, obtain fire-resistant copolyesters master batch of the present invention.Suitable FBT is to the tone b value of the fire-resistant copolyesters master batch effect that is greatly improved.
Fire-resistant copolyesters master batch of the present invention can use the polymerization of still formula, the semi-continuous polymerization of discontinuous, the method for continuous polymerization to produce.
The section of the fire-resistant copolyesters master batch that obtains and normal polyester is being carried out spinning after with 1: 1~9: 1 mixed under the molten condition; Obtain fire-retardant polyester fibre; Make that phosphorus element content is 5000~7500ppm in the fiber; Cobalt element content is 3~20ppm, and DEG content is below 2.5wt%, and fusing point is 240 ℃~255 ℃.
This fire-retardant polyester fibre is widely used in decoration material field such as curtain, carpet and Che Nei goods, materials and equipments.
Description of drawings
Fig. 1 is the preparation flow sketch of this fire-retardant polyester fiber, wherein:
A: polyester
B: fire-resistant copolyesters master batch
C: screw rod machine
D: polyester is carried pipe arrangement
E: screw mixer
F: spinning machine
The specific embodiment
Through embodiment the present invention is done more detailed explanation below.In addition, the physics value among the embodiment is measured by following method.
(1) the intrinsic viscosity IV of polyester
Under 25 ℃, measure as solvent with o-chlorphenol.
(2) (the equivalent/ton) of the terminal groups carboxy CO OH in the polyester
, measure on automatic titration device (COM-550 of flat natural pond industry manufactured) with the NaOH aqueous solution of concentration 0.02mol/L down as solvent with o-cresol at 25 ℃.
(3) content of diethylene glycol (DEG) DEG (wt%)
As solvent, with 1, heating for dissolving after 6-ethylene glycol/methanol mixed adds methyl alcohol then and cleaned 10 minutes with ultrasonic cleaner with MEA.Add acid then and carry out neutralisation treatment, after the filtration, use gas chromatograph (the system GC-14A of Shimadzu Seisakusho Ltd.) to measure filtrating.
(4) tenor
Phosphorus content and metal element content are analyzed FLX:X-RAY SPECTROMETER RIX2000, claim that a certain amount of sample puts into aluminum pot and after being pressed into cake with trigger squeeze behind the heating and melting on the heating plate, put into the RIX2000 fluorescent x-ray analysis apparatus and test.
(5) tone
Spectral photometric colour measuring meter TOUCH PANEL SPECTRO COLOUR METER, SC-T uses the C-2 light source to calibrate in machine, and the yarn of getting then about 40g carries out the tone test, surveys and removes average three times.
(6) anti-flammability
Fire-retardant raw yarn carries out the flame retardant rating evaluation through after woven, washing, loss of weight, dyeing and washing according to French NF P92-503/504/505 combustion test.The NFP92-503 experimental technique is exactly that the residual combustion time is in the very strict combustion test below 5 seconds with electrical heating heat run appearance cloth igniting afterwards in 20 seconds in advance.Flame retardant rating has four grades of M4~M1, and the M1 flame retardant rating is best, and M4 is the poorest.
(7) fusing point (Tm)
Use differential scanning calorimetry (DSC) (DSC) to measure fire-retardant raw yarn fusing point.Get fire-retardant raw yarn 0.005g 50~280 ℃ of intensification scopes; Speed with 16 ℃ of programs of per minute heats up and cooling test, after the end that heats up for the first time, sample is carried out quenching handle; And then carry out the heating schedule second time, carry out cooling process again after the end that heats up.
Embodiment 1
An esterifying kettle, a polycondensation vessel are accomplished in being aggregated on the 150kg level two still polymerization production lines of fire-resistant copolyesters master batch.With 130kg terephthalic acid (TPA) and 56kg ethylene glycol in the making beating still after the making beating; Infeed and carry out esterification in the esterifying kettle that leaves half esterifying liquid of last consignment of; The esterification quantity of distillate reach theoretical value 90% after stop esterification; After oligomer moved into polycondensation vessel, add stabilizing agent phosphoric acid then, make its amount count 10ppm with phosphorus atoms with respect to the fire-resistant copolyesters master batch that generates; The toner cobalt acetate makes its amount count 10ppm with respect to the fire-resistant copolyesters master batch that generates with cobalt atom; Add antimony oxide 400ppm, antioxidant 1000ppm; Add fire retardant FR-100 (structural formula C), make its amount count 18000ppm with phosphorus atoms.Vacuumize after all interpolation is accomplished and carry out polycondensation, IV reaches 0.65 o'clock stripping.250 ℃ of esterification temperatures, slurry service time 4 hours, reaction time of esterification 5 hours; 290 ℃ of condensation temperatures, being extracted into the vacuum time from normal pressure is 60 minutes, final vacuum below 200 handkerchiefs, 3 hours 30 minutes polycondensation time.
After dry 4 hours, temperature is mentioned dry 8 hours of 120 ℃ of continuation to the master batch that polymerization obtains again through DV drying machine 80 degree.Dried fire-retardant master granule is transported to blender and mixes from the half delustring PET that tinuous production is transported to blender through pipe arrangement through double screw extruder, and getting into the fire-retardant master granule of blender and the weight ratio of half delustring PET is 1: 2; Carry out spinning after the mixing, extend, obtain fire-retardant polyester fibre.
Through test; The phosphorus element content of obtained flame-retardant polyester fiber is 5952ppm; Cobalt element content is 4ppm; Fusing point (Tm) is 247 ℃ (polyester test fusing points that getting heats up for the first time obtains), and POY yarn (precursor of this fire-retardant polyester fibre) intensity is at 2.06CN/dtex, and the intensity of DTY yarn is at 3.96CN/dtex; The anti-flammability of fabric reaches M1, the light resistance level Four, and more than the heat resistance level Four, whiteness b value is 1.52.
Add fire retardant FR-100 (structural formula C), make its amount count 15000ppm with phosphorus atoms, other are with embodiment 1.The DCO data are at subordinate list.
Embodiment 3
Add fire retardant FR-100 (structural formula C), make its amount count 30000ppm with phosphorus atoms, the weight ratio of fire-retardant master granule and half delustring PET is 1: 4, and other are with embodiment 1.The DCO data are at subordinate list.
Embodiment 4
Add fire retardant FR-100 (structural formula C), make its amount count 45000ppm with phosphorus atoms, the weight ratio of fire-retardant master granule and half delustring PET is 1: 5, and other are with embodiment 1.The DCO data are at subordinate list.
Embodiment 5
Add the toner cobalt acetate, make its amount count 50ppm with respect to the fire-resistant copolyesters master batch that generates with cobalt atom, other are with embodiment 1.The DCO data are at subordinate list.
Embodiment 6
Add the toner cobalt acetate, make its amount count 100ppm with respect to the fire-resistant copolyesters master batch that generates with cobalt atom, other are with embodiment 1.The DCO data are at subordinate list
Embodiment 7
Add stabilizing agent phosphoric acid, make its amount count 50ppm with respect to the fire-resistant copolyesters master batch that generates with phosphorus atoms, other are with embodiment 1.The DCO data are at subordinate list.
Embodiment 8
Add stabilizing agent phosphoric acid, make its amount count 100ppm with respect to the fire-resistant copolyesters master batch that generates with phosphorus atoms, other are with embodiment 1.The DCO data are at subordinate list.
Embodiment 9
Add fire brake ZB-101 (structural formula A), make its amount count 18000ppm with phosphorus atoms, other are with embodiment 1.The DCO data are at subordinate list.
Embodiment 10
Add fire retardant FR-100 (structural formula C) and ZB-101 (structural formula A), make both count 18000ppm with phosphorus atoms in the total amount, other are with embodiment 1.The DCO data are at subordinate list.
Embodiment 11
Reduce FBT, be 280 ℃, other are with embodiment 1.The DCO data are at subordinate list.
More than in each embodiment and the comparative example abbreviation to be called for short concrete title following:
(1) FBT: final polycondensation reaction temperature
(2) EG: ethylene glycol
(3) A0: antimony oxide
(4) PC-50: titanium compound (E.I.Du Pont Company's Titanium series catalyst)
(5) IR1010: antioxidant IR1010
(6) PA: phosphoric acid
(7) PTA: terephthalic acid (TPA)
(8) CoA: cobalt acetate
(9) FBT: polymerisation gets final temperature
(10) FR-100: phenyl phosphorus fire retardant
(11) ZB-101: side chain phosphorus fire retardant.
Subordinate list
Claims (4)
1. fire-retardant polyester fibre, it is characterized in that: with respect to this fire-retardant polyester fibre total amount, wherein phosphorus element content is 5000~7500ppm, and cobalt element content is 3-20ppm, and DEG content is below 2.5wt%, and the fire-retardant polyester fibre fusing point is 240 ℃~255 ℃.
2. fire-retardant polyester fibre according to claim 1 is characterized in that: said P elements is from the response type phosphorus fire retardant shown in the following structural formula one or more:
R wherein
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8Be H, CH
3, (CH
2)
nOH, (CH
2)
nCOOH, or (CH
2)
nCH
3, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8Identical or inequality, n is between 1~5.
3. the production method of the described fire-retardant polyester fibre of claim 1 is characterized in that: comprise the steps:
(1) carry out copolymerization by aromatic acid, dihydroxylic alcohols and response type phosphorus fire retardant, and add cobalt compound in polycondensation phase, obtain the flame-proof copolyester master batch, wherein phosphorus element content is 10000~50000ppm, and cobalt element content is 5~120ppm;
(2) normal polyester section and flame-proof copolyester master batch are being carried out spinning after with the mixed of 1: 1~9: 1 weight under the molten condition; Obtain fire-retardant polyester fibre; Wherein phosphorus element content is 5000~7500ppm, and the fire-retardant polyester fibre fusing point is 240 ℃~255 ℃.
4. the production method of fire-retardant polyester fibre according to claim 3 is characterized in that: one or more in the phosphorus fire retardant that said response type phosphorus fire retardant is following structure:
R wherein
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8Be H, CH
3, (CH
2)
nOH, (CH
2)
nCOOH, or (CH
2)
nCH
3, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8Identical or inequality, n is between 1~5.
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CN107326458A (en) * | 2017-06-22 | 2017-11-07 | 江苏飞翔化工股份有限公司 | A kind of flame-retardant polyester fiber and preparation method thereof |
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