CN107998981A - Polyester hyper-dispersant and its preparation, and a kind of preparation method of isocyanates - Google Patents
Polyester hyper-dispersant and its preparation, and a kind of preparation method of isocyanates Download PDFInfo
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- CN107998981A CN107998981A CN201711270318.1A CN201711270318A CN107998981A CN 107998981 A CN107998981 A CN 107998981A CN 201711270318 A CN201711270318 A CN 201711270318A CN 107998981 A CN107998981 A CN 107998981A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/16—Amines or polyamines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/10—Preparation of derivatives of isocyanic acid by reaction of amines with carbonyl halides, e.g. with phosgene
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
- C08G65/33306—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group acyclic
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33348—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group
- C08G65/33355—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group cyclic
- C08G65/33358—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group cyclic aromatic
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33348—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group
- C08G65/33362—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group heterocyclic
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- General Chemical & Material Sciences (AREA)
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- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention provides a kind of polyester hyper-dispersant and its preparation, and a kind of preparation method of isocyanates.Polyester hyper-dispersant provided by the invention, has following structure formula (I):Wherein, the R in formula (I)1The residue of NCO is sloughed for diisocyanate or poly isocyanate sloughs the residue of NCO；R2The residue of terminal hydroxy group is sloughed for one-ended hydroxy polyethylene oxide；R3To slough NH2Amino acid residue, the amino acid has at least one segment containing COOH and at least one contains NH2Segment；In formula (I), 0 ＜ m≤9,0 ＜ n≤9.Prepare isocyanates into polyester hyper-dispersant incorporated in the present invention in salt process, the mobility of diamine hydrochloride solution to avoid the generation of caking phenomenon, can be increased, improve production efficiency.
Description
Technical field
The present invention relates to the preparing technical field of isocyanates, more particularly to a kind of polyester hyper-dispersant and its preparation side
Method, the method for further relating to prepare isocyanates using the polyester hyper-dispersant.
Background technology
Aliphatic and alicyclic diisocyanate (ADI) have become the research of the major polyurethane company in the whole world and scientific research institution
Hot spot, its product with excellent color inhibition, it is corrosion-resistant, durable be widely used in the performance such as flexible coating, car paint, adhesive and
The fields such as medical material.
At present, the main path for preparing isocyanates is liquid phase light phosgenation.Liquid phase light phosgenation prepares isocyanates can
It is divided into cold-hot phosgenated method and into salt light phosgenation (abbreviation salt forming method).Cold-hot phosgenated method passes through cold reaction for primary amine with phosgene
Corresponding isocyanates is made with two stages of thermal response, but this method presence can not reduce the disadvantages such as the generation of ureas accessory substance
End.Then amine hydrochlorate or carbonic acid is made first in corresponding amine and the sour gas such as reaction such as hydrogen chloride, carbon dioxide by salt forming method
Salt (process is known as into salt process), can be effective then by the amine salt and phosgene reaction (process is known as phosgenation process)
Ground suppresses ureas accessory substance in photochemical process.
In method disclosed by Chinese Patent Application Publication CN200680022170, its salification process is in superatmospheric
0.01Mpa, carries out at 120 DEG C of temperature.Although high-temperature pressurizing can reduce hydrochloride viscosity, salt-forming conversions rate and space-time are improved
Efficiency, but there is both sides defect：On the one hand, simply suitable for the higher diamines of high temperatures, and can serious shadow
Ring the color number into salt and photochemical solution；On the other hand, it is exceedingly fast under high temperature into salt speed, considers the shifting heat and diamines of reaction kettle
Parcel problem.
In method disclosed by Published U.K. Patent application GB1086782A, its into salt phosgenation condition be diamines and chlorination
Hydrogen is at 0-60 DEG C into salt, and hydrochloride reaction density is in below 5.5wt%.This method conversion ratio is very high.However, although this method exists
Reaction can reduce the generation of accessory substance under low temperature, low concentration, but space-time yield is not high, while need distillation removing substantial amounts of
Solvent, reduces its economy.
To sum up, the industrialized principal element of salt liquid phase light phosgenation is constrained at present as the inclined into salinity of raw material diamines
It is low, cause benefit during sky can not be improved with economic benefit.Particularly short-chain aliphatic or alicyclic diamine in salification process by
Small in molecular weight, the viscosity build of the hydrochloride slurry of gained is rapid, brings stirring, disperses, moves the rough sledding such as hot difficulty, leads
It is caused to be unable to reach higher concentration.For example, into salt process, if concentration of the diamines in atent solvent is set to 6-
10%, then the organic solvent dissolved with raw material amine with hydrogen chloride gas mixed process, with the progress of reaction, hydrochloride
The viscosity of slurry rises rapidly, and in the reaction in rear stage, hydrochloride can form caking and be difficult to make it in bottom and kettle wall, stirring
It is scattered, cause production efficiency to reduce.
Therefore, it is necessary to develop a kind of new method for preparing isocyanates into salt liquid phase phosgenation, to solve hydrochloride knot
Block is difficult to disperse, the inferior drawback of low production efficiency.
The content of the invention
The present invention is to make up the deficiencies in the prior art, there is provided a kind of polyester hyper-dispersant and preparation method thereof, also provides profit
The method for preparing isocyanates with the polyester hyper-dispersant.Prepare isocyanates into polyester incorporated in the present invention in salt process
Hyper-dispersant, to avoid the generation of caking phenomenon, can increase the mobility of diamine hydrochloride solution, improve production efficiency.
For the present invention to reach its purpose, the technical solution of use is as follows：
First aspect present invention provides a kind of polyester hyper-dispersant, has following structure formula (I):
Wherein, the R in formula (I)1The residue of-NCO is sloughed for diisocyanate or poly isocyanate sloughs the residual of-NCO
Base；
R2The residue of terminal hydroxy group is sloughed for one-ended hydroxy polyethylene oxide；
R3- NH is sloughed for amino acid2Residue, the amino acid has at least one segment containing-COOH and at least one
Containing-NH2Segment；
In formula (I), 0 ＜ m≤9,0 ＜ n≤9.M and n is R respectively1On the number of corresponding group that is connected.The polyester
When hyper-dispersant is the mixture of structure formula (I) compound, m and n refer in mixture the average value of m and n in each molecule
Average value, thus, m and n may be non-integer, it is also possible to be integer.
The polyester hyper-dispersant of the present invention, when preparing isocyanates applied to salt forming method, the polyester is being introduced into salt process
Hyper-dispersant, it forms the anchoring group absorption of ammonium salt class and is formed in diamine hydrochloride particle surface, and by its solvent chain
Steric hindrance separates diamine hydrochloride particle, phenomena such as avoiding uniting, lump, significantly improves into salinity and effect, so that
Substantially increase the yield of isocyanate products.
The polyester hyper-dispersant of the present invention, it is preferred that the diisocyanate is aliphatic diisocyanate, alicyclic two
One or more in isocyanates and aromatic diisocyanate.The preferable poly isocyanate is two isocyanide of aliphatic
One or more polymer in acid esters, alicyclic diisocyanate and aromatic diisocyanate, more preferably dimer,
One or more in tripolymer, pentamer, heptamer and nine aggressiveness, still more preferably one kind in tripolymer and pentamer
It is or a variety of.As a kind of example, in a kind of specific preferred embodiment, the diisocyanate includes but not limited to Isosorbide-5-Nitrae-fourth
Diisocyanate, penta diisocyanate of 1,5-, hexamethylene diisocyanate, anti-form-1,4- cyclohexylene diisocyanates, toluene two are different
Cyanate, methyl diphenylene diisocyanate, m-xylylene diisocyanate and a cyclohexyldimethylene diisocyanate
One or more in ester etc.；The poly isocyanate is preferably one or more polymerizations in above-mentioned diisocyanate
Thing, is, for example, that the one or more in dimer, tripolymer, pentamer, heptamer and nine aggressiveness, more preferably tripolymer and five are poly-
One or more in body.
The polyester hyper-dispersant of the present invention, as a preferred embodiment, the one-ended hydroxy polyethylene oxide have as follows
Structure formula (II)：
R in polyester hyper-dispersant of the present invention2The terminal hydroxy group polyethylene oxide of preferably formula (II) takes off residual after terminal hydroxy group
Base.Reach more preferable promotion in being prepared for isocyanates into salt process to further improve polyester hyper-dispersant of the present invention
Dispersion effect, a is preferably 6-21 in formula (II), to obtain preferable R2Chain length；More preferably, a is more preferably 8-13.Using above-mentioned
Preferable a values, the R in polyester hyper-dispersant2Chain length will not be long or too short, it, which can be played, more preferably promotes dispersion effect, and one
Aspect can provide enough steric hindrances, on the other hand will not produce too strong affinity with medium and cause polyester hyper-dispersant
Parsed from by dispersion such as diamine hydrochloride particle surface, be not easy to Fold occur, so as to can effectively avoid particle
Flocculate or reassemble.
The one-ended hydroxy polyethylene oxide of structure formula (II) is a kind of existing compound, can obtain from commercial channel, also may be used
Be made with reference to existing process, for example, paper (synthesis of amphipathic block-star copolymers of the prosperous of Kang Ke based on PEO-PCL with
Characterize [D] Zhengzhou：Material system of Zhengzhou University, 2011) in, the compound and preparation method thereof is just described, to this no longer one by one
Repeat.
The polyester hyper-dispersant of the present invention, it is preferred that the one-ended hydroxy polyethylene oxide is number-average molecular weight 300-
The combination of one or more one-ended hydroxy polyethylene oxide in 1000；Preferred number-average molecular weight is 400-600.
The polyester hyper-dispersant of the present invention, in a kind of preferred solution, the amino acid is selected from glycine, alanine, bright ammonia
One or more in acid, phenylalanine and glutamic acid.
The polyester hyper-dispersant of the present invention, it is preferred that the ratio of m and m+n is more than 0 and less than 100%, further preferably
For 10-60%, more preferably 30-50%；The ratio of n and m+n is the more preferably 40-90% more than 0 and less than 100%,
More preferably 50-70%.
The polyester hyper-dispersant of the present invention, more preferably, the number-average molecular weight of the polyester hyper-dispersant is 700-
3000.When applied to salt forming method prepared by the polyester hyper-dispersant of the present invention isocyanates, in order to preferably overcome into salt worker
The obtained intergranular active force of diamine hydrochloride in sequence, and more effective dispersing groups are provided, polyester of the invention surpasses
The number-average molecular weight of dispersant is more preferably 800-3000, is still more preferably 1500-2000.
Second aspect of the present invention provides the preparation method of polyester hyper-dispersant described above, includes the following steps：
1) diisocyanate or poly isocyanate are subjected to end capping reaction with one-ended hydroxy polyethylene oxide；
2) into the reaction system of step 1) add amino acid blocked, the amino acid have it is at least one containing-
The segment of COOH and at least one contain-NH2Segment.
The preparation method of polyester hyper-dispersant of the present invention, in preferable scheme, hydroxyl in one-ended hydroxy polyethylene oxide,
Diisocyanate or the-NCO in the poly isocyanate ,-NH in amino acid2The molar ratio of this three is 0.3-0.5:1:0.5-
0.7, it is, for example, 0.4：1：0.6.
The preparation method of polyester hyper-dispersant of the present invention, in preferable scheme, step 1) is sealed in the presence of a catalyst
End reaction, the catalyst in diethylenediamine, dibutyl tin laurate, stannous octoate and N-methylmorpholine one
Kind is a variety of, more preferably dibutyl tin laurate and/or stannous octoate；Preferably, the dosage of catalyst is different based on two
The 0.02-0.2wt% of cyanate or poly isocyanate quality, more preferably 0.05-0.1wt%.
When the present invention prepares polyester hyper-dispersant, raw material diisocyanate used or poly isocyanate and one-ended hydroxy
The primary amine reaction in hydroxyl, amino acid in polyethylene oxide, it is preferred to use relatively low reaction temperature is low, such as 50-100 DEG C.
It is endless using preferable reaction temperature, the xanthochromia that can more effectively avoid isocyanate-monomer that polymerization occurs and trigger, reaction
Congruent phenomenon.The diisocyanate more preferably used is aromatic isocyanate, and the poly isocyanate more preferably used is virtue
The polymer of fragrant race's isocyanates, more to reduce residual-NCO shadows caused by reaction process in polyester hyper-dispersant
Ring.
The preparation method of polyester hyper-dispersant of the present invention, in preferable scheme, the reaction temperature of step 1) is preferably 50-
100 DEG C, more preferably 60-80 DEG C；The reaction temperature of step 2) is preferably 50-100 DEG C, more preferably 60-80 DEG C.
The preparation method of polyester hyper-dispersant of the present invention, in preferable scheme, in step 1), in the presence of esters solvent into
Row reacts, and preferably adds esters solvent in step 2) to adjust the solid content of obtained polyesters oversubscription granular media, preferably contains admittedly
Measure as 20-50wt%, more preferably 30-40wt%.In a kind of preferred embodiment, esters solvent preferably uses acetic acid fourth
One or more in ester, propyl acetate, isopropyl acetate etc..In a kind of preferred embodiment, in step 1), one-ended hydroxy is gathered
Ethylene oxide is dissolved in esters solvent in advance obtains one-ended hydroxy polyethylene oxide solution, one-ended hydroxy polycyclic oxygen in the solution
The mass concentration of ethane is preferably 30-50wt%, more preferably 35-40wt%.
The preparation method of polyester hyper-dispersant of the present invention, in preferable scheme, step 2) is in reaction end, reaction system
In-NCO residual content and reaction system in-NCO initial content ratio≤1wt%, more preferably≤0.3wt%.It is described
" initial content of-NCO " refers to prepare the reaction system of polyester hyper-dispersant in the initial contained-NCO content of reaction.As
A kind of embodiment, reaction process can specifically be monitored using the method for di-n-butylamine titration-NCO content, this prison
The concrete operations of control are well known in the art, this is repeated no more.Added in the preferred solution of the present invention, in step 1) excessive
Diisocyanate or poly isocyanate carry out end capping reaction so that the reaction was complete for one-ended hydroxy polyethylene oxide.
The polyester hyper-dispersant of the present invention especially suitable for salt forming method prepare isocyanates into salt process.
Third aspect present invention provides a kind of method for preparing isocyanates, including into salt process and phosgenation process,
Polyester hyper-dispersant is added when diamine hydrochloride solution is prepared in the process into salt, the polyester hyper-dispersant is described above
Polyester hyper-dispersant or preparation method described above made from polyester hyper-dispersant.
In the present invention prepares the method for isocyanates, into salt process ,-the COOH in polyester hyper-dispersant of the invention
With one end-NH in raw material diamines2Reaction generation carboxylic acid ammonium, and in diamines the other end-NH2Continue and HCl reaction generation hydrochloric acid
Salt, obtained two kinds of ammonium salt groups can be used as anchoring group；It is poly- formed with carboxylic acid ammonium's structure and hydrochloride structure at this time
Ester hyper-dispersant and diamine hydrochloride particle are closely linked in the form of ion pair, pass through the solvation of polyethylene oxide
Long-chain, which forms steric hindrance, to be made to be located remotely from each other so as to form good dispersion effect between diamine hydrochloride particle.Based on this hair
The introducing of bright polyester hyper-dispersant, preparation method of the invention can effectively reduce into obtained diamine hydrochloride solution in salt process
Viscosity, improve diamines into salinity and efficiency.
The method that the present invention prepares isocyanates, in preferable scheme, in the process into salt, the use of polyester hyper-dispersant
Measure as the 0.5-3wt% of diamines quality, more preferably 1-2wt%.
The method that the present invention prepares isocyanates, it is described to include the following steps into salt process in preferable scheme：Will be molten
Agent, diamines and polyester hyper-dispersant are mixed evenly, and are passed through HCl gases, and diamine hydrochloride solution is made；
The method for preparing isocyanates using the present invention, into salt process, the concentration of diamines can compared to existing process
To be applicable in a wider context, for example, relative to the gross mass of solvent, diamines and polyester hyper-dispersant, diamines is dense in the present invention
Degree can be 5-40wt%, and under two larger amine concentrations, present invention gained diamine hydrochloride solution still has preferable flowing
Property and easy to stirring.In preferred scheme, based on the gross mass of solvent, diamines and polyester hyper-dispersant, the diamines
Concentration (i.e. mass percent) is more preferably 6-30wt%, more preferably 10-20wt%, with obtain the production efficiency of higher with
And it is easier to the diamine hydrochloride solution being dispersed with stirring.
The method that the present invention prepares isocyanates, in preferable scheme, the solvent is selected from 120-170 DEG C of boiling point under normal pressure
Aromatic hydrocarbon, esters of gallic acid solvent in one or more, preferably this kind of solvent, shows in the reaction system of the present invention
Reactionlessness, will not react with raw material and polyester hyper-dispersant etc..It is further preferred that the aromatic hydrocarbon solvent include but
It is not limited to benzene,toluene,xylene, ethylo benzene, cumene, butyl benzene, cyclohexylbenzene, tetrahydronaphthalene, chlorobenzene, o-dichlorohenzene, first
One or more in base naphthalene, biphenyl and triphenyl methane, more preferably chlorobenzene, o-dichlorohenzene, butyl benzene, ortho-xylene and isopropyl
One or more in base benzene etc..The esters of gallic acid solvent includes but not limited to ethyl acetate, butyl acetate, pentyl acetate, water
One or more in poplar acid methyl esters, repefral, dibutyl phthalate and methyl benzoate.The solvent
One or more more preferably in aromatic hydrocarbon solvent.
The method that the present invention prepares isocyanates, in preferable scheme, the general structure of diamines used into salt process
For R (NH2)2, the general structure of prepared isocyanates is R (NCO)2, wherein R is the aliphatic at least containing 2 carbon atoms
Alkyl or alicyclic alkyl.The method that the present invention prepares isocyanates, it is also particularly suitable for the less diamines of molecular weight, will not
Occur in the prior art since the diamines (such as 1,4- butanediamine, 1,5- pentanediamines, 1,6- hexamethylene diamines etc.) of relatively small molecular weight exists
Salification process medium viscosity rises rapid and causes scatter operation the drawback such as to be difficult to carry out.It is further preferred that the R is to contain 2-
The aliphatic alkyl or alicyclic alkyl of 8 carbon atoms, preferred carbon number are 2-6.It is further preferred that described two
Amine includes but not limited to 1,4- butanediamine, 1,5- pentanediamines, 1,6- hexamethylene diamines, anti-form-1,4- cyclohexanediamine, m-phenylenedimethylim-
One or more in diamines, cyclohexyldimethylene diamines and isophorone diamine, more preferably Putriscine, 1,5-
Pentanediamine, 1,6- hexamethylene diamines.Isocyanates obtained by the present invention is preferably but not limited to 1,4- fourths diisocyanate, 1,5- penta 2
Isocyanates, hexamethylene diisocyanate, anti-form-1,4- cyclohexylene diisocyanates, toluene di-isocyanate(TDI), diphenyl methane two
Isocyanates, m-xylylene diisocyanate, cyclohexyldimethylene diisocyanate and isophorone diisocyanate
One or more in ester, more preferably Isosorbide-5-Nitrae-fourth diisocyanate, 1,5-, penta diisocyanate and 1, hexamethylene-diisocyanate
In one or more.
In the preferred solution of the present invention, present inventor has found that, when preparing isocyanates, reaction temperatures affect
The chlorinated derivative of the saturation solubility of HCl, reaction solution color number and accessory substance amine in the particle diameter of diamine hydrochloride particle, solvent
Deng.Present inventor find when temperature be less than 0 DEG C when, diamine hydrochloride particle diameter increase, can influence into salt efficiency and then
Photochemical efficiency；When temperature is higher than 50 DEG C, the color number of reaction solution is higher into salt process, and reaction solution is in dark yellow or deeper face
Color, influences whether the color number of photochemical liquid, and can reduce the saturation solubilities of HCl in a solvent, reduces into salt efficiency；Work as temperature
During higher, the chlorinated derivative of amine can increase, and then influence product hydrolysis chlorine.In the preferred solution of the present invention, into salt process,
Preferable reaction temperature is 0 DEG C -50 DEG C, more preferably 5-30 DEG C, more preferably 10-20 DEG C.
The method that the present invention prepares isocyanates, in a kind of preferred embodiment, used in step 1)
HCl gases preference ranking reaches more than 3.0N, and Fe mass of ions content is less than the HCl gases of 0.5ppm.
The method that the present invention prepares isocyanates, in preferable scheme, the phosgenation process includes the following steps：By institute
Diamine hydrochloride solution and phosgene reaction are stated, prepares the photochemical liquid of isocyanates.Reaction can specifically carry out under normal pressure.
The method that the present invention prepares isocyanates, in preferable scheme, reaction temperature is preferably in 90- in phosgenation process
In the range of 180 DEG C, further preferred 120-170 DEG C, more preferably 140-160 DEG C, to improve reaction speed and product yield, at the same time
Side reaction can also be reduced, such as reduces tar content, avoid or reduce the generation of chloro impurity, especially reduces monochloro for isocyanide
Acid and esters content.Present inventor find, in phosgenation process, if photochemical reaction temperature at higher than 180 DEG C for a long time into
OK, the heat endurance difference of the short chain isocyanates in product causes its polymerization, and then increases tar content, is unfavorable for product receipts
The raising of rate, temperature raise the generation that can also cause chloro impurity, and especially monochloro can increase for isocyanate content；And temperature
Less than 90 DEG C, diamine hydrochloride slows with phosgene reaction, and the decomposition rate of the carbamyl chloride of generation can also reduce.
The method that the present invention prepares isocyanates, can also further comprise refining step.In a kind of embodiment, essence
Process processed includes carrying out the photochemical liquid of isocyanates de- phosgene, desolventizing, detar, rectifying, specific process for refining
Operate well known in the art, this is repeated no more.
Technical solution provided by the invention has the advantages that：
Prepare isocyanates into polyester hyper-dispersant incorporated in the present invention in salt process, the hair of caking phenomenon can be avoided
It is raw, the viscosity of diamine hydrochloride solution is reduced, its mobility is added, drastically increases production efficiency.
Isocyanates preparation method provided by the invention, low into obtained diamine hydrochloride solution viscosity in salt process,
5000cp can be less than, be more smaller than 2000cp in preferred solution, solid particle dispersions are uniform.To obtain higher reaction efficiency,
Into salt process Central Plains material amine mass content be positively retained at 15-30wt%, higher than existing salt forming method raw material amine mass content (about
10%), technique of the invention, the content of its raw material amine also may be up to 40wt%.
Carboxylic acid ammonium's structure that the polyesters dispersant of the present invention is formed in salt-forming stage and raw material diamines after into salt,
Polyesters dispersant and raw material diamine hydrochloride can be gradually decomposed under excessive HCl atmosphere, does not influence raw material diamines into salt
With the conversion ratio in photochemical stage, final dispersant enters in tar, the problems such as not influencing the separation of product.
The method of isocyanates produced according to the present invention, the conversion ratio of raw material diamines can reach more than 94%, preparation it is different
Cyanate indices are suitable with traditional handicraft, and one-pot production capacity improves 0.5-2 times compared with traditional handicraft, has saved production cost.
By isocyanates excellent performance made from the preparation method of the present invention, multiple fields are can be widely applied to, such as
Obtained 1,4- fourths diisocyanate, penta diisocyanate of 1,5-, hexamethylene diisocyanate etc. can be used for biomedical material
Preparation；Such as the isocyanates such as hexamethylene diisocyanate, anti-form-1,4- cyclohexylene diisocyanates can be used for adhesive, resistance to
The preparation of xanthochromia car paint, coating.
Prepare isocyanates into polyester hyper-dispersant incorporated in the present invention in salt process, diamines is into remaining to after salt
Disperse the generation in a solvent, avoiding caking phenomenon of uniting evenly；The viscosity of hydrochloride slurry is reduced, adds its flowing
Property, easy to shift slurry；Solid particle dispersions are uniform, improve salt-forming reaction efficiency；So that phosgenation process obtain it is highly concentrated
Spend the photochemical liquid of isocyanates.At the same time introduce polyester hyper-dispersant can high degree of dispersion raw material amine, advantageously reduce ureas by-product
Generation.
Embodiment
For a better understanding of the technical solution of the present invention, with reference to the embodiment content that the present invention is further explained,
But present disclosure is not limited only to following embodiments.
If involved molecular weight is not specified in following embodiments, equal number average molecular.
Primary raw material used in embodiment or comparative example is illustrated below：
One-ended hydroxy polyethylene oxide, lark prestige, Mn=428；
One-ended hydroxy polyethylene oxide, lark prestige, Mn=604；
One-ended hydroxy polyethylene oxide, lark prestige, Mn=956；
One-ended hydroxy polyethylene oxide, lark prestige, Mn=384；
One-ended hydroxy polyethylene oxide, lark prestige, Mn=296；
Leucine, An Naiji, 98%；
Phenylalanine, lark prestige, 97%；
Alanine, lark prestige, 99%；
Glycine, lark prestige, 98%；
Glutamic acid, lark prestige, 99%；
Diisocyanate and polyisocyanate, Wan Hua companies；
GC purity test instruments：Agilent, pillar：DB-5, fid detector, 260 DEG C of injector temperature, detector temperature
300 DEG C, carrier gas：Nitrogen (10mL/min), split ratio 10：1, sample size：20ul；
Viscosity test instrument：BROOKFIELD viscosimeter LVDV-1Prime, rotor：LV3, test condition：30℃.
Embodiment 1-5 is the preparation embodiment of polyester oversubscription granular media.
[embodiment 1]
By the one-ended hydroxy polyethylene oxide 42.8g of number-average molecular weight about 428 (0.1mol, structural formula are shown in formula (II), wherein
For a values 9) to add solvent acetic acid butyl ester 64.2g, it is 40wt% to make solid content, obtains one-ended hydroxy polyethylene oxide solution.
25gMDI (0.1mol, diphenyl methane two are added in the four-hole boiling flask equipped with blender, thermometer and condenser pipe
Isocyanates) and catalyst dibutyltin dilaurylate 0.06g, in the case where at the uniform velocity stirring, prepared single-ended hydroxyl is added dropwise in Slow Isothermal
Base polyethylene oxide solution.Completion of dropwise addition is warming up to 60 DEG C.
When in reaction system-NCO content be reaction system in-NCO initial contents 50wt% when, add 89.3g acetic acid
Butyl ester reduces system viscosity.Above-mentioned mixed liquor is added in 11.3g leucines (0.1mol), end capping reaction is carried out at 80 DEG C, instead
When answering the residual content of-NCO in system to be the 1wt% of-NCO initial contents in reaction system, reaction terminates.
The polyester hyper-dispersant 1 that solid content is 34wt% is obtained, its average molecular weight is 791, and structural formula is shown in formula (I), its
In R1For methyl diphenylene diisocyanate residue (sloughing-NCO), R2The one-ended hydroxy polyethylene oxide residue for being 9 for a values
(sloughing terminal hydroxy group), R3(- NH is sloughed for leucine residue2), the average value that the average value of m is 1, n is 1.
The Structural Identification information of polyester oversubscription granular media is as follows made from the present embodiment：
1H NMR(CDCl3,500MHz):δ 3.81 (2H, ArCH 2Ar), 6.0 (2H, ArN of δHCONH), δ 8.0 (1H,
ArNHCOO)；13C NMR：δ41.3(ArCH2Ar), 157.7 (NH of δCONH),δ154.8(NHCOO)。
[embodiment 2]
By the one-ended hydroxy polyethylene oxide 48.3g of number-average molecular weight about 604 (0.08mol, structural formula are shown in formula (II), its
For middle a values 13) to add solvent acetic acid butyl ester 90g, it is 35wt% to make solid content, obtains one-ended hydroxy polyethylene oxide solution.
37.7gXDI tripolymer (0.067mol, benzene are added in the four-hole boiling flask equipped with blender, thermometer and condenser pipe
Dimethylene diisocyanate tripolymer) and octoate catalyst stannous 0.08g, in the case where at the uniform velocity stirring, Slow Isothermal is added dropwise and prepares
One-ended hydroxy polyethylene oxide solution.Completion of dropwise addition is warming up to 70 DEG C.
When in reaction system-NCO content be reaction system in-NCO initial contents 60wt% when, add 106.5g acetic acid
Butyl ester reduces system viscosity.And add above-mentioned mixed liquor in 19.8g phenylalanines (0.12mol), carry out blocking at 70 DEG C anti-
Should, when the residual content of-NCO is the 0.3wt% of-NCO initial contents in reaction system in reaction system, reaction terminates.
The polyester hyper-dispersant 2 that solid content is about 35wt% is obtained, its average molecular weight is 1585.Structural formula is shown in formula (I),
R therein1For benzene dimethylene diisocyanate tripolymer residue (sloughing-NCO), R2The one-ended hydroxy polycyclic oxygen for being 13 for a values
Ethane residue (sloughs terminal hydroxy group), R3(- NH is sloughed for phenylalanine residue2), the average value that the average value of m is 1.2, n is 1.8.
The Structural Identification information of polyester oversubscription granular media is as follows made from the present embodiment：
1H NMR(CDCl3,500MHz):δ 4.42 (9.6H, ArCH 2NHCONH), 4.22 (2.4H, ArC of δH 2NHCOO), δ
6.0 (3.6H, ArNHCONH), δ 8.0 (1.2H, NHCOO)；13CNMR：δ163.2(NHCONH),δ159.5(NCON), δ 157.8
(NHCOO)。
[embodiment 3]
By the one-ended hydroxy polyethylene oxide 76.48g of number-average molecular weight about 956 (0.08mol, structural formula are shown in formula (II), its
For middle a values 21) to add solvent acetic acid butyl ester 130g, it is 37wt% to make solid content, obtains one-ended hydroxy polyethylene oxide solution.
35gTDI tripolymer (0.067mol, toluene are added in the four-hole boiling flask equipped with blender, thermometer and condenser pipe
Diisocyanate trimer) and octoate catalyst stannous 0.06g, in the case where at the uniform velocity stirring, the single-ended hydroxyl configured is added dropwise in Slow Isothermal
Base polyethylene oxide solution.Completion of dropwise addition is warming up to 80 DEG C.
When reaction system-NCO content is the 60wt% of-NCO initial contents in reaction system, 69.3g acetic acid fourths are added
Ester reduces system viscosity.And add above-mentioned mixed liquor in 10.7g alanine (0.12mol), end capping reaction is carried out at 60 DEG C, instead
When answering the residual content of-NCO in system to be the 0.15wt% of-NCO initial contents in reaction system, reaction terminates.
The polyester hyper-dispersant 3 that solid content is about 38wt% is obtained, its average molecular weight is 1831.Structural formula is shown in formula (I),
R therein1For toluene diisocyanate trimer residue (sloughing-NCO), R2The one-ended hydroxy polyethylene oxide for being 13 for a values is residual
Base (sloughs terminal hydroxy group), R3(- NH is sloughed for alanine residue2), the average value that the average mean of m is 1.2, n is 1.8.
The Structural Identification information of polyester oversubscription granular media is as follows made from the present embodiment：
1H NMR(CDCl3,500MHz):δ 2.35 (9H, ArCH 3), δ 6.0 (3.6H, ArNHCONH), δ 8.0 (1.2H,
NHCOO)；13CNMR：δ157.7(NHCONH),δ148.8(NCON), 154.8 (NH of δCOO)。
[embodiment 4]
By the one-ended hydroxy polyethylene oxide 46g of number-average molecular weight about 384, (0.12mol, structural formula are shown in formula (II), wherein a
Be worth makes solid content be 40wt% 8) to add solvent acetic acid butyl ester 69g, obtains one-ended hydroxy polyethylene oxide solution.
35gTDI pentamer mixtures are added in the four-hole boiling flask equipped with blender, thermometer and condenser pipe
(0.04mol) and catalyst n-methyl morpholine 0.05g, in the case where at the uniform velocity stirring, prepared one-ended hydroxy polycyclic is added dropwise in Slow Isothermal
Solution of ethylene oxide.Completion of dropwise addition is warming up to 80 DEG C.
When in reaction system-NCO content be reaction system in-NCO initial contents 60wt% when, add 55.3g acetic acid
Butyl ester reduces system viscosity.And add above-mentioned mixed liquor in 6g glycine (0.08mol), end capping reaction is carried out at 100 DEG C, instead
When answering the residual content of-NCO in system to be the 0.02wt% of-NCO initial contents in reaction system, reaction terminates.
The polyester hyper-dispersant 4 that solid content is about 37wt% is obtained, its average molecular weight is 1864.Structural formula is shown in formula (I),
R therein1For toluene di-isocyanate(TDI) pentamer residue (sloughing-NCO), R2The one-ended hydroxy polyethylene oxide for being 8 for a values is residual
Base (sloughs terminal hydroxy group), R3(- NH is sloughed for glycine residue2), the average value that the average value of m is 2, n is 3.
The Structural Identification information of polyester oversubscription granular media is as follows made from the present embodiment：
1H NMR(CDCl3,500MHz):δ 2.35 (15H, ArCH 3), δ 6.0 (6H, ArNHCONH), δ 8.0 (2H,
NHCOO)；13CNMR：δ157.7(NHCONH),δ148.2(NCON), 154.8 (NH of δCOO)。
[embodiment 5]
By the one-ended hydroxy polyethylene oxide 18g of number-average molecular weight about 296, (0.06mol, structural formula are shown in formula (II), wherein a
It is worth 6) to add solvent acetic acid butyl ester 27g, it is 40wt% to make solid content, obtains one-ended hydroxy polyethylene oxide solution.
Nine aggressiveness of 35gTDI heptamers and TDI is added in the four-hole boiling flask equipped with blender, thermometer and condenser pipe
(NCO total content 0.2mol, the molar ratio of nine aggressiveness of TDI heptamers and TDI is 1 to mixture in mixture：And catalyst two 1)
Ethylene diamine 0.05g, in the case where at the uniform velocity stirring, prepared one-ended hydroxy polyethylene oxide solution is added dropwise in Slow Isothermal.Knot is added dropwise
Beam is warming up to 80 DEG C.
When in reaction system-NCO content be reaction system in-NCO initial contents 70wt% when, add 98.3g acetic acid
Butyl ester reduces system viscosity.And add above-mentioned mixed liquor in 20.58g glutamic acid (0.14mol), carry out blocking at 50 DEG C anti-
Should, react and terminate when the residual content of-NCO is the 0.8wt% of-NCO initial contents in reaction system in reaction system.
The polyester hyper-dispersant 5 that solid content is about 37% is obtained, its average molecular weight is about 2933.6.The polyester is ultra-dispersed
Body is R1See formula (I) compound and R for the structural formula of TDI heptamer residues1See that formula (I) is changed for the structural formula of nine aggressiveness residues of TDI
(molar ratio of the two is 1 to the mixture of compound:1), the R in the structure formula (I) of products therefrom2The one-ended hydroxy for being 6 for a values is gathered
Ethylene oxide residue (sloughs terminal hydroxy group), R3(- NH is sloughed for glutaminic acid residue2), the average value that the average value of m is 2.4, n is
5.6。
The Structural Identification information of polyester oversubscription granular media is as follows made from the present embodiment：
1H NMR(CDCl3,500MHz):δ 2.35 (24H, ArCH 3), δ 6.0 (11.2H, ArNHCONH), δ 8.0 (2.4H,
NHCOO)；13CNMR：δ157.7(NHCONH),δ148.2(NCON), 154.8 (NH of δCOO).
Embodiment 6-12 is the preparation embodiment of isocyanates.
[embodiment 6]
Using with reflux condensing tube, agitating paddle, thermometer, hydrogen chloride, phosgene be blown into pipe, raw material amine ingress pipe 5L it is anti-
Answer device.
Into salt process (the 1,4- butanediamine salt-forming reaction for having carried out 5%)：200g (2.3mol) 1 is put into reactor,
4- butanediamine, 1g polyester hyper-dispersant 1 and 3799g chlorobenzenes are made into mixed liquor.Then, by the temperature control in reactor at 0 DEG C,
By hydrogen chloride gas pipe is blown into start to be passed through hydrogen chloride gas into reactor with the speed of 120L/h, with 3 it is small when be passed through
Finish.Further hydrogen chloride gas progress 10min is passed through with the speed of 50L/h to cure to obtain diamine hydrochloride solution.By gained
The viscosity that solution is measured using viscosimeter is 460cP, is characterized through GC, and unreacted dissociate is not detected by HCl, solid
Amine.
Phosgenation process：When diamine hydrochloride solution being warming up to 80 DEG C in reactor, by phosgene be blown into pipe with
The speed of 100L/h is blown into phosgene, until temperature rises to 90 DEG C, when insulation makes its reaction 18 small.After reaction, into system
Nitrogen is blown into, thus removes unreacted phosgene and the hydrogen chloride gas of generation.Then desolventizing, obtains Isosorbide-5-Nitrae-fourth diisocyanate
Ester crude product.After rectification under vacuum purifies, product 292.4g, GC (gas-chromatography) test purity 99.4wt% are obtained, yield is
91.9%, the tar of generation about 3.8%.
[embodiment 7]
Using with reflux condensing tube, agitating paddle, thermometer, hydrogen chloride, phosgene be blown into pipe, raw material amine ingress pipe 5L it is anti-
Answer device.
Into salt process (the 1,5- pentanediamines salt-forming reaction for having carried out 10%)：400g (3.9mol) 1 is put into reactor,
5- pentanediamines, 4g polyester hyper-dispersant 2 and 3596g ortho-xylenes are made into mixed liquor.Then, the temperature control in reactor is existed
10 DEG C, pipe is blown into by hydrogen chloride gas and starts to be passed through hydrogen chloride gas into reactor with the speed of 200L/h, with 3 it is small when lead to
Enter to finish.Further hydrogen chloride gas progress 10min is passed through with the speed of 50L/h to cure to obtain diamine hydrochloride solution.By institute
The viscosity that the solution obtained is measured using viscosimeter is 820cP, characterizes, is not detected by HCl, solid unreacted through GC
Unhindered amina.
Phosgenation process：When diamine hydrochloride solution being warming up to 100 DEG C in reactor, by phosgene be blown into pipe with
The speed of 160L/h is blown into phosgene, until temperature rises to 140 DEG C, when insulation makes its reaction 4.5 small.After reaction, to system
Nitrogen is inside blown into, thus removes unreacted phosgene and the hydrogen chloride gas of generation.Then desolventizing, obtains 1,5-, penta 2 isocyanides
Acid esters crude product.After rectification under vacuum purifies, product 582.8g, GC (gas-chromatography) test purity 99.4wt% are obtained, yield is
96.4%, the tar of generation about 2.1%.
[embodiment 8]
Using with reflux condensing tube, agitating paddle, thermometer, hydrogen chloride, phosgene be blown into pipe, raw material amine ingress pipe 5L it is anti-
Answer device.
Into salt process (the 1,6- hexamethylene diamines salt-forming reaction for having carried out 15%)：600g (5.2mol) 1 is put into reactor,
6- hexamethylene diamines, 9g polyester hyper-dispersant 3 and 3391g isopropylbenzenes are made into mixed liquor.Then, by the temperature control in reactor 30
DEG C, pipe is blown into by hydrogen chloride gas and starts to be passed through hydrogen chloride gas into reactor with the speed of 260L/h, with 3 it is small when be passed through
Finish.Further hydrogen chloride gas progress 10min is passed through with the speed of 50L/h to cure to obtain diamine hydrochloride solution.By gained
The viscosity that is measured using viscosimeter of solution be 1350cP, characterized through GC, unreacted trip be not detected by HCl, solid
From amine.
Phosgenation process：When diamine hydrochloride solution being warming up to 100 DEG C in reactor, by phosgene be blown into pipe with
The speed of 180L/h is blown into phosgene, until temperature rises to 150 DEG C, when insulation makes its reaction 5.5 small.After reaction, to system
Nitrogen is inside blown into, thus removes unreacted phosgene and the hydrogen chloride gas of generation.Then desolventizing, obtains oneself two isocyanides of 1,6-
Acid esters crude product.After rectification under vacuum purifies, product 830.4g, GC test purity 99.2wt% is obtained, yield 95.6%, generation is about
2.2% tar.
[embodiment 9]
Using with reflux condensing tube, agitating paddle, thermometer, hydrogen chloride, phosgene be blown into pipe, raw material amine ingress pipe 5L it is anti-
Answer device.
Into salt process (having carried out 20% anti-form-1, the salt-forming reaction of 4- cyclohexanediamine)：800g is put into reactor
(7.0mol) anti-form-1,4- cyclohexanediamine, 16g polyester hyper-dispersant 4 and 3184g o-dichlorohenzenes are made into mixed liquor.Then, will be anti-
The temperature control in device is answered to be blown into pipe at 15 DEG C by hydrogen chloride gas and start to be passed through chlorine into reactor with the speed of 340L/h
Change hydrogen, with 3 it is small when be passed through and finish.Further hydrogen chloride gas progress 10min is passed through with the speed of 50L/h to cure to obtain two
Amide hydrochloride.The viscosity that the solution of gained is measured using viscosimeter is 1920cP, is characterized through GC, in HCl, solid
It is not detected by unreacted unhindered amina.
Phosgenation process：When diamine hydrochloride solution being warming up to 100 DEG C in reactor, by phosgene be blown into pipe with
The speed of 200L/h is blown into phosgene, until temperature rises to 160 DEG C, when insulation makes its reaction 7 small.After reaction, into system
Nitrogen is blown into, thus removes unreacted phosgene and the hydrogen chloride gas of generation.Then desolventizing, obtains anti-form-1,4- hexamethylenes
Diisocyanate crude product.After rectification under vacuum purifies, product 1106.3g, GC test purity 99.4wt% is obtained, yield is
95.1%, the tar of generation about 2.6%.
[embodiment 10]
Using with reflux condensing tube, agitating paddle, thermometer, hydrogen chloride, phosgene be blown into pipe, raw material amine ingress pipe 5L it is anti-
Answer device.
Into salt process (the meta-xylylenediamine salt-forming reaction for having carried out 30%)：1200g is put into reactor
(8.8mol) meta-xylylenediamine, 36g polyester hyper-dispersant 5 and 2764g butyl benzenes are made into mixed liquor.Then, will react
Temperature control in device is blown into pipe at 50 DEG C, by hydrogen chloride gas and starts to be passed through chlorination into reactor with the speed of 460L/h
Hydrogen, with 3 it is small when be passed through and finish.Further hydrogen chloride gas progress 10min is passed through with the speed of 50L/h to cure to obtain diamines
HCI solution.The viscosity that the solution of gained is measured using viscosimeter is 3520cP, is characterized through GC, in HCl, solid not
Detect unreacted unhindered amina.
Phosgenation process：When diamine hydrochloride solution being warming up to 100 DEG C in reactor, by phosgene be blown into pipe with
The speed of 180L/h is blown into phosgene, until temperature rises to 170 DEG C, when insulation makes its reaction 10.5 small.After reaction, to system
Nitrogen is inside blown into, thus removes unreacted phosgene and the hydrogen chloride gas of generation.Then desolventizing, obtains m-phenylenedimethylim-
Diisocyanate crude product.After rectification under vacuum purifies, product 1568.3g, GC test purity 99.3wt% is obtained, yield is
94.8%, the tar of generation about 3.5%.
[embodiment 11]
Using with reflux condensing tube, agitating paddle, thermometer, hydrogen chloride, phosgene be blown into pipe, raw material amine ingress pipe 5L it is anti-
Answer device.
Into salt process：Cyclohexyldimethylene diamines, 48g polyester oversubscription between 1600g (11.3mol) are put into reactor
Powder 1 is made into mixed liquor with 2352g o-dichlorohenzenes.Then, the temperature control in reactor is passed through into hydrogen chloride gas at 5 DEG C
Pipe is blown into start to be passed through hydrogen chloride gas into reactor with the speed of 600L/h, with 3 it is small when be passed through and finish.Further with 50L/
The speed of h is passed through hydrogen chloride gas progress 10min and cures to obtain diamine hydrochloride solution.The solution of gained is measured using viscosity
The viscosity obtained is 4690cP, is characterized through GC, unreacted unhindered amina is not detected by HCl, solid.
Phosgenation process：When diamine hydrochloride solution being warming up to 100 DEG C in reactor, by phosgene be blown into pipe with
The speed of 190L/h is blown into phosgene, until temperature rises to 180 DEG C, when insulation makes its reaction 15 small.After reaction, into system
Nitrogen is blown into, thus removes unreacted phosgene and the hydrogen chloride gas of generation.Then desolventizing, obtains two methylene of a cyclohexyl
Group diisocyanate crude product.After rectification under vacuum purifies, product 2.32.1g, GC test purity 99.2wt% is obtained, yield is
93.7%, the tar of generation about 4.9%.
[embodiment 12]
Using with reflux condensing tube, agitating paddle, thermometer, hydrogen chloride, phosgene be blown into pipe, raw material amine ingress pipe 5L it is anti-
Answer device.
Into salt process (the isophorone diamine salt-forming reaction for having carried out 20%)：800g (4.7mol) is put into reactor
Isophorone diamine, 16g polyester hyper-dispersant 1 and 3184g o-dichlorohenzenes are made into mixed liquor.Then, by the temperature in reactor
Control is blown into pipe by hydrogen chloride gas and starts to be passed through hydrogen chloride gas into reactor with the speed of 250L/h, with 3 at 20 DEG C
Hour, which is passed through, to be finished.Further with the speed of 50L/h be passed through hydrogen chloride gas carry out 10min cure to obtain diamine hydrochloride it is molten
Liquid.The viscosity that the solution of gained is measured using viscosimeter is 1740cP, characterizes through GC, is not detected by not in HCl, solid
The unhindered amina of reaction.
Phosgenation process：When HCI solution being warming up to 100 DEG C in reactor, pipe is blown into 120L/h by phosgene
Speed be blown into phosgene, until temperature rises to 150 DEG C, when insulation makes its reaction 7 small.After reaction, nitrogen is blown into system
Gas, thus removes unreacted phosgene and the hydrogen chloride gas of generation.Then desolventizing, it is thick to obtain isophorone diisocyanate
Product.After rectification under vacuum purifies, product 997.5g, GC test purity 99.3wt%, yield 95.5%, generation about 2.5% are obtained
Tar.
[comparative example 1]
Using with reflux condensing tube, agitating paddle, thermometer, hydrogen chloride, phosgene be blown into pipe, raw material amine ingress pipe 5L it is anti-
Answer device.
Into salt process (the 1,5- pentanediamines salt-forming reaction for having carried out 10%)：400g (3.9mol) 1 is put into reactor,
5- pentanediamines are made into mixed liquor with 3600g o-dichlorohenzenes.Then, the temperature control in reactor is passed through into hydrogen chloride at 10 DEG C
Gas insufflation tube starts to be passed through hydrogen chloride gas into reactor with the speed of 200L/h, with 3 it is small when be passed through and finish.Further with
The speed of 50L/h is passed through hydrogen chloride gas progress 10min and cures to obtain diamine hydrochloride solution.The solution of gained is used into viscosity
The viscosity measured is 2620cP, is characterized through GC, and unreacted unhindered amina is not detected by HCl, solid.
Phosgenation process：When HCI solution being warming up to 100 DEG C in reactor, pipe is blown into 160L/h by phosgene
Speed be blown into phosgene, until temperature rises to 140 DEG C, when insulation makes its reaction 4.5 small.After reaction, it is blown into system
Nitrogen, thus removes unreacted phosgene and the hydrogen chloride gas of generation.Then desolventizing, it is thick to obtain 1,5-, penta diisocyanate
Product.After rectification under vacuum purifies, product 556.8g, GC test purity 99.7wt%, yield 92.1%, generation about 3.3% are obtained
Tar.
Comparing embodiment 7 and comparative example 1 are as it can be seen that the two prepares isocyanates under substantially the same conditions, and embodiment 7
Compared with comparative example 1 has more in the diamine hydrochloride solution into the polyester hyper-dispersant that the present invention is added in salt process, acquisition
Low viscosity, and final obtained isocyanates has the yield of higher
[comparative example 2]
Using with reflux condensing tube, agitating paddle, thermometer, hydrogen chloride, phosgene be blown into pipe, raw material amine ingress pipe 5L it is anti-
Answer device.
Into salt process (having carried out 20% anti-form-1, the salt-forming reaction of 4- cyclohexanediamine)：800g is put into reactor
(7.0mol) anti-form-1,4- cyclohexanediamine are made into mixed liquor with 3200g o-dichlorohenzenes.Then, by the temperature control in reactor
At 15 DEG C, pipe is blown into by hydrogen chloride gas and starts to be passed through hydrogen chloride gas into reactor with the speed of 340L/h, with 3 it is small when
It is passed through and finishes.Further hydrogen chloride gas progress 10min is passed through with the speed of 50L/h to cure to obtain diamine hydrochloride solution, it is quiet
Postpone in HCI solution unite, caking phenomenon.The viscosity that the solution of gained is measured using viscosimeter is 7000cP, through GC
Characterization, detects the unreacted unhindered aminas of 0.2wt% in HCl, solid (relative to the quality of raw material amine).
Phosgenation process：When HCI solution being warming up to 100 DEG C in reactor, pipe is blown into 200L/h by phosgene
Speed be blown into phosgene, until temperature rises to 160 DEG C, when insulation makes its reaction 7 small, reaction solution does not reach clarification.Stop reaction,
Nitrogen is blown into system, thus removes unreacted phosgene and the hydrogen chloride gas of generation.Then desolventizing, obtain it is trans-
1,4- cyclohexylene diisocyanate crude products.After rectification under vacuum purifies, product 1020.2g, GC test purity 99.8wt%, yield are obtained
For 87.7%, the tar of generation about 8.3%.
Comparing embodiment 9 and comparative example 2 are as it can be seen that the two prepares isocyanates under substantially the same conditions, and embodiment 9
The polyester hyper-dispersant of the present invention is added, the diamine hydrochloride solution of 20% mass content is carried out into after salt, photochemical and separation, obtained
To higher product yield, therefore in high concentration under salt system, the effect of polyester hyper-dispersant is more notable.
By above example as it can be seen that polyester hyper-dispersant using the present invention prepares isocyanates, into salt process
The diamines hydrochloric acid that can be obtained compared with low viscosity has solution, improves its mobility, scattered in a solvent beneficial to it, avoids caking of uniting
The generation of phenomenon.Tar content is relatively low in obtained product, beneficial to the product for obtaining more lustful number.In addition, utilize the present invention's
The features such as polyester hyper-dispersant prepares isocyanates, the also high conversion rate with diamines, and product yield is high.
It will be understood by those skilled in the art that under the teaching of this specification, the present invention can be made some modifications or
Adjustment.These modifications or adjustment should also be as within the scope of the claims in the present invention.
Claims (16)
1. a kind of polyester hyper-dispersant, it is characterised in that there is following structure formula (I):
Wherein, the R in formula (I)1The residue of-NCO is sloughed for diisocyanate or poly isocyanate sloughs the residue of-NCO；
R2The residue of terminal hydroxy group is sloughed for one-ended hydroxy polyethylene oxide；
R3- NH is sloughed for amino acid2Residue, the amino acid have at least one segment containing-COOH and it is at least one contain-
NH2Segment；
In formula (I), 0 ＜ m≤9,0 ＜ n≤9.
2. polyester hyper-dispersant according to claim 1, it is characterised in that the diisocyanate is two isocyanide of aliphatic
One or more in acid esters, alicyclic diisocyanate and aromatic diisocyanate；
The poly isocyanate is in aliphatic diisocyanate, alicyclic diisocyanate and aromatic diisocyanate
One or more polymer, is preferably the one or more in dimer, tripolymer, pentamer, heptamer and nine aggressiveness.
3. polyester hyper-dispersant according to claim 1, it is characterised in that the one-ended hydroxy polyethylene oxide has such as
Lower structure formula (II)：
Wherein, a in formula (II) is 6≤a≤21；
Preferably, the one-ended hydroxy polyethylene oxide is that one or more one-ended hydroxies in number-average molecular weight 300-1000 are gathered
The combination of ethylene oxide.
4. polyester hyper-dispersant according to claim 1, it is characterised in that the amino acid be selected from glycine, alanine,
One or more in leucine, phenylalanine and glutamic acid.
5. according to claim 1-4 any one of them polyester hyper-dispersants, it is characterised in that the ratio of m and m+n is more than 0
And it is preferably 10-60% less than 100%；The ratio of n and m+n is more than 0 and less than 100%, is preferably 40-90%.
6. according to claim 1-4 any one of them polyester hyper-dispersants, it is characterised in that the number of the polyester hyper-dispersant
Average molecular weight is 700-3000, is preferably 800-3000, more preferably 1500-2000.
7. such as the preparation method of claim 1-6 any one of them polyester hyper-dispersants, it is characterised in that including following step
Suddenly：
1) diisocyanate or poly isocyanate are subjected to end capping reaction with one-ended hydroxy polyethylene oxide；
2) add amino acid into the reaction system of step 1) to be blocked, the amino acid contains-COOH's with least one
Segment and at least one contain-NH2Segment.
8. preparation method according to claim 7, it is characterised in that hydroxyl in one-ended hydroxy polyethylene oxide, two different
Cyanate or the-NCO in the poly isocyanate ,-NH in amino acid2The molar ratio of this three is 0.3-0.5:1:0.5-0.7.
9. according to claim 7-8 any one of them preparation methods, it is characterised in that step 1) carries out in the presence of a catalyst
End capping reaction, the catalyst is in diethylenediamine, dibutyl tin laurate, stannous octoate and N-methylmorpholine
It is one or more；
Preferably, the dosage of catalyst is the 0.02-0.2wt% based on diisocyanate or poly isocyanate quality.
10. according to claim 7-8 any one of them preparation methods, it is characterised in that the reaction temperature of step 1) is 50-
100℃；The reaction temperature of step 2) is 50-100 DEG C；
Preferably, in step 1), reacted in the presence of esters solvent, esters solvent is preferably added in step 2) to adjust system
The solid content of the polyester hyper-dispersant obtained；The esters solvent is preferably in butyl acetate, propyl acetate and isopropyl acetate
It is one or more；
Preferably, in reaction end ,-NCO initially contains step 2) in the residual content and reaction system of-NCO in reaction system
Ratio≤1wt% of amount；
Preferably, excessive diisocyanate or poly isocyanate are added in step 1).
11. a kind of method for preparing isocyanates, including into salt process and phosgenation process, it is characterised in that described into salt
Polyester hyper-dispersant is added when diamine hydrochloride solution is prepared in process, the polyester hyper-dispersant is any for claim 1-6
Polyester hyper-dispersant made from polyester hyper-dispersant or claim 7-10 any one of them preparation methods described in.
12. according to the method for claim 11, it is characterised in that in the process into salt, the dosage of polyester hyper-dispersant
To be preferably 1-2wt% into the 0.5-3wt% of diamines quality used in salt process.
13. according to claim 11-12 any one of them methods, it is characterised in that described to include the following steps into salt process：
Solvent, diamines and polyester hyper-dispersant are mixed, are passed through HCl gases, diamine hydrochloride solution is made；
Preferably, the gross mass based on solvent, diamines and polyester hyper-dispersant, the concentration of the diamines is 5-40wt%；
Preferably, one kind or more in aromatic hydrocarbon, esters of gallic acid solvent of the solvent selected from 120-170 DEG C of boiling point under normal pressure
Kind.
14. according to claim 11-12 any one of them methods, it is characterised in that the knot of diamines used into salt process
Structure general formula is R (NH2)2, the general structure of prepared isocyanates is R (NCO)2, wherein R is at least containing 2 carbon atoms
Aliphatic alkyl or alicyclic alkyl, preferably aliphatic alkyl or alicyclic alkyl containing 2-8 carbon atom.
15. according to claim 11-12 any one of them methods, it is characterised in that the reaction temperature into salt process is
0-50 DEG C, be preferably 5-30 DEG C.
16. according to claim 11-12 any one of them methods, it is characterised in that the phosgenation process includes following step
Suddenly：By the diamine hydrochloride solution and phosgene reaction, the photochemical liquid of isocyanates is prepared；
Preferably, the reaction temperature in phosgenation process is 90-180 DEG C, is preferably 120-170 DEG C.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115894296A (en) * | 2022-11-17 | 2023-04-04 | 万华化学集团股份有限公司 | Isocyanate composition, modified isocyanate, polyurethane resin and optical material |
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| US4897087A (en) * | 1988-11-30 | 1990-01-30 | Mobil Oil Corporation | Diisocyanate derivatives as ashless fuel dispersants and detergents and fuel compositions containing same |
| CN105440238A (en) * | 2014-09-18 | 2016-03-30 | 赢创德固赛有限公司 | Addition compounds suitable as dispersants or anti-sedimentation agents |
| CN106674463A (en) * | 2017-02-08 | 2017-05-17 | 上海金狮化工有限公司 | Polyurethane pigment dispersing agent and method for preparing same |
| CN107337615A (en) * | 2016-08-09 | 2017-11-10 | 万华化学集团股份有限公司 | A kind of preparation method of isocyanates |
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2017
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4897087A (en) * | 1988-11-30 | 1990-01-30 | Mobil Oil Corporation | Diisocyanate derivatives as ashless fuel dispersants and detergents and fuel compositions containing same |
| CN105440238A (en) * | 2014-09-18 | 2016-03-30 | 赢创德固赛有限公司 | Addition compounds suitable as dispersants or anti-sedimentation agents |
| CN107337615A (en) * | 2016-08-09 | 2017-11-10 | 万华化学集团股份有限公司 | A kind of preparation method of isocyanates |
| CN106674463A (en) * | 2017-02-08 | 2017-05-17 | 上海金狮化工有限公司 | Polyurethane pigment dispersing agent and method for preparing same |
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| CN115894296A (en) * | 2022-11-17 | 2023-04-04 | 万华化学集团股份有限公司 | Isocyanate composition, modified isocyanate, polyurethane resin and optical material |
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