CN105032490A - Complex catalyst and application thereof to preparation of mixed diisocyanate trimer - Google Patents
Complex catalyst and application thereof to preparation of mixed diisocyanate trimer Download PDFInfo
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- CN105032490A CN105032490A CN201510424577.XA CN201510424577A CN105032490A CN 105032490 A CN105032490 A CN 105032490A CN 201510424577 A CN201510424577 A CN 201510424577A CN 105032490 A CN105032490 A CN 105032490A
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Abstract
The present invention belongs to the technical field of catalysts, and discloses a complex catalyst and application thereof to preparation of a mixed diisocyanate trimer. The complex catalyst comprises three components including an alkali metal salt catalyst, a cyclic organic compound and aliphatic long-chain organic ether alcohol, or the three components and a diluent. The application is as below: under protection of N2, adding the complex catalyst to a container filled with hexamethylene diisocyanate, rising the temperature, dropwise adding toluene diisocyanate, continuing rising the temperature and insulating; stopping the reaction, when the NCO of material falls to 36% or less, terminating the reaction, separating, removing monomers, and diluting, so as to obtain the mixed diisocyanate trimer. The prepared complex catalyst has good catalysis effect, improves the synthesis efficiency of the mixed diisocyanate trimer, and enhances the stability of the mixed diisocyanate trimer structure, so that the trimer has better performance.
Description
Technical field
The invention belongs to the technical field of catalyst, relate to a kind of catalyst compounded, particularly a kind of catalyst compounded and application in preparation mixing diisocyanate trimer.
Background technology
Diisocyanate trimer is all the study hotspot of polyurethane field all the time.Diisocyanate monomer autohemagglutination under normal temperature or heating state is slow, even can not there is self-polymeric reaction in part vulcabond, so need to add catalyst to promote vulcabond autohemagglutination, the catalytic performance of catalyst has great impact for vulcabond self-polymeric reaction efficiency.Existing catalyst is most comparatively remarkable to aromatics vulcabond catalytic effect, and it is more weak to fats vulcabond catalytic effect, therefore, in aromatics vulcabond and fats vulcabond copolymerization system, the catalytic effect of these catalyst is undesirable.Simultaneously the kind of catalyst and consumption can produce considerable influence to the physical and chemical indexes of vulcabond polymerization product and performance, therefore select efficient high-selectivity catalyst particularly important for catalyzing and synthesizing diisocyanate trimer.Current selectable catalyst type is numerous, such as quaternary ammonium salt catalyst, amines catalyst and base metal catalysts etc.Research find amines catalyst as DMP-30, quaternary ammonium salts catalyst as first quaternary ammonium salt for aliphatic diisocyanate almost without catalytic effect.Base metal catalysts has good catalytic effect for vulcabond self-polymeric reaction, but due to base metal catalysts can not be miscible with vulcabond self-polymeric reaction system, be only scattered among material with suspended particulate form, catalytic efficiency is restricted.In addition, after reaction terminating, need from product, filter to isolate base metal catalysts particle, this adds operation easier and production process undoubtedly.
As everyone knows, toluene diisocyanate trimer yellowing resistance in application process is poor, and hexamethylene diisocyanate trimer physical property such as hardness adhesive force in application process is poor.Therefore adopt special process, toluene di-isocyanate(TDI) and hexamethylene diisocyanate are carried out poly reaction with proper proportion, the color inhibition mixing diisocyanate trimer product having higher building rationality energy can be obtained.But because hexamethylene diisocyanate and toluene di-isocyanate(TDI) reactivity gap are comparatively large, the structure of more difficult control product and molecular ratios in mixing three collecting process.Ideally in target product, the ratio of hexamethylene diisocyanate and toluene di-isocyanate(TDI) is about 1:2 or 2:1.For realizing in mixing three collecting process, hexamethylene diisocyanate and toluene di-isocyanate(TDI) carry out in proportion, select a kind of effective catalyst to be the basis of testing.The catalyst of high catalytic efficiency can reduce the gap of hexamethylene diisocyanate and toluene di-isocyanate(TDI) reactivity, makes the NCO in two kinds of vulcabond participate in trimerization reaction simultaneously.
Summary of the invention
In order to overcome shortcoming and defect of the prior art, primary and foremost purpose of the present invention is to provide a kind of catalyst compounded.The present invention has prepared a kind of ternary built homogeneous phase high-efficient alkali metallic catalyst by introducing organic coordination compounds, this catalyst overcome base metal catalysts catalysis vulcabond in collecting process with reaction system inconsistent problem, reduce the reactivity of different vulcabond, after efficient catalytic mixing vulcabond, obtain a kind of mixing diisocyanate trimer of better performances.
Another object of the present invention is to provide above-mentioned catalyst compounded application.
Object of the present invention is achieved through the following technical solutions:
A kind of catalyst compounded by alkali metal salt catalyst, cyclic organic compounds and the organic ether alcohol of aliphatic long-chain three kinds of one-tenth are grouped into or are made up of described three kinds of compositions and diluent.
A kind of catalyst compounded be by alkali metal salt catalyst, cyclic organic compounds and the organic ether alcohol of aliphatic long-chain three kinds of compositions or three kinds of compositions and mixing diluents evenly obtain.
Described alkali metal salt catalyst be in alkali metal carboxylate or alkali metal alcoholates more than one; Described alkali metal salt catalyst be preferably in sodium acetate, potassium acetate, caustic alcohol or potassium ethoxide more than one.
Described cyclic organic compounds be in crown ether or cyclodextrin more than one.
Described cyclic organic compounds is 12-crown-4,15-hat-5,18-hat-6, dibenzo-18 crown-6, bicyclohexane is-18-hat-6, alpha-cyclodextrin also, in beta-schardinger dextrin-or gamma-cyclodextrin more than one, particularly preferably 15-hat-5,18-hat-6, more than one in dibenzo-18 crown-6 or beta-schardinger dextrin-.
The organic ether alcohol of described aliphatic long-chain is more than one in polyethylene glycol or polyethylene glycol monoether, and one or more particularly preferably in the polyethylene glycol of molecular weight 200 ~ 600 or poly glycol monomethyl ether are used in combination.
In described catalyst compounded system, as catalyst compounded solvent while the organic ether alcohol of aliphatic long-chain participates in coordination.
In described three kinds of compositions, the mass percentage of alkali metal salt catalyst is 10% ~ 30%, and the mass percentage of cyclic organic compounds is 15% ~ 60%, 10% ~ 75% of the mass percentage of the organic ether alcohol of aliphatic long-chain.
Selected diluent is more than one in alcohols solvent, ether alcohol kind solvent, esters solvent and ketones solvent.Described alcohols solvent is single hydroxyl alcohol.Described catalyst compounded middle diluent and the total mass values of three kinds of compositions are any number.
In described built agent, the mass percentage of diluent is 0 ~ 50%, is more preferably 0 ~ 30%.
Described catalyst compounded application in preparation mixing diisocyanate trimer, comprises the following steps:
At N
2under the condition of protection and stirring; catalyst compounded adding is equipped with in the container of hexamethylene diisocyanate; be warming up to 50 ~ 80 DEG C; drip toluene di-isocyanate(TDI), be warming up to 60 ~ 90 DEG C of insulation reaction after dropwising, when material NCO is down to less than 36% cessation reaction; be separated; remove monomer, latting drown, obtain mixing diisocyanate trimer.
Described catalyst compounded addition is 0.005% ~ 5% of material gross mass, more preferably 0.01% ~ 1%.Described catalyst compounded addition manner is disposable or adds in batches.Described toluene di-isocyanate(TDI) time for adding is 1 ~ 3 hour.Described material is catalyst compounded, hexamethylene diisocyanate and toluene di-isocyanate(TDI).
The mass ratio of described hexamethylene diisocyanate and toluene diisocynate toluene ester is (1.5 ~ 3): 1.
Described toluene di-isocyanate(TDI) is one or both in 2,4-toluene di-isocyanate(TDI) or 2,6-toluene di-isocyanate(TDI); Described toluene di-isocyanate(TDI) is preferably TDI-80.
Described mixing diisocyanate trimer preparation process does not need to add additional solvent.
The terminator of described cessation reaction is chlorobenzoyl chloride or phosphoric acid.The rotating speed of described stirring is 100 ~ 200r/min.
In vulcabond self-polymeric reaction system, the catalytic action of alkali metal class catalyst mainly comes from anionicsite, alkali metal ion mainly plays inducing action, and in system introduce can with the phase transfer catalyst of alkali metal ion complexing, the declines between alkali metal ion and anion can be made, improve the compatibility of major catalyst and organic phase, thus significantly improve the catalytic effect of catalyst.
The present invention adopts cyclic crown ether class material and the organic ether alcohol of aliphatic long-chain as phase transfer catalyst simultaneously, and they can form comparatively stable complex with alkali metal ion.Phase transfer catalyst can be dispersed in aqueous phase and organic phase, ionized catalyst thus can be helped to be dissolved in organic phase thus improve reaction rate.Crown ether is preced with-6 inclusion alkali metal for 18-, because the footpath, chamber of 18-hat-6 is close with alkali metal ion size, so it has stronger inclusion ability for alkali metal ion.Containing the functional group of complexing can be had with metal ion in a large number on the organic ether alcohol strand of aliphatic long-chain, thus there is complexing Na
+, K
+isoionic ability.The structural formula of crown ether inclusion alkali metal ion is as follows:
On the other hand, be liquid under the organic ether alcohol normal temperature of medium molecule chain fatty race, and crown ether and cyclodextrin mostly are solid-state, in catalyst compounded preparation process, the organic ether alcohol of aliphatic long-chain can while a certain amount of alkali metal ion of coordination, as the solvent of composite catalyst, promote crown ether, cyclodextrin and alkali metal salt generation complexation reaction.And will lower than crown ether in aliphatic long-chain organic ether raw polyol price, therefore it participates in compositely can reducing catalyst compounded cost to a certain extent.
Simultaneously, the active hydroxy group of the organic ether alcohol of aliphatic long-chain can react with NCO in reaction system, this to make in product in part trimeric molecules structure also complexing have alkali metal ion, can NCO to a certain extent in anakmetomeres, improve product reactivity in the application further.And this type of hydroxy radical content is unsuitable too much, too much hydroxyl can the isocyanate group content of direct loss system.
Compared with prior art, tool of the present invention has the following advantages:
(1) utilize complexation reaction, make cyclic organic ligand as crown ether inclusion alkali metal ion, make existing base metal catalysts can be dissolved in organic phase mutually, remove the operational sequence using this type of catalyst to need to be separated after the reaction insoluble catalyst particle from;
(2) utilize complexation reaction, alkali metal ion, by after inclusion, makes the easier attack NCO of organic anion part, improves the catalytic effect of base metal catalysts to a certain extent;
(3) utilize ternary built, while ensureing that alkali metal ion is completely composite, save composite cost, ensure that reaction system active isocyanate base is not by excess loss as far as possible;
(4) catalyst compounded in the present invention catalytic effect is extremely strong, and namely a small amount of catalyst can reach intended catalyzed effect, thus improves mixing diisocyanate trimer combined coefficient;
(5) the present invention adopts hexamethylene diisocyanate consumption higher than the synthesizing formula of toluene di-isocyanate(TDI), and by dripping the synthesis mode of toluene di-isocyanate(TDI), ensure mixed trimer Middle molecule ratio uniform to a certain extent, make product have good yellowing resistance.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further described in detail, but embodiments of the present invention are not limited thereto.Below in embodiment, unless stated otherwise, percentage (%) is all mass percents.
Embodiment 1-5
A catalyst compounded application in preparation mixing diisocyanate trimer, comprises the following steps:
At N
2under protection, 600g hexamethylene diisocyanate is joined in the four-hole boiling flask that paddle, thermometer and dropping funel are housed, open and stir (rotating speed of stirring is 200r/min), add as shown in table 1 catalyst compounded, be warming up to 60 DEG C, 300g toluene di-isocyanate(TDI) (TDI-80) is added drop-wise in four-hole bottle, within 2 hours, drips off; 70 DEG C of insulation reaction are warming up to after dropwising, when in system, NCO is down to less than 36%, add the chlorobenzoyl chloride cessation reaction of 40% of catalytic amount weight, material removed monomer through thin film evaporator and utilizes solvent ethyl acetate latting drown to be about 50% to solid content, obtaining the mixing diisocyanate trimer that diisocyanate monomer content is less than 0.4%.The physical and chemical performance of described mixing diisocyanate trimer is as shown in table 2.
The consumption that table 1 embodiment 1-5 is catalyst compounded and compound scheme
The physico-chemical parameter of table 2 embodiment 1-5 product
Embodiment 6-10
A catalyst compounded application in preparation mixing diisocyanate trimer, comprises the following steps:
At N
2under protection, hexamethylene diisocyanate (addition of hexamethylene diisocyanate is as shown in table 3) is joined in the four-hole boiling flask that paddle, thermometer and dropping funel are housed, open and stir (rotating speed of stirring is 150r/min), (mass percentage of potassium acetate is 10% to add 0.3g catalyst compounded; The mass percentage of 18-hat-6 is 15%; The mass percentage of polyethylene glycol-600 is 75%), be warming up to 60 DEG C, toluene di-isocyanate(TDI) is added drop-wise to (toluene di-isocyanate(TDI) amount and toluene di-isocyanate(TDI) time for adding are in table 3) in four-hole boiling flask, 70 DEG C of insulations are warming up to after dropwising, appropriate chlorobenzoyl chloride cessation reaction is added when NCO is down to less than 36%, material removed monomer through thin film evaporator and utilizes solvent ethyl acetate latting drown to be about 50% to solid content, obtaining the mixing diisocyanate trimer that diisocyanate monomer content is less than 0.4%.The physical and chemical performance of described mixing diisocyanate trimer is as shown in table 4.
Table 3 embodiment 6-10 vulcabond addition and time for adding
The physical and chemical performance of table 4 embodiment 6-10 product
Embodiment 11-15
A catalyst compounded application in preparation mixing diisocyanate trimer, comprises the following steps:
At N
2under protection, 600g hexamethylene diisocyanate is joined in the four-hole boiling flask that paddle, thermometer and dropping funel are housed, open and stir (rotating speed of stirring is 200r/min), (potassium acetate mass percentage is 10% to add 0.3g catalyst compounded; It is 15% that 18-is preced with-6 mass percentage; Polyethylene glycol-600 mass percentage is 75%), heat up (see table 5), 300g toluene di-isocyanate(TDI) is added drop-wise in four-hole bottle, within 2 hours, drips off; Dropwise rear intensification and be incubated (described temperature is in table 5), appropriate chlorobenzoyl chloride cessation reaction is added when NCO is down to less than 36%, by material after thin film evaporator removes monomer and utilizes solvent ethyl acetate latting drown, obtain the mixing diisocyanate trimer product that diisocyanate monomer content is less than 0.4%.The physical and chemical performance of described mixing diisocyanate trimer is as shown in table 6.
Table 5 embodiment 11-15 temperature parameter
Table 6 embodiment 11-15 product physical and chemical indexes
Comparative example 1
At N
2under protection; 600g hexamethylene diisocyanate is joined in the four-hole boiling flask that paddle, thermometer and dropping funel are housed; open and stir (200r/min); add the catalyst of the DMP-30 of 0.5g; be warming up to 60 DEG C; 300g toluene di-isocyanate(TDI) (TDI-80) is added drop-wise in four-hole bottle; within 2 hours, drip off; 70 DEG C of insulations are warming up to after dropwising; decline slowly after in material, NCO is down to 41%; add 0.52g chlorobenzoyl chloride cessation reaction, material is removed monomer process through thin film evaporator.There is mass crystallization in processing procedure, product poor fluidity in thin film evaporation process, be difficult to obtain target product.
Comparative example 2
At N
2under protection, 600g hexamethylene diisocyanate is joined paddle is housed, in the four-hole boiling flask of thermometer and dropping funel, open and stir (speed of agitator is 200r/min), add 0.5g potassium acetate as catalyst, be warming up to 60 DEG C, 300g toluene di-isocyanate(TDI) (TDI-80) is added drop-wise in four-hole bottle, within 2 hours, drip off, 70 DEG C of insulations are warming up to after dropwising, decline slowly after in material, NCO is down to 39%, add 0.72g chlorobenzoyl chloride cessation reaction, filter operation is carried out to material, material after filtration removes monomer through thin film evaporator and utilizes solvent latting drown to solid content to be 50%, obtain the mixing diisocyanate trimer product that diisocyanate monomer content is less than 0.4%.The NCO obtaining product is 9.15%, and viscosity is 320cp.
Comparative example 3
At N
2under protection, 600g hexamethylene diisocyanate and 300g toluene di-isocyanate(TDI) (TDI-80) are joined paddle is housed, in the four-hole boiling flask of thermometer, open and stir (speed of agitator is 200r/min), be warming up to 70 DEG C and be incubated, add 0.5g potassium acetate as catalyst, decline slowly after material NCO is down to 39%, add 0.72g chlorobenzoyl chloride cessation reaction, filter operation is carried out to material, material after filtration removes monomer through thin film evaporator and utilizes solvent latting drown to solid content to be 50%, obtain the mixing diisocyanate trimer product that diisocyanate monomer content is less than 0.4%.Have crystal to occur in separation process, but can obtain target product, sample viscosity is larger.The product NCO obtained is 8.87%, and viscosity is 480cp.
In comparative example 1, used catalyst is industrial comparatively conventional trimer catalyst at present, but this catalyst performance is gentleness more difficult realization mixing trimerization comparatively, and cause being mainly in product toluene diisocyanate trimer, this type of tripolymer is meeting crystallization in thin film evaporation process, does not substantially have mobility.
Comparative example 2, using not composite potassium acetate as catalyst, can prepare mixed trimer, but needs isolated by filtration potassium acetate to carry out separation again to obtain product, and obtains active in composite catalyst from catalyst amount and terminal NCO.
Hexamethylene diisocyanate just mixes with toluene di-isocyanate(TDI) in reaction by comparative example 3, toluene di-isocyanate(TDI) autohemagglutination and mixed polymerization can be caused after adding catalyst to carry out simultaneously, structural instability may be caused, and toluene diisocyanate trimer can affect the mobility of separation, therefore, toluene di-isocyanate(TDI) drips and can obtain better product.
Each embodiment is only in order to illustrate technical scheme of the present invention above, is not intended to limit; Although with reference to foregoing embodiments to invention has been detailed description, those of ordinary skill in the art is to be understood that: it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein some or all of technical characteristic; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the scope of various embodiments of the present invention technical scheme.
Claims (10)
1. one kind catalyst compounded, it is characterized in that: by alkali metal salt catalyst, cyclic organic compounds and the organic ether alcohol of aliphatic long-chain three kinds of one-tenth are grouped into or are made up of described three kinds of compositions and diluent.
2. catalyst compounded according to claim 1, it is characterized in that: described alkali metal salt catalyst be in alkali metal carboxylate or alkali metal alcoholates more than one; Described cyclic organic compounds be in crown ether or cyclodextrin more than one; The organic ether alcohol of described aliphatic long-chain is more than one in polyethylene glycol or polyethylene glycol monoether; Selected diluent is more than one in alcohols solvent, ether alcohol kind solvent, esters solvent and ketones solvent.
3. catalyst compounded according to claim 2, it is characterized in that: described alkali metal salt catalyst is more than one in sodium acetate, potassium acetate, caustic alcohol or potassium ethoxide;
Described cyclic organic compounds is 12-crown-4,15-hat-5,18-hat-6, dibenzo-18 crown-6, and bicyclohexane is-18-hat-6, alpha-cyclodextrin also, in beta-schardinger dextrin-or gamma-cyclodextrin more than one;
The organic ether alcohol of described aliphatic long-chain is more than one in the polyethylene glycol of molecular weight 200 ~ 600 or the poly glycol monomethyl ether of molecular weight 200 ~ 600;
Described alcohols solvent is single hydroxyl alcohol.
4. catalyst compounded according to claim 1, it is characterized in that: in described three kinds of compositions, the mass percentage of alkali metal salt catalyst is 10% ~ 30%, the mass percentage of cyclic organic compounds is 15% ~ 60%, 10% ~ 75% of the mass percentage of the organic ether alcohol of aliphatic long-chain.
5. catalyst compounded according to claim 1, it is characterized in that: be by alkali metal salt catalyst, cyclic organic compounds and the organic ether alcohol of aliphatic long-chain three kinds of compositions or three kinds of compositions and mixing diluents evenly obtain.
6. catalyst compounded application in preparation mixing diisocyanate trimer according to any one of Claims 1 to 5, is characterized in that: comprise the following steps:
At N
2under the condition of protection and stirring; catalyst compounded adding is equipped with in the container of hexamethylene diisocyanate; be warming up to 50 ~ 80 DEG C; drip toluene di-isocyanate(TDI), be warming up to 60 ~ 90 DEG C of insulation reaction after dropwising, when material NCO is down to less than 36% cessation reaction; be separated; remove monomer, latting drown, obtain mixing diisocyanate trimer.
7. apply according to claim 6, it is characterized in that: described catalyst compounded addition is 0.005% ~ 5% of material gross mass;
The mass ratio of described hexamethylene diisocyanate and toluene diisocynate toluene ester is (1.5 ~ 3): 1.
8. apply according to claim 7, it is characterized in that: described catalyst compounded addition is 0.01% ~ 1% of material gross mass.
9. apply according to claim 6, it is characterized in that: described toluene di-isocyanate(TDI) time for adding is 1 ~ 3 hour;
Described toluene di-isocyanate(TDI) is one or both in 2,4-toluene di-isocyanate(TDI) or 2,6-toluene di-isocyanate(TDI).
10. apply according to claim 6, it is characterized in that: the terminator of described cessation reaction is chlorobenzoyl chloride or phosphoric acid.
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| CN107973897A (en) * | 2017-11-30 | 2018-05-01 | 华南理工大学 | A kind of dispersible mixed and modified TDI trimer curing agents of water and preparation method thereof |
| CN108499606A (en) * | 2017-02-24 | 2018-09-07 | 万华化学集团股份有限公司 | A kind of neighbour's sulfydryl aryl N-heterocyclic carbine metal composition catalyst and its preparation method and application |
| CN110062794A (en) * | 2016-10-18 | 2019-07-26 | 科思创德国股份有限公司 | Hard conating with high chemistry and mechanical resistance |
| CN113667080A (en) * | 2021-07-01 | 2021-11-19 | 华南理工大学 | HDI-TDI mixed polymer curing agent and preparation method thereof |
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| CN113667080A (en) * | 2021-07-01 | 2021-11-19 | 华南理工大学 | HDI-TDI mixed polymer curing agent and preparation method thereof |
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Application publication date: 20151111 |