CN102702476A - Preparation method for hexamethylene diisocyanate biruet - Google Patents
Preparation method for hexamethylene diisocyanate biruet Download PDFInfo
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- CN102702476A CN102702476A CN2012101874916A CN201210187491A CN102702476A CN 102702476 A CN102702476 A CN 102702476A CN 2012101874916 A CN2012101874916 A CN 2012101874916A CN 201210187491 A CN201210187491 A CN 201210187491A CN 102702476 A CN102702476 A CN 102702476A
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Abstract
The invention discloses a preparation method for hexamethylene diisocyanate biruet, according to the method, azeotrope formed by a mixture of deionized water and a polar aprotic solvent is heated into a temperature of 30-100 DEG C; hexamethylene diisocyanate monomer is put into a reactor, and the temperature is maintained at 90-140 DEG C; the azeotrope is dropped into the reactor at a dropping speed of 0.05-0.20g/min; the temperature is increased into 110-150 DEG C in a mixing state, and the azeotrope is reacted for 1-4h; the temperature is reduced below 40 DEG C for cooling and discharging; and the discharging material enters into a separation device for separating a solvent and hexamethylene diisocyanate biruet ingredient, and a solid content of hexamethylene diisocyanate biruet ingredient is adjusted between 50 percent and 90 percent by a diluent. According to the preparation method, new solvent is not needed for addition, production formula and operation process are not required to be changed, only the monomer of isocyanate and water are added to realize continuous production, and the real clean production is realized via zero-release.
Description
Technical field
The present invention relates to the preparation method of topmost polyisocyanate prepolymers hexamethylene diisocyanate (HDI) biuret in the high-decoration polyurethane coating of external application, specifically prepare the method for the low monomeric HDI biuret of free isocyanate through water azeotrope dripping method.
Background technology
U.S. Pat 3124605 discloses the method that the legal system of dripping is equipped with the HDI biuret; The HDI biuret transparent color and luster that this method obtains; Has good consistency with hydroxy component; But still have following weak point: (1) reaction system belongs to inhomogeneous reaction, and efficient is low, and reacts bad control.Because water and diisocyanate monomer are difficult to dissolve each other; When water droplet is added to two-phase interface; Can not satisfy the excessive greatly requirement of actual vulcabond; And the reaction that this nonhomogeneous system takes place can generate a large amount of insoluble white polyureas, also further influenced the generation of main reaction, and the yield of biuret structure is low.(2) loss of water is big especially.Because the activity of HDI is lower, the reaction that generates biuret belongs to the cross-linking type reaction again, in order in reaction process, to obtain enough speed of reaction; Must suitably react under the high temperature; This patent directly adds to pyritous HDI with lower boiling water droplet and can cause the instant vaporization of water and run off, and the loss of water causes real reaction amount and theoretical charging capacity to have deviation, causes difficulty to technological design; The water vapour that runs off is in the reactor wall liquefaction back and HDI vapor generation side reaction of lesser temps; Cause having on the reactor wall a large amount of white polyureas, necessary stopping production cleaning reaction device brings inconvenience to continuous production in actual production process.
U.S. Pat 3358010 discloses and has adopted the method for the tertiary alcohol as biuretized reagent and isocyanate-monomer prepared in reaction HDI biuret, though can reduce the generation of polyureas, the biuret productive rate has been improved 3-5 doubly.Yet because the tertiary alcohol and HDI temperature of reaction be up to 200 ℃, the product colour that makes is darker, the stability in storage variation.And isocyanate-monomer and tertiary alcohol reaction can generate the part unsaturated olefin, and the separation of this material has also increased manufacturing cost.
U.S. Pat 4051165 discloses the preparation method of another kind of improved HDI biuret; With N, N-dimethylhydrazine catalyzer and water are hybridly prepared into urea chloride or gather the solution of urea chloride, drip to get into reaction system; To shorten to 0.5-1 hour the reaction times; Space time yield has improved 3-5 doubly, and the product physicals improves a lot, and gloss retention strengthens greatly.Yet the introducing of catalyzer makes the product stock degradation, and problem this method of the separation unsaturated hydrocarbons that US 3358010 exists still exists.
Disclosed in the U.S. Pat 4320068 is to select for use ethylidenehydroxylamine as biuretized reagent, takes dropwise adding mode to prepare the HDI biuret; Ethylidenehydroxylamine and HDI reactive behavior are higher; Greatly reduce temperature of reaction; One one-step hydrolysis very easily takes place and generates acid amides in the by product acetonitrile in the presence of acid or alkali; Further hydrolysis generates acid, and these by products rest on that the physicals to product must be influential in the product, and still there is separation problem in this method.And ethylidenehydroxylamine is more expensive than price with water, and production cost improves greatly.
The scheme of disclosed preparation HDI biuret is in the U.S. Pat 4192936: with alcohol; Drip after the biuretized reagent mix such as amine and water; Though the speed when having increased single dripping; Under identical isocyanic ester/biuretized reagent mole proportioning, the carbonic acid gas that mixes biuretized reagent system generation obviously reduces.But this method does not fundamentally solve the heterogeneous problem of water and isocyanate-monomer.No matter be to add separately to dewater the outer biuretized reagent that contains active hydrogen or mix the various biuretized reagent of adding, all increased the complicacy of system, introduced new by product.
In the prior art, the technology that reduces unreacted isocyanate-monomer comprises molecular sieve, SX, chemical synthesis, film evaporation method and short-path distillation.
U.S. Pat 4061662 discloses through making polymkeric substance realize removing the technical scheme of unreacted isocyanate-monomer through molecular sieve; But have shortcomings such as molecular sieve desorption difficulty, cause a large amount of monomer wasted, the desired molecule sieve can not reuse, and causes cost high, contaminate environment.
Solvent extration utilizes the free isocyanate monomer deliquescent different in specific mixed solvent with polymkeric substance; The free isocyanate monomer is extracted through the technology of repeatedly soaking, dissolve, washing, with the treated again recovery of extraction liquid isocyanate-monomer wherein.This method needs high amounts of solvents multiple extraction, and technology is loaded down with trivial details, and production efficiency is very low, and extraction liquid will handle again, and production cost is higher.Publication number is that publication number is the method for manufacture that the one Chinese patent application of CN 1939949A discloses a kind of low free toluene diisocyanate (TDI) trimer curing agent; This method utilizes high-selectivity catalyst to improve Synthesis conversion; Utilize solidifying agent to be insoluble to some solvent simultaneously and characteristic that the TDI monomer can dissolve, in building-up process, add the phase transition solvent, make solidifying agent in case generate just separate out from system; And catalyzer and TDI monomer be present in proceed in the solvent reaction; Thereby effectively reduce the content of free TDI in the solidifying agent, the phase transition solvent is removed in last underpressure distillation, but residual phase transition solvent can influence performance of products.
Chemical synthesis is through formulating of recipe and special synthesis technique, adopts chemical reaction or uses method such as effective catalyst to make the isocyanate-monomer that remains in the solidifying agent reach the purpose of elimination.U.S. Pat 5925781 discloses a kind of reduction free isocyanate monomer methods; This method is earlier with 2; The polyester polyol reaction of 4-TDI and molecular weight ranges 3000-8000; Introduce liquid diphenylmethanediisocyanate (MDI) again and react away unnecessary alcohol, use micromolecular methyl alcohol to eliminate free 2,4-TDI at last.Publication number is that back trimerization method is adopted in the Chinese invention patent application of CN 1424345A; On the basis of fs addition reaction; Increased single step reaction, introduced catalyzer and remove free TDI with the trimerization method, end article is 50% consolidates when containing; Its NCO content is 7-9%, and contained free TDI content is 1.0-2.0%.Publication number is that the Chinese invention patent application of CN 101456940A is introduced the low acetylacetic ester elimination free TDI of reactivity ratio's hydroxyl in subordinate phase.Publication number is the preparation method that the one Chinese patent application of CN 1424367A discloses a kind of isocyanate trimerization body solidifying agent of pure modification; In building-up process, introduce the fatty alcohol of the small molecular weight that contains 1-2 hydroxyl; Fatty alcohol and TDI reaction generate affixture; In system, play the effect that increases the trimer curing agent consistency, the relative solid content of the product that obtains is 50% o'clock, and the weight percentage of NCO group is 7.4%.The present production status of China is exactly to adopt present method to produce solidifying agent in order to satisfy environmental requirement; The solidifying agent NCO content of producing is low; Viscosity is big, and period of storage is less than half a year, and free isocyanate content is higher than 1.0% all the time; And be difficult to reach highly filled, can not solve basic problem.
The main equipment of thin film evaporation and molecular distillation method is thin-film evaporator and high vacuum system.Under the high temperature negative pressure, make solidifying agent pass through column plate rapidly with filminess, the free isocyanate monomer is steamed.Publication number is the separation method that discloses a kind of polyurethane curing agent free monomers in the Chinese invention patent application of CN 1389500A; The polyurethane curing agent that this method synthetic in advance 50% contains admittedly; Add high boiling extraction agent and carry out short-path distillation with the extraction entrainment agent; Free TDI content is lower than 0.5% in the product that finally obtains, extraction agent content 1%.But, owing to introduced high boiling extraction agent and extraction entrainment agent, cause the load of thin-film evaporator unstable, industrialization continuity is bad, unstable product quality, the film performance that makes simultaneously is also influential.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of productive rate height, yellowing resistance can be good, has the preparation method of the monomeric hexamethylene diisocyanate biuret of low free isocyanate.
Method of the present invention utilizes the azeotrope dripping method of water and high boiling point polar aprotic solvent to prepare, and suppresses the generation of insoluble polyureas, has improved the productive rate of HDI biuret; The present invention has reduced the toxicity of product through the content of free HDI in the tripping device minimizing HDI biuret.
The object of the invention is realized through following technical scheme:
A kind of preparation method of hexamethylene diisocyanate biuret, it comprises following process step:
(1) deionized water is mixed the azeotrope that forms with polar aprotic solvent and be heated to 30-100 ℃, insulation, for use; The mass percent that said polar aprotic solvent accounts for azeotrope is 10-70%; Said polar aprotic solvent is pimelinketone, mibk, 3-methyl-2-butanone; Ethylene glycol ether acetate, 2-Butoxyethyl acetate, 1-Methoxy-2-propyl acetate, propylene-glycol ethyl ether acetic acid acid esters, N; Dinethylformamide, N; N-N,N-DIMETHYLACETAMIDE, N, one or more in dinethylformamide, tetramethylene sulfone, METHYL SULFONYL METHANE. and the DMSO 99.8MIN.;
(2) under nitrogen protection, earlier the hexamethylene diisocyanate monomer is put into reaction vessel, holding temperature is at 90-140 ℃; The gained azeotrope is added drop-wise in the said reaction vessel, and rate of addition is 0.05-0.20g/min; After dripping end, continue under whipped state, to be warming up to 110-150 ℃ of reaction 1-4h; Be cooled to then below 40 ℃, cooling discharging obtains the hexamethylene diisocyanate biuret; The mol ratio of said hexamethylene diisocyanate monomer and deionized water is 4-10:1;
(3) the hexamethylene diisocyanate biuret that step (2) is obtained is isolated polar aprotic solvent and hexamethylene diisocyanate biuret component with the input speed entering tripping device of 3-13g/min; Hexamethylene diisocyanate biuret component is regulated solid content between the 50-90% with letdown solvent dun, makes the low monomeric hexamethylene diisocyanate biuret of free isocyanate.
Further; Said tripping device is made up of first stage separation device and second-stage separation device, and the separation temperature of said first stage separation device is controlled at 100-200 ℃, and the one-level condenser temperature is controlled at 10-40 ℃; Vacuum degree control is at 100-10000Pa; The separation temperature of second-stage separation device is controlled at 150-230 ℃, and the secondary condenser temperature is controlled at 2-20 ℃, and vacuum degree control is at 10-1000Pa.
Said first stage separation device and second-stage separation device are inner-cooled molecular still or external-cooling type thin-film evaporator.
The hexamethylene diisocyanate biuret that step (2) obtains preferably gets into first stage separation device and second-stage separation device through sparger.
Said letdown solvent dun is preferably vinyl acetic monomer, n-propyl acetate, Iso Butyl Acetate, n-butyl acetate, isobutyl acetate, ethylene glycol ether acetate or 1-Methoxy-2-propyl acetate.
The viscosity of the monomeric hexamethylene diisocyanate biuret of said low free isocyanate is that 500-2000mPas, nco value are that 10-24wt%, free isocyanate monomer content are 0.01-0.5wt%, and solids content is 50-100wt%.
The present invention with separated from solvent, can improve the intermiscibility of HDI and water again in order to form the azeotrope of higher during subsequent technique separates, and selected polar aprotic solvent is pimelinketone, mibk, 3-methyl-2-butanone; Ethylene glycol ether acetate, 2-Butoxyethyl acetate, 1-Methoxy-2-propyl acetate, propylene-glycol ethyl ether acetic acid acid esters; N, dinethylformamide, DMAC N,N, N, dinethylformamide; Tetramethylene sulfone, METHYL SULFONYL METHANE., DMSO 99.8MIN. or wherein both above combinations.The consumption of polar aprotic solvent of the present invention has very big influence to the compatibility of water and isocyanic ester: consumption is lower than 10wt% (total amount is water and solvent quality sum), can not effectively improve the boiling point of water, and water still has a large amount of losses in the dropping process; The solvent proportion is low excessively, and is not enough so that water that drips and isocyanate-monomer uniform mixing.For reducing the thin film evaporation load, solvent load should be the least possible, and therefore the consumption of preferred above-mentioned solvent is the 10-70wt% of azeotrope total amount.
The rate of addition of said azeotrope also has very big influence to the mixing uniformity of system; It is excessive to drip the too fast moisture part of causing; It is long to drip long response time, and raw material runs off more, and system produces superpolymer; The product color variation, therefore preferred azeotrope rate of addition is 0.05-0.20g/min.
The low time of isocyanic ester and water temperature of reaction, the content of three molecule aggregation bodies and five molecule aggregation bodies was high more more in short-term, and coating initial stage gloss is high more; The higher time of temperature of reaction, the increase of nine molecule aggregation body burdens can cause coating initial stage glossy to descend when longer, and gloss retention descends.Yet temperature is lower than 100 ℃, and a large amount of polyureas side reactions will take place, and also are difficult to obtain biuret structure; Temperature of reaction is higher than 150 ℃, and product colour is darker, the coating deterioration in physical properties, and therefore, preferred holding stage temperature is 110-150 ℃.Preferred soaking time 1-4hr.
With respect to prior art, the present invention has following advantage and beneficial effect:
(1) polar aprotic solvent has played function served as bridge at water and isocyanic ester two in mutually, guarantees that homogeneous reaction can take place for water and isocyanic ester dripping moment, and reaction is easy to control, and has increased the productive rate of biuret.
(2) azeotrope of solvent and water formation has increased water evaporable boiling point, has reduced the vaporization of water in the dropping process, has guaranteed the temperature of technological process, greatly reduces the scale formation of reactor vessel wall.
(3) through adopting thin-film evaporator; Input speed to material is regulated; The load of stabilizing films vaporizer makes material at high temperature have the suitable residence time, and sparger is scattered in material rapidly the film of 0.1-2mm; Increase heat transfer area, condition of high vacuum degree has been strengthened the evaporation of isocyanate-monomer.Adopt this method of evaporating, the HDI biuret can contain the free isocyanate monomer that is less than about 0.5% weight, and light constituent is clarifying, and at room temperature keeps transparent.Light constituent can be repeated to use to produce more HDI biuret after check and analysis.
(4) the HDI biuret of compound method of the present invention preparation have that the free isocyanate monomer content is low, viscosity is low, characteristics such as even molecular weight distribution,, NCO content height good with the consistency of resin.
Embodiment
For better understanding the present invention, below in conjunction with embodiment the present invention is carried out detailed explanation, but the scope that the present invention requires to protect is not limited to the scope that embodiment representes.
Embodiment 1
A kind of preparation method of hexamethylene diisocyanate biuret, it comprises the steps:
(1) deionized water is mixed the azeotrope that forms with pimelinketone and be heated to 30 ℃, insulation, for use; Wherein to account for the mass percent of azeotrope be 10% to the polar aprotic solvent pimelinketone;
(2) under nitrogen protection, earlier the hexamethylene diisocyanate monomer is put into reaction vessel, holding temperature is at 90 ℃; The described azeotrope of step (1) is added drop-wise in the said reaction vessel through peristaltic pump, and rate of addition is 0.05g/min; After dripping end, continue under whipped state, to be warming up to 110 ℃ reaction 1h; Be cooled to then below 35 ℃, cooling discharging obtains the hexamethylene diisocyanate biuret; The mol ratio of hexamethylene diisocyanate monomer and deionized water is 4:1;
(3) the hexamethylene diisocyanate biuret that step (2) is obtained passes through sparger with the input speed of 3g/min and gets into first stage separation device and second-stage separation device, and first stage separation device and second-stage separation device are the external-cooling type vaporizer.The separation temperature of said first stage separation device is controlled at 100 ℃; The one-level condenser temperature is controlled at 10 ℃, and vacuum degree control is at 100Pa, and the separation temperature of second-stage separation device is controlled at 150 ℃; The secondary condenser temperature is controlled at 2 ℃; Vacuum degree control is isolated polar aprotic solvent and hexamethylene diisocyanate biuret at 10Pa, and the hexamethylene diisocyanate biuret is regulated the mass percent to 50% of solid content with the letdown solvent dun vinyl acetic monomer.Through test, make free hexamethylene diisocyanate monomer content and be 0.01%, viscosity is that 500mPas, nco value are 10% hexamethylene diisocyanate biuret.
Embodiment 2
A kind of preparation method of hexamethylene diisocyanate biuret, it comprises the steps:
(1) with deionized water and polar aprotic solvent N, dinethylformamide and DMAC N,N mix the azeotrope that forms and are heated to 100 ℃, and insulation is for use; The mass percent that said polar aprotic solvent N, dinethylformamide and DMAC N,N (1:1) account for azeotrope is 70%;
(2) under nitrogen protection, earlier the hexamethylene diisocyanate monomer is put into reaction vessel, holding temperature is at 140 ℃; The described azeotrope of step (1) is added drop-wise in the said reaction vessel through peristaltic pump, and rate of addition is 0.20g/min; After dripping end, continue under whipped state, to be warming up to 150 ℃ of reaction 4h; Be cooled to then below 40 ℃, cooling discharging obtains the HDI biuret; The mol ratio of said hexamethylene diisocyanate monomer and deionized water is 10:1;
(3) the hexamethylene diisocyanate biuret that step (2) is obtained passes through sparger with the input speed of 13g/min and gets into first stage separation device and second-stage separation device, and tripping device is the inner-cooled vaporizer.The separation temperature of first stage separation device is controlled at 200 ℃; The one-level condenser temperature is controlled at 40 ℃, and vacuum degree control is at 10000Pa, and the separation temperature of second-stage separation device is controlled at 230 ℃; The secondary condenser temperature is controlled at 20 ℃; Vacuum degree control is isolated polar aprotic solvent and hexamethylene diisocyanate biuret component at 1000Pa, and hexamethylene diisocyanate biuret component is regulated the mass percent to 90% of solid content with the letdown solvent dun n-propyl acetate.Through test, make free hexamethylene diisocyanate monomer content and be 0.5%, viscosity is that 2000mPas, nco value are 24% hexamethylene diisocyanate biuret.
Embodiment 3
A kind of preparation method of hexamethylene diisocyanate biuret, it comprises the steps:
(1) deionized water is mixed the azeotrope that forms with polar aprotic solvent 3-methyl-2-butanone, ethylene glycol ether acetate and 2-Butoxyethyl acetate and be heated to 70 ℃, insulation, for use; The mass percent that said polar aprotic solvent 3-methyl-2-butanone, ethylene glycol ether acetate and 2-Butoxyethyl acetate (three's volume ratio is 1:1:2) account for azeotrope is 35%;
(2) under nitrogen protection, earlier the hexamethylene diisocyanate monomer is put into reaction vessel, holding temperature is at 120 ℃; The described azeotrope of step (1) is added drop-wise in the said reaction vessel through peristaltic pump, and rate of addition is 0.16g/min; After dripping end, continue under whipped state, to be warming up to 200 ℃ of reaction 3h; Be cooled to then below 40 ℃, cooling discharging obtains the HDI biuret; The mol ratio of said hexamethylene diisocyanate monomer and deionized water is 8:1;
(3) the hexamethylene diisocyanate biuret that step (2) is obtained is scattered in the film of 1.5mm through sparger entering first stage separation device and second-stage separation device with the input speed of 5-8g/min; The separation temperature of said first stage separation device is controlled at 180 ℃; The one-level condenser temperature is controlled at 30 ℃; Vacuum degree control is at 1000Pa, and the separation temperature of second-stage separation device is controlled at 200 ℃, and the secondary condenser temperature is controlled at 10 ℃; Vacuum degree control is at 100Pa; Wherein used heating medium can be selected steam or deep fat, isolates polar aprotic solvent component and hexamethylene diisocyanate biuret component, and said hexamethylene diisocyanate biuret component is regulated the mass percent to 70% of solid content with the letdown solvent dun ethylene glycol ether acetate.Through test, make free hexamethylene diisocyanate monomer content and be 0.25%, viscosity is that 1200mPas, nco value are 16% hexamethylene diisocyanate biuret.
Embodiment 4
A kind of preparation method of hexamethylene diisocyanate biuret, it comprises the steps:
(1) with deionized water and polar aprotic solvent N, dinethylformamide and tetramethylene sulfone mix the azeotrope that forms and are heated to 60 ℃, and insulation is for use; Said polar aprotic solvent N, the mass percent that dinethylformamide and tetramethylene sulfone (both volume ratios are 1:1) account for azeotrope is 35%;
(2) under nitrogen protection, earlier the hexamethylene diisocyanate monomer is put into reaction vessel, holding temperature is at 100 ℃; The described azeotrope of step (1) is added drop-wise in the said reaction vessel through peristaltic pump, and rate of addition is 0.12g/min; After dripping end, continue under whipped state, to be warming up to 200 ℃ of reaction 3h; Be cooled to then below 40 ℃, cooling discharging obtains the HDI biuret; The mol ratio of said hexamethylene diisocyanate monomer and deionized water is 6-8:1;
(3) the hexamethylene diisocyanate biuret that step (2) is obtained passes through sparger with the input speed of 5g/min and gets into first stage separation device and second-stage separation device; First stage separation device is the external-cooling type vaporizer, and second-stage separation device is the inner-cooled vaporizer.The separation temperature of said first stage separation device is controlled at 120 ℃; The one-level condenser temperature is controlled at 30 ℃, and vacuum degree control is at 300Pa, and the separation temperature of second-stage separation device is controlled at 180 ℃; The secondary condenser temperature is controlled at 8 ℃; Vacuum degree control is isolated polar aprotic solvent component and hexamethylene diisocyanate biuret component at 80Pa, and hexamethylene diisocyanate biuret component is regulated the mass percent to 63% of solid content with the letdown solvent dun ethylene glycol ether acetate.Through test, make free hexamethylene diisocyanate monomer content and be 0.18%, viscosity is that 700mPas, nco value are 13% hexamethylene diisocyanate biuret.
In above-mentioned embodiment, the percentage composition of NCO group is to detect with the dibutylamine volumetry; The content of solidifying agent middle reaches divorce cyanate ester monomer adopts gas chromatographic detection.Solids content is pressed GB/T 19252-89, and viscosity adopts GB/T9751.1-2008 to test.The transformation efficiency of water according to: the carbonic acid gas that reaction produces is taken out of with the nitrogen gas stream outlet; The standard mouth carbon dioxide absorption bottle that carbon dioxide absorber (technical grade calcium hydroxide) is housed absorbs; The increment of weighing absorption bottle calculates the growing amount of carbonic acid gas, because 1 mole of water produces 1 mole of carbon dioxide; Can calculate the reacting weight of water actual participation according to the growing amount of carbonic acid gas, thereby obtain the transformation efficiency of water.
Polar aprotic solvent of the present invention passes through to detect to separate afterwards and after the new raw materials mix with free hexamethylene diisocyanate monomer and reacts; All recycles; Need not add new solvent and change production formula and operating procedure; Only need to replenish isocyanate-monomer and water realization serialization production, zero release realizes real cleaner production.
Claims (6)
1. the preparation method of a hexamethylene diisocyanate biuret is characterized in that, comprises the steps:
(1) deionized water is mixed the azeotrope that forms with polar aprotic solvent and be heated to 30-100 ℃, insulation, for use; The mass percent that said polar aprotic solvent accounts for azeotrope is 10-70%; Said polar aprotic solvent is pimelinketone, mibk, 3-methyl-2-butanone; Ethylene glycol ether acetate, 2-Butoxyethyl acetate, 1-Methoxy-2-propyl acetate, propylene-glycol ethyl ether acetic acid acid esters, N; Dinethylformamide, N; N-N,N-DIMETHYLACETAMIDE, N, one or more in dinethylformamide, tetramethylene sulfone, METHYL SULFONYL METHANE. and the DMSO 99.8MIN.;
(2) under nitrogen protection, earlier the hexamethylene diisocyanate monomer is put into reaction vessel, holding temperature is at 90-140 ℃; The gained azeotrope is added drop-wise in the said reaction vessel, and rate of addition is 0.05-0.20g/min; After dripping end, continue under whipped state, to be warming up to 110-150 ℃ of reaction 1-4h; Be cooled to then below 40 ℃, cooling discharging obtains the hexamethylene diisocyanate biuret; The mol ratio of said hexamethylene diisocyanate monomer and deionized water is 4-10:1;
(3) the hexamethylene diisocyanate biuret that step (2) is obtained is isolated polar aprotic solvent and hexamethylene diisocyanate biuret component with the input speed entering tripping device of 3-13g/min; Hexamethylene diisocyanate biuret component is regulated solid content between the 50-90% with letdown solvent dun, makes the low monomeric hexamethylene diisocyanate biuret of free isocyanate.
2. the preparation method of hexamethylene diisocyanate biuret according to claim 1 is characterized in that, said tripping device is made up of first stage separation device and second-stage separation device; The separation temperature of said first stage separation device is controlled at 100-200 ℃; The one-level condenser temperature is controlled at 10-40 ℃, and vacuum degree control is at 100-10000Pa, and the separation temperature of second-stage separation device is controlled at 150-230 ℃; The secondary condenser temperature is controlled at 2-20 ℃, and vacuum degree control is at 10-1000Pa.
3. the preparation method of hexamethylene diisocyanate biuret according to claim 2 is characterized in that, said first stage separation device and second-stage separation device are inner-cooled molecular still or external-cooling type thin-film evaporator.
4. the preparation method of hexamethylene diisocyanate biuret according to claim 2 is characterized in that, the hexamethylene diisocyanate biuret that step (2) obtains gets into first stage separation device and second-stage separation device through sparger.
5. the preparation method of hexamethylene diisocyanate biuret according to claim 1; It is characterized in that said letdown solvent dun is vinyl acetic monomer, n-propyl acetate, Iso Butyl Acetate, n-butyl acetate, isobutyl acetate, ethylene glycol ether acetate or 1-Methoxy-2-propyl acetate.
6. the preparation method of hexamethylene diisocyanate biuret according to claim 1; It is characterized in that: the viscosity of the monomeric hexamethylene diisocyanate biuret of said low free isocyanate is that 500-2000mPas, nco value are that 10-24wt%, free isocyanate monomer content are 0.01-0.5wt%, and solids content is 50-100wt%.
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| CN111635498A (en) * | 2020-05-11 | 2020-09-08 | 上海嘉宝莉涂料有限公司 | Modified polyurea and application thereof |
| CN115925580A (en) * | 2022-11-22 | 2023-04-07 | 宁夏瑞泰科技股份有限公司 | Method for recycling HDI rectification residues and biuret polyisocyanate |
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| CN115925580B (en) * | 2022-11-22 | 2024-06-07 | 宁夏瑞泰科技股份有限公司 | Method for recycling HDI rectification residues and biuret polyisocyanate |
| CN116041224A (en) * | 2023-01-31 | 2023-05-02 | 美瑞新材料股份有限公司 | Preparation method of hexamethylene diisocyanate biuret curing agent |
| CN116041224B (en) * | 2023-01-31 | 2024-02-13 | 美瑞新材料股份有限公司 | Preparation method of hexamethylene diisocyanate biuret curing agent |
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