CN101885824B - Fluorine-containing phosphoric polyurethane elastomer and preparation method thereof - Google Patents

Abstract

其中的-R-为：

具有优异的表面性能、热稳定性、阻燃性及机械性能，可应用于多种复杂环境下，大大的拓宽了聚氨酯弹性体的应用范围。The invention discloses a class of fluorine-containing and phosphorus-containing polyurethane elastomers and a preparation method thereof, which is characterized in that fluorine and phosphorus elements are simultaneously introduced into the polyurethane elastomer by means of the previously prepared fluorine-containing and phosphorus-containing diamine; the obtained fluorine-containing Phosphorus-containing polyurethane elastomer, its structure is:

where -R- is:

With excellent surface properties, thermal stability, flame retardancy and mechanical properties, it can be applied in a variety of complex environments, greatly broadening the application range of polyurethane elastomers.

Description

A kind of fluorine-containing phosphorus-containing polyurethane elastomer and preparation method thereof

technical field

The invention belongs to the technical field of polyurethane elastomers, and in particular relates to fluorine-containing and phosphorus-containing polyurethane elastomers and a preparation method thereof.

Background technique

According to the introduction of "Journal of Shanghai Jiaotong University" 2006, Vol. 40, No. 7, pages 1239-1243, fluorine-containing polyurethane elastomer is a kind of polymer material with special functions. The introduction of fluorine not only maintains the original characteristics of polyurethane elastomers, but also endows them with excellent weather resistance, chemical resistance, high service temperature, pollution resistance and low friction. According to "Thermosetting Resins" 2005, Vol. 20, No. 5, pages 40-45, phosphorus is an important flame-retardant element, and phosphorus-containing intrinsically flame-retardant polymers can meet strict fire protection requirements without flame-retardant treatment, and are environmentally friendly. friendly. Compared with conventional flame retardant polymers, intrinsically flame retardant polymers do not have the problems of flame retardant volatilization, dissolution, migration and exudation, and have high flame retardant efficiency. Fluorine-containing polyurethane elastomers have excellent surface properties, but poor flame-retardant properties, while phosphorus-containing polyurethane elastomers have excellent flame-retardant effects, but poor surface properties; Performance, but also has excellent surface performance requirements.

Contents of the invention

The present invention proposes a kind of fluorine-containing phosphorus-containing polyurethane elastomer and a preparation method thereof, in order to overcome the deficiency that the above-mentioned prior art cannot satisfy the requirements of both good flame retardancy and excellent surface properties.

The fluorine-containing phosphorus-containing polyurethane elastomer of the present invention is characterized in that it has the following chemical structure:

其中的-R-为：

where -R- is:

The preparation method of the fluorine-containing and phosphorus-containing polyurethane elastomer of the present invention comprises the following steps: dehydrating the polymer polyol for 2 to 4 hours under the conditions of a vacuum of 133-266Pa and 110-125°C, and dehydrating the polymer polyol with toluene The diisocyanate molar ratio is 1:1.6~2.6 Add toluene diisocyanate (TDI), react at 60~80°C for 2~3 hours to make a polyurethane prepolymer; the polyurethane prepolymer and diamine are in a molar ratio of 1 : 0.80～0.95 dissolved in butanone, 1,4-dioxane or N,N-dimethylformamide solvent and placed in the mold, cured at 65±5℃ to form a film, and then placed in 130±5 React in an oven at ℃ for 3 to 4 hours to obtain a polyurethane elastomer;

The polymer polyol is polyester diol or polyether diol;

The amount of butanone, 1,4-dioxane or N,N-dimethylformamide is such that the total solid mass percentage reaches 30% to 50%;

It is characterized by:

The diamine is a fluorine-containing phosphorus-containing diamine, which is prepared by the following steps:

(1) the concentrated sulfuric acid that accounts for the mass percentage concentration of 95-98% and accounts for the mass percentage of 14%～20% of the total mass fraction of the reaction mixture in the o-chlorobenzotrifluorotoluene In concentrated nitric acid with a concentration of 65-68%, nitrate at 20-50°C for 2-6 hours to obtain 2-chloro-5-nitro-trifluorotoluene;

(2) The molar ratio of 2-chloro-5-nitro-trifluorotoluene and phosphorus-containing bisphenol or phosphorus-containing diamine is 2:1 in a strong polar solvent at 80-150°C for 12-36 hours After the reaction is over, the solvent is distilled off under reduced pressure, and the product is recrystallized with ethylene glycol monomethyl ether or ethanol to obtain the corresponding dinitro compound;

(3) the dinitro compound obtained is mixed with ethanol aqueous solution, iron powder, hydrochloric acid, be 1: 6～8 by dinitro compound and iron powder mol ratio, the mass percentage concentration of hydrochloric acid is 36%～38%, The mass ratio of dinitro compound to hydrochloric acid is 15-18:1, the mass percentage concentration of ethanol in the ethanol aqueous solution is 55%-70%, the mass ratio of dinitro compound to ethanol aqueous solution is 1.5-2:1, and the temperature is 70-80°C React for 3 to 6 hours, filter, add ammonia water to the obtained filtrate to adjust the pH to neutral, then filter, then distill the filtrate under normal pressure to remove the organic phase, and obtain the corresponding fluorine-containing phosphorus-containing diamine;

The phosphorus-containing bisphenol or phosphorus-containing diamine in the step (2) is selected from bis(3-hydroxyphenoxy)phenyl phosphate, 10-(2',5'-dihydroxyphenyl)-9,10 -dihydro-9-oxa-10-phosphaphenanthrene-10-oxide compound, phenyl diaminophosphoric acid diamide or phenylphosphoric diamide; the strong polar solvent is N, N-dimethylformamide ( DMF) or dimethylacetamide (DMAc).

The fluorine-containing phosphorus-containing diamine is bis[3-(2-trifluoromethyl-4-aminophenoxy)]triphenyl phosphate or 10-[2′,5′-bis(2-trifluoromethyl Base-4-aminophenoxy)phenyl]-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or N,N'-bis(2-trifluoromethyl- 4-aminophenyl) diamidophenyl phosphate or phenyl-N,N'-bis(2-trifluoromethyl-4-aminophenyl) diamide phosphate.

The mold can be an iron mold or a polytetrafluoroethylene mold; usually a polytetrafluoroethylene mold is preferred so that the polyurethane elastomer obtained by the reaction is easy to fall off.

The fluorine-containing and phosphorus-containing polyurethane elastomer of the present invention has not been reported so far, and is a new type of organic compound.

Since the preparation method of the present invention uses the fluorine-containing and phosphorus-containing diamine prepared earlier, fluorine and phosphorus elements are introduced into the polyurethane elastomer at the same time, which overcomes the inability of the previous polyurethane elastomer to meet the requirements of good flame retardancy, At the same time, it has the disadvantage of excellent surface properties.

The fluorine-containing phosphorus-containing polyurethane elastomer prepared by the method of the invention has excellent surface properties, excellent thermal stability, flame retardancy and good physical and mechanical properties.

Detailed ways

The present invention will be further described below in conjunction with specific examples.

Example 1:

80 grams of o-chlorobenzotrifluorotoluene and 60 grams of mass percent concentration are mixed with 95% vitriol oil, keep room temperature, and then dropwise added to the mixture by 90 grams of mass percent concentration of 65% concentrated nitric acid and 64 grams of mass percent concentration of A mixture of 95% concentrated sulfuric acid. Control the reaction temperature at 45°C and stir the reaction for 4 hours. The reactant was poured into 1 liter of ice water, the solid was separated, washed with deionized water until the pH was neutral, and distilled under reduced pressure to obtain pure 2-chloro-5-nitro-trifluorotoluene.

135 grams of 2-chloro-5-nitro-trifluorotoluene prepared above were dissolved in 200 grams of N,N-dimethylformamide (DMF), and after it was completely dissolved, 45 grams of potassium carbonate, 115 grams of di (3-Hydroxyphenoxy)phenyl phosphate. After reacting at 80°C for 36 hours, the reactant was cooled and filtered to remove the precipitate, and the filtrate was distilled under reduced pressure to remove DMF, then poured into ethylene glycol monomethyl ether for recrystallization, and the obtained crystal was vacuum-dried for 24 hours to obtain bis[3 -(2-Trifluoromethyl-4-nitrophenoxy)phenyl]phenylphosphate.

In the 500ml four-neck bottle that stirrer, constant pressure dropping funnel and reflux device are equipped with, add 8 grams of concentration and be that 38% hydrochloric acid, 69 grams of iron powder, 75 grams of mass percent concentration are 70% ethanol aqueous solution and 151 grams of di (3-(2-Trifluoromethyl-4-nitrophenoxy)phenyl)phenylphosphate, refluxed for 4 hours. Filtrate, adjust the filtrate to neutral by adding ammonia water, stir for 0.5 hours, and then remove the organic phase by atmospheric distillation of the filtrate to obtain bis[3-(2-trifluoromethyl-4-aminophenoxy)]phosphoric acid tris phenyl esters.

100 grams of polyester diol (M=1000) was dehydrated at a vacuum of 133 Pa and 125° C. for 2 hours, then 28 grams of toluene diisocyanate (TDI) was added, and a polyurethane prepolymer was obtained after reacting at 80° C. for 2 hours.

Get 100 grams of this polyurethane prepolymer, add 25 grams of bis[3-(2-trifluoromethyl-4-aminophenoxy)] triphenyl phosphate, be dissolved in 290 grams of methyl ethyl ketone, the mixed solution Pour it into a polytetrafluoroethylene mold, first solidify at 70°C to form a film, and then put it in an oven at 135°C for 3 hours of vulcanization reaction to obtain a fluorine-containing phosphorus-containing polyurethane elastomer.

After testing, the surface tension of the above-mentioned fluorine-containing phosphorus-containing polyurethane elastomer is 25.0mN/m, the water contact angle is 92.6°, the temperature T ₁₀ when the thermal weight loss rate is 10% is 319°C, and the limiting oxygen index LOI is 27.4%. The tensile strength is 27.5MPa, and the elongation at break is 652%.

Example 2:

80 grams of o-chlorobenzotrifluorotoluene and 60 grams of mass percentage concentration are mixed with 96% vitriol oil, keep room temperature, then in the mixture, it is added dropwise that 80 grams of mass percentage concentration is 66% of concentrated nitric acid and 100 grams of mass percentage concentration is A mixture of 96% concentrated sulfuric acid. Control the reaction temperature at 20°C, stir and react for 6 hours; pour the reactant into 1 liter of ice water, separate the solid, wash with deionized water until the pH is neutral, and distill under reduced pressure to obtain the pure product 2-chloro-5-nitro - Trifluorotoluene.

135 grams of 2-chloro-5-nitro-trifluorotoluene prepared above were dissolved in 200 grams of DMAc, and after it was completely dissolved, 45 grams of potassium carbonate, 97 grams of 10-(2′,5′-dihydroxy Phenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, after reacting at 130°C for 24 hours, the reactant was cooled and filtered to remove the precipitate, and the filtrate was distilled under reduced pressure After removing DMAc, pour it into ethylene glycol monomethyl ether for recrystallization, and vacuum-dry the resulting crystals for 24 hours to obtain 10-(2′,5′-bis(2-trifluoromethyl-4-nitrophenoxy yl)phenyl))-9,10-dihydro-9oxa-10-phosphaphenanthrene-10-oxide.

In the 500ml four-neck bottle that agitator, constant pressure dropping funnel and reflux device are equipped, add 9 gram concentration and be that 37% hydrochloric acid, 88 gram iron powder, 85 gram mass percent concentration are 65% ethanol aqueous solution and 139 gram 10 -[2′,5′-bis(2-trifluoromethyl-4-aminophenoxy)phenyl]-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide , refluxed for 4 hours, filtered, the filtrate was adjusted to neutral by adding ammonia water, stirred for 0.5 hours, filtered to remove the solid, and then the filtrate was concentrated by atmospheric distillation and crystallized for 12 hours, the obtained crystal was recrystallized with ethanol aqueous solution, and the obtained crystal was vacuum Drying for 24 hours gave 10-(2′,5′-bis(2-trifluoromethyl-4-aminophenoxy)phenyl))-9,10-dihydro-9oxa-10-phospha Phenanthrene-10-oxide.

Dehydrate 100 grams of polyether diol (M=1000) at a vacuum of 266 Pa and 120°C for 3 hours, then add 35 grams of toluene diisocyanate (TDI), and react at 70°C for 2.5 hours to obtain a polyurethane prepolymer;

Get this polyurethane prepolymer 100 grams, add 43 grams of 10-(2',5'-bis(2-trifluoromethyl-4-aminophenoxy)phenyl))-9,10-dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide, dissolved in 300 grams of 1,4-dioxane, poured the mixture into a polytetrafluoroethylene mold, and first solidified at 65°C to form a film. Then put it into an oven at 125°C for 4 hours of vulcanization reaction to obtain a fluorine-containing phosphorus-containing polyurethane elastomer.

The surface tension of the above-mentioned fluorine-containing phosphorus-containing polyurethane elastomer is 24.8mN/m, the water contact angle is 95.8°, the T ₁₀ is 325°C, the LOI is 28.1%, the tensile strength is 23.5MPa, and the elongation at break is 734%. .

Example 3:

40 gram o-chlorobenzotrifluorotoluene and 30 gram mass percentage concentration are mixed the vitriol oil of 97%, keep room temperature, then add dropwise in the mixture by 40 gram mass percentage concentration be the concentrated nitric acid of 67% and 50 gram mass percentage concentration be A mixed solution composed of 97% concentrated sulfuric acid was controlled at a reaction temperature of 50°C and stirred for 2 hours; the reactant was poured into 1 liter of ice water, the solid was separated, washed with deionized water until the pH was neutral, and distilled under reduced pressure to obtain Pure 2-Chloro-5-nitro-trifluorotoluene.

135 grams of 2-chloro-5-nitro-benzobenzotrifluoride prepared above were dissolved in 300 grams of DMAc, and 45.5 grams of potassium carbonate and 48 grams of phenyl phosphoric acid diamidate were added. After reacting at 150°C for 12 hours, the reactant was cooled and filtered to remove the precipitate, and the filtrate was distilled under reduced pressure to remove DMAc, and then poured into ethylene glycol monomethyl ether for recrystallization. After vacuum drying for 24 hours, phenyl bis(2-trifluoromethyl-4-nitrophenoxy)phosphate was obtained.

In the 500ml four-neck bottle that stirrer, constant pressure dropping funnel and reflux device are equipped with, add 10 gram concentration and be that 37% hydrochloric acid, 107 gram iron powder and 90 gram mass percent concentration are 60% ethanol aqueous solution and 151 gram di (3-(2-Trifluoromethyl-4-nitrophenoxy)phenyl)phenyl phosphate, refluxed for 4 hours, then added ammonia water to adjust to neutral, stirred for 0.5 hours, and filtered to remove the solid. Concentrate the filtrate by atmospheric distillation, crystallize for 12 hours, recrystallize the obtained crystals with ethanol aqueous solution, and vacuum dry the obtained crystals for 24 hours to obtain N,N'-bis(2-trifluoromethyl-4-aminophenyl)phosphoric acid Diamidophenyl ester.

200 g of polyether diol (M=2000) was dehydrated at a vacuum of 199 Pa and 115°C for 3.5 hours, then 35 g of toluene diisocyanate (TDI) was added, and reacted at 65°C for 2.8 hours to obtain a polyurethane prepolymer.

Get 100 grams of the polyurethane prepolymer, add 19 grams of N, N'-bis(2-trifluoromethyl-4-aminophenyl) diamidophenyl phosphate, dissolve in 257 grams of N, N-dimethylformaldehyde amide, pour the mixture into a polytetrafluoroethylene mold, first solidify at 65°C to form a film, and then put it into a 130°C oven for vulcanization reaction for 3.5 hours to obtain a fluorine-containing phosphorus-containing polyurethane elastomer.

The surface tension of the above-mentioned fluorine-containing phosphorus-containing polyurethane elastomer is 20.4mN/m, the water contact angle is 99.3°, the T ₁₀ is 318°C, the LOI is 28.8%, the tensile strength is 22.8MPa, and the elongation at break is 792%. .

Example 4:

80 grams of o-chlorobenzotrifluorotoluene and 60 grams of mass percent concentration are mixed with 98% vitriol oil, keep room temperature, and then dropwise added to the mixture by 70 grams of mass percent concentration of 68% concentrated nitric acid and 120 grams of mass percent concentration of A mixed solution composed of 98% concentrated sulfuric acid was controlled at a reaction temperature of 45° C., and stirred for 4 hours. The reactant was poured into 1 liter of ice water, the solid was separated, washed with deionized water until the pH was neutral, and distilled under reduced pressure to obtain pure 2-chloro-5-nitro-trifluorotoluene.

135 grams of 2-chloro-5-nitro-benzotrifluoride prepared above were dissolved in 300 grams of DMAc, and 45.5 grams of potassium carbonate and 44 grams of phenylphosphoric diamide were added. Reacted at 140°C for 30 hours, the reactant was cooled and filtered to remove the precipitate, the filtrate was distilled off under reduced pressure to remove DMAc, and then poured into ethylene glycol monomethyl ether for recrystallization, and the obtained crystal was vacuum-dried for 24 hours to obtain phenylphosphoryl di( 2-trifluoromethyl-4-nitroaniline).

In the 500ml four-necked bottle that stirrer, constant pressure dropping funnel and reflux device are equipped with, add 10 gram concentration and be that 36% hydrochloric acid, 108 gram iron powder, 95 gram mass percentage concentration are 55% ethanol aqueous solution and 147 gram benzene Phosphoryl bis(2-trifluoromethyl-4-nitroaniline), refluxed for 4 hours, then added ammonia water to adjust to neutrality, stirred for 0.5 hours, and filtered to remove solid; the filtrate was concentrated by atmospheric distillation and crystallized for 12 hours, The obtained crystals were recrystallized with ethanol aqueous solution, and the obtained crystals were vacuum-dried for 24 hours to obtain phenyl-N,N'-bis(2-trifluoromethyl-4-aminophenyl)phosphoric acid diamide.

200 grams of polyester diol (M=2000) was dehydrated at a vacuum of 266 Pa at 115° C. for 3.5 hours, then 45 grams of toluene diisocyanate (TDI) was added, and reacted at 60° C. for 3 hours to obtain a polyurethane prepolymer.

Get 100 grams of this polyurethane prepolymer, add 29 grams of phenyl-N, N'-bis (2-trifluoromethyl-4-aminophenyl) phosphoric acid diamide, dissolve in 129 grams of N, N-dimethyl Formamide, pour the mixture into a polytetrafluoroethylene mold, first solidify at 65°C to form a film, and then place it in an oven at 130°C for 3.5 hours of vulcanization reaction to obtain a fluorine-containing phosphorus-containing polyurethane elastomer.

The surface tension of the above-mentioned fluorine-containing phosphorus-containing polyurethane elastomer is 19.6mN/m, the water contact angle is 102.2°, the T ₁₀ is 312°C, the LOI is 29.4%, the tensile strength is 26.6MPa, and the elongation at break is 710%. .

Claims (4)

1. A class of fluorine-containing and phosphorus-containing polyurethane elastomers, characterized in that they have the following chemical structures:

where -R- is:

2. The preparation method of the fluorine-containing and phosphorus-containing polyurethane elastomer according to claim 1, comprising the following steps: dehydrating the polymer polyol for 2 to 4 hours under the conditions of 133 to 266 Pa and 110 to 125° C. The molar ratio of polyol to toluene diisocyanate is 1:1.6~2.6. Add toluene diisocyanate and react at 60~80°C for 2~3 hours to make a polyurethane prepolymer; the polyurethane prepolymer and diamine are according to the molar ratio of 1: 0.80～0.95 dissolved in methyl ethyl ketone, 1,4-dioxane or N,N-dimethylformamide solvent and placed in the mold, first cured at 65±5°C to form a film, and then placed in 130± React in an oven at 5°C for 3 to 4 hours to obtain a polyurethane elastomer; The polymer polyol is polyester diol or polyether diol; The amount of butanone, 1,4-dioxane or N,N-dimethylformamide is such that the total solid mass percentage reaches 30% to 50%; It is characterized by: The diamine is a fluorine-containing phosphorus-containing diamine, which is prepared by the following steps: (1) the concentrated sulfuric acid that accounts for the mass percentage concentration of 95-98% and accounts for the mass percentage of 14%～20% of the total mass fraction of the reaction mixture in the o-chlorobenzotrifluorotoluene In concentrated nitric acid with a concentration of 65-68%, nitrate at 20-50°C for 2-6 hours to obtain 2-chloro-5-nitro-trifluorotoluene; (2) The molar ratio of 2-chloro-5-nitro-trifluorotoluene and phosphorus-containing bisphenol or phosphorus-containing diamine is 2:1 in a strong polar solvent at 80-150°C for 12-36 hours After the reaction is over, the solvent is distilled off under reduced pressure, and the product is recrystallized with ethylene glycol monomethyl ether or ethanol to obtain the corresponding dinitro compound; (3) the dinitro compound obtained is mixed with ethanol aqueous solution, iron powder, hydrochloric acid, be 1: 6～8 by dinitro compound and iron powder mol ratio, the mass percentage concentration of hydrochloric acid is 36%～38%, The mass ratio of dinitro compound to hydrochloric acid is 15-18:1, the mass percentage concentration of ethanol in the ethanol aqueous solution is 55%-70%, the mass ratio of dinitro compound to ethanol aqueous solution is 1.5-2:1, and the temperature is 70-80°C React for 3 to 6 hours, filter, add ammonia water to the obtained filtrate to adjust the pH to neutral, then filter, then distill the filtrate under normal pressure to remove the organic phase, and obtain the corresponding fluorine-containing phosphorus-containing diamine; The phosphorus-containing bisphenol or phosphorus-containing diamine in the step (2) is selected from bis(3-hydroxyphenoxy)phenyl phosphate, 10-(2',5'-dihydroxyphenyl)-9,10 -dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diaminophosphoric acid phenyl ester or phenylphosphoric diamide; the strong polar solvent is N, N-dimethylformamide or Dimethylacetamide. 3. the preparation method of fluorine-containing phosphorus-containing polyurethane elastomer as claimed in claim 2 is characterized in that said fluorine-containing phosphorus-containing diamine is two [3-(2-trifluoromethyl-4-aminophenoxy)] Triphenyl phosphate or 10-[2′,5′-bis(2-trifluoromethyl-4-aminophenoxy)phenyl]-9,10-dihydro-9-oxa-10-phospha Phenanthrene-10-oxide or N, N'-bis(2-trifluoromethyl-4-aminophenyl) diamidophenyl phosphate or phenyl-N,N'-bis(2-trifluoromethyl- 4-aminophenyl) phosphoric acid diamide. 4. The preparation method of fluorine-containing and phosphorus-containing polyurethane elastomer as claimed in claim 2, characterized in that the mold is made of iron or polytetrafluoroethylene.