CN101254474B - Catalyst for isocyanate trimerization, preparation and use method - Google Patents
Catalyst for isocyanate trimerization, preparation and use method Download PDFInfo
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- CN101254474B CN101254474B CN2008100199908A CN200810019990A CN101254474B CN 101254474 B CN101254474 B CN 101254474B CN 2008100199908 A CN2008100199908 A CN 2008100199908A CN 200810019990 A CN200810019990 A CN 200810019990A CN 101254474 B CN101254474 B CN 101254474B
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- catalyst
- isocyanate trimerization
- isocyanate
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Abstract
The invention discloses a catalyst used for isocyanate trimerization and the preparation method and the application thereof. The catalyst has the structural formula shown in the right figure, whereinLn is a metal of yttrium and lanthanide families, R1-R8 is H, C1-C4 linear-chain or branched-chain hydrocarbon, S is a coordinating or non-coordinating solvent. Compared with the prior art, the invention realizes the synthesis of isocyanates by selective trimerization of isocyanate compounds (R-N=C=O), particularly high-efficiency selective catalytic trimerization of various substituted aromatic isocyanate compounds; and has the advantages of mild reaction conditions, high activity, good selectivity and less byproducts.
Description
Technical field
The present invention relates to be used for the catalyst of polymeric isocyanate and preparation thereof, using method, particularly is the catalyst of chlorinated isocyanurates and preparation thereof, using method with isocyanate ester compound selectivity trimerization.
Background technology
The trimerization product isocyanuric acid ester (chlorinated isocyanurates) of isocyanates can anti-400 ℃ of high temperature, have fire-retardant and increase the non-deformability and the anti-hydrolysis ability of polyurethane network.Effective trimerization of isocyanates is very important to production high-quality sex change urethanes chlorinated isocyanurates foam economically.The triaryl isocyanates is the effective active agent that epsilon-caprolactams is polymerized to nylon-6, and has the fire-retardant pressure layer material that thermal resistance ability, fire retardancy, chemical stability and good film forming characteristics are used for doing electric equipment because of it.The monomer that can also be used to do the crosslinking agent of plastics and make waterproof, transparent, shock-resistant copolymer resins.(Tang，J.；Mohan，T.；Verkade，J.G.J.Org.Chem.1994，59，4931，andreferences therein；Tang，J.；Verkade，J.G.Angew.Chem.，Int.Ed.Engl.1993，32，896，and references therein)
The catalyst type of catalysis isocyanates trimerization is a lot, such as electroneutral lewis base, anionic lewis base, acylate, tertiary amine, metal alkoxide etc.Yet these catalyst generally all have following shortcoming: severe reaction conditions, and catalyst activity is low; Catalyst is difficult to separate with additive; Selectivity is low, often is mixed with dimer or carbodiimides accessory substance, and the accessory substance that is difficult to expect that is brought by the active group of catalyst itself.(Kogon，I.C.J.Am.Chem.Soc.1966，78，4911；Kogon，I.C.J.Org.Chem.1969，24，83；Jones，I.E.；Savill，N.G.J.Chem.Soc.1967，43925；Herbetman，S.J.Org.Chem.1966，30，1259.；Nambu，Y.；Endo，T.J.Org.Chem.1993，58，1932)。
In recent years find also that some main groups and transition metal organic coordination compound also have goodish catalytic action to the isocyanates type of polymerization, wherein representative four sulphur ring-type organotin (IV) complexs { (CyNC (R) NCy) [N (SiMe that Darrin S.Richeson research group report is arranged
3)
2] SnS
4, Cy=cyclohexyl; R=Me,
tBu., this complex can be efficiently, catalysis aromatic isocyanate class trimerization is a chlorinated isocyanurates apace.(Foley，S.R.；Yap，G.P.A.；Richeson，D.S.Organometallics.1999，18，4700)
Divalence organotin and germanium complex [Me
3SiNC (
tBu) NSiMe
3] M[N (SiMe
3)
2] (M=Sn, Ge), this complex also can be efficiently, selectivity catalysis aromatic isocyanate class trimerization is a chlorinated isocyanurates apace.(Foley，S.R.；Zhou，Y.L.；Yap，G.P.A.；Richeson，D.S.Inorg.Chem.2000，39，924)。
Bivalent Tin complex [Me
3SiNC (Me) NSiMe
3]
2Sn, this complex can catalysis aromatic isocyanate class dimerization or trimerizations, and selectivity is relatively poor.(Foley，S.R.；Zhou，Y.L.；Yap，G.P.A.；Richeson，D.S.Inorg.Chem.2000，39，924)
Recently, report monomer calcium Cabbeen (DIPP-N=(Ph is arranged
2) P)
2CCa (THF)
2(DIPP=2,6-diisopropylphenyl) catalysis cyclohexyl isocyanate trimerization that can be very slow and the quick trimerization of catalysis phenyl isocyanate.(Orzechowski，L.；Harder，S.Organometallics.2007，26，2144.)
The catalyst system and catalyzing that is used for the rare earth compounding of catalysis phenyl isocyanate trimerization has only cyclopentadienyl complex Cp '
2LnN
iPr
2(THF) (Cp '=MeC
5H
4, Ln=Y, Er, Yb) or Cp
2LnCl/n-BuLi (Cp=C
5H
5, Ln=Sm Dy), and is used for the non-cyclopentadienyl system of catalysis phenyl isocyanate trimerization rare earth catalyst also do not report for work (Mao, L.; Shen, Q.; Xue, M.; Sun, J.Organomatallics 1997,16, and 3711.; Zhou, X.; Zhang, L.; Zhu, M.; Cai, R.; Weng, L.Organometallics 2001,20, and 5700).
In addition, the report for catalysis isocyanates living polymerization also has [(a) Patten, T.E.; Novak, B.M.J.Am.Chem.Soc.1996,118,1906; (b) Ahn, J.H.; Shin, Y.D.; Nath, G.Y.; Park, S.Y.; Rahman, M.S.; Samal, S.; Lee, J.S.J.Am.Chem.Soc.2005,127,4132; (c) Rahman, M.S.; Samal, S.; Lee, J.S.Macromolecules.2006,39,5009.].
Closely during the decade, non-cyclopentadienyl rare earth metal complex is just becoming the focus that the Organometallic scholars study after the rare earth metallocene complex.In all kinds of non-cyclopentadienyl rare earth metal complexs, the rare earth metal aminate that contains the Ln-N key because of its can be changed easily or modify with the substituting group on the N atom, can satisfy the sterically hindered requirement and the charge effect requirement of rare earth metal complex central metal greatly, and effectively improve the dissolubility of gained complex, and then becoming one of field, the vitochemical forward position of rare earth metal, the relevant rare earth metal aminate of Shang Weijian is at the report of catalysis isocyanates selectivity trimerization.
Summary of the invention
It is the catalyst of chlorinated isocyanurates that technical problem to be solved by this invention provides a kind of catalysis isocyanate ester compound selectivity trimerization.
Another one technical problem to be solved by this invention provides above-mentioned Preparation of catalysts, using method.
The technical scheme of technical solution problem of the present invention is: be used for the catalyst of isocyanate trimerization, have following structure:
In the formula, Ln is a kind of in yttrium and the lanthanide series metal, R
1～R
8Be H, C
1～C
4Straight or branched alkyl, S are ligand solvent.
Described C
1～C
4Straight-chain alkyl is methyl, ethyl, propyl group, and butyl, branched hydrocarbyl are isopropyl, isobutyl group.
R wherein
1, R
2And R
3Can be identical or different; R
4, R
5And R
6Can be identical or different; R
7And R
8Also can be identical or different; R
1, R
2, R
3And R
4, R
5, R
6Between also can be identical or inequality.
Preferred R
1, R
2, R
4And R
5Be isopropyl, R
3And R
6Be H, R
7And R
8Be methyl.S can or not have ligand solvent for oxolane or ether or glycol dimethyl ether, and preferred ligand solvent is oxolane or does not have ligand solvent.
Preparation method of the present invention is: with silicon bridge di-amine and trivalent rare earth metals amido complex [(Me
3Si)
2N]
3Ln
III(the Li (THF) of μ-Cl)
3(Ln be in yttrium and the lanthanide series metal a kind of) obtains by metathesis reaction in organic solvent.Specifically finish by following reaction method:
By structural formula be
Corresponding silicon bridge di-amine and [(Me
3Si)
2N]
3Ln
III(the Li (THF) of μ-Cl)
3(Ln=yttrium and lanthanide series metal) is by 1: the mol ratio of 0.8-1.2, in organic solvent, to react 12～24 hours, and reaction temperature is 80～110 ℃, can obtain containing the silicon bridge connection rare earth metal aminate of respective ligand.
Described organic solvent is: toluene.
Using method of the present invention is: in the organic solvent that is dissolved with a certain amount of isocyanates, add the prepared catalyst of the present invention, after 25～80 ℃ of reactions are not less than 12 hours, add the water cessation reaction, extract organic facies, drying, filter, concentrated filtrate gets final product, and the mol ratio of isocyanates and catalyst is 100: 1～3.
Described organic solvent is oxolane or toluene or carrene.
The present invention compared with prior art, can be chlorinated isocyanurates with isocyanate ester compound (R-N=C=O) selectivity trimerization, but different substituted aroma isocyanate ester compounds of efficient selective catalysis particularly, has the reaction condition gentleness, active high, selectivity is good, the characteristics that accessory substance is few.
The specific embodiment
Non-limiting examples is described below:
Intermediate [(Me
3Si)
2N]
3Ln
III(the Li (THF) of μ-Cl)
3Literature method (the E.H.Sheng. that the preparation of (Ln=yttrium and lanthanide series metal) is published with reference to people such as Wang Shaowu; S.W.Wang.; G.S.Yang.; S.L.Zhou.; L.Cheng.; K.H.Zhang.; Z.X.Huang.Organometallics 2003,22, and 684).
Embodiment 1:
Will (2,6-
iPr
2-C
6H
3) NH
2(10.0mL 53.02mmol) is dissolved in the tetrahydrofuran solution (50.0mL) and places ice-water bath, and (1.43M behind hexane solution 53.02mmol), is warming up to room temperature and stirs and spend the night slowly to drip the 37.10mL n-BuLi.Once more reactant mixture is placed ice-water bath, slowly splash into ClSiMe
2CH
2Cl (3.50mL, 26.51mmol).Dropwise, be warming up to and begin heating after the room temperature, keeps 50 ℃ to react 12 hours.Extract solvent, obtain light yellow oil.Extract product with 10.0mL * 3 n-hexanes, merge extract and be concentrated into 10mL.Place a couple of days down at 0 ℃, obtain white, needle-shaped crystals 3.82 grams, productive rate 34%.Results of elemental analyses (%): calculated value (C
27H
44N
2Si): C, 76.35; H, 10.44; N, 6.60.Measured value: C, 76.70; H, 10.16; N, 6.49.
Its structural formula is:
Embodiment 2:
Under the room temperature, to being dissolved with (CH
2SiMe
2) [(2,6-
iPr
2-C
6H
3) NH]
2(1.16g, adding is dissolved with [(Me in 10.0mL toluene solution 2.73mmol)
3Si)
2N]
3Y
III(the Li (THF) of μ-Cl)
3(2.263g, 50.0mL toluene solution 2.73mmol), room temperature reaction are heated to 80 ℃ after 6 hours again, react 12 hours.After extracting solvent, extract product, merge extract and be concentrated into 10mL with 10.0mL * 2 n-hexanes.Place a couple of days down at 0 ℃, obtain clear crystal 0.995g, productive rate 49%.Results of elemental analyses (%): calculated value (C
37H
68N
3OSi
3Y): C, 59.72; H, 9.21; N, 5.65.Measured value: C, 59.77; H, 9.03; N, 5.73.
Its structural formula is:
Embodiment 3:
Under the room temperature, to being dissolved with (CH
2SiMe
2) [(2,6-
iPr
2-C
6H
3) NH]
2(1.35g, adding is dissolved with [(Me in 10.0mL toluene solution 3.17mmol)
3Si)
2N]
3Yb
III(the Li (THF) of μ-Cl)
3(2.897g, 50.0mL toluene solution 3.17mmol), room temperature reaction are heated to 110 ℃ after 6 hours again, react 12 hours.After extracting solvent, extract product, merge extract and be concentrated into 10mL with 10.0mL * 2 n-hexanes.Place a couple of days down at 0 ℃, obtain red crystals 2.34g, productive rate 89%.Results of elemental analyses (%): calculated value (C
33H
60N
3Si
3Yb): C, 52.42; H, 8.00; N, 5.56.Measured value: C, 52.79; H, 7.94; N, 5.23.
Its structural formula is:
Embodiment 4:
Under the room temperature, to being dissolved with (CH
2SiMe
2) [(2,6-
iPr
2-C
6H
3) NH]
2(0.796g, adding is dissolved with [(Me in 10.0mL toluene solution 1.88mmol)
3Si)
2N]
3Sm
III(the Li (THF) of μ-Cl)
3(1.67g, 50.0mL toluene solution 1.88mmol), room temperature reaction are heated to 80 ℃ after 6 hours again, react 12 hours.After extracting solvent, extract product, merge extract and be concentrated into 10mL with 10.0mL * 2 n-hexanes.Place a couple of days down at 0 ℃, obtain yellow crystals 1.20g, productive rate 79%.Results of elemental analyses (%): calculated value (C
33H
60N
3Si
3Sm): C, 54.04; H, 8.25; N, 5.73.Measured value: C, 54.33; H, 8.31; N, 5.48.
Its structural formula is:
Embodiment 5:
Under the room temperature, to being dissolved with (CH
2SiMe
2) [(2,6-
iPr
2-C
6H
3) NH]
2(0.879g, adding is dissolved with [(Me in 10.0mL toluene solution 2.07mmol)
3Si)
2N]
3Dy
III(the Li (THF) of μ-Cl)
3(1.87g, 50.0mL toluene solution 2.07mmol), room temperature reaction are heated to 80 ℃ after 6 hours again, react 12 hours.After extracting solvent, extract product, merge extract and be concentrated into 10mL with 10.0mL * 2 n-hexanes.Place a couple of days down at 0 ℃, obtain look crystal 1.37g, productive rate 81%.Results of elemental analyses (%): calculated value (C
37H
68N
3OSi
3Dy): C, 54.35; H, 8.38; N, 5.14.Measured value: C, 54.44; H, 8.07; N, 5.45.
Its structural formula is:
Embodiment 6:
Under the room temperature, to being dissolved with (CH
2SiMe
2) [(2,6-
iPr
2-C
6H
3) NH]
2(0.974g, adding is dissolved with [(Me in 10.0mL toluene solution 2.30mmol)
3Si)
2N]
3Nd
III(the Li (THF) of μ-Cl)
3(2.03g, 50.0mL toluene solution 2.30mmol), room temperature reaction are heated to 80 ℃ of reactions 12 hours after 6 hours again.After extracting solvent, extract product, merge extract and be concentrated into 10mL with 10.0mL * 2 n-hexanes.Place a couple of days down at 0 ℃, obtain look crystal 1.40g, productive rate 76%.Results of elemental analyses (%): calculated value (C
33H
60N
3Si
3Nd): C, 54.49; H, 8.31; N, 5.78.Measured value: C, 54.68; H, 8.37; N, 5.42.
Its structural formula is:
Embodiment 7:
In the tetrahydrofuran solution that is dissolved with phenyl isocyanate (290g) (5L), add the prepared catalyst of 2.9 gram embodiment 2,25 ℃ of reactions 12 hours, add water (1L) cessation reaction, use the extracted by ether organic facies, behind the adding anhydrous sodium sulfate drying, filter, concentrated filtrate obtains white solid isocyanuric acid phenyl ester 267.3g, productive rate 92%.
The yield of isocyanuric acid phenyl ester according to: the method for the quality of gained isocyanuric acid phenyl ester/phenyl isocyanate inventory is calculated.
Embodiment 8:
Except that the catalyst that adds was the prepared catalyst of embodiment 3, all the other were identical with embodiment 7.
Embodiment 9:
Except that the catalyst that adds was the prepared catalyst of embodiment 4, all the other were identical with embodiment 7.
Embodiment 10:
Except that the catalyst that adds was the prepared catalyst of embodiment 5, all the other were identical with embodiment 7.
Embodiment 11:
Except that the catalyst that adds was the prepared catalyst of embodiment 6, all the other were identical with embodiment 7.
The yield of the isocyanuric acid phenyl ester that embodiment 7-11 is prepared is as shown in table 1:
Table 1
| Yield (%) | |
| Embodiment 7 | 92 |
| Embodiment 8 | 99 |
| Embodiment 9 | 99 |
| Embodiment 10 | 99 |
| Embodiment 11 | 99 |
Shown in the table 1: embodiment 8 prepared catalyst are best catalyst.
Embodiment 12:
Except that used solvent was toluene, all the other were identical with 8 embodiment.
The yield of the isocyanuric acid phenyl ester that embodiment 12 is prepared is 66%.
Embodiment 12 explanations, solvent THF is better than solvent toluene.
Embodiment 13:
Except that used raw material was the benzyl isocyanate ester, all the other were identical with embodiment 8.
Embodiment 14:
Except that used raw material was right-isopropyl isocyanate, all the other were identical with embodiment 8.
Embodiment 15:
Except that used raw material was cyclohexyl isocyanate, all the other were identical with embodiment 8.
Embodiment 16:
Except that used raw material was isopropyl isocyanate, all the other were identical with embodiment 8.
The yield of the variety classes chlorinated isocyanurates that embodiment 13-16 is prepared is as shown in table 2:
Table 2:
| Yield (%) | |
| Embodiment 13 | 99 |
| Embodiment 14 | 99 |
| Embodiment 15 | 10 |
| Embodiment 16 | 11 |
Table 2 shows: the yield of aromatic series chlorinated isocyanurates is than high many of the yield of aliphatic chlorinated isocyanurates among the embodiment 13-16.
Embodiment 17:
Except that reaction temperature is 50 ℃, all the other are identical with embodiment 7.
Embodiment 18:
Except that reaction temperature is 80 ℃, all the other are identical with embodiment 12.
The yield of the isocyanuric acid phenyl ester that embodiment 17,18 is prepared is respectively 99%, 99%.
Embodiment 17,18 explanations, along with the rising of temperature, the yield of isocyanuric acid phenyl ester improves a lot.
Embodiment 19:
The amount that adds except that catalyst is that all the other are identical with embodiment 12 5.8 grams.
Embodiment 20:
The amount that adds except that catalyst is that all the other are identical with embodiment 12 8.7 grams.
The yield people of the isocyanuric acid phenyl ester that embodiment 19,20 is prepared is respectively 83%, 99%.
Embodiment 19,20 explanations, along with the increase of catalyst amount, the yield of isocyanuric acid phenyl ester also can improve a lot.
Embodiment 21:
Except that the reaction time is 24 hours, all the other are identical with embodiment 12.
Embodiment 22:
Except that the reaction time is 24 hours, all the other are identical with embodiment 19.
The yield people of the isocyanuric acid phenyl ester that embodiment 21,22 is prepared is respectively 99%, 99%.
Embodiment 21,22 explanations, along with the prolongation in reaction time, the yield of isocyanuric acid phenyl ester also can improve a lot.
Claims (10)
1. be used for the catalyst of isocyanate trimerization, it is characterized in that: have following structure:
In the formula, Ln is a kind of in yttrium and the lanthanide series metal, R
1～R
8Be H, C
1～C
4Straight or branched alkyl, S are ligand solvent or do not have ligand solvent.
2. the catalyst that is used for isocyanate trimerization according to claim 1 is characterized in that: R
1, R
2And R
3Can be identical or different; R
4, R
5And R
6Can be identical or different; R
7And R
8Also can be identical or different; R
1, R
2, R
3And R
4, R
5, R
6Between also can be identical or inequality.
3. the catalyst that is used for isocyanate trimerization according to claim 2 is characterized in that: described C
1～C
4Straight-chain alkyl is methyl, ethyl, propyl group, and butyl, branched hydrocarbyl are isopropyl, isobutyl group.
4. the catalyst that is used for isocyanate trimerization according to claim 3 is characterized in that: described R
1, R
2, R
4And R
5Be isopropyl, R
3And R
6Be H, R
7And R
8Be methyl.
5. the catalyst that is used for isocyanate trimerization according to claim 1 is characterized in that: S is oxolane or ether or glycol dimethyl ether or does not have ligand solvent.
6. the catalyst that is used for isocyanate trimerization according to claim 1 is characterized in that: described ligand solvent is oxolane or does not have ligand solvent.
7. the described Preparation of catalysts method that is used for isocyanate trimerization of claim 1 is characterized in that: by structural formula be
Corresponding silicon bridge di-amine and [(Me
3Si)
2N]
3Ln
III(the Li (THF) of μ-Cl)
3By 1: the mol ratio of 0.8-1.2, in organic solvent, to react 12～24 hours, reaction temperature is 80～110 ℃, can obtain containing the silicon bridge connection rare earth metal aminate of respective ligand, described Ln is a kind of in yttrium and the lanthanide series metal.
8. the Preparation of catalysts method that is used for isocyanate trimerization according to claim 7 is characterized in that described organic solvent is a toluene.
9. the described using method that is used for the catalyst of isocyanate trimerization of claim 1, it is characterized in that: in the organic solvent that is dissolved with a certain amount of isocyanates, add the prepared catalyst of the present invention, after 25～80 ℃ of reactions are not less than 12 hours, add the water cessation reaction, extract organic facies, drying is filtered concentrated filtrate, get final product, the mol ratio of isocyanates and catalyst is 100: 1～3.
10. the using method that is used for the catalyst of isocyanate trimerization according to claim 9 is characterized in that: described organic solvent is oxolane or toluene or carrene.
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| CN104163906B (en) * | 2014-03-07 | 2018-01-05 | 华东理工大学 | One kind is used for isocyanate trimerization, catalyst and its application of the isocyanates with epoxy annulation |
| CN107913730B (en) * | 2017-11-30 | 2020-04-10 | 万华化学集团股份有限公司 | Imine type quaternary ammonium salt catalyst, preparation method thereof and polyisocyanate composition |
| CN109012748B (en) * | 2018-07-27 | 2021-03-16 | 安徽师范大学 | Pyridine substituted pyrrole based rare earth metal catalyst and preparation method and application thereof |
| CN114262302B (en) * | 2022-01-04 | 2023-09-29 | 山东新和成维生素有限公司 | Method for synthesizing diisocyanate trimer, catalyst and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6653432B2 (en) * | 1999-12-29 | 2003-11-25 | Rhodia Chimie | Condensation polymerization method for isocyanates |
| CN1899693A (en) * | 2005-07-21 | 2007-01-24 | 戈尔德施米特有限公司 | Trimerization catalysts |
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2008
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6653432B2 (en) * | 1999-12-29 | 2003-11-25 | Rhodia Chimie | Condensation polymerization method for isocyanates |
| CN1899693A (en) * | 2005-07-21 | 2007-01-24 | 戈尔德施米特有限公司 | Trimerization catalysts |
Non-Patent Citations (2)
| Title |
|---|
| 高喜平等.异氰酸酯三聚研究进展.化学推进剂与高分子材料3 4.2005,3(4),10-13,18. |
| 高喜平等.异氰酸酯三聚研究进展.化学推进剂与高分子材料3 4.2005,3(4),10-13,18. * |
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