CN105985514A - Preparation method of flame-retardant polyester composition - Google Patents
Preparation method of flame-retardant polyester composition Download PDFInfo
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- CN105985514A CN105985514A CN201510094205.5A CN201510094205A CN105985514A CN 105985514 A CN105985514 A CN 105985514A CN 201510094205 A CN201510094205 A CN 201510094205A CN 105985514 A CN105985514 A CN 105985514A
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Abstract
The invention discloses a preparation method of a flame-retardant polyester composition which can inhibit generation of by-products and prevent depression of a melting point of a polymer and has the excellent flame-retardant property. According to the method, when polyester is prepared by taking dicarboxylic acid or a derivative thereof and dihydric alcohol as main raw materials, slurry prepared from a phosphorus compound shown as a following formula 1 (please see the formula in the description) and ethylene glycol according to the weight ratio of 10:90-50:50 is added in 80 minutes before a polymerization reaction starts according to the weight that the phosphorous element content in the polyester composition is 0.3 wt%-1.1 wt%, wherein in the formula 1, R1 is an alkyl group or an acryl group or a hydroxyl group with 1-18 carbon atoms.
Description
Technical field
The present invention relates to the preparation method of a kind of flame-retardant polyester composition.The detailed fusing point relating to suppress the formation of polyreaction by-product and gained polymer blend declines problem, and productivity is good and has the preparation method of flame-retardant polyester composition of excellent fire-retardancy.
Background technology
Polyester has the characteristic of excellence, is widely used as fiber, thin film, resin.Meanwhile, the consciousness of taking precautions against natural calamities in recent years is strengthened, and the requirement to anti-flammability also increases.
The technology giving polyester flame-retardant is broadly divided into three kinds.Detailed is after the products formed to polymer blend carries out post-treatment, fire retardant is made to be attached to products formed surface or the method penetrating into inside, or the method being mixed into fire retardant during polymer blend molding, or when preparing polyester polymers, add the method that fire retardant carries out copolymerization, these methods are generally used when fiber applications.
In said method, the method giving anti-flammability by post-treatment, if compositions is the occasion of fibre, wash and with friction, fire retardant is come off to cause degraded performance, produce the problem that feel is coarse.The method that the method for fire retardant blending is fire retardant to be mixed at preparatory phase or the spinning phase of polyester, but the problem that fire retardant oozes out on polymer blend surface can occur so that produce and be restricted.
On the other hand, the method adding fire retardant copolymerization as polyester when manufacturing, is to carry out copolymerization in the polymerization reaction system that phosphorous copolymerization fire retardant adds to polyester.
Such as, patent document 1 discloses that a kind of there is excellent flame retardancy and the excellent polyester fiber of resistance to hydrolyzable.But, this phosphorus compound added in the esterification stage, and in course of reaction, by-product diethylene glycol generates in a large number, causes the fusing point of polyester to decline, and the physical property of compositions reduces.It addition, patent document 2 discloses that a kind of flame-resistant copolymerized ester and flame-retardant polyester fiber, anti-dripping melt and the fire-retardant polyester copolymer of the fire excellence that certainly disappears and the flame retardant fiber formed by this flame-resistant copolymerized body.Anti-dripping melt during igniting, the certainly fire that disappears are improved really, but are added with the ethylene glycol solution of phosphorus compound, can generate substantial amounts of by-product diethylene glycol.
Additionally, a kind of method that patent document 3 discloses that fire retardant resin composition, carrying capacity of environment during in order to alleviate manufacture and burn, the low problem of physical property of suppression polyester based resin, use two axle mixing rolls to add phosphorus compounds, and the fire retardant resin composition obtained can be with steady production polyester.By using two axle mixing rolls to add phosphorus compound, really the low problem of physical property of polyester resin can be suppressed, phosphorus compound can also be added in a large number simultaneously, but phosphorus compound skewness in the polymer, some part making polyester does not reaches fire resistance, is especially not suitable for the fiber applications that quality uniformity requirements is strict.
It addition, patent document 4 discloses that a kind of process for copolymerization, when the preparation polyester with polyethylene terephthalate or polybutylene terephthalate (PBT) as main component, add the phosphorus-containing compound of (9-phosphabicyclononane) derivant.But, owing to there is thermal response in fire retardant preparation process, generate substantial amounts of diethylene glycol.
Meanwhile, patent documentation 3 is all to use special phosphorus compound with patent documentation 4, lacks the versatility of technology, it is impossible to be widely used.
As it has been described above, have studied various flame-retardant polyester composition, not yet finding phosphorus compound to add the by-product generated in course of reaction few, gained melting point polyester declines few, and the preparation method of the good flame retardant polyester composition of productivity, is expected to exploitation from now on.
[list of references]:
No. 7-197319 bulletin of [patent documentation 1] Unexamined Patent,
No. 2008-179715 bulletin of [patent documentation 2] JP,
No. 2012-251078 bulletin of [patent documentation 3] JP,
No. 05-140283 bulletin of [patent documentation 4] Unexamined Patent.
Summary of the invention
According to background above, it is an object of the invention to provide the preparation method of a kind of flame-retardant polyester composition, preparatory phase at flame-retardant polyester composition can suppress the generation of by-product diethylene glycol, do not result in the decline of melting point polyester, productivity is good, and the physical property of flame-retardant polyester composition declines few.
The technical solution of the present invention is as follows:
In order to solve the problem that conventional art does not solve, present inventor has performed deep self-criticism and complete in the present invention.
That is by the preparation method of the combined polymerization fire-retardant polyester of the present invention, the object of the invention can be reached.I.e. when preparing polyester with dihydroxylic alcohols for primary raw material with dicarboxylic acids or derivatives thereof, the slurry that will be formed by weight 10:90 ~ 50:50 with ethylene glycol by the phosphorus compound shown in following formula 1, it is the amount of 0.3 ~ 1.1wt% with phosphorus element content in polymer blend, it is added in 80 minutes before polyreaction starts
Formula 1,
Wherein R1 is the alkyl of carbon number 1 ~ 18, aryl or hydroxyl.
Preparation method according to the flame-retardant polyester composition that the present invention provides, the generation of conventional flame retardant polyester composition preparatory phase diethylene glycol by-product can be suppressed, the decline of suppression melting point polyester, during by carrying out high viscosity with high melting point polyester composite molding or solid phase etc., its preparation engineering does not has obstacle, can apply to various environment, is particularly well-suited to the industrial applications such as safety net, anti-scorching net, with the purposes such as family life textile such as curtain, interior decoration, chair cover, and dress material purposes.
The flame-retardant polyester composition excellent fireproof performance that the present invention obtains, the amount of diethylene glycol is at below 3.0wt%, and fusing point is more than 230 DEG C.
Detailed description of the invention
The present invention will be described in detail below.
The preparation method of flame-retardant polyester composition of the present invention is, with dicarboxylic acids or derivatives thereof and dihydroxylic alcohols for primary raw material prepare polyester time, the slurry that will be formed by weight 10:90 ~ 50:50 with ethylene glycol by the phosphorus compound shown in following formula 1, it is the amount of 0.3 ~ 1.1wt% with phosphorus element content in polymer blend, it is added in 80 minutes before polyreaction starts
Formula 1,
Wherein R1 is the alkyl of carbon number 1 ~ 18, aryl or hydroxyl.
The dicarboxylic acids composition of the present invention is aromatic binary carboxylic acid, the various dicarboxylic acid components such as the acid of chain fatty race, Zhi Huan race binary acid.From the standpoint of the mechanical property of polymer blend, thermostability and resistance to hydrolyzable, aromatic binary carboxylic acid is relatively good.Especially polymerism and the mechanical property of p-phthalic acid, M-phthalic acid and how diacid is relatively good.
Glycol component of the present invention can select various dihydroxylic alcohols.nullSuch as ethylene glycol、1，2-propylene glycol、1，Ammediol、Butanediol、2-methyl isophthalic acid，Ammediol、Hexanediol、The aliphatic dihydroxy alcohols such as neopentyl glycol，Cycloaliphatic diols is cyclohexanedimethanol、Hexamethylene diethanol、Decahydro how dimethanol、Decahydro how diethanol、Norbornane dimethanol、Norbornane diethanol、Three second cyclododecane dimethanols、Three second cyclododecane diethanol、Tetracyclododecane dimethanol、Tetracyclododecane diethanol、Carbon phosphorus dimethyl ester、The saturated alicyclic one-level dihydroxylic alcohols such as carbon phosphorus diethylester、2，6-dihydroxy-9-oxabicyclo [3，3，1] nonane、3，9-bis-(2-hydroxyl-1，1-dimethyl ethyl) 2，4，8，10-tetra-oxa-[5，5] hendecane (spiral shell glycol)、5-methylol-5-ethyl-2-(1，1-dimethyl-2-ethoxy)-1，3-dioxane、Soquads etc. are containing 1 grade of dihydroxylic alcohols of cyclic ether saturation isomerism ring、And other cyclohexane dicarboxylic alcohol、Dicyclohexyl-4，4 '-dihydroxylic alcohols、2，2-bis-(4-hydroxyl ring triethanol propane)、2，2-bis-(4-(2-hydroxy ethoxy) cyclohexyl) propane、Pentamethylene. dihydroxylic alcohols、3-methyl isophthalic acid，2-Pentamethylene. dihydroxylic alcohols、4-Pentamethylene .-1，3-dihydroxylic alcohols、The various ester ring type dihydroxylic alcohols such as diamantane (obsolete) dihydroxylic alcohols、Third diphenol A、Third diphenol S、Styrene glycol、9，9-bis-(4-(2-hydroxy ethoxy) phenyl) alkene、The aromatic ring-shaped dihydroxylic alcohols such as 9-9 '-two (4-hydroxy phenyl) alkene.And it is possible to the two or more composition of summary is combined using.
Further, necessary occasion can add heat-resisting stabilizing agent, antioxidant, antistatic additive, UV absorbent, pigment, fluorescent whitening agent, delustering agent etc..
In the preparation method of the flame retardant polyester of the present invention, the phosphorus compound used as fire retardant can be 2-ethoxy (benzene) phosphonic acids, 2-carboxyethyl-tert-butyl phosphonic acids, 2-carboxyethyl-1,1-dimethyl ethyl phosphonic acids, 2-carboxyethyl (Nai Ji) phosphonic acids, 2-carboxyethyl (Tolylsulfanvl) phosphonic acids, 2-carboxyethyl-2, the solid flame retardants such as 5-dimethyl benzene phosphonic acids, 2-carboxyethyl (cyclohexyl) phosphonic acids, 2-carboxyethyl-4-chlorphenyl phosphonic acids, 3-carboxyethyl (benzene) phosphonic acids, 4-carboxyethyl (benzene) phosphonic acids, are preferably used 2-ethoxy (benzene) phosphonic acids.
Simultaneously, it is necessary to aforementioned phosphorus compound with the weight ratio of ethylene glycol as 10:90 ~ the dispergated pulp-like of 50:50 is added.
Pulp-like of the present invention is that the solids in liquid exist with scattered state.It addition, solution refers to the mixture of liquid condition, there is not the material existed with solid state.
It is to say, solid phosphorus compound at least part of slurry existed in solid form in ethylene glycol is pulp-like in the present invention.
Phosphorus compound adds with the slurry of ethylene glycol, directly add to reaction system before the reaction with phosphorus compound or add in the form of a solution compared with, the modulation time of additive can cripetura.By phosphorus compound acidification in slurry preparation vessel so can be suppressed, the prior by-product diethylene glycol that can suppress easily to generate under acid state.Meanwhile, the acid degree in slurry preparation vessel is inhibited by, and the acidification to polymerization reaction system suppresses the most effective, and the generation of the by-product diethylene glycol produced during polyreaction also can be suppressed.
In the preparation method of the flame-retardant polyester composition of the present invention, it is more than 10wt% by controlling relative to the ratio of phosphorus compound Yu the slurry phosphorus compound of ethylene glycol, in polymerization reaction system, does not adds the ethylene glycol of excess, the side reaction of diethylene glycol can be suppressed.Polymerization reaction time also can cripetura simultaneously.It is to say, because the most directly adding, polyreaction does not exist excess ethylene glycol, time and the energy of evaporation excess ethylene glycol outside polymerization reaction system can be alleviated.And, the existence of excess ethylene glycol can increase the generation amount of diethylene glycol so that the tone of polyester deteriorates, low quality.
Meanwhile, due to slurry, there is reasonable mobility when below 50wt% relative to the ratio of slurry phosphorus compound, can prevent from adding the accumulation of phosphorus compound in pipe arrangement and the diffusion in the gas phase portion in polymerization reaction trough.Adding in slurry form, in polyreaction, the compatibility performance of the intermediate polyester that dicarboxylic acid component is formed with glycol component significantly improves simultaneously.According to such result, can prevent phosphorus compound from flowing out outside system together along with the ethylene glycol flowed out in polyreaction so that the amount of the combined polymerization phosphorus compound in polyester is stable, i.e. the stay in grade such as the physical property of flame-retardant polyester composition and fire resistance.Phosphorus compound and the preferred 15:85 ~ 45:55 of weight ratio, more preferably 20:80 ~ 40:60 of ethylene glycol.
It addition, the amount of the phosphorus compound flowed out outside polymerization reaction system together along with ethylene glycol can be tried to achieve by following formula 1.The rate of dispersing of phosphorus compound is preferably at below 10wt%.
Rate of dispersing (wt%)=(the P1-P2)/P1 of phosphorus compound
Formula 2
(P1: the addition of phosphorus compound, P2 in terms of P elements: the content of phosphorus compound in obtained flame-retardant polyester in terms of P elements)
The rate of dispersing of phosphorus compound is when below 10wt%, and the phosphorus compound discharged outside polymerization reaction system tails off so that manufacturing cost aspect comparative superiority.Meanwhile, recycling the occasion of the ethylene glycol that polymerization reaction engineering is discharged, the P elements residual hindering polyreaction is fewer, is conducive to reclaiming highly purified ethylene glycol.Phosphorus compound rate of dispersing is more preferably at below 8wt%, most preferably at below 6wt%.
In the present invention, phosphorus compound must add with the slurry of ethylene glycol in 80 minutes before polyreaction starts in polymerization reaction system.If adding within 80 minutes, phosphorus compound acidification in polymerization reaction system can be alleviated, the generation of diethylene glycol side reaction under suppression acid state.Within the interpolation time of slurry preferably before polyreaction starts 60 minutes, more preferably within 50 minutes.
The addition of phosphorus compound is that 0.3 ~ 1.1wt% is added by the content in terms of P elements of the phosphorus compound of combined polymerization in flame retardant polyester composition.The phosphorus compound of combined polymerization has the fire resistance of excellence with P elements polymer blend when more than 0.3wt%.Meanwhile, the phosphorus compound of combined polymerization when below 1.1wt%, can maintain the physical property that polymer blend is original in terms of P elements, the problem not having polymerisation reactivity low inferior obstruction manufacturing engineering behaviour's industry.The phosphorus compound of combined polymerization is preferably 0.5 ~ 1.0wt%, more preferably 0.6 ~ 0.9wt% in terms of P elements.
The phosphorus compound of the present invention and the slurry of ethylene glycol are preferably being modulated in 90 minutes that polymerization reaction system adds before starting.Adding the slurry of 90 minutes internal modulation phosphorus compounds before starting and ethylene glycol to polymerization reaction system, the generation of diethylene glycol side reaction under the acidification of slurry and acid state can suppressed.The modulation period of slurry is preferably within adding 70 minutes before starting in polymerization reaction system, within more preferably 60 minutes.
In the present invention when preparation is with the flame-retardant polyester composition of the phosphorus compound combined polymerization of specified quantitative, the phosphorus compound containing extra fine quality ratio and adds in specific period internal modulation with the slurry of ethylene glycol.
The preparation method of the flame-retardant polyester composition of the present invention, it is possible to generate the side reaction of diethylene glycol during suppression polyreaction, and the diethylene glycol content flame-retardant polyester composition at below 3.0wt% can be obtained.The diethylene glycol content of obtained flame-retardant polymer blend of the present invention is preferably at below 2.5wt%, more preferably at below 2.0wt%.
Meanwhile, low diethylene glycol content can suppress the fusing point of polyester to decline, and obtains the flame-retardant polyester composition of fusing point more than 230 DEG C.Fusing point is more than 230 DEG C, and during by carrying out high viscosity with high melting point polyester composite molding or solid phase etc., its preparation engineering does not has obstacle, say, that can prepare the flame-retardant polyester composition that can apply to various environment.The fusing point of the flame-retardant polyester composition that the present invention prepares is preferably more than 233 DEG C, more preferably more than 235 DEG C.
Obtained flame-retardant polymer blend of the present invention manufactures the method for fiber can use existing known method.The silk that do not extends that polymer blend melts discharge such as can be used first to crimp the two sections of engineering methods extended afterwards, the direct fabrics extension method that spinning engineering and extension line project are carried out continuously, high speed spinning processes etc..It is also possible to use half to extend the method extended after silk batches.Furthermore, the most also can carry out corresponding false twisting processing.
Spinning temperature is usually set to higher 20 ~ 80 DEG C than melting point polyester.Setting if high more than 20 DEG C, can prevent polymer from solidifying blocking in spinning-drawing machine pipe arrangement than melting point polyester.On the other hand, setting if high less than 80 DEG C than melting point polyester, can suppress the deterioration that polymer is excessive, prevent the physical properties inferior such as fibre strength.
Further, the generation of fracture of wire and filoplume in order to suppress spinning engineering, extend residual degree of the stretching preferably 10 ~ 40wt% of silk.
The flame-retardant polyester composition of the gained present invention carries out the flame-retardant polyester fiber that melt spinning method prepares, and has physical property and the fire resistance of excellence.
The purposes of the fiber formed by obtained flame-retardant polymer blend of the present invention is not particularly limited, it is particularly well-suited to the industrial applications such as safety net and anti-scorching net, the purposes such as the family life textile with curtain, interior decoration, chair cover etc., are also applied for dress material purposes.
It is exemplified below embodiment the present invention is specifically described.Physics value in embodiment measures by the following method.
(1) intrinsic viscosity of flame-retardant polyester composition
0.8g sample 10ml o-chlorphenol is completely dissolved, is measured under the conditions of 25 DEG C.
(2) fusing point of flame-retardant polyester composition
Use differential scanning calorimeter (TAInstruments society DSC2200(Differential
Scanning Calorimeter), it is warming up to after 280 DEG C be quenched in the developmental tube of 0 DEG C with the programming rate of 20 DEG C/minute, becoming the sample after noncrystalline state to heat up with the speed of 20 DEG C/minute again, be measured dissolving peak with standard JIS K7121, the summit at this dissolving peak is fusing point.Meanwhile, judged by following benchmark:
More than 230 DEG C: qualified,
Less than 230 DEG C: defective.
(3) phosphorus element content
7g sample is carried out melted formation tabular, is carried out the mensuration of intensity by fluorescent x-ray analyser (electrically society's fluorescent x-ray analysis apparatus 3270 type of science), according to the calibration curve that the sample of known phosphorus element content is pre-made, carry out the mensuration of phosphorus element content.
(4) rate of dispersing of phosphorus compound
Calculate the rate of dispersing of phosphorus compound with following formula 1, judge according to following benchmark:
Phosphorus compound disperses rate (wt%)=(P1-P2)/P1 formula 2
(P1: the addition of phosphorus compound, P2 in terms of P elements: the content of phosphorus compound in obtained flame-retardant polyester in terms of P elements)
Below 10wt%: qualified,
More than 10wt%: defective.
(5) anti-flammability (the residual scorching rates more than 3 seconds)
After obtaining extending silk by method described below, make textile with longitudinally 25/inch, the density of horizontal 20/inch, this cylinder is compiled thing and uses JIS
The presence or absence of L1091 A-1 method 32 times more than 3 seconds residual inflammation of test, the residual scorching rate more than 3 seconds uses following benchmark to judge:
10% less than
: ◎ is qualified the best,
More than 10% 15% less than: zero is qualified,
More than 15%
: × defective.
(6) diethylene glycol content
After sample carbinolamine is carried out hydrolyzable, with 1,6-hexanediol/methanol is diluted, then with in p-phthalic acid and after, try to achieve according to the peak area of gas chromatogram.Meanwhile, in polymer blend, the amount of diethylene glycol judges according to following benchmark:
Below 3.0wt%: qualified,
More than 3.0wt%: defective.
(7) fiber number
Measure 100m and extend the weight of silk, calculate 100 times of this weight, average for 3 times with same method measure and calculation, be fiber number.
(8) intensity and degree of stretching
The Tensilon using Orientekkusu society draws a testing machine, the initial stage sample of the test 20cm length intensity (cN/dtex) when drawing Zhang Sudu 2cm/ disjunction and splitting, degree of stretching (%), averages after follow-on test 5 times.
Embodiment 1
(polymerization)
It is maintained in the esterifying kettle of 245 DEG C to the p-phthalic acid dihydroxy ethyl ester containing 1950 weight portions and temperature, put into containing 1100 weight portion p-phthalic acids and the slurry of 480 weight portion ethylene glycol, divide and supply for 3 hours, while discharging the water of generation during esterification outside system, carry out esterification.The oligomer generated after reaction takes 1300 weight portions divide a word with a hyphen at the end of a line to polymerization reaction kettle.
Then, before polyreaction starts 40 minutes, 65 weight portion 2-ethoxy (phenyl) phosphonic acids and the slurries of 150 weight portion ethylene glycol modulated in advance are added in oligomer, then the antimony oxide of 500ppm is added, the temperature of reaction system is slowly risen to 290 DEG C from 250 DEG C, simultaneously along with the discharge of ethylene glycol, the pressure of reaction system reduces to 50Pa.
And, 2-ethoxy (phenyl) phosphonic acids is to add the modulation in 50 minutes before starting in polymerization reaction system with the slurry of ethylene glycol.
Being passed through nitrogen recovery normal pressure when arriving the determined current value of blender in reaction system makes polyreaction stop, and flame-retardant polyester composition spues from the bottom of polymeric kettle with strip, and pelletizing after cooling and solidifying obtains the granule of flame-retardant polyester composition.The intrinsic viscosity of gained polyester is 0.75, the content of diethylene glycol is 1.7wt%, fusing point is 239 DEG C, phosphorus element content is 0.67wt%, obtains the fire-retardant polyester that quality is good.Further, the rate of dispersing of phosphorus compound is 5.5wt%.
(spinning process)
The polyester granulate obtained uses screw extruder to be measured by dosing pump after carrying out melting under conditions of 300 DEG C, keeps spinning temperature 300 DEG C to flow into mouth gold.The strand spued from mouth gold carries out cooling down through air cooling device, oil supply, be directly crimped, and then extends with the extension ratio of 6 times, obtains 1840dtex-144 long filament, and the fire-retardant polyester of intensity 7.1cN/dtex, degree of stretching 20.0% extends silk.
Anti-flammability (the residual scorching rates more than 3 seconds) is less than 10%, the most well.
Embodiment 2
Phosphorus compound, with the slurry of ethylene glycol, in addition to becoming 10wt% relative to the concentration of slurry phosphorus compound, uses method similarly to Example 1 to obtain flame-retardant polyester composition.The rate of dispersing of phosphorus compound can reduce compared with Example 1.On the other hand, if the interpolation quantitative change of ethylene glycol is many, although the growing amount of the by-product diethylene glycol produced by ethylene glycol increased compared with Example 1, but not problem, and fibrous physical property is the best with anti-flammability.
Embodiment 3
Phosphorus compound, with the slurry of ethylene glycol, in addition to becoming 50wt% relative to the concentration of slurry phosphorus compound, uses method similarly to Example 1 to obtain flame-retardant polyester composition.Although the rate of dispersing of phosphorus compound is somewhat the highest, but owing to the addition of ethylene glycol is fewer, ethylene glycol the by-product diethylene glycol growing amount generated is fewer, and fibrous physical property is good with anti-flammability.
Comparative example 1,2
The slurry formed about phosphorus compound and ethylene glycol, in comparative example 1 relative to slurry phosphorus compound concentration be 5wt%, the concentration of phosphorus compound is beyond 55wt% in comparative example 2, uses method similarly to Example 1 to prepare flame-retardant polyester composition.Although the phosphorus compound of comparative example 1 disperses, rate ratio is relatively low, but the growing amount of the by-product diethylene glycol generated by ethylene glycol is the most, although the growing amount of comparative example 2 diethylene glycol is fewer, but the rate of dispersing of phosphorus compound is higher, the most bad.
Comparative example 3
Except the interpolation of phosphorus compound is the most in a form of slurry but in addition to adding with the solution form formed with ethylene glycol, and remaining method similarly to Example 1 prepares flame-retardant polyester composition.The growing amount of result by-product diethylene glycol is the most, and the rate of dispersing of phosphorus compound is higher simultaneously, bad.
And, phosphorus compound with the solution of ethylene glycol is, adds in modulation container by ethylene glycol with relative to the phosphorus compound that ethylene glycol is 30wt%, stirs and be warming up to 60 DEG C, keep the state stirring and dissolving 50 minutes of 60 DEG C, obtain the solution of the ethylene glycol of phosphorus compound.
Embodiment 4, comparative example 4
The interpolation of the phosphorus compound of embodiment 4 be period 80 minutes before reaction starts, comparative example 4 be to react 110 minutes before starting, remaining method similarly to Example 1 prepares flame-retardant polyester composition.Although the growing amount of embodiment 4 diethylene glycol compared with Example 1 increased, but fibrous physical property is the best with fire resistance.On the other hand, in comparative example 4, the growing amount of diethylene glycol is the most, produces the problem that melting point polyester is low.
Embodiment 5 ~ 7
The amount of the phosphorus compound of combined polymerization, with P elements calculate embodiment 5 as 0.30wt%, embodiment 6 as 0.75wt%, embodiment 7 as 1.10wt%, remaining method similarly to Example 1 prepares flame-retardant polyester composition.Although in embodiment 5, the residual scorching rate more than 3 seconds is higher than embodiment 1, but also can meet fire resistance.Although the rate of dispersing of phosphorus compound is higher than embodiment 1 in embodiment 6, but good flame resistance, and fibrous physical property might as well.
Comparative example 5,6
The amount of the phosphorus compound of combined polymerization, with P elements calculate comparative example 5 as 0.20wt%, comparative example 6 as 1.25wt%, remaining method similarly to Example 1 prepares flame-retardant polyester composition.In comparative example 5, the fewer anti-flammability of copolymerization resultant of phosphorus compound is low.In comparative example 6, the rate of dispersing of phosphorus compound is higher, and polymerisation reactivity is remarkably decreased.
Embodiment 8,9
Modulation phosphorus compound and the time of ethylene glycol slurry, embodiment 8 is to add 90 minutes before starting in polymerization reaction system, and embodiment 9 is 120 minutes, and remaining method similarly to Example 1 prepares flame-retardant polyester composition.Although some is many compared with Example 1 for embodiment 8 and the growing amount of diethylene glycol in embodiment 9, but fibrous physical property and anti-flammability are relatively good.
Comparative example 7
The kind of phosphorus compound is changed under normal temperature and pressure state the [(6-oxo-6H-dibenzo [c for liquid condition solution, e] [1,2] the own ring of oxygen phospha-6-base) methyl] double (2-hydroxyethyl) ester of succinic acid, outside the slurry replacing phosphorus compound described in embodiment 1 and ethylene glycol to be formed adds in polymerization reaction system, remaining method similarly to Example 1 prepares flame-retardant polyester composition.When polyester manufactures, the rate of dispersing of phosphorus compound is higher, and anti-flammability is bad.
Phosphorus compound 1:2-ethoxy (benzene) phosphonic acids,
Phosphorus compound 2:[(6-oxo-6H-dibenzo [c, e] [1,2] oxygen phospha own ring-6-base) methyl] double (2-hydroxyethyl) ester of succinic acid.
Claims (3)
1. the preparation method of flame-retardant polyester composition, it is characterized in that: with dicarboxylic acids or derivatives thereof and dihydroxylic alcohols for primary raw material prepare polyester time, the slurry that will be formed by weight 10:90 ~ 50:50 with ethylene glycol by the phosphorus compound shown in following formula 1, it is the amount of 0.3 ~ 1.1wt% with phosphorus element content in polymer blend, it is added in 80 minutes before polyreaction starts
Formula 1,
Wherein R1 is the alkyl of carbon number 1 ~ 18, aryl or hydroxyl.
2. according to the preparation method of the flame-retardant polyester composition described in claim 1, it is characterized in that: the phosphorus compound shown in described formula 1 is 2-ethoxy (phenyl) phosphonic acids.
The preparation method of flame-retardant polyester composition the most according to claim 1 and 2, is characterized in that: adding the slurry that phosphorus compound shown in formula 1 described in 90 minutes internal modulations before starting is formed with ethylene glycol to polymerization reaction system.
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| JP2002348364A (en) * | 2001-05-29 | 2002-12-04 | Nippon Ester Co Ltd | Method for manufacturing copolyester |
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| JP5998541B2 (en) * | 2012-03-13 | 2016-09-28 | 東レ株式会社 | Method for producing polyester composition |
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| JP6500637B2 (en) | 2019-04-17 |
| JP2016160429A (en) | 2016-09-05 |
| CN105985514B (en) | 2018-11-30 |
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