CN105001267A - Fire retardant, namely 4-thiodiphosphorus caged phosphite compound, and a preparation method therefor - Google Patents
Fire retardant, namely 4-thiodiphosphorus caged phosphite compound, and a preparation method therefor Download PDFInfo
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- CN105001267A CN105001267A CN201510404783.4A CN201510404783A CN105001267A CN 105001267 A CN105001267 A CN 105001267A CN 201510404783 A CN201510404783 A CN 201510404783A CN 105001267 A CN105001267 A CN 105001267A
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- -1 phosphite compound Chemical class 0.000 title claims abstract description 56
- 239000003063 flame retardant Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 238000000746 purification Methods 0.000 claims abstract description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract 10
- 238000006243 chemical reaction Methods 0.000 claims description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 63
- 238000003756 stirring Methods 0.000 claims description 44
- 239000000047 product Substances 0.000 claims description 34
- JMXMXKRNIYCNRV-UHFFFAOYSA-N bis(hydroxymethyl)phosphanylmethanol Chemical compound OCP(CO)CO JMXMXKRNIYCNRV-UHFFFAOYSA-N 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 238000009835 boiling Methods 0.000 claims description 23
- 238000005194 fractionation Methods 0.000 claims description 23
- 238000010792 warming Methods 0.000 claims description 23
- 239000012265 solid product Substances 0.000 claims description 21
- 238000001291 vacuum drying Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims description 18
- 239000011574 phosphorus Substances 0.000 claims description 18
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 claims description 16
- 238000004821 distillation Methods 0.000 claims description 15
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical group [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 14
- 230000002195 synergetic effect Effects 0.000 claims description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 12
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical group COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007983 Tris buffer Substances 0.000 claims description 6
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 125000000532 dioxanyl group Chemical group 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 17
- 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 abstract description 8
- 239000000463 material Substances 0.000 abstract description 8
- 229920000728 polyester Polymers 0.000 abstract description 5
- 239000003822 epoxy resin Substances 0.000 abstract description 3
- 229920000647 polyepoxide Polymers 0.000 abstract description 3
- 229920000098 polyolefin Polymers 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract 2
- VGMSVGFQEIYLCS-UHFFFAOYSA-N OC(O)(O)[PH2]=S Chemical compound OC(O)(O)[PH2]=S VGMSVGFQEIYLCS-UHFFFAOYSA-N 0.000 abstract 1
- 239000004814 polyurethane Substances 0.000 abstract 1
- 229920002635 polyurethane Polymers 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 239000012065 filter cake Substances 0.000 description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 238000000354 decomposition reaction Methods 0.000 description 21
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 13
- 239000002032 methanolic fraction Substances 0.000 description 10
- 239000002031 ethanolic fraction Substances 0.000 description 9
- 238000009413 insulation Methods 0.000 description 8
- 239000003610 charcoal Substances 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- ZOGYOOUMDVKYLM-UHFFFAOYSA-N phosphane phosphorous acid Chemical compound P.OP(O)O ZOGYOOUMDVKYLM-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- Fireproofing Substances (AREA)
Abstract
The invention relates to a fire retardant, namely a 4-thiodiphosphorus caged phosphite compound, and a preparation method therefor. The compound has a structure as shown in the specification. The preparation method is as follows: under the protection of nitrogen, equimolar trihydroxymethyl phosphine sulfide and phosphite triester are heated to 100-160 DEG C and react for 6-12 hours in the presence of a catalyst; and purification treatment is performed to obtain 4-thiodiphosphorus caged phosphite. The compound is a high-phosphorus-content fire retardant and is excellent in flame retardant property and suitable for use as a fire retardant for materials such as polyester, polyurethane, epoxy resin, unsaturated resin, polyolefin and the like. Moreover, the production process is simple, the equipment investment is low, and the industrialized production is easy to realize.
Description
Technical field
The present invention relates to a kind of phosphorus sulphur synergistic fire retardant 4-sulfo-with two phosphorus bi-ester of phosphite of cage and preparation method thereof, be specifically related to a kind of 4-sulfo--2,6,7-trioxa-1,4-bis-phosphabicyclo [2.2.2] octane compound and preparation method thereof, this compound is suitable as the fire retardant of the materials such as polyester, urethane, epoxy resin, unsaturated polyester, polyolefine.
Background technology
Since 20th century, the development of organic synthesis macromolecular material has had significant progress, especially plastics, synthetic rubber and fiber and other material have become a part indispensable in people's daily life, but also the moment threatens the security of the lives and property of people to the fire caused by it, therefore adds the major issue that fire retardant has become urgently to be resolved hurrily to reduce occurrence index in these materials.Halogenated flame retardant was once use maximum fire retardants, but due to defects such as its toxic pollutants, after RoHS Directive is promulgated, made traditional halogenated flame retardant suffer abandoning of people gradually.Environmentally friendly fire retardant is more and more subject to the favor of people, what develop especially in recent years take phosphoric as the Organic phosphonate system fire retardant of main ignition-proof element, and be more subject to the high praise of people, it is high that this based flame retardant has thermostability, carbon-forming performance is good, advantages of environment protection during burning.
The invention discloses a kind of phosphorus sulphur synergistic fire retardant 4-sulfo-with two phosphorus bi-ester of phosphite of cage and preparation method thereof.The compounds of this invention is cage structure, have that phosphorus content is high, good stability, phosphorus sulphur dual element cooperative flame retardant usefulness are high, with the advantage such as material compatibility is good.Organic phosphine key (C-P key) in molecule can bring stability to compound, and the stability of cage ring structure to compound also has contribution.Present invention process is simple, belongs to green preparation process, has extraordinary development prospect.
Summary of the invention
An object of the present invention is to propose a kind of phosphorus sulphur synergistic fire retardant 4-sulfo-with the two phosphorus bi-ester of phosphite of cage, and its flame-retarded efficiency is high, good processability, can overcome deficiency of the prior art.
For achieving the above object, present invention employs following technical scheme:
A kind of phosphorus sulphur synergistic fire retardant 4-sulfo-is with the two phosphorus bi-ester of phosphite of cage, and it is characterized in that, the structure of this compound is shown below:
Another object of the present invention is to propose the preparation method of a kind of phosphorus sulphur synergistic fire retardant 4-sulfo-with the two phosphorus bi-ester of phosphite of cage, its technique is simple, and facility investment is few, is easy to large-scale production, and the method is:
In the reactor that efficient fractionation plant is housed; under nitrogen protection; add equimolar trishydroxymethyl phosphine sulfide and tris phosphite, under stirring, then add a certain amount of catalyzer; be warming up to 100-160 DEG C of reaction 8-12h; control column top temperature by separate the boiling temperature of generation alcohol, the stopped reaction when the alcohol fractionated out reaches theoretical amount, is cooled to less than 20 DEG C; purified process, obtains product 4-sulfo-with the two phosphorus phosphorous acid ester of cage.
The method also can be:
In the reactor that efficient fractionation plant is housed; under nitrogen protection, organic solvent, equimolar trishydroxymethyl phosphine sulfide and tris phosphite is added, under stirring; add a certain amount of catalyzer again; be warming up to 100-160 DEG C of reaction 6-10h, control column top temperature by separate the boiling temperature of generation alcohol, the stopped reaction when the alcohol fractionated out reaches theoretical amount; underpressure distillation removing organic solvent again; be cooled to less than 20 DEG C, purified process, obtain product 4-sulfo-with the two phosphorus phosphorous acid ester of cage.
Tris phosphite described above is trimethyl phosphite or triethyl-phosphite.
Organic solvent described above is dioxane, methyl-phenoxide, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, toluene, dimethylbenzene or chlorobenzene, and its consumption volume milliliter number is 3-7 times of trishydroxymethyl phosphine sulfide quality grams.
A certain amount of catalyzer described above is sodium methylate, triethylamine, pyridine, dimethylamino pyridine or sodium hydroxide, and its consumption is the 1%-2% of trishydroxymethyl phosphine sulfide quality.
Purification process described above is the frozen water adding product Theoretical Mass grams 2-3 times of volume milliliter number, stir 30min, make faint yellow solid product be scattered in water, filter, frozen water drip washing, drain, vacuum-drying.
Phosphorus sulphur synergistic fire retardant 4-sulfo-of the present invention is faint yellow solid with the two phosphorus phosphorous acid ester of cage, product yield is 85.7%-95.0%, fusing point: 87 ± 2 DEG C, decomposition temperature: 279 ± 5 DEG C, it is suitable as the fire retardant of the materials such as polyester, urethane, epoxy resin, unsaturated polyester, polyolefine, and this phosphorus sulphur synergistic fire retardant 4-sulfo-is shown below with preparation technology's principle of the two phosphorus phosphorous acid ester of cage:
R is-CH
3or-CH
2cH
3
Compared with prior art, beneficial effect of the present invention is:
1. phosphorus sulphur synergistic fire retardant 4-sulfo-of the present invention with the two phosphorus bi-ester of phosphite phosphorus content of cage up to 33.7%, sulphur content reaches 17.4%, total effectively ignition-proof element content is up to 51.1%, it contains cage ring structure, and symmetry is good, good stability, decomposition temperature is high, phosphorus sulphur dual element cooperative flame retardant usefulness is high, and good with the consistency of macromolecular material, and processing characteristics is excellent.
2. phosphorus sulphur synergistic fire retardant 4-sulfo-of the present invention is with raw material trishydroxymethyl phosphine sulfide inherently a kind of excellent response type organic phosphine fire retardant of the two phosphorus bi-ester of phosphite use of cage, with phosphite reactions, introduce polyester structure again, turn improve the content of phosphorus simultaneously, while making product obtain good flame retardant resistance, turn increase antioxidant capacity.
3. the alcohol produced in the preparation technology of phosphorus sulphur synergistic fire retardant 4-sulfo-of the present invention with the two phosphorus bi-ester of phosphite of cage can all be recycled, and has good environmental benefit and economic benefit.
4. phosphorus sulphur synergistic fire retardant 4-sulfo-of the present invention with the preparation technology of the two phosphorus bi-ester of phosphite of cage and equipment simple, convenient operation, with low cost, be easy to mass-producing and transform and produce.
Accompanying drawing explanation
In order to the stuctures and properties spy further illustrating product provides following accompanying drawing.
1,4-sulfo-is with the infrared spectrogram of the two phosphorus phosphorous acid ester of cage, refers to Figure of description Fig. 1;
Fig. 1 shows, at 2936cm
-1place is the stretching vibration peak of methylene radical c h bond; 1408cm
-1place is the flexural vibration peak of methylene radical c h bond; 1205cm
-1and 1187cm
-1place is the stretching vibration peak of C-O key; 986cm
-1place is the stretching vibration peak of P-O key; 858cm
-1place is the stretching vibration peak of C-P key; 695cm
-1place is the stretching vibration peak of P=S double bond.
2,4-sulfo-is with the nuclear magnetic spectrum figure of the two phosphorus phosphorous acid ester of cage, refers to Figure of description Fig. 2;
Fig. 2 shows, deuterated dimethyl sulfoxide makes solvent, and δ 3.65-3.85 place is the H peak of methylene radical; δ 2.50 place is the H peak of deuterated dimethyl sulfoxide solvent.
3,4-sulfo-is with the differential thermal figure of the two phosphorus phosphorous acid ester of cage, refers to Figure of description Fig. 3;
Fig. 3 shows, temperature is 279 DEG C and starts weightless; During rate of weight loss 50%, temperature is 434 DEG C; To the resistates still having 33% during final temperature 800 DEG C, illustrate that product has good thermostability.
Specific embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described further.
Embodiment 1 is in the 100ml four-hole boiling flask that agitator, thermometer, efficient fractionation plant are housed, catch up with the air in most bottle with nitrogen, add 15.60g (0.1mol) trishydroxymethyl phosphine sulfide and 12.40g (0.1mol) trimethyl phosphite.Under stirring, add 0.28g Triethylamine catalyst again, heat and continue to pass into nitrogen, be warming up to 120 DEG C of reaction 11h, all the time column top temperature is controlled not higher than 65 DEG C, fractionate out the methyl alcohol (reclaim and use) that reaction produces, the stopped reaction when methanol fraction reaches theoretical amount, be cooled to less than 20 DEG C, add 50ml frozen water, stir 30min, faint yellow solid product is made to be scattered in water, filter, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum-drying, obtain product 4-sulfo-with the two phosphorus phosphorous acid ester of cage, productive rate is 87.5%, fusing point: 87 ± 2 DEG C, decomposition temperature: 279 ± 5 DEG C.
Embodiment 2 is in the 100ml four-hole boiling flask that agitator, thermometer, efficient fractionation plant are housed, catch up with the air in most bottle with nitrogen, add 15.60g (0.1mol) trishydroxymethyl phosphine sulfide and 12.40g (0.1mol) trimethyl phosphite.Under stirring, add 0.30g pyridine catalyst again, heat and continue to pass into nitrogen, be warming up to 130 DEG C of reaction 10h, all the time column top temperature is controlled not higher than 65 DEG C, fractionate out the methyl alcohol (reclaim and use) that reaction produces, the stopped reaction when methanol fraction reaches theoretical amount, be cooled to less than 20 DEG C, add 45ml frozen water, stir 30min, faint yellow solid product is made to be scattered in water, filter, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum-drying, obtain product 4-sulfo-with the two phosphorus phosphorous acid ester of cage, productive rate is 88.6%, fusing point: 87 ± 2 DEG C, decomposition temperature: 279 ± 5 DEG C.
Embodiment 3 is in the 100ml four-hole boiling flask that agitator, thermometer, efficient fractionation plant are housed, catch up with the air in most bottle with nitrogen, add 15.60g (0.1mol) trishydroxymethyl phosphine sulfide and 12.40g (0.1mol) trimethyl phosphite.Under stirring, add 0.16g sodium methoxide catalyst again, heat and continue to pass into nitrogen, be warming up to 140 DEG C of reaction 9h, all the time column top temperature is controlled not higher than 65 DEG C, fractionate out the methyl alcohol (reclaim and use) that reaction produces, the stopped reaction when methanol fraction reaches theoretical amount, be cooled to less than 20 DEG C, add 40ml frozen water, stir 30min, faint yellow solid product is made to be scattered in water, filter, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum-drying, obtain product 4-sulfo-with the two phosphorus phosphorous acid ester of cage, productive rate is 90.7%, fusing point: 87 ± 2 DEG C, decomposition temperature: 279 ± 5 DEG C.
Embodiment 4 is in the 250ml four-hole boiling flask that agitator, thermometer, efficient fractionation plant are housed, the air in most bottle is caught up with nitrogen, add 105ml dioxane, 15.60g (0.1mol) trishydroxymethyl phosphine sulfide and 12.40g (0.1mol) trimethyl phosphite.Under stirring, add 0.22g sodium methoxide catalyst, heat and continue to pass into nitrogen, be warming up to 100 DEG C of insulation reaction 8h, control column top temperature not higher than 65 DEG C, fractionate out the methyl alcohol (reclaim and use) that reaction produces, the stopped reaction when methanol fraction reaches theoretical amount, underpressure distillation eliminates dioxane again, be cooled to less than 20 DEG C, add 40ml frozen water, stir 30min, faint yellow solid product is made to be scattered in water, filter, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum-drying, obtain product 4-sulfo-with the two phosphorus phosphorous acid ester of cage, productive rate is 92.0%, fusing point: 87 ± 2 DEG C, decomposition temperature: 279 ± 5 DEG C.
Embodiment 5 is in the 250ml four-hole boiling flask that agitator, thermometer, efficient fractionation plant are housed, the air in most bottle is caught up with nitrogen, add 80ml methyl-phenoxide, 15.60g (0.1mol) trishydroxymethyl phosphine sulfide and 12.40g (0.1mol) trimethyl phosphite.Under stirring, add 0.19g sodium hydroxide catalyst, heat and continue to pass into nitrogen, be warming up to 150 DEG C of reaction 6h, all the time column top temperature is controlled not higher than 65 DEG C, fractionate out the methyl alcohol (reclaim and use) that reaction produces, the stopped reaction when methanol fraction reaches theoretical amount, underpressure distillation eliminates methyl-phenoxide again, be cooled to less than 20 DEG C, add 45ml frozen water, stir 30min, faint yellow solid product is made to be scattered in water, filter, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum-drying, obtain product 4-sulfo-with the two phosphorus phosphorous acid ester of cage, productive rate is 94.5%, fusing point: 87 ± 2 DEG C, decomposition temperature: 279 ± 5 DEG C.
Embodiment 6 is in the 150ml four-hole boiling flask that agitator, thermometer, efficient fractionation plant are housed, the air in most bottle is caught up with nitrogen, add 60ml diethylene glycol dimethyl ether, 15.60g (0.1mol) trishydroxymethyl phosphine sulfide and 12.40g (0.1mol) trimethyl phosphite.Under stirring, add 0.20g dimethylamino pyridine catalyzer, heat and continue to pass into nitrogen, be warming up to 160 DEG C of reaction 6h, all the time column top temperature is controlled not higher than 65 DEG C, fractionate out the methyl alcohol (reclaim and use) that reaction produces, the stopped reaction when methanol fraction reaches theoretical amount, underpressure distillation eliminates diethylene glycol dimethyl ether again, be cooled to less than 20 DEG C, add 40ml frozen water, stir 30min, faint yellow solid product is made to be scattered in water, filter, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum-drying, obtain product 4-sulfo-with the two phosphorus phosphorous acid ester of cage, productive rate is 95.0%, fusing point: 87 ± 2 DEG C, decomposition temperature: 279 ± 5 DEG C.
Embodiment 7 is in the 250ml four-hole boiling flask that agitator, thermometer, efficient fractionation plant are housed, the air in most bottle is caught up with nitrogen, add 90ml ethylene glycol diethyl ether, 15.60g (0.1mol) trishydroxymethyl phosphine sulfide and 12.40g (0.1mol) trimethyl phosphite.Under stirring, add 0.28g sodium hydroxide catalyst, heat and continue to pass into nitrogen, be warming up to 120 DEG C of reaction 8h, all the time column top temperature is controlled not higher than 65 DEG C, fractionate out the methyl alcohol (reclaim and use) that reaction produces, the stopped reaction when methanol fraction reaches theoretical amount, underpressure distillation eliminates ethylene glycol diethyl ether again, be cooled to less than 20 DEG C, add 55ml frozen water, stir 30min, faint yellow solid product is made to be scattered in water, filter, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum-drying, obtain product 4-sulfo-with the two phosphorus phosphorous acid ester of cage, productive rate is 93.4%, fusing point: 87 ± 2 DEG C, decomposition temperature: 279 ± 5 DEG C.
Embodiment 8 is in the 250ml four-hole boiling flask that agitator, thermometer, efficient fractionation plant are housed, the air in most bottle is caught up with nitrogen, add 100ml toluene, 15.60g (0.1mol) trishydroxymethyl phosphine sulfide and 12.40g (0.1mol) trimethyl phosphite.Under stirring, add 0.16g Triethylamine catalyst, heat and continue to pass into nitrogen, be warming up to 110 DEG C of reaction 8h, all the time column top temperature is controlled not higher than 65 DEG C, fractionate out the methyl alcohol (reclaim and use) that reaction produces, the stopped reaction when methanol fraction reaches theoretical amount, underpressure distillation eliminates toluene again, be cooled to less than 20 DEG C, add 50ml frozen water, stir 30min, faint yellow solid product is made to be scattered in water, filter, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum-drying, obtain product 4-sulfo-with the two phosphorus phosphorous acid ester of cage, productive rate is 92.9%, fusing point: 87 ± 2 DEG C, decomposition temperature: 279 ± 5 DEG C.
Embodiment 9 is in the 150ml four-hole boiling flask that agitator, thermometer, efficient fractionation plant are housed, the air in most bottle is caught up with nitrogen, add 50ml dimethylbenzene, 15.60g (0.1mol) trishydroxymethyl phosphine sulfide and 12.40g (0.1mol) trimethyl phosphite.Under stirring, add 0.20g sodium methoxide catalyst, heat and continue to pass into nitrogen, be warming up to 140 DEG C of reaction 7h, all the time column top temperature is controlled not higher than 65 DEG C, fractionate out the methyl alcohol (reclaim and use) that reaction produces, the stopped reaction when methanol fraction reaches theoretical amount, underpressure distillation eliminates dimethylbenzene again, be cooled to less than 20 DEG C, add 45ml frozen water, stir 30min, faint yellow solid product is made to be scattered in water, filter, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum-drying, obtain product 4-sulfo-with the two phosphorus phosphorous acid ester of cage, productive rate is 94.2%, fusing point: 87 ± 2 DEG C, decomposition temperature: 279 ± 5 DEG C.
Embodiment 10 is in the 250ml four-hole boiling flask that agitator, thermometer, efficient fractionation plant are housed, the air in most bottle is caught up with nitrogen, add 70ml chlorobenzene, 15.60g (0.1mol) trishydroxymethyl phosphine sulfide and 12.40g (0.1mol) trimethyl phosphite.Under stirring, add 0.26g pyridine catalyst, heat and continue to pass into nitrogen, be warming up to 130 DEG C of reaction 7h, all the time column top temperature is controlled not higher than 65 DEG C, fractionate out the methyl alcohol (reclaim and use) that reaction produces, the stopped reaction when methanol fraction reaches theoretical amount, underpressure distillation eliminates chlorobenzene again, be cooled to less than 20 DEG C, add 45ml frozen water, stir 30min, faint yellow solid product is made to be scattered in water, filter, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum-drying, obtain product 4-sulfo-with the two phosphorus phosphorous acid ester of cage, productive rate is 93.6%, fusing point: 87 ± 2 DEG C, decomposition temperature: 279 ± 5 DEG C.
Embodiment 11 is in the 100ml four-hole boiling flask that agitator, thermometer, efficient fractionation plant are housed, catch up with the air in most bottle with nitrogen, add 15.60g (0.1mol) trishydroxymethyl phosphine sulfide and 16.60g (0.1mol) triethyl-phosphite.Under stirring, add 0.20g Triethylamine catalyst again, heat and continue to pass into nitrogen, be warming up to 120 DEG C of insulation reaction 12h, control column top temperature not higher than 78 DEG C, fractionate out the ethanol (reclaim and use) that reaction produces, the stopped reaction when ethanol fraction reaches theoretical amount, be cooled to less than 20 DEG C, add 40ml frozen water, stir 30min, faint yellow solid product is made to be scattered in water, filter, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum-drying, obtain product 4-sulfo-with the two phosphorus phosphorous acid ester of cage, productive rate is 85.7%, fusing point: 87 ± 2 DEG C, decomposition temperature: 279 ± 5 DEG C.
Embodiment 12 is in the 100ml four-hole boiling flask that agitator, thermometer, efficient fractionation plant are housed, catch up with the air in most bottle with nitrogen, add 15.60g (0.1mol) trishydroxymethyl phosphine sulfide and 16.60g (0.1mol) triethyl-phosphite.Under stirring, add 0.24g dimethylamino pyridine catalyzer again, heat and continue to pass into nitrogen, be warming up to 140 DEG C of reaction 10h, all the time column top temperature is controlled not higher than 78 DEG C, fractionate out the ethanol (reclaim and use) that reaction produces, the stopped reaction when ethanol fraction reaches theoretical amount, be cooled to less than 20 DEG C, add 45ml frozen water, stir 30min, faint yellow solid product is made to be scattered in water, filter, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum-drying, obtain product 4-sulfo-with the two phosphorus phosphorous acid ester of cage, productive rate is 87.3%, fusing point: 87 ± 2 DEG C, decomposition temperature: 279 ± 5 DEG C.
Embodiment 13 is in the 100ml four-hole boiling flask that agitator, thermometer, efficient fractionation plant are housed, catch up with the air in most bottle with nitrogen, add 15.60g (0.1mol) trishydroxymethyl phosphine sulfide and 16.60g (0.1mol) triethyl-phosphite.Under stirring, add 0.18g sodium methoxide catalyst again, heat and continue to pass into nitrogen, be warming up to 160 DEG C of reaction 9h, all the time column top temperature is controlled not higher than 78 DEG C, fractionate out the ethanol (reclaim and use) that reaction produces, the stopped reaction when ethanol fraction reaches theoretical amount, be cooled to less than 20 DEG C, add 40ml frozen water, stir 30min, faint yellow solid product is made to be scattered in water, filter, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum-drying, obtain product 4-sulfo-with the two phosphorus phosphorous acid ester of cage, productive rate is 89.4%, fusing point: 87 ± 2 DEG C, decomposition temperature: 279 ± 5 DEG C.
Embodiment 14 is in the 250ml four-hole boiling flask that agitator, thermometer, efficient fractionation plant are housed, the air in most bottle is caught up with nitrogen, add 100ml dioxane, 15.60g (0.1mol) trishydroxymethyl phosphine sulfide and 16.60g (0.1mol) triethyl-phosphite.Under stirring, add 0.18g Triethylamine catalyst, heat and continue to pass into nitrogen, be warming up to 100 DEG C of insulation reaction 9h, control column top temperature not higher than 78 DEG C, fractionate out the ethanol (reclaim and use) that reaction produces, the stopped reaction when ethanol fraction reaches theoretical amount, underpressure distillation eliminates dioxane again, be cooled to less than 20 DEG C, add 55ml frozen water, stir 30min, faint yellow solid product is made to be scattered in water, filter, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum-drying, obtain product 4-sulfo-with the two phosphorus phosphorous acid ester of cage, productive rate is 90.5%, fusing point: 87 ± 2 DEG C, decomposition temperature: 279 ± 5 DEG C.
Embodiment 15 is in the 250ml four-hole boiling flask that agitator, thermometer, efficient fractionation plant are housed, the air in most bottle is caught up with nitrogen, add 80ml methyl-phenoxide, 15.60g (0.1mol) trishydroxymethyl phosphine sulfide and 16.60g (0.1mol) triethyl-phosphite.Under stirring, add 0.30g sodium hydroxide catalyst, heat and continue to pass into nitrogen, be warming up to 150 DEG C of insulation reaction 7h, control column top temperature not higher than 78 DEG C, fractionate out the ethanol (reclaim and use) that reaction produces, the stopped reaction when ethanol fraction reaches theoretical amount, underpressure distillation eliminates methyl-phenoxide again, be cooled to less than 20 DEG C, add 45ml frozen water, stir 30min, faint yellow solid product is made to be scattered in water, filter, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum-drying, obtain product 4-sulfo-with the two phosphorus phosphorous acid ester of cage, productive rate is 93.3%, fusing point: 87 ± 2 DEG C, decomposition temperature: 279 ± 5 DEG C.
Embodiment 16 is in the 150ml four-hole boiling flask that agitator, thermometer, efficient fractionation plant are housed, the air in most bottle is caught up with nitrogen, add 60ml diethylene glycol dimethyl ether, 15.60g (0.1mol) trishydroxymethyl phosphine sulfide and 16.60g (0.1mol) triethyl-phosphite.Under stirring, add 0.25g dimethylamino pyridine catalyzer, heat and continue to pass into nitrogen, be warming up to 160 DEG C of insulation reaction 7h, control column top temperature not higher than 78 DEG C, fractionate out the ethanol (reclaim and use) that reaction produces, the stopped reaction when ethanol fraction reaches theoretical amount, underpressure distillation eliminates diethylene glycol dimethyl ether again, be cooled to less than 20 DEG C, add 40ml frozen water, stir 30min, faint yellow solid product is made to be scattered in water, filter, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum-drying, obtain product 4-sulfo-with the two phosphorus phosphorous acid ester of cage, productive rate is 93.9%, fusing point: 87 ± 2 DEG C, decomposition temperature: 279 ± 5 DEG C.
Embodiment 17 is in the 250ml four-hole boiling flask that agitator, thermometer, efficient fractionation plant are housed, the air in most bottle is caught up with nitrogen, add 90ml ethylene glycol diethyl ether, 15.60g (0.1mol) trishydroxymethyl phosphine sulfide and 16.60g (0.1mol) triethyl-phosphite.Under stirring, add 0.23g pyridine catalyst, heat and continue to pass into nitrogen, be warming up to 120 DEG C of insulation reaction 8h, control column top temperature not higher than 78 DEG C, fractionate out the ethanol (reclaim and use) that reaction produces, the stopped reaction when ethanol fraction reaches theoretical amount, underpressure distillation eliminates ethylene glycol diethyl ether again, be cooled to less than 20 DEG C, add 40ml frozen water, stir 30min, faint yellow solid product is made to be scattered in water, filter, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum-drying, obtain product 4-sulfo-with the two phosphorus phosphorous acid ester of cage, productive rate is 91.0%, fusing point: 87 ± 2 DEG C, decomposition temperature: 279 ± 5 DEG C.
Embodiment 18 is in the 150ml four-hole boiling flask that agitator, thermometer, efficient fractionation plant are housed, the air in most bottle is caught up with nitrogen, add 50ml dimethylbenzene, 15.60g (0.1mol) trishydroxymethyl phosphine sulfide and 16.60g (0.1mol) triethyl-phosphite.Under stirring, add 0.28g sodium methoxide catalyst, heat and continue to pass into nitrogen, be warming up to 140 DEG C of insulation reaction 7h, control column top temperature not higher than 78 DEG C, fractionate out the ethanol (reclaim and use) that reaction produces, the stopped reaction when ethanol fraction reaches theoretical amount, underpressure distillation eliminates dimethylbenzene again, be cooled to less than 20 DEG C, add 45ml frozen water, stir 30min, faint yellow solid product is made to be scattered in water, filter, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum-drying, obtain product 4-sulfo-with the two phosphorus phosphorous acid ester of cage, productive rate is 92.8%, fusing point: 87 ± 2 DEG C, decomposition temperature: 279 ± 5 DEG C.
Embodiment 19 is in the 250ml four-hole boiling flask that agitator, thermometer, efficient fractionation plant are housed, the air in most bottle is caught up with nitrogen, add 70ml chlorobenzene, 15.60g (0.1mol) trishydroxymethyl phosphine sulfide and 16.60g (0.1mol) triethyl-phosphite.Under stirring, add 0.25g sodium hydroxide catalyst, heat and continue to pass into nitrogen, be warming up to 130 DEG C of insulation reaction 8h, control column top temperature not higher than 78 DEG C, fractionate out the ethanol (reclaim and use) that reaction produces, the stopped reaction when ethanol fraction reaches theoretical amount, underpressure distillation eliminates chlorobenzene again, be cooled to less than 20 DEG C, add 50ml frozen water, stir 30min, faint yellow solid product is made to be scattered in water, filter, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum-drying, obtain product 4-sulfo-with the two phosphorus phosphorous acid ester of cage, productive rate is 92.1%, fusing point: 87 ± 2 DEG C, decomposition temperature: 279 ± 5 DEG C.
Embodiment main technologic parameters prepared by table 1
The product 4-sulfo-of above-mentioned preparation is also applied in polyester PBT with the two phosphorus phosphorous acid ester of cage by inventor.The limiting oxygen index(LOI) of reference: GB/T2406-2008 " Plastics Combustion method for testing performance-oxygen index method " test sample product.In PBT, add the product of different ratios, at 225 DEG C, extrude with forcing machine, system grows into 15cm, and diameter is the batten of 3mm, and tests its flame retardant properties, and the LOI result recorded is as shown in table 2:
Table 2 product 4-sulfo-is with the two fire-retardant data of phosphorus phosphorous acid ester in PBT of cage
| Addition % | LOI％ | Drippage situation | Become charcoal |
| 0 | 21 | Fast drippage | Do not become charcoal |
| 10 | 25 | Slow drippage | Do not become charcoal |
| 20 | 31 | Do not drip | Become charcoal |
| 30 | 36 | Do not drip | Become charcoal |
As shown in Table 2, when 4-sulfo-is 20% with the two addition of phosphorus phosphorous acid ester in PBT of cage, limiting oxygen index(LOI) value is 31%, and reached difficult combustion rank, and do not had melting to drip, carbon-forming performance is fine.Thus can find out that product 4-sulfo-has good flame-retarded efficiency with the two phosphorus phosphorous acid ester of cage to PBT material.
Claims (7)
1. phosphorus sulphur synergistic fire retardant 4-sulfo-is with the two phosphorus bi-ester of phosphite of cage, and it is characterized in that, the structure of this compound is shown below:
2. phosphorus sulphur synergistic fire retardant 4-sulfo-is with a preparation method for the two phosphorus phosphorous acid ester of cage, and it is characterized in that, the method is:
In the reactor that efficient fractionation plant is housed; under nitrogen protection; add equimolar trishydroxymethyl phosphine sulfide and tris phosphite, under stirring, then add the catalyzer relative to trishydroxymethyl phosphine sulfide quality 1%-2%; be warming up to 100-160 DEG C of reaction 8-12h; control column top temperature by separate the boiling temperature of generation alcohol, the stopped reaction when the alcohol fractionated out reaches theoretical amount, is cooled to less than 20 DEG C; purified process, obtains product 4-sulfo-with the two phosphorus phosphorous acid ester of cage.
3. phosphorus sulphur synergistic fire retardant 4-sulfo-is with a preparation method for the two phosphorus bi-ester of phosphite of cage, and it is characterized in that, the method is:
In the reactor that efficient fractionation plant is housed; under nitrogen protection; add organic solvent, equimolar trishydroxymethyl phosphine sulfide and tris phosphite; under stirring; add the catalyzer relative to trishydroxymethyl phosphine sulfide quality 1%-2% again; be warming up to 100-160 DEG C of reaction 6-10h; control column top temperature by separate the boiling temperature of generation alcohol; the stopped reaction when the alcohol fractionated out reaches theoretical amount; underpressure distillation removing organic solvent again; be cooled to less than 20 DEG C, purified process, obtain product 4-sulfo-with the two phosphorus phosphorous acid ester of cage.
4. as described in claim 2 and 3,4-sulfo-, with the preparation method of the two phosphorus bi-ester of phosphite of cage, is characterized in that: described tris phosphite is trimethyl phosphite or triethyl-phosphite.
5. as claimed in claim 3 4-sulfo-with the preparation method of the two phosphorus bi-ester of phosphite of cage, it is characterized in that: described organic solvent is dioxane, methyl-phenoxide, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, toluene, dimethylbenzene or chlorobenzene, its consumption volume milliliter number is 3-7 times of trishydroxymethyl phosphine sulfide quality grams.
6. as described in claim 2 and 3,4-sulfo-, with the preparation method of the two phosphorus bi-ester of phosphite of cage, is characterized in that: described catalyzer is sodium methylate, triethylamine, pyridine, dimethylamino pyridine or sodium hydroxide.
7. as described in claim 2 and 3 4-sulfo-with the preparation method of the two phosphorus bi-ester of phosphite of cage, it is characterized in that: described purification process is the frozen water adding product Theoretical Mass grams 2-3 times of volume milliliter number, stir 30min, faint yellow solid product is made to be scattered in water, filter, frozen water drip washing, drain, vacuum-drying.
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| EP0666266A1 (en) * | 1994-02-08 | 1995-08-09 | Hoechst Aktiengesellschaft | Process for the preparation of trismethylolalkane phosphite |
| CN101230274A (en) * | 2007-12-27 | 2008-07-30 | 南京师范大学 | Method for preparing annular phosphonate or annular phosphate flame retardant |
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| EP0666266A1 (en) * | 1994-02-08 | 1995-08-09 | Hoechst Aktiengesellschaft | Process for the preparation of trismethylolalkane phosphite |
| CN101230274A (en) * | 2007-12-27 | 2008-07-30 | 南京师范大学 | Method for preparing annular phosphonate or annular phosphate flame retardant |
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Denomination of invention: Flame retardant 4-thio cage diphosphate compound and its preparation method Granted publication date: 20180202 Pledgee: Zhejiang Nanxun Rural Commercial Bank branch Linghu Limited by Share Ltd. Pledgor: Zhejiang Rui hi tech materials Limited by Share Ltd. Registration number: Y2024330000544 |