CN103242254B - Preparation method of HDI-TDI (Hexamethylene Diisocyanate-Toluene Diisocynate) polyurethane tripolymer - Google Patents
Preparation method of HDI-TDI (Hexamethylene Diisocyanate-Toluene Diisocynate) polyurethane tripolymer Download PDFInfo
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Abstract
The invention discloses a preparation method of an HDI-TDI (Hexamethylene Diisocyanate-Toluene Diisocynate) polyurethane tripolymer. The preparation method comprises the following steps of: (1) synthesis: adding toluene diisocynate and hexamethylene diisocyanate by mass ratio of 1:2-4 into a reaction kettle; adding a catalyst; reacting for 3.5-5 hours at 50-80 DEG C, then, adding an acid terminating agent, stirring for half an hour and stopping reaction; (2) post-treatment: separating the product obtained by the step (1) by a film evaporator, and controlling the temperature at 120-200 DEG C and pressure at 10-1000Pa, and then, adding a diluting solvent into the product separated to control the solid content of the product at 50-60% to obtain the HDI-TDI polyurethane tripolymer. The HDI-TDI polyurethane tripolymer prepared by the method provided by the invention is small in molecular weight, uniform in molecules, and fast to dry and high in transparency and fullness in application. Compared with the TDI tripolymer, the HDI-TDI tripolymer has good anti-yellowing performance.
Description
Technical field
The present invention relates to paint field, particularly relate to a kind of HDI-TDI urethane trimer preparation method.
Background technology
Polyurethane coating is one of performance brilliance, most widely used solvent based coating.Trimerization polyisocyanates is a kind of hardened resin, and release solvent fast, has higher reactive behavior.It is applicable to the requirement of quick-drying, high-decoration furniture production line, and therefore many research institutions fall over each other to study the synthetic and application of polyisocyanates.At present, trimerization polyisocyanates mainly contains TDI tripolymer and HDI tripolymer is main, in the application of TDI tripolymer, can accelerate coating film forming, there is certain photoextinction simultaneously, large usage quantity in trimerization polyisocyanates, but TDI tripolymer does not have yellowing resistance, has influence on its range of application.The anti-yellowing property that HDI tripolymer has had, but HDI is expensive, general with requiring in high industrial coating out of doors, but HDI tripolymer is relative and TDI tripolymer, and the dry speed of paint film is slow.HDI-TDI urethane tripolymer has above two kinds of trimerical advantages concurrently simultaneously, has certain yellowing resistance, and the dry speed of paint film is fast, and price is also moderate, is a kind of product with extensive market outlook.
Under the effect of certain catalyzer, can there is self-polymerization and generate isocyanuric acid ester six-membered ring structure (claiming tripolymer) (structural formula is as follows) in the tolylene diisocyanate (TDI) of three molecules and the hexamethylene diisocyanate (HDI) of two molecules.The existence of the isocyanurate ring in HDI-TDI urethane tripolymer is given it good thermostability and chemical stability, and terpolymerization is irreversible.Due to the strong sucting electronic effect of isocyanuric acid ester six-ring, in cause in molecule-NCO group, the potential difference of C=N key increases, reactive increasing, and speed of response is accelerated, therefore crosslinking curing film forming promptly in the time combining with hydroxy component, makes that film degree of crosslinking is large, hardness is high, tack is good; By thin film evaporation aftertreatment, this urethane tripolymer has that viscosity is low, volatility is little, toxicity is low, functionality advantages of higher.This just makes HDI-TDI tripolymer can be used as the supporting thing of a kind of high-grade urethane to be used widely.
For the trimerical broad prospect of application of HDI-TDI urethane, from eighties of last century fifties, just there are many research institutions and transnational company to conduct extensive research it abroad, and there is this series products in phase early 1970s, obtain and developed rapidly in decades, many value products are developed, and have obtained application very widely.In nowadays domestic coating industry, with hydroxy resin consistency poor and product free monomers content high unfriendly to environment be two large defects of restricted T DI-tripolymer application.In order to improve the consistency of product and hydroxy resin, what have takes incomplete reaction method, in the time that reaction proceeds to 50-60% degree, with regard to stopped reaction, then remove remaining monomer, can make like this even molecular weight distribution of product, reduce viscosity, strengthen the compatibility with other component.Comparatively speaking, domesticly fall behind aspect two at this: the poor-performing of product on the one hand; On the other hand, common product free monomers content all more than 2%, even have up to 7% left and right.The reason that causes this phenomenon is that technique means falls behind on the one hand, and processing unit lacks, and the domestic specific equipment that there is no larger removal free monomer, is that environmental protection, legislation on labour protection are unsound on the other hand at present.Along with people are to environmental protection and healthy attention, polyurethane curing agent will be to low free monomer, high solid future development.
Summary of the invention
Based on this, the object of this invention is to provide a kind of HDI-TDI urethane trimer preparation method.
Concrete technical scheme is as follows:
A kind of HDI-TDI urethane trimer preparation method, comprises the steps:
(1) synthetic: hexamethylene diisocyanate (HDI) and tolylene diisocyanate (TDI) to be joined in reactor by the mass ratio of 1:2～1:3, add catalyzer, at 50-80 DEG C, reaction 3.5-5 hour, then add acids terminator, stir after half an hour stopped reaction;
(2) aftertreatment: the product that step (1) is obtained adopts thin-film evaporator to separate, controls temperature at 120～200 DEG C, and pressure is 10～1000Pa; Then the product obtaining after separating is added to diluting solvent, the solid content of controlling product is 50-60%, obtains described HDI-TDI urethane tripolymer.
In an embodiment, described catalyzer is Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH or TBAH therein, the 0.1-0.3%(mass percent that the addition of described catalyzer is total charging capacity).
In an embodiment, the mode that adds of described catalyzer is: add once every half an hour in three batches therein.
In an embodiment, described acids terminator is sulfuric acid, phosphoric acid or Benzoyl chloride therein, the 0.3-0.5%(mass percent that the addition of described acids terminator is total charging capacity).
In an embodiment, described diluting solvent is ethyl acetate and/or butylacetate therein.
In an embodiment, the content of the HDI-TDI urethane tripolymer free monomers that this preparation method prepares is less than 0.5% therein.
Principle of the present invention can resolve to:
Adopt a kind of basic catalyst, at low temperatures, synthesize the HDI-TDI urethane tripolymer crude product of the small molecules amount of the relative homogeneous of molecular weight, by adding acid terminator, make catalyst failure.Recycling HDI-TDI urethane tripolymer is a kind of heat-sensitive substance, in short period of time, there is certain fluidity, by decompression thin film evaporation, remove free poisonous TDI monomer, use again solvent cut, make low free monomer, height admittedly containing HDI-TDI urethane tripolymer.
The present invention is with traditional tripolymer synthetic method difference, not HDI monomer and the TDI monomer of xanthochromia of raw material that the present invention adopts, adopt basic catalyst, early stage is under low temperature, the excessive condition of TDI monomer, synthetic HDI-TDI urethane tripolymer molecular weight is little, molecule homogeneous, does not adopt high temperature polymerization to reduce product middle reaches divorced cyanate ester monomer, but by later stage evaporation process.For solving the degree of depth polymerization causing due to catalyzer in evaporative process, adopt basic catalyst, make the method for catalyst failure by acid terminator in synthetic latter stage, thereby can make the HDI-TDI urethane tripolymer of low free monomer, high solids content.
The HDI-TDI urethane tripolymer that preparation method of the present invention obtains has the following advantages:
1, consistency is good, has good consistency with nitro-cotton, acrylic polyol, chlorinated resin etc., there will not be and mixes the problem that uses clouding, separates out.
2, free poisonous monomer content is low, the HDI-TDI urethane tripolymer that adopts the inventive method to make, and free monomer (HDI+TDI) content is less than 0.5%, reaches non-toxic polyurethane curing agent level.
The HDI-TDI urethane tripolymer that adopts method of the present invention to make, molecular weight is little, molecule homogeneous, in application, fast, the transparency of dry speed and fullness ratio are high, compared with TDI tripolymer, have good anti-yellowing property.
Embodiment
By specific embodiment, the present invention is further elaborated below.
Embodiment 1
A kind of HDI-TDI urethane trimer preparation method, comprises the steps:
(1) synthetic: 500kg tolylene diisocyanate (TDI) and 1200kg hexamethylene diisocyanate (HDI) are joined in reactor, pass into nitrogen protection, open stirring, heat to 50 DEG C, then dividing 3 times adds Tetramethylammonium hydroxide catalyzer 2.4Kg in reactor, add once every half an hour, after all adding 70 DEG C of reactions, detected NCO content every 1 hour, be down to 34% when NCO content, be cooled to 40 DEG C, add 4Kg phosphoric acid terminator, stir after half an hour stopped reaction;
(2) aftertreatment: the product that step (1) is obtained adopts thin-film evaporator to separate, controls temperature at 160 DEG C, and pressure is 100Pa; Then the product obtaining after separating is added to ethyl acetate diluting solvent, the solid content of controlling product is 50-60%, obtains described HDI-TDI urethane tripolymer.
The trimerical physical and chemical performance data of HDI-TDI urethane that above-mentioned preparation method obtains are as follows:
Clear, colorless liquid, solid content is 60%, and unreacted NCO group is 10.1%, and viscosity is that ((25 DEG C), hexamethylene diisocyanate and tolylene diisocyanate (HDI+TDI) free in product they are 0.42% to 980mPa.s.
Embodiment 2
A kind of HDI-TDI urethane trimer preparation method, comprises the steps:
(1) synthetic: 400kg tolylene diisocyanate (TDI) and 1000kg hexamethylene diisocyanate (HDI) are joined in reactor and joined in reactor, pass into nitrogen protection, open stirring, heat to 60 DEG C, then dividing 3 times adds tetraethyl ammonium hydroxide catalyzer 2.5Kg in reactor, add once every half an hour, after all adding 75 DEG C of reactions, detected NCO content every 1 hour, be down to 33% when NCO content, be cooled to 40 DEG C, add 3Kg phosphoric acid terminator, stir after half an hour stopped reaction;
(2) aftertreatment: the product that step (1) is obtained adopts thin-film evaporator to separate, controls temperature at 170 DEG C, and pressure is 80Pa; Then the product obtaining after separating is added to ethyl acetate diluting solvent, the solid content of controlling product is 50-60%, obtains described HDI-TDI urethane tripolymer.
The trimerical physical and chemical performance data of HDI-TDI urethane that above-mentioned preparation method obtains are as follows:
Clear, colorless liquid, solid content is 60%, and unreacted NCO group is 10.3%, and viscosity is that ((25 DEG C), hexamethylene diisocyanate and tolylene diisocyanate (HDI+TDI) free in product they are 0.4% to 1000mPa.s.
Embodiment 3
A kind of HDI-TDI urethane trimer preparation method, comprises the steps:
(1) synthetic: 500kg tolylene diisocyanate (TDI) and 1100kg hexamethylene diisocyanate (HDI) are joined in reactor, pass into nitrogen protection, open stirring, heat to 55 DEG C, then dividing 3 times adds TPAOH catalyzer 2Kg in reactor, add once every half an hour, after all adding 75 DEG C of reactions, detected NCO content every 1 hour, be down to 35% when NCO content, be cooled to 40 DEG C, add 3.5Kg phosphoric acid terminator, stir after half an hour stopped reaction;
(2) aftertreatment: the product that step (1) is obtained adopts thin-film evaporator to separate, controls temperature at 180 DEG C, and pressure is 100Pa; Then the product obtaining after separating is added to butylacetate diluting solvent, the solid content of controlling product is 50-60%, obtains described HDI-TDI urethane tripolymer.
The trimerical physical and chemical performance data of HDI-TDI urethane that above-mentioned preparation method obtains are as follows:
Clear, colorless liquid, solid content is 60%, and unreacted NCO group is 9.7%, and viscosity is that ((25 DEG C), hexamethylene diisocyanate and tolylene diisocyanate (HDI+TDI) free in product they are 0.33% to 1050mPa.s.
Embodiment 4
A kind of HDI-TDI urethane trimer preparation method, comprises the steps:
(1) synthetic: 600kg tolylene diisocyanate (TDI) and 1500kg hexamethylene diisocyanate (HDI) are joined in reactor, pass into nitrogen protection, open stirring, heat to 60 DEG C, then dividing 3 times adds TBAH catalyzer 2.4Kg in reactor, add once every half an hour, after all adding 80 DEG C of reactions, detected NCO content every 1 hour, be down to 34% when NCO content, be cooled to 40 DEG C, add 3.6Kg phosphoric acid terminator, stir after half an hour stopped reaction;
(2) aftertreatment: the product that step (1) is obtained adopts thin-film evaporator to separate, controls temperature at 160 DEG C, and pressure is 100Pa; Then the product obtaining after separating is added to butylacetate and butylacetate mixed diluting solvent, the solid content of controlling product is 50-60%, obtains described HDI-TDI urethane tripolymer.
The trimerical physical and chemical performance data of HDI-TDI urethane that above-mentioned preparation method obtains are as follows:
Clear, colorless liquid, solid content is 60%, and unreacted NCO group is 10.1%, and viscosity is that ((25 DEG C), hexamethylene diisocyanate and tolylene diisocyanate (HDI+TDI) free in product they are 0.33% to 1080mPa.s.
Embodiment 5
A kind of HDI-TDI urethane trimer preparation method, comprises the steps:
(1) synthetic: 400kg tolylene diisocyanate (TDI) and 1200kg hexamethylene diisocyanate (HDI) are joined in reactor, pass into nitrogen protection, open stirring, heat to 65 DEG C, then dividing 3 times adds Tetramethylammonium hydroxide catalyzer 3Kg in reactor, add once every half an hour, after all adding 75 DEG C of reactions, detected NCO content every 1 hour, be down to 35% when NCO content, be cooled to 40 DEG C, add 4.5Kg phosphoric acid terminator, stir after half an hour stopped reaction;
(2) aftertreatment: the product that step (1) is obtained adopts thin-film evaporator to separate, controls temperature at 160 DEG C, and pressure is 100Pa; Then the product obtaining after separating is added to butylacetate and butylacetate mixed diluting solvent, the solid content of controlling product is 50-60%, obtains described HDI-TDI urethane tripolymer.
The trimerical physical and chemical performance data of HDI-TDI urethane that above-mentioned preparation method obtains are as follows:
Clear, colorless liquid, solid content is 60%, and unreacted NCO group is 10.2%, and viscosity is that ((25 DEG C), hexamethylene diisocyanate and tolylene diisocyanate (HDI+TDI) free in product they are 0.38% to 1100mPa.s.
Application performance test:
Table 1 is that embodiment 1,2,3 and general T DI tripolymer and HDI tripolymer are applied fundamental property comparison aspect light top coat top coat:
Table 1
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (4)
1. a HDI-TDI urethane trimer preparation method, is characterized in that, comprises the steps:
(1) synthetic: tolylene diisocyanate and hexamethylene diisocyanate to be joined in reactor by the mass ratio of 1:2～4, add catalyzer, at 50-80 DEG C, reaction 3.5-5 hour, then add acids terminator, stir after half an hour stopped reaction;
(2) aftertreatment: the product that step (1) is obtained adopts thin-film evaporator to separate, controls temperature at 120～200 DEG C, and pressure is 10～1000Pa; Then the product obtaining after separating is added to diluting solvent, the solid content of controlling product is 50-60%, obtains described HDI-TDI urethane tripolymer;
Described catalyzer is Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH or TBAH, the 0.1-0.3% that the addition of described catalyzer is total charging capacity;
Described acids terminator is sulfuric acid, phosphoric acid or Benzoyl chloride, the 0.3-0.5% that the addition of described acids terminator is total charging capacity.
2. HDI-TDI urethane trimer preparation method according to claim 1, is characterized in that, the mode that adds of described catalyzer is: add once every half an hour in three batches.
3. HDI-TDI urethane trimer preparation method according to claim 1, is characterized in that, described diluting solvent is ethyl acetate and/or butylacetate.
4. HDI-TDI urethane trimer preparation method according to claim 1, is characterized in that, the content of the HDI-TDI urethane tripolymer free monomers that this preparation method prepares is less than 0.5%.
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| CN108059912A (en) * | 2018-01-02 | 2018-05-22 | 河北晨阳工贸集团有限公司 | Aqueous polyurethane finishing coat for gas turbine blower blade and preparation method thereof |
| CN110273304B (en) * | 2019-06-24 | 2021-09-14 | 中国化工集团曙光橡胶工业研究设计院有限公司 | Anti-adhesion coating composition for nuclear radiation protective clothing fabric |
| KR102569223B1 (en) * | 2021-06-02 | 2023-08-22 | 애경케미칼주식회사 | Urethane acrylate compound comprising 1,6-hexamethylene diisocyanate and 2,4-toluene diisocyanate isocyanurate type trimer structure and the photo curable composition with high strength and high thermal resistance for 3D printing using thereof |
| CN113667080B (en) * | 2021-07-01 | 2022-06-14 | 华南理工大学 | HDI-TDI mixed polymer curing agent and preparation method thereof |
| CN114369216B (en) * | 2021-12-31 | 2023-11-03 | 鹤山市华轩涂料有限公司 | HMDI-TDI trimer and preparation method and application thereof |
| CN115286986B (en) * | 2022-06-28 | 2023-08-15 | 上海嘉宝莉涂料有限公司 | Skin-feel matte varnish for woodware, and preparation method and application thereof |
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| AT375652B (en) * | 1982-10-29 | 1984-08-27 | Valentina Alexandro Postnikova | METHOD FOR PRODUCING ARYLALIPHATIC POLYISOZYANURATES |
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