CN102050836A - Phosphorus-containing polyisocyanate and preparation method thereof - Google Patents
Phosphorus-containing polyisocyanate and preparation method thereof Download PDFInfo
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- CN102050836A CN102050836A CN201010594764XA CN201010594764A CN102050836A CN 102050836 A CN102050836 A CN 102050836A CN 201010594764X A CN201010594764X A CN 201010594764XA CN 201010594764 A CN201010594764 A CN 201010594764A CN 102050836 A CN102050836 A CN 102050836A
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Abstract
The invention relates to phosphorus-containing polyisocyanate and a preparation method thereof. The preparation method of the phosphorus-containing polyisocyanate comprises the following steps of: adding diisocyanate in a reactor, and adding phosphorus-containing polyol under stirring, wherein the molar ratio of the alcoholic hydroxyl group of the phosphorus-containing polyol to the diisocyanate is 1.0:(3.0-7.0) and the reaction temperature is controlled between 45 DEG C and 65 DEG C; controlling the time for dropping the phosphorus-containing polyol to be 2-4h; continuously reacting for 3-5h after dropping; stopping the reaction after sampling to measure the content of isocyanate to be consistent; separating the unreacted diisocyanate after the reaction to ensure that the content of the diisocyanate is smaller than or equal to 0.6 percent; and then adding a urethane-grade solvent to prepare into a required concentration. The phosphorus-containing polyisocyanate provided by the invention can be directly used as a fire retarding curing agent for polyurethane and other high molecular materials and can also be used as an adhesion enhancement additive of a coating; meanwhile, a conversional isocyanate end-capping reagent is adopted for end capping processing, thus a blocked polyisocyanate can be obtained. The structural formula of the phosphorus-containing polyisocyanate is shown as the specification.
Description
Technical field
The present invention relates to phosphorous polyisocyanic acid ester structure and preparation method thereof.
Background technology
Polyurethane coating is one of best coating variety of over-all properties, extensively as coating and invisible coatings such as car paint, woodwork coating, building external paint, metal anti-corrosive paint and space flight, aviation, naval vessels, tanks.Polyurethane coating curing agent is a class polyisocyanate compound, is the indispensable integral part of polyurethane coating.But polyurethane curing agent is of less types at present, and flame retardant properties, sticking power, environmental-protecting performance etc. are practical requirement fully.Therefore more and more urgent to the demand of functional urethane solidifying agent.The aggregate demand of polyurethane curing agent is about ten thousand tons of average annual 60-100, so China's polyurethane curing agent has vast market prospect.
Polyurethane curing agent is actually the prepolymer of urethane, generally have plural NCO functional group, polyurethane prepolymer has a variety of, TDI-TMP prepolymer (toluene diisocyanate-trimethylolpropane prepolymer) be wherein develop the earliest, most widely used a kind of.The most representative is Bayer (Bayer) company's T D1-TMP affixture, and the trade mark is Desmodur L, and this product has advanced level in the world, and the content of free monomer TDI is below 0.5%.The Chen Huan of chemical institute of the domestic South China Science ﹠ Engineering University seminar of admiring has carried out systematic research to the purification techniques of this affixture.
Life-time service is found, also there are problems such as easy yellowing, free isocyanate toxicity be big in the TDI-TMP prepolymer, therefore German Bayer company in 1958 at first prepares successful HDI biuret product (trade names are Desmodur N), and has done deep research and extension and used.The HDI biuret is the triisocyanate prepolymer that has biuret structure (OCN-NH-CO-NH-) with HDI and water synthetic, belongs to the aliphatic polyurethane solidifying agent.Owing to do not have unsaturated link(age) on its carbon atom, so its anti-yellowing property is fabulous.The HDI biuret has good thermotolerance, has good consistency with polyvalent alcohol or general solvent, and is splendid with solvent resistance after the polymer cure that contains polyvalent alcohol, is widely used as high-grade paint, tackiness agent, elastomeric solidifying agent.DesmodurN 75 (solid content 75%) steady quality of Germany Bayer company.Utilize the trimerization reaction of isocyanic ester in addition, also can synthesize multicomponent isocyanate and be used for coating curing agent.
But up to the present, the polyurethane coating curing agent kind can not practical requirement, and little functional polyurethane curing agent emerges.Along with the raising of environmental protection standard with to the requirement of equalization day by day of coating use properties, higher requirement is proposed final use propertieies such as the flame retardant properties of coating, weathering resistance, sticking power.
As everyone knows, coating system contains phosphoric, not only can give the Flame Retardancy energy, and with nitrogen, silicon, etc. have a cooperative flame retardant effect.Phosphorous coating has fabulous sticking power to polar substrates simultaneously.
Summary of the invention
The objective of the invention is to overcome the deficiency of existing multicomponent isocyanate solidifying agent flame retardant resistance, sticking power etc., and provide a kind of phosphorous polyisocyanates and preparation method thereof, it is main raw material that the present invention adopts the pure and mild general vulcabond of phosphorus contained multicomponent, preparation phosphorus contained multicomponent oligomeric isocyanates, it can also can be used as ADHESION OF PAINTS power enhancement additive directly as the flame retardant resistance solidifying agent use of urethane and other macromolecular materials; Adopt general isocyanate-terminated dose to carry out termination process simultaneously, can obtain the closure multicomponent isocyanate.
The object of the present invention is achieved like this:
Phosphorous polyisocyanates of the present invention, its general structure is as follows: wherein P is a phosphorus atom, and H is a hydrogen atom, and C is a carbon atom, and N is a nitrogen-atoms:
X is alkylidene group or heterochain alkylidene group, wherein the heteroatoms of heterochain alkylidene group is oxygen, nitrogen, sulphur or phosphorus, and R is alkylidene group or arylidene in the synthetic isocyanic ester raw material that is adopted.
Described isocyanic ester raw material is a vulcabond, described vulcabond is 2, the 4-tolylene diisocyanate, 2, the 6-tolylene diisocyanate, 2,4-tolylene diisocyanate and 2, the mixture of 6-tolylene diisocyanate, 1, hexamethylene-diisocyanate, isophorone diisocyanate, Methylcyclohexyl diisocyanate, dicyclohexyl methane diisocyanate, xylylene diisocyanate, ditane-4,4 '-vulcabond or hydrogenation ditane-4,4 '-vulcabond and other vulcabond that can adopt according to ultimate principle of the present invention.
The preparation method of phosphorous polyisocyanates, it is characterized in that carrying out according to the following steps: in the dry reaction still of temperature control device, agitator, reflux exchanger, drying installation is housed, add vulcabond, temperature is controlled at 35-75 ℃, under evenly stirring, add phosphorus-containing polyol, and the alcoholic extract hydroxyl group of phosphorus-containing polyol and the mol ratio of vulcabond are 1.0: 3.0-7.0, and control reaction temperature is between 45-65 ℃; The time that drips phosphorus-containing polyol is controlled at finished in 2-4 hour; Under 45-65 ℃ of temperature, continue reaction 3-5 hour; Sampling, after employing Di-n-Butyl Amine method mensuration isocyanate content is constant, stopped reaction; After reaction finishes, adopt solvent extration, film evaporation method or trimerization method in the general method of purification of polyurethane curing agent to separate unreacted vulcabond, make diisocyanate content≤0.6% reach corresponding national standards, adding ammonia ester level solvent is made into and needs concentration.
But in reactor, add an amount of general catalyzer accelerated reaction.
Described ammonia ester level solvent is common solvent such as ethyl acetate, butylacetate, pimelinketone or the toluene that meets the polyurethane industrial standard.
The present invention has following beneficial effect:
(1) to adopt inorganic phosphorus chemical industry by product be basic raw material for operational path provided by the invention, for the clean and effective utilization of phosphor resource provides a new approach, helps the sustainable sound development of phosphorous chemical industry industry.
(2) the phosphorous polyisocyanate curing agent that obtains of the present invention, not phosphorous oxygen key, this product excellent hydrolysis resistance, phosphorus content is adjustable, does not influence the storge quality of raw material and combination material thereof, and can improve the use properties of film forming matter, as flame retardant resistance, sticking power etc.
(3) the phosphorous polyisocyanate curing agent that obtains with the present invention is a raw material, adopts general isocyanate-terminated technology, can obtain phosphorated dead front type multicomponent isocyanate.
Embodiment
The present invention will be described in detail below in conjunction with embodiment:
Embodiment just lists and provides representational reaction conditions and step, but also not only comprises these contents, and according to the difference of employing raw material, relevant speciality technician can suitably adjust reaction conditions according to ultimate principle of the present invention.
Embodiment 1: the trishydroxymethyl phosphine oxide---the preparation of 2,4 toluene diisocyanate affixture
In the dry reaction still of temperature control device, agitator, reflux exchanger, drying installation is housed, add 2,4 toluene diisocyanate 650Kg, be warming up to 50 ℃, stir and evenly drip 140Kg trishydroxymethyl phosphine oxide down, the control rate of addition makes the temperature of reaction mixture be no more than 55 ℃; After being added dropwise to complete, under this temperature, continue reaction 3 hours, sampling finishes reaction according to the constant back of Di-n-Butyl Amine method test isocyanate content, reaction finishes the back cooling discharge, adopt film evaporation method to remove unreacted 2, the 4-tolylene diisocyanate makes 2,4 toluene diisocyanate content≤0.6%; According to ammonium phosphomolybdate spectrophotometry test phosphorus content is 4.3% (theoretical phosphorus content 4.7%), calculates productive rate 〉=97% according to the trishydroxymethyl phosphine oxide; Adding ammonia ester level butyl acetate solvent is adjusted to desired concn and is product.
Embodiment 2: the trishydroxymethyl phosphine oxide---the preparation of hexamethylene diisocyanate affixture
In the dry reaction still of temperature control device, agitator, reflux exchanger, drying installation is housed, add hexamethylene diisocyanate 750Kg, be warming up to 55 ℃, stir and evenly drip 140Kg trishydroxymethyl phosphine oxide down, the control rate of addition makes the temperature of reaction mixture be no more than 60 ℃; After being added dropwise to complete, continue reaction 4 hours under this temperature, sampling finishes reaction according to the constant back of Di-n-Butyl Amine method test isocyanate content, cooling discharge adopts film evaporation method to remove unreacted hexamethylene diisocyanate, make hexamethylene diisocyanate content≤0.6% that dissociates; According to ammonium phosphomolybdate spectrophotometry test phosphorus content is 4.5% (theoretical phosphorus content 4.8%), calculates productive rate 〉=98% according to the trishydroxymethyl phosphine oxide; Adding ammonia ester level cyclohexanone solvent is adjusted to desired concn and is product.
3: three-(N-methyl, N '-hydroxyethyl) aminomethyl phosphine oxide of embodiment---2, the preparation of 6-tolylene diisocyanate affixture
In the dry reaction still of temperature control device, agitator, reflux exchanger, drying installation is housed, add 2,6-tolylene diisocyanate 690Kg, be warming up to 50 ℃, stir and evenly drip 311Kg three-(N-methyl down, N '-hydroxyethyl) aminomethyl phosphine oxide, the control rate of addition makes the temperature of reaction mixture be no more than 55 ℃; After being added dropwise to complete, continue reaction 5 hours under this temperature, sampling finishes reaction according to the constant back of Di-n-Butyl Amine method test isocyanate content, cooling discharge, it is unreacted 2 to adopt film evaporation method to remove, the 6-tolylene diisocyanate, make 2,6-toluene diisocyanate content≤0.6%; According to ammonium phosphomolybdate spectrophotometry test phosphorus content is 3.3% (theoretical phosphorus content 3.7%), calculates productive rate 〉=97% according to three-(N-methyl, N '-hydroxyethyl) aminomethyl phosphine oxides.Adding ammonia ester level toluene solvant is adjusted to desired concn and is product.
4: three-(N-ethyl, N '-hydroxyethyl) aminomethyl phosphine oxide---preparation of hexamethylene diisocyanate affixture of embodiment
In the dry reaction still of temperature control device, agitator, reflux exchanger, drying installation is housed, add 1, hexamethylene-diisocyanate 700Kg, be warming up to 55 ℃, stir even Dropwise 35 3Kg three-(N-ethyl down, N '-hydroxyethyl) aminomethyl phosphine oxide, the control rate of addition makes the temperature of reaction mixture be no more than 60 ℃; After being added dropwise to complete, continue reaction 3 hours under this temperature, sampling finishes reaction according to the constant back of Di-n-Butyl Amine method test isocyanate content, cooling discharge adopts film evaporation method to remove unreacted hexamethylene diisocyanate, make hexamethylene diisocyanate content≤0.6% that dissociates; According to ammonium phosphomolybdate spectrophotometry test phosphorus content is 3.2% (theoretical phosphorus content 3.6%), calculates productive rate 〉=98% according to three-(N-ethyl, N '-hydroxyethyl) aminomethyl phosphine oxides.Adding ammonia ester level butyl acetate solvent is adjusted to desired concn and is product.
Embodiment 5: the trihydroxyethyl phosphine oxide---the preparation of tolylene diisocyanate affixture
In the dry reaction still of temperature control device, agitator, reflux exchanger, drying installation is housed, add 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate mixture 670Kg, be warming up to 50 ℃, stir and evenly drip 182Kg trihydroxyethyl phosphine oxide down, the control rate of addition makes the temperature of reaction mixture be no more than 60 ℃; After being added dropwise to complete, continue reaction 3 hours under this temperature, sampling finishes reaction according to the constant back of Di-n-Butyl Amine method test isocyanate content, and cooling discharge adopts film evaporation method to remove unreacted tolylene diisocyanate mixture, makes its content≤0.6%.According to ammonium phosphomolybdate spectrophotometry test phosphorus content is 4.1% (theoretical phosphorus content 4.4%), calculates productive rate 〉=97% according to the trihydroxyethyl phosphine oxide.Adding ammonia ester level cyclohexanone solvent is adjusted to desired concn and is product.
Claims (5)
1. phosphorous polyisocyanates is characterized in that: its general structure is as follows, and wherein P is a phosphorus atom, and H is a hydrogen atom, and C is a carbon atom, and N is a nitrogen-atoms:
X is alkylidene group or heterochain alkylidene group, and wherein the heteroatoms of heterochain alkylidene group is oxygen, nitrogen, sulphur or phosphorus, and R is alkylidene group or arylidene in the synthetic isocyanic ester raw material that is adopted.
2. phosphorous polyisocyanates according to claim 1 is characterized in that: described isocyanate material is a vulcabond; Described vulcabond is 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate and 2, the mixture of 6-tolylene diisocyanate, 1, hexamethylene-diisocyanate, isophorone diisocyanate, Methylcyclohexyl diisocyanate, dicyclohexyl methane diisocyanate, xylylene diisocyanate, ditane-4,4 '-vulcabond or hydrogenation ditane-4,4 '-vulcabond and other general vulcabond.
3. the preparation method of phosphorous polyisocyanates, it is characterized in that carrying out according to the following steps: in the dry reaction still of temperature control device, agitator, reflux exchanger, drying installation is housed, add vulcabond, temperature is controlled at 35-75 ℃, under evenly stirring, add phosphorus-containing polyol, and the alcoholic extract hydroxyl group of phosphorus-containing polyol and the mol ratio of vulcabond are 1.0: 3.0-7.0, and control reaction temperature is between 45-65 ℃; The time that drips phosphorous trivalent alcohol is controlled at finished in 2-4 hour; Under 45-65 ℃ of temperature, continue reaction 3-5 hour; Sampling, after employing Di-n-Butyl Amine method mensuration isocyanate content is constant, stopped reaction; After reaction finishes, adopt solvent extration, film evaporation method or trimerization method in the general method of purification of polyurethane curing agent to separate unreacted vulcabond, make diisocyanate content≤0.6% reach corresponding national standards, adding ammonia ester level solvent is made into and needs concentration.
4. the preparation method of phosphorous polyisocyanates according to claim 3 is characterized in that: add an amount of general catalyzer accelerated reaction in reactor.
5. according to the preparation method of claim 3 or 4 described phosphorous polyisocyanates, it is characterized in that: described ammonia ester level solvent is ethyl acetate, butylacetate, pimelinketone, dimethylbenzene or toluene.
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Application publication date: 20110511 |