CN88101082A - New preparation process of fire retardant tetrakis-hydroxymethyl-phosphonium chloride (thpc) with catalytic method - Google Patents
New preparation process of fire retardant tetrakis-hydroxymethyl-phosphonium chloride (thpc) with catalytic method Download PDFInfo
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- CN88101082A CN88101082A CN 88101082 CN88101082A CN88101082A CN 88101082 A CN88101082 A CN 88101082A CN 88101082 CN88101082 CN 88101082 CN 88101082 A CN88101082 A CN 88101082A CN 88101082 A CN88101082 A CN 88101082A
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Abstract
The present invention proposes a kind of catalysis method and prepare 4 (THPC) novel process.In this novel process, adopted catalyzer replacement mercury, potassium platinichlorides such as zinc chloride, make cost reduce, processing unit is simplified.The invention allows for THPC the preparation method of high flame retardant fire retardant of the materials such as the cotton handled, polyester-cotton blend, wallpaper, timber, fiberboard that are main raw material preparation simultaneously.
Description
The present invention relates to the application that catalysis method prepares 4 fire retardant novel process and 4 fire retardant.
4, promptly to be called for short THPC be a kind of fire retardant that uses textiles more widely etc. to tetrakis hydroXymethyl Phosphonium Chloride, has high flame retardant and water-wash resistance.THPC is made in the laboratory by A.Hoffman the earliest, he utilizes aluminium phosphide and water effect to produce phosphine gas, feeds formaldehyde and concentrated hydrochloric acid solution then, boils off volatile component and water after reaction is finished, obtain THPC white crystal (J.Am.Chem.Sec.43,1684(1921)).W.A.Reeves and F.F Francis etc. are again than having reported this preparation process (J.Am.Chem.Soc.77.3923(1955) in more detail) and applied for patent (U.S.Pat.2743299(1956)).It is catalyzer that R.Martin has reported with heavy metals such as mercury, adopts the A.Hoffman process to prepare the method (U.S.Pat.2912466(1959) of THPC).It is catalyzer that k.Moedritger has reported with the potassium platinichloride, adopts the A.Hoffman process to prepare the method (U.S.Pat4101587(1978) of THPC).
Using mercury, potassium platinichloride etc. is to cost an arm and a leg as the shortcoming of catalyzer, and the stopper that contains in the formaldehyde can influence catalytic effect.
Task of the present invention is to propose a kind of catalysis method to prepare THPC fire retardant novel process, and the preparation method of the fire retardant of a kind of THPC of containing is provided.
The present invention is as catalyzer with zinc oxide, aluminum oxide, stannic oxide, zinc hydroxide, aluminium hydroxide, stannic hydroxide, zinc chloride, aluminum chloride, tin chloride etc., adopt the A.Hoffman process, select suitable reaction conditions to prepare the novel process of THPC.Primary process is as follows:
1. the preparation of phosphuret-(t)ed hydrogen.The enough water of in a phosphine gas generator, packing into, about 10 minutes of logical nitrogen is fully caught up with the air in the pure qi (oxygen) body producer, adds aluminium phosphide then, the generation of aluminium phosphide and water effect at this moment phosphine gas, reaction formula is as follows:
2. in a reactor that has a whipping appts, pack into 35～37% formaldehyde solution, 35～36% hydrochloric acid and little amount of catalyst.
3. control reaction temperature is 40～50 ℃, and about 10 minutes of logical nitrogen is fully caught up with the air in the clean reactor, starts agitator then, feeds phosphine gas equably in reactor.Above-mentioned reactant ratio is a formaldehyde: hydrochloric acid: phosphuret-(t)ed hydrogen=4.05～4.25: 1.0: 1.5～1.7(mole).Obtain a kind of colourless transparent solution of slightly formaldehyde odor after having reacted.Reaction formula is as follows:
4. resulting reaction solution is boiled off volatile component and moisture at 70～80 ℃, can obtain the THPC80% aqueous solution, continue to boil off moisture content, can obtain a kind of crystallization crude product, crude product places and is equipped with in the moisture eliminator that solid sodium hydroxide is a siccative, obtain white THPC crystal after the drying, 149～150 ℃ of fusing points, productive rate 99%.
5. adopt Glacial acetic acid to carry out recrystallization (1 gram THPC: 40 milliliters of Glacial acetic acid), obtain pure THPC crystal, 151 ℃ of fusing points.Measure infrared spectra, wherein 1040cm
-1The strong peak at place is a C-O key absorption peak.
Catalyzer of the present invention is cheap, obtains easily, and excellent catalytic effect does not have toxicity, can reduce material loss, shortens the reaction times, and reaction yield reaches 99%, and the stopper that contains in the formaldehyde (for example methyl alcohol) can not influence catalytic effect.
In order to the THPC fire retardant of top method preparation, can prepare the fire retardant of a kind of high flame retardant, weather resistance and water-wash resistance with urea, water, this fire retardant can be used for handling textiless such as cotton, polyester-cotton blend; Also can be used to handle wallpaper, fiberboard, timber etc.
Catalyzer of the present invention can be used for preparing chlorination four hydroxyethyl phosphorus, compounds such as chlorination four acrinyl phosphorus and chlorination four hydroxyl cyclohexyl phosphorus, and hydroxide tetra methylol phosphorus (THPOH) and sulfuric acid tetra methylol phosphorus chemical substances such as (THPS).
Embodiment 1:
(1) preparation of phosphuret-(t)ed hydrogen: about 900 ml waters of in a phosphine gas generator, packing into, about 10 minutes of logical nitrogen, fully catch up with the air in the pure qi (oxygen) body producer, divide then to add for several times about 180 gram aluminium phosphide, aluminium phosphide and water effect at this moment produces phosphine gas.
(2) get 1000 milliliters of three-necked bottles, load onto agitator, 665 grams, 37% formaldehyde solution of packing into, 170 milliliter of 36% hydrochloric acid and 4 gram aluminum chlorides, about 10 minutes of logical nitrogen is fully caught up with the air of clean reactor.40～50 ℃ of conditioned reaction temperature are started agitator, feed phosphine gas equably.Having led to about 102 gram phosphine gas (3.0 moles) backs refluxed about 30 minutes.Obtain having the colourless transparent solution of formaldehyde odor after having reacted.
(3) this reaction solution is boiled off volatile component and moisture at 70～80 ℃, can obtain THPC 80% aqueous solution, continue to boil off moisture content, can obtain the white crystals crude product, crude product places one to be equipped with in the moisture eliminator that solid sodium hydroxide is a siccative, obtain white THPC crystal 3 76 grams after the drying, 149～150 ℃ of fusing points, productive rate 99%.
Embodiment 2:
The THPC for preparing above can be mixed with colourless, scentless CTU-1 fire retardant with urea, water etc., and this fire retardant has high flame retardant and water-wash resistance, can be used to handle textiless such as cotton, polyester-cotton blend etc., and it is as follows to fill a prescription:
The THPC(80% aqueous solution) 25～27 parts
11～13 parts in urea
0.2 part in sodium hydroxide
60～64 parts in water
Embodiment 3:
The THPC for preparing above can be mixed with colourless, scentless CTU-2 fire retardant with urea, water etc., and this fire retardant has high flame retardant and weather resistance, can be used for handling wallpaper, fiberboard, timber etc.It is as follows to fill a prescription:
The THPC(80% aqueous solution) 23～25 parts
7～9 parts in urea
0.2 part in sodium hydroxide
66～70 parts in water
Claims (6)
1, a kind of employing formaldehyde solution, concentrated hydrochloric acid and phosphine gas are raw material, and catalysis method synthesizes fire retardant THPC novel process, and reaction formula is as follows:
It is characterized in that in the process shown in the reaction formula (2) that catalyzer is aluminum oxide, zinc oxide, stannic oxide, zinc hydroxide, aluminium hydroxide, stannic hydroxide, zinc chloride, aluminum chloride, tin chloride and the salt that can produce zinc chloride, aluminum chloride, tin chloride with the hydrochloric acid effect.
2, according to the synthetic THPC fire retardant novel process of the described catalysis method of claim 1, the raw material ratio that it is characterized in that process shown in the reaction formula (2) is a formaldehyde: hydrochloric acid: phosphuret-(t)ed hydrogen=4.05～4.25: 1.0: 1.5～1.7(mole).
3, according to the synthetic THPC fire retardant novel process of the described catalysis method of claim 1, the temperature of reaction that it is characterized in that process shown in the reaction formula (2) is 40 ℃～50 ℃.
4, according to the synthetic THPC fire retardant novel process of the described catalysis method of claim 1, it is characterized in that used catalyzer can be used for preparing chlorination four hydroxyethyl phosphorus in the reaction formula (2), compounds such as chlorination four acrinyl phosphorus and chlorination four hydroxyl cyclohexyl phosphorus, and hydroxide tetra methylol phosphorus (THPOH), with sulfuric acid tetra methylol phosphorus (THPS), these chemical substances also are the flames retardant for textile with high flame retardant.
5, according to the synthetic THPC fire retardant novel process of the described catalysis method of claim 1, it is characterized in that prepared THPC fire retardant, can be with urea, water, by following prescription
The THPC(80% aqueous solution) 25～27 parts
11～13 parts in urea
0.2 part in sodium hydroxide
60～64 parts in water
The fire retardant for preparing a kind of high flame retardant and water-wash resistance, this fire retardant can be used for handling textiless such as cotton, polyester-cotton blend.
6, according to the synthetic THPC fire retardant novel process of the described catalysis method of claim 1, it is characterized in that prepared THPC fire retardant, can be with urea, water, by following prescription
The THPC(80% aqueous solution) 23～25 parts
7～9 parts in urea
0.2 part in sodium hydroxide
66～70 parts in water
The fire retardant for preparing a kind of high flame retardant and weather resistance, this fire retardant can be used for handling wallpaper, fiberboard, timber etc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88101082 CN88101082A (en) | 1988-02-27 | 1988-02-27 | New preparation process of fire retardant tetrakis-hydroxymethyl-phosphonium chloride (thpc) with catalytic method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88101082 CN88101082A (en) | 1988-02-27 | 1988-02-27 | New preparation process of fire retardant tetrakis-hydroxymethyl-phosphonium chloride (thpc) with catalytic method |
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| CN88101082A true CN88101082A (en) | 1988-12-21 |
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| CN 88101082 Pending CN88101082A (en) | 1988-02-27 | 1988-02-27 | New preparation process of fire retardant tetrakis-hydroxymethyl-phosphonium chloride (thpc) with catalytic method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924517A (en) * | 2012-10-18 | 2013-02-13 | 昆明理工大学 | Process for preparing tetramethylolphosphonium chloride by catalyzing phosphines with copper chlorides |
-
1988
- 1988-02-27 CN CN 88101082 patent/CN88101082A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924517A (en) * | 2012-10-18 | 2013-02-13 | 昆明理工大学 | Process for preparing tetramethylolphosphonium chloride by catalyzing phosphines with copper chlorides |
| CN102924517B (en) * | 2012-10-18 | 2015-06-03 | 昆明理工大学 | Process for preparing tetramethylolphosphonium chloride by catalyzing phosphines with copper chlorides |
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