CN101805620A - Polymer type phosphor-containing fire retardant, preparation method and application thereof - Google Patents
Polymer type phosphor-containing fire retardant, preparation method and application thereof Download PDFInfo
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- CN101805620A CN101805620A CN 201010150013 CN201010150013A CN101805620A CN 101805620 A CN101805620 A CN 101805620A CN 201010150013 CN201010150013 CN 201010150013 CN 201010150013 A CN201010150013 A CN 201010150013A CN 101805620 A CN101805620 A CN 101805620A
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- fire retardant
- pnx
- ethylene glycol
- phosphorus oxychloride
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229920000642 polymer Polymers 0.000 title claims abstract description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 80
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 238000004821 distillation Methods 0.000 claims description 18
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 15
- 238000005516 engineering process Methods 0.000 claims description 13
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000006260 foam Substances 0.000 claims description 12
- 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 class 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 claims description 10
- 238000009413 insulation Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- BZCGWAXQDLXLQM-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O.ClP(Cl)(Cl)=O BZCGWAXQDLXLQM-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 description 6
- 230000001476 alcoholic effect Effects 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000012974 tin catalyst Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- -1 Phosphorus oxychloride Ethylene glycol Chemical compound 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- JTRONPPAUSSTQI-UHFFFAOYSA-N ethane-1,2-diol;ethanol Chemical compound CCO.OCCO JTRONPPAUSSTQI-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 238000007039 two-step reaction Methods 0.000 description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/14—Macromolecular materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/093—Polyol derivatives esterified at least twice by phosphoric acid groups
-
- 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
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
- C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention belongs to the field of chemical materials, and discloses a polymer type phosphor-containing fire retardant, a preparation method and application thereof. The invention discloses the polymer type phosphor-containing fire retardant PNX is a compound shown in formula (1): n is an integer of between 5 and 8; and the molecular weight of the fire retardant is between 900 and 1,400. The method for preparing the fire retardant PNX comprises the following steps: reacting phosphorus oxychloride with ethylene glycol in nitrogen environment through a chemical reaction shown in a reaction formula (1) to prepare a compound (2); and preparing the fire retardant PNX by the compound (2) and absolute ethanol through a chemical reaction shown in a reaction formula (2) under the action of a catalyst aluminum chloride. The fire retardant PNX belongs to halogen-free series fire retardant, is in accordance with the concept of national green and environment-friendly development, ensures the phosphor content reaches 18 to 20 percent, and has excellent fire retardant performance.
Description
Technical field
The invention belongs to the chemical material field, relate to a kind of polymer type phosphor-containing fire retardant and preparation method thereof and application.
Background technology
Based on the requirement of environmental protection and Sustainable development, some halogenated flame retardants are disabled, also have some also to treat for the discretion of people institute, and application is restricted.From the promulgation of 2003 ROHS of European Union and two instructions of WEEE, the application of phosphorus-halogenide fire retardant also has been subjected to certain restriction, thereby makes the cry of environmental protection Halogen phosphorus flame retardant more and more higher.
Summary of the invention
The objective of the invention is above-mentioned deficiency, a kind of polymer type phosphor-containing fire retardant is provided at prior art.
Another object of the present invention provides the preparation technology of this fire retardant.
Another purpose of the present invention provides the application of this fire retardant.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of polymer type phosphor-containing fire retardant PNX, its chemical formula is as follows:
By ultimate analysis, polymer type phosphor-containing fire retardant PNX one compounds of the present invention is elementary composition to be: P19.75%～19.95%, and C 32.63%～33.12%, and H 6.23%～6.37%, and O 40.8%～40.19%.
Infrared spectroscopy shows 1300cm
-1There is characteristic peak at the place, proves to have P=O; There is characteristic peak at 1180cm-1 and 980cm-1 place, prove to have P-O-C; At 1392cm
-1, 1464cm
-1The absorption peak at place and the absorption peak between 2800～3000cm-1 show CH
2, CH
3Existence.
The preparation technology of fire retardant PNX of the present invention is characterized in that obtaining compound (2) by the chemical reaction shown in the reaction formula (1) by phosphorus oxychloride and ethylene glycol in nitrogen environment; Compound (2) obtains fire retardant PNX by the chemical reaction shown in the reaction formula (2) with dehydrated alcohol under the effect of catalyzer aluminum chloride.
n＝5～8
，n＝5～8
The preparation technology of fire retardant PNX of the present invention specifically is made up of following steps:
(1) suction phosphorus oxychloride in No. 1 reactor is cooled to 10～15 ℃, feeds nitrogen in still, and flow velocity is 0.5～3m
3/ h protects anti-oxidation, and slowly drips ethylene glycol, is warming up to 15～25 ℃ after dropwising, stirring reaction 0.5～3h; Stop logical nitrogen, with excessive POCl
3Underpressure distillation steams, and distillation finishes, cooling, and discharging feeds No. 2 reactors;
(2) in No. 2 reactors, drop into catalyst A lCl
3, stirring 0.5～1h, controlled temperature drips dehydrated alcohol at 10～13 ℃, is warming up to 20～30 ℃ after dropwising, insulation 3～6h; The low pressure suction filtration is removed catalyzer; Filtrate washing 2～6 times, underpressure distillation is removed moisture and is promptly got fire retardant PNX after having washed at every turn.
Wherein, the mol ratio of described phosphorus oxychloride, ethylene glycol, dehydrated alcohol and aluminum chloride is a phosphorus oxychloride: ethylene glycol: dehydrated alcohol: aluminum chloride=3～7: 1: 3.5～4.5: 0.004～0.008, and preferred 5: 1: 4.0～4.2: 0.004.
A speed of described dropping ethylene glycol is 110～140g/min, and the hydrochloric acid that produces in the dropping process absorbs with the HCl absorption tower.
A speed of described dropping dehydrated alcohol is 400～580g/min, and the hydrochloric acid that produces in the dropping process absorbs with the HCl absorption tower.
In the described step (1) pressure of underpressure distillation be-0.1～-0.05MPa, distillation temperature is 45～60 ℃.
In the described step (2) pressure of underpressure distillation be-0.1～-0.05MPa, distillation temperature is 105 ℃.
Described phosphorus oxychloride purity is more than or equal to 98.5%, and ethylene glycol purity is more than or equal to 99.5%, and dehydrated alcohol purity purity is more than or equal to 99.5%.
The application of fire retardant PNX of the present invention in flexible urethane foam.
Unaccomplished matter of the present invention is the routine techniques in this area.
Beneficial effect of the present invention:
Fire retardant PNX provided by the invention belongs to the Halogen phosphorus flame retardant, meets the theory of national environmental protection development, and phosphorus content is up to 18%～20%, and flame retardant properties is superior.Use in flexible urethane foam, half of addition too late fire retardant TCPP, MPPDP can obtain equal flame retardant effect, and not produce toxic smog.
Preparation method provided by the invention have flow process simple, continuously, production efficiency is high and advantage such as constant product quality.
Embodiment
Embodiment 1
(1) with vacuum pump suction phosphorus oxychloride 767.5Kg in No. 1 reactor,, be cooled to 10～15 ℃, in still, feed nitrogen, flow velocity is 2m
3/ h protects anti-oxidation, and slowly drips ethylene glycol 62Kg, drips time 8h, is warming up to 18 ℃ after dropwising, and stirs material 1h; Stop logical nitrogen, with excessive POCl
3-0.1MPa, 55 ℃ of underpressure distillation steam, and distillation finishes, cooling, discharging feeds No. 2 reactors;
(2) in No. 2 reactors, drop into catalyst A lCl
3533.4g stir 0.5h, with icy salt solution temperature of reaction is controlled at 10～13 ℃, drip dehydrated alcohol 184Kg, drip time 6h, be warming up to about 25 ℃ insulation reaction 4h after dropwising; The low pressure suction filtration is removed catalyzer; Filtrate washing 3 times wash afterwards at-0.1MPa at every turn, and 105 ℃ of underpressure distillation are removed moisture and promptly got fire retardant PNX.
Embodiment 2
Present embodiment by many groups of experiments, changes the mol ratio of raw material according to the preparation technology of embodiment 1 respectively, and catalyst levels, temperature of reaction are to obtain optimised process.
2.1 the first step reaction raw materials mol ratio
The ratio (as table 1) of phosphorus oxychloride and ethylene glycol in the reaction of the change the first step, other conditions are carried out the first step reaction with embodiment 1, and wherein temperature refers to drip the temperature of ethylene glycol.
Table 1
| Phosphorus oxychloride | Ethylene glycol | Temperature | |
| The 1st group | ??2 | ??1 | ??10～15℃ |
| The 2nd group | ??3 | ??1 | ??10～15℃ |
| The 3rd group | ??5 | ??1 | ??10～15℃ |
| The 4th group | ??7 | ??1 | ??10～15℃ |
| The 5th group | ??8 | ??1 | ??10～15℃ |
By analysis, the 1st group of polymerization degree is 10～15, and the polymerization degree is too high, the material thickness, cooling back becomes to solidify shape, should not with the second step stirring reaction; The 2nd～4 group of polymerization degree 5～8, the polymerization degree is moderate, and liquid is easy to the reaction of second step, and is best with compound (2) performance of the 3rd group of preparation especially; The 5th group of polymerization degree 1～3, the polymerization degree is low excessively, and phosphorus oxychloride is excessive too many, and energy consumption consumption is many.So selecting the mol ratio of phosphorus oxychloride and ethylene glycol is 3～7: 1, preferred 5: 1.
2.2 the second step reaction raw materials mol ratio
Only change second step reaction alcoholic acid add-on (as table 2), other conditions are carried out two-step reaction with embodiment 1, and wherein temperature refers to drip ethylene glycol and alcoholic acid temperature.
Table 2
| ??POCl 3 | Ethylene glycol | Ethanol | ??AlCl 3 | Temperature | |
| The 1st group | ??5 | ??1 | ??3.0 | ??0.004 | ??10～15℃ |
| The 2nd group | ??5 | ??1 | ??3.5 | ??0.004 | ??10～15℃ |
| The 3rd group | ??5 | ??1 | ??3.8 | ??0.004 | ??10～15℃ |
| The 4th group | ??5 | ??1 | ??4.0 | ??0.004 | ??10～15℃ |
| ??POCl 3 | Ethylene glycol | Ethanol | ??AlCl 3 | Temperature | |
| The 5th group | ??5 | ??1 | ??4.2 | ??0.004 | ??10～15℃ |
| The 6th group | ??5 | ??1 | ??4.5 | ??0.004 | ??10～15℃ |
The assay result shows that the 1st group reaction is incomplete, also has the Cl element residual, and product yield is low, has only 60%; The 2nd～5 group reaction is complete, and product yield is up to 82～87%; The 6th group reaction is complete, product yield 87%, but the washing distillation has the ethanol cut to steam, and proves that ethanol is excessive.So selecting ethylene glycol and alcoholic acid mol ratio is 1: 3.5～4.5, wherein the highest with the 4th～5 group of productive rate, so preferred ethylene glycol and alcoholic acid mol ratio are 1: 4.0～4.2.
2.3 the selection of the second step catalysts consumption
Only change the second step catalysts consumption (as table 3), other conditions are carried out two-step reaction with embodiment 1, and wherein temperature refers to drip ethylene glycol and alcoholic acid temperature.
Table 3
| ??POCl 3 | Ethylene glycol | Ethanol | ??AlCl 3 | Temperature | |
| The 1st group | ??5 | ??1 | ??4.0 | ??0.001 | ??10～15℃ |
| The 2nd group | ??5 | ??1 | ??4.0 | ??0.002 | ??10～15℃ |
| The 3rd group | ??5 | ??1 | ??4.0 | ??0.004 | ??10～15℃ |
| The 4th group | ??5 | ??1 | ??4.0 | ??0.006 | ??10～15℃ |
| The 5th group | ??5 | ??1 | ??4.0 | ??0.008 | ??10～15℃ |
1st, 2 group reaction times were grown needs 12h, wherein drips 8h, insulation 4h; The 2nd group, reaction times 8h wherein drips 6h, during insulation 2h; The 3rd～5 group reaction time 6h wherein drips 4h, insulation 2h.So selecting catalyst is 0.004～0.008: 1 with the ratio of ethylene glycol, preferred 0.004; 1.
2.4 the selection of the second step temperature of reaction
Only change the reaction of second step and drip alcoholic acid temperature (table 4), other conditions are carried out two-step reaction with embodiment 1.
Table 4
| Group | The 1st group | The 2nd group | The 3rd group | The 4th group | The 5th group |
| Temperature (℃) | ??0～4 | ??4～8 | ?8～10 | ??10～15 | ??15～20 |
The result shows: the 1st～3 group reaction is for up to more than the 10h, and wherein Dropwise 5 h is incubated 5～6h and yield and is up to 73%; The 4th group reaction time 6h, wherein Dropwise 5 h is incubated 1h, and yield is high by 88.2%; The 5th group reaction time 5h wherein drips 4h, insulation 1h yield 80%; So select 10～15 ℃ to be the second step temperature of reaction.
In sum, the present invention selects phosphorus oxychloride: ethylene glycol: dehydrated alcohol: the mol ratio of aluminum chloride is 3～7: 1: 3.5～4.5: 0.004～0.008, and preferred 5: 1: 4.0～4.2: 0.004; The second step temperature of reaction is 10～15 ℃.
Embodiment 3
Respectively with fire retardant PNX of the present invention and phosphorus halogenated flame retardant T
101(four (β-chloroethyl)-ethylene bis phosphoric acids) makes an addition to automobile with in the flexible urethane foam, and preparation technology is a common process, and prescription separately and performance see Table 5 and table 6.
Table 5.T
101Fire-retardant prescription and performance with flexible urethane foam
| Prescription | Umber | Performance | Index |
| Polyether glycol (the averagemolecular wt amount is 3000, the Pacific Ocean, Zhejiang company limited) | ??100 | Density/kgm -3 | ??22.4 |
| Water | ??3.75 | Be pressed into distortion loading/kpa | |
| Diethanolamine | ??1.30 | ??25％ | ??2.52 |
| Amine catalyst | ??0.25 | ??65％ | ??63.0 |
| Tin catalyst | ??0.30 | Rebound degree | ??20 |
| Tensio-active agent | ??0.20 | Elongation | ??110 |
| ??T 101 | ??5.0 | Tear strength/kpa | ??10 |
| Trimeric cyanamide | ??30.0 | Compression variable (50% distortion) | ??30％ |
| ??TDI | ??57.7 | Weightlessness/g | ??49 |
| Oxygen index % | ??31 |
Prescription and performance that table 6.PNX is fire-retardant with flexible urethane foam
| Prescription | Umber | Performance | Index |
| Polyether glycol (the averagemolecular wt amount is 3000, the Pacific Ocean, Zhejiang company limited) | ??100 | Density/kgm -3 | ??22.4 |
| Water | ??3.75 | Be pressed into distortion loading/kpa | |
| Diethanolamine | ??1.30 | ??25％ | ??2.65 |
| Prescription | Umber | Performance | Index |
| Amine catalyst | ??0.25 | ??65％ | ??65.0 |
| Tin catalyst | ??0.30 | Rebound degree | ??20 |
| Tensio-active agent | ??0.20 | Elongation | ??110 |
| ??PNX | ??2.0 | Tear strength/kpa | ??10 |
| Trimeric cyanamide | ??30.0 | Compression variable (50% distortion) | ??28％ |
| ??TDI | ??57.7 | Weightlessness/g | ??47 |
| Oxygen index/% | ??33 |
From table 5 and table 6 as can be seen PNX reach T
10140% of addition, just can reach equal flame retardant effect, the also slightly high and fire-retardant flexible urethane foam of T101 of its oxygen index, and the fire-retardant flexible urethane foam of PNX do not produce toxic smog when doing combustion test, and the fire-retardant flexible urethane foam of T101 produces toxic smog when doing combustion test.
Embodiment 4
Respectively fire retardant PNX of the present invention and phosphorus halogenated flame retardant MPPDP are made an addition in the flexible urethane foam, preparation technology is a common process, and prescription separately and performance see Table 7 and table 8.
Prescription and performance that table 7.MPPDP is fire-retardant with flexible urethane foam
| Prescription | Umber | Performance | Index |
| Polyether glycol (the averagemolecular wt amount is 3000, the Pacific Ocean, Zhejiang company limited) | ??100 | Density/kgm -3 | ??32 |
| ??TDI(80/20) | ??43.6 | Oxygen index/% | ??23.5(17.5) * |
| Water | ??3.3 | Combustion time/s | ??35.5 |
| Whipping agent | ??3.0 | Burning length/mm | ??26.3 |
| Silicone oil | ??2.0 | Combustionvelocity/mms | ??0.74(1.62) * |
| Amine catalyst | ??0.25 | Tensile strength/kpa | ??70(78) * |
| Tin catalyst | ??0.25 | Elongation/% | ??130(150) * |
| Prescription | Umber | Performance | Index |
| ??MPPDP | ??12 | Rebound degree/% | ??45(52) * |
Prescription and performance that table 8.PNX is fire-retardant with flexible urethane foam
| Prescription | Umber | Performance | Index |
| Polyether glycol (the averagemolecular wt amount is 3000, the Pacific Ocean, Zhejiang company limited) | ??100 | Density/kgm -3 | ??32 |
| ??TDI(80/20) | ??43.6 | Oxygen index/% | ??29.5(17.5) * |
| Water | ??3.3 | Combustion time/s | ??31 |
| Whipping agent | ??3.0 | Burning length/mm | ??22 |
| Silicone oil | ??2.0 | Combustionvelocity/mms | ??0.71(1.62)?? * |
| Amine catalyst | ??0.25 | Tensile strength/kpa | ??72(78) * |
| Tin catalyst | ??0.25 | Elongation/% | ??132(150) * |
| ??PNX | ??12 | Rebound degree/% | ??46(52) * |
Add 12% MPPDP fire retardant as can be seen from table 7 and table 8, flame retardant resistance is to reaching V-2, and adds 12% PNX fire retardant, and flame retardant resistance reaches the V-0 rank, and all the other performance variation are little.
*Numerical value is blank value in the bracket.
Claims (10)
1. polymer type phosphor-containing fire retardant PNX is characterized in that this fire retardant is the compounds shown in the general formula (1):
2. the preparation method of the described fire retardant PNX of claim 1 is characterized in that obtaining compound (2) by the chemical reaction shown in the reaction formula (1) by phosphorus oxychloride and ethylene glycol in nitrogen environment; Compound (2) obtains fire retardant PNX by the chemical reaction shown in the reaction formula (2) with dehydrated alcohol under the effect of catalyzer aluminum chloride;
The integer of n=5～8;
, the integer of n=5～8.
3. preparation method according to claim 2 is characterized in that concrete steps are as follows:
(1) suction phosphorus oxychloride in No. 1 reactor is cooled to 10～15 ℃, feeds nitrogen in still, and flow velocity is 0.5～3m
3/ h, and slowly drip ethylene glycol, be warming up to 15～25 ℃ after dropwising, stirring reaction 0.5～3h; Stop logical nitrogen, excessive phosphorus oxychloride underpressure distillation is steamed, distillation finishes, cooling, and gained liquid feeds No. 2 reactors in the still kettle;
(2) in No. 2 reactors, drop into catalyst A lCl
3, stirring 0.5～1h, controlled temperature drips dehydrated alcohol at 10～15 ℃, is warming up to 20～30 ℃ after dropwising, insulation 3～6h; The low pressure suction filtration is removed catalyzer; Filtrate washing 2～6 times, underpressure distillation is removed moisture and is promptly got fire retardant PNX after having washed at every turn.
4. according to claim 2 or 3 described preparation technologies, the mol ratio that it is characterized in that described phosphorus oxychloride, ethylene glycol, dehydrated alcohol and aluminum chloride is a phosphorus oxychloride: ethylene glycol: dehydrated alcohol: aluminum chloride=3～7: 1: 3.5～4.5: 0.004～0.008.
5. preparation technology according to claim 4, the mol ratio that it is characterized in that described phosphorus oxychloride, ethylene glycol, dehydrated alcohol and aluminum chloride is the phosphorus oxychloride phosphorus oxychloride: ethylene glycol: dehydrated alcohol: aluminum chloride=5: 1: 4.0～4.2: 0.004.
6. preparation technology according to claim 3 is characterized in that a speed of described dropping ethylene glycol is 110～140g/min, and the hydrochloric acid that produces in the dropping process absorbs with the HCl absorption tower.
7. preparation technology according to claim 3 is characterized in that a speed of described dropping dehydrated alcohol is 400～580g/min, and the hydrochloric acid that produces in the dropping process absorbs with the HCl absorption tower.
8. preparation technology according to claim 3, it is characterized in that in the described step (1) pressure of underpressure distillation be-0.1～-0.05MPa, distillation temperature is 45～60 ℃.
9. preparation technology according to claim 3, it is characterized in that in the described step (2) pressure of underpressure distillation be-0.1～-0.05MPa, distillation temperature is 105 ℃.
10. the application of the described fire retardant PNX of claim 1 in the preparation flexible urethane foam.
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| CN 201010150013 CN101805620B (en) | 2010-04-19 | 2010-04-19 | Polymer type phosphor-containing fire retardant, preparation method and application thereof |
| PCT/CN2011/073615 WO2011131153A1 (en) | 2010-04-19 | 2011-05-03 | Polymer type phosphor-containing flame retardant, preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011131153A1 (en) * | 2010-04-19 | 2011-10-27 | 江苏大明科技有限公司 | Polymer type phosphor-containing flame retardant, preparation method and application thereof |
| CN102250140A (en) * | 2011-05-24 | 2011-11-23 | 北京化工大学 | Polyphosphinate monomer, polyphosphinate and preparation method of polyphosphinate |
| CN102561036A (en) * | 2011-12-30 | 2012-07-11 | 太原理工大学 | Polypropylene-based dimethyl phosphate flame retardant and preparation method thereof |
| CN102558606A (en) * | 2012-01-11 | 2012-07-11 | 福州大学 | Reactive halogen-free organic phosphate ester flame retardant and flame-retardant polyurethane elastomer |
| CN103804692A (en) * | 2014-02-12 | 2014-05-21 | 东北林业大学 | Preparation method of phosphonate flame retardant containing high phosphorus content and applying to polyurethane foam |
| TWI572678B (en) * | 2012-07-20 | 2017-03-01 | 朗盛德意志有限公司 | Halogen-free poly (alkylene phosphates) |
| CN106699804A (en) * | 2016-11-28 | 2017-05-24 | 宣城市聚源精细化工有限公司 | Production method of flame retardant for polyurethane foaming plastic |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112961362A (en) * | 2020-10-29 | 2021-06-15 | 广东广山新材料股份有限公司 | Polymeric flame retardant and preparation method and application thereof |
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| CN101805620B (en) * | 2010-04-19 | 2012-12-19 | 江苏大明科技有限公司 | Polymer type phosphor-containing fire retardant, preparation method and application thereof |
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| US6548627B1 (en) * | 1999-04-19 | 2003-04-15 | Clariant Gmbh | Flame-retardant phosphorus-modified epoxy resins |
| CN101293896A (en) * | 2007-04-29 | 2008-10-29 | 江苏雅克化工有限公司 | Preparation of low polyphosphate |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011131153A1 (en) * | 2010-04-19 | 2011-10-27 | 江苏大明科技有限公司 | Polymer type phosphor-containing flame retardant, preparation method and application thereof |
| CN102250140A (en) * | 2011-05-24 | 2011-11-23 | 北京化工大学 | Polyphosphinate monomer, polyphosphinate and preparation method of polyphosphinate |
| CN102561036A (en) * | 2011-12-30 | 2012-07-11 | 太原理工大学 | Polypropylene-based dimethyl phosphate flame retardant and preparation method thereof |
| CN102561036B (en) * | 2011-12-30 | 2013-11-06 | 太原理工大学 | Polypropylene-based dimethyl phosphate flame retardant and preparation method thereof |
| CN102558606A (en) * | 2012-01-11 | 2012-07-11 | 福州大学 | Reactive halogen-free organic phosphate ester flame retardant and flame-retardant polyurethane elastomer |
| TWI572678B (en) * | 2012-07-20 | 2017-03-01 | 朗盛德意志有限公司 | Halogen-free poly (alkylene phosphates) |
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| CN103804692A (en) * | 2014-02-12 | 2014-05-21 | 东北林业大学 | Preparation method of phosphonate flame retardant containing high phosphorus content and applying to polyurethane foam |
| CN103804692B (en) * | 2014-02-12 | 2016-04-20 | 东北林业大学 | A kind of preparation method being applied in the phosphonate fire retardant of the high content of phosphorus of polyurethane foam |
| CN106699804A (en) * | 2016-11-28 | 2017-05-24 | 宣城市聚源精细化工有限公司 | Production method of flame retardant for polyurethane foaming plastic |
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| CN101805620B (en) | 2012-12-19 |
| WO2011131153A1 (en) | 2011-10-27 |
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