CN1389500A - Separation process of free monomer for polyurethane curing agent - Google Patents
Separation process of free monomer for polyurethane curing agent Download PDFInfo
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- CN1389500A CN1389500A CN 02134225 CN02134225A CN1389500A CN 1389500 A CN1389500 A CN 1389500A CN 02134225 CN02134225 CN 02134225 CN 02134225 A CN02134225 A CN 02134225A CN 1389500 A CN1389500 A CN 1389500A
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- agent
- solidifying agent
- solvent
- curing agent
- polyurethane curing
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Abstract
A method of separation of the dissociative monomer in the polyamido ester solidifying agent, incldues the following steps: (1) get rid of the solvent in the solidifying agent; (2) add the extracting agent and the extractive smuggling agent to the solidifying agent, then make the molecular distillation and the distilled leaving is the solidifying agent; (3) dilute the solidifying agnet; compared with the chemical-reaction method and the vacuum-distilling method, this method can reduce the content of the dissociative monomer in the polyamido ester, at the same time it can't augment the relative molecular weight and the distribution of the relative molecular weight, and reduce the compatibility of the solidifying agent with the hydroxy ester; and the gained solid content can be optionally adjusted and even reach the weight of 80-100 % of the high solid content.
Description
Technical field
The present invention relates to the Separation ﹠ Purification of high viscosity thermosensitive polymer, particularly be applicable to separation and the purification of coating with residual free deleterious isocyanate-monomer 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.
According to modern environmental requirement, polyurethane coating must solve two technical barriers, and the one, improve solids content, reduce solvent to greatest extent.The 2nd, reduce free diisocyanate content in the polyurethane curing agent, promptly develop nontoxic solidifying agent.
The free diisocyanate monomer content height (toxicity is big) that China's polyurethane curing agent kind is single at present, solids content is low, residual.The method that reduces residual monomer in the polyurethane curing agent comprises: chemical reaction method, solvent extration, molecular sieve adsorption and vacuum distillation method etc.
Chemical reaction method is the method that adopts chemical catalysis, and by formulating of recipe and special synthesis technique, methods such as use effective catalyst make the monomer that remains in the solidifying agent eliminate by various reactions.Adopt chemical process to reduce the residual monomer content complex process, reaction time consumption is long, and product viscosity is higher, and molecular weight is bigger, and molecular weight distribution is inhomogeneous, and the consistency between hydroxy resin is bad, has reduced the performance of polyurethane coating.
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, the solidifying agent polymkeric substance then can not dissolve and separate out in bottom, divide the hydrocarbon mixture solvent that goes to the upper strata, add fresh hydrocarbon mixture 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 product performance.
Molecular sieve adsorption technology is simple, has shortcomings such as molecular sieve desorption difficulty;
External at present employing thin-film evaporator reduces residual monomer in the solidifying agent, is a kind of effective means, but the equipment complexity, the energy consumption height.The polyurethane curing agent relative molecular mass that China produces use at present is bigger, and viscosity is big, and solidifying agent is mobile relatively poor when adopting thin-film evaporator separating residual monomer, often stops up thin-film evaporator, causes and separates failure.
Summary of the invention
The present invention is directed to the shortcoming that prior art exists, a kind of separation method of efficient, economic polyurethane curing agent free monomers is provided, separate the poisonous free isocyanate monomer in the polyurethane curing agent, overcome shortcomings such as existing technology practicality is narrow, energy consumption height.
The separation method of polyurethane curing agent free monomers of the present invention comprises the following steps:
(1), the solvent in the removal solidifying agent;
(2), add extraction agent and extraction entrainment agent, carry out molecular distillation, heating up in a steamer excess is solidifying agent;
(3), dilution solidifying agent.
When the solids content of the solidifying agent after the dilution reached 75% weight, free monomer content wherein can packaging final prod less than 1.0% weight.
Described (1) step is also referred to as the preliminary degassing, can be in 1000-1.013 * 10
5Pa removes 50-90% solvent in the solidifying agent down; With 80% is the best.The solvent of removing can directly use.
Described extraction agent can be as the solvent and the thinner of solidifying agent, and water content is lower than 0.3%.Comprise: benzene,toluene,xylene, 200# solvent oil, heavy aromatics, vinyl acetic monomer, N-BUTYL ACETATE, Iso Butyl Acetate, ethylene glycol ether acetate, 2-Butoxyethyl acetate, 1-Methoxy-2-propyl acetate, propylene glycol monobutyl ether acetate, S-100, S-150, S-200 wherein one or more.Its consumption accounts for the 10-30% weight of total amount.
Dissolving cured dose of described extraction entrainment agent energy, water content is lower than 0.1%, and solvent boiling point is higher than 200 ℃.Comprising: S-150, S-200, propylene glycol monobutyl ether acetate, butyl carbitol acetate, Diethylene Glycol monobutyl ether acetate, diethylene glycol ether acetic ester, dimethyl phthalate, diethyl phthalate, butyl phthalate, dioctyl phthalate (DOP), dimethyl terephthalate (DMT), diethyl terephthalate and dibutyl terephthalate wherein one or more, consumption accounts for the 2-15% weight of total amount.
Separation principle of the present invention can be interpreted as: contain solvent in the polyurethane curing agent, viscosity is lower, not solvent-laden solidifying agent, and under higher temperature, its viscosity is very big, and its flowability is very poor, almost can not flow; We are by adding suitable extraction agent and entrainment agent, make solidifying agent in the molecule vaporizer, carry out the gradient distillation, solidifying agent descends with molecule vaporizer inwall, the slow gradient evaporation of solvent and monomer, when solidifying agent reached evaporator outlet, solvent in the solidifying agent and residual monomer were almost all steamed, the solidifying agent of purifying is discharged through extrusion equipment, adjust solids content through thinner, can obtain highly filled, the polyurethane curing agent kind that free monomer content is low.
The present invention compared with prior art has following advantage:
1, compare with vacuum distillation method with chemical reaction method, when this method reduced polyurethane curing agent free monomers content, the relative molecular mass and the relative molecular mass that can not increase solidifying agent distributed, and can not reduce the consistency of solidifying agent and hydroxy resin; The solids content of the solidifying agent that it obtains can arbitrarily be adjusted, even can reach highly filled 80-100% weight.
2, compare with existing inner-cooled film evaporation method, separating technology is simple, the wide adaptability of separation of material viscosity, and the scope of monomer content is big, the solidifying agent that high viscosity that particularly existing thin-film evaporator can not be handled and isocyanate content are lower than 10% weight.
The invention will be further described below by example.
Embodiment
Example 1
Adopting tolylene diisocyanate (TDI) and 1mol TriMethylolPropane(TMP) (TMP) the synthesis of solid content of 3mol is 45%, and free TDI content is 7% polyurethane coating curing agent, and adopting dimethylbenzene and N-BUTYL ACETATE is solvent; With this solidifying agent at 160 ℃, carry out the elementary degassing under the normal pressure, add 20% the butyl carbitol acetate and the mixture of S-150 solvent then, carrying out molecular distillation under 180 ℃, the situation of 140Pa, to obtain product be that solids content is 98%, and TDI content is 0.70% polyurethane curing agent.And with experimental result and at 180 ℃, 100Pa vacuum distilling compared in 30 minutes, saw Table 1.This technology of table 1 explanation reduces the monomeric physicals that does not influence solidifying agent simultaneously of free TDI.
The comparison of table 1 extraction molecule distillating method and vacuum distilling
Example 2
| Project | The equal molecular mass of relative number | Relative molecular mass distributes | TDI％ | Residual extraction agent, % | 50% viscosity, cp |
| Former solidifying agent | 1400 | ?1.89 | ?7.0 | ?0 | ?200 |
| Vacuum distilling | 5000 | ?10.0 | ?5.0 | ?0 | ?2000 |
| This technology | 1560 | ?2.03 | ?0.70 | ?1.5 | ?300 |
(relative molecular mass is 1000 to adopt the 1mol polyester diol, hydroxy radical content 3.30%) TDI with 1.6mol reacts the synthesis of polyurethane prepolymer, its relative molecular mass is 2000, the free TDI monomer content is 3.5% (50% solids content), after this polyurethane prepolymer carried out the elementary degassing by the condition in the example 1, the S-200 of interpolation 10% and the mixed solvent of dimethyl phthalate, at 220 ℃, carry out molecular distillation under the 100Pa, obtain 97.% polyurethane prepolymer, the content of the TDI that it is residual is 0.80%, through producing 100 kilograms in batches, after dilution, obtain 50% solids content, TDI content is 0.32%, the residual extraction solvent is 1.0%, coating film gloss after constructing, hardness and time of drying change little.
Example 3
The TDI tripolymer that certain system lacquer factory produces, its solids content is 45%, residual free TDI monomer content is 2.5%; This producer offers our 500 kilograms of solidifying agent, we with this solidifying agent at 160 ℃, carry out the elementary degassing under the 1000Pa, add 10% the diester (DBE) and the mixture of dibutyl phthalate then, at 200 ℃, molecular distillation under the 120Pa, obtaining solids content is 99%, free monomer content is 0.5% solidifying agent, after the dilution of dimethylbenzene and N-BUTYL ACETATE as the solidifying agent of hydroxyl alkyd resins, the hardness that test determination is filmed is compared with former lacquer with sticking power and is changed not quite, and impact resistance and coating film gloss obtain bigger raising, do not detect free TDI monomer in the construction environment.
Claims (7)
1, a kind of separation method of polyurethane curing agent free monomers is characterized in that comprising the following steps:
(1), the solvent in the removal solidifying agent;
(2), add extraction agent and extraction entrainment agent, carry out molecular distillation, heating up in a steamer excess is solidifying agent;
(3), dilution solidifying agent.
2, the separation method of polyurethane curing agent free monomers according to claim 1 is characterized in that described (1) step is in 1000-1.013 * 10
5Pa removes 50-90% solvent in the solidifying agent down.
3, the separation method of polyurethane curing agent free monomers according to claim 2 is characterized in that in 1000-1.013 * 10
5Pa removes 80% solvent in the solidifying agent down.
4, the separation method of polyurethane curing agent free monomers according to claim 1 and 2 is characterized in that described extraction agent is the solvent and the thinner of solidifying agent, and water content is lower than 0.3%.
5, the separation method of polyurethane curing agent free monomers according to claim 4, it is characterized in that described extraction agent is benzene,toluene,xylene, 200# solvent oil, heavy aromatics, vinyl acetic monomer, N-BUTYL ACETATE, Iso Butyl Acetate, ethylene glycol ether acetate, 2-Butoxyethyl acetate, 1-Methoxy-2-propyl acetate, propylene glycol monobutyl ether acetate, S-100, S-150, S-200 wherein one or more, its consumption accounts for the 10-30% weight of total amount.
6, the separation method of polyurethane curing agent free monomers according to claim 1 and 2 is characterized in that dissolving cured dose of described extraction entrainment agent, and water content is lower than 0.1%, and solvent boiling point is higher than 200 ℃.
7, the separation method of polyurethane curing agent free monomers according to claim 6, it is characterized in that, described extraction entrainment agent is S-150, S-200, propylene glycol monobutyl ether acetate, butyl carbitol acetate, Diethylene Glycol monobutyl ether acetate, diethylene glycol ether acetic ester, dimethyl phthalate, diethyl phthalate, butyl phthalate, dioctyl phthalate (DOP), dimethyl terephthalate (DMT), diethyl terephthalate and dibutyl terephthalate wherein one or more, consumption accounts for the 2-15% weight of total amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02134225 CN1389500A (en) | 2002-06-24 | 2002-06-24 | Separation process of free monomer for polyurethane curing agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02134225 CN1389500A (en) | 2002-06-24 | 2002-06-24 | Separation process of free monomer for polyurethane curing agent |
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| CN1389500A true CN1389500A (en) | 2003-01-08 |
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Cited By (4)
| 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 |
| CN104592483A (en) * | 2015-01-14 | 2015-05-06 | 嘉宝莉化工集团股份有限公司 | Environment-friendly polyurethane curing agent as well as preparation method and application of curing agent |
| 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 |
| CN114195974A (en) * | 2021-12-06 | 2022-03-18 | 季华实验室 | Polyurethane prepolymer and preparation method thereof, and polyurethane product |
-
2002
- 2002-06-24 CN CN 02134225 patent/CN1389500A/en active Pending
Cited By (5)
| 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 |
| CN104592483A (en) * | 2015-01-14 | 2015-05-06 | 嘉宝莉化工集团股份有限公司 | Environment-friendly polyurethane curing agent as well as preparation method and application of curing agent |
| CN104592483B (en) * | 2015-01-14 | 2017-06-06 | 嘉宝莉化工集团股份有限公司 | Environment-protecting polyurethane curing agent and its preparation method and application |
| 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 |
| CN114195974A (en) * | 2021-12-06 | 2022-03-18 | 季华实验室 | Polyurethane prepolymer and preparation method thereof, and polyurethane product |
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