CN103242254A - 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.The trimerization polyisocyanates is a kind of hardened resin, and release solvent has high reaction activity and high fast.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 of polyisocyanates and use.At present, the trimerization polyisocyanates mainly contains the TDI tripolymer and the HDI tripolymer is main, and the TDI tripolymer can be accelerated the coating film forming in using, has certain photoextinction simultaneously, large usage quantity in the trimerization polyisocyanates, but the TDI tripolymer does not have yellowing resistance, has influence on its range of application.The HDI tripolymer has good anti-yellowing property, but HDI is expensive, and is general with in the demanding industrial coating out of doors, but the HDI tripolymer relatively with the TDI tripolymer, paint film is done speed slowly.HDI-TDI urethane tripolymer has above two kinds of trimerical advantages simultaneously concurrently, has certain yellowing resistance, and it is fast that paint film is done speed, and price is also moderate, is a kind of product with extensive market outlook.
Under the effect of certain catalyzer, self-polymerization can take place and generate isocyanuric acid ester six-membered ring structure (claiming tripolymer) (structural formula is as follows) in the hexamethylene diisocyanate (HDI) of the tolylene diisocyanate of three molecules (TDI) and two molecules.The existence of the isocyanurate ring in the HDI-TDI urethane tripolymer is given it thermostability and chemical stability preferably, and terpolymerization is irreversible.Because the strong sucting electronic effect of isocyanuric acid ester six-ring, cause in the molecule-the NCO group in the potential difference of C=N key increase, reactive increasing, speed of response is accelerated, therefore crosslinking curing film forming promptly when making up with hydroxy component makes that the degree of crosslinking of filming is big, hardness is high, tack is good; By the thin film evaporation aftertreatment, this urethane tripolymer has that viscosity is low, volatility is little, toxicity is low, the functionality advantages of higher.This just makes the HDI-TDI tripolymer can be used as the supporting thing of a kind of high-grade urethane and is used widely.
At the trimerical broad prospect of application of HDI-TDI urethane, just there are many research institutions and transnational company that it has been carried out research widely abroad the fifties from eighties of last century, and in phase early 1970s this series products appears, obtained in decades to develop rapidly, many value products are developed, and have obtained using very widely.In nowadays domestic coating industry, unfriendly to environment with hydroxy resin consistency difference and product free monomers content height is the two big defectives that restricted T DI-tripolymer is used.In order to improve the consistency of product and hydroxy resin, what have takes the incomplete reaction method, namely when reaction proceeds to the 50-60% degree, with regard to stopped reaction, remove residual monomers then, can make the even molecular weight distribution of product like this, 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 is all more than 2%, in addition have up to about 7%.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 does not still have larger removal free monomer is that environmental protection, legislation on labour protection are unsound on the other hand at present.Along with the attention of people to environmental protection and health, polyurethane curing agent will develop to low free monomer, high solid direction.
Summary of the invention
Based on this, the purpose 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) mass ratio by 1:2～1:3 is joined in the reactor, and the adding catalyzer is under 50-80 ℃, reacted 3.5-5 hour, add the acids terminator then, stir half an hour after, stopped reaction;
(2) aftertreatment: the product that step (1) is obtained adopts thin-film evaporator to separate, and the control temperature is at 120～200 ℃, and pressure is 10～1000Pa; The product that will obtain after will separating then adds diluting solvent, and the solid content of control product is 50-60%, namely gets described HDI-TDI urethane tripolymer.
Among embodiment, described catalyzer is Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH or TBAH therein, and the addition of described catalyzer is the 0.1-0.3%(mass percent of total charging capacity).
Among embodiment, the adding mode of described catalyzer is therein: add once every half an hour in three batches.
Among embodiment, described acids terminator is sulfuric acid, phosphoric acid or Benzoyl chloride therein, and the addition of described acids terminator is the 0.3-0.5%(mass percent of total charging capacity).
Among embodiment, described diluting solvent is ethyl acetate and/or butylacetate therein.
Among 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 molecular weight 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, have certain flowability in short period of time, by the decompression thin film evaporation, remove free poisonous TDI monomer, use solvent cut again, make low free monomer, height and contain HDI-TDI urethane tripolymer admittedly.
The present invention is with traditional tripolymer synthetic method difference, the raw material that the present invention adopts is HDI monomer and the TDI monomer of xanthochromia not, adopt basic catalyst, early stage is under low temperature, the excessive condition of TDI monomer, synthetic HDI-TDI urethane tripolymer molecular weight is little, the molecule homogeneous does not adopt high temperature polymerization to reduce product middle reaches divorce cyanate ester monomer, but by the later stage evaporation process.For solving the degree of depth polymerization that causes owing to catalyzer in the evaporative process, adopt basic catalyst, make the method for catalyst failure in synthetic latter stage by acid terminator, 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, with nitro-cotton, acrylic polyol, chlorinated resin etc. good consistency is arranged, and the problem of using clouding, separating out can not occur mixing.
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 reaches the non-toxic polyurethane curing agent level less than 0.5%.
The HDI-TDI urethane tripolymer that adopts method of the present invention to make, molecular weight is little, and the molecule homogeneous does in the application that speed is fast, transparency and fullness ratio height, compares with the TDI tripolymer, has good anti-yellowing property.
Embodiment
Below by specific embodiment the present invention is further elaborated.
Embodiment 1
A kind of HDI-TDI urethane trimer preparation method comprises the steps:
(1) synthetic: that 500kg tolylene diisocyanate (TDI) and 1200kg hexamethylene diisocyanate (HDI) are joined in the reactor, feed nitrogen protection, open stirring, heat to 50 ℃, divide 3 times then with in the Tetramethylammonium hydroxide catalyzer 2.4Kg adding reactor, add once every half an hour, all add the back 70 ℃ of reactions, detected NCO content every 1 hour, be down to 34% when NCO content, be cooled to 40 ℃, add 4Kg phosphoric acid terminator, after stirring half an hour, stopped reaction;
(2) aftertreatment: the product that step (1) is obtained adopts thin-film evaporator to separate, and the control temperature is at 160 ℃, and pressure is 100Pa; The product that will obtain after will separating then adds the ethyl acetate diluting solvent, and the solid content of control product is 50-60%, namely gets described HDI-TDI urethane tripolymer.
The trimerical physical and chemical performance data of the HDI-TDI urethane that above-mentioned preparation method obtains are as follows:
Clear, colorless liquid, solid content are 60%, and unreacted NCO group is 10.1%, and viscosity is that ((25 ℃), hexamethylene diisocyanate and tolylene diisocyanate (HDI+TDI) free in the product are 0.42% to 980mPa.s.
Embodiment 2
A kind of HDI-TDI urethane trimer preparation method comprises the steps:
(1) synthetic: as 400kg tolylene diisocyanate (TDI) and 1000kg hexamethylene diisocyanate (HDI) joined to join in the reactor in the reactor, feed nitrogen protection, open stirring, heat to 60 ℃, divide 3 times then with in the tetraethyl ammonium hydroxide catalyzer 2.5Kg adding reactor, add once every half an hour, all add the back 75 ℃ of reactions, detected NCO content every 1 hour, be down to 33% when NCO content, be cooled to 40 ℃, add 3Kg phosphoric acid terminator, after stirring half an hour, stopped reaction;
(2) aftertreatment: the product that step (1) is obtained adopts thin-film evaporator to separate, and the control temperature is at 170 ℃, and pressure is 80Pa; The product that will obtain after will separating then adds the ethyl acetate diluting solvent, and the solid content of control product is 50-60%, namely gets described HDI-TDI urethane tripolymer.
The trimerical physical and chemical performance data of the HDI-TDI urethane that above-mentioned preparation method obtains are as follows:
Clear, colorless liquid, solid content are 60%, and unreacted NCO group is 10.3%, and viscosity is that ((25 ℃), hexamethylene diisocyanate and tolylene diisocyanate (HDI+TDI) free in the product are 0.4% to 1000mPa.s.
Embodiment 3
A kind of HDI-TDI urethane trimer preparation method comprises the steps:
(1) synthetic: that 500kg tolylene diisocyanate (TDI) and 1100kg hexamethylene diisocyanate (HDI) are joined in the reactor, feed nitrogen protection, open stirring, heat to 55 ℃, divide 3 times then with in the TPAOH catalyzer 2Kg adding reactor, add once every half an hour, all add the back 75 ℃ of reactions, detected NCO content every 1 hour, be down to 35% when NCO content, be cooled to 40 ℃, add 3.5Kg phosphoric acid terminator, after stirring half an hour, stopped reaction;
(2) aftertreatment: the product that step (1) is obtained adopts thin-film evaporator to separate, and the control temperature is at 180 ℃, and pressure is 100Pa; The product that will obtain after will separating then adds the butylacetate diluting solvent, and the solid content of control product is 50-60%, namely gets described HDI-TDI urethane tripolymer.
The trimerical physical and chemical performance data of the HDI-TDI urethane that above-mentioned preparation method obtains are as follows:
Clear, colorless liquid, solid content are 60%, and unreacted NCO group is 9.7%, and viscosity is that ((25 ℃), hexamethylene diisocyanate and tolylene diisocyanate (HDI+TDI) free in the product are 0.33% to 1050mPa.s.
Embodiment 4
A kind of HDI-TDI urethane trimer preparation method comprises the steps:
(1) synthetic: that 600kg tolylene diisocyanate (TDI) and 1500kg hexamethylene diisocyanate (HDI) are joined in the reactor, feed nitrogen protection, open stirring, heat to 60 ℃, divide 3 times then with in the TBAH catalyzer 2.4Kg adding reactor, add once every half an hour, all add the back 80 ℃ of reactions, detected NCO content every 1 hour, be down to 34% when NCO content, be cooled to 40 ℃, add 3.6Kg phosphoric acid terminator, after stirring half an hour, stopped reaction;
(2) aftertreatment: the product that step (1) is obtained adopts thin-film evaporator to separate, and the control temperature is at 160 ℃, and pressure is 100Pa; The product that will obtain after will separating then adds butylacetate and butylacetate mixed diluting solvent, and the solid content of control product is 50-60%, namely gets described HDI-TDI urethane tripolymer.
The trimerical physical and chemical performance data of the HDI-TDI urethane that above-mentioned preparation method obtains are as follows:
Clear, colorless liquid, solid content are 60%, and unreacted NCO group is 10.1%, and viscosity is that ((25 ℃), hexamethylene diisocyanate and tolylene diisocyanate (HDI+TDI) free in the product are 0.33% to 1080mPa.s.
Embodiment 5
A kind of HDI-TDI urethane trimer preparation method comprises the steps:
(1) synthetic: that 400kg tolylene diisocyanate (TDI) and 1200kg hexamethylene diisocyanate (HDI) are joined in the reactor, feed nitrogen protection, open stirring, heat to 65 ℃, divide 3 times then with in the Tetramethylammonium hydroxide catalyzer 3Kg adding reactor, add once every half an hour, all add the back 75 ℃ of reactions, detected NCO content every 1 hour, be down to 35% when NCO content, be cooled to 40 ℃, add 4.5Kg phosphoric acid terminator, after stirring half an hour, stopped reaction;
(2) aftertreatment: the product that step (1) is obtained adopts thin-film evaporator to separate, and the control temperature is at 160 ℃, and pressure is 100Pa; The product that will obtain after will separating then adds butylacetate and butylacetate mixed diluting solvent, and the solid content of control product is 50-60%, namely gets described HDI-TDI urethane tripolymer.
The trimerical physical and chemical performance data of the HDI-TDI urethane that above-mentioned preparation method obtains are as follows:
Clear, colorless liquid, solid content are 60%, and unreacted NCO group is 10.2%, and viscosity is that ((25 ℃), hexamethylene diisocyanate and tolylene diisocyanate (HDI+TDI) free in the product are 0.38% to 1100mPa.s.
The application performance test:
Table 1 be embodiment 1,2,3 and general T DI tripolymer and HDI tripolymer aspect light top coat top coat, use fundamental property relatively:
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 claim of the present invention.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 (6)
1. a HDI-TDI urethane trimer preparation method is characterized in that, comprises the steps:
(1) synthetic: tolylene diisocyanate and the hexamethylene diisocyanate mass ratio by 1:2～4 is joined in the reactor, add catalyzer, under 50-80 ℃, react 3.5-5 hour, add the acids terminator then, after stirring half an hour, stopped reaction;
(2) aftertreatment: the product that step (1) is obtained adopts thin-film evaporator to separate, and the control temperature is at 120～200 ℃, and pressure is 10～1000Pa; The product that will obtain after will separating then adds diluting solvent, and the solid content of control product is 50-60%, namely gets described HDI-TDI urethane tripolymer.
2. HDI-TDI urethane trimer preparation method according to claim 1, it is characterized in that, described catalyzer is Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH or TBAH, and the addition of described catalyzer is the 0.1-0.3% of total charging capacity.
3. HDI-TDI urethane trimer preparation method according to claim 1 and 2 is characterized in that, the adding mode of described catalyzer is: add once every half an hour in three batches.
4. HDI-TDI urethane trimer preparation method according to claim 1 is characterized in that, described acids terminator is sulfuric acid, phosphoric acid or Benzoyl chloride, and the addition of described acids terminator is the 0.3-0.5% of total charging capacity.
5. HDI-TDI urethane trimer preparation method according to claim 1 is characterized in that, described diluting solvent is ethyl acetate and/or butylacetate.
6. 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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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN110273304A (en) * | 2019-06-24 | 2019-09-24 | 中国化工集团曙光橡胶工业研究设计院有限公司 | A kind of Antiblock coating composition taking fabric for nuclear radiation protection |
| CN113667080A (en) * | 2021-07-01 | 2021-11-19 | 华南理工大学 | HDI-TDI mixed polymer curing agent and preparation method thereof |
| CN114369216A (en) * | 2021-12-31 | 2022-04-19 | 鹤山市华轩涂料有限公司 | HMDI-TDI tripolymer and preparation method and application thereof |
| CN115286986A (en) * | 2022-06-28 | 2022-11-04 | 上海嘉宝莉涂料有限公司 | Skin-feel matte clear finish paint for woodware, and preparation method and application thereof |
| KR20220162949A (en) * | 2021-06-02 | 2022-12-09 | 애경화학 주식회사 | 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 |
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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 |
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| 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 |
| KR20220162949A (en) * | 2021-06-02 | 2022-12-09 | 애경화학 주식회사 | 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 |
| 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 |
| CN113667080A (en) * | 2021-07-01 | 2021-11-19 | 华南理工大学 | HDI-TDI mixed polymer curing agent and preparation method thereof |
| CN114369216A (en) * | 2021-12-31 | 2022-04-19 | 鹤山市华轩涂料有限公司 | HMDI-TDI tripolymer and preparation method and application 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 |
| CN115286986A (en) * | 2022-06-28 | 2022-11-04 | 上海嘉宝莉涂料有限公司 | Skin-feel matte clear finish paint for woodware, 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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