CN1272368C - Separating method for isocyanate monomer of urethane curing agent - Google Patents
Separating method for isocyanate monomer of urethane curing agent Download PDFInfo
- Publication number
- CN1272368C CN1272368C CN 200410027560 CN200410027560A CN1272368C CN 1272368 C CN1272368 C CN 1272368C CN 200410027560 CN200410027560 CN 200410027560 CN 200410027560 A CN200410027560 A CN 200410027560A CN 1272368 C CN1272368 C CN 1272368C
- Authority
- CN
- China
- Prior art keywords
- diisocyanate
- curing agent
- solidifying agent
- acid
- polyurethane curing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to a method for separating isocyanate in a polyurethane solidifying agent, which comprises the steps that acid which accounts for 0.01% to 0.5% of the total quantity of the solidifying agent is added to the polyurethane solidifying agent and is used as a reaction inhibiting agent, and a distilling entrainer which accounts for 8% to 60% of the total quantity of the solidifying agent is added into the solidifying agent; three stages of separation are carried out by adopting an internal cooling type film evaporator or an external cooling type film evaporator, evaporating residues separated from the second stage separation or the third stage separation are pumped into a diluting container by a pump, a solvent is put into the diluting container in advance, the solvent is heated to 80 to 140 DEG C, and the solid content of the solidifying agent obtained by stirring and dilution is from 35% to 85%. The present invention has the advantages of high solid content of the obtained solidifying agent, and low isocyanate content and viscosity.
Description
Technical field
The present invention relates to the Separation ﹠ Purification of the easy cure polymer of high viscosity thermo-sensitivity, particularly be fit to coating or tackiness agent separation method with the deleterious isocyanate-monomer of residual free in the polyurethane curing agent.
Background technology
The polyurethane coating appearance of film is fine, hardness is big, corrosion-resistant, chemicals-resistant, is one of best coating variety of over-all properties.Polyurethane adhesive also has similar feature and bonding strength big, and according to modern environmental requirement, polyurethane coating or tackiness agent must solve two technical barriers, and the one, improve solid content and reduce solvent to greatest extent.The 2nd, reduce free two (many) isocyanate content in the polyurethane curing agent, promptly develop nontoxic solidifying agent.
The free isocyanate monomer content height that China's polyurethane curing agent kind is single at present, solid content is low, residual, toxicity is big, and the method that reduces residual monomer in the polyurethane curing agent comprises chemical reaction method, solvent extration, supercritical extraction, molecular sieve adsorption and vacuum distillation method etc.
Chemical reaction method is the method that adopts chemical catalysis, by formulating of recipe and special synthesis technique, the monomer that uses method such as effective catalyst to make to remain in the solidifying agent by autohemagglutination or and other substance reaction eliminate.Adopt chemical process to reduce the residual monomer content complex process, the product viscosity height, molecular weight is bigger, molecular weight distribution is inhomogeneous, and is poor with the consistency of hydroxy resin, reduced the performance of polyurethane coating, the most important thing is to be configured to the solidifying agent of high solids content, do not meet environmental requirement.
Solvent extration adopts hydrocarbon mixture to join in the solidifying agent primary products, the free isocyanate-monomer is dissolvable in water in the hydrocarbon mixture, and the solidifying agent polymkeric substance then can not dissolve and separate out at bottom, divides the hydrocarbon mixture solvent that goes to the upper strata, add fresh mixed solvent again, the product that extracted several times obtains purifying.But the extraction process route is long, operational difficulty, and efficient is low, difficult solvent recovery, residual solvent can influence the performance of product, and in addition, solvent is necessary can not be moisture, realizes that simultaneously these require difficulty very big, and separation solvent and the required energy consumption of monomer are big, very uneconomical.
Supercritical extraction and solvent-extracted principle are closely similar, adopt carbonic acid gas, the hydro carbons etc. can be in dissolved monomer under the supercritical state and material and polyurethane curing agent head product that can not dissolve polymer mix, take away monomer wherein, monomer separates with extraction agent, isolating monomer enters reactor system solidifying agent again, extraction agent returns extraction again, this law separation efficiency height through overdraft.But this method and solvent extration are relatively, and facility investment and running cost are higher.
Molecular sieve adsorption technology is simple, but has the shortcoming of molecular sieve desorption monomer difficulty, causes a large amount of monomer wasted, and the desired molecule sieve can not reuse and cause cost height, contaminate environment.
Generally adopting thin-film evaporator to reduce residual monomer in the solidifying agent at present abroad, is a kind of efficient ways.The polyurethane curing agent relative molecular weight that China produces use at present is bigger, the viscosity height, and the flowability of solidifying agent is poor when adopting thin-film evaporator to separate residual monomer, often stops up thin-film evaporator, causes separating failure.
Summary of the invention
The present invention is directed to shortcomings such as the polyurethane curing agent solid content that existing separation method obtains is low, isocyanate content is high, viscosity is big, flowability is bad, the separation method of isocyanic ester in a kind of efficient, economic polyurethane curing agent is provided, and the solidifying agent solid content height that obtains, isocyanate content is low, viscosity is little.
The separation method of isocyanic ester comprises the following steps: in the polyurethane curing agent of the present invention
The first step, in polyurethane curing agent, add account for solidifying agent total amount ten thousand/5/1,000 acid as reaction suppressor, add 8%～60% distillation entrainment agent of solidifying agent total amount;
Described acid comprises wherein one or more mixture of Benzoyl chloride, Acetyl Chloride 98Min., phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, formic acid, acetate or oxalic acid;
Described distillation entrainment agent comprises wherein one or more mixture of S-150, S-200, propylene glycol monobutyl ether acetate, butyl carbitol acetate, Diethylene Glycol monobutyl ether acetate, diethylene glycol ether acetic ester, methyl benzoate, ethyl benzoate, propyl benzoate, phenylformic acid fourth fat, dimethyl phthalate, diethyl phthalate, dibutyl phthalate;
The thin-film evaporator of second step, employing inner-cooled or the thin-film evaporator of external-cooling type carry out three grades of separation, the separation temperature of one-level between 90～180 ℃, pressure is between 2000～30000Pa, the separation temperature of secondary between 120～210 ℃, pressure between 10～600Pa, three grades separation temperature between 140～240 ℃, pressure is between 9～400Pa;
The 3rd step, the steaming excess that will come out from secondary or three grades of separation add solvent in advance with pump suction latting drown containers in the latting drown container, solvent is heated between 80～140 ℃, and the solid content of the solidifying agent that agitation and dilution obtains is between 35%-85%; Used solvent comprises wherein one or more mixtures of vinyl acetic monomer, N-BUTYL ACETATE, toluene, dimethylbenzene, pimelinketone, methylethylketone, oxytol acetate.
Solid content mass fraction after the dilution reaches at 75% o'clock, and its NCO content is greater than 12.8%, and free monomer mass fraction wherein is less than 0.5%, packaging final prod, the requirement that quality product meets international standards.
The present invention adds distillation entrainment agent and reaction suppressor, can reduce the side reaction of solidifying agent when distillation, is convenient to isolating carrying out.
The described polyurethane curing agent of the first step can be with diisocyanate monomer synthetic urethane tripolymer, or be 1.9-3.0 by the equivalence ratio of NCO and OH: 1 proportioning adds vulcabond and contains the poly-hydroxy organism through dehydration, having under the situation of dehydrated solvent, at 55～120 ℃ of reactions 2～6 hours, the base polyurethane prepolymer for use as that obtains;
Described urethane tripolymer comprises wherein one or more mixtures such as toluene diisocyanate trimer, hexamethylene diisocyanate trimer, diphenylmethanediisocyanate tripolymer, xylylene diisocyanate tripolymer, isophorone diisocyanate trimer, Methylcyclohexyl diisocyanate tripolymer, dicyclohexyl methane diisocyanate tripolymer.
Described vulcabond comprises wherein one or more mixtures of tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, Methylcyclohexyl diisocyanate, hydrogenation MDI, isophorone diisocyanate, PPDI, inferior xylylene vulcabond.
Described dehydrated solvent comprises wherein one or more mixture of toluene, dimethylbenzene, vinyl acetic monomer, N-BUTYL ACETATE, pimelinketone, methylethylketone;
The polyethers, glycol ether, triglycol that described poly-hydroxy organism comprises polyester, all size of various dibasic alcohol, TriMethylolPropane(TMP), tetramethylolmethane, all size be one or more mixture wherein.
Principle of the present invention can be interpreted as: polyurethane curing agent is the easy polymeric polymer substance of thermo-sensitivity, has general high molecular feature, do not having under the situation of solvent, needing high temperature to flow distills, but high temperature can quicken side reaction, low temperature does not have the flowability will occluding device, if according to its chemical reaction characteristic, in pretreated process, add reaction suppressor and extraction entrainment agent and reduce its side reaction when distillation, flowability when increasing its distillation will help isolating carrying out.
The present invention compared with prior art has following advantage:
1, compares with vacuum distillation method with chemical reaction method, when this method reduces polyurethane curing agent free monomers content, can not enlarge markedly the relative molecular weight and the molecular weight distribution of solidifying agent, can significantly not reduce the consistency of solidifying agent and hydroxy resin, its solid content of the solidifying agent that obtains can be adjusted arbitrarily, and solid content can be up to 80%.
2, compare with solvent or supercritical extraction, this law technology is simple, energy consumption is low, operability is stronger.
3, compare with absorption method, this law is polluted very little, does not almost have; Cost is low.
Embodiment
Embodiment 1
The NCO/OH equivalence ratio that adopts tolylene diisocyanate (TDI) and TriMethylolPropane(TMP) (TMP) is 1.9 proportioning, add N-BUTYL ACETATE as solvent, at 2 hours synthetic solid contents of 55 ℃ of reactions is 50% solidifying agent 3Kg, and free TDI content is 3.1% polyurethane curing agent.In the synthetic solidifying agent, add ten thousand/be that the phosphoric acid and 8% of 0.3g is the 240g methyl benzoate, in described thin-film evaporator of second step, this solidifying agent is carried out flash trapping stage at 90 ℃, 2000Pa, carrying out secondary under 120 ℃, the situation of 10Pa separates, squeeze into the latting drown container with pump then, under 60 ℃, be configured to 75% solution, obtain product, its free TDI mass content 0.42%, NCO content is 12.7%.
Embodiment 2
Adopting tolylene diisocyanate (TDI) and hexamethylene diisocyanate (HDI) is that the NCO/OH equivalence ratio of 1: 1 mixture and TriMethylolPropane(TMP) (TMP) is 2.3 proportioning by mass ratio, the mixture that adds N-BUTYL ACETATE and dimethylbenzene is as solvent, at 4 hours synthetic solid contents of 55 ℃ of reactions is 50% solidifying agent 3Kg, and free-diisocyanate content is 8.5% polyurethane curing agent.Adding 2/10000ths in the synthetic solidifying agent is that the phosphoric acid and 10% of 0.6g is that 300g methyl benzoate and 10% is the 300g butyl benzoate, in described thin-film evaporator of second step, this solidifying agent is carried out flash trapping stage at 90 ℃, 2000Pa, carrying out secondary under 120 ℃, the situation of 10Pa separates, squeeze into the latting drown container with pump then, under 60 ℃, be configured to 75% solution, obtain product, its free TDI mass content 0.42%, NCO content is 12.7%.
Embodiment 3
(relative molecular weight is 1000 to poly-penta dibasic alcohol of the hexamethylene diisocyanate (HDI) of employing 190mol and 100mol, hydroxy radical content is 3.3%) add in the reactor, adding the dehydration pimelinketone reacted 6 hours at 120 ℃ as solvent, synthetic solid content is 50%, free TDI content is 8.9% polyurethane curing agent, the phosphoric acid and the 15kg S-200 solvent that add 200g then, this solidifying agent is gone on foot in the described thin-film evaporator at 180 ℃ second, 30000Pa carries out the one-level distillation, at 210 ℃, carry out secondary distillation under the situation of 600Pa, at 240 ℃, carry out three-stage distillation under the 400Pa, squeeze into the latting drown container with pump then, under 140 ℃, be configured to 80% solution, obtain product, its free TDI mass content 0.15%, NCO content is 7.9%.
Embodiment 4
The TDI tripolymer 500kg that adopts certain system lacquer factory to provide, its free monomer content is 2.5%, the Benzoyl chloride and the 200Kg butyl carbitol acetate that this solidifying agent are added 0.3kg in pre-processing device, this solidifying agent is carried out the one-level distillation at 130 ℃, 10000Pa in described thin-film evaporator of second step, under 160 ℃, the situation of 100Pa, carry out the secondary distillation distillation, squeeze into the latting drown container with pump then, under 120 ℃, be configured to 50% solution, obtain product, its free TDI mass content 0.35%.
Claims (5)
1, the separation method of isocyanic ester in a kind of polyurethane curing agent is characterized in that comprising the following steps:
The first step, in polyurethane curing agent, add account for solidifying agent total amount ten thousand/5/1,000 acid as reaction suppressor, add 8%～60% distillation entrainment agent of solidifying agent total amount;
Described acid comprises wherein one or more mixture of Benzoyl chloride, Acetyl Chloride 98Min., phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, formic acid, acetate or oxalic acid;
Described distillation entrainment agent comprises wherein one or more mixture of S-150, S-200, propylene glycol monobutyl ether acetate, butyl carbitol acetate, Diethylene Glycol monobutyl ether acetate, diethylene glycol ether acetic ester, methyl benzoate, ethyl benzoate, propyl benzoate, phenylformic acid fourth fat, dimethyl phthalate, diethyl phthalate, dibutyl phthalate;
The thin-film evaporator of second step, employing inner-cooled or the thin-film evaporator of external-cooling type carry out three grades of separation, the separation temperature of one-level between 90～180 ℃, pressure is between 2000～30000Pa, the separation temperature of secondary between 120～210 ℃, pressure between 10～600Pa, three grades separation temperature between 140～240 ℃, pressure is between 9～400Pa;
The 3rd step, the steaming excess that will come out from secondary or three grades of separation add solvent in advance with pump suction latting drown containers in the latting drown container, solvent is heated between 80～140 ℃, and the solid content of the solidifying agent that agitation and dilution obtains is between 35%-85%;
Used solvent comprises wherein one or more mixtures of vinyl acetic monomer, N-BUTYL ACETATE, toluene, dimethylbenzene, pimelinketone, methylethylketone, oxytol acetate.
2, the separation method of isocyanic ester in the polyurethane curing agent according to claim 1 is characterized in that the described polyurethane curing agent of the first step is with diisocyanate monomer synthetic urethane tripolymer.
3, the separation method of isocyanic ester in the polyurethane curing agent according to claim 2 is characterized in that described vulcabond comprises wherein one or more mixtures of tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, Methylcyclohexyl diisocyanate, hydrogenation MDI, isophorone diisocyanate, PPDI, inferior xylylene vulcabond; Described urethane tripolymer comprises one or more mixtures in toluene diisocyanate trimer, hexamethylene diisocyanate trimer, diphenylmethanediisocyanate tripolymer, xylylene diisocyanate tripolymer, isophorone diisocyanate trimer, Methylcyclohexyl diisocyanate tripolymer, the dicyclohexyl methane diisocyanate tripolymer.
4, the separation method of isocyanic ester in the polyurethane curing agent according to claim 1, it is characterized in that the described polyurethane curing agent of the first step is that equivalence ratio by NCO and OH is 1.9-3.0: 1 proportioning adds vulcabond and contains the poly-hydroxy organism through dehydration, having under the situation of dehydrated solvent, at 55～120 ℃ of reactions 2～6 hours, the base polyurethane prepolymer for use as that obtains.
5, the separation method of isocyanic ester in the polyurethane curing agent according to claim 4 is characterized in that described vulcabond comprises wherein one or more mixtures of tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, Methylcyclohexyl diisocyanate, hydrogenation MDI, isophorone diisocyanate, PPDI, inferior xylylene vulcabond; Described dehydrated solvent comprises wherein one or more mixture of toluene, dimethylbenzene, vinyl acetic monomer, N-BUTYL ACETATE, pimelinketone, methylethylketone; The polyethers, glycol ether, triglycol that described poly-hydroxy organism comprises polyester, all size of various dibasic alcohol, TriMethylolPropane(TMP), tetramethylolmethane, all size be one or more mixture wherein.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410027560 CN1272368C (en) | 2004-06-11 | 2004-06-11 | Separating method for isocyanate monomer of urethane curing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410027560 CN1272368C (en) | 2004-06-11 | 2004-06-11 | Separating method for isocyanate monomer of urethane curing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1583846A CN1583846A (en) | 2005-02-23 |
| CN1272368C true CN1272368C (en) | 2006-08-30 |
Family
ID=34601401
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410027560 Expired - Fee Related CN1272368C (en) | 2004-06-11 | 2004-06-11 | Separating method for isocyanate monomer of urethane curing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1272368C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103497662A (en) * | 2013-08-28 | 2014-01-08 | 广西梧州龙鱼漆业有限公司 | Polyether-modified polyurethane curing agent and preparation method thereof |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101463141B (en) * | 2008-04-14 | 2012-05-09 | 江门新时代合成材料有限公司 | Environment friendly type separation method for isocyanate in polyurethane curing agent |
| CN102718724A (en) * | 2012-03-14 | 2012-10-10 | 江苏天竹化工科技有限公司 | Preparation method of environment-friendly and light resistant isocyanate trimer curing agent |
| CN104497265B (en) * | 2014-12-11 | 2018-03-30 | 淄博正大聚氨酯有限公司 | The preparation method of low-free TDI polyurethane elastomeric prepolymer |
| CN105837789B (en) * | 2016-04-11 | 2019-02-01 | 上海华峰新材料研发科技有限公司 | The method of extraction removing solvent in aqueous polyurethane production process |
| CN109824865B (en) * | 2018-12-26 | 2021-09-07 | 万华化学集团股份有限公司 | Preparation method of polyisocyanate curing agent with storage stability and curing agent |
| CN109824863A (en) * | 2019-02-22 | 2019-05-31 | 上海稻畑精细化工有限公司 | A kind of preparation method of polyurethane curing agent |
| CN111205436A (en) * | 2020-01-10 | 2020-05-29 | 上海稻畑精细化工有限公司 | Polyurethane curing agent and preparation method thereof |
| CN115181245B (en) * | 2022-08-16 | 2024-03-15 | 广东鼎立森新材料有限公司 | HDI/IPDI curing agent, preparation method, application and thermosetting PU adhesive film |
-
2004
- 2004-06-11 CN CN 200410027560 patent/CN1272368C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103497662A (en) * | 2013-08-28 | 2014-01-08 | 广西梧州龙鱼漆业有限公司 | Polyether-modified polyurethane curing agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1583846A (en) | 2005-02-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1272368C (en) | Separating method for isocyanate monomer of urethane curing agent | |
| CN101717571A (en) | Method for preparing non-toxic polyurethane curing agent with high solid content | |
| CN101475680B (en) | Method for synthesizing hexamethylene diisocyanate (HDI) biuret | |
| EP2894192A3 (en) | Decomposition Reaction Apparatus, System for Producing Raw Material for Recycled Resin Composition, Method for Producing Raw Material for Recycled Resin Composition, Raw Material for Recycled Resin Composition, and Formed Article | |
| CN102659997A (en) | Preparation method of polyurethane prepolymer with low free isocyanate monomer | |
| CN101463141B (en) | Environment friendly type separation method for isocyanate in polyurethane curing agent | |
| CN105254532A (en) | Method for separating acetonitrile-methanol-benzene ternary azeotrope through three-tower pressure-swing distillation | |
| EP0976719A1 (en) | Apparatus and method for decomposing and recovering isocyanate compound | |
| CN114163598B (en) | Bio-based polyol derived self-repairing polyurethane and preparation method thereof | |
| CN101045798A (en) | Recovery and using method of solution and unreaction monomer in process of producting polymer by solution polymerization process | |
| CN100351297C (en) | Low free tolylene diisocynate polyurethane solidifying agent and its preparation method | |
| CN110818818A (en) | Environment-friendly synthesis method of epoxidized gutta percha, epoxy anticorrosive paint and preparation method | |
| CN1729167A (en) | Method for the production of isocyanates | |
| CN109705281A (en) | A method of preparing polymer polyatomic alcohol | |
| CN1425702A (en) | Process for preparing low free toluene diisocyanate curing agent | |
| CN112679297A (en) | Preparation method of high-purity dicyclopentadiene | |
| CN101056847A (en) | Method for producing polyisocyanates | |
| CN112479806A (en) | Separation method of mixture of 2-chloro-3, 3, 3-trifluoropropene and 2-chloro-1, 1,1, 2-tetrafluoropropane | |
| WO2004106472A1 (en) | A process and apparatus for producing a gas from hydrates | |
| CN107652467A (en) | A kind of preparation method of compound phosphite antioxidant | |
| CN1247520C (en) | Technique and equipment for synthesizing diaryl carbonate through catalyzing rectification | |
| KR101957476B1 (en) | Dual cross-linkable low temperature cure blocked isocyanates and composition comprising the same | |
| CN112851878A (en) | High-solid-content polymer polyol and preparation method thereof | |
| CN115925580B (en) | Method for recycling HDI rectification residues and biuret polyisocyanate | |
| CN111848359A (en) | Method for separating phenolic substances in medium and low temperature coal tar |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |