CN110468464A - A kind of industrial yarn high-strength fire-retarding polyester slice and preparation method thereof - Google Patents
A kind of industrial yarn high-strength fire-retarding polyester slice and preparation method thereof Download PDFInfo
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- CN110468464A CN110468464A CN201910799995.5A CN201910799995A CN110468464A CN 110468464 A CN110468464 A CN 110468464A CN 201910799995 A CN201910799995 A CN 201910799995A CN 110468464 A CN110468464 A CN 110468464A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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Abstract
The present invention relates to a kind of industrial yarn high-strength fire-retarding polyester slices and preparation method thereof, it is additive particular by conventional polyester slice and the phosphonium flame retardant containing active function groups, flame retardant polyester slice is prepared by being blended, then pass through the method for solid state polycondensation, highly viscous high-strength fire-retarding polyester slice is prepared, its inherent viscosity of high-strength fire-retarding polyester slice is 1.05~1.25 dL/g, average molecular weight is 35000~45000, molecular weight distribution index PDI is 1.05~1.08, phosphorus content is 0.1~2.0 wt%, and limit oxygen index is 28~36%.The high-strength fire-retarding polyester slice is used for the preparation of flame-resistant terylene industrial yarn, and the especially fields such as advertising cloth, fire hose, military luggage oil sac are with important application prospects.
Description
Technical field
The invention belongs to industrial yarn production technical fields, and in particular to a kind of high-strength fire-retarding polyester slice and its preparation
Method.
Background technique
Polyester industrial fiber has the performances such as high-strength and high-modulus, impact resistance, endurance as one kind of high-performance fiber, extensive
Applied to fields such as automobile-used track traffic, aerospace, fire-fightings；And flame retardant polyester industrial yarn is as framework material, in military cable
The military domains such as rope, base camp tent, military case braces, flexible gun cover, military flexible oil sac have broad application prospects.But
The modified serious mechanical performance for influencing industrial yarn of existing polyester flame-retardant, and method for modifying flame brings even more serious molten drop
With flue gas content, defence equipment and the safety using officers and men are seriously affected, has limited polyester material in high fire-protection rate
Field application；It is difficult to meet current defence equipment to high-performance, the growth requirement of lighting, flexibility.
According to the characteristic of polyester material combustion process heats of combustion, accelerate polyester in conjunction with phosphonium flame retardant heats of combustion feature
Melting drippage, researcher develop with the monomers such as CEPPA, DDP, DOPO, HMPPA be copolymerized phosphor-containing flame-retardant copolyester, and
Civilian field of polyester fiber is used widely.But in the prevalence of the lower (< 0.45 of the molecular weight of phosphorous copolyester itself
DL/g), phosphorus content is (2.0 wt% of <) on the low side, big for fire-retardant master granule additive amount, causes flame retardant effect difference and difficulty of processing big etc.
Problem.And bad dispersibility, which is blended, in, powder fire retardant low by phosphorous copolyester molecular weight is influenced, and fire retardant is to fire resistance fibre machine
Tool performance influences greatly, to cause current fire-retardant polyester fibre intensity generally relatively low, flame retardant polyester industrial yarn intensity is difficult to break through 6.5
The intensity index of cN/dtex；And the fields such as corresponding military hawser, military case braces, military flexible oil sac, it is required that fiber
Intensity need to be greater than 7.0 cN/dtex, and percent thermal shrinkage is low.Base camp tent, flexible gun cover simultaneously, not only need high intensity, simultaneously
Also need the performances such as high fire-retardance and softness, and my army is at present still using fibres such as high-cost nylon industry silk, aramid fibers
Material is tieed up, cost performance is very poor, and the property pretended is poor；Simultaneously compared with the equipment of foreign military, there is also quality weightings, and price is high, sternly
Remake the about flexibility, lightweight of my army's military equipment, large-scale development.
Yuan Fang group introduces phosphonium flame retardant using CEPPA as comonomer, by copolyreaction on main chain, and phosphorus content is
5000ppm, and the various coloured flame-retardant polyester industrial yarns of LOI > 30%, strength loss are big.
Outstanding husband's share (ZL 200810301392.X, a kind of blending fire retardant-type terylene industrial filament and its production technology) with
Inorganic fire retardants (aluminium hydroxide, magnesium hydroxide and zinc borate) is flame-proof modifier, after being blended with conventional low-viscosity polyester, then
Inherent viscosity is obtained as 0.99-1.07 dL/g slice through solid state polycondensation technique, introduces the organic phosphorus oil of high temperature resistant in spinning process
Agent, thus realize industrial yarn high flame resistance, LOI > 36%.
Donghua University and Jiangsu Jin Ze new material (ZL201510688938.1, a kind of preparation of high-strength fire-retarding polyester filament
Method) with fire retardant (ammonium polyphosphate, antimony pentoxide, polyvinyl chloride) for flame-proof modifier, when being copolymerized by the screw rod of design
Fire retardant is introduced, obtains flame retardant polyester slice, fibre strength can arrive 9-12 cN/dtex, LOI > 35% after spinning.Simultaneously herein
On the basis of, inventor (ZL201510688847.8, ZL201510688803.5), which develops, aoxidizes phosphorus, acrylic acid with phenyl dichloro
It is the copoly type fire retardant and its high-strength fire-retarding fiber of modified monomer with ethylene glycol.Fibre strength > 6.9 cN/dtex, LOI >
33%.But the method is difficult to be industrialized, and in the design process of fire retardant, and has no thermal stability and hydrolysis
The analysis of stability.
Modification by copolymerization is that current application maturation the most is also the most possible method realized and stablize high-strength fire-retarding industrial yarn.It is ancient
Track road (ZL 201110076163.4) passes through leading-in end hydroxyl in polymerization process using DDP as the phosphor-containing flame-retardant copolyester of comonomer
Base DDP fire retardant prepares the fire-retardant slice of 0.61 dL/g of low viscosity, arrives through the promotion of solid state polycondensation technique intrinsic viscosity
0.9-1.0 dL/g, fiber reach 6.6-6.7 cN/dtex, and DDP adds 8% its LOI > 30%.
With common flame retardant polyester slice (CEPPA, 6500ppm), solid phase increases horse distance of travel of roc (Hai Li get) et al. after drying
It is glutinous, then carry out spinning and obtain stable flame-resistant terylene industrial yarn, breaking strength is 6.52 cN/dtex, and elongation at break is
17.1%, limit oxygen index 31.5%.
Zhang Dehui (ancient track road) et al. is glued fire-retardant with the phosphorous common flame retardant polyester slice (0.67 dg/L) of side chain type and height
Solid state polycondensation is carried out after polyester slice (1.03 dL/g) mixing, then melt spinning is obtained with high-strength fire-retarding polyester industrial yarn；
Its breaking strength can be improved to 7.0 cN/dtex or more, and limit oxygen index can remain 30.0%.
Constant force chemical fibre (ZL 201210085770.1) discloses a kind of difunctional acid anhydrides of phosphonium flame retardant, utilizes acid
Esterification during increasing stick that acid anhydride and polyester connect section terminal hydroxy group reaches increasing stick purpose；The synthesis of phosphonium flame retardant is excessively multiple
The problems such as miscellaneous, and acid anhydrides increasing stick rate is too fast.
Outstanding husband's share discloses the method that (ZL 200810301416.1) uses spinning oil to oil, on industrial yarn surface
One layer of flame retardant coating is formed, realizes the flame-retardant modified of industrial yarn；Flame retardant coating is using phosphorous or bromide fire retardant and cooperates nothing
Machine fire retardant composition, by the way that high temperature resistant finish is being sprayed on fiber between the rolling of drawing-off heat and setting roll again after fibre spinning,
Realization finish oils and curing process；Oil content 1.5-3.5% in fiber, LOI > 36%.
But the embodiment of above-mentioned announcement is all there is the intensity of fiber is lower, it is flame-retardant modified after fiber mechanical performance shadow
Ring big problem, it is difficult to meet high-strength fire-retarding polyester industrial yarn in the application in the fields such as high-end fire-fighting, military.Summary of the invention
Goal of the invention: purpose of the invention is to overcome the shortcomings in the prior art, provides a kind of with excellent fire-retardant, high
The performances such as viscous, heatproof stabilization, the high-strength fire-retarding polyester slice and preparation method thereof prepared for industry polyester industrial yarn.
Technical solution: in order to solve the above-mentioned technical problem, a kind of industrial yarn of the present invention is cut with high-strength fire-retarding polyester
Piece, it is made using active phosphonium flame retardant and polyester slice as raw material using melt blending and stepwise solid phase increasing stick, melting temperature
Degree is 250~260 DEG C, melts 52~65 kJ/g of enthalpy, and inherent viscosity is 1.05~1.25 dL/g, and average molecular weight is
35000~45000, molecular weight distribution index PDI are 1.05~1.08, and phosphorus content is 0.1~2.0 wt%, and limit oxygen index is
28~36%.
A kind of preparation method of industrial yarn high-strength fire-retarding polyester slice, it includes the following steps,
(1) preparation of active phosphonium flame retardant
First by phosphonium flame retardant 10- (2,5- dihydroxy phenyl) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxide
(ODOPB) mixed with epoxychloropropane, then add catalyst benzyltriethylammoinium chloride react 60 at 80~90 DEG C~
Then 90min adds NaOH aqueous solution, 30~45min is stirred at room temperature, adds ethyl acetate and water after reaction
Mixed solvent extracted, obtain organic phase, it is then dry with anhydrous sodium sulfate, then second is removed using the method for distillation under pressure
Active phosphonium flame retardant is prepared in acetoacetic ester, and the fusing point of the activity phosphonium flame retardant is 165~168 DEG C；
Wherein the molar ratio of the ODOPB and epoxychloropropane be 1:2~1:10, the catalyst benzyltriethylammoinium chloride with
The mass fraction of ODOPB is 1:10~1:20, and the concentration of the NaOH aqueous solution is 1~5 mol/L, NaOH aqueous solution with
The mass ratio of ODOPB is 1:2~1:4, and it is 1:1 that the mixed solution of the ethyl acetate and water, which is volume ratio, and mixed solution
The mass ratio of quality and ODOPB are 1:0.5~1:1；
(2) preparation of phosphor-containing flame-proof slice
The active phosphonium flame retardant and polyester slice being prepared using step (1) is raw materials, using the method for melt blending, preparation
Obtain phosphor-containing flame-proof slice；
Wherein the active phosphonium flame retardant accounts for the 1%~20% of phosphor-containing flame-proof slice gross mass, and the characteristic of the polyester slice is viscous
Degree is 0.6~0.75dL/g, and content of carboxyl end group is 20~34 mmol/kg, and the melt blending temperature is 260~285 DEG C；
(3) preparation of high-strength fire-retarding polyester slice
Using phosphor-containing flame-proof polyester slice as raw material, high-strength fire-retarding polyester slice is prepared in the method viscosified using stepwise solid phase；
Wherein the stepwise solid phase increasing stick is divided into cryogenic vacuum increasing stick, high-temperature vacuum increasing stick and high temperature increasing stick three phases；
The cryogenic vacuum increasing stick temperature is 170~190 DEG C, 1~5kPa of vacuum degree, 2.0~3.5h of residence time, cryogenic vacuum
Inherent viscosity control after increasing stick is 0.80~0.85dL/g, and molecular weight distribution index PDI is 1.15~1.25；
The high-temperature vacuum increasing stick temperature is 230~240 DEG C, 0.5~1.5kPa of vacuum degree, 1.0~1.5h of residence time, high temperature
Inherent viscosity control after vacuum increasing stick is 0.85~0.87dL/g, and it is 1.03~1.06 that molecular weight distribution, which controls PDI,；
The high temperature increasing stick process is protection gas with nitrogen, and high temperature increasing stick temperature is 210~220 DEG C, 8.0~12h of residence time,
Inherent viscosity control after high temperature increasing stick is 1.05~1.25dL/g, and it is 1.05~1.08 that molecular weight distribution, which controls PDI,.
It is described activity phosphonium flame retardant reaction equation be,
The utility model has the advantages that compared with prior art, the present invention its remarkable advantage is:
It is modified matrix that the present invention, which utilizes the side chain type phosphonium flame retardant ODOPB with rigidity benzene ring structure, by its end group
After epoxidation modification, the phosphonium flame retardant with reactivity is prepared, there is lower fusing point using itself, in polyester
Terminal hydroxy group and carboxyl end group are reacted, and achieve the purpose that improve molecular weight of polyesters, and are utilized low true during increasing stick
Null process and the reaction of propagation that molecular weight is carried out higher than the melting temperature menstruation regulating of phosphonium flame retardant, avoid leading due to higher temperature
The epoxy bond activation energy of cause is excessively high, and reacting too fast causes molecular weight of polyesters rate of rise too fast, on the one hand leads to polyester itself
Degradation, molecular weight distribution is excessive when on the other hand leading to its increasing stick, the increasing stick process of poor quality for being difficult to use in the later period after increasing stick.Together
When for needing the polyester slice practicability of increasing stick wider, the control of reduced content of carboxyl end group is not needed, in 30mmol/
Still there is very excellent increasing stick effect in the slice of kg, mainly utilize the active phosphonium flame retardant having compared with low melting point, benefit
With itself excellent epoxy group, it is able to carry out increasing stick reaction under the conditions of lower temperature, avoids existing increasing stick temperature
Height is spent, and higher carboxyl end group causes polyester side reaction excessive, the problems such as serious quality of degrading is turned to be yellow；And by using point
Thickening degree volume process is walked, low temperature increasing stick is carried out first with epoxy-modified ODOPB, then carries out the increasing stick mistake of high-temperature vacuum again
Journey aspirates the small molecules such as the oligomer generated during increasing stick by the swabbing effect during high-temperature vacuum, improves and increases
The molecular weight and reduction molecular weight distribution of glutinous polyester slice, improve the quality of slice, avoid conventional high temperature increasing stick process
In, small molecule oligomer is excessive, causes polyester slice molecular weight distribution wide, influences later period spinning process, causes in spinning process
The problems such as spinneret maintenance period is short, and precipitate is more, and drawing-off hot-rolling coking is serious.There is high degree of rigidity structure and right by introducing
Claim the ODOPB system of structure, further promote the symmetry of amorphous area in copolyester section, while further increasing amorphous area
Orientation texture improves the stability of amorphous area, while in increasing stick process due to its reactivity of epoxy-modified ODOPB itself
Greatly, therefore during increasing stick it is distributed in polyester molecule middle-of-chain, to further increase its fire-retardant stability.The application
The industrial yarn of exploitation high-strength fire-retarding polyester slice the performances such as is stablized with excellent fire-retardant, high viscous, heatproof, is used for industry
The fields such as the preparation of polyester industrial yarn, especially fig leaf, lamp house cloth, fire hose, high-strength luggage oil sac have important answer
Use prospect.
Detailed description of the invention
Fig. 1 is the infared spectrum of active phosphonium flame retardant in the present invention.
Specific embodiment
Embodiment 1
A kind of preparation method of industrial yarn high-strength fire-retarding polyester slice, it includes the following steps,
(1) preparation of active phosphonium flame retardant
According to a certain percentage phosphonium flame retardant 10- (2,5- dihydroxy phenyl) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10-
Oxide (ODOPB) and epoxychloropropane mixing, it is anti-at 80~90 DEG C then to add catalyst benzyltriethylammoinium chloride
60~90min is answered, NaOH aqueous solution is then added, 30~45min is stirred at room temperature, adds acetic acid second after reaction
The mixed solvent of ester and water is extracted, and organic phase is obtained, then dry with anhydrous sodium sulfate, in the method using distillation under pressure
Ethyl acetate is removed, active phosphonium flame retardant is prepared, the fusing point of the active phosphonium flame retardant is 165~168 DEG C.
The molar ratio of the ODOPB and epoxychloropropane are 1:2；The catalyst benzyltriethylammoinium chloride with
The mass fraction of ODOPB is 1:10；The concentration of the NaOH aqueous solution is 1mol/L, the quality of NaOH aqueous solution and ODOPB
Than for 1:2；The mixed solution of ethyl acetate and water is that volume ratio is 1:1, and the quality of mixed solution and the mass ratio of ODOPB are
1:0.5。
(2) preparation of phosphor-containing flame-proof slice
Active phosphonium flame retardant and the normal polyester slice being prepared with step (1) are raw material, using the method for melt blending,
Phosphor-containing flame-proof slice is prepared.
Mass fraction in the active phosphonium flame retardant and phosphor-containing flame-proof slice is 1%；
It is 0.6dL/g, content of carboxyl end group 20mmol/kg that the normal polyester slice, which is inherent viscosity,；
The melt blending temperature is 260~285 DEG C.
(3) preparation of high-strength fire-retarding polyester slice
Using phosphor-containing flame-proof polyester slice as raw material, using the method for stepwise solid phase thickening degree, high-strength fire-retarding polyester is prepared and cuts
Piece.
The stepwise solid phase increasing stick is divided into cryogenic vacuum increasing stick, high-temperature vacuum increasing stick and high temperature increasing stick three phases；
The cryogenic vacuum increasing stick temperature is 170~190 DEG C, 1~5kPa of vacuum degree, residence time 2.0h, and cryogenic vacuum increases
Inherent viscosity control after glutinous is 0.80dL/g, and molecular weight distribution index PDI is 1.25；
The high-temperature vacuum increasing stick temperature is 230~240 DEG C, 0.5~1.5kPa of vacuum degree, residence time 1.0h, and high temperature is true
Inherent viscosity control after empty increasing stick is 0.85dL/g, and it is 1.06 that molecular weight distribution, which controls PDI,；
The high temperature increasing stick process is protection gas with nitrogen, and high temperature increasing stick temperature is 210~220 DEG C, residence time 8.0h, high
Inherent viscosity control after warm increasing stick is 1.05dL/g, and it is 1.08 that molecular weight distribution, which controls PDI,.
Embodiment 2
A kind of preparation method of industrial yarn high-strength fire-retarding polyester slice, it includes the following steps,
(1) preparation of active phosphonium flame retardant
According to a certain percentage phosphonium flame retardant 10- (2,5- dihydroxy phenyl) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10-
Oxide (ODOPB) and epoxychloropropane mixing, it is anti-at 80~90 DEG C then to add catalyst benzyltriethylammoinium chloride
60~90min is answered, NaOH aqueous solution is then added, 30~45min is stirred at room temperature, adds acetic acid second after reaction
The mixed solvent of ester and water is extracted, and organic phase is obtained, then dry with anhydrous sodium sulfate, in the method using distillation under pressure
Ethyl acetate is removed, active phosphonium flame retardant is prepared, the fusing point of the active phosphonium flame retardant is 165~168 DEG C.
The molar ratio of the ODOPB and epoxychloropropane are 1:10；The catalyst benzyltriethylammoinium chloride with
The mass fraction of ODOPB is 1:20；The concentration of the NaOH aqueous solution is 5 mol/L, the quality of NaOH aqueous solution and ODOPB
Than for 1:4；The mixed solution of ethyl acetate and water is that volume ratio is 1:1, and the quality of mixed solution and the mass ratio of ODOPB are
1:1。
(2) preparation of phosphor-containing flame-proof slice
Active phosphonium flame retardant and the normal polyester slice being prepared with step (1) are raw material, using the method for melt blending,
Phosphor-containing flame-proof slice is prepared.
Mass fraction in the active phosphonium flame retardant and phosphor-containing flame-proof slice is 20%；
The normal polyester slice is that inherent viscosity is 0.75dL/g, and content of carboxyl end group is 34 mmol/kg；
The melt blending temperature is 260~285 DEG C.
(3) preparation of high-strength fire-retarding polyester slice
Using phosphor-containing flame-proof polyester slice as raw material, using the method for stepwise solid phase thickening degree, high-strength fire-retarding polyester is prepared and cuts
Piece.
The stepwise solid phase increasing stick is divided into cryogenic vacuum increasing stick, high-temperature vacuum increasing stick and high temperature increasing stick three phases；
The cryogenic vacuum increasing stick temperature is 170~190 DEG C, 1~5kPa of vacuum degree, residence time 3.5h, and cryogenic vacuum increases
Inherent viscosity control after glutinous is 0.85dL/g, and molecular weight distribution index PDI is 1.15；
The high-temperature vacuum increasing stick temperature is 230~240 DEG C, 0.5~1.5kPa of vacuum degree, residence time 1.5h, and high temperature is true
Inherent viscosity control after empty increasing stick is 0.87dL/g, and it is 1.03 that molecular weight distribution, which controls PDI,；
The high temperature increasing stick process is protection gas with nitrogen, and high temperature increasing stick temperature is 210~220 DEG C, residence time 12h, high
Inherent viscosity control after warm increasing stick is 1.25dL/g, and it is 1.05 that molecular weight distribution, which controls PDI,.
Embodiment 3
A kind of preparation method of industrial yarn high-strength fire-retarding polyester slice, it includes the following steps,
(1) preparation of active phosphonium flame retardant
According to a certain percentage phosphonium flame retardant 10- (2,5- dihydroxy phenyl) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10-
Oxide (ODOPB) and epoxychloropropane mixing, it is anti-at 80~90 DEG C then to add catalyst benzyltriethylammoinium chloride
60~90min is answered, NaOH aqueous solution is then added, 30~45min is stirred at room temperature, adds acetic acid second after reaction
The mixed solvent of ester and water is extracted, and organic phase is obtained, then dry with anhydrous sodium sulfate, in the method using distillation under pressure
Ethyl acetate is removed, active phosphonium flame retardant is prepared, the fusing point of the active phosphonium flame retardant is 165~168 DEG C.
The molar ratio of the ODOPB and epoxychloropropane are 1:5；The catalyst benzyltriethylammoinium chloride with
The mass fraction of ODOPB is 1:10；The concentration of the NaOH aqueous solution is 5 mol/L, the quality of NaOH aqueous solution and ODOPB
Than for 1:2.5；It is 1:1 that the mixed solution of ethyl acetate and water, which is volume ratio, and the mass ratio of the quality of mixed solution and ODOPB
For 1:0.5.
Fig. 1 is the infrared spectrogram of raw material ODOPB and active phosphonium flame retardant, 1490 cm-1With 1583 cm-1Place is virtue
The vibration absorption peak of fragrant ring skeleton, 1278 cm-1Place is the stretching vibration absworption peak of P-Ar key, 1219 cm-1Place is P=O key
Stretching vibration absworption peak, 1039 cm-1There is the vibration absorption peak that peak is Ar-O key in place.From ODOPB and active phosphonium flame retardant
Infrared spectrogram can be seen that above-mentioned each peak and all also exist.And it can be seen that 3620 cm in map-1The absorption peak of-the OH at place disappears
It loses, illustrates that the hydroxyl of ODOPB is reacted with epoxychloropropane.Active phosphonium flame retardant is in 916 cm-1Place and 2926
cm-1Locate each appearance one peak, the respectively vibration peak of the vibration peak of epoxy group and methylene, illustrates the epoxy group of epoxychloropropane
It has been connected on ODOPB with methylene.3218cm-1The peak at place is moved to 3445 cm-1Place, and peak narrows, this may be to be formed point
In son caused by hydrogen bond.
(2) preparation of phosphor-containing flame-proof slice
Active phosphonium flame retardant and the normal polyester slice being prepared with step (1) are raw material, using the method for melt blending,
Phosphor-containing flame-proof slice is prepared.
Mass fraction in the active phosphonium flame retardant and phosphor-containing flame-proof slice is 10%；
The normal polyester slice is that inherent viscosity is 0.65dL/g, and content of carboxyl end group is 28 mmol/kg；
The melt blending temperature is 260~285 DEG C.
(3) preparation of high-strength fire-retarding polyester slice
Using phosphor-containing flame-proof polyester slice as raw material, using the method for stepwise solid phase thickening degree, high-strength fire-retarding polyester is prepared and cuts
Piece.
The stepwise solid phase increasing stick is divided into cryogenic vacuum increasing stick, high-temperature vacuum increasing stick and high temperature increasing stick three phases；
The cryogenic vacuum increasing stick temperature is 170~190 DEG C, 1~5kPa of vacuum degree, residence time 2..5h, and cryogenic vacuum increases
Inherent viscosity control after glutinous is 0.80dL/g, and molecular weight distribution index PDI is 1.20；
The high-temperature vacuum increasing stick temperature is 230~240 DEG C, 0.5~1.5kPa of vacuum degree, residence time 1.5h, and high temperature is true
Inherent viscosity control after empty increasing stick is 0.87dL/g, and it is 1.03 that molecular weight distribution, which controls PDI,；
The high temperature increasing stick process is protection gas with nitrogen, and high temperature increasing stick temperature is 210~220 DEG C, residence time 10h, high
Inherent viscosity control after warm increasing stick is 1.20dL/g, and it is 1.05 that molecular weight distribution, which controls PDI,.
Embodiment 4
A kind of preparation method of industrial yarn high-strength fire-retarding polyester slice, it includes the following steps,
(1) preparation of active phosphonium flame retardant
According to a certain percentage phosphonium flame retardant 10- (2,5- dihydroxy phenyl) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10-
Oxide (ODOPB) and epoxychloropropane mixing, it is anti-at 80~90 DEG C then to add catalyst benzyltriethylammoinium chloride
60~90min is answered, NaOH aqueous solution is then added, 30~45min is stirred at room temperature, adds acetic acid second after reaction
The mixed solvent of ester and water is extracted, and organic phase is obtained, then dry with anhydrous sodium sulfate, in the method using distillation under pressure
Ethyl acetate is removed, active phosphonium flame retardant is prepared, the fusing point of the active phosphonium flame retardant is 165~168 DEG C.
The molar ratio of the ODOPB and epoxychloropropane are 1:10；The catalyst benzyltriethylammoinium chloride with
The mass fraction of ODOPB is 1:10；The concentration of the NaOH aqueous solution is 5 mol/L, the quality of NaOH aqueous solution and ODOPB
Than for 1:3；The mixed solution of ethyl acetate and water is that volume ratio is 1:1, and the quality of mixed solution and the mass ratio of ODOPB are
1:0.5。
(2) preparation of phosphor-containing flame-proof slice
Active phosphonium flame retardant and the normal polyester slice being prepared with step (1) are raw material, using the method for melt blending,
Phosphor-containing flame-proof slice is prepared.
Mass fraction in the active phosphonium flame retardant and phosphor-containing flame-proof slice is 5%；
The normal polyester slice is that inherent viscosity is 0.67dL/g, and content of carboxyl end group is 20 mmol/kg；
The melt blending temperature is 260~285 DEG C.
(3) preparation of high-strength fire-retarding polyester slice
Using phosphor-containing flame-proof polyester slice as raw material, using the method for stepwise solid phase thickening degree, high-strength fire-retarding polyester is prepared and cuts
Piece.
The stepwise solid phase increasing stick is divided into cryogenic vacuum increasing stick, high-temperature vacuum increasing stick and high temperature increasing stick three phases；
The cryogenic vacuum increasing stick temperature is 170~190 DEG C, 1~5kPa of vacuum degree, residence time 3.5h, and cryogenic vacuum increases
Inherent viscosity control after glutinous is 0.80dL/g, and molecular weight distribution index PDI is 1.20；
The high-temperature vacuum increasing stick temperature is 230~240 DEG C, 0.5~1.5kPa of vacuum degree, residence time 1.5h, and high temperature is true
Inherent viscosity control after empty increasing stick is 0.87dL/g, and it is 1.05 that molecular weight distribution, which controls PDI,；
The high temperature increasing stick process is protection gas with nitrogen, and high temperature increasing stick temperature is 210~220 DEG C, residence time 12h, high
Inherent viscosity control after warm increasing stick is 1.15dL/g, and it is 1.06 that molecular weight distribution, which controls PDI,.
Comparative example 1
Comparative example 1 is that normal polyester is sliced liquid phase increasing stick technique, and normal polyester slice is using content of carboxyl end group
20mmol/kg, the polyester slice being prepared.
Comparative example 2
Comparative example 2 is that normal polyester is sliced liquid phase increasing stick technique, and normal polyester slice is using content of carboxyl end group
30mmol/kg, the polyester slice being prepared.
Comparative example 3
Comparative example 3 is substantially the same manner as Example 3, the difference is that ODOPB is used to be modified for active phosphonium flame retardant, is prepared into
The polyester slice arrived.
Comparative example 4
Comparative example 4 is substantially the same manner as Example 3, the difference is that is be prepared is poly- without cryogenic vacuum increasing stick technical process
Ester slice.
Comparative example 5
Comparative example 5 is substantially the same manner as Example 3, the difference is that is be prepared is poly- without high-temperature vacuum increasing stick technical process
Ester slice.
Comparative example 6
Comparative example 6 is substantially the same manner as Example 3, the difference is that then first carry out high-temperature vacuum increasing stick process carries out cryogenic vacuum again
Increasing stick process, the polyester slice being prepared.
Implementation result
Following table is the performance indicator of polyester slice:
The Testing index of all samples is detected according to relevant testing standard, and the index of slice is according to Q/SY LY8029-
2013 industrial yarn grade polyester chips are detected；Its flame retardant property is according to FZ/T 50017-2011 polyester fiber flame retardant property
Test method oxygen index method standard is detected；Molecular weight distribution is using tetrachloroethanes as solvent, using gel permeation chromatography GPC
It is detected；LOI after alkali cleaning, at plain cloth, then uses the sodium hydroxide of 0.1mol/L molten using terylene industrial filament nonwoven fabric
Liquid, the hot water alkali process 15min in 80 DEG C are detected referring next to FZ/T 50017-2011 standard.
Comparative example 1 is the high viscosity polyester slice that existing conventional polyester slice is prepared by solid state polycondensation, existing
Technique is under lower content of carboxyl end group, and intrinsic viscosity is high, and molecular weight distribution is relatively narrow, and conventional high carboxyl end group is used to contain
The polyester slice of amount carries out increasing stick, will lead to it during increasing stick, the degradation of molecular weight, to reduce molecular weight and raising
Molecular weight distribution, thus the quality during reducing increasing stick.And increasing stick mistake is carried out by the phosphonium flame retardant with reactivity
Journey, using the epoxy terminated group of cryogenic vacuum process and carboxyl end group and terminal hydroxy group and the reaction process of transesterification, to have more
Wide increasing stick carboxyl end group, and by further high-temperature vacuum increasing stick process, to improve molecule during polyester increasing stick
Amount and reduction molecular weight distribution；And change the cryogenic vacuum increasing stick process and high-temperature vacuum increasing stick process during its increasing stick,
Cause its molecular weight distribution to broaden, influence the product of product after increasing stick, is especially the absence of low temperature increasing stick process, will lead to its epoxy
Reaction rate is too fast, and the processes such as crosslinking are likely to occur on strand, so that molecular weight distribution is wide, poor quality.
The present invention provides a kind of thinking and methods, and there are many method and the approach for implementing the technical solution, the above institute
Stating is only the preferred embodiment of the present invention, it is noted that for those skilled in the art, is not being departed from
Under the premise of the principle of the invention, several improvements and modifications can also be made, these improvements and modifications also should be regarded as guarantor of the invention
Range is protected, all undefined components in this embodiment can be implemented in the prior art.
Claims (2)
1. a kind of industrial yarn high-strength fire-retarding polyester slice, it is characterised in that: it is with active phosphonium flame retardant and polyester slice
Raw material is made using melt blending and stepwise solid phase increasing stick, and melting temperature is 250~260 DEG C, melts 52~65 kJ/ of enthalpy
G, inherent viscosity are 1.05~1.25 dL/g, and average molecular weight is 35000~45000, and molecular weight distribution index PDI is 1.05
~1.08, phosphorus content is 0.1~2.0 wt%, and limit oxygen index is 28~36%.
2. a kind of preparation method of industrial yarn according to claim 1 high-strength fire-retarding polyester slice, it is characterised in that: it
Include the following steps,
(1) preparation of active phosphonium flame retardant
First by phosphonium flame retardant 10- (2,5- dihydroxy phenyl) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxide
(ODOPB) mixed with epoxychloropropane, then add catalyst benzyltriethylammoinium chloride react 60 at 80~90 DEG C~
Then 90min adds NaOH aqueous solution, 30~45min is stirred at room temperature, adds ethyl acetate and water after reaction
Mixed solvent extracted, obtain organic phase, it is then dry with anhydrous sodium sulfate, then second is removed using the method for distillation under pressure
Active phosphonium flame retardant is prepared in acetoacetic ester, and the fusing point of the activity phosphonium flame retardant is 165~168 DEG C；
Wherein the molar ratio of the ODOPB and epoxychloropropane be 1:2~1:10, the catalyst benzyltriethylammoinium chloride with
The mass fraction of ODOPB is 1:10~1:20, and the concentration of the NaOH aqueous solution is 1~5 mol/L, NaOH aqueous solution with
The mass ratio of ODOPB is 1:2~1:4, and it is 1:1 that the mixed solution of the ethyl acetate and water, which is volume ratio, and mixed solution
The mass ratio of quality and ODOPB are 1:0.5~1:1；
(2) preparation of phosphor-containing flame-proof slice
The active phosphonium flame retardant and polyester slice being prepared using step (1) is raw materials, using the method for melt blending, preparation
Obtain phosphor-containing flame-proof slice；
Wherein the active phosphonium flame retardant accounts for the 1%~20% of phosphor-containing flame-proof slice gross mass, and the characteristic of the polyester slice is viscous
Degree is 0.6~0.75dL/g, and content of carboxyl end group is 20~34 mmol/kg, and the melt blending temperature is 260~285 DEG C；
(3) preparation of high-strength fire-retarding polyester slice
Using phosphor-containing flame-proof polyester slice as raw material, high-strength fire-retarding polyester slice is prepared in the method viscosified using stepwise solid phase；
Wherein the stepwise solid phase increasing stick is divided into cryogenic vacuum increasing stick, high-temperature vacuum increasing stick and high temperature increasing stick three phases；
The cryogenic vacuum increasing stick temperature is 170~190 DEG C, 1~5kPa of vacuum degree, 2.0~3.5h of residence time, cryogenic vacuum
Inherent viscosity control after increasing stick is 0.80~0.85dL/g, and molecular weight distribution index PDI is 1.15~1.25；
The high-temperature vacuum increasing stick temperature is 230~240 DEG C, 0.5~1.5kPa of vacuum degree, 1.0~1.5h of residence time, high temperature
Inherent viscosity control after vacuum increasing stick is 0.85~0.87dL/g, and it is 1.03~1.06 that molecular weight distribution, which controls PDI,；
The high temperature increasing stick process is protection gas with nitrogen, and high temperature increasing stick temperature is 210~220 DEG C, 8.0~12h of residence time,
Inherent viscosity control after high temperature increasing stick is 1.05~1.25dL/g, and it is 1.05~1.08 that molecular weight distribution, which controls PDI,.
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