CN103402978A - Process for preparing polyisocyanates containing biuret groups - Google Patents
Process for preparing polyisocyanates containing biuret groups Download PDFInfo
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- CN103402978A CN103402978A CN2012800112932A CN201280011293A CN103402978A CN 103402978 A CN103402978 A CN 103402978A CN 2012800112932 A CN2012800112932 A CN 2012800112932A CN 201280011293 A CN201280011293 A CN 201280011293A CN 103402978 A CN103402978 A CN 103402978A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/46—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups containing any of the groups, X being a hetero atom, Y being any atom, e.g. acylureas
- C07C275/58—Y being a hetero atom
- C07C275/62—Y being a nitrogen atom, e.g. biuret
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
- C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups
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Abstract
The present invention relates to a process for preparing polyisocyanates containing biuret groups from di- or polyisocyanates with diamines.
Description
The present invention relates to a kind of method of the polymeric polyisocyanate that contains biuret group by vulcabond or polymeric polyisocyanate and diamines preparation.
DE19633404 has put down in writing the method for using the mixing equipment with high shear forces to prepare the polymeric polyisocyanate that contains biuret group.This application mentions, uses acid catalyst while having at the same time water or uncle-butanols.The shortcoming that adds water or release aqua is that isocyanate groups is degraded to amido, this be because isocyanic ester industrial by corresponding amine preparation.Other shortcomings are formation reaction gas, particularly carbonic acid gas and iso-butylene in reaction process, and this can produce gas/liquid reactions mixture and exhaust flow.The water-free embodiment clearly implemented all at high temperature carries out and generates light product.In the industrial factory for this purpose, iso-butylene---definite is tail gas stream---also must incinerate.
Water or uncle-butanols and other compounds that discharge water under biuretized reaction conditions are called biuret agent (biuretizing agent) hereinafter.
EP-A1716080 discloses a kind of method of the isocyanic ester that contains biuret group by vulcabond and water or water vapour preparation equally, is to control reaction, and water is introduced with the form in batches of minimum batch.
DE102004060739 has put down in writing a kind of method for preparing the polymeric polyisocyanate of biuret-containing group, and described method for example adds water as the biuret agent under high shear forces.The method presents by the biuret agent carries out the common deficiency that biuretized reaction produces.
As substituting of the method that adds the biuret agent put down in writing so far, to the also existing research of method for preparing the biuret groups polymeric polyisocyanate by vulcabond and diamine reactant.For the reaction of vulcabond and biuret agent, the advantage of this method is not at first for all generating undesired by product iso-butylene (from the trimethyl carbinol) and carbonic acid gas.
Another advantage is, uses in theory the diamines raw material more cheap than vulcabond to replace the vulcabond raw material of about sixth.Vulcabond usually by diamines by expensive phosgenation or by preparing without phosgene technique.Owing to can save the conversion of diamines to vulcabond for a part of raw material, therefore, use the method for vulcabond and diamines to make the reaction of water more satisfactory.
At first its shortcoming is, diamines and the insoluble or slightly soluble suspended solids of the common generation of vulcabond mixing, or further in reaction process, can further react the polymeric polyisocyanate that generation contains biuret group.If solid is too much and/or too large, will be in equipment generating material deposition and latch up phenomenon, or can generate muddy product, or may become oversize for the post-heating time that is converted into the solubility biuret, or this post-heating needs too high temperature.
DE2261065 has put down in writing a kind of method of the polymeric polyisocyanate that contains biuret group by vulcabond and amine preparation.Its shortcoming is, the residence time of reaction mixture long (for example, referring to, the embodiment 16 of patent application), this is uneconomic and causes unacceptable product variable color.The method also can generate insoluble gel secondary component (referring to DE2609995, page 4).
DE2609995 has put down in writing a kind of by making the gaseous state diamines pass into the method that vulcabond prepares the polymeric polyisocyanate that contains biuret group under 100-250 ℃.Its shortcoming is, required additional cost when the thermal stresses that diamines produces in evaporative process or decompression.The shortcoming that passes into gas is, the mass transfer between gas phase and liquid phase is limited, and this has detrimental action to space-time yield.After this method, for improving color and luster, in 120-195 ℃, preferably 160-180 ℃ of thermal treatment 6-10 hour is necessary, its result causes space-time yield to reduce.
EP3505 has put down in writing a kind of method for preparing biuret in vulcabond and the diamines advection nozzle mixing equipment that raw material mixes with high combined power therein.The shortcoming of the method is, uses the temperature of reaction that is up to 250 ℃.In addition, need to use special device (advection nozzle).Particularly, for hexa-methylene 1, the 6-vulcabond, generate more oligomer and by product, and this causes viscosity rise, and the content of NCO undesirably reduces, and the ability of diluting with non-polar solvent decline (referring to EP277353, page 2).
EP12973 has put down in writing the method that strong acid preparation that a kind of use mixes by carboxylamine acid anhydride and isocyanic ester contains the biuret group polymeric polyisocyanate.Its shortcoming is, for obtaining containing the biuret group clarified liq, the residence time of reaction mixture is long, and this causes unacceptable product variable color.
EP277353 has put down in writing a kind of method that contains the biuret group polymeric polyisocyanate for preparing, and reactant wherein reacts under higher than 250 ℃.It still demonstrates, and monomer stability reduces slightly and dilution stability reduces (referring to EP1158013, page 2).
EP1158013 has put down in writing a kind of method of biuret that prepared under the acidic substance as catalyzer exist in the temperature higher than 170 ℃ by vulcabond and diamines.Embodiment has not been described in making the mixing section of clear more described component has been mixed, and raw material is carried out to rapid heating simultaneously.Usually can use in prior art and not make static state or the dynamic apparatus of specified in more detail more, still, preferably using do not comprise any internals the simple reaction pipe as mixing section.The shortcoming of this method is, identical with the situation of EP277353, and product prepared by the method for using the biuret agent by chromatic number is higher.Its shortcoming is, the impact of the still higher temperature of mentioning in embodiment on product stability and colour generation (color generation), and required high energy consumption for this purpose.The HDI feeding temperature is 250 ℃ or 230 ℃ (embodiment 2).The temperature of mixture rises to 280 ℃ or 260 ℃ (referring to EP2287151, corresponding to the comparing embodiment 2 of EP1158013).Because mixture is unstable at this temperature, therefore, be necessary mixture is carried out cooling fast.
EP2287151 is with reference to EP1158013.Its difference is that the part of the logistics of hexamethylene diisocyanate only adds in subordinate phase.Its advantage is to have better mutability in the first stage with the hexamethylene diisocyanate of constant volume flow and the ratio of mixture of hexamethylene-diamine, there is higher catalyst concn in the mixture of hexamethylene diisocyanate and hexamethylene-diamine, and the hexamethylene diisocyanate of second part of volume can reaction mixture.Its top temperature is 255 ℃, and this is all disadvantageous to the colour generation at this temperature and stability.
DE-C119707576 has put down in writing a kind of method of the aromatic polyisocyanate that contains biuret group by isocyanic ester and diamines preparation, in the method, diamines and isocyanic ester be the reacting phase mutual reactance in single mixed chamber, then in the single-stage stirred vessel or in optional multi-stage cascade agitator, reacts to terminal.
EP918809(=US6414184) put down in writing by isocyanic ester and corresponding diamines or water or released the method that aqua prepares biuret, in the method, having made to be in contact with one another under the high shear forces of reactant in electric hybrid module.Rotor-stator assembly, Ultra-Turrax, super mixer and shearing disk mixing tank (shear disk mixer) have been mentioned.The binding mode (passing through centrifugal force) of rotary fixed-bed reactor (rotating fixed-bed reactor) obviously is different from mixing region the binding mode without the reactor of stator.
WO2008/110492 has put down in writing a kind of method that contains the biuret group polymeric polyisocyanate for preparing, and in the method, makes diamines and vulcabond in mixing equipment, use minimum combined power to mix mutually.As mixing equipment, mentioned various mixing equipment, and clearly be disclosed in mixing pump component is mixed.
But, not about using the clearly instruction of which kind of technique device for this mixing.
The object of the present invention is to provide a kind of for prepared the technique device of biuret by isocyanic ester and diamines, with those under comparable reaction conditions and/or use the product that the device of prior art (comprising the method for not using the biuret agent to prepare biuret) makes to compare, in described device, the color of product shoals, and has at least retained stability in storage of the prior art simultaneously.
Realize this purpose by the method that contains the biuret group polymeric polyisocyanate by following material preparation:
A) at least one (ring) aliphatic vulcabond and/or polymeric polyisocyanate,
B) at least one (ring) aliphatic diamine that contains two primary aminos and/or secondary amino group,
C) optionally at least one acid and
D) at least one solvent optionally,
E) optionally at water or at least one, release under the hydrate existence, and comprise
F) optionally at least one is selected from following stablizer: urea, ammonia, biuret, urea derivatives and methane amide,
I) by component a), b) and optional c) and optional d) and/or e) and/or f) in mixing equipment, mix, and
Ii) will derive from i) reaction mixture feed at least one wherein said reaction mixture reaction unit of heat-treating in,
Wherein, described mixing equipment has at least rotation fixed-bed reactor of the acceleration effect of 100g at least one to the liquid phase in mixing equipment.Herein, " g " is for having value for 9.81m/s
2universal gravity constant.
The invention has the advantages that, compare with using method well known in the prior art, can be in the situation that produce the polymeric polyisocyanate that contains biuret group that still less problem (comprise and generate solid) obtains having low colour by method of the present invention or device.
The filling of rotary fixed-bed reactor (packaging) is the addition reaction zones that other mixing tanks did not have such as rotor-stator assembly, Ultra-Turrax, super mixer and shearing disk mixing tank.Various filler units (packing elements) are carried out to multistage mixing.With other mixing equipment, compare, the retention time in high-shear region in rotary fixed-bed reactor is obviously elongated.
With the mixed phase ratio in alternative, mix in rotary fixed-bed reactor and generate still less and meticulousr agglomerate.But generate solid by the good mixing minimally.
Therefore, another advantage of the present invention is, as for example, with solvent (40% the concentration based on biuret and lower than 40% concentration) dilution, can obtain having by diamines and vulcabond reacting in rotary fixed-bed reactor the transparent products of the stability in storage of good or improvement.
With regard to method of the present invention, suitable vulcabond and polymeric polyisocyanate are a) (ring) aliphatic isocyanate, contain at least 2, preferably 2-6, particularly preferably 2-4, very particularly preferably 2-3 and be just in time 2 compounds that are bonded to as the isocyanate groups on the carbon atom of aliphatic system and/or an alicyclic system part especially.
Suitable vulcabond is preferably the vulcabond that contains 4-20 carbon atom.
Alicyclic diisocyanate is the compound that contains at least one alicyclic ring system.
The compound of aliphatic isocyanate for only containing straight or branched, i.e. fatty compounds.
In this article, term " aliphatic series " and " alicyclic " are referred to as (ring) aliphatic series.
Particularly preferred aliphatic vulcabond is tetramethylene diisocyanate, hexamethylene diisocyanate (the diisocyanate based hexane of 1,6-), eight methylene diisocyanates, the decamethylene vulcabond, ten dimethylene diisocyanates, ten tetramethylene diisocyanate, the derivative of lysinediisocyanate, the tetramethyl-eylylene diisocyanate, 2,4,4-trimethyl cyclohexane vulcabond and/or 2,2,4-trimethyl cyclohexane vulcabond or tetramethyl-hexane diisocyanate, particularly preferred alicyclic diisocyanate is Isosorbide-5-Nitrae-diisocyanate based hexane, the diisocyanate based hexane of 1,3-or the diisocyanate based hexane of 1,2-, 4,4 '-bis-(isocyanato-cyclohexyl) methane or 2,4 '-bis-(isocyanato-cyclohexyl) methane, 1-isocyanato--3,3,5-trimethylammonium-5-(isocyanato-methyl) hexanaphthene (different Buddhist ketone vulcabond), 1,3-bis-(isocyanato-methyl) hexanaphthene or 1,4-bis-(isocyanato-methyl) hexanaphthene or 2,4-bis-isocyanato-s-1-methylcyclohexane or 2,6-bis-isocyanato-s-1-methylcyclohexane, and 3 (or 4)-bis-(isocyanato-methyl), three ring [5.2.1.0
2.6] decane, 8 (or 9)-bis-(isocyanato-methyl) three ring [5.2.1.0
2.6] the decane isomer mixture.Described aliphatic series and alicyclic isocyanate are preferably hexamethylene diisocyanate or different Buddhist ketone vulcabond, particularly preferably hexamethylene diisocyanate.Can also there is the mixture of above-mentioned vulcabond.
Reason due to the preparation method, 2,2,4-tri-methyl hexamethylene 1,6-vulcabond and 2,4,4-tri-methyl hexamethylene 1, the 6-vulcabond usually take ratio as 1.5:1-1:1.5, preferably 1.2:1-1:1.2, particularly preferably 1.1:1-1:1.1 and very particularly preferably the isomer mixture of 1:1 obtain.
Industrial, for example, the method that can put down in writing in DE-C2005309 and DE-A2404773 prepares vulcabond by the phosgenation of diamines, or can in EP-B-0126299 (US-A-4596678), EP-B-0126300 (US-A-4596679), EP-A-0355443 (US-A-5087739) and EP-A-0568782, put down in writing prepare vulcabond without phosgenation (urethane decomposition).According to the present invention, no matter isocyanic ester used is by without phosgenation or obtain unimportant by the preparation method containing phosgene.
Preferred above-mentioned two kinds of vulcabond prepared by method equally.
The chloride content that derives from the vulcabond of phosgenation is generally 100-800 mg/kg (measuring by the Wickbold method), and by the chloride content of the isocyanic ester prepared without phosgene method lower than 80 mg/kg, preferably lower than 60 mg/kg, particularly preferably lower than 40 mg/kg, very particularly preferably lower than 20 mg/kg and particularly lower than 10 mg/kg.
Total bromine content (measuring by the Wickbold method) is usually less than 100 mg/kg, preferably lower than 50 mg/kg and especially lower than 20 mg/kg.
Measure the content of hydrolyzable chlorine according to ASTM D4663-98, for lower than 200 ppm by weight, preferably lower than 40 ppm by weight, particularly preferably lower than 30 ppm by weight and very particularly preferably lower than 20 ppm by weight.
The polymeric polyisocyanate that contains biuret group is by with at least one, preferably just in time for a kind of diamines b) mix and react.
The molecular weight of the conventional primary amine that only contains aliphatic series and/or alicyclic combination and/or the organic diamine of secondary amine group is lower than 300.The example is 1，2-diaminoethane, 1，2-diaminopropane, 1,3-diaminostilbene, the 1-dimethylpropane, 1,3-diamino-2, the 2-dimethylpropane, 1,3-diaminopropanes, 1,4-Diaminobutane, 1,5-1,5-DAP, the neopentane diamines, 1,5-diamino-2-methylpentane, 1，6-diaminohexane, 1,6-diamino-2,2,4-trimethyl cyclohexane and/or 1,6-diamino-2,4,4-trimethyl cyclohexane, Isosorbide-5-Nitrae-diamino hexane and/or 1,5-diamino hexane, 1,1-bis-(amino methyl) pentamethylene, 2,4--diaminostilbene-methylcyclohexane and/or 2,6-diaminostilbene-methylcyclohexane, 1-amino-3,3,5-trimethylammonium-5-amino methyl hexanaphthene (different Buddhist ketone diamines), 1,2-bis-(amino methyl)-4-methylcyclohexane, 1,8-diamino-octane, 1,3-bis-(amino methyl) hexanaphthene and/or Isosorbide-5-Nitrae-bis-(amino methyl) hexanaphthene, 4,4'-diamino-dicyclohexyl methane or 3,3 '-dimethyl-4,4 '-diamino-dicyclohexyl methane, the inferior diphenyl-methyl diamines (TMXDA) of tetramethyl-.Can also use any mixture of described diamines.Particularly preferably 4,4'-diamino-dicyclohexyl methane, different Buddhist ketone diamines and 1，6-diaminohexane, very particularly preferably different Buddhist ketone diamines and 1，6-diaminohexane and particularly 1，6-diaminohexane.
In addition, also can use the diamines of polyethers (preferably polyoxyethylene glycol and polypropylene glycol), wherein preferred 3-oxa-pentane-1,5-diamines, 4,9-dioxa dodecane-1,12-diamines, 4,7,10-trioxa tridecane-1,13-diamines, propylene oxide derivative are (as purchased from Huntsman or BASF SE
or polyetheramine D230, D400, D2000, D4000), the polyethylene/polypropylene derivative (as
eDR-176, ED-600, ED-900, ED-2003, HK-511), and polytetrahydrofuran derivative (as polytetrahydrofuran amine 1700), and polytetrahydrofuran-polypropylene glycol derivative (as
tHF-100, THF-140, XTJ-542, XTJ-559).Also can use mixture in every kind of situation.
Can also use triamine, polyethers triamine for example, as the 3-aminomethyl-1,2,6-hexamethylene-diamine, 4-aminomethyl-1,2,8-eight methylene diamine; Polyetheramine, as purchased from BASF SE.
The advantage of directly biuretized---being that amine and isocyanic ester direct reaction generate biuret---is, with amine, replaces water and needn't at first by amine, generate isocyanic ester, then isocyanic ester is hydrolyzed to amine again by water.
In addition, by saving hydrolysing step, can avoid formation reaction gas, particularly as the carbonic acid gas in byproduct of reaction and tail gas (and iso-butylene).
Directly other biuretized advantages are, the selection of amine is not limited to the amine by available isocyanate-monomer specified (passing through direct hydrolysis).
Directly biuretized other are also advantageous in that, needn't use and basic molecular structure identical in the isocyanate-monomer situation.
In the implementation process of the inventive method, above-mentioned isocyanic ester a) and diamines b) to be equivalent to isocyanate group, with the equivalent ratio that amino is at least 4:1, react, preferred 4:1-50:1, particularly preferably 5:1-40:1 and particularly 5:1-30:1, in this calculating be considered as primary amino the group of monofunctional.The raw material meter of these data based on used.
Isocyanic ester a) the transformation efficiency of total mass is preferably 5-70%, preferably 10-55%, particularly preferably 20-40%.In reaction, diamines b) complete reaction, and excessive isocyanic ester a) is distilled and removes.
Diamines b) can liquid or the form of gas introduce reaction, preferably with the form of liquid, introduce.
Described reaction is optionally at least one catalyzer c) existence under carry out.
An advantage of the inventive method is, can save catalyzer.
Yet possible embodiment of the present invention provides a kind of scheme that has catalyzer.
In a preferred embodiment, can save catalyzer at the temperature higher than 170 ℃.
In a further preferred embodiment, by be up to 190 ℃, particularly be up to 180 ℃, particularly be up at the temperature of 170 ℃ and add the catalyzer can accelerated reaction.
Described catalyzer can be known OH-acid compound in DE-A14443885 for example.Its advantage is to have relative non-volatility, therefore, in reaction process, can be optionally as salt filtering or can be used as the compound that does not produce interference and be retained in final product and same formation does not produce in the degradation production or by product of interference from reaction mixture.Other advantage is that described acid has good catalytic activity.
In the implementation process of the inventive method, any acid all can be used as catalyzer, preferably pKa<10, particularly preferably pKa<9 and the protonic acid of pKa<8 very particularly preferably.
Available protonic acid is that for example hydrosulfate, particularly its aliphatic series, branched aliphatic or araliphatic group are containing the tetraalkyl monoammonium sulfate of individual, preferred 4-20 the carbon atom of 1-30.
Other examples are sulfonic acid, as methylsulfonic acid, ethyl sulfonic acid, propanesulfonic acid, 2-toluenesulphonic acids or 4-toluenesulphonic acids, Phenylsulfonic acid, ring ten disulfonic acid, camphorsulfonic acid or naphthalene 1-sulfonic acid or naphthalene-2-sulfonic acid; And monocarboxylic acid and dicarboxylic acid, as formic acid, acetic acid, propionic acid, butyric acid, trimethylacetic acid, stearic acid, naphthenic acid, oxalic acid, propanedioic acid, succinic acid, hexanodioic acid, phenylformic acid or phthalic acid.
In these acid, if the dicarboxylic acid of mentioning under reaction conditions significantly to measure the release water outlet, for example be greater than 10 % by mole of institute's consumption, be preferably greater than 8 % by mole, particularly preferably be greater than 5 % by mole and very particularly preferably be greater than 3 % by mole, more preferred these dicarboxylic acid, because these dicarboxylic acid can discharge the water as the biuret agent by forming acid anhydrides.
Have now found that, for example in EP – A – 259233, described (virtue) aliphatic carboxylic acid of record has relatively low effect.
Have now found that, preferably use and through finding that useful especially acid is: phosphoric acid and/or its (monoalkyl and/or) dialkyl or its (single aryl and/or) diaryl ester and/or hydrosulfate.Preferably use its aliphatic series, branched aliphatic, araliphatic or aromatic group monoalkyl and/or dialkyl or single aryl and/or the diaryl ester containing the phosphoric acid of 1-30, preferred 4-20 carbon atom.
Particularly preferably use di(2-ethylhexyl)phosphate isopropyl esters, di(2-ethylhexyl)phosphate (2-ethylhexyl) ester, di(2-ethylhexyl)phosphate (normal-butyl) ester and phosphoric acid double hexadecyl ester.
In another embodiment, can use the derivative of the more lower valency acid of phosphoric acid, for example phosphonous acid.
In another embodiment, described filler comprises the solid ingredient of catalytic activity, as acid ion exchangers.It can replace adding the catalyzer of feedstream wholly or in part.
Described acid in the 0.01-1.0 % by weight based on vulcabond total amount used, preferably the 0.02-0.5 % by weight and very preferably the amount of 0.05-0.5 % by weight for method of the present invention.Described acid can be used as solution in suitable solvent or the form of suspension adds.Described acid preferably adds with the form of not diluted.
Other available catalyzer are, for example strong inorganic Lewis acid or
acid, as boron trifluoride, aluminum chloride, sulfuric acid, phosphoric acid, hydrochloric acid; And/or nitrogenous alkali and inorganic and/or organic acid salt, as one section to the 6th page first complete segment record of having most of the page 3 of DE-A-1931055, this document at this mode by reference include this specification sheets in.
As needs, can further add a small amount of stablizer f), described stablizer is selected from derivative or the methane amide of the urea put down in writing in WO96/25444, ammonia, biuret, urea, preferred urea, N-MU, N-ethyl carbamide, N, N-dimethyl urea, N, N '-dimethyl urea, N, N-diethyl urea, N, N '-diethyl urea, ethylidene-urea or phenylurea, particularly preferably urea.
Aforementioned stable agent (for example urea) is water-soluble or solvent optionally.If the method is without CO
2existence under carry out, more not preferably water as solvent.
Described stablizer is in 0.01-2.0 % by mole, the preferably amount use of 0.05-1 % by mole of isocyanic ester in (a).
In a preferred embodiment, these stablizers are dissolved in or are scattered in the solvent d that at least one is listed as follows) in.
In order to suppress better the formation of insoluble polyureas, can optionally use in addition solvent d) as stablizer
The solvent that is suitable for this purpose is, ether for example, as diox or tetrahydrofuran (THF); The alkoxyalkyl carboxylicesters, as oxalic acid triglycol ester, butylacetate, acetic acid 1-methoxy-propyl-2-ester, acetic acid methoxy ethyl-2-ester, propylene glycol diacetate; Ketone, as 2-butanone, 4-methyl-2 pentanone, pimelinketone; Aromatic solvent, for example toluene, dimethylbenzene, containing aromatic mixtures, chlorobenzene, the orthodichlorobenzene of 8-20 carbon atom; Hexane; The mixture of hydrocarbon and/or trialkyl phosphine acid esters.Also preferably N-Methyl pyrrolidone and other N-(ring) alkyl pyrrolidine, as N-Methyl pyrrolidone, N-ethyl pyrrolidone, N-n-butylpyrrolioine ketone and N-cyclohexyl pyrrolidone.
According to the present invention, preferably use acetic acid methoxyl group propyl ester, acetic acid methoxyl group ethyl ester, trimethyl phosphite 99, tricresyl phosphate n-butyl and triethyl phosphate.
Can also use any mixture of solvent for use.
As use solvent, preferably diamines is dissolved in to this solvent and this two amine aqueous solution is introduced in reaction.In the case, the concentration of diamines in solvent is that 2-100(is solvent-free) % by weight, preferably 5-30 % by weight, particularly preferably 10-25 % by weight and 15-20 % by weight very particularly preferably.
Yet a preferred embodiment of the present invention is provided at the reaction of carrying out under solvent-free existence.
Verbindung) can be that liquid water and vaporous water or at least one are released hydrate.The described hydrate of releasing can be that for example uncle-butanols maybe can discharge by generating acid anhydrides the dicarboxylic acid of water, or contains the compound of crystal water.More preferably do not add this compounds.
Reaction mixture can also comprise inert gas flow, as comprises a kind of liquid state or gaseous state inertia stream.Preferably with gaseous form, introduce described inertia stream.Available inert media is for not obvious under reaction conditions---to a certain extent lower than 5 % by mole, preferably lower than 2 % by mole, particularly preferably lower than 1 % by mole---all gas reacted with isocyanic ester stream, the air-flow that comprises amine and/or catalyzer.The example is CO, N
2, He, Ar, hydro carbons (as methane) etc., and their mixture.Preferably use argon gas and/or nitrogen.Particularly preferably use nitrogen.
According to the present invention, will rotate fixed bed catalyst as step I) reactor.
For realizing purpose of the present invention, rotation fixed-bed reactor (also referred to as rotation, filling (packed) bed or hypergravity (hi-gee) reactor) are interpreted as referring to that wherein liquid phase is with the solid-state component close contact of different speed of relative movement and rotation, thereby liquid phase is disperseed and the reactor of mixing.
Preferred rotation fixed-bed reactor can have the rotation solid-state component that structurized or non-structured rotation solid packing is mixed by it as liquid phase.
In a preferred form, described reactor comprises continuous gas phase.Herein, high glue spread and stream of liquid droplets appear on filler.For realizing purpose of the present invention, the three-phase system that coating stream is filler, liquid and gas.Stream of liquid droplets is liquid-gas (or liquid-liquid) diphasic system, and after polymeric polyisocyanate and diamine components are just mixed, its mixture overflows from the outward flange of filler.The existence of gas phase makes it possible to form coating and three-phase.The gas phase amount should at least make in filler and have continuous gas phase.
Fig. 1 shows the illustrative approach schematic diagram that can be used for rotation fixed-bed reactor of the present invention.
In figure, the implication of reference number is as follows:
1 introduces liquid ((ring) aliphatic vulcabond and/or polymeric polyisocyanate a) with (ring) aliphatic diamine b)
2 fillers/rotor
3 shells
4 pneumatic outlets (via tubular shaft)
5 liquid exits
6 drive shafts
7 gas inletes (for example rare gas element)
R
1: the shell radius
R
2: the outside radius between turning axle and filler, the thickness of mixing region
R
3: the inside radius between turning axle and filler
H
1: outer cover height
H
2: packed height
With regard to assembly 2, can mention the assembly formed by for example structurized internals (as filler (comprising the filler of being made by wire netting and fabric), static mixer, metal shim, metal sheet (thin plate, waved plate and/or porous plate)) and non-structured porous system (as bed or filler assembly or open-cell foam structure) herein.
Filler is optionally stable by strut.In a preferred embodiment, for preventing that possible deposition of solids from not used described strut.
The advantage of described rotation fixed-bed reactor is, by the fixing holder assembly, and its height H
2part filler and changing relatively.This can keep constant velocity profile while making the volumetric flow rate variation in mixing tank.
(ring) aliphatic vulcabond and/or polymeric polyisocyanate a) and (ring) aliphatic diamine b) can introduce respectively.For example, it can pass through a plurality of independently nozzles or spray gun feed.
By (ring) aliphatic vulcabond and/or polymeric polyisocyanate a) and (ring) aliphatic diamine b) introduce after, liquid stream passes outwards through filler and flows from centre, then with that mix and form reaction at least partly via outside liquid exit outflow mixing tank.
According to the present invention, in mixing tank, to the acceleration effect of liquid phase, be at least 100g, preferably 100-2000g, particularly preferably 500-1000g.High acceleration has reduced the buildup effect of liquid on countercurrent direction.Can improve flux and space-time yield by this method.
In mixing tank, the speed of liquid phase is generally the 0.001-1 meter per second, preferably the 0.003-0.05 meter per second.
For guaranteeing to rotate in fixed reactor the existence of gas phase, make wherein filler can not overflow and guarantee thus the good mixing effect preferably to add rare gas element.
In further method is selected, described method is not in the situation that exist rare gas element to carry out.For pass into Arius (substream) under sufficiently high rotating speed, also can form in device and there is subatmospheric gas phase by this method.
In the embodiment that Fig. 1 describes, introduce air-flow via shell, with flow through filler again discharging via quill shaft of liquid stream countercurrent direction.
Described liquid is introduced usually at the temperature higher than at least 30 ℃ of amine fusing points; With regard to hexamethylene-diamine, preferably higher than 60 ℃, particularly higher than 80 ℃.
Mix preferably at rotation fixed-bed reactor i) temperature out higher than 120 ℃, carry out under particularly higher than 140 ℃.Preferably the upper limit of temperature is selected to make i) the temperature of liquid exit not higher than the reactor ii of following reaction) temperature.In the case, should consider to rotate (ring) aliphatic vulcabond in fixed-bed reactor and/or polymeric polyisocyanate a) and (ring) aliphatic diamine b) heat of reaction release.
Mixing step i) in, the upper limit of reaction mixture temperature is lower than 270 ℃, preferably not higher than 250 ℃.
In a preferred modification, described temperature is not higher than 200 ℃.
The absolute pressure in mixing equipment exit is 0.3 bar to 10 bar, preferably 0.6 bar to 7 bar, particularly preferably 0.8 bar to 5 bar.
In mixing tank, raw material a) and b) and catalyzer c) with or not with solvent and with or not with rare gas element and with or not with Verbindung) mix.
With regard to step I i) reaction unit with regard to, can use the stop formula reactor (residence reactor) of all routines, for example agitator, ejection-type loop reactor (jet loop reactors), tubular reactor, container, chromatographic column.Can also in conjunction with or use the device of a plurality of types.For example, agitator can be combined with tubular reactor.The stirred vessel of series connection also can be as the reaction unit of present method.
When reaction unit is comprised of one or more stirred vessels, preferably the flow state is set to make and be take newton number (Newton number) that power input is feature and be not inversely proportional to the Reynolds number (Reynolds number) formed by the stirring diameter when the rotation speed change.Preferably the flow state is set and is made newton number and Reynolds number when rotation speed change not be funtcional relationship.
At described reactor, be during not containing the tubular reactor of internals, Reynolds number is preferably at least 2300, and particularly preferably at least 2700, be very particularly preferably at least 3000, particularly at least 4000, at least 7000 or especially at least 10000.
Preferably use at least one to form therein longitudinal stream and diameter and the length ratio stirred vessel for 1:1.2-1:10, preferred 1:1.5-1:6.
In stirred vessel, the power input of unit volume should be at least 0.1 watt/liter, preferably at least 0.3 watt/liter, particularly preferably at least 0.5 watt/liter.Generally speaking, be up to 20 watts/liter, preferably be up to 6 watts/liter and particularly preferably to be up to 2 watts/liter be enough.
Power can be applied by the agitator of all available types, for example, and inclined paddle type agitator (inclined blade stirrers), anchor stirrer, disk stirrer, turbine agitator, beam type agitator (beam stirrer).Preferably use disk stirrer and turbine agitator.
A plurality of agitators can also be installed on axle.Preferably on the section of each series connection of axle, use an agitator.The 0.1-0.9 that the diameter of mixing component is the stirred vessel diameter doubly, is preferably the 0.2-0.6 of stirrer diameter doubly.
Can with or operate the stirred vessel of described stirred vessel or series connection without baffle plate.Preferably use the baffle plate operation.Each section is used 1-10 baffle plate usually, preferably 2-4 baffle plate operated.
Reaction mixture leaves mixing step i) after, reaction unit entered.As rare gas element exists, in a preferred embodiment, described reaction unit can be mainly vertical means (for example vertical tube type reactor, chromatographic column or slender axles stirred vessel (slim stirred vessel)).In the case, reaction mixture can (also flow with liquid phase and rare gas element) or (with the inert gas flow adverse current) charging from top from bottom, preferably from bottom feed.
The rare gas element of any charging all can be discharged at any point of this system.Preferably only after reacting completely, reaction mixture discharges.
Reaction unit ii) retention time in is preferably 1 minute to 8 hours, and preferably 1 minute to 8 hours, particularly preferably 30 minutes to 6 hours and very particularly preferably 1 to 4 hour.When advantageously being selected to make terminal, arrives theoretical nco value in the reaction times.The nco value that when theoretical nco value has formed the amount of biuret group of expected in theory for the amine when all uses, described reaction mixture has.
Reaction section ii) temperature in zone is 30-300 ℃, preferably 80-300 ℃, particularly preferably 120-250 ℃.
Absolute pressure in reaction unit is the 0.3-100 bar, preferably 0.5-10 bar, particularly preferably 0.6-4 bar, particularly preferably 0.8-2 bar.
Catalyzer c) add mixing equipment i) in reaction mixture.In addition, sneaking into of catalyst stream can be independently at reaction unit ii) in carry out or carry out at a plurality of points.Preferably catalyzer is sneaked in one of them material stream of rotation fixed-bed reactor charging.Particularly preferably catalyst stream is incorporated in the material that the contains isocyanate groups stream that enters mixing equipment.
In the simplest embodiment, the present invention includes mixing device i) and reaction unit ii) combination.In the case, then to isocyanic ester material stream a) and catalyzer c) carry out premix and merge and the material stream b that contains amine) mixes introducing reaction unit ii after passing through mixing equipment then).In the case, mixing equipment i) and reaction unit ii) needn't be device independently, still, reaction unit ii) can also directly with mixing equipment, be connected.
At mixing equipment i) in, described reaction can start immediately after component is mixed, and makes reaction needn't be limited to reaction unit ii).
In further embodiment, isocyanic ester material stream can only be introduced in the downstream of mixing equipment, for example between mixing equipment and reaction unit, introduces or directly introduce reaction unit.Mixing merit now (mixing work) is less than the mixing merit of isocyanic ester and amine material stream.Result is, if the mixing temperature in mixing equipment, higher than the temperature in rear reaction, will carry out cooling fast to product before reaction unit and/or in reaction unit.
(ring) aliphatic vulcabond and/or polymeric polyisocyanate and catalyzer continuous charging, to mixing equipment, and are introduced to the mixture of amine and optional solvent abreast wherein.Discharge continuously the crude product that comprises biuret oligomer and excess monomer.Then by distillation, described crude product is carried out to aftertreatment.
Generally speaking, in the last handling process of the major portion of the unreacted isocyanic ester of separation (a), should obtain the product of the isocyanic ester that does not discharge harmful amount the polymeric polyisocyanate of the biuret group from comprising generation.The content of usually wishing to obtain monomer whose isocyanic ester (a) lower than 1 % by weight, preferably lower than 0.5 % by weight, particularly preferably lower than 0.3 % by weight and very preferably lower than the product of 0.2 % by weight, the polymeric polyisocyanate meter based on containing biuret group.Advantageously, 50 ℃ in the temperature range of selected temperature of reaction in reaction to (a) in excessive vulcabond carry out decompression separation, for example by distillation, remove.
The short-path evaporator that the device that is used for this purpose is flasher, falling-film evaporator, thin-film evaporator or the distillation column that optionally superposes.
Described distillation is usually at 0.1-300hPa, preferably carry out lower than 200hPa and under particularly preferably lower than the pressure of 100hPa
Advantageously, can be by the unreacted vulcabond separating and reclaim by this method a) again for reaction.
If use solvent in reaction, equally preferably by distillation, isolate solvent from reaction mixture.Condition and the equipment of distillation are for example, identical with the condition of removing excess diisocyanate and equipment.
The present invention further provides a kind of by under the existence at least one acid and optional a kind of solvent being prepared by vulcabond and diamine reactant to the method for the polymeric polyisocyanate that contains biuret group, described method is included in mixing equipment (I) (ring) aliphatic vulcabond and/or polymeric polyisocyanate material stream 1 is flowed to 9 with diamines material stream 2 and with recirculation solvent material, as existed, also with the excess diisocyanate 13 of recirculation, under existing, mixes mutually by least one catalyzer, then be fed at least one reaction unit (II) by the mixture of the diamines that obtains and vulcabond and make its reaction generate the polymeric polyisocyanate that contains biuret group, then by distilling the solvent to any existence, excessive vulcabond and the polymeric polyisocyanate that contains biuret group are separated from each other, and make the solvent of any existence and excessive vulcabond be recycled to mixing equipment (I) (referring to Fig. 2).
Preferably (ring) aliphatic vulcabond and/or polymeric polyisocyanate 1 and 13 are mixed and together with add the rotation fixed-bed reactor.
In one embodiment, method of the present invention can be carried out under a kind of solvent exists, as shown in Figure 2:
In a possible embodiment, aforesaid method comprises mixing equipment (I), at least one reaction unit (II), two water distilling apparatus (III) and (IV) and optional other mixing equipment (V) and optional gas distillation unit (VI).There is enough purity products as long as can access, can also replace described distillation unit (III) to (VI) with any other distillation cell arrangement of different quantities
According to rotation fixed-bed reactor of the present invention, the excess isocyanate 13 of vulcabond and/or polymeric polyisocyanate material stream 1 and diamines material stream 2 and solvent streams 9 and recirculation---material stream 1 and/or 13 wherein optionally mixes with catalyzer 15---is mutually mixed in mixing equipment (I).In the case, fresh solvent streams 8 can reduce or be set as possibly zero significantly.
Preferably diamines as material stream 17 but not material stream 2 with the solvent 7 of recirculation, in combined upstream unit (V), mix, and using this mixture as expecting that flowing 9 is fed in mixed cell (I).In the case, material stream 2 is zero.
Then, add at least one reaction unit (II) by the diamines obtained in mixed cell (I) with the mixture of vulcabond and/or polymeric polyisocyanate and it is reacted and generate the polymeric polyisocyanate that contains biuret group.
In a specific embodiment, between mixing equipment (I) and reaction unit (II) or more preferably do not carry out the most possible cooling in reaction unit.This selects in order to reduce deposition higher than 190 ℃, especially necessary during particularly higher than the temperature of 200 ℃-270 ℃ in mixing device (I); In the case, for preventing colour generation and, for security consideration (automatic heating decomposition), should keep as far as possible shorter cooling time.
In further specific embodiment, the part isocyanate component is introduced between mixing equipment (I) and reaction unit (II) or preferably introduced in reaction unit (II).The advantage of doing like this is, in the situation that the temperature in mixing section is relatively high, does not need whole isocyanate components all is heated to high temperature, or can be undertaken cooling by second Arius.In addition, when using catalyzer, the advantage of doing like this is, the catalyst concn higher (constant density of catalyst residue amount in final product) in the mixing process in mixing equipment at isocyanic ester and amine component.
Then the reaction mixture 4 obtained being fed to the first distillation unit (III)---wherein excessive vulcabond is separated together with the low material stream 5 that boils with solvent.
Distillation unit (III) can have one or more theoretical trays; Preferably there is multistage theoretical tray, preferably at least two-stage, particularly preferably at least three grades, very particularly preferably at least flasher, falling-film evaporator, thin-film evaporator and/or the short-path evaporator of level Four series connection.
From the effluent 6 required product for containing the biuret group polymeric polyisocyanate of distillation unit (III), it can further be processed and usually without other purifying.
Then, the steam that will distill unit (III) discharge---contains excessive vulcabond and solvent---and is fed to other distillation unit (IV), wherein, solvent (preferably having the boiling point lower than vulcabond) is separated from the excess diisocyanate as bottom stream 10 as the low material stream 7 that boils of gaseous state.
Distillation unit (IV) is for example to have the distillation unit of individual, preferred 10-30 the theoretical plate number of 5-40.
In order to remove the impurity of the relative high molecular contained in excess diisocyanate from bottom stream 10, this material stream optionally can be introduced to preferred multi-step evaporator (VI), for example introduce falling-film evaporator.Purified vulcabond 13 is discharged from top, then optionally with catalyzer 15, mixes and is fed to mixed cell (I), bottom stream 14 is abandoned simultaneously.
In a preferred embodiment, at evaporation element (VI) while existing, directly new vulcabond and/or polymeric polyisocyanate are not fed to mixed cell via material stream 1, but are mixed with material stream 10 it as material stream 11, then this mixture 12 is distilled.This distillation to new vulcabond charging realizes that product is in the particularly improvement on quality of colour qualitatively usually.
Another preferred embodiment as shown in Figure 3, and is different from the embodiment shown in Fig. 2 on distillation unit (III) and arranging (IV):
In this embodiment, the reaction mixture 4 that at first will derive from reaction unit (II) is fed to preferably has 5-40, the distillation unit (IV) that particularly preferably there is 10-30 theoretical tray, solvent 7 is separated as low-boiling-point substance, and the material stream 15 of the polymeric polyisocyanate that will comprise excess diisocyanate and contain biuret group is discharged in bottom, and preferably charging is most multistage, preferred two-stage at least, particularly preferably at least three grades, the flasher that very preferably at least level Four is connected, falling-film evaporator, the distillation unit (III) of thin-film evaporator and/or short-path evaporator.
Wherein, excessive vulcabond is discharged and recirculation as mentioned above as steam 10, and the polymeric polyisocyanate 6 that will contain biuret group is discharged as bottom stream.
In a preferred embodiment, the recycle stream of isocyanic ester and new (ring) aliphatic vulcabond charging are merged.
In a preferred simplified embodiment, the distillation plant IV in Fig. 2 be can save, and can rotation fixed-bed reactor or (ring) aliphatic vulcabond and/or polymeric polyisocyanate material stream 1 be introduced with separating of solvent without (ring) aliphatic vulcabond by distillating material stream 5.
In a preferred embodiment, solvent streams is introduced to (ring) aliphatic vulcabond and/or polymeric polyisocyanate material stream 1 and/or (ring) aliphatic diamine material stream 2 and/or material stream 15(catalyzer).
In a preferred embodiment, do not use solvent, vulcabond is separated in water distilling apparatus (III) from biuret, mix with new vulcabond and/or polymeric polyisocyanate, optionally add catalyzer and this material stream and diamines material stream are introduced to the rotation fixed-bed reactor independently.
Preferably optional catalyzer is added in vulcabond and/or polymeric polyisocyanate material stream rather than add separately.
In another embodiment, only catalyzer is added to the downstream that rotates fixed-bed reactor and the upstream of reaction unit.
Method of the present invention provides transparent products usually, its have according to DIN ISO6271 lower than 100APHA, preferably lower than 50APHA, particularly preferably lower than the colour of 20APHA, and/or according to the DIN53019Part1(rotational viscosimeter) 23 ℃ under be 1000-15000mPas, the preferred viscosity of 1000-10000mPas.
Especially, it is that 2000-15000mPas, preferred 2500-10000mPas(are 100% based on solids content that topcoating industry needs viscosity, under 23 ℃, measures, and shearing rate is 100s
-1) the polyisocyanate of biuret-containing group.If necessary, can be with this polymeric polyisocyanate of solvent cut, available above-mentioned solvent cut for example, solvent ethyl acetate, butylacetate, acetic acid methoxyl group propyl ester, dimethylbenzene and containing the mixture of the aromatic substance of 8-20 carbon atom, and their mixture.
Except the polymeric polyisocyanate of biuret-containing group, the polymeric polyisocyanate that contains urea diketone (uretdione) and/or carbodiimide group and/or isocyanuric acid ester that can also comprise small amount, and, under alcohol exists, also can comprise the polymeric polyisocyanate that contains allophanate (allophanate) group.
Because method of the present invention is in the situation that not moisture or release hydrate and carry out, do not generate carbonic acid gas (CO in the inventive method
2), it can be partly dissolved in reaction mixture and/or can partly form the gas phase except reaction mixes.
Owing to there not being carbonic acid gas in reaction mixture, do not generate the polymeric polyisocyanate containing oxadiazines three ketone groups.Generally speaking, the ratio that contains the polymeric polyisocyanate of oxadiazines three ketone groups in reaction mixture of the present invention is lower than 1 % by weight, preferably lower than 0.75 % by weight, particularly preferably lower than 0.5 % by weight, very particularly preferably lower than 0.3 % by weight and particularly lower than 0.1 % by weight.
The polymeric polyisocyanate that contains biuret group that can be obtained by method of the present invention can also then reversibly be protected by protecting group.
The polymeric polyisocyanate that contains biuret group that can be obtained by method of the present invention is used in topcoating industry usually, and can be used in the coating composition of single component for example or bicomponent polyurethane coating, for example, in the industrial surface coatings art, particularly at flyer, the top coat of boats and ships or oversize vehicle, the top coat of aerogenerator, the top coat of timber or plastics, in the top coat of automobile (particularly OEM coating or automobile reparation) or decorative surface coating, for priming paint, surfacer (primer-surfacer), bottom, uncoloured finishing coat (topcoats), painted finishing coat and transparent varnish.Coating composition is particularly suitable for needing the application of extra high application reliability, outside weathering resistance, photostabilization, solvent resistance and/or chemical-resistant.Curing not obvious for the coating composition of the object of the invention.In automotive industry, carry out multiple layers of cured especially, for example the multiple layers of cured of transparent surface coating and bottom (being called two-in-one) or surfacer, transparent surface coating and bottom (being called three-in-one) increases day by day.
Reference symbol in Fig. 1
1 introduce liquid (ring) aliphatic vulcabond and/or polymeric polyisocyanate a) with (ring) aliphatic diamine b)
2 fillers/rotor
3 shells
4 pneumatic outlets (via tubular shaft)
5 liquid exits
6 drive shafts
7 gas inletes (for example rare gas element)
R
1: the shell radius
R
2: the outside radius between turning axle and filler, the thickness of mixing region
R
3: the inside radius between turning axle and filler
H
1: outer cover height
H
2: packed height
The reference symbol of Fig. 2 and Fig. 3
1: introduce liquid (ring) aliphatic vulcabond and/or polymeric polyisocyanate
2: introduce liquid (ring) aliphatic diamine
3: (ring) aliphatic vulcabond between rotation fixed-bed reactor and reaction unit and/or the reaction mixture of polymeric polyisocyanate and (ring) aliphatic diamine
4: at (ring) aliphatic vulcabond in reaction unit downstream and/or the reaction mixture of polymeric polyisocyanate and (ring) aliphatic diamine
5: by the overhead product of (ring) aliphatic vulcabond and solvent composition
6: the polymeric polyisocyanate of biuret-containing
7: recirculation solvent (optional)
8: novel solvent (optional)
9: introduce liquid solvent (optional)
10: from (ring) aliphatic vulcabond, separate (ring) aliphatic vulcabond with solvent
11: new (ring) aliphatic vulcabond and/or polymeric polyisocyanate
12: redistilled (ring) aliphatic vulcabond or new (ring) aliphatic vulcabond and/or polymeric polyisocyanate and the mixture with (ring) aliphatic vulcabond separated solvent from (ring) aliphatic vulcabond
13: (ring) aliphatic vulcabond of recirculation
14: isolated distillation residue in the vulcabond still-process
15: catalyzer (optional)
16: catalyzer (optional)
The 17:(ring) aliphatic diamine
(I): the rotation fixed-bed reactor
(II): reaction unit
(III): for separating of the distillation plant of (ring) aliphatic vulcabond (optional solvent) and the polymeric polyisocyanate 6 that contains biuret
(IV): distillation plant
(V): for the mixing equipment of solvent
(VI): distillation plant
Claims (18)
1. the method for a polymeric polyisocyanate that contains biuret group by the preparation of following material
A) at least one (ring) aliphatic vulcabond and/or polymeric polyisocyanate,
B) at least one (ring) aliphatic diamine that contains two primary aminos and/or secondary amino group,
C) optionally at least one acid and
D) at least one solvent optionally,
E) optionally at water or at least one, release under the hydrate existence, and
F) optionally at least one is selected from following stablizer: urea, ammonia, biuret, urea derivatives and methane amide,
I) by component a), b) and optional c) and optional d) and/or e) and/or f) in mixing equipment, mix, and
Ii) will derive from i) reaction mixture feed at least one wherein said reaction mixture reaction unit of heat-treating in,
Wherein said mixing equipment has at least rotation fixed-bed reactor of the acceleration effect of 100g at least one to liquid phase in mixing equipment.
2. method according to claim 1, wherein said (ring) aliphatic vulcabond and/or polymeric polyisocyanate are selected from tetramethylene diisocyanate, hexamethylene diisocyanate (1,6-, bis-isocyanato-hexanes), eight methylene diisocyanates, the decamethylene vulcabond, ten dimethylene diisocyanates, ten tetramethylene diisocyanate, the derivative of lysinediisocyanate, the tetramethyl-eylylene diisocyanate, 2,4,4-trimethyl cyclohexane vulcabond and/or 2,2,4-trimethyl cyclohexane vulcabond, the tetramethyl-hexane diisocyanate, Isosorbide-5-Nitrae-bis-isocyanato-hexane, 1,3-, bis-isocyanato-hexanes or the diisocyanate based hexane of 1,2-, 4,4 '-bis-(isocyanato-cyclohexyl) methane or 2,4 '-bis-(isocyanate group cyclohexyl) methane, 1-isocyano--3,3,5-trimethylammonium-5-(isocyanato-methyl) hexanaphthene (different Buddhist ketone vulcabond), 1,3-bis-(isocyanato-methyl) hexanaphthene or 1,4-bis-(isocyanato-methyl) hexanaphthene and 2,4-bis-isocyanato-s-1-methylcyclohexane and composition thereof, particularly hexamethylene diisocyanate (1,6-, bis-isocyanato-hexanes) and different Buddhist ketone vulcabond.
3. according to the described method of above-mentioned any one claim, wherein said (ring) aliphatic diamine is selected from 1，2-diaminoethane, 1，2-diaminopropane, 1,3-diaminopropanes, 1,3-diaminostilbene, the 1-dimethylpropane, 1,3-diamino-2, the 2-dimethylpropane, 1,4-Diaminobutane, 1,5-1,5-DAP, the neopentane diamines, 1,5-diamino-2-methylpentane, 1，6-diaminohexane, 1,6-diamino-2,2,4-trimethyl cyclohexane and/or 1,6-diamino-2,4,4-trimethyl cyclohexane, Isosorbide-5-Nitrae-diamino hexane and/or 1,5-diamino hexane, 1,1-bis-(amino methyl) pentamethylene, 2,4--diaminostilbene-methylcyclohexane and/or 2,6-diaminostilbene-methylcyclohexane, 1-amino-3,3,5-trimethylammonium-5-amino methyl hexanaphthene (different Buddhist ketone diamines), 1,2-bis-(amino methyl)-4-methylcyclohexane, 1,8-diamino-octane, 1,3-bis-(amino methyl) hexanaphthene and/or Isosorbide-5-Nitrae-bis-(amino methyl) hexanaphthene, 4,4'-diamino-dicyclohexyl methane, 3,3 '-dimethyl-4,4 '-diamino-dicyclohexyl methane, inferior diphenyl-methyl diamines of tetramethyl-(TMXDA) and composition thereof, and particularly 1，6-diaminohexane and different Buddhist ketone diamines.
4. according to the described method of above-mentioned any one claim, wherein said component is a) hexamethylene diisocyanate (1,6-bis-isocyanide roots close hexane) and described components b) be 1, the 6-diamino hexane, or described component is a) different Buddhist ketone vulcabond and components b) be different Buddhist ketone diamines, or described component is a) hexamethylene diisocyanate and components b) be different Buddhist ketone diamines or cycloaliphatic diamine.
5. according to the described method of above-mentioned any one claim, wherein component a) and b) amine based on different in form.
6. according to the described method of above-mentioned any one claim, wherein isocyanate groups described in the reaction and amino equivalence ratio are 4:1 at least.
7. according to the described method of above-mentioned any one claim, wherein use the protonic acid of pKa<10 as catalyzer c).
8. method according to claim 7, wherein said sour c) be di(2-ethylhexyl)phosphate isopropyl esters, di(2-ethylhexyl)phosphate (2-ethylhexyl) ester, di(2-ethylhexyl)phosphate (normal-butyl) ester and phosphoric acid double hexadecyl ester.
9. method according to claim 7, wherein introduce isocyanic ester material stream by described acid.
10. according to the described method of above-mentioned any one claim, wherein conversion unit ii) in the residence time be 15 minutes to 8 hours.
11. according to the described method of above-mentioned any one claim, wherein have at least one solvent d).
12. method according to claim 9, wherein said solvent d) be selected from ether, You Xuan diox, tetrahydrofuran (THF); Alkoxyalkyl carboxylicesters, preferably oxalic acid triglycol ester, ethyl acetate, butylacetate, acetic acid 1-methoxy-propyl-2-ester, acetic acid methoxy ethyl-2-ester, propylene glycol diacetate; Ketone, preferably 2-butanone, 4-methyl-2 pentanone, pimelinketone; Hexane, toluene, dimethylbenzene, containing aromatic mixtures, chlorobenzene, orthodichlorobenzene, trialkyl phosphine acid esters and N-(ring) alkyl pyrrolidine of 8-20 carbon atom.
13. according to the described method of above-mentioned any one claim, the downstream of wherein part of the isocyanic ester material of described (ring) aliphatic vulcabond and/or polymeric polyisocyanate (a) stream only being introduced to mixing equipment (I).
14., according to the described method of above-mentioned any one claim, the temperature in wherein said mixing equipment (I) and described reaction unit (II) is lower than 200 ℃.
15. according to the described method of above-mentioned any one claim, the temperature in wherein said mixing equipment (I) higher than the temperature in 200 ℃ and reaction unit (II) lower than 200 ℃.
16. the polymeric polyisocyanate that contains biuret group obtained according to above-mentioned any one claim, its colour according to DIN ISO6271 is lower than 100APHA.
17., according to the described polymeric polyisocyanate that contains biuret group of claim 16, it is 1000-15000mPas according to the viscosity of DIN53019 first part (rotational viscosimeter) under 23 ℃.
18. according to any one claim in claim 16-17 or the purposes of the polymeric polyisocyanate that contains biuret group that obtain according to any one claim in claim 1-15 in coating composition, described coating composition is for single component or bicomponent polyurethane coating, flyer for the industrial surface coatings art, the top coat of boats and ships or oversize vehicle, the top coat of aerogenerator, the top coat of timber or plastics, the top coat of automobile, in OEM coating or automobile reparation as priming paint, filler, bottom, uncoloured finishing coat, painted finishing coat and transparent varnish.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP11156783 | 2011-03-03 | ||
| EP11156783.0 | 2011-03-03 | ||
| PCT/EP2012/053660 WO2012117099A1 (en) | 2011-03-03 | 2012-03-02 | Process for preparing polyisocyanates containing biuret groups |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103402978A true CN103402978A (en) | 2013-11-20 |
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ID=45815528
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| CN2012800112932A Pending CN103402978A (en) | 2011-03-03 | 2012-03-02 | Process for preparing polyisocyanates containing biuret groups |
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| Country | Link |
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| EP (1) | EP2681189A1 (en) |
| CN (1) | CN103402978A (en) |
| WO (1) | WO2012117099A1 (en) |
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| CN103724234A (en) * | 2014-01-03 | 2014-04-16 | 万华化学集团股份有限公司 | Method for preparing polyisocyanate containing biuret |
| CN105601565A (en) * | 2014-11-20 | 2016-05-25 | 万华化学集团股份有限公司 | Method for preparing polyisocyanate containing biuret structure with stable storage |
| CN108559048A (en) * | 2018-04-19 | 2018-09-21 | 山东师范大学 | A kind of pH sensitive biodegradable polyurethane urea material and preparation method thereof |
| CN108586293A (en) * | 2018-04-19 | 2018-09-28 | 济南羽时信息科技有限公司 | A kind of biodegradable high intensity polyurethane polyetherester urea foam and preparation method thereof |
| CN110023431A (en) * | 2016-10-07 | 2019-07-16 | 巴斯夫欧洲公司 | The method for preparing the polyisocyanate of (ring) aliphatic vulcabond for flocculating in a solvent stable |
| CN110483337A (en) * | 2018-05-14 | 2019-11-22 | 中国科学院过程工程研究所 | A kind of separation and purification system and method for benzene dimethylene diisocyanate product |
| CN111171893A (en) * | 2018-11-13 | 2020-05-19 | 中国石油天然气股份有限公司 | Preparation method of polyurea lubricating grease |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8933262B2 (en) | 2011-05-24 | 2015-01-13 | Basf Se | Process for preparing polyisocyanates from biomass |
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|---|---|---|---|---|
| CN103724234A (en) * | 2014-01-03 | 2014-04-16 | 万华化学集团股份有限公司 | Method for preparing polyisocyanate containing biuret |
| CN103724234B (en) * | 2014-01-03 | 2015-07-15 | 万华化学集团股份有限公司 | Method for preparing polyisocyanate containing biuret |
| CN105601565A (en) * | 2014-11-20 | 2016-05-25 | 万华化学集团股份有限公司 | Method for preparing polyisocyanate containing biuret structure with stable storage |
| CN105601565B (en) * | 2014-11-20 | 2018-05-15 | 万华化学集团股份有限公司 | A kind of preparation method of the polyisocyanates of the biuret-containing structure of stable storage |
| CN110023431A (en) * | 2016-10-07 | 2019-07-16 | 巴斯夫欧洲公司 | The method for preparing the polyisocyanate of (ring) aliphatic vulcabond for flocculating in a solvent stable |
| CN110023431B (en) * | 2016-10-07 | 2021-09-03 | 巴斯夫欧洲公司 | Process for preparing polyisocyanates which are flocculation-stable in solvents |
| CN108586293A (en) * | 2018-04-19 | 2018-09-28 | 济南羽时信息科技有限公司 | A kind of biodegradable high intensity polyurethane polyetherester urea foam and preparation method thereof |
| CN108559048A (en) * | 2018-04-19 | 2018-09-21 | 山东师范大学 | A kind of pH sensitive biodegradable polyurethane urea material and preparation method thereof |
| CN108586293B (en) * | 2018-04-19 | 2020-07-14 | 济南羽时信息科技有限公司 | Biodegradable high-strength polyether ester type polyurethane urea foam and preparation method thereof |
| CN108559048B (en) * | 2018-04-19 | 2021-01-08 | 山东师范大学 | PH value sensitive biodegradable polyurethane urea material and preparation method thereof |
| CN110483337A (en) * | 2018-05-14 | 2019-11-22 | 中国科学院过程工程研究所 | A kind of separation and purification system and method for benzene dimethylene diisocyanate product |
| CN110483337B (en) * | 2018-05-14 | 2020-08-28 | 中国科学院过程工程研究所 | System and method for separating and refining xylylene diisocyanate product |
| CN111171893A (en) * | 2018-11-13 | 2020-05-19 | 中国石油天然气股份有限公司 | Preparation method of polyurea lubricating grease |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012117099A1 (en) | 2012-09-07 |
| EP2681189A1 (en) | 2014-01-08 |
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