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
- Publication number
- CN103242254A CN103242254A CN2013101440235A CN201310144023A CN103242254A CN 103242254 A CN103242254 A CN 103242254A CN 2013101440235 A CN2013101440235 A CN 2013101440235A CN 201310144023 A CN201310144023 A CN 201310144023A CN 103242254 A CN103242254 A CN 103242254A
- Authority
- CN
- China
- Prior art keywords
- hdi
- tdi
- tripolymer
- preparation
- product
- 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.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000004814 polyurethane Substances 0.000 title abstract description 6
- 229920002635 polyurethane Polymers 0.000 title abstract description 6
- ODYFMMXCYGDDCM-UHFFFAOYSA-N C1(=CC=CC=C1)C.C(CCCCCN=C=O)N=C=O Chemical compound C1(=CC=CC=C1)C.C(CCCCCN=C=O)N=C=O ODYFMMXCYGDDCM-UHFFFAOYSA-N 0.000 title abstract 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims abstract description 33
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000007865 diluting Methods 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 41
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 34
- 239000000178 monomer Substances 0.000 claims description 16
- 239000013638 trimer Substances 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000010409 thin film Substances 0.000 claims description 9
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical group [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 229940043232 butyl acetate Drugs 0.000 claims description 7
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 7
- 150000007513 acids Chemical class 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 3
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 6
- 238000004383 yellowing Methods 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000010408 film Substances 0.000 description 4
- 239000005056 polyisocyanate Substances 0.000 description 4
- 229920001228 polyisocyanate Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- -1 isocyanuric acid ester Chemical class 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000005829 trimerization reaction Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000006115 industrial coating Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
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%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310144023.5A CN103242254B (en) | 2013-04-23 | 2013-04-23 | Preparation method of HDI-TDI (Hexamethylene Diisocyanate-Toluene Diisocynate) polyurethane tripolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310144023.5A CN103242254B (en) | 2013-04-23 | 2013-04-23 | Preparation method of HDI-TDI (Hexamethylene Diisocyanate-Toluene Diisocynate) polyurethane tripolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103242254A true CN103242254A (en) | 2013-08-14 |
| CN103242254B CN103242254B (en) | 2014-09-24 |
Family
ID=48922159
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310144023.5A Active CN103242254B (en) | 2013-04-23 | 2013-04-23 | Preparation method of HDI-TDI (Hexamethylene Diisocyanate-Toluene Diisocynate) polyurethane tripolymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103242254B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 | A kind of 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3240613A1 (en) * | 1982-10-29 | 1984-05-03 | Angelina Arkad'evna Blagonravova | Arylaliphatic polyisocyanurates and process for their preparation |
| US4518761A (en) * | 1981-11-10 | 1985-05-21 | Bayer Aktiengesellschaft | Process for the preparation of mixed trimers from organic isocyanates, the mixed trimers obtained according to the process and the use thereof for the production of polyurethanes |
| JP2004156029A (en) * | 2002-10-15 | 2004-06-03 | Yokohama Rubber Co Ltd:The | Primer composition |
| CN102492113A (en) * | 2011-12-01 | 2012-06-13 | 山西省应用化学研究所 | Method for preparing waterborne polyurethane adhesive based on hexamethylene diisocyanate (HDI)-toluene diisocynate (TDI) |
-
2013
- 2013-04-23 CN CN201310144023.5A patent/CN103242254B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4518761A (en) * | 1981-11-10 | 1985-05-21 | Bayer Aktiengesellschaft | Process for the preparation of mixed trimers from organic isocyanates, the mixed trimers obtained according to the process and the use thereof for the production of polyurethanes |
| DE3240613A1 (en) * | 1982-10-29 | 1984-05-03 | Angelina Arkad'evna Blagonravova | Arylaliphatic polyisocyanurates and process for their preparation |
| JP2004156029A (en) * | 2002-10-15 | 2004-06-03 | Yokohama Rubber Co Ltd:The | Primer composition |
| CN102492113A (en) * | 2011-12-01 | 2012-06-13 | 山西省应用化学研究所 | Method for preparing waterborne polyurethane adhesive based on hexamethylene diisocyanate (HDI)-toluene diisocynate (TDI) |
Non-Patent Citations (2)
| Title |
|---|
| 夏卫华等: "异氰脲酸酯固化剂的研究进展", 《材料保护》, vol. 34, no. 9, 30 September 2001 (2001-09-30), pages 27 - 29 * |
| 扬洪俊: "HDI-TDI三聚体及聚氨酯涂料", 《涂料工业》, no. 6, 27 December 1986 (1986-12-27), pages 1 - 5 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 | A kind of 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103242254B (en) | 2014-09-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103242254B (en) | Preparation method of HDI-TDI (Hexamethylene Diisocyanate-Toluene Diisocynate) polyurethane tripolymer | |
| CN101899127B (en) | Polyurethane modified acrylic resin and preparation method thereof | |
| CN101230124B (en) | Curing agent 4,4'-biphenyl methane diisocyanate prepolymer and preparation method thereof | |
| CN107793544A (en) | A kind of environment-friendly polyurethane curing agent and its preparation method and application | |
| CN102212182B (en) | Curing agent methylene diphenyl diisocyanate tripolymer and method for preparing same | |
| CN102659997B (en) | Preparation method of polyurethane prepolymer with low free isocyanate monomer | |
| CN101274977B (en) | Curing agent 1,6- hexamethylene diisocyanate prepolymer and preparation thereof | |
| CN102617827B (en) | Curing agent modified 1,6-hexamethylene diisocyanate biuret (HDI biuret) and preparation method thereof | |
| CN106366291A (en) | Self-emulsifying anionic water-based polyurethane curing agent and preparation method thereof | |
| CN101481449A (en) | Wet impregnated polyurethane resin for high hydrolysis resistance synthetic leather and preparation thereof | |
| CN105175661A (en) | Polyurethane-acrylic ester composite emulsion of core-shell interpenetrating polymer network structure and preparation method thereof | |
| CN108003313A (en) | A kind of block type polycarbodiimide water cross-linking agent and preparation method thereof | |
| CN102731798B (en) | Self-emulsifying water-borne epoxy resin emulsion and preparation method thereof | |
| CN103772618B (en) | A kind of leather finish polymerization of acrylic modified polyurethane resin and preparation method thereof | |
| CN105440272A (en) | Preparation method of polyaspartic acid ester resin | |
| CN101775120A (en) | Curing agent diisocyanate prepolymer and preparation method thereof | |
| Li et al. | CO2 derived amino-alcohol compounds for preparation of polyurethane adhesives | |
| CN115322332A (en) | Fluorescent bio-based polyurethane capable of being rapidly self-repaired and preparation method thereof | |
| CN106065060A (en) | A kind of high-performance water-based polyurethane resin and preparation method thereof | |
| CN101307126B (en) | MDI trimer curing agent and method for preparing same | |
| CN105733379A (en) | Preparation method of high-solid acrylic polyurethane coating | |
| CN101698697B (en) | Polyurethane resin and synthetic method thereof | |
| CN106366280A (en) | Self-emulsifying type nonionic waterborne polyurethane curing agent and preparing method thereof | |
| CN114369216B (en) | HMDI-TDI trimer and preparation method and application thereof | |
| CN1283631C (en) | Process for preparing isophorone diisocyanate trimer compositions |
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 |