CN1789241B - Process for preparing liquid, storage-stable, low-color-index organic isocyanates containing carbodiimide and/or uretonimine groups - Google Patents
Process for preparing liquid, storage-stable, low-color-index organic isocyanates containing carbodiimide and/or uretonimine groups Download PDFInfo
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- CN1789241B CN1789241B CN 200510137038 CN200510137038A CN1789241B CN 1789241 B CN1789241 B CN 1789241B CN 200510137038 CN200510137038 CN 200510137038 CN 200510137038 A CN200510137038 A CN 200510137038A CN 1789241 B CN1789241 B CN 1789241B
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- trifluoromethanesulfonic acid
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Abstract
The invention relates to a method for producing liquid, storage-stable, low-color-index isocyanate mixtures containing Carbodiimide (CD) and/or Uretonimine (UI) groups, to the isocyanate mixtures produced by said method and to their use for producing blends with other isocyanates or for producing prepolymers containing isocyanate groups and polyurethane plastics, preferably polyurethane foams.
Description
Technical field
The present invention relates to a kind of preparation liquid state, stable storing, colour index low, contain (UI) method of the isocyanate mixture of group of carbodiimide (CD) and/or uretonimine (uretone imine), thus the isocyanate mixture that makes of method and they produce with the blend of other isocyanic ester or production contain the prepolymer of isocyanate groups and urethane plastic-optimization polyurethane foam materials-in application.
Background technology
The isocyanate mixture that contains CD and/or UI group can be simply by using the effective catalyst of cyclopentenes phosphine (phospholine) series, particularly the effective catalyst of cyclopentene oxide phosphine series is produced according to the method among US-A-2853473, US-A-6120699 and the EP-A-515933.
On the one hand; the cyclopentenes phosphine catalyst particularly high catalytic activity of cyclopentene oxide phosphine catalyst is desired; so that under the temperature condition of gentleness, make carbodiimide reaction activation; but on the other hand, also do not know to have any method can guarantee that the katalysis of cyclopentenes phosphine or cyclopentene oxide phosphine effectively stops without restriction up to now.The isocyanic ester of carbodiimideization tends to take place afterreaction, that is, they can be because of generating CO
2And gasify.This will cause the increase of pressure in the storage vessel for example, particularly at high temperature.
The trial of seeking the effective means that stops the effect of cyclopentenes phosphine catalyst is not few.This type of terminator mentions that in the specification sheets of for example DE-A-2537685, EP-A-515933, EP-A-609698 and US-A-6120699 it comprises for example halogenide of acid, acyl chlorides (acid chloride), chloroformic acid, silylanizing acid and main group element.It is effective inadequately to stop katalysis with acid, and wherein acid also can exist with the form of acyl chlorides.
According to the open text of EP-A-515933, by the isocyanate mixture that contains CD/UI of cyclopentenes phosphine catalyst preparation with at least with the catalyst system therefor equimolar amount, preferably for example trimethyl silyl trifluoromethayl sulfonic acid ester (TMST) of 1-2 times of molar weight stops.Yet, facts have proved that the isocyanic ester of producing by this mode that contains CD/UI generally is not suitable for producing prepolymer, promptly these contain the reaction product of isocyanic ester and the polyvalent alcohol of CD/UI.The reaction product of being produced in view of the above by the isocyanic ester of polyvalent alcohol and CD/UI modification tends to gasification, and this can cause the rising of pressure in the transmission container, or causes occurring bubbling in the process of these products of operation.
This problem can stop the cyclopentenes phosphine catalyst than (for example, the ratio with catalyzer is 5:1 to 10:1) by the high molar equivalent that uses silylanizing acid to use according to EP-A-515933 and be avoided.But the colour index of isocyanic ester of finding the CD/UI modification of gained in fact, subsequently again is on duty mutually.Therefore, like this too with the prepolymer of their production.
If use the acids termination cyclopentenes phosphine catalyst according to the trifluoromethayl sulfonic acid type of US-A-6120699, the result also is the same.The colour index of the prepolymer that is made by these materials has certain degree ground to increase.
Summary of the invention
Therefore, the invention provides a kind of method for preparing liquid state, stable storing, contains the lighter isocyanate mixture of carbodiimide and/or uretonimine groups, this method does not have those above-mentioned defectives, and produces liquid state, stable storing, isocyanate mixture that colour index is low.
These and other advantage of the present invention and benefit can be understood from following the specific embodiment of the present invention.
Embodiment
Now for illustrative purposes, present invention is described.Except in operation embodiment, unless opposite indication is perhaps arranged, the numeral of all expression quantity, percentage ratio, OH number, functionality etc. all is interpreted as modifying with term " about " in all situations in the specification sheets.Here equivalent weight and the molecular weight that provides with dalton (Da) is respectively number average equivalent weight and number-average molecular weight, unless opposite indication is arranged.
The present invention relates to the method that a kind of preparation has the organic isocyanate of carbodiimide and/or uretonimine groups, wherein with the catalyzer of cyclopentenes phosphine class to one or more Kazakhstan gloomy (Hazen) colour index≤100APHA, preferably≤organic isocyanate of 50APHA carries out the part carbodiimideization, stop the carbodiimide reaction then, the method is characterized in that and use alkylating agent as terminator.
The Hazen colour index can be according to DIN/EN/ISO6271-2 (draft, in September, 2002), do not have solvent, with water as a reference, bed thickness is to measure under 5 centimetres the situation.Employed metering facility can be for example Dr.Lange LICO300 photometer.
The strong alkylating agent of preferred use.Alkylating agent is that general formula is the material of R-X, and wherein R represents organic radical, and X is so-called leavings group.In strong alkylating agent, X constitutes good leavings group, the i.e. very low base of nucleophilic degree.In other words, if X is very weak from strong acid HX thereby alkalescence, then X constitutes good leavings group.Trialkyl oxygen compound, trifluoromethayl sulfonic acid ester and dialkylsulfates exemplify the Chemistry at Jerry March work Advanced Organic, the third edition (1985), John Wiley﹠amp as the compound that has good leavings group; Sons publishes, in the 135th page.
The invention still further relates to the organic isocyanate with carbodiimide and/or uretonimine groups that can obtain by aforesaid method.These organic isocyanates with carbodiimide and/or uretonimine groups at room temperature are liquid, and depend on CD/UI content and/or employed isocyanic ester, and (for example, 0 ℃) also is liquid at low temperatures.
The present invention also provides according to the application of the organic isocyanate with carbodiimide and/or uretonimine groups of the present invention in the blend of producing with other isocyanic ester, or the application in the improved prepolymer that contains isocyanate groups of production colour index.
At last, the present invention also provides according to the organic isocyanate with carbodiimide and/or uretonimine groups of the present invention and the isocyanic ester blend and/or the application of the improved prepolymer of colour index in urethane plastic is produced of being produced by their.
Amazingly be, the isocyanate mixture that liquid state, stable storing, colour index are low can be by obtaining according to method of the present invention, the instruction of this and DE-A-2504334 forms contrast, in DE-A-2504334, for example the catalyst deactivation effect of carrying out with alkylating agent is considered to not enough.
Alkylating agent also is disclosed among the US-A-4424288, be used for making the catalyzer deactivation, wherein thick polyphenylene polymethylene polymeric polyisocyanate is as raw material, this raw material can be made (' thick MDI ') by aniline-formaldehyde condensation, phosgenation subsequently, wherein contains the methylenediphenyl diisocyanates isomer of 70 weight % at most.But raw material itself has been dark, so can not obtain the product of light color by this method.
Any Hazen colour index≤100APHA, preferably≤organic isocyanate of 50APHA can be used as the raw material of the inventive method.But foundation method of the present invention preferably is used for carrying out the carbodiimideization of organic diisocyanate, and it uses in polyurethane chemistry.
Below listed be specially suitable:
Aromatic diisocyanate, such as Toluene-2,4-diisocyanate, 4-and/or Toluene-2,4-diisocyanate, 6-vulcabond (TDI), 2,2 '-, 2,4 '-and/or 4, any mixture of 4 '-methylenediphenyl diisocyanates (MDI) or this class aromatic diisocyanate,
The polyisocyanate mixtures of methylenediphenyl series, wherein contain the monomer methylenediphenyl diisocyanates isomer of 80 weight % to 100 weight % and the polyisocyanates that is higher than two functional methylenediphenyl series of 0 to 20 weight %, wherein the methylenediphenyl diisocyanates isomer is 4 of 0 to 100 weight %, 4 '-methylenediphenyl diisocyanates, 2 of 100 weight % to 0,2 of 4 '-methylenediphenyl diisocyanates and 0 to 8 weight %, 2 '-methylenediphenyl diisocyanates, and the summation of given percentage ratio is 100%.
The organic isocyanate that is preferably used as raw material is aromatic diisocyanate especially, such as Toluene-2,4-diisocyanate, and 4-and/or Toluene-2,4-diisocyanate, 6-vulcabond (TDI), 2,2 '-, 2,4 '-and/or 4, any mixture of 4 '-methylenediphenyl diisocyanates (MDI) or this class aromatic diisocyanate.For 2,2 '-, 2,4 '-and/or 4, the any mixture of 4 '-methylenediphenyl diisocyanates (MDI) or this class aromatic diisocyanate, in the raw material (organic isocyanate) 2,2 '-, 2,4 '-and/or 4, the total amount of 4 '-methylenediphenyl diisocyanates is at least 85 weight %, and the methylenediphenyl diisocyanates isomer is 4 of 0 to 100 weight %, 4 '-methylenediphenyl diisocyanates, 2 of 100 to 0 weight %, 2 of 4 '-methylenediphenyl diisocyanates and 0 to 8 weight %, 2 '-methylenediphenyl diisocyanates, and the summation of given percentage ratio is 100%, is particularly preferred.For 2,2 '-, 2,4 '-and/or 4, the any mixture of 4 '-methylenediphenyl diisocyanates (MDI) or this class aromatic diisocyanate, in the raw material (organic isocyanate) 2,2 '-, 2,4 '-and/or 4, the total amount of 4 '-methylenediphenyl diisocyanates is at least 90 weight %, and the methylenediphenyl diisocyanates isomer is 4 of 0 to 100 weight %, 4 '-methylenediphenyl diisocyanates, 2 of 100 weight % to 0,2 of 4 '-methylenediphenyl diisocyanates and 0 to 8 weight %, 2 '-methylenediphenyl diisocyanates, and the summation of given percentage ratio is 100%, is more particularly preferred.Especially, for 2,2 '-, 2,4 '-and/or 4, the any mixture of 4 '-methylenediphenyl diisocyanates (MDI) or this class aromatic diisocyanate, in the raw material (organic isocyanate) 2,2 '-, 2,4 '-and/or 4, the total amount of 4 '-methylenediphenyl diisocyanates is at least 99 weight %, the methylenediphenyl diisocyanates isomer is 4 of 0 to 100 weight %, 4 '-methylenediphenyl diisocyanates, 2 of 100 to 0 weight %, 2 of 4 '-methylenediphenyl diisocyanates and 0 to 8 weight %, 2 '-methylenediphenyl diisocyanates, and the summation of given percentage ratio is 100%, is the most particularly preferred.
Carry out in the presence of the catalyzer of cyclopentenes phosphine class according to method of the present invention.The catalyzer of cyclopentenes phosphine class is known, for example from EP-A-515933 and US-A-6120699.The typical example of these catalyzer is mixtures of the cyclopentene oxide phosphine of for example known in the art, following general formula.
The usage quantity of catalyzer depends on the quality of isocyanate material.The simplest mode of determining catalytic amount in various situations is to carry out pretest.
The carbodiimide reaction is carried out under 50 ℃ to 150 ℃ temperature routinely, preferably carries out under 60 ℃ to 100 ℃.But, obvious higher temperature of reaction also be fine (up to 280 ℃).Best temperature of reaction depends on used isocyanate material and/or catalyzer, can determine in simple pretest.
Carbodiimideization is sent out and should be generally reached 3% to 50% in carbodiimide degree (the carbodiimide degree is the percentage ratio of the total amount of the isocyanate groups that exists in respect to isocyanate material of the isocyanate groups of carbodiimideization), preferably reaches termination in 5% to 30% o'clock.
The carbodiimide degree can be determined by measuring nco value in the process of carrying out in the inventive method, and nco value is for example determined by volumetry well known by persons skilled in the art or former method of bit analysis.Suitable original position analytical procedure is for example near-infrared analysis or middle infrared analysis.
The carbodiimide degree also can be confirmed by the amount of the carbonic acid gas of for example overflowing from reaction mixture in the process that the inventive method is carried out.Like this, the cubing value of carbonic acid gas just provides on the arbitrfary point of time, about the information of the carbodiimide degree that realized.
In addition, other suitable ex situ known to those skilled in the art or original position course monitoring method also can use in principle.
In order to stop the carbodiimide reaction, with catalyzer at least equimolar amount, good especially be the excessive 1-20 of mole number doubly, best be the excessive 1-10 of mole number doubly alkylating agent or the mixture of various alkylating agents as terminator.The mixture of alkylating agent or various alkylating agents preferably uses as unique terminator.
Alkylating agent is the catalyzer of cyclopentene oxide phosphine class can be carried out hydrocarbylation according to inferring, and thereby makes it to lose activity.Therefore, all can by the hydrocarbonylation effect catalyzer of cyclopentene oxide phosphine class is lost activity and thereby the alkylating agent that stopped the carbodiimide reaction be suitable terminator of the present invention.Suitable alkylating agent can be by those skilled in the art by test is more easily definite simply.
The ester or the trialkyl oxygen compound of the ester that preferred alkylating agent is a trifluoromethanesulfonic acid, mineral acid (preferred strong inorganic acid).
The ester of suitable trifluoromethanesulfonic acid particularly structure is CF
3-SO
3-R
1Compound, R wherein
1Be fat (ring) family or arylated alkyl, R
1Can also randomly contain carbon and hydrogen element in addition.R
1Can have branching or linear carbochain and also can randomly have one or more carbon-to-carbon Multiple Bonds.Preferably the aliphatic ester of trifluoromethanesulfonic acid particularly preferably is trifluoromethanesulfonic acid methyl esters, trifluoromethanesulfonic acid ethyl ester, trifluoromethanesulfonic acid propyl ester, trifluoromethanesulfonic acid butyl ester and trifluoromethanesulfonic acid phenylester.
The ester of suitable strong inorganic acid is the ester of sulfuric acid or phosphoric acid for example, and promptly structure is SO
2(OR
3)
2Or OP (OR
3)
3Compound, R wherein
3Be fat (ring) family or arylated alkyl, R
3Also can randomly contain carbon and hydrogen element in addition.R
3Can have branching or linear carbochain and also can randomly have one or more carbon-to-carbon Multiple Bonds.Preferably the vitriolic aliphatic ester particularly preferably is methyl-sulfate, ethyl sulfate.
Suitable trialkyl oxygen compound is that for example structure is R
4 3The compound of OY, wherein R
4Be methyl or ethyl.Y represents non-nucleophilicity negatively charged ion, such as tetrafluoroborate, hexafluoro-phosphate radical or hexafluoroantimonic anion.
Replace unique use alkylating agent as the another kind of terminator select be according to the present invention with alkylating agent and acid and/or acyl chlorides and/or sulphonate as additional stabilizers.By also using additional stabilizers, can reduce the usage quantity of alkylating agent.This stablizer can add simultaneously with terminator, or adds in subsequent step.
Optional halogenated, aliphatic and/or alicyclic and/or aromatics monobasic, binary and/or polycarboxylic acid such as acetate, hexanodioic acid, cyclohexane dicarboxylic acid, α-Lv Bingsuan, phenylformic acid, phthalic acid, m-phthalic acid etc., and sulfonic acid, HCl, sulfuric acid and/or phosphoric acid or their monobasic and/or dibasic ester such as dibutyl phosphate, can be used as acid.Can be used as acyl chlorides derived from the acyl chlorides of optional halogenated, aliphatic and/or alicyclic and/or aromatics monobasic, binary and/or polycarboxylic acid or sulfonic acid and urea chloride such as normal-butyl urea chloride.Methyl tosylate, ethyl p-toluenesulfonate can be used as for example sulphonate.
Corresponding to organic isocyanate with carbodiimide and/or uretonimine groups, the total amount of the additional stability agent that adds is 10ppm to 1000ppm (1ppm is 1 weight part/1000000 weight parts), that more excellent is 10ppm to 500ppm, and that more excellent is 50ppm to 250ppm.
The reaction product of carbodiimideization can contain the colouring stabilizer that adds routinely in the isocyanic ester.Be not crucial the opportunity that adds these stablizers.Colouring stabilizer can join before carbodiimideization in the isocyanate material or after reaction one finishes and join in the reaction product.Also can in raw material and reaction product, all add colouring stabilizer.This type of stablizer generally all is known to those skilled in the art, can comprise the material that for example is selected from sterically hindered phenol, phosphorous acid ester and tertiary amine.Colouring stabilizer can be distinguished separately and to use or mix use mutually with other representative in the identical and different material group.The usage quantity of colouring stabilizer is on the order of magnitude known to those skilled in the art, and with respect to the reaction product of isocyanate material or carbodiimideization, this one matter or this mixture are usually at 100ppm to 10000ppm.
Have found that, by foundation method of the present invention, alkylating agent added separately or with add as the acid of additional stability agent and/or acyl chlorides and/or sulphonate combination, can both stop the katalysis of cyclopentenes phosphine effectively, and make the isocyanic ester product again simultaneously and obtain lower colour index by the prepolymer that it makes.When foundation prior art (EP-A-515933) is used silylanizing acid as terminator, only add a large amount of silylanizing acid, the catalytic effect of cyclopentenes phosphine is promptly stopped effectively, but this can cause isocyanate mixture that so makes and the prepolymer colour index increase that is made by it.
The prepolymer that contains isocyanate groups by make according to method of the present invention have carbodiimide and/organic isocyanate of uretonimine groups and the conventional polyol reaction in the polyurethane chemistry make.Suitable polyvalent alcohol is that molecular weight is that 62 gram/moles are to 599 gram/moles, preferably 62 gram/moles are to the monovalence and the multivalence alcohol of 300 gram/moles, such as ethylene glycol, TriMethylolPropane(TMP), propylene glycol-1,2, butyleneglycol-1,2 or butyleneglycol-2,3, hexylene glycol, ethohexadiol, dodecyl glycol and/or octadecyl glycol, but specifically known molecular weight is that 600 gram/moles are to 8000 gram/moles in the polyurethane chemistry, preferably 800 gram/moles are to the high molecular weight polyether and/or the polyester polyol of 4000 gram/moles, and it has two at least, normally 2 to 8, preferably 2 to 4 primary hydroxyls and/or secondary hydroxy groups.This type of examples of polyhydric alcohols is disclosed in US-PS4218543, and the 7th hurdle the 29th walks in the 9th hurdle the 32nd row.
According to the advantage of method of the present invention will become apparent to those skilled in the art that the isocyanic ester that promptly contains carbodiimide and/or uretonimine groups and the prepolymer produced by its can stably stored and color more shallow.
These have carbodiimide and/organic isocyanate of uretonimine groups and be the quite valuable raw material that is used to produce urethane plastic by the prepolymer of they and polyol reaction production, wherein the production of urethane plastic is by realizing through polyaddition method (for example, with polyether glycol and polyester polyol send out should) with polyvalent alcohol.
Embodiment
The present invention further sets forth by following embodiment, but is not limited to following examples.
Raw material:
Isocyanic ester 4,4-methylenediphenyl diisocyanates, NCO content: 33.6 weight % (DESMODUR44M, Bayer AG)
The industrial grade mixture of cyclopentene oxide phosphine class catalyzer 1-methyl isophthalic acid-oxo-1-phosphorus heterocycle penta-2-alkene and 1-methyl isophthalic acid-oxo-1-phosphorus heterocycle penta-3-alkene, the concentration in toluene is 10%.
The polyethers of polyvalent alcohol propylidene and ethylidene oxide unit, 80%-90% uncle OH group, functionality is 3, and the OH value is that 28 milligrams of KOH/ grams and viscosity are 1200mPas (MULTRANOL3901Bayer Corp.) down for 25 ℃
Production stage with organic isocyanate of carbodiimide and/or uretonimine groups:
10 kilograms are breathed out gloomy colour index＜15APHA, contain 3 of 750ppm, the technical grade 4 of 5-di-t-butyl-4-hydroxytoluene, 4 '-MDI (DESMODUR44M) is at N
2/ be heated to 60 ℃ under stirring, add 250 milligrams of catalyst solution (2.5ppm; 0.2 mmole).With reaction mixture at N
2/ stir down and heated 240 minutes to about 95 ℃.Add relevant terminator and stop the carbodiimide reaction, and continue to stir 1 hour.In the foundation embodiments of the invention, trifluoromethanesulfonic acid methyl esters (TFMSME) or trifluoromethanesulfonic acid ethyl ester (TFMSEE) and optional m-phthaloyl chloride (IPDC) use by the amount in the table.Trifluoromethyl silyl trifluoromethanesulfonic acid (TMST) uses in reference example 1 and 2, and trifluoromethanesulfonic acid (TFMSS) uses in reference example 3, and usage quantity separately as shown in Table.The result is summarised in the following table.
Production stage with prepolymer of the organic isocyanate of carbodiimide and/or uretonimine groups and polyvalent alcohol:
At 50 ℃ and N
2/ stir down, in every kind of isocyanic ester that 500 grams make according to above-mentioned steps, add 167 gram MULTRANOL3901, and with mixture at 80 ℃ and N
2/ continued to keep 2 hours under stirring.The analysis of prepolymer was carried out at second day.In order to determine the stability of prepolymer, carry out isothermal pressure test (12 hours/90 ℃).The result is summarised in the following table.
Breathe out gloomy colour index according to DIN/EN/ISO6271-2 (draft, in September, 2002) do not have solvent, with water as a reference, bed thickness is to measure under 5 centimetres the situation.The metering facility that uses can be for example Dr.Lange LICO300 photometer.
Reference example 1 and 2 clearly illustrates that TMST stops the increase of dosage ground stability is had influence pro, although this diminishes color (breathing out gloomy).Reference example 3 shows that again terminator trifluoromethanesulfonic acid (TFMSS) is to color favorable influence so not.In an embodiment of the present invention, compare with reference example 1, stability improves, and has kept colour index (breathing out gloomy) preferably simultaneously.
Though illustrative purposes is described in detail the present invention for example in preamble, but should be understood that these write up only is for this purpose, persons skilled in the art can be made amendment to it, and do not deviate from the spirit and scope of the present invention, remove by claims institute limitr.
Claims (7)
1. a production has the method for the organic isocyanate of carbodiimide group and/or uretonimine groups, wherein one or more organic isocyanates of breathing out gloomy colour index≤100APHA carry out the part carbodiimideization with the catalyzer of cyclopentenes phosphine class and reaction stops to carbodiimide, its improvement comprises that it is CF that described alkylating agent is selected from structure with the reaction of alkylating agent termination carbodiimide
3-SO
3-R
1The ester of trifluoromethanesulfonic acid, R wherein
1Represent aliphatic, alicyclic or araliphatic base.
2. the method for claim 1 is characterized in that, described alkylating agent comprises the aliphatic ester of trifluoromethanesulfonic acid.
3. the method for claim 1 is characterized in that, described alkylating agent comprises trifluoromethanesulfonic acid methyl esters, trifluoromethanesulfonic acid ethyl ester, trifluoromethanesulfonic acid propyl ester, trifluoromethanesulfonic acid butyl ester or trifluoromethanesulfonic acid pentyl ester.
4. the method for claim 1 also is included in adding acid and/or acyl chlorides and/or sulphonate in the step that stops the carbodiimide reaction.
5. organic isocyanate by making with carbodiimide group and/or uretonimine groups as each described method among the claim 1-4.
6. method of producing the isocyanic ester blend, its improvement comprise introduces the organic isocyanate with carbodiimide group and/or uretonimine groups as claimed in claim 5.
7. method of producing urethane or isocyanate-terminated prepolymer, its improvement comprises introduces the organic isocyanate with carbodiimide group and/or uretonimine groups as claimed in claim 5.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510137038 CN1789241B (en) | 2005-12-12 | 2005-12-12 | Process for preparing liquid, storage-stable, low-color-index organic isocyanates containing carbodiimide and/or uretonimine groups |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510137038 CN1789241B (en) | 2005-12-12 | 2005-12-12 | Process for preparing liquid, storage-stable, low-color-index organic isocyanates containing carbodiimide and/or uretonimine groups |
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|---|---|
| CN1789241A CN1789241A (en) | 2006-06-21 |
| CN1789241B true CN1789241B (en) | 2010-09-29 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102006000822A1 (en) * | 2006-01-05 | 2007-07-12 | Bayer Materialscience Ag | Process for the preparation of liquid, storage stable carbodiimide and / or uretonimine containing organic isocyanates |
| EP2510063A1 (en) * | 2009-12-09 | 2012-10-17 | Bayer Intellectual Property GmbH | Polyisocyanurate-coated parts and the use thereof in offshore applications |
| CN102718683B (en) * | 2012-06-05 | 2014-08-06 | 万华化学集团股份有限公司 | Method for preparing low-chromatic number isocyanate and isocyanate prepared by same |
| KR20190042598A (en) * | 2016-09-08 | 2019-04-24 | 코베스트로 도이칠란트 아게 | A process for preparing a storage-stable organic isocyanate of a liquid having a carbodiimide and / or uretonimine group and having a low color number |
| CN107879951B (en) | 2017-10-20 | 2020-01-31 | 万华化学集团股份有限公司 | light-colored modified isocyanate mixture and preparation method thereof |
| CN111689874B (en) * | 2020-07-11 | 2022-07-12 | 万华化学（宁波）有限公司 | Method for reducing color number of carbodiimide modified organic isocyanate, low-color-number isocyanate and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4120884A (en) * | 1976-02-18 | 1978-10-17 | Basf Aktiengesellschaft | Storage-stable, liquid polyisocyanates possessing carbodiimide groups, and process for their manufacture |
| US4260554A (en) * | 1978-08-30 | 1981-04-07 | Basf Aktiengesellschaft | Storage-stable, liquid carbodiimide modified polyisocyanates and process for their manufacture |
| US5202358A (en) * | 1991-05-28 | 1993-04-13 | Bayer Aktiengesellschaft | Process for the preparation of liquid storable organic isocyanates containing carbodiimide and/or uretone imine groups and their use for the preparation of polyurethane plastics |
| US6120699A (en) * | 1998-09-21 | 2000-09-19 | Basf Corporation | Storage stable methylene bis(phenylisocyanate) compositions |
-
2005
- 2005-12-12 CN CN 200510137038 patent/CN1789241B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4120884A (en) * | 1976-02-18 | 1978-10-17 | Basf Aktiengesellschaft | Storage-stable, liquid polyisocyanates possessing carbodiimide groups, and process for their manufacture |
| US4260554A (en) * | 1978-08-30 | 1981-04-07 | Basf Aktiengesellschaft | Storage-stable, liquid carbodiimide modified polyisocyanates and process for their manufacture |
| US5202358A (en) * | 1991-05-28 | 1993-04-13 | Bayer Aktiengesellschaft | Process for the preparation of liquid storable organic isocyanates containing carbodiimide and/or uretone imine groups and their use for the preparation of polyurethane plastics |
| US6120699A (en) * | 1998-09-21 | 2000-09-19 | Basf Corporation | Storage stable methylene bis(phenylisocyanate) compositions |
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|---|---|
| CN1789241A (en) | 2006-06-21 |
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