CN1181765A - Process for preparing a storage-stable mixture of polyisocyanate and phosphate - Google Patents
Process for preparing a storage-stable mixture of polyisocyanate and phosphate Download PDFInfo
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- CN1181765A CN1181765A CN96193363A CN96193363A CN1181765A CN 1181765 A CN1181765 A CN 1181765A CN 96193363 A CN96193363 A CN 96193363A CN 96193363 A CN96193363 A CN 96193363A CN 1181765 A CN1181765 A CN 1181765A
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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
- C08G18/776—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur phosphorus
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
- C08G18/3882—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having phosphorus bound to oxygen only
- C08G18/3885—Phosphate compounds
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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
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Materials For Medical Uses (AREA)
- Paints Or Removers (AREA)
Abstract
A process of the invention for preparing a liquid, storage-stable composition containing an organic polyisocyanate and an acid phosphate is disclosed. The process includes the following steps of (1) heating a mixture of a polyisocyanate and an acid phosphate at a temperature in the range of from 60 DEG C to 190 DEG C for a time such that no phase separation occurs upon cooling the reaction mixture to ambient temperature, the mixture containing dissolved gases; and (2) subjecting the mixture to a negative pressure sufficient to remove at least a portion of the dissolved gases therefrom. The negative pressurization significantly slows the rate of carbon dioxide evolution thereafter and therefore enables much longer term storage-stability than is obtainable when the negative pressurization step is not performed, beacause it reduces problems associated with pressurization of containers.
Description
The present invention relates to the field of the polyisocyanates and the phosphate mixture in polyisocyanates field, particularly storage-stable.
The mixture of known polyisocyanates and phosphoric acid ester has various different purposes.For example, it can be used as the binder resin that Wood composite material is had the character peeled off.When making shaving board and analog material, these polyisocyanate mixtures are particularly useful as tackiness agent.For example can be referring to United States Patent (USP) U.S.3,428,592; 3,440,189; 3,557,263; 3,636,199; 3,870,665; 3,919,017 and 3,930,110.Although some kinds in these mixtures can be accomplished storage-stable relatively, they can not deposit solid or (for example be divided into two kinds of liquid phases in short relatively period, can be referring to United States Patent (USP) U.S.4,258,169, Re.31,703 and Japanese Patent JP618469), regrettably, they still have the trend that produces carbonic acid gas to cross certain hour, and it can bring some problems in the standing storage process.For large-scale shipment, for example with the railcar shipment, the generation of carbonic acid gas can utilize snifting valve to control; But when loading and transporting on a small scale, the solution of problem is just very difficult, and during for example with bucket or small vessels shipment, they are not equipped with snifting valve usually, so may be because of the supercharging explosion.
The invention solves the supercharging problem of container.The present invention has improved the polyisocyanates of producing storage-stable and the method for phosphate ester acid mixture, and wherein this mixture has gas dissolved, and it comprises mixture is placed the time that keeps being enough to remove at least a part of gas dissolved under the negative pressure.Comparatively preferably gas dissolved is reduced by at least 10% (weight).And find, this air-exhaust method preferably is enough to remove at least 90% gas dissolved in the mixture, comparatively preferably is at least time of 99% under the vacuum of pressure less than 50 mmhg (2 inch of mercury), mixture obviously shows gas generated decline as a result.This invention thereby alleviate or the small vessels pressure having eliminated those and be used to load and transport and store this mixture increases relevant problem.
Among the present invention the mixture of used polyisocyanates/P contained compound can from plurality of raw materials with prepare through different routes.For example in one embodiment of the invention, starting raw material comprises one or more P contained compounds that original position produces, and when this material will contact with special metal is surperficial, it can be used as stripper.It is the starting raw material preparation with polyisocyanates and phosphate ester acid.Here preferably the polyisocyanates of organic multiple isocyanate and corresponding 100 parts of weight is the mixture of 1 to 20 part phosphate ester acid, also can use the mixture of two or more phosphate ester acids, this phosphate ester acid is selected from the compound that following structural formula is represented:
In the structural formula, R selects from following groups independently: the aryl that contains the alkyl of at least 3 carbon, the alkenyl that contains at least 3 carbon, aryl, replaced by at least one alkyl, the alkyl (acyl group wherein is for containing the residue of the fatty monocarboxylic acid of two carbon at least) and the following group of structure that are replaced by at least one acyloxy:
R in the following formula
1Select the aryl that can replace from alkyl, aryl with by at least one alkyl, represent hydrogen for one among A and the B, another is selected in 2-three chloroethyls from hydrogen, methyl, chloromethyl and 2,2; The chalcogen of X for from oxygen and sulphur, selecting; M is that mean value is the number of 1-25.
When the above-mentioned initiator of definition, term " alkyl that contains at least three carbon " means saturated unit price aliphatic group, straight chain or side chain, and have at least three carbon atoms in the molecule.The example of these groups has: propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl and those have group such as triacontyl, tetracontyl and the isomeric form thereof of more carbon atoms.The term " alkyl " that uses is if not mentioned carbonatoms also comprises methyl and ethyl naturally.
Term " alkenyl that contains at least three carbon " means unit price straight or branched aliphatic group, and it contains two keys at least and contain at least three carbon atoms in molecule.For example allyl group, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonene base, decene base, undecenyl, dodecenyl succinic, tridecylene base, tetradecene base, 15 carbene bases, cetene base, heptadecene base, vaccenic acid base, 19 carbene bases, eicosylene base, heneicosene base, two dodecenyl succinic, tricosene base, tetracosa carbon thiazolinyl, triacontylene base, 35 carbene bases also comprise its isomer.
Term " aryl " refers to remove a resulting univalent perssad of hydrogen atom from aromatic hydrocarbon.For example phenyl, naphthyl, xenyl, terphenyl.Term " aryl that is replaced by at least one alkyl " refers to aforesaid aryl, has at least one alkyl (as mentioned above) substituting group.For example tolyl, xylyl, butylbenzene base, hot phenyl, nonyl phenyl, the last of the ten Heavenly stems phenyl, the last of the ten Heavenly stems tolyl, octadecyl phenyl.
Term " the fatty monocarboxylic acid that contains two carbon at least " refers to contain the paraffinic acid or the alkenoic acid of at least two carbon atoms.For example acetate, propionic acid, butyric acid, caproic acid, sad, lauric acid, stearic acid, oleic acid, undecylenic acid, dodecenoic acid, iso-crotonic acid, palmitinic acid.
The molecular formula of setting forth above (I) and (II) in each radicals R and R
1Can be replaced by one or more inert substituents arbitrarily, promptly do not contained reactive hydrogen atom thereby nonreactive substituting group replacement when polyisocyanates exists.This class substituted radical such as alkoxyl group, dialkyl group sulfydryl, alkenyloxy, two alkene sulfydryls, chlorine, bromine, iodine, fluorine, cyano group.
Molecular formula (I) and phosphate ester acid (II) mostly are greatly to be known in this area, and available method preparation as known in the art.For example, phosphate ester acid (I) and (II) can utilize Kosolapof at " organo phosphorous compounds (Organophosphorus Compounds) " (John Wiley and Sons with Vanadium Pentoxide in FLAKES or oxygen phosphoric sulfide by corresponding alcohol or mercaptan R-XH (R and X are as previously mentioned), Inc, NewYork, 1950) the described method prepared in reaction of 220-221 page or leaf.Carry out this reaction and obtain list or bisgallic acid formula phosphoric acid ester, need, mixture can be separated, for example, and can be saloid by their barium salt of method fractional crystallization and the class of top document description.The list and the bisgallic acid formula phosphoric acid ester that obtain according to above-mentioned reaction can be used as starting raw material of the present invention.
In the presence of organic multiple isocyanate, the heating phosphate ester acid, no matter have or not other reactants such as phosphoryl chloride, phosgene and analogue, all molecular formula might be changed into the product that contains corresponding pyrophosphate and sulfur containing analogs such as thiophosphatephosphorothioate and burnt thiophosphatephosphorothioate for (I) and phosphate ester acid (II).If press hereinafter described careful control heating condition, but product is the homogeneous liquid that a standing storage does not have any trend that is separated.
At United States Patent (USP) U.S.4,258,169, Re.31,703 and the disclosure of Japanese Patent JP618469 before, this result of condition who exists some may cause forming the phase stable product is beat all.The previous prediction molecular formula may be reacted by following equation for (I) or phosphate ester acid (II) and organic isocyanate, wherein R as mentioned above, R represent the residue of organic isocyanate, from the simplicity consideration, the latter is expressed as monomeric form:
Think that reaction will form pyrophosphate and some polyphosphates (if having monoesters to exist) of expection.Reaction expection simultaneously can form amine (IV) intermediate corresponding to initial isocyanic ester.Amine (IV) expection can be immediately forms urea with extra isocyanate reaction.If usefulness is polyisocyanates, can form polyureas, under the normal circumstances, it should be insoluble to the product of reaction, can come with isolated in solid form immediately or after placing for some time.
When temperature was lower than 60 ℃, above-mentioned situation had appearred in phosphate ester acid (I) or (II) and organic multiple isocyanate reaction really.When being lower than 190 ℃, when finding to reduce to room temperature (15-25 ℃), even long-time the placement do not deposit solid product yet but if temperature of reaction is higher than said temperature.
Yet, temperature of reaction and not exclusive important factor.Heat-up time is also very important, is generally the improvement of the phase stability of guaranteeing reaction product, and temperature of reaction is high more, and the time of heating is just short more.For example, even when temperature of reaction was low to moderate 60 ℃, heat-up time was also restricted, and the further heating of overtime can cause pyrophosphate to be converted into those be sure oing it is the compound of higher poly phosphate.When the part of occupying in reaction product as the latter reached sufficiently high level, with the postcooling reaction product, poly phosphate came out with the immiscible liquid layer isolated in form of polyisocyanates with one usually.Furtherly, there is not the conversion of top said pyrophosphate, high more temperature of reaction, the time that phosphate ester acid and polyisocyanates reaction allow is just short more.
The minimum value of being carried above temperature is lower than has perhaps surpassed in the time of can obtaining the time of homogeneous liquid product heat-up time, and the complete chemical constitution of the resultant product that is separated is not accurately known, but this is to understanding the present invention and not really important.Only as explaining, the by product that it is mentioned above no matter being understood to obtains whether proving conclusively in above-mentioned discussion, and scope of the present invention and meaning are not limited to these situations.
The time of this method recited above can change with polyisocyanates and the different of used phosphate ester acid concentration with specific phosphate ester acid with temperature.The suitable time under a certain particular case is easy to by testing definite.When usually the reaction times can be from 60 ℃ several hours drop to temperature range top value (190 ℃) one minute or shorter.As previously mentioned, used temperature is high more, and the reaction times should be short more, in order to avoid produce unfavorable result.
According to the present invention, the mode that phosphate ester acid and organic multiple isocyanate are mixed can influence the production ability of stable composition mutually to a certain extent.Be in a usual manner under many situations, at room temperature two reactants mixed that then at said temperature scope internal heating mixture, heat-up time, scope was to determine according to obtained desired result under the selective reaction temperature.But preferred elder generation is preheating to selected temperature of reaction with polyisocyanates, adds phosphate ester acid then in the polyisocyanates of preheating.When operation is carried out in batches, can take disposable charging to add mode or interior slow adding mode of for some time.
The inventive method also can take continuous mode to implement, polyisocyanates (preferred preheating) and the phosphate ester acid heating region of flowing through, and heating region keeps as preceding having determined the temperature of scope.Adjust the mixture by heating region flow velocity so that its residence time in the mixing zone corresponding with the reaction times of selection.Various conventional equipments can be used for this purpose.A kind of useful especially device is therein mixture to be heated form with film to be dispersed throughout on the wall of well heater.Typical example of this device such as United States Patent (USP) U.S.No.2, illustrated in 927,634.In another embodiment, polyisocyanates (preferred preheating) and phosphate ester acid are fed in the stirred reactor with a suitable ratio continuously, and reactant remains on temperature required in the reactor.Reaction mixture is to emit from reactor with the same rate mutually that the new reaction agent adds, and control adds consistent with the reaction times of selection with the residence time that guarantees mixture in reactor with the opportunity of the material of emitting.When the preparation mixture, carbonic acid gas is emitted continuously.
No matter the inventive method is to carry out, all to wish to be reflected under anaerobic and the no moisture and carry out in batches or in a continuous manner, and is promptly the same with the operation of usually conduct polyisocyanates, under rare gas element such as nitrogen, carry out.For example may need inert gas environment like this or blow with rare gas element.Thereby no matter reaction is to carry out in nitrogen or in the air, it is saturated that situation all is that final mixture is mainly contained the gas dissolved institute of the carbonic acid gas of emitting.Yet if blow with nitrogen, mixture will mainly contain nitrogen, because the carbon dioxide that nitrogen is emitted polyisocyanates and phosphate ester acid reaction has been driven away.In certain embodiments, other gases also might exist on a small quantity.
Used polyisocyanates and phosphate ester acid (I) and ratio (II) can change in a big way in the inventive method, are favourable but adopt the phosphate ester acid with respect to 1 to 20 part of weight of 100 parts of heavy polyisocyanates.In a preferred embodiment, the consumption of phosphate ester acid is by containing from 0.1, be preferably from 3 in the polyisocyantates composition produced according to the invention, to 15, preferably to 10, the optimum phosphate ester acid of choosing 8 weight percents determines.
The polyisocyanates of using in the inventive method can be any organic multiple isocyanate that contains at least two isocyanate group in the per molecule.The example of organic multiple isocyanate have diphenylmethanediisocyanate ,-and right-phenylene vulcabond, chlorine phenylene vulcabond, α, α-eylylene diisocyanate, 2,4-and 2,6-inferior cresyl vulcabond and can buy the above-mentioned back two kinds of mixture of isomers that obtain, comprise triphenylmethane triisocyanate, 4,4-two isocyanato-diphenyl ether and poly methylene poly phenyl poly isocyanates.A kind of polyisocyanates in back is for containing the mixture of 25 to 90 weight percent methylene-biss (phenyl isocyanate), and the mixture rest part is a functionality greater than 2.0 poly methylene poly phenyl poly isocyanate.These polyisocyanates and its preparation method all are as known in the art, for example referring to United States Patent (USP) U.S.Nos.2,683,730; 2,950,263; 3,12,008 and 3,097,191.
These polyisocyanates of back also can various modified form obtain.A kind of is the raw material that contains poly methylene poly phenyl poly isocyanate, it the excess temperature scope be 150 ℃ to 300 ℃ thermal treatments, increase to the value of scope between 800 to 1500 centipoises (cps) until its viscosity (25 ℃).Another kind of modified form is according to United States Patent (USP) U.S.No.3,793,362, and with the poly methylene poly phenyl poly isocyanate that a spot of epoxide was handled, this processing is used to reduce its acidity.Poly methylene poly phenyl poly isocyanate also can prepolymer and the quasi-prepolymer form use, be the product of polyisocyanates and a small amount of polyol reaction gained, also can come the form of partially end-blocked polyisocyanates to use by method as known in the art and monohydroxy-alcohol reaction.The methane diphenyl vulcabond of carbodiimide modification also can be used.
The inventive method is preferably used poly methylene poly phenyl poly isocyanate.The methylene-bis (phenyl isocyanate) that contains 35 to 65 weight percents in the preferred especially poly methylene poly phenyl poly isocyanate that uses.Also preferably use viscosity to be lower than 500 centipoises (cps), more preferably for being lower than 300cps, most preferably being the polyisocyanates that is lower than 200cps.
It is (I) and any phosphate ester acid (II) that the inventive method can be used molecular formula, but the R in the preferred formula represents alkyl or alkenyl, and X represents 0; Particularly R representative contains the alkyl of 8 to 18 carbon or alkenyl and X and represent 0 have and be easy to get and the cheap phosphate ester acid of superiority.Preferred especially use is selected from and contains C
8To C
18The mono phosphoric acid ester of alkyl and dibasic acid esters and composition thereof.
With regard to being separated, (this method has more detailed description in US4258169 and Re.31703 as stated above, these two pieces of documents are all incorporated this paper by reference into) available liquid polyisocyanate composition is more stable than those polyisocyanates of handling through this mode/phosphate mixtures storage usually, but it is from producing the carbonic acid gas aspect, and stability is still than poor by the mixture of the inventive method preparation.The present invention particularly influences the storage-stable this respect at carbonic acid gas.
Second step of the present invention has improved very effectively and has produced the relevant stability of carbonic acid gas, and soon mixture is handled being enough to remove under the negative pressure of at least a portion gas dissolved.In preferred embodiments, negative pressure is the vacuum that is enough to remove at least 10% gas dissolved, more preferably is at least 95%, most preferredly is at least 99%.For removing dissolved gases, preferred negative pressureization (vacuum tightness) is lower than 50 mmhg (2 inch of mercury), more preferably for being lower than 10 mmhg (0.4 inch of mercury) with realizing high level like this.Change according to the concentration that applies phosphate ester acid in negative pressure and the polyisocyanates working lipe that vacuumizes processing.But the time of negative pressureization preferably was at least 15 minutes, more preferably was at least 30 minutes, and most preferred is 1 to 3 hour.In an embodiment preferred, keep-uping pressure is lower than 10 mmhg (0.4 inch of mercury), continues the above-mentioned most preferred evacuation time.
The device of implementing negative pressureization comprises vacuum pump, injector, vent fan or other conventional equipments.
By the stable in storage polyisocyantates composition of the inventive method preparation as binding resin, in by this area currently known methods prepare aspect the shaving board particularly useful, existing narration in these documents that " background technology " part is quoted in the above.This composition used in the technology of the present invention has following advantage, bonding mutually in the time of can preventing shaving board and this sheet material of compacting between the metallic surface of used backing plate platform and pressing plate platform.For this special use, promptly as the binding resin of shaving board, wish but be not requisite be that polyisocyantates composition of the present invention has the range of viscosities of from 100 to 3000 centipoises (cps), is beneficial to its convenient processing in the device of producing shaving board.The viscosity of above-mentioned scope is easy to obtain by using initial viscosity to handle to the poly methylene poly phenyl poly isocyanate of the 1000cps order of magnitude and by the inventive method as 25cps.This also is another reason of using a kind of like this polyisocyanates in a preferred embodiment of the invention.
At polyisocyantates composition of the present invention during as the binding resin of preparation shaving board, before heating and pressurization, polyisocyantates composition can water miscible liquid or the dispersion form be applied on the shaving board bits.For being easy to its formation, wish to use a kind of emulsifying agent or dispersion agent.If necessary, this reagent can be incorporated in the polyisocyantates composition of the present invention, so that the shaving board producer need not to use extra reagent just can prepare required emulsion or dispersion.This reagent can be those emulsifying agent and dispersion agents known in the art, as to comprise negatively charged ion and non-ionic type.These reagent for example have, pure and mild two or more oxyethane, propylene oxide, butylene oxide ring and the cinnamic segmented copolymer of polyoxyethylene and polyoxypropylene; Alkoxylated alkyl group phenol gathers-(oxygen ethene) ethanol as Nonylphenoxy; Oxyalkylated lipidol is as ethoxylation and the propenoxylated lipidol that contains 4 to 18 carbon atoms; The glyceryl ester of saturated and unsaturated fatty acids is as the glyceryl ester of stearic acid, oleic acid and ricinoleate acid; The polyoxyalkylene esters of lipid acid is as the polyoxyalkylene esters of stearic acid, lauric acid, oleic acid and class acidoid; Fatty amide is as two alkanolamides of stearic acid, lauric acid, oleic acid and class acidoid; And sulfonate, vitriol, carboxylate salt and sarcosinate, as Sodium dodecylbenzene sulfonate, calcium dodecylbenzene sulphonate and sodium lauryl sulphate." chemical encyclopedia (Encyclopedia of ChemicalTechnology) " second edition (Interscience press, NewYork 1969) 19 volume 531-554 have detailed explanation to these raw materials.But as known in the art, the long-term storage stability of final composition may be destroyed because of the existence of specific salts in some cases.
The solvent or the thinner that contain non-reactive hydrogen optionally use.In the preferred embodiment of the invention, these raw materials that contain non-reactive hydrogen comprise the polyol and the monohydroxy compound of esterification.
The following examples have been described and have been used mode of the present invention and technology, have provided to realize best mode of the present invention.Yet they do not plan not should be understood on any degree to limit the scope of the invention yet.
Embodiment 1
With acid mono phosphoric acid ester and two lauryl ester mixture (TRYFAC*5573, Henkel company product) reacts as phosphate ester acid and polyisocyanates, this polyisocyanates is the poly methylene poly phenyl poly isocyanate (PAPI*27 of the methylene radical (phenyl isocyanate) that contains about 46.5 weight percents, Dow company product), and equivalent is 135.5, is 173cps during 25 ℃ of viscosity.Initial polyisocyanates is 900 pounds, joins in the stainless steel reactor that is equipped with stirring and nitrogen spray orifice.Be stirred and heated to 80 ℃, 32.6 pounds TRYFAC*5573 added the bubbling that the carbonic acid gas that produces with control causes with 5-10 minute interval.After adding TRYFAC*, react on 80 ℃ of heating 2 hours.Can be observed the bubbling of reaction mixture always.Reaction finishes the back and cuts off nitrogen gas stream, and (0-55mmHg, 0-2inHg), temperature remains on 80 ℃, then product is chilled to room temperature to apply vacuum.Then cut off vacuum, emit product, be stored in the stove in 43-49 ℃, the pressure change record is as shown in table 1.NCO content is 30.1 weight percents in the end product.Comparative examples A
For pressure in sample that when storage embodiment 1 is described and the comparative sample bucket advance the speed different, carried out following reaction, promptly with identical preparation method but do not experience this step of negative pressureization and prepare comparative sample (Comparative Example A An sample).
Be preparation Comparative Example A An sample, the TRYFAC*5573 of about 900 pounds of PAPI*27 and 3.5 weight percents was heated 2 hours in 80 ℃ under nitrogen.Product is not applied vacuum.Product is cooled to room temperature, puts into a heavy regular barrel (50 pounds pressure criteria per square inch), carries out about 12 days normal shipment.In the bucket pressure warning unit is housed.Put it in 60 ℃ the stove and carry out pressure change research.The outcome record of pressure change is in table 1 after for some time.
-expression is not fetched data
| The fate that begins one's study | Embodiment 1 sample psi pressure | Comparative examples A sample psi pressure |
| ????0 | ????0 | ????0.0 |
| ????2 | ????- | ????2.8 |
| ????6 | ????0 | ????3.5 |
| ????8 | ????- | ????4.3 |
| ????10 | ????- | ????5.3 |
| ????14 | ????0 | ????7.5 |
| ????20 | ????0 | ????- |
| ????37 | ????0 | ????- |
| ????69 | ????3 | ????- |
| ????97 | ????4 | ????- |
| ????132 | ????6 | ????- |
| ????160 | ????9 | ????- |
| ????199 | ????11 | ????- |
Claims (10)
1. method for preparing the polyisocyantates composition of liquid storage-stable, it comprises (1) mixture for some time at 60-190 ℃ of temperature range internal heating polyisocyanates and phosphate ester acid, no phenomenon of phase separation takes place after the room temperature so that reaction mixture is cooled to, and contains dissolved gases in the reaction mixture; (2) mixture is placed be enough to remove under the negative pressure of at least a portion gas dissolved.
2. the desired method of claim 1, wherein negative pressure is less than 50 mmhg.
3. the desired method of claim 2, wherein at least 95% gas dissolved is removed.
4. the desired method of claim 1, wherein negative pressure is less than 10 mmhg.
5. the desired method of claim 4, wherein at least 99% gas dissolved is removed.
6. the desired method of claim 1, wherein organic multiple isocyanate is a poly methylene poly phenyl poly isocyanate, phosphate ester acid is selected from and contains C
8To C
18The mono phosphoric acid ester of alkyl and two alkyl esters and composition thereof.
7. the desired method of claim 6, wherein phosphate ester acid is selected from acid phosphoric acid Lauryl Ester, phosphoric acid tridecyl ester, phosphoric acid decyl ester and composition thereof.
8. the desired method of claim 6, wherein the phosphate ester acid amount is 3 to 10 weight percents.
9. the desired method of claim 1, wherein polyisocyanates is the polyphenyl polymethylene polyisocyanates of viscosity less than 500 centipoises.
10. in the liquid polyisocyanate composition method of preparation storage-stable, contain the stripper that original position forms in the composition, this method is included in 60 to 190 ℃ temperature range internal heating one mixture, and this mixture contains organic multiple isocyanate and with respect to a kind of phosphate ester acid compound with following molecular formula of 1 to 20 part of weight of 100 parts of heavy polyisocyanates:
Also can be the mixture of two or more phosphate ester acids; R selects from following groups independently: the alkyl that contains at least 3 carbon atoms; the alkenyl that contains at least three carbon atoms; aryl; the aryl that is replaced by at least one alkyl; the alkyl that is replaced by at least one acyloxy, wherein acyl group for the residue of the mono carboxylic acid of aliphatic series that contains 2 carbon atoms at least and
R wherein
1From following groups, select: alkyl, aryl and the aryl that is replaced by at least one alkyl are represented hydrogen for one among A and the B, and another is selected in 2-three chloroethyls from hydrogen, methyl, chloromethyl, 2,2; X is the chalcogen of selecting in oxygen and the sulphur; M is that mean value is a number of 1 to 25; Heating for some time is not so that reaction mixture has phenomenon of phase separation during to room temperature takes place; Contain dissolved gases in the mixture; The improvement of this method comprises reaction mixture is placed this step under the negative pressure that is enough to remove at least a portion gas dissolved.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US42306095A | 1995-04-17 | 1995-04-17 | |
| US08/423,060 | 1995-04-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1181765A true CN1181765A (en) | 1998-05-13 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96193363A Pending CN1181765A (en) | 1995-04-17 | 1996-03-26 | Process for preparing a storage-stable mixture of polyisocyanate and phosphate |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0821706A1 (en) |
| JP (1) | JPH11503786A (en) |
| KR (1) | KR19990007809A (en) |
| CN (1) | CN1181765A (en) |
| AU (1) | AU5431996A (en) |
| BR (1) | BR9608163A (en) |
| CA (1) | CA2218254A1 (en) |
| CO (1) | CO4410409A1 (en) |
| MX (1) | MX9707969A (en) |
| NO (1) | NO974785D0 (en) |
| WO (1) | WO1996033231A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101190973B (en) * | 2006-11-10 | 2012-08-08 | 拜尔材料科学股份公司 | Plastic composite element and method for the production thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10046612A1 (en) * | 2000-09-20 | 2002-03-28 | Basf Ag | Reproducible production of purification agent comprises dissolving phosphoric acid and isocyanate and/or polyisocyanate in solvent |
| US20130245222A1 (en) * | 2012-03-15 | 2013-09-19 | Basf Se | Modified isocyanate compositions and mehtods of preparing the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE864326A (en) * | 1977-03-01 | 1978-08-28 | Asahi Chemical Ind | PROCESS FOR PREPARING AN ORGANIC POLYISOCYANATE |
| US4257995A (en) * | 1979-05-03 | 1981-03-24 | The Upjohn Company | Process for preparing particle board and polyisocyanate-phosphorus compound release agent composition therefor |
| US4258169A (en) * | 1980-03-26 | 1981-03-24 | The Upjohn Company | Polyisocyanate compositions containing in-situ formed pyrophosphate mold release agent and process of making |
| US4382108A (en) * | 1981-12-21 | 1983-05-03 | The Upjohn Company | Novel compositions and process |
-
1995
- 1995-06-23 CO CO95027884A patent/CO4410409A1/en unknown
-
1996
- 1996-03-26 CA CA002218254A patent/CA2218254A1/en not_active Abandoned
- 1996-03-26 JP JP8531745A patent/JPH11503786A/en active Pending
- 1996-03-26 MX MX9707969A patent/MX9707969A/en unknown
- 1996-03-26 CN CN96193363A patent/CN1181765A/en active Pending
- 1996-03-26 AU AU54319/96A patent/AU5431996A/en not_active Abandoned
- 1996-03-26 WO PCT/US1996/004120 patent/WO1996033231A1/en not_active Application Discontinuation
- 1996-03-26 EP EP96911430A patent/EP0821706A1/en not_active Withdrawn
- 1996-03-26 BR BR9608163A patent/BR9608163A/en not_active Application Discontinuation
- 1996-03-26 KR KR1019970707332A patent/KR19990007809A/en not_active Application Discontinuation
-
1997
- 1997-10-16 NO NO974785A patent/NO974785D0/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101190973B (en) * | 2006-11-10 | 2012-08-08 | 拜尔材料科学股份公司 | Plastic composite element and method for the production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1996033231A1 (en) | 1996-10-24 |
| NO974785L (en) | 1997-10-16 |
| BR9608163A (en) | 1999-02-09 |
| NO974785D0 (en) | 1997-10-16 |
| KR19990007809A (en) | 1999-01-25 |
| AU5431996A (en) | 1996-11-07 |
| EP0821706A1 (en) | 1998-02-04 |
| CO4410409A1 (en) | 1997-01-09 |
| JPH11503786A (en) | 1999-03-30 |
| MX9707969A (en) | 1997-12-31 |
| CA2218254A1 (en) | 1996-10-24 |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |