CN1425702A - Process for preparing low free toluene diisocyanate curing agent - Google Patents
Process for preparing low free toluene diisocyanate curing agent Download PDFInfo
- Publication number
- CN1425702A CN1425702A CN 03113570 CN03113570A CN1425702A CN 1425702 A CN1425702 A CN 1425702A CN 03113570 CN03113570 CN 03113570 CN 03113570 A CN03113570 A CN 03113570A CN 1425702 A CN1425702 A CN 1425702A
- Authority
- CN
- China
- Prior art keywords
- toluene diisocyanate
- preparation
- solidifying agent
- low free
- free toluene
- Prior art date
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- Granted
Links
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 66
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title description 4
- 238000000605 extraction Methods 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 21
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 238000004821 distillation Methods 0.000 claims abstract description 9
- 239000012429 reaction media Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000007599 discharging Methods 0.000 claims abstract description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 238000005829 trimerization reaction Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- -1 cyclic aliphatic hydrocarbon Chemical class 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 5
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical class COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 claims description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 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 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical class [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 claims description 3
- WAVGXIXQMBSEMK-UHFFFAOYSA-N lithium;phenol Chemical compound [Li].OC1=CC=CC=C1 WAVGXIXQMBSEMK-UHFFFAOYSA-N 0.000 claims description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 2
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 2
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical class [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 2
- 229940059574 pentaerithrityl Drugs 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 2
- 229930195733 hydrocarbon Natural products 0.000 abstract 2
- 150000002430 hydrocarbons Chemical class 0.000 abstract 2
- 230000000379 polymerizing effect Effects 0.000 abstract 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 238000007865 diluting Methods 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 abstract 1
- 239000003112 inhibitor Substances 0.000 abstract 1
- 239000000178 monomer Substances 0.000 abstract 1
- 229920005862 polyol Polymers 0.000 abstract 1
- 150000003077 polyols Chemical class 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000013638 trimer Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- 125000004185 ester group Chemical group 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000001012 protector Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 125000005910 alkyl carbonate group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000005474 octanoate group Chemical group 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The preparation process of low free toluene diisocyanate as curing agent includes the following steps: reaction between toluene diisocyanate and polyol in the NCO/OH molar ratio 2-3 at 50-80 deg.c with reaction medium SO2, gamma-butrrolactone, dimethhyl sulfoxide, dimethyl carboxy diacid ester; adding polyisocyanate polymerizing catalyst when the content of NCO is 15-16 % for further reaction and adding polyisocyanate polymerizing inhibitor when the content of NCO is 14-15%; adding fatty hydrocarbon and/or cyclic fatty hydrocarbon as extracting agent for multiple extraction, eliminating the extracting agent through letting stand or distillation; and diluting and discharging pre-polymer. The present invention can prepare curing agent with low chroma, low visosity and high NCO content and no toluene diisocyanate monomer and other toxic matter.
Description
Technical field
The present invention relates to a kind of preparation method of polyurethane curing agent.
Background technology
At present, the production method of domestic the most frequently used polyurethane curing agent is to adopt TriMethylolPropane(TMP) and tolylene diisocyanate reaction prepolymer, and this prepolymer illustrates that modular construction is as follows:
This prepolymer in process of production, it is TDI that the tolylene diisocyanate of failing to react is in a large number arranged, because the gas phase toxicity of tolylene diisocyanate is big, so must remove.Along with the establishment of various countries' environmental regulation and the enhancing of people's environmental consciousness, the free toluene diisocyanate content of solidifying agent more and more is restricted in traditional solvent based coating.Therefore, exploitation low free toluene diisocyanate solidifying agent has become one of important directions of polyurethane coating exploitation, and the low free toluene diisocyanate solidifying agent that requires to develop both can satisfy environmental requirement, and satisfied chemical property can be provided again.The method that reduces at present free toluene diisocyanate has four kinds of film evaporation methods, back chemical method, MDI substitution method, extraction process, but they respectively have weak point.The investment of film evaporation method is big, because the product after the evaporation becomes solid, so operational difficulty.The content of the solidifying agent free toluene diisocyanate of back chemical method preparation is higher, the curing agents instability.The content of the solidifying agent free toluene diisocyanate that the MDI substitution method is produced is to have reduced, but after introducing MDI, the xanthochromia performance depreciation.Extraction process should be reasonable method.
Mentioned a kind of extraction process among the U.S. Pat .3883577, it provides with acetonitrile as the effect medium, this solvent has good avidity to the high-molecular weight polyisocyanates, only part is miscible with the extraction agent aliphatic hydrocarbon, and the boiling point of this solvent is low, is easy to remove with distillation, and can not cause side reaction, but the solidifying agent color that this method obtains is darker, and the loss amount of acetonitrile is bigger simultaneously, is not suitable for suitability for industrialized production.
Summary of the invention
Purpose of the present invention mainly is the problems referred to above at existing extraction process existence, a kind of preparation method of low free toluene diisocyanate solidifying agent is provided, make the content of free tolylene diisocyanate in the solidifying agent that makes very low, curing agents is unaffected simultaneously.
The object of the present invention is achieved like this: the step that the present invention includes following order:
(1) tolylene diisocyanate and polyvalent alcohol react in reaction media under 50-80 ℃ and form prepolymer, the mol ratio that the consumption of reactant tolylene diisocyanate and polyvalent alcohol satisfies NCO/OH is 2-3, and reaction media is selected from sulfurous gas, gamma-butyrolactone, dimethyl sulfoxide (DMSO), carboxylic two dimethyl phthalates;
When the weight percentage that (2) to survey free NCO group be the free cyano acid ester group is 15-16%, this moment, the weight percentage of free toluene diisocyanate was 12-13%, add a kind of polyisocyanates catalyst for trimerization, its total consumption is 0.02～0.15% of a preceding step gained prepolymer cures agent total mass, continue reaction down at 50-70 ℃, when the weight percentage of surveying free NCO group is reduced to 14-15%, this moment, the weight percentage of free toluene diisocyanate can drop to 8-9%, added polyisocyanates trimerization stopper stopped reaction;
(3) add extraction agent, repeatedly extract, extraction agent is aliphatic hydrocarbon or cyclic aliphatic hydrocarbon or their mixture, total consumption of extraction agent is 5～6 times of preceding step gained prepolymer cures agent total mass, the extraction agent major part is removed by standing demix, remaining extraction agent is removed by distillation, and when the prepolymer cures agent became transparent liquid, the common solvent of using polyisocyanates was with the discharging of prepolymer latting drown.
Polyvalent alcohol is selected from one of following or their any proportioning mixture among the present invention: ethylene glycol, propylene glycol, Diethylene Glycol, neopentyl glycol, dipropylene glycol, butyleneglycol, trihydroxybutane, TriMethylolPropane(TMP), tetramethylolmethane.
Temperature of reaction in the first step of the present invention preferably is controlled at 65-75 ℃; Temperature of reaction in second step preferably is controlled at 60-65 ℃.
In the first step of the present invention, it is better that the weight of reaction media accounts for the 20-30% of gross weight.
It is one of following that polyisocyanates catalyst for trimerization among the present invention is selected from: Whitfield's ointment lithium salts, acetate lithium salts, stearic acid lithium salts, phenol lithium, lithium hydroxide, isocaprylic acid tin, triethylenediamine.
Polyisocyanates trimerization stopper is selected from one of following among the present invention: phosphoric acid, Benzoyl chloride, sulfuric acid, two ethylhexyl phosphoric acid hydrogen salt.
Extraction agent among the present invention is selected from sherwood oil, normal hexane, hexanaphthene, methylcyclohexane or their any proportioning mixture.Extraction preferably divides to be finished for 4-7 time.
Distillation temperature of the present invention generally is controlled at 75-100 ℃ carries out under vacuum, preferably is controlled at 85-90 ℃ and carries out under negative pressure condition.In still-process, can add a certain amount of antioxidant, prevent variable color.
The solids content of the prepolymer cures agent of the present invention's preparation often adopts 30-80%, is preferably 70-80%.The letdown solvent dun that polyisocyanates is commonly used is ethyl acetate, butylacetate, alkyl carbonate, ketone etc.
The invention discloses a kind of chemistry and physical reaction system of new preparation low free toluene diisocyanate solidifying agent, this reaction system comprises: 1. chemical reaction, it comprises the pre-polymerization of (1) tolylene diisocyanate and polyvalent alcohol, (2) under the situation that a kind of polyisocyanates catalyst for trimerization exists, continue reaction, free toluene diisocyanate is further reduced; 2. physics system, the reaction media of a kind of solvent as tolylene diisocyanate and polyvalent alcohol is provided, this solvent has good avidity to the high-molecular weight tolylene diisocyanate, only small part is miscible with the extraction agent aliphatic hydrocarbon that is used to extract unreacted tolylene diisocyanate or cyclic aliphatic hydrocarbon, and can not cause side reaction.
With raw material tolylene diisocyanate, TriMethylolPropane(TMP), neopentyl glycol is example, illustrates that chemical equation of the present invention is as follows:
Technique effect of the present invention is: the present invention can make the solidifying agent of low colourity and viscosity, high NCO content by simple operation technology, and do not contain monomeric tolylene diisocyanate and other toxic substances substantially, harmless substantially to the operator that use this material.
The prepared solidifying agent of the present invention is compared as follows with the relevant performance of general solidifying agent:
Embodiment
Embodiment one:
The tolylene diisocyanate of 522g is joined in the reactor that whipping appts, charging opening, thermometer and drying nitrogen protector be housed; add carboxylic two dimethyl phthalate 165.9g then; be warmed up to and divide 6 batches of mixtures that add 91g TriMethylolPropane(TMP) and 50.5g neopentyl glycol after 50 ℃; be 30 minutes each pitch time, then 70 ℃ of insulations 3.5 hours.
When the weight percentage of surveying free NCO group is 15～16%, add polyisocyanate trimer catalyzer phenol lithium 0.17g, after reacting 3 hours under 65 ℃, got the weight percentage of a free NCO of sample detection every 30 minutes, reaction lasts till that making NCO content drop to 14 ± 0.5% backs adds polyisocyanate trimer stopper phosphoric acid 0.08g termination reactions.
Sherwood oil 4147g divided join in the reactor for 5 times, stir 15 minutes at every turn after, left standstill 5 minutes, vacuumize sherwood oil is driven in the still kettle, by the still kettle distillation sherwood oil is separated from free toluene diisocyanate, sherwood oil refluxes and enters storage tank by behind the condenser.Repeatedly extraction reaches the purpose of continuous extraction free toluene diisocyanate.Behind the re-extract 5 times, treat to stop extraction behind weight percentage≤0.5% of free TDI.The extraction liquid of being emitted by the still kettle bottom after extraction finishes is squeezed into storage tank, uses during in order to preparation next time solidifying agent.
After extraction finished, reactor was warmed up to 85 ℃, steam sherwood oil remaining in the solidifying agent make solidifying agent transparent after, in reactor, add a certain amount of letdown solvent dun ethyl acetate at once, make and contain 75% product admittedly.
It is 75% that last resulting solidifying agent contains admittedly, it is a kind of colourless liquid that is about 70-120S 25 ℃ of Ge Shi pipe viscosity, wherein the weight percentage of free TDI is 0.3-0.5%, and the free cyano acid ester group i.e. weight percentage of free NCO group is 11.5 ± 0.5%.
Product 67 gram of embodiment one gained and Synolac 200 restrain the performance of coating paint film as follows:
Under 25 ℃, surface drying time: 25min, do solid work the time: 20h,
Test performance after 5 days:
Impact (cm) 54;
Crooked (mm) 1.2;
Sticking power (level) 1-2;
Pencil hardness (H) 3.
Embodiment two:
The tolylene diisocyanate of 783g is joined in the reactor that whipping appts, charging opening, thermometer and drying nitrogen protector be housed; add gamma-butyrolactone 231.1g then; be warmed up to and divide 6 batches of mixtures that add 91g TriMethylolPropane(TMP) and 50.5g neopentyl glycol after 50 ℃; be 30 minutes each pitch time, then 70 ℃ of insulations 3.5 hours.
When the weight percentage of surveying free NCO group is 15-16%, add polyisocyanate trimer octoate catalyst tin 0.58g (0.05%), after reacting 3 hours under 65 ℃, got the weight percentage of a free NCO of sample detection every 30 minutes, reaction lasts till that making NCO content drop to 14 ± 0.5% backs adds polyisocyanate trimer stopper Benzoyl chloride 0.27g termination reactions.
Hexanaphthene 5778.1g divided join in the reactor for 6 times, stir 15 minutes at every turn after, left standstill 5 minutes.Vacuumize hexanaphthene is driven in the still kettle, by the still kettle distillation hexanaphthene is separated from free toluene diisocyanate, hexanaphthene refluxes and enters storage tank by behind the condenser.Repeatedly extraction reaches the purpose of continuous extraction free toluene diisocyanate.Behind the re-extract 6 times, treat to stop extraction behind weight percentage≤0.5% of free TDI.The extraction liquid of being emitted by the still kettle bottom after extraction finishes is squeezed into storage tank, uses during in order to preparation next time solidifying agent.
After extraction finished, reactor was warmed up to 85 ℃, steam hexanaphthene remaining in the solidifying agent make solidifying agent transparent after, in reactor, add a certain amount of letdown solvent dun ethyl acetate at once, make and contain 75% product admittedly.
It is 75.2% that last resulting solidifying agent contains admittedly, it is a kind of colourless liquid that is about 80-120S 25 ℃ of Ge Shi pipe viscosity, wherein the weight percentage of free TDI is 0.4-0.5%, and the free cyano acid ester group i.e. weight percentage of free NCO group is 12.0 ± 0.5%.
Product 67 gram of embodiment two and Synolac 200 restrain the performance of coating paint film as follows:
Under 25 ℃, surface drying time: 23min, do solid work the time: 19h,
Test performance after 5 days:
Impact (cm) 56;
Crooked (mm) 1.4;
Sticking power (level) 1-2;
Pencil hardness (H) 3.
Embodiment three:
The tolylene diisocyanate of 652.5g is joined in the reactor that whipping appts, charging opening, thermometer and drying nitrogen protector be housed; add dimethyl sulfoxide (DMSO) 337g then; divide 6 batches after being warmed up to 50 ℃ and add the 134g TriMethylolPropane(TMP); be 30 minutes each pitch time, then 70 ℃ of insulations 3.0 hours.
When the weight percentage of surveying free NCO group is 15-16%, add polyisocyanate trimer catalyzer stearic acid lithium salts 1.68g, after reacting 2.5 hours under 65 ℃, got the weight percentage of a free NCO of sample detection every 30 minutes, reaction lasts till that making NCO content drop to 14 ± 0.5% backs adds polyisocyanate trimer stoppers pair ethylhexyl phosphoric acid hydrogen salt 0.94g termination reactions.
Normal hexane 5617.5g divided join in the reactor for 5 times, stir 15 minutes at every turn after, left standstill 5 minutes.Vacuumize normal hexane is driven in the still kettle, by the still kettle distillation normal hexane is separated from free toluene diisocyanate, normal hexane refluxes and enters storage tank by behind the condenser.Repeatedly thereby extraction reaches the purpose of continuous extraction free toluene diisocyanate.Behind the re-extract 5 times, treat to stop extraction behind weight percentage≤0.5% of free TDI.The extraction liquid of being emitted by the still kettle bottom after extraction finishes is squeezed into storage tank, uses during in order to preparation next time solidifying agent.
After extraction finished, reactor was warmed up to 85 ℃, steam normal hexane remaining in the solidifying agent make solidifying agent transparent after, in reactor, add a certain amount of letdown solvent dun ethyl acetate at once, make and contain 75% product admittedly.
It is 74.5% that last resulting solidifying agent contains admittedly, it is a kind of colourless liquid that is about 70-110S 25 ℃ of Ge Shi pipe viscosity, wherein the weight percentage of free TDI is 0.3-0.5%, and the free cyano acid ester group i.e. weight percentage of free NCO group is 11.5 ± 0.5%.
Product 67 gram of embodiment three gained and Synolac 200 restrain the performance of coating paint film as follows:
Under 25 ℃, surface drying time: 24min, do solid work the time: 20h,
Test performance after 5 days:
Impact (cm) 55;
Crooked (mm) 1.5;
Sticking power (level) 1-2;
Pencil hardness (H) 3.
Embodiment four:
Will be among the embodiment one the extraction part change, the amount that promptly at every turn adds extraction agent is reduced to original 50%; Extract 10 times, finally till the content of free TDI is less than 0.5%.
Product 67 gram of embodiment four and Synolac 200 restrain the performance of coating paint film as follows:
Under 25 ℃, surface drying time: 25min, do solid work the time: 19h,
Test performance after 5 days:
Impact (cm) 54;
Crooked (mm) 1.4;
Sticking power (level) 2;
Pencil hardness (H) 3.
Claims (10)
1. the preparation method of a low free toluene diisocyanate solidifying agent is characterized in that comprising the step of following order:
(1) tolylene diisocyanate and polyvalent alcohol react in reaction media under 50-80 ℃ and form prepolymer, wherein to satisfy the mol ratio of NCO/OH be 2-3 to the consumption of reactant tolylene diisocyanate and polyvalent alcohol, and reaction media is selected from sulfurous gas, gamma-butyrolactone, dimethyl sulfoxide (DMSO), carboxylic two dimethyl phthalates;
When (2) weight percentage of the free NCO group of survey is 15-16%, add a kind of polyisocyanates catalyst for trimerization, its total consumption is the 0.02-0.15% of preceding step gained prepolymer cures agent gross weight, continue reaction down at 50-70 ℃, when the weight percentage of surveying free NCO group is reduced to 14-15%, add polyisocyanates trimerization stopper stopped reaction;
(3) add extraction agent, repeatedly extract, extraction agent is aliphatic hydrocarbon or cyclic aliphatic hydrocarbon or their mixture, total consumption of extraction agent is 5-6 a times of preceding step gained prepolymer cures agent gross weight, the extraction agent major part is removed by standing demix, remaining extraction agent is removed by distillation, when the prepolymer cures agent becomes transparent liquid, with polyisocyanates solvent commonly used with the discharging of prepolymer latting drown.
2. the preparation method of low free toluene diisocyanate solidifying agent according to claim 1, it is characterized in that: described polyvalent alcohol is selected from one of following or their mixture, ethylene glycol, propylene glycol, Diethylene Glycol, neopentyl glycol, dipropylene glycol, butyleneglycol, trihydroxybutane, TriMethylolPropane(TMP), tetramethylolmethane.
3. the preparation method of low free toluene diisocyanate solidifying agent according to claim 1, it is characterized in that: described polyisocyanates catalyst for trimerization is selected from, Whitfield's ointment lithium salts, acetate lithium salts, stearic acid lithium salts, phenol lithium, lithium hydroxide, isocaprylic acid tin, triethylenediamine.
4. the preparation method of low free toluene diisocyanate solidifying agent according to claim 1 is characterized in that: described polyisocyanates trimerization stopper is selected from phosphoric acid, Benzoyl chloride, sulfuric acid, two ethylhexyl phosphoric acid hydrogen salt.
5. the preparation method of low free toluene diisocyanate solidifying agent according to claim 1 is characterized in that: described extraction agent is selected from sherwood oil, normal hexane, hexanaphthene, methylcyclohexane or their mixture.
6. the preparation method of low free toluene diisocyanate solidifying agent according to claim 1 is characterized in that: the temperature of reaction of first step is preferably 65-75 ℃.
7. the preparation method of low free toluene diisocyanate solidifying agent according to claim 1 is characterized in that: the temperature of reaction of second step is preferably 60-65 ℃.
8. the preparation method of low free toluene diisocyanate solidifying agent according to claim 1 is characterized in that: described repeatedly extraction preferably divides to be finished for 4-7 time.
9. the preparation method of low free toluene diisocyanate solidifying agent according to claim 1 is characterized in that: described distillation temperature is controlled at 75-100 ℃ and carries out under vacuum.
10. the preparation method of low free toluene diisocyanate solidifying agent according to claim 1 is characterized in that: in first step, it is better that the weight of reaction media accounts for the 20-30% of gross weight.
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| CN100351297C (en) * | 2004-01-10 | 2007-11-28 | 广州秀珀化工有限公司 | Low free tolylene diisocynate polyurethane solidifying agent and its preparation method |
| CN101649036B (en) * | 2009-08-20 | 2011-12-28 | 广州市合工大实力新材料研究院有限公司 | polyisocyanate curing agent and preparation method thereof |
| CN101698696B (en) * | 2009-07-01 | 2012-07-25 | 北京高盟新材料股份有限公司 | Method for preparing water-dispersible aqueous curing agent for composite adhesive |
| CN102643407A (en) * | 2012-05-08 | 2012-08-22 | 上海东大聚氨酯有限公司 | Preparation method for isophorone diisocyanate (IPDI) prepolymer for coating curing |
| CN103086991A (en) * | 2013-01-04 | 2013-05-08 | 甘肃银光聚银化工有限公司 | Method for preparing low-free curing agent with solid content of 75% by synthesis of 65/35 toluene diisocynate (TDI) |
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| CN104072721A (en) * | 2014-07-08 | 2014-10-01 | 福建师范大学 | Preparation method of polyurethane curing agent based on TDI-TMP (toluene diisocynate-trimethylolpropane) |
| CN104761702A (en) * | 2015-03-25 | 2015-07-08 | 田福东 | Polyurethane curing agent |
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| CN105001401A (en) * | 2015-05-07 | 2015-10-28 | 珠海联固化学工业有限公司 | Polyurethane curing agent with high solid content and low free TDI and preparation method thereof |
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| CN101649036B (en) * | 2009-08-20 | 2011-12-28 | 广州市合工大实力新材料研究院有限公司 | polyisocyanate curing agent and preparation method thereof |
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| CN103086991B (en) * | 2013-01-04 | 2016-01-06 | 甘肃银光聚银化工有限公司 | A kind of use 65/35 tolylene diisocyanate synthesizes the preparation method of 75% solid content, low free solidifying agent |
| CN103086991A (en) * | 2013-01-04 | 2013-05-08 | 甘肃银光聚银化工有限公司 | Method for preparing low-free curing agent with solid content of 75% by synthesis of 65/35 toluene diisocynate (TDI) |
| CN103936961A (en) * | 2014-04-30 | 2014-07-23 | 中国海洋石油总公司 | Thick oil demulsifying agent and preparation method thereof |
| CN104072721A (en) * | 2014-07-08 | 2014-10-01 | 福建师范大学 | Preparation method of polyurethane curing agent based on TDI-TMP (toluene diisocynate-trimethylolpropane) |
| CN104072721B (en) * | 2014-07-08 | 2016-05-04 | 福建师范大学 | The preparation method of the polyurethane curing agent based on TDI-TMP |
| CN104761702A (en) * | 2015-03-25 | 2015-07-08 | 田福东 | Polyurethane curing agent |
| CN105001401A (en) * | 2015-05-07 | 2015-10-28 | 珠海联固化学工业有限公司 | Polyurethane curing agent with high solid content and low free TDI and preparation method thereof |
| CN104910674A (en) * | 2015-06-17 | 2015-09-16 | 牛无畏 | Curing agent with high density and strong adhesive force and preparation method of curing agent |
| CN105754070A (en) * | 2016-03-16 | 2016-07-13 | 上海展辰涂料有限公司 | Low-free-TDI tripolymer curing agent and preparation method thereof |
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| 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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