CN104558569B - A kind of flame retardant polyester and its manufacture method - Google Patents
A kind of flame retardant polyester and its manufacture method Download PDFInfo
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Abstract
The present invention relates to a kind of flame retardant polyester and its manufacture method.Contain phosphorus-containing compound construction unit in the flame retardant polyester, and relative to flame retardant polyester total amount phosphorus element content be 8000~12000ppm, diethylene glycol content be below 2.0wt%.The polyester is mainly made by terephthalic acid (TPA) and ethylene glycol by esterification and polymerisation, after esterification terminates, before polymerisation starts, adds phosphonium flame retardant, when fire retardant adds, control polymerization temperature in the kettle is at 210~230 DEG C.The excellent in flame retardance of the polyester, crystallinity is good, maintains the fusing point of conventional polyester.The dry-hot shrinkage of fiber is excellent as made by the polyester, is suitable for the nonflammable materials such as curtain.
Description
Technical field
The present invention relates to a kind of flame retardant polyester of high content of phosphorus and its manufacture method.
Background technology
Polyester fiber using polyethylene terephthalate as representative, because it has excellent mechanical strength and heat-resisting
Performance, thus be widely used in and make clothes dress material.But because polyester fiber belongs to flammable product, greatly limit its
It is required that the application in fire-retardant field.With the raising of people's fire-fighting consciousness, research of the countries in the world to fire-retardant polyester fibre and should
With becoming increasingly active, various fire-retardant polyester fibre products constantly come out.
Fire retardant is phosphonium flame retardant mostly used by polyester fiber at present, and the production technology of existing fire resistance fibre
It is increasingly mature.Current fire-retardant polyester fibre fabric is mostly used for the buntings such as automobile, curtain, to its color style, color fastness
Height ask also high.Fire-retardant polyester fibre in the market, in general it is that the fiber that phosphorus content is below 8000ppm produces
Product, these fire resistance fibre products can reach certain flame retardant effect while its fusing point is kept.Exceed on phosphorus content
8000ppm fire resistance fibre product, although also there is the technology introduction of correlation, as copolymerization phosphorus compound amount increases, polyester
Crystallinity decline, the fusing point of polyester declines to a great extent, and causes fibre shrinkage to raise, so that final products are big in feel
Give a discount.
Chinese patent application CN201110073511.2 discloses a kind of fire-retardant polyester fibre and its production method, wherein phosphorus
Constituent content is 5000~7500ppm, and DEG content is hindering in below 2.5wt% according to the fire resistance fibre that this patent obtains
Compared in combustion performance with more than phosphorus content 8000ppm fire-retardant kind, also a certain distance.According to French flame-retardant standard M0~
Outstanding 1 rank of the fire-retardant kinds of more than M4 levels 8000ppm kind more fire-retardant than below 8000ppm, phosphorus content is in below 8000ppm
When fiber fire resistance be M2, the fire resistance of phosphorus content fiber in more than 8000ppm is M1.
Japanese Patent Laid-Open H07-102418 discloses a kind of flame retardancy polyester fiber, phosphorus member in the polyester copolymerization fiber
Cellulose content is 1000~40000ppm.By controlling DEG content in 4mol% in the patent（Equivalent to 2.2wt%）Control below
The fusing point of polyester fiber makes it be unlikely to too low, once but phosphorus element content is more than 8000ppm, excessive phosphorus in polyester fiber
Compound still can cause fiber melt degradation, although this polyester fiber fire resistance is preferable, its shrinkage factor is higher,
Have an impact to the feel of fabric, greatly limit its application.While this patent does not provide high phosphorus amount high flame retardant, maintain
The method of polyester high working property energy and prompting.
The content of the invention
It is an object of the invention to provide a kind of flame retardant polyester with excellent flame retardant performance and crystal property, polyester tool
There is a good processing characteristics, the physical property of fiber therefrom is also good..
The present invention technical solution be：
A kind of flame retardant polyester, one or more of phosphorus-containing compounds as shown in formula 1, formula 2 and formula 3 are contained in the flame retardant polyester
Construction unit, and be 8000~12000ppm relative to flame retardant polyester total amount phosphorus element content, the vitrifying temperature of the flame retardant polyester
Spend TgFor 75~80 DEG C, (Tc- Tg)/phosphorus element content is 0.01~0.006 DEG C/ppm,
Formula 1,
Formula 2,
Formula 3.
Flame retardant polyester recited above, relative to flame retardant polyester total amount, preferably phosphorus element content is 9000~11000ppm,
The diethylene glycol content of flame retardant polyester is 1.4~2.0wt%.
The invention also discloses a kind of manufacture method of above-mentioned flame retardant polyester.Ester is carried out including terephthalic acid (TPA) and ethylene glycol
Change reaction and polymerisation, after esterification terminates, before polymerisation starts, one kind shown in adding type 4, formula 5 and formula 6 or
Several phosphonium flame retardants, when adding fire retardant, control polymerize temperature in the kettle at 210~230 DEG C,
Formula 4,
Formula 5,
Formula 6.
Polyester easily forms accessory substance diethylene glycol (DEG) in the course of the polymerization process（DEG）, diethylene glycol content is too high in system to cause
The problems such as crystallinity deterioration of polyester, poor heat resistance, spinning workability be poor, the difficult control of yarn shrinkage.Typically with fire-retardant
The addition of agent, the poised state of reaction system can change, diethylene glycol (DEG) are readily formed in polymerization system, is at this time controlled
The temperature of reaction system is very important, if the suitable scope of the temperature departure of reaction system, easier formation two is sweet
Alcohol..The temperature when present invention adds fire retardant by controlling efficiently controls reaction speed in the range of 210~230 DEG C,
Crystal property accessory substance such as DEG generation is influenceed, so as to effectively improve the crystallinity moulding processability of flame retardant polyester.Temperature mistake
The high glass transition temperature T for easily making flame retardant polyestergStep-down, (Tc- TgThe value of)/phosphorus element content can also become big.Temperature is too low then
The reaction speed of polyester can be influenceed, influences the production performance of polyester.
In flame retardant polyester of the present invention, relative to flame retardant polyester total amount, phosphorus element content is 8000~12000ppm.
When phosphorus element content is less than 8000ppm, the fire resistance of fiber can only achieve French flame-retardant standard M2 levels or can not obtain
Good fire-retardant stability, the desired effect of the present invention can not be met；If phosphorus element content is more than 12000ppm, except cost
Outside improving, the crystallinity of polyester fiber can also deteriorated, fusing point drastically declines, and percent thermal shrinkage is too high, and fiber process is difficult, influences
The feel and using effect of final products.The present invention is 8000~12000ppm by controlling phosphorus element content, can make fiber
Fire resistance reaches outside required value, and the processing characteristics of polyester fiber and common performance can also be maintained.
When adding fire retardant, preferably to be added in the form of the esterifying liquid of fire retardant and ethylene glycol, i.e., by fire retardant and second
Glycol carry out esterification formed esterifying liquid after add again, the phosphorus element content in the esterifying liquid configured be 2.0~
12.0wt%, the acid number of esterifying liquid is 50~300mgKOH/g.When phosphorus content in esterifying liquid is too high, esterifying liquid itself can be reduced
Esterification yield, improve the acid number of esterifying liquid, the esterifying liquid of high acid value can cause the DEG content in reaction system to rise；But it is esterified
When phosphorus content in liquid is too low, that is, adding the amount of the incidental ethylene glycol of same amount of fire retardant can increase, which improves
Reaction system alcohol so also easily causes the DEG content of system to rise, while cost also rises the mol ratio of acid.Therefore, exist
When fire retardant is added in the form of the esterifying liquid of ethylene glycol, the acid number of the content of P elements and esterifying liquid is to reaction in esterifying liquid
DEG content has a great impact in system.In addition, the acid number of the concentration of esterifying liquid, esterifying liquid is to micro impurity in polyester
Generation will also result in influence.Preferably by controlling in esterifying liquid phosphorus element content in 2.0~12.0wt% in the method for the present invention
In the range of, esterifying liquid acid number is effectively reduced and controlled the content of DEG in flame retardant polyester in the range of 50~300mgKOH/g,
The generation of micro impurity in polyester is controlled, so as to maintain the low DEG content of flame retardant polyester, makes (Tc- Tg)/phosphorus element content
In the range of 0.01~0.006 DEG C/ppm, flame retardant polyester now is easiest to process and used, while obtained polyester is fine
The fire resistance of dimension and other physical and mechanical properties are also more excellent.
Specific method of the present invention is：Terephthalic acid (TPA) and ethylene glycol are first subjected to esterification, in esterification
After end, polymerisation start before addition the ethylene glycol esterifying liquid containing one or more of fire retardants shown in 4~formula of formula 6, addition
During fire retardant control polymeric kettle in temperature at 210~230 DEG C, and control addition fire retardant and polymerization catalyst and other modification
The addition time of agent, polymerization vacuum heated up after starting, and vacuum is reached within 40~60 minutes, vacuum is low within 60 minutes
In 200Pa, polymerization start temperature is 210~260 DEG C, polymerize 270~290 DEG C of final temperature.
The flame retardant polyester obtained by above-mentioned production method, DEG content is low, accounts for below the 2.0wt% of flame retardant polyester, glass
Glass temperature TgFor 75~80 DEG C, melting temperature TmFor 230~250 DEG C, there are excellent heat resistance and crystallinity；In addition, the resistance
Phosphorus element content in retardant polyester is in 8000~12000ppm, by controlling the phosphorus in the acid number of fire retardant esterifying liquid, esterifying liquid
Content, and shorten the time of addition fire retardant, reduce addition temperature and polymerization start temperature, so as to obtain (Tc- Tg)/phosphorus
Constituent content be 0.01~0.006 DEG C/ppm flame retardant polyester, (Tc- Tg)/phosphorus element content value within the range fire retardant poly-
Ester has excellent interior molecules construction, and flame retardant polyester foreign matter growing amount in spinning process is reasonably controlled, spinning pressure
Power rises slowly, and Yarn Strength is high, and thermal finalization is good, and dry-hot shrinkage is low, excellent performance.
In addition, the fire resistance of flame retardant polyester of the present invention is good, in polyester P element contain for 8000~
12000ppm, more than M1 can be reached by the NFP of the standard anti-flammabilitys tested, and the crystallinity of polyester is good, maintains common
The fusing point of polyester.For the DEG content of the polyester in below 2.0wt%, crystallinity is good, after the polyester is made into fiber, fiber it is dry
Percent thermal shrinkage is excellent, and strength and elongation will not be deteriorated with the increase of phosphorus element content, on fast light, crocking resistance also very
It is superior, it is suitable for the nonflammable materials such as curtain.
The method of testing of some parameters involved in the present invention is as follows：
（1）DEG content（wt%）
Heat and melt using monoethanolamine as solvent, after being mixed with 1.6- ethylene glycol/methanol, then add methanol ultrasonic wave
Cleaning 10 minutes.Then add acid and carry out neutralisation treatment, after filtering, use gas chromatograph（Shimadzu Seisakusho Ltd. GC-14A）Survey
Determine filtrate.
（2）Phosphorus element content
Phosphorus element content analyzes FLX:X-RAY SPECTROMETER RIX2000, weigh a certain amount of sample and be put into aluminum pot
The RIX2000 fluorescent x-ray analysis apparatus of company's production of science is put into after being pressed into cake with trigger squeeze after heating melting on hot plate
In tested（In advance standard curve is made using standard P content sample）.
（3）Strength and elongation is accumulated
By sample in cupping machine（ORIENTEC is produced（Tensilon）UCT-100）On with JIS-L1013（1999）
8.5.1 the constant speed elongation condition in standard test is measured.Sample length is 20cm, draw speed is 20cm/ points, experiment time
Number is 10 times.Strength and elongation product can be tried to achieve by following formula,
Strength and elongation product=intensity（cN/dtex）×（Elongation at break (%)0.5）.
（4）Dry-hot shrinkage
Yarn samples 10 circles × 1m/ circles, and yarn is naturally drooped and is suspended on damping in the environment of 25 DEG C of temperature, humidity 60%
12 hours, on long table is surveyed, grammes per square metre G is determined into yarn suspension, measures former long L1（G=D × 0.9 × 0.1 × the number of turns × 2（D：Yarn
Fiber number））.The yarn surveyed is placed in thermostatic drying chamber, it is 180 DEG C × 15min to keep temperature in case, and then natural cooling, takes
Damping 12 hours in the environment of 25 DEG C of temperature, humidity 60% are hung over after going out, the good yarn suspension of damping determines grammes per square metre G, measures L2.Root
Dry-hot shrinkage is calculated according to following equation：
Damp and hot shrinkage factor（%）=（（L1- L2）/L1））×100%.
（5）Anti-flammability
Fire resistance fibre by it is woven, washing, sizing, dyeing, shape again after, according to French NF P combustion tests carry out it is fire-retardant
Grade is evaluated.Fire-retardant to have M0~M4,5 ranks, M0 is best, and M4 is worst, wherein M0：Non-ignitable, M1：High fire-retardance, M2：Fire-retardant, M3：
Flammable, M4：It is inflammable.
（6）Crystallinity（Tg/Tc/TmTest）
Its fusing point is determined using differential scanning calorimetry (DSC) (DSC), test temperature is from 50~280 DEG C, with 16 DEG C/min's
Speed heats up, and is warming up to for the first time up to being quenched after 280 DEG C, is then warming up to 280 DEG C again, then cools to 50 DEG C, Tg/Tc/Tm
Using second heating data,
P elements and crystallization sexual intercourse=(Tc- Tg)/phosphorus element content.
（7）The method of testing of fire retardant acid number
Weigh 0.2g samples（It is accurate to 0.0001g）In conical flask, add 50ml water to mix, add 10g/L instructions phenolphthalein solutions 2
Drop, blush is titrated to standard potassium hydroxide solution (0.05mol/L), and 10s colour-fast is terminal,
Fire retardant acid number=（Standard potassium hydroxide solution concentration × standard potassium hydroxide solution usage amount × 56.1）÷ is fire-retardant
Agent example weight.
Embodiment
Below by embodiment, the present invention will be described in more detail, and specific test data is shown in Table 1.
Embodiment 1
It is standby to configure the ethylene glycol esterifying liquid of fire retardant, fire retardant as shown in Equation 4 is mixed with ethylene glycol, is configured to phosphorus
The esterifying liquid A that content is 5.8wt%, acid number is 76mgKOH/g.
Will to 1150g phthalic acids and 530g ethylene glycol esterification after, before polymerisation add 215g aforementioned arrangements into
Fire retardant esterifying liquid A, for addition temperature control at 210 DEG C, 50min has added fire retardant, polymerization catalyst antimony glycol and phosphorus
Compound stabilizer, system reaches below 200Pa vacuum after 40min, and polymerization start temperature is 210 DEG C, after heating starts
120min reaches final 285 DEG C of polymerization temperature.In final gained polyester, relative to flame retardant polyester total amount, the content of P elements is
8012ppm, DEG content 1.6wt%.
Obtained flame-retardant polyester passes through drying, carries out melt spinning, in the specific implementation, employ 275 DEG C spinning temperature,
2700m/ points of obtained preoriented yarns, when then false twisting is processed, preferably 160 DEG C~190 DEG C of a heater temperature, the setting of two heater temperatures
It is set as 0.93 less than preferably 130 DEG C~170 DEG C, relaxation rate.Model 167T-48F false twist yarn, its strength and elongation product is made
For 18.7, dry-hot shrinkage 11.7%, flame retardancy test results M1.
Embodiment 2
270g esterifying liquid A are added before polymerization, and other are with embodiment 1, and the content of P elements is in obtained flame-retardant polyester
10025ppm, DEG content 1.7wt%, other the results are shown in Table 1.
Embodiment 3
330g esterifying liquid A are added before polymerization, and other are with embodiment 1, and the content of P elements is in obtained flame-retardant polyester
12019ppm, DEG content 1.8wt%, other the results are shown in Table 1.
Embodiment 4
When adding fire retardant esterifying liquid, addition temperature is 220 DEG C, and other are shown in Table with embodiment 1, obtained flame-retardant polyester property
1。
Embodiment 5
When adding fire retardant esterifying liquid, addition temperature is 230 DEG C, and other are shown in Table with embodiment 1, obtained flame-retardant polyester property
1。
Embodiment 6
It is standby to configure the ethylene glycol esterifying liquid of fire retardant, fire retardant as shown in Equation 4 is mixed with ethylene glycol, is configured to phosphorus
The esterifying liquid B that content is 6.5wt%, acid number is 85mgKOH/g.Other are shown in Table 1 with embodiment 1, obtained flame-retardant polyester property.
Embodiment 7
It is standby to configure the ethylene glycol esterifying liquid of fire retardant, fire retardant as shown in Equation 5 is mixed with ethylene glycol, is configured to phosphorus
The esterifying liquid C that content is 11.0wt%, acid number is 220mgKOH/g.
Before polymerisation add 145g aforementioned arrangements into fire retardant esterifying liquid C, other are the same as embodiment 1, obtained flame-retardant
Polyester property is shown in Table 1.
Embodiment 8
It is standby to configure the ethylene glycol esterifying liquid of fire retardant, fire retardant as shown in Equation 6 is mixed with ethylene glycol, is configured to phosphorus
The esterifying liquid D that content is 4.5wt%, acid number is 63mgKOH/g.
Before polymerisation add 440g aforementioned arrangements into fire retardant esterifying liquid D, addition temperature control at 220 DEG C, its
He is shown in Table 1 with embodiment 1, obtained flame-retardant polyester property.
Embodiment 9
Add 205g esterifying liquid A and 174g esterifying liquid D respectively before polymerisation, with embodiment 1, obtained flame-retardant gathers for other
Ester performance is shown in Table 1.
Comparative example 1
160g esterifying liquid A are added before polymerisation, when adding fire retardant esterifying liquid, addition temperature is 250 DEG C, and other are same
Embodiment 1, the content of P elements is 6032ppm in obtained flame-retardant polyester, and DEG content 2.0wt%, other the results are shown in Table 1.
Comparative example 2
460g esterifying liquid A are added before polymerisation, when adding fire retardant esterifying liquid, addition temperature is 250 DEG C, and other are same
Embodiment 1, the content of P elements is 17205ppm in obtained flame-retardant polyester, and DEG content 2.2wt%, other the results are shown in Table 1.
Comparative example 3
It is standby to configure the ethylene glycol esterifying liquid of fire retardant, fire retardant as shown in Equation 4 is mixed with ethylene glycol, is configured to phosphorus
The esterifying liquid E that content is 13wt%, acid number is 360mgKOH/g.
98g esterifying liquid E are added before polymerisation, other are with embodiment 1, and the content of P elements is in obtained flame-retardant polyester
8051ppm, DEG content 2.6wt%, other the results are shown in Table 1.
Comparative example 4
It is standby to configure the ethylene glycol esterifying liquid of fire retardant, fire retardant as shown in Equation 6 is mixed with ethylene glycol, is configured to phosphorus
The esterifying liquid F that content is 1wt%, acid number is 52mgKOH/g.
1565g esterifying liquid E are added before polymerisation, when adding fire retardant esterifying liquid, addition temperature is 250 DEG C, other
With embodiment 1, the content of P elements is 10022ppm in obtained flame-retardant polyester, and DEG content 2.2wt%, other the results are shown in Table 1.
Claims (3)
1. a kind of manufacture method of flame retardant polyester, it is made by terephthalic acid (TPA) and ethylene glycol by esterification and polymerisation,
It is characterized in that：After esterification terminates, before polymerisation starts, the one kind or several of addition structure as shown in formula 4, formula 5 and formula 6
Kind phosphonium flame retardant, when fire retardant adds, control polymerize temperature in the kettle at 210~230 DEG C,
Formula 4,
Formula 5,
Formula 6,
When adding the fire retardant, to be added in the form of the esterifying liquid of fire retardant and ethylene glycol, the phosphorus content in esterifying liquid is 2.0
~12.0wt%, the acid number of esterifying liquid is 50~300mgKOH/g；
Containing one or more of phosphorus-containing compound construction units as shown in formula 1, formula 2 and formula 3 in the flame retardant polyester, and relatively
In the glass transition temperature T that flame retardant polyester total amount phosphorus element content is 8000~12000ppm, the flame retardant polyestergFor 75~80 DEG C,
(Tc- Tg)/phosphorus element content is 0.01~0.006 DEG C/ppm,
Formula 1,
Formula 2,
Formula 3.
2. the manufacture method of flame retardant polyester according to claim 1, it is characterized in that：Relative to flame retardant polyester total amount, P elements
Content is 9000~11000ppm.
3. the manufacture method of flame retardant polyester according to claim 1 or claim 2, it is characterized in that：It is sweet relative to flame retardant polyester total amount, two
Alcohol content is 1.4~2.0wt%.
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| CN106366302B (en) * | 2016-08-26 | 2018-02-09 | 东华大学 | A kind of fire-retardant hydrophilic polyester resin and preparation method thereof |
| CN110294840B (en) * | 2019-06-25 | 2021-08-10 | 三峡大学 | Synthetic method of UV-LED curing vinyl-terminated water-based flame-retardant polyester |
| CN110951223A (en) * | 2019-12-06 | 2020-04-03 | 江苏垶恒复合材料有限公司 | High-flame-retardant recycled PET material and preparation method thereof |
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| CN101376690A (en) * | 2007-08-30 | 2009-03-04 | 中国石化上海石油化工股份有限公司 | Preparation of flame-retardant polyester for preparing fiber |
| EP2090618A2 (en) * | 2008-02-15 | 2009-08-19 | Schill + Seilacher "Struktol" Aktiengesellschaft | Hardenable epoxy resin formulation with polyester flame retardant |
| CN101838388A (en) * | 2009-03-18 | 2010-09-22 | 东丽纤维研究所（中国）有限公司 | Flame-retardant polyester with low diglycol content and production method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101376690A (en) * | 2007-08-30 | 2009-03-04 | 中国石化上海石油化工股份有限公司 | Preparation of flame-retardant polyester for preparing fiber |
| EP2090618A2 (en) * | 2008-02-15 | 2009-08-19 | Schill + Seilacher "Struktol" Aktiengesellschaft | Hardenable epoxy resin formulation with polyester flame retardant |
| CN101838388A (en) * | 2009-03-18 | 2010-09-22 | 东丽纤维研究所（中国）有限公司 | Flame-retardant polyester with low diglycol content and production method and application thereof |
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