CN104119538A - Flame retardant and preparation method thereof, and flame-retardant polyester and application thereof - Google Patents
Flame retardant and preparation method thereof, and flame-retardant polyester and application thereof Download PDFInfo
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Abstract
The invention discloses a flame retardant and a preparation method thereof, and a flame-retardant polyester containing the flame retardant and an application thereof. The flame retardant is formed by polymerizing flame-retardant monomers with glycol, and has the polymerization degree above 4. When the flame-retardant polyester is synthesized, the flame retardant can be added during an esterification reaction or a condensation polymerization reaction for synthesizing the polyester, and can be mixed with the polyester so as to be added together. The obtained flame-retardant polyester has durable and excellent flame retardance, and has the characteristics of high melting point, high heat stability and good spinnability. Thus, the flame-retardant polyester can be used for preparing flame-retardant fibers, films, resins and the like.
Description
Technical field
The present invention relates to a kind of fire retardant, the preparation method of this fire retardant, the flame retardant polyester that contains this fire retardant and the purposes of this flame retardant polyester.
Background technology
Along with the raising of people's fire-fighting consciousness, research and the application and development of countries in the world to flame retardant polyester and fiber becomes increasingly active, and various flame retardant polyesters and fiber product constantly come out.
The method for modifying flame of polyester has two kinds of blend and copolymerization.Copolymerization method is in polyester production process, to add the compound that contains two or more active function groups and contain certain ignition-proof element to do flame-retardant monomer to pass through the flame-retardant modified polyester of copolymerization, compared with blending method, because its product flame retardant properties is stable, lasting and good spinnability becomes the Main Means of current polyester flame-retardant modification.But, due to adding of flame-retardant monomer, Tg, the Tc of polyester, Tm, Tp, △ Hm, degree of crystallinity etc. are all linear and decline, cause physicals and the resistance toheat of polyester to decline to a great extent, affect the processing effects such as its spinning, false twisting, dyeing, make the color and luster variation of polyester slice and even final fabric, xanthochromia b value increase.
Main halogen-containing or phosphorous for the fire retardant of polyester flame-retardant modification, because halogen belongs to gas phase fire retardant mechanism, have and be fuming greatly and easily produce halogen gas and the shortcoming of corrosion processing equipment substantially all adopts phosphonium flame retardant at present.But existing phosphor-containing flame-retardant copolyester generally all exists thermal characteristics or poor mechanical property, and when spinning, yarn orientation and intensity are low, be therefore necessary further to research and develop high performance flame retardant polyester.In addition, fire-retardant polyester fibre fabric is used for greatly the bunting of automobile, curtain etc., to its color style, colour fastness (especially light fastness) require high.
summary of the invention:
The object of the present invention is to provide a kind of fire retardant, the preparation method of this fire retardant, the flame retardant polyester that contains this fire retardant and the purposes of this flame retardant polyester.
Technical solution of the present invention is:
A kind of fire retardant, this fire retardant comprises as shown in the formula one or more in compound shown in 1～formula 5,
formula 1
formula 2
formula 3
formula 4
formula 5
In formula, n, m, s, u, v are respectively more than 4 integers, and preferably n, m, s, u, v are respectively 8～50 integer.Described R
1, R
3, R
5, R
7, R
9be respectively the alkylidene group of carbonatoms 0～20 or the aromatic base of carbonatoms 6～20, R
8for the alkylidene group of carbonatoms 1～20 or the aromatic base of carbonatoms 6～20, R
2, R
4, R
6, R
10be respectively the alkyl of hydrogen base or carbonatoms 1～20.
The preparation method of above-mentioned fire retardant will carry out esterification suc as formula the flame-retardant monomer shown in 6～formula 10 and glycol respectively at 60～220 DEG C, and then carries out polyreaction under 120～290 DEG C of vacuum conditions,
formula 6
formula 7
formula 8
formula 9
formula 10.
Common to produce what use when flame retardant polyester by copolymerization process be all flame-retardant monomer or its esterifying liquid of small molecules amount, and the regularity that adds membership and destroy polyester chain of small molecules thing, reduces polyester second-order transition temperature, fusing point etc., and the thermotolerance of polyester declines larger.Even if use the method for blend, under the effect of threaded rod shear shear force, small molecules flame-retardant monomer also can react with polyester.
The thermotolerance of the flame-retardant monomer esterifying liquid of the flame-retardant monomer of small molecules amount or small molecules amount is poor in addition, just starts above to decompose at 220 DEG C.The present invention by the method for the esterification between flame-retardant monomer and glycol and polyreaction, obtains having the fire retardant of certain molecular weight by this, no matter with which kind of form, this fire retardant is added and is entered in polyester, and the regularity of polyester chain is destroyed and reduced.And the fire retardant with certain molecular weight has good thermotolerance, decomposition temperature is more than 300 DEG C, reduce greatly so its side reaction is corresponding in use, the properties such as fusing point, thermotolerance and the color and luster of the flame retardant polyester obtaining are better than the flame retardant polyester that uses small molecules flame-retardant monomer or its esterifying liquid to obtain.In when burning, having the fire retardant of certain molecular weight, it is higher than the one-tenth carbon of small molecules flame-retardant monomer or esterifying liquid, and the anti-drippage of corresponding flame retardant polyester might as well.
N, m, s, u, v in above-mentioned formula 1～formula 5 are respectively more than 4 integers, if the polymerization degree of fire retardant is very little, the performance of the flame retardant polyester that itself and pet reaction obtain is close when directly using flame-retardant monomer, and the thermotolerance of fire retardant and the flame retardant polyester that obtained by it can not get improving; Along with the raising of the fire retardant polymerization degree, its thermotolerance is also improving constantly, but excessive when the polymerization degree, as reaches 120 when above, the copolyreaction of fire retardant and polyester raw material or understand variation with the comixing compatibility of polyester.In the present invention, preferably fire retardant polymerization degree n, m, s, u, v are respectively 8～50 o'clock, the thermotolerance of fire retardant is compared common flame-retardant monomer and is improved significantly, and the copolyreaction of fire retardant and polyester raw material or all no problem with the comixing compatibility of polyester, can obtain all flame retardant polyesters of excellence of flame retardant properties and resistance toheat.
In the present invention, can be ethylene glycol, propylene glycol, butyleneglycol, pentanediol, 2 with the glycol of flame-retardant monomer copolymerization, 2-dimethyl propylene glycol, 1,2-propylene glycol, 1,2-butyleneglycol, 2, long chain diols such as 3-butyleneglycol, Isosorbide-5-Nitrae-cyclohexanedimethanol or with the glycol of functional group's side chain, also can form fire retardant when synthesizing flame retardant polyester with flame-retardant monomer polymerization.
The production method of fire retardant is specially, and will at 60～220 DEG C, carry out esterification suc as formula the flame-retardant monomer shown in 6～formula 10 and glycol first respectively, and the mol ratio of flame-retardant monomer and glycol is 1:1.5～10; Then by the esterification products obtaining under catalyst action, under vacuum, the condition of 120～290 DEG C, carry out polymerization, obtain respectively the fire retardant more than 4 suc as formula the polymerization degree shown in 1～formula 5.The catalyzer of polymerization stage can be the anti-applications catalyst of conventional polyester, is mainly zinc class, antimony class and titanium class, as zinc acetate, antimonous oxide, antimony glycol, tetrabutyl titanate etc.This polymerization degree obtains by said temperature and catalyst levels, the time of polyreaction, the isoparametric moderate control of power of agitator, and these parameters all belong to the conventional category of polyreaction.
In the time using the fire retardant being made by aforesaid method, can in the fire retardant suc as formula structure shown in 1～formula 5, select as required one and use separately, also can mix and use with arbitrary combination and ratio.
The invention also discloses the flame retardant polyester that contains above-mentioned fire retardant, this fire retardant can form by add fire retardant copolymerization in the polyreaction of polyester, also fire retardant and polyester can be obtained by blending reaction.
In front a kind of scheme, polyester is mainly obtained through over-churning and polycondensation by diprotic acid and dibasic alcohol, in esterification or polycondensation, adds fire retardant, and in flame retardant polyester, the content of fire retardant accounts for 0.2%～4.0% of final flame retardant polyester weight in phosphoric.Described diprotic acid can be the terephthalic acid or derivatives thereof of various purity, and dibasic alcohol can be the aliphatic dihydroxy alcohols such as ethylene glycol, propylene glycol, butyleneglycol.In the polyreaction of polyester, can also add as required the additive of various functions, as static inhibitor, sulfonic acid group compound, opalizer, anti ultraviolet agent etc.
In first scheme, polyester and fire retardant are carried out to blending extrusion, obtain flame retardant polyester, wherein the content of fire retardant accounts for 0.2%～4.0% of final flame retardant polyester weight in phosphoric.Concrete, first the vibrin section that does not contain flame-retardant composition being dried, drying temperature is 80～150 DEG C, the moisture content of dry rear section is below 100ppm; Then dried polyester slice and fire retardant are dropped into by a certain percentage in twin screw extruder, mix extrude, granulation, obtain a kind of flame retardancy polyester, wherein the ratio of polyester slice and fire retardant accounts for 0.2%～4.0% calculating of final flame retardant polyester weight according to phosphoric in fire retardant.Here said polyester can be polyethylene terephthalate (PET), Poly(Trimethylene Terephthalate) (PTT), polybutylene terephthalate (PBT) etc., in polyester, also can contain just like static inhibitor, containing various functional reagents such as sulfonic acid group compound, opalizer, anti ultraviolet agents.
No matter be above-mentioned the first scheme or first scheme, in the flame retardant polyester finally obtaining, the content of fire retardant all accounts for 0.2%～4.0% of flame retardant polyester weight in phosphoric, and preferably 1.0%～4.0%.
Directly prepare flame retardant polyester in the mode of polymerization or blend with micromolecular flame-retardant monomer, in fire retardant, phosphorus element content accounts for flame retardant polyester weight 0.8% when above, and the fusing point of flame retardant polyester is less than 240 DEG C substantially, and thermotolerance is bad.Therefore if obtain the flame retardant polyester of good flame retardant effect, will certainly add the usage quantity that increases fire retardant, cause the fusing point of flame retardant polyester further to decline, poor heat resistance.
The present invention is just by there being the use suc as formula fire retardant shown in 1～formula 5 of certain polymerization degree, even account for 4.0% of flame retardant polyester weight in phosphoric fire retardant in flame retardant polyester, its fusing point still can remain on more than 240 DEG C, make this flame retardant polyester not only there is high-melting-point, high heat resistance, also there is lasting, good flame retardant properties, and good spinnability.
Above-mentioned flame retardant polyester can be applicable to the various fields that have fire-retardant requirement, as fiber, film, resin etc.
The evaluation method the present invention relates to has:
(1) fusing point (Tm):
Use differential scanning calorimeter (DSC) to measure its fusing point, probe temperature is from 50～280 DEG C, with 16 DEG C/min.
(2) molecular weight determination (GPC):
By Waters 1515 type gel permeation chromatographs, make moving phase with tetrahydrofuran (THF), record weight-average molecular weight Mw, then pass through formula: the polymerization degree=Mw/ repeated structural unit molecular weight, obtains the approximate polymerization degree.
(3) limiting oxygen index(LOI) (LOI):
Fiber or the fabric of by JIS L 1,091 1999 E methods, flame retardant polyester being cut into slices or make are tested, cut into slices or the fiber worked out or the limiting oxygen index(LOI) (LOI) of fabric are evaluated its flame retardant properties by mensuration, the flame retardant resistance of the higher explanation flame retardant polyester of LOI value is better.
Embodiment
Below by embodiment, technical scheme of the present invention is explained in more detail, but the present invention is not limited to these embodiments.
Embodiment 1
Fire retardant A: the flame-retardant monomer shown in formula 6 and the each 300g of ethylene glycol are carried out to transesterification reaction at 120 DEG C, in esterification products, add 0.5g zinc acetate, 0.3g antimonous oxide, under vacuum, the condition of 220 DEG C, carry out polymerization, control vacuum tightness below 200Pa, after polymerization 2.5 hours, obtain fire retardant A as shown in Equation 1.The weight-average molecular weight Mw that records this fire retardant by Waters 1515 type gel permeation chromatographs, calculates its polymerization degree in 15 left and right.
Flame retardant polyester: the EG of the PTA of 1300g and 560g made to slurry and move in reaction kettle of the esterification, keeping temperature of reaction to stir 4 hours at 240～250 DEG C; Judge that by by product esterification rate reaches 97% and carboxylate moved into polymeric kettle 1500g when above.At room temperature, in polymeric kettle, add stablizer phosphatase 11 30ppm, catalyst acetic acid lithium 1000ppm, accounts for the fire retardant A of final flame retardant polyester 1.2wt% in phosphoric, separately in polymeric kettle, can also add TITANIUM DIOXIDE DELUSTRANT, Titanium series catalyst etc.Above-mentioned substance is carried out to polymerization with conventional condensation methods in polymeric kettle, make flame retardant polyester.The test result of flame retardant polyester specific performance is in table 1.
Embodiment 2
Fire retardant B: the flame-retardant monomer shown in formula 7 is reacted to the fire retardant B obtaining as shown in Equation 2 according to the method for embodiment 1 with 1,2-PD.The weight-average molecular weight Mw that records this fire retardant by Waters 1515 type gel permeation chromatographs, calculates its polymerization degree in 15 left and right.
Flame retardant polyester: add the fire retardant A that accounts for final flame retardant polyester 1.2wt% in phosphoric in polymeric kettle, other make flame retardant polyester with embodiment 1.The test result of flame retardant polyester specific performance is in table 1.
Embodiment 3
Fire retardant C: the flame-retardant monomer shown in formula 8 is reacted to the fire retardant C obtaining as shown in Equation 3 according to the method for embodiment 1 with Isosorbide-5-Nitrae-cyclohexanedimethanol.The weight-average molecular weight Mw that records this fire retardant by Waters 1515 type gel permeation chromatographs, calculates its polymerization degree in 15 left and right.
Flame retardant polyester: add the fire retardant C that accounts for final flame retardant polyester 1.2wt% in phosphoric in polymeric kettle, other make flame retardant polyester with embodiment 1.The test result of flame retardant polyester specific performance is in table 1.
Embodiment 4
Fire retardant D: fire retardant A and B are mixed according to the ratio of weight 1:1.
Flame retardant polyester: add the fire retardant D that accounts for final flame retardant polyester 1.2wt% in phosphoric in polymeric kettle, other make flame retardant polyester with embodiment 1.The test result of flame retardant polyester specific performance is in table 1.
Embodiment 5
Fire retardant E: fire retardant A, B and C are mixed according to the ratio of weight 2:3:4.
Flame retardant polyester: add the fire retardant E that accounts for final flame retardant polyester 2.2wt% in phosphoric in polymeric kettle, other make flame retardant polyester with embodiment 1.The test result of flame retardant polyester specific performance is in table 1.
Embodiment 6
In polymeric kettle, add the fire retardant A that accounts for final flame retardant polyester 4.0wt% in phosphoric, other make flame retardant polyester with embodiment 1.The test result of flame retardant polyester specific performance is in table 1.
Embodiment 7
In polymeric kettle, add the fire retardant A that accounts for final flame retardant polyester 0.6wt% in phosphoric, other make flame retardant polyester with embodiment 1.The test result of flame retardant polyester specific performance is in table 1.Embodiment 8
In polymeric kettle, add the fire retardant A that accounts for final flame retardant polyester 0.2wt% in phosphoric, other make flame retardant polyester with embodiment 1.The test result of flame retardant polyester specific performance is in table 1.Embodiment 9
Fire retardant F: taking the flame-retardant monomer shown in formula 6 and ethylene glycol as raw material, according to the method for embodiment 1, adjust the polycondensation time, obtaining the final polymerization degree is the fire retardant F as shown in Equation 1 of 10 left and right.
Flame retardant polyester: add the fire retardant F that accounts for final flame retardant polyester 2.2wt% in phosphoric in polymeric kettle, other make flame retardant polyester with embodiment 1.The test result of flame retardant polyester specific performance is in table 1.
Embodiment 10
Fire retardant G: taking the flame-retardant monomer shown in formula 6 and ethylene glycol as raw material, according to the method for embodiment 1, adjust the polycondensation time, obtaining the final polymerization degree is the fire retardant G as shown in Equation 1 of 3 left and right.
Flame retardant polyester: add the fire retardant G that accounts for final flame retardant polyester 1.2wt% in phosphoric in polymeric kettle, other make flame retardant polyester with embodiment 1.The test result of flame retardant polyester specific performance is in table 1.
Embodiment 11
Fire retardant H: taking the flame-retardant monomer shown in formula 6 and ethylene glycol as raw material, according to the method for embodiment 1, adjust the polycondensation time, obtaining the final polymerization degree is the fire retardant H as shown in Equation 1 of 50 left and right.
Flame retardant polyester: add the fire retardant H that accounts for final flame retardant polyester 1.2wt% in phosphoric in polymeric kettle, other make flame retardant polyester with embodiment 1.The test result of flame retardant polyester specific performance is in table 1.
Embodiment 12
Fire retardant I: taking the flame-retardant monomer shown in formula 6 and ethylene glycol as raw material, according to the method for embodiment 1, adjust the polycondensation time, obtaining the final polymerization degree is the fire retardant I as shown in Equation 1 of 90 left and right.
Flame retardant polyester: add the fire retardant I that accounts for final flame retardant polyester 3.2wt% in phosphoric in polymeric kettle, other make flame retardant polyester with embodiment 1.The test result of flame retardant polyester specific performance is in table 1.
Embodiment 13
Fire retardant J: according to the method for embodiment 1, respectively the flame-retardant monomer shown in formula 6～formula 8 is reacted with 1,2-PD, and adjusting reaction time, obtain respectively the fire retardant in 50 left and right suc as formula the polymerization degree shown in 1～formula 3, then by these 3 kinds of fire retardants with etc. weight ratio mix.
Flame retardant polyester: add the fire retardant J that accounts for final flame retardant polyester 3.2wt% in phosphoric in polymeric kettle, other make flame retardant polyester with embodiment 1.The test result of flame retardant polyester specific performance is in table 1.
Embodiment 14
Selecting limiting viscosity is the half delustring PET polyester slice 1000g of 0.7dl/g, first section is placed in hot air drier and is dried 4～5 hours under 80 DEG C of conditions, put under 120 DEG C of conditions of vacuum drying oven again and be dried 12～36 hours, the water content of dried section is below 100ppm.Above-mentioned dried PET section is put into the hopper of twin screw extruder, screw rod 1 is carried half delustring PET polyester slice, screw rod 2 is carried fire retardant A, then carry out twin screw mix extrude, granulation, the addition of fire retardant A accounts for the 1.2wt% of final fire-retardant polyester with phosphoric metering.The test result of flame retardant polyester specific performance is in table 1.
Miscible granulation process parameters is: the each district of twin screw extruder temperature, a district: 200 DEG C; 2nd district: 260 DEG C; 3rd district: 270 DEG C; 4th district: 270 DEG C; 5th district: 270 DEG C; 6th district: 270 DEG C; 7th district: 270 DEG C; 8th district: 270 DEG C; 9th district: 260 DEG C; Screw pressure: 0.2Mpa; Screw speed: 160rpm; After water-bath is cooling, be to cut into grain under 80rpm pelletizing speed at dicing machine rotating speed.
Embodiment 15
Fire retardant during with dried PET section blend changes fire retardant B into, and other make flame retardant polyester with embodiment 14.The test result of flame retardant polyester specific performance is in table 1.
Embodiment 16
Fire retardant during with dried PET section blend changes fire retardant C into, and other make flame retardant polyester with embodiment 14.The test result of flame retardant polyester specific performance is in table 1.
Embodiment 17
Fire retardant during with dried PET section blend changes fire retardant J into, and other make flame retardant polyester with embodiment 14.The test result of flame retardant polyester specific performance is in table 1.
Embodiment 18
Fire retardant K: the flame-retardant monomer shown in formula 9 is reacted to the fire retardant K obtaining as shown in Equation 4 according to the method for embodiment 1 with Isosorbide-5-Nitrae-cyclohexanedimethanol.The weight-average molecular weight Mw that records this fire retardant by Waters 1515 type gel permeation chromatographs, calculates its polymerization degree in 15 left and right.
Flame retardant polyester: add the fire retardant K that accounts for final flame retardant polyester 1.2wt% in phosphoric in polymeric kettle, other make flame retardant polyester with embodiment 1.The test result of flame retardant polyester specific performance is in table 1.
Embodiment 19
Fire retardant L: the flame-retardant monomer shown in formula 9 is reacted to the fire retardant L obtaining as shown in Equation 5 according to the method for embodiment 1 with 1,2-PD.The weight-average molecular weight Mw that records this fire retardant by Waters 1515 type gel permeation chromatographs, calculates its polymerization degree in 15 left and right.
Flame retardant polyester: add the fire retardant L that accounts for final flame retardant polyester 1.2wt% in phosphoric in polymeric kettle, other make flame retardant polyester with embodiment 1.The test result of flame retardant polyester specific performance is in table 1.
Embodiment 20
Fire retardant during with dried PET section blend changes fire retardant L into, and other make flame retardant polyester with embodiment 14.The test result of flame retardant polyester specific performance is in table 1.
Embodiment 21
Fire retardant M: according to the method for embodiment 1, respectively the flame-retardant monomer shown in formula 6～formula 10 is reacted with 1,2-PD, and adjusting reaction time, obtain respectively the fire retardant in 50 left and right suc as formula the polymerization degree shown in 1～formula 5, then by this in 5 fire retardant with etc. weight ratio mix.
Fire retardant during with dried PET section blend changes fire retardant M into, and other make flame retardant polyester with embodiment 14.The test result of flame retardant polyester specific performance is in table 1.
Comparative example 1
Use monomer fire retardant as shown in Equation 6 to prepare flame retardant polyester with embodiment 1, its test result is in table 1.
Comparative example 2
Use monomer fire retardant as shown in Equation 7 to prepare flame retardant polyester with embodiment 1, its test result is in table 1.
Comparative example 3
Use monomer fire retardant as shown in Equation 8 to prepare flame retardant polyester with embodiment 1, its test result is in table 1.
Comparative example 4
Monomer fire retardant shown in formula 6～formula 8, to wait part by weight to mix, is prepared to flame retardant polyester with embodiment 1, and its test result is in table 1.
Comparative example 5
Use monomer fire retardant as shown in Equation 9 to prepare flame retardant polyester with embodiment 1, its test result is in table 1.
Comparative example 6
Use monomer fire retardant as shown in Equation 10 to prepare flame retardant polyester with embodiment 1, its test result is in table 1.
Comparative example 7
Monomer fire retardant shown in formula 6～formula 10, to wait part by weight to mix, is prepared to flame retardant polyester with embodiment 1, and its test result is in table 1.
Table 1
Claims (8)
1. a fire retardant, is characterized in that: this fire retardant comprises as shown in the formula one or more in compound shown in 1～formula 5,
formula 1
formula 2
formula 3
formula 4
formula 5
In formula, n, m, s, u, v are respectively more than 4 integers, described R
1, R
3, R
5, R
7, R
9be respectively the alkylidene group of carbonatoms 0～20 or the aromatic base of carbonatoms 6～20, R
8for the alkylidene group of carbonatoms 1～20 or the aromatic base of carbonatoms 6～20, R
2, R
4, R
6, R
10be respectively the alkyl of hydrogen base or carbonatoms 1～20.
2. fire retardant according to claim 1, is characterized in that: described n, m, s, u, v are respectively 8～50 integer.
3. a preparation method for fire retardant described in claim 1, is characterized in that: the method is will at 60～220 DEG C, to carry out esterification suc as formula the flame-retardant monomer shown in 6～formula 10 and glycol respectively, and then carries out polyreaction under 120～290 DEG C of vacuum conditions,
formula 6
formula 7
formula 8
formula 9
formula 10.
4. a flame retardant polyester that contains fire retardant described in claim 1, mainly by diprotic acid and dibasic alcohol through over-churning and polycondensation, it is characterized in that: in esterification or polycondensation, add fire retardant, its content accounts for 0.2%～4.0% of flame retardant polyester weight in phosphoric.
5. a flame retardant polyester that contains fire retardant described in claim 1, is characterized in that: polyester and fire retardant are carried out to blending extrusion, obtain flame retardant polyester, wherein the content of fire retardant accounts for 0.2%～4.0% of final flame retardant polyester weight in phosphoric.
6. according to the flame retardant polyester described in claim 4 or 5, it is characterized in that: in this flame retardant polyester, the content of fire retardant accounts for 1.0%～4.0% of flame retardant polyester weight in phosphoric.
7. according to the flame retardant polyester described in claim 4 or 5, it is characterized in that: the fusing point of this flame retardant polyester is more than 240 DEG C.
Described in a claim 4 or 5 flame retardant polyester in the application of preparing in fire-retardant fibre, film, resin.
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| CN106366302A (en) * | 2016-08-26 | 2017-02-01 | 东华大学 | Flame-retardant hydrophilic polyester resin and preparing method thereof |
| CN106977884A (en) * | 2016-01-18 | 2017-07-25 | 中国石油化工股份有限公司 | Atactic polyester composition and preparation method thereof and flame retardant polyester composition and preparation method thereof |
| CN106977706A (en) * | 2016-01-18 | 2017-07-25 | 中国石油化工股份有限公司 | Atactic polyester composition and preparation method thereof and flame retardant polyester composition and preparation method thereof |
| CN107326458A (en) * | 2017-06-22 | 2017-11-07 | 江苏飞翔化工股份有限公司 | A kind of flame-retardant polyester fiber and preparation method thereof |
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| CN114634688A (en) * | 2022-04-26 | 2022-06-17 | 华润化学材料科技股份有限公司 | Flame-retardant polyester with good toughness and preparation method thereof |
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| CN106279765A (en) * | 2015-06-11 | 2017-01-04 | 东丽纤维研究所（中国）有限公司 | A kind of fire retardant and preparation method thereof, use the copolyesters of this fire retardant and the preparation method of copolyesters and purposes |
| CN106279765B (en) * | 2015-06-11 | 2019-06-25 | 东丽纤维研究所（中国）有限公司 | A kind of fire retardant and preparation method thereof uses the copolyesters of the fire retardant and the preparation method of copolyesters and purposes |
| CN106977706A (en) * | 2016-01-18 | 2017-07-25 | 中国石油化工股份有限公司 | Atactic polyester composition and preparation method thereof and flame retardant polyester composition and preparation method thereof |
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| CN106366302A (en) * | 2016-08-26 | 2017-02-01 | 东华大学 | Flame-retardant hydrophilic polyester resin and preparing method thereof |
| CN107881580A (en) * | 2016-09-29 | 2018-04-06 | 中国石化仪征化纤有限责任公司 | A kind of continuous producing method of fire-retardant polyester fibre |
| CN107881580B (en) * | 2016-09-29 | 2020-05-01 | 中国石化仪征化纤有限责任公司 | Continuous production method of flame-retardant polyester fiber |
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| CN114634688A (en) * | 2022-04-26 | 2022-06-17 | 华润化学材料科技股份有限公司 | Flame-retardant polyester with good toughness and preparation method thereof |
| CN114634688B (en) * | 2022-04-26 | 2023-09-01 | 华润化学材料科技股份有限公司 | Flame-retardant polyester with good toughness and preparation method thereof |
| CN116515094A (en) * | 2023-07-04 | 2023-08-01 | 中国天辰工程有限公司 | Preparation method of flame-retardant degradable polyester and degradable copolymerized flame retardant |
| CN116515094B (en) * | 2023-07-04 | 2023-09-29 | 中国天辰工程有限公司 | Preparation method of flame-retardant degradable polyester and degradable copolymerized flame retardant |
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