CN109438686A - A kind of flame retardant polyester containing the liquid flame retardant based on diphenylphosphoryl propionic acid binaryglycol ester - Google Patents
A kind of flame retardant polyester containing the liquid flame retardant based on diphenylphosphoryl propionic acid binaryglycol ester Download PDFInfo
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- CN109438686A CN109438686A CN201811443684.7A CN201811443684A CN109438686A CN 109438686 A CN109438686 A CN 109438686A CN 201811443684 A CN201811443684 A CN 201811443684A CN 109438686 A CN109438686 A CN 109438686A
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- Prior art keywords
- flame retardant
- propionic acid
- diphenylphosphoryl
- binaryglycol ester
- acid binaryglycol
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 82
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229920000728 polyester Polymers 0.000 title claims abstract description 46
- 239000007788 liquid Substances 0.000 title claims abstract description 43
- 150000002148 esters Chemical class 0.000 title claims abstract description 40
- WDBPYVIWNRQTHC-UHFFFAOYSA-N 2-diphenylphosphorylpropanoic acid Chemical compound C=1C=CC=CC=1P(=O)(C(C(O)=O)C)C1=CC=CC=C1 WDBPYVIWNRQTHC-UHFFFAOYSA-N 0.000 title claims abstract description 38
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 63
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000654 additive Substances 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 10
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 32
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 32
- 235000019260 propionic acid Nutrition 0.000 claims description 16
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 11
- -1 diglycol ester Chemical class 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- 125000004464 hydroxyphenyl group Chemical group 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 4
- 239000001639 calcium acetate Substances 0.000 claims description 4
- 235000011092 calcium acetate Nutrition 0.000 claims description 4
- 229960005147 calcium acetate Drugs 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229960000314 zinc acetate Drugs 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims 1
- 229940100996 sodium bisulfate Drugs 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000032050 esterification Effects 0.000 description 10
- 238000005886 esterification reaction Methods 0.000 description 10
- 238000009987 spinning Methods 0.000 description 10
- 125000004208 3-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C([H])C(*)=C1[H] 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 238000006068 polycondensation reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RSSDWSPWORHGIE-UHFFFAOYSA-N $l^{1}-phosphanylbenzene Chemical compound [P]C1=CC=CC=C1 RSSDWSPWORHGIE-UHFFFAOYSA-N 0.000 description 1
- 241000876833 Emberizinae Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005360 mashing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6926—Dicarboxylic acids and dihydroxy compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Fireproofing Substances (AREA)
Abstract
This application involves a kind of flame retardant polyesters containing the liquid flame retardant based on diphenylphosphoryl propionic acid binaryglycol ester, are made of following raw material components: p-phthalic acid, ethylene glycol, additive and the liquid flame retardant based on diphenylphosphoryl propionic acid binaryglycol ester；Wherein, the liquid flame retardant based on diphenylphosphoryl propionic acid binaryglycol ester includes with the diphenylphosphoryl propionic acid binaryglycol ester by structure shown in the following general formula (I):
Description
Technical field
This application involves flame retardant polyester technical fields.Specifically, this application involves one kind containing based on diphenylphosphoryl propionic acid
The flame retardant polyester of the liquid flame retardant of binaryglycol ester.
Background technique
3- hydroxy phenyl phosphinylidyne propionic acid (CEPPA) is a kind of white powder fire retardant, is commonly used for chemical fibre nylon polyesters
Fire retardant, structure are as follows:
3- hydroxy phenyl phosphinylidyne propionic acid category response type (copoly type) phosphorus system environment friendly flame retardant, the permanent resistance suitable for polyester
Combustion is modified, and being widely used in weaving, fire-retardant, spinning is fire-retardant, chemical fibre is fire-retardant, the flame retardant area of various dress materials, bunting etc..Addition
Flame retardant polyester product spinning property after 3- hydroxy phenyl phosphinylidyne propionic acid has compared with conventional PET and is sliced phase with normal polyester
Same spinning and tensile property, flame retardant polyester product have excellent thermal stability, do not decompose during the spinning process, spinning
Live free from extraneous odour, can be improved the antistatic property of polyester product, good spinnability, and fiber has good weavability, can pass through
Any spinning system carries out spinning processing, and fabric can get permanent fire retardant performance.With p-phthalic acid (PTA), ethylene glycol
(EG) when being copolymerized, the additive amount of 3- hydroxy phenyl phosphinylidyne propionic acid is usually 2.5~4.5%, and the phosphorus content of flame retardant polyester slice is
0.35-0.60%, the anti-flammability limit oxygen index after spinning fabric are 30~36%.
But in the use process of CEPPA, following deficiency is still had: firstly, because the structure of CEPPA includes phosphoric acid and carboxylic
Sour structure causes it that stronger acidity is presented, and can corrode chemical industry equipment in Reusability, shortens service life of equipment；Secondly,
When directly reacting to prepare flame retardant polyester with PTA and EG using CEPPA, acid CEPPA can promote EG that polycondensation reaction occurs,
It generates diglycol (DEG), causes the DEG content in polyester slice higher, it is subsequent that this can negatively affect polyester slice
Spinning properties.
For this purpose, this field is there is still a need for developing, a kind of diglycol content is low to be contained based on diphenylphosphoryl propionic acid diethyl two
The flame retardant polyester of the liquid flame retardant of alcohol ester.
Summary of the invention
A kind of low the containing of diglycol content that be designed to provide of the application is based on diphenylphosphoryl propionic acid diethyl two
The flame retardant polyester of the liquid flame retardant of alcohol ester, thus solve it is above-mentioned in the prior art the technical issues of.Specifically, the application
Flame retardant polyester is by p-phthalic acid, ethylene glycol, catalyst and liquid flame retardant based on diphenylphosphoryl propionic acid binaryglycol ester
It is made.Herein disclosed liquid flame retardant includes the modified hydroxy phenyl phosphinylidyne propionic acid of spent glycol, converts thereof into phenyl
Phosphinylidyne propionic acid binaryglycol ester, significantly reduces the acidity of liquid flame retardant.In addition, passing through the specific neutral salt catalyst of selection
It is catalyzed reacting for hydroxy phenyl phosphinylidyne propionic acid and ethylene glycol, significantly reduces gained liquid flame retardant diphenylphosphoryl propionic acid diethyl
The content of diglycol in diol ester, and then the content of diglycol in subsequent flame retardant polyester can be reduced.
To achieve the goals above, the application provides following technical proposals.
In the first aspect, the application provides a kind of containing the liquid flame retardant based on diphenylphosphoryl propionic acid binaryglycol ester
Flame retardant polyester is made of following raw material components: p-phthalic acid, ethylene glycol, additive and be based on diphenylphosphoryl propionic acid two
The liquid flame retardant of glycol ester；
Wherein, the liquid flame retardant based on diphenylphosphoryl propionic acid binaryglycol ester includes having to pass through the following general formula (I) institute
Show the diphenylphosphoryl propionic acid binaryglycol ester of structure:
Wherein, group R1, R2, R3, R4 and R5 each independently represent hydrogen atom, linear chain or branched chain C1-C6 alkyl.
In a kind of embodiment of first aspect, group R1, R2, R3, R4 and R5 each independently represent methyl, second
Base, propyl, isopropyl, normal-butyl or isobutyl group.
In a kind of embodiment of first aspect, group R1, R2, R3, R4 and R5 are hydrogen atom.
In a kind of embodiment of first aspect, the liquid flame retardant based on diphenylphosphoryl propionic acid binaryglycol ester
It is prepared by following methods:
Under 140-180 DEG C of reaction temperature, and under conditions of there is neutral salt catalyst, makes to have and pass through the following general formula
(II) the hydroxy phenyl phosphinylidyne propionic acid and glycol reaction predetermined amount of time of structure shown in obtain having through the following general formula (I)
The diphenylphosphoryl propionic acid binaryglycol ester of shown structure；
Its formula of (II) is as follows:
In logical formula (II), group R1, R2, R3, R4 and R5 each independently represent hydrogen atom, linear chain or branched chain C1-C6
Alkyl；
Its formula of (I) is as follows:
In logical formula (I), group R1, R2, R3, R4 and R5 each independently represent hydrogen atom, linear chain or branched chain C1-C6
Alkyl.
In a kind of embodiment of first aspect, the reaction carries out under 140-160 DEG C of reaction temperature.
In a kind of embodiment of first aspect, the predetermined amount of time is 8-14 hours.
In a kind of embodiment of first aspect, the neutrality salt catalyst is calcium acetate, zinc acetate, nickel acetate or sulphur
One or more of sour hydrogen sodium.
In a kind of embodiment of first aspect, the additive includes antimony glycol, cobalt acetate and trimethyl phosphate.
It in a kind of embodiment of first aspect, is counted on the basis of quality, one in diphenylphosphoryl propionic acid binaryglycol ester
The content of condensed binaryglycol ester is less than or equal to 0.50%.
In a kind of embodiment of first aspect, the fusing point of the flame retardant polyester is less than or equal to 222 DEG C.
Compared with prior art, the beneficial effects of the present application are as follows by there are specific neutral salt catalyst the case where
Under, using glycol-modified hydroxy phenyl phosphinylidyne propionic acid, obtain low in acidity and low diglycol content based on phenyl phosphorus
The liquid flame retardant of acyl propionic acid binaryglycol ester.The liquid flame retardant preparation process of the application is simple, small to chemical industry equipment corrosion,
The spinning properties of subsequent polyester product will not be negatively affected.
Flame retardant polyester is prepared by using based on the liquid flame retardant of diphenylphosphoryl propionic acid binaryglycol ester, it can be significant
The content for reducing the diglycol in obtained flame-retardant polyester, can also improve the form and aspect of polyester, its fusing point is reduced to 222 DEG C
Below.
Specific embodiment
Term "comprising", " comprising ", " having " and their derivative are not excluded for any other component, step or mistake
The presence of journey, and whether disclose in this application with these other components, step or process unrelated.To eliminate any query,
Unless expressly stated, otherwise in the application it is all use term "comprising"s, " comprising ", or " having " composition may include appoint
What additional additive, auxiliary material or compound.On the contrary, in addition to necessary to operating characteristics those, term " substantially by ...
Composition " excludes any other component, step or process except the hereinafter described range of any term.Term " by ...
Composition " does not include any component, step or the process for not specifically describing or listing.Unless expressly stated, otherwise term "or" refers to
Separate member listed or any combination thereof.
Embodiment
Below in conjunction with the embodiment of the present invention, clear and complete description is carried out to technical solution of the present invention.Such as nothing
It illustrates, reagent used and raw material can all be bought by commercial sources.
Fire-retardant FRW embodiment
Embodiment 1
The ethylene glycol of the 3- hydroxy phenyl phosphinylidyne propionic acid of 428kg and 950kg are put into reaction kettle, starts blender, adds
Enter the calcium acetate of 1kg, close feeding port, be passed through nitrogen protection, starts heater, be heated to material from room temperature in 2 hours
140℃.It keeps the negative pressure of about -0.9MPa to remove the moisture generated during the reaction and stops reaction after reaction about 8 hours,
Obtain the liquid diphenylphosphoryl propionic acid binaryglycol ester of 550kg.Measuring its conversion rate of esterification is 97.5%, and DEG content is
0.50%.
Embodiment 2
The ethylene glycol of the 3- hydroxy phenyl phosphinylidyne propionic acid of 428kg and 950kg are put into reaction kettle, starts blender, adds
Enter the zinc acetate of 1kg, close feeding port, be passed through nitrogen protection, starts heater, be heated to material from room temperature in 2 hours
160℃.It keeps the negative pressure of about -0.9MPa to remove the moisture generated during the reaction, after reaction about 12 hours, stops anti-
It answers, obtains the liquid diphenylphosphoryl propionic acid binaryglycol ester of 555kg.Measuring its conversion rate of esterification is 98.5%, and DEG content is
0.45%.
Embodiment 3
The ethylene glycol of the 3- hydroxy phenyl phosphinylidyne propionic acid of 428kg and 950kg are put into reaction kettle, starts blender, adds
Enter the nickel acetate of 1kg, close feeding port, be passed through nitrogen protection, starts heater, be heated to material from room temperature in 2 hours
180℃.It keeps the negative pressure of about -0.9MPa to remove the moisture generated during the reaction, after reaction about 12 hours, stops anti-
It answers, obtains the liquid diphenylphosphoryl propionic acid binaryglycol ester of 545kg.Measuring its conversion rate of esterification is 96.5%, and DEG content is
0.50%.
Embodiment 4
The ethylene glycol of the 3- hydroxy phenyl phosphinylidyne propionic acid of 428kg and 950kg are put into reaction kettle, starts blender, adds
Enter the calcium acetate of 1kg, close feeding port, be passed through nitrogen protection, starts heater, be heated to material from room temperature in 2 hours
150℃.It keeps the negative pressure of about -0.9MPa to remove the moisture generated during the reaction, after reaction about 14 hours, stops anti-
It answers, obtains the liquid diphenylphosphoryl propionic acid binaryglycol ester of 560kg.Measuring its conversion rate of esterification is 99.2%, and DEG content is
0.35%.
Comparative example 1
The ethylene glycol of the 3- hydroxy phenyl phosphinylidyne propionic acid of 428kg and 950kg are put into reaction kettle, starts blender, adds
Enter the sodium acetate of 1kg, close feeding port, be passed through nitrogen protection, starts heater, be heated to material from room temperature in 2 hours
140℃.It keeps the negative pressure of about -0.9MPa to remove the moisture generated during the reaction and stops reaction after reaction about 8 hours,
Obtain the liquid diphenylphosphoryl propionic acid binaryglycol ester of 450kg.Measuring its conversion rate of esterification is 79.8%, and DEG content is
5.2%.
Flame retardant polyester synthetic example
Embodiment 5
The present embodiment is related to synthesizing flame retardant polyester, and wherein p-phthalic acid PTA is purchased from constant force petrochemical industry, and ethylene glycol is purchased from upper
Extra large petrochemical industry, antimony glycol, cobalt acetate and trimethyl phosphate are conventional commercial product.Liquid flame retardant used in the present embodiment is
According to liquid flame retardant prepared by embodiment 4, mass concentration 44.8%, phosphorus content 6.5%.
The specific synthesis process of polyester slice is as follows:
PTA, ethylene glycol, liquid flame retardant, antimony glycol, cobalt acetate and tricresyl phosphate are added in the reaction kettle of the esterification of 80L
Methyl esters, wherein phosphorus additive amount is 6800ppm, after mashing uniformly, starts pressurization esterification, and after esterification, esterification material is moved
Liquid subsequently enters high vacuum stage of Fig to batch condensation polymerization reactor into low vacuum and middle vacuum, and final condensation temperature is 280 DEG C, vacuum
Degree is 200Pa, and polycondensation 4 hours, discharging, Cast Strip pelletizing filled packet.
The present embodiment test production process is smooth, process stabilizing, and concrete technology condition is as shown in table 1.
1 test technology condition of table
| The stage of reaction | Interior temperature/DEG C | Capital temperature/DEG C | Pressure | Time |
| Esterification | 220-245 | 130-140 | 0.22-0.28MPa | 4-5h |
| Low vacuum | 245-255 | / | Vacuum degree 0.1MPa | 45min |
| Middle vacuum | 255-260 | / | - | 45min |
| Final minification is poly- | 260-280 | / | Vacuum degree≤100Pa | 3-5 hours |
Embodiment 6
The raw material sources and process of embodiment 6 are identical as embodiment 5, but phosphorus additive amount is 6480ppm, final polycondensation temperature
Degree is 276 DEG C, vacuum degree 100Pa, and the polycondensation time is 4 hours.
Embodiment 7
The raw material sources and process of embodiment 7 are identical as embodiment 5, but phosphorus additive amount is 6480ppm, final polycondensation temperature
Degree is 276 DEG C, vacuum degree 80Pa, and the polycondensation time is 3.5 hours.
Comparative example 2
The experimentation of comparative example 2 is same as Example 5, but liquid flame retardant is commercially available fire retardant CEPPA, and quality is dense
Degree is 45%, phosphorus content 6.3%.When just polyester synthesis is tested, phosphorus additive amount is 6800ppm, and final condensation temperature is 286
DEG C, vacuum degree 200Pa, the polycondensation time is 4.5 hours.
The flame retardant polyester test result of embodiment 5-7 and comparative example 2 is as shown in table 2.
The flame retardant polyester test result of table 2. embodiment 5-7 and comparative example 2
As can be known from the results of Table 2, preferable according to the flame retardant polyester form and aspect of the application, DEG content is lower, and fusing point is lower.
The above-mentioned description to embodiment is that this Shen can be understood and applied for the ease of those skilled in the art
Please.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiments without paying creative labor.Therefore, the application is not limited to implementation here
Example, those skilled in the art make according to herein disclosed content in the case where not departing from the application scope and spirit
It improves and modifies within all scope of the present application.
Claims (10)
1. a kind of flame retardant polyester containing the liquid flame retardant based on diphenylphosphoryl propionic acid binaryglycol ester, by following raw material components
It is made: p-phthalic acid, ethylene glycol, additive and the liquid flame retardant based on diphenylphosphoryl propionic acid binaryglycol ester；
Wherein, the liquid flame retardant based on diphenylphosphoryl propionic acid binaryglycol ester includes having through knot shown in the following general formula (I)
The diphenylphosphoryl propionic acid binaryglycol ester of structure:
Wherein, group R1, R2, R3, R4 and R5 each independently represent hydrogen atom, linear chain or branched chain C1-C6 alkyl.
2. contain the flame retardant polyester of the liquid flame retardant based on diphenylphosphoryl propionic acid binaryglycol ester as described in claim 1,
It is characterized in that, group R1, R2, R3, R4 and R5 each independently represent methyl, ethyl, propyl, isopropyl, normal-butyl or isobutyl
Base.
3. contain the flame retardant polyester of the liquid flame retardant based on diphenylphosphoryl propionic acid binaryglycol ester as described in claim 1,
It is characterized in that, group R1, R2, R3, R4 and R5 are hydrogen atom.
4. contain the flame retardant polyester of the liquid flame retardant based on diphenylphosphoryl propionic acid binaryglycol ester as described in claim 1,
It is characterized in that, the liquid flame retardant based on diphenylphosphoryl propionic acid binaryglycol ester is prepared by following methods:
Under 140-180 DEG C of reaction temperature, and under conditions of the neutral salt catalyst of presence, make to have through the following general formula (II)
The hydroxy phenyl phosphinylidyne propionic acid and glycol reaction predetermined amount of time of shown structure obtain having by shown in the following general formula (I)
The diphenylphosphoryl propionic acid binaryglycol ester of structure；
Its formula of (II) is as follows:
In logical formula (II), group R1, R2, R3, R4 and R5 each independently represent hydrogen atom, linear chain or branched chain C1-C6 alkane
Base；
Its formula of (I) is as follows:
In logical formula (I), group R1, R2, R3, R4 and R5 each independently represent hydrogen atom, linear chain or branched chain C1-C6 alkyl.
5. contain the flame retardant polyester of the liquid flame retardant based on diphenylphosphoryl propionic acid binaryglycol ester as claimed in claim 4,
It is characterized in that, the reaction carries out under 140-160 DEG C of reaction temperature.
6. contain the flame retardant polyester of the liquid flame retardant based on diphenylphosphoryl propionic acid binaryglycol ester as claimed in claim 4,
It is characterized in that, the predetermined amount of time is 8-14 hours.
7. contain the flame retardant polyester of the liquid flame retardant based on diphenylphosphoryl propionic acid binaryglycol ester as claimed in claim 4,
It is characterized in that, the neutrality salt catalyst is one or more of calcium acetate, zinc acetate, nickel acetate or sodium bisulfate.
8. contain the flame retardant polyester of the liquid flame retardant based on diphenylphosphoryl propionic acid binaryglycol ester as claimed in claim 4,
It is characterized in that, the additive includes antimony glycol, cobalt acetate and trimethyl phosphate.
9. contain the flame retardant polyester of the liquid flame retardant based on diphenylphosphoryl propionic acid binaryglycol ester as claimed in claim 4,
It is characterized in that, is counted on the basis of quality, the content of diglycol ester is less than or waits in diphenylphosphoryl propionic acid binaryglycol ester
In 0.50%.
10. contain the flame retardant polyester of the liquid flame retardant based on diphenylphosphoryl propionic acid binaryglycol ester as claimed in claim 4,
It is characterized in that, the fusing point of the flame retardant polyester is less than or equal to 222 DEG C.
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| CN201811443684.7A CN109438686A (en) | 2018-11-29 | 2018-11-29 | A kind of flame retardant polyester containing the liquid flame retardant based on diphenylphosphoryl propionic acid binaryglycol ester |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111747984A (en) * | 2019-03-28 | 2020-10-09 | 远东新世纪股份有限公司 | Manufacturing method of phosphorus-based flame retardant and phosphoryl carboxylate mixture |
| CN112409567A (en) * | 2020-11-11 | 2021-02-26 | 长春工业大学 | Preparation method of P-N type flame retardant based on DOPO |
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| JPH04364196A (en) * | 1991-06-10 | 1992-12-16 | Sanyo Chem Ind Ltd | Reactive flame-retardant comprising phosphinic acid derivative and production of the same derivative |
| CN1563141A (en) * | 2004-04-08 | 2005-01-12 | 自贡三立药化有限责任公司 | Method for preparing flame-resisting polyester in phosphorus series |
| CN101200820A (en) * | 2006-12-13 | 2008-06-18 | 中国石油天然气集团公司 | Method for preparing flame-proof polyester fiber |
| CN101333287A (en) * | 2007-06-29 | 2008-12-31 | 厦门翔鹭化纤股份有限公司 | Method for preparing fire retardant co-polymerization modified polyester |
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| JPH04364196A (en) * | 1991-06-10 | 1992-12-16 | Sanyo Chem Ind Ltd | Reactive flame-retardant comprising phosphinic acid derivative and production of the same derivative |
| CN1563141A (en) * | 2004-04-08 | 2005-01-12 | 自贡三立药化有限责任公司 | Method for preparing flame-resisting polyester in phosphorus series |
| CN101200820A (en) * | 2006-12-13 | 2008-06-18 | 中国石油天然气集团公司 | Method for preparing flame-proof polyester fiber |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111747984A (en) * | 2019-03-28 | 2020-10-09 | 远东新世纪股份有限公司 | Manufacturing method of phosphorus-based flame retardant and phosphoryl carboxylate mixture |
| CN112409567A (en) * | 2020-11-11 | 2021-02-26 | 长春工业大学 | Preparation method of P-N type flame retardant based on DOPO |
| CN112409567B (en) * | 2020-11-11 | 2022-05-10 | 长春工业大学 | Preparation method of P-N type flame retardant based on DOPO |
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