CN101885824B - Fluorine-containing phosphoric polyurethane elastomer and preparation method thereof - Google Patents
Fluorine-containing phosphoric polyurethane elastomer and preparation method thereof Download PDFInfo
- Publication number
- CN101885824B CN101885824B CN201010231578XA CN201010231578A CN101885824B CN 101885824 B CN101885824 B CN 101885824B CN 201010231578X A CN201010231578X A CN 201010231578XA CN 201010231578 A CN201010231578 A CN 201010231578A CN 101885824 B CN101885824 B CN 101885824B
- Authority
- CN
- China
- Prior art keywords
- fluorine
- phenyl
- hours
- nitro
- polyurethane elastomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- ZKIBFASDNPOJFP-UHFFFAOYSA-N CNP(NC)(Oc1ccccc1)=O Chemical compound CNP(NC)(Oc1ccccc1)=O ZKIBFASDNPOJFP-UHFFFAOYSA-N 0.000 description 1
- PPMCQGKJNUEEBN-UHFFFAOYSA-N CNP(c1ccccc1)(NC)=O Chemical compound CNP(c1ccccc1)(NC)=O PPMCQGKJNUEEBN-UHFFFAOYSA-N 0.000 description 1
- BKZMQMBRLXRMGQ-UHFFFAOYSA-N COc1cccc(OP(Oc2ccccc2)(Oc2cc(OC)ccc2)=O)c1 Chemical compound COc1cccc(OP(Oc2ccccc2)(Oc2cc(OC)ccc2)=O)c1 BKZMQMBRLXRMGQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a fluorine-containing phosphoric polyurethane elastomer and a preparation method thereof, and is characterized in that the previously prepared fluorine-containing phosphoric diamine is adopted to introduce fluorine element and phosphorus element into a polyurethane elastomer at the same time; the obtained fluorine-containing phosphoric polyurethane elastomer has a structure shown in the specification, wherein -R-is also shown in the specification; and the fluorine-containing phosphoric polyurethane elastomer also has excellent surface property, thermal stability, fire resistance and mechanical behavior, can be applied to various complicated environments and greatly widens the application range of the polyurethane elastomer.
Description
Technical field
The invention belongs to the polyurethane elastomer technical field, be specifically related to fluorine-containing phosphorous polyurethane elastomer and preparation method thereof.
Background technology
Introduce according to " Shanghai Communications University's journal " 2006 40 volumes the 7th phase 1239-1243 page or leaf, the fluorinated polyurethane elastomer body is one type of macromolecular material with specific function.The introducing of fluorine had both kept the original characteristic of polyurethane elastomer, gave its remarkable weathering resistance, resistant to chemical media property, higher use temperature, resistance to crocking and low frictional properties again.Introduce according to " thermosetting resin " 2005 20 volumes the 5th phase 40-45 page or leaf, phosphorus is important ignition-proof element, and phosphorous INSTINCT FLAME RETARDANT POLYMERS does not need fire-retardant finish can satisfy strict fire protection requirement, and environmentally friendly.Compare with the fire-retardant superpolymer of routine, INSTINCT FLAME RETARDANT POLYMERS does not exist fire retardant volatilization, stripping, moves and oozes out problem, and flame retarding efficiency is high.Fluorinated polyurethane elastomer surface excellent performance, but flame retardant properties is not good, and phosphorous polyurethane elastomer flame retardant effect is remarkable, but surface property is not good; Present existing polyurethane elastomer can't satisfy and both had flame retardant properties preferably, has the requirement of excellent surface property simultaneously again.
Summary of the invention
The present invention proposes fluorine-containing phosphoric polyurethane elastomer and preparation method thereof, can't satisfy and not only has preferably flame retardant properties simultaneously but also have a deficiency that excellent surface property requires to overcome above-mentioned prior art.
Fluorine-containing phosphorous polyurethane elastomer of the present invention is characterized in that having the following chemical structure:
Fluorine-containing phosphorous method for preparing polyurethane elastic body of the present invention; May further comprise the steps: in vacuum tightness is under 133～266Pa and 110～125 ℃ of conditions polymer polyatomic alcohol to be dewatered 2～4 hours; By polymer polyatomic alcohol and tolylene diisocyanate mol ratio is 1: 1.6～2.6 adding tolylene diisocyanates (TDI); 60～80 ℃ of reactions 2～3 hours, process base polyurethane prepolymer for use as; Is 1: 0.80～0.95 to be dissolved in butanone, 1 with this base polyurethane prepolymer for use as and diamines according to mol ratio; 4-dioxy six alkane or N, the dinethylformamide solvent is placed in the mould, prior to 65 ± 5 ℃ of film-formings; Put into 130 ± 5 ℃ of baking ovens again and reacted 3～4 hours, get polyurethane elastomer;
Said polymer polyatomic alcohol is polyester diol or polyether Glycols;
Said butanone, 1,4-dioxy six alkane or N, the consumption of dinethylformamide reaches 30%～50% for making the total solids mass percent;
It is characterized in that:
Said diamines is fluorine-containing phosphorous diamines, adopts following steps to prepare:
(1) be that the vitriol oil of 95-98% and the mass percent concentration that accounts for reaction mixture total mass mark 14%～20% are in the concentrated nitric acid of 65-68% with chlorobenzotrifluoride at the mass percent concentration that accounts for reaction mixture total mass mark 42%～54%; 20～50 ℃ nitrated 2～6 hours, obtain 2-chloro-5-nitro-phenylfluoroform;
(2) with this 2-chloro-5-nitro-phenylfluoroform and phosphorous bis-phenol or phosphorous diamine be in molar ratio 2: 1 in intensive polar solvent in 80～150 ℃ of reactions 12-36 hour; Reaction finishes the back underpressure distillation and removes solvent; Spent glycol monomethyl ether or ethyl alcohol recrystallization product obtain corresponding two nitro-compound;
(3) with resulting pair of nitro-compound and aqueous ethanolic solution, iron powder, mixed in hydrochloric acid, be 1: 6～8 by two nitro-compounds and iron powder mol ratio, the mass percent concentration of hydrochloric acid is 36%～38%; Two nitro-compounds and hydrochloric acid mass ratio are 15～18: 1; The ethanol mass percent concentration was 55%～70% in the aqueous ethanolic solution, and two nitro-compounds and aqueous ethanolic solution mass ratio are 1.5～2: 1,70～80 ℃ of reactions 3～6 hours; Filter; Gained is filtrated to add and is refiltered after ammoniacal liquor transfers to pH neutrality, should filtrate under normal pressure, to distill to remove organic phase again, promptly obtains corresponding fluorine-containing phosphorous diamines;
Phosphorous bis-phenol in the said step (2) or phosphorous diamine be selected from two (3-hydroxyphenoxy) phenyl-phosphate, 10-(2 ', 5 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound, diamino-phenyl-phosphate or phenyl phosphoryl diamine; Said intensive polar solvent is N, dinethylformamide (DMF) or N,N-DIMETHYLACETAMIDE (DMAc).
Said fluorine-containing phosphorous diamines be two [3-(2-trifluoromethyl-4-amino-benzene oxygen)] triphenylphosphates or 10-[2 '; 5 '-two (2-trifluoromethyl-4-amino-benzene oxygen) phenyl]-9; The 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound or N; N '-two (2-trifluoromethyl-4-aminophenyl) di(2-ethylhexyl)phosphate acid amides phenyl ester or phenyl-N, N '-two (2-trifluoromethyl-4-aminophenyl) di(2-ethylhexyl)phosphate acid amides.
Said mould can be selected irony mould or tetrafluoroethylene mould for use; Usually the preferably polytetrafluoroethylene mould comes off so that react the polyurethane elastomer that obtains easily.
Fluorine-containing phosphorous polyurethane elastomer of the present invention does not see as yet that so far relevant report is arranged, and is one type of new organic cpds.
Because preparation method of the present invention is by means of the fluorine-containing phosphorous diamines for preparing earlier; Fluorine element and phosphoric in polyurethane elastomer, have been introduced simultaneously; Overcome in the past polyurethane elastomer and can not satisfy and both had flame retardant properties preferably, had the shortcoming of excellent surface property simultaneously again.
The fluorine-containing phosphorous polyurethane elastomer that adopts the inventive method to prepare has thermostability, flame retardant resistance and the good physical and mechanical properties of excellent surface property, excellence.
Embodiment
Below in conjunction with specific embodiment the present invention is further specified.
Embodiment 1:
With 80 gram chlorobenzotrifluorides and 60 gram mass percentage concentrations is that 95% the vitriol oil mixes; Keep room temperature, in mixture, dripping by 90 gram mass percentage concentrations is that 65% concentrated nitric acid and 64 gram mass percentage concentrations are the mixed solution that 95% the vitriol oil is formed again.Control reaction temperature was 45 ℃ of stirring reactions 4 hours.Reactant is poured in 1 liter of frozen water, isolated solid, be washed till pH neutrality with deionized water, underpressure distillation gets pure article 2-chloro-5-nitro-phenylfluoroform.
The 2-chloro-5-nitro-phenylfluoroform of the above-mentioned preparation of 135 grams is dissolved in 200 gram N, in the dinethylformamide (DMF), treats that it dissolves the back fully and adds 45 gram salt of wormwood, 115 gram two (3-hydroxyphenoxy) phenyl-phosphates.80 ℃ the reaction 36 hours after; With reactant cold filtration disgorging; Pour recrystallization in the ethylene glycol monomethyl ether into after filtrate decompression distillation removes DMF,, obtain two [3-(2-trifluoromethyl-4-nitrophenoxy) phenyl] phenyl-phosphate the xln vacuum-drying of gained 24 hours.
Adding 8 gram concentration are that 38% hydrochloric acid, 69 gram iron powders, 75 gram mass percentage concentrations are aqueous ethanolic solution and 151 gram two (3-(2-trifluoromethyl-4-nitrophenoxy) phenyl) phenyl-phosphates of 70% in the 500ml four-necked bottle that whisking appliance, constant pressure funnel and reflux are housed, and reflux 4 hours.Filter, filtrating is added ammoniacal liquor transfer to neutrality, stirred 0.5 hour, again this filtrating air distillation is removed organic phase, obtain two [3-(2-trifluoromethyl-4-amino-benzene oxygen)] triphenylphosphate.
Is 133Pa, 125 ℃ of dehydrations 2 hours with 100 gram polyester diol (M=1000) in vacuum tightness, adds tolylene diisocyanate (TDI) 28 gram again, obtains base polyurethane prepolymer for use as 80 ℃ of reactions after 2 hours.
Get this base polyurethane prepolymer for use as 100 grams; Add 25 gram two [3-(2-trifluoromethyl-4-amino-benzene oxygen)] triphenylphosphates; Be dissolved in the butanone of 290 grams, this mixed solution is poured in the tetrafluoroethylene mould, earlier at 70 ℃ of film-formings; Put into 135 ℃ of baking oven vulcanization reactions again 3 hours, and promptly got fluorine-containing phosphorous polyurethane elastomer.
Through detecting, the surface tension of above-mentioned fluorine-containing phosphorous polyurethane elastomer is 25.0mN/m, and water contact angle is 92.6 °, and the thermal weight loss rate is 10% o'clock a temperature T
10Be 319 ℃, limiting oxygen index(LOI) LOI is 27.4%, and tensile strength is 27.5MPa, elongation at break 652%.
Embodiment 2:
With 80 gram chlorobenzotrifluorides and 60 gram mass percentage concentrations is that 96% the vitriol oil mixes; Keep room temperature, in mixture, dripping by 80 gram mass percentage concentrations is that 66% concentrated nitric acid and 100 gram mass percentage concentrations are the mixed solution that 96% the vitriol oil is formed again.Control reaction temperature is at 20 ℃, stirring reaction 6 hours; Reactant is poured in 1 liter of frozen water, isolated solid, be washed till pH neutrality with deionized water, underpressure distillation obtains pure article 2-chloro-5-nitro-phenylfluoroform.
The 2-chloro-5-nitro-phenylfluoroform of the above-mentioned preparation of 135 grams is dissolved among the 200 gram DMAc, treat that it dissolves fully after, add 45 gram salt of wormwood, 97 gram 10-(2 '; 5 '-dihydroxy phenyl)-9,10-dihydro-9 oxa-s-10-phospho hetero phenanthrene-10-oxide compound, 130 ℃ the reaction 24 hours after; With reactant cold filtration disgorging; Pour recrystallization in the ethylene glycol monomethyl ether into after distillation removes DMAc to this filtrate decompression again, with the xln vacuum-drying of gained 24 hours, obtain 10-(2 '; 5 '-two (2-trifluoromethyl-4-nitrophenoxy) phenyl))-9,10-dihydro-9 oxa-s-10-phospho hetero phenanthrene-10-oxide compound.
In the 500ml four-necked bottle that whisking appliance, constant pressure funnel and reflux are housed, adding 9 gram concentration and be 37% hydrochloric acid, 88 gram iron powders, 85 gram mass percentage concentrations and be 65% aqueous ethanolic solution and 139 gram 10-[2 ', 5 '-two (2-trifluoromethyl-4-amino-benzene oxygen) phenyl]-9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound; Refluxed 4 hours, and filtered, filtrating is added ammoniacal liquor transfer to neutrality; Stirred 0.5 hour, solids removed by filtration concentrates this filtrating air distillation again; Crystallization 12 hours; The gained crystal is used the aqueous ethanolic solution recrystallization, with the xln vacuum-drying of gained 24 hours, obtain 10-(2 '; 5 '-two (2-trifluoromethyl-4-amino-benzene oxygen) phenyl))-9,10-dihydro-9 oxa-s-10-phospho hetero phenanthrene-10-oxide compound.
Is 266Pa, 120 ℃ of dehydrations 3 hours with 100 gram polyether Glycols (M=1000) in vacuum tightness, adds tolylene diisocyanate (TDI) 35 gram again, after 2.5 hours, obtains base polyurethane prepolymer for use as 70 ℃ of reactions;
Get this base polyurethane prepolymer for use as 100 grams, the 10-of adding 43 grams (2 ', 5 '-two (2-trifluoromethyl-4-amino-benzene oxygen) phenyl))-9; 10-dihydro-9 oxa-s-10-phospho hetero phenanthrene-10-oxide compound is dissolved in 300 grams 1, in 4-dioxy six alkane; This mixed solution is poured in the tetrafluoroethylene mould; At 65 ℃ of film-formings, put into 125 ℃ of baking oven vulcanization reactions again 4 hours earlier, promptly get fluorine-containing phosphorous polyurethane elastomer.
Surface tension through detecting above-mentioned fluorine-containing phosphorous polyurethane elastomer is 24.8mN/m, and water contact angle is 95.8 °, T
10Be 325 ℃, LOI is 28.1%, and tensile strength is 23.5MPa, elongation at break 734%.
Embodiment 3:
With 40 gram chlorobenzotrifluorides and 30 gram mass percentage concentrations is that 97% the vitriol oil mixes; Keep room temperature; In mixture, dripping by 40 gram mass percentage concentrations is that 67% concentrated nitric acid and 50 gram mass percentage concentrations are the mixed solution that 97% the vitriol oil is formed again; Control reaction temperature is 50 ℃, stirring reaction 2 hours; Reactant is poured in 1 liter of frozen water, isolated solid, be washed till pH neutrality with deionized water, underpressure distillation obtains pure article 2-chloro-5-nitro-phenylfluoroform.
The 2-chloro-5-nitro-phenylfluoroform of the above-mentioned preparation of 135 grams is dissolved among the 300 gram DMAc, adds 45.5 gram salt of wormwood, 48 gram diamino-phenyl-phosphates.150 ℃ of reactions with reactant cold filtration disgorging, were poured recrystallization in the ethylene glycol monomethyl ether into after the filtrate decompression distillation removes DMAc after 12 hours.Vacuum-drying 24 hours obtains two (2-trifluoromethyl-4-nitrophenoxy) phenyl-phosphate.
Adding 10 gram concentration are that 37% hydrochloric acid, 107 gram iron powders and 90 gram mass percentage concentrations are aqueous ethanolic solution and 151 gram two (3-(2-trifluoromethyl-4-nitrophenoxy) phenyl) phenyl-phosphates of 60% in the 500ml four-necked bottle that whisking appliance, constant pressure funnel and reflux are housed; Refluxed 4 hours; Add ammoniacal liquor then and transfer to neutrality; Stirred solids removed by filtration 0.5 hour.The air distillation of will filtrating concentrates, crystallization 12 hours, and the gained crystal is used the aqueous ethanolic solution recrystallization, with the xln vacuum-drying that obtains 24 hours, gets N, N '-two (2-trifluoromethyl-4-aminophenyl) di(2-ethylhexyl)phosphate acid amides phenyl ester.
Is 199Pa, 115 ℃ of dehydrations 3.5 hours with 200 gram polyether Glycols (M=2000) in vacuum tightness, adds tolylene diisocyanate (TDI) 35 gram again, after 2.8 hours, obtains base polyurethane prepolymer for use as 65 ℃ of reactions.
Get this base polyurethane prepolymer for use as 100 grams, add 19 gram N, N '-two (2-trifluoromethyl-4-aminophenyl) di(2-ethylhexyl)phosphate acid amides phenyl ester; Be dissolved in 257 gram N; In the dinethylformamide, this mixed solution is poured in the tetrafluoroethylene mould, earlier at 65 ℃ of film-formings; Put into 130 ℃ of baking oven vulcanization reactions again 3.5 hours, and promptly obtained fluorine-containing phosphorous polyurethane elastomer.
Surface tension through detecting above-mentioned fluorine-containing phosphorous polyurethane elastomer is 20.4mN/m, and water contact angle is 99.3 °, T
10Be 318 ℃, LOI is 28.8%, and tensile strength is 22.8MPa, elongation at break 792%.
Embodiment 4:
With 80 gram chlorobenzotrifluorides and 60 gram mass percentage concentrations is that 98% the vitriol oil mixes; Keep room temperature; In mixture, dripping by 70 gram mass percentage concentrations is that 68% concentrated nitric acid and 120 gram mass percentage concentrations are the mixed solution that 98% the vitriol oil is formed again; Control reaction temperature is 45 ℃, stirring reaction 4 hours.Reactant is poured in 1 liter of frozen water, isolated solid, be washed till pH neutrality with deionized water, underpressure distillation obtains pure article 2-chloro-5-nitro-phenylfluoroform.
The 2-chloro-5-nitro-phenylfluoroform of the above-mentioned preparation of 135 grams is dissolved among the 300 gram DMAc, adds 45.5 gram salt of wormwood, 44 gram phenyl phosphoryl diamines.140 ℃ of reactions 30 hours, reactant cold filtration disgorging was poured recrystallization in the ethylene glycol monomethyl ether into after filtrate decompression distillation removed DMAc, to gained crystal vacuum-drying 24 hours, phenyl phosphinylidyne two (2-trifluoromethyl-4-N-methyl-p-nitroaniline).
Adding 10 gram concentration are that 36% hydrochloric acid, 108 gram iron powders, 95 gram mass percentage concentrations are 55% aqueous ethanolic solution and 147 gram phenyl phosphinylidynes, two (2-trifluoromethyls-4-N-methyl-p-nitroaniline) in the 500ml four-necked bottle that whisking appliance, constant pressure funnel and reflux are housed; Refluxed 4 hours; Add ammoniacal liquor then and transfer to neutrality; Stirred solids removed by filtration 0.5 hour; The air distillation of will filtrating concentrates, crystallization 12 hours, and the gained crystal is used the aqueous ethanolic solution recrystallization, with the xln vacuum-drying that obtains 24 hours, gets phenyl-N, N '-two (2-trifluoromethyl-4-aminophenyl) di(2-ethylhexyl)phosphate acid amides.
Is 266Pa, 115 ℃ of dehydrations 3.5 hours with 200 gram polyester diol (M=2000) in vacuum tightness, adds tolylene diisocyanate (TDI) 45 gram again, 60 ℃ of reactions after 3 hours base polyurethane prepolymer for use as.
Get this base polyurethane prepolymer for use as 100 grams, add 29 gram phenyl-N, N '-two (2-trifluoromethyl-4-aminophenyl) di(2-ethylhexyl)phosphate acid amides; Be dissolved in 129 gram N; In the dinethylformamide, this mixed solution is poured in the tetrafluoroethylene mould, earlier at 65 ℃ of film-formings; Put into 130 ℃ of baking oven vulcanization reactions again 3.5 hours, and promptly got fluorine-containing phosphorous polyurethane elastomer.
Surface tension through detecting above-mentioned fluorine-containing phosphorous polyurethane elastomer is 19.6mN/m, and water contact angle is 102.2 °, T
10Be 312 ℃, LOI is 29.4%, and tensile strength is 26.6MPa, elongation at break 710%.
Claims (4)
1. fluorine-containing phosphoric polyurethane elastomer is characterized in that having the following chemical structure:
2. the said fluorine-containing phosphorous method for preparing polyurethane elastic body of claim 1; May further comprise the steps: in vacuum tightness is under 133～266Pa and 110～125 ℃ of conditions polymer polyatomic alcohol to be dewatered 2～4 hours; By polymer polyatomic alcohol and tolylene diisocyanate mol ratio is 1: 1.6～2.6 adding tolylene diisocyanates; 60～80 ℃ of reactions 2～3 hours, process base polyurethane prepolymer for use as; Is 1: 0.80～0.95 to be dissolved in butanone, 1 with this base polyurethane prepolymer for use as and diamines according to mol ratio; 4-dioxy six alkane or N, the dinethylformamide solvent is placed in the mould, prior to 65 ± 5 ℃ of film-formings; Put into 130 ± 5 ℃ of baking ovens again and reacted 3～4 hours, get polyurethane elastomer;
Said polymer polyatomic alcohol is polyester diol or polyether Glycols;
Said butanone, 1,4-dioxy six alkane or N, the consumption of dinethylformamide reaches 30%～50% for making the total solids mass percent;
It is characterized in that:
Said diamines is fluorine-containing phosphorous diamines, adopts following steps to prepare:
(1) be that the vitriol oil of 95-98% and the mass percent concentration that accounts for reaction mixture total mass mark 14%～20% are in the concentrated nitric acid of 65-68% with chlorobenzotrifluoride at the mass percent concentration that accounts for reaction mixture total mass mark 42%～54%; 20～50 ℃ nitrated 2～6 hours, obtain 2-chloro-5-nitro-phenylfluoroform;
(2) with this 2-chloro-5-nitro-phenylfluoroform and phosphorous bis-phenol or phosphorous diamine be in molar ratio 2: 1 in intensive polar solvent in 80～150 ℃ of reactions 12-36 hour; Reaction finishes the back underpressure distillation and removes solvent; Spent glycol monomethyl ether or ethyl alcohol recrystallization product obtain corresponding two nitro-compound;
(3) with resulting pair of nitro-compound and aqueous ethanolic solution, iron powder, mixed in hydrochloric acid, be 1: 6～8 by two nitro-compounds and iron powder mol ratio, the mass percent concentration of hydrochloric acid is 36%～38%; Two nitro-compounds and hydrochloric acid mass ratio are 15～18: 1; The ethanol mass percent concentration was 55%～70% in the aqueous ethanolic solution, and two nitro-compounds and aqueous ethanolic solution mass ratio are 1.5～2: 1,70～80 ℃ of reactions 3～6 hours; Filter; Gained is filtrated to add and is refiltered after ammoniacal liquor transfers to pH neutrality, should filtrate under normal pressure, to distill to remove organic phase again, promptly obtains corresponding fluorine-containing phosphorous diamines;
Phosphorous bis-phenol in the said step (2) or phosphorous diamine be selected from two (3-hydroxyphenoxy) phenyl-phosphate, 10-(2 ', 5 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound, diamino-phenyl-phosphate or phenyl phosphoryl diamine; Said intensive polar solvent is N, dinethylformamide or N,N-DIMETHYLACETAMIDE.
3. like the said fluorine-containing phosphorous method for preparing polyurethane elastic body of claim 2; Be characterised in that said fluorine-containing phosphorous diamines be two [3-(2-trifluoromethyl-4-amino-benzene oxygen)] triphenylphosphates or 10-[2 '; 5 '-two (2-trifluoromethyl-4-amino-benzene oxygen) phenyl]-9; The 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound or N, N '-two (2-trifluoromethyl-4-aminophenyl) di(2-ethylhexyl)phosphate acid amides phenyl ester or phenyl-N, N '-two (2-trifluoromethyl-4-aminophenyl) di(2-ethylhexyl)phosphate acid amides.
4. like the said fluorine-containing phosphorous method for preparing polyurethane elastic body of claim 2, be characterised in that said mould selects irony mould or tetrafluoroethylene mould for use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010231578XA CN101885824B (en) | 2010-07-15 | 2010-07-15 | Fluorine-containing phosphoric polyurethane elastomer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010231578XA CN101885824B (en) | 2010-07-15 | 2010-07-15 | Fluorine-containing phosphoric polyurethane elastomer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101885824A CN101885824A (en) | 2010-11-17 |
| CN101885824B true CN101885824B (en) | 2012-05-23 |
Family
ID=43071933
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010231578XA Active CN101885824B (en) | 2010-07-15 | 2010-07-15 | Fluorine-containing phosphoric polyurethane elastomer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101885824B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237723A (en) * | 2015-10-09 | 2016-01-13 | 滁州环球聚氨酯科技有限公司 | Preparation method of heat-conduction polyurethane material |
| CN105237730A (en) * | 2015-10-09 | 2016-01-13 | 滁州环球聚氨酯科技有限公司 | Preparation method of heat-resistant heat-conduction polyurethane material |
| CN105732715A (en) * | 2016-01-27 | 2016-07-06 | 厦门大学 | Phosphorus-containing fluorine-containing synergic flame-retardant compound and preparation method thereof |
| CN108864399B (en) * | 2018-07-06 | 2020-12-29 | 汕头大学 | Organic silicon modified flame-retardant polyurethane and preparation thereof |
| CN109354667B (en) * | 2018-09-11 | 2022-08-16 | 东莞市吉鑫高分子科技有限公司 | Wear-resistant antifouling thermoplastic polyurethane elastomer and preparation method thereof |
| CN111349234B (en) * | 2020-04-30 | 2022-03-11 | 深圳市前海博扬研究院有限公司 | Flame-retardant phosphorus-containing polyaspartic ester and synthesis method thereof |
| CN113354790A (en) * | 2021-06-25 | 2021-09-07 | 上海伟星新材料科技有限公司 | Fluorine-containing and phosphorus-containing waterborne polyurethane material and preparation method thereof |
| CN114657796B (en) * | 2022-05-17 | 2022-10-04 | 江苏恒力化纤股份有限公司 | Flame-retardant coating nylon fabric and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1569917A (en) * | 2004-05-11 | 2005-01-26 | 四川大学 | Polyurethane material with side chain possessing fluorophosphatidylcholine and its preparation method |
-
2010
- 2010-07-15 CN CN201010231578XA patent/CN101885824B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1569917A (en) * | 2004-05-11 | 2005-01-26 | 四川大学 | Polyurethane material with side chain possessing fluorophosphatidylcholine and its preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 徐文总等.含氟聚氨酯弹性体的制备与表征.《中国皮革》.2010,第39卷(第11期),35-40. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101885824A (en) | 2010-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101885824B (en) | Fluorine-containing phosphoric polyurethane elastomer and preparation method thereof | |
| CN104844781B (en) | A kind of graphene chemical modification hard polyurethane foams | |
| CN111548476B (en) | Flame-retardant environment-friendly polyurethane material and preparation method thereof | |
| CN104892886B (en) | A kind of hard resistance combustion polyurethane foam of low flue gas release | |
| CN101775119B (en) | Preparation method of environmental sensitive polyurethane film | |
| CN109400649B (en) | Preparation of single-component intumescent flame retardant and application of single-component intumescent flame retardant in flame-retardant epoxy resin | |
| CN116875264A (en) | High-temperature-resistant hydrolysis-resistant heat-conducting polyurethane structural adhesive and preparation method thereof | |
| CN108976774A (en) | A kind of high-ductility flame retardant polyurethane composite material | |
| CN105367604A (en) | Phosphorus-nitrogen-containing star-type charring agent and preparation method thereof | |
| CN103342799A (en) | Fluorine-containing, phosphorus-containing and silicon-containing epoxy resin and preparation method for same | |
| CN101245023A (en) | Process for producing 2,2-bis[2,4-diaminophenyloxy)phenyl]hexafluoropropane | |
| CN104017163B (en) | The application of a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants | |
| CN116790138B (en) | Modified graphene and preparation method of modified graphene slurry | |
| CN103012720B (en) | Polyurethane resin for tetramethylguanidine ionic liquid-modified waterborne synthetic leather and manufacturing method thereof | |
| CN111559970B (en) | Surface wetting agent with polysulfonic acid structure and preparation method thereof | |
| CN102643544B (en) | Fluorine-containing polyimide infrared low-emissivity thin film material and preparation method thereof | |
| CN115782344A (en) | Polyurethane composite board for building exterior wall insulation and preparation process thereof | |
| CN102286149A (en) | Polyphosphazene-semi-aromatic amide material and preparation method thereof | |
| CN110591132B (en) | Carbon fiber prepreg | |
| CN101260053A (en) | Method for preparing 2,2-di[3-amino-4-(2,4-diaminophenoxy)phenyl]hexafluoropropane | |
| CN101250128A (en) | Method for preparing 1,4-di(2,4-diamino phenoxy) naphthalene | |
| CN117820375A (en) | Phosphorus-containing polyol and preparation method and application thereof | |
| CN104974350B (en) | Nitro polyphenylene oxide phosphonitrile and preparation method thereof | |
| CN102418278A (en) | Method for preparing cation polyurethane antistatic agent for terylene | |
| CN101284788B (en) | Preparation method of 2,3-di(2,4-dinitro phenoxy)naphthalin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |