CN109575211A - Oligomeric coordination heterozygosis organo-metallic catalyst and the preparation method and application thereof - Google Patents
Oligomeric coordination heterozygosis organo-metallic catalyst and the preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4808—Mixtures of two or more polyetherdiols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
Abstract
The invention discloses a kind of oligomeric coordination heterozygosis organo-metallic catalysts and the preparation method and application thereof.Oligomeric coordination heterozygosis organo-metallic catalyst of the invention has following structure [A-Me1‑A‑B‑Me2]n；Wherein: A is penta alkyl C of ring5H5-；Me1、Me2It is metal ion selected from the following: Ca, Ce, Fe, Ni, Ti, Bi, Zn respectively；N is greater than 1；B is-RCOO—.Catalyst of the present invention can be used for the various fields of polyurethane material, include unfoamed polyurethane (CASE), soft foam, rigid foam, composite material etc..Catalyst of the present invention is environmentally protective, without hypertoxic heavy metal, while there are very strong targeting catalysis characteristics, it is low to the catalytic reaction activity of moisture and isocyanates, phenomena such as bubble, the scale, bulge of polyurethane product appearance can be better solved, greatly reduce rejection rate.
Description
Technical field
The present invention relates to catalyst fields, more particularly to a kind of oligomeric organic gold of coordination heterozygosis for polyurethane processing
Metal catalyst.
Background technique
Polyurethane product is widely used, and in order to which bubble-free polyurethane product is made, extends polyurethane resin in mold
Flowing time accelerates post curing rate simultaneously, needs to delay gel using catalyst in process, use in conventional method
The best catalyst of effect is organic heavy metal mercury, lead class catalyst and emerging organo-bismuth zinc catalyst；But organic gold
Belonging to mercury, lead class catalyst has severe toxicity, is easy pollution environment, and when use needs to protect, comparatively laborious, has potential harm to personnel；
And organo-bismuth zinc catalyst still has stronger catalytic action to the reaction of moisture and isocyanates, and polyurethane product is caused easily to go out
The bad phenomenons such as existing bubble, scale, bubbling, high rejection rate.
In order to overcome the above-mentioned deficiencies of the prior art, the present invention provides a kind of oligomeric coordination heterozygosis metal organic catalysis
Agent.
Summary of the invention
Oligomeric coordination heterozygosis organo-metallic catalyst of the invention is the reaction product of metallocene acid and inorganic metal salt,
Its general formula is as follows:
[A-Me1-A-B-Me2]n；
Wherein:
A is penta alkyl C of ring5H5-；
Me1、Me2It is metal ion selected from the following: Ca, Ce, Fe, Ni, Ti, Bi, Zn respectively；
N is greater than 1；
B is-RCOO—。
In some embodiments, oligomeric coordination heterozygosis organo-metallic catalyst of the invention has the following structure,
Wherein: Me1、Me2It is metal ion selected from the following: Ca, Ce, Fe, Ni, Ti, Bi, Zn respectively；N is oneself of 2 to 50
So number.It will be understood by those skilled in the art that catalyst of the present invention can be the mixed of the oligomer of different oligomeric degree
Close object.
Preferably, in some embodiments, Me1For Ni ion or Fe ion, Me2For Zn ion, Bi ion or Ce from
Son.
The present invention also provides the preparation methods of organo-metallic catalyst described above, include the following steps:
1. being reacted 1-2 hours in tetrahydrofuran (THF) with cyclopentadiene and sodium hydroxide, sodium cyclopentadiene is generated, then
Metal chloride is added and carries out displacement reaction, is reacted 2 hours under the conditions of 70-80 DEG C, then under the conditions of 68-72 DEG C, keeps 2-3
Hour, THF is removed with vacuum rotary steam device, obtains metallocene compound；
2. gained metallocene compound is reacted with butyl lithium, and it is passed through carbon dioxide gas to reaction system, flowed back
Under the conditions of kept for 2-3 hours, reaction temperature keep 70-80 DEG C, products therefrom hydrolyze in water both metallocene acid；
3. inorganic metal salt is added to be removed after reacting 1-2 hours under the conditions of being maintained at 60-70 DEG C with the method for stratification
Water-phase product is gone, metallic compound is collected；With the repeated multiple times washing reaction product of water, to remove remaining soluble inorganic metal
Salt；
4. collecting product and under the conditions of 105 DEG C, is kept for 2-3 hours, the water in product is removed with the mode of vacuum dehydration
Point.Both organo-metallic catalyst is obtained.
The present invention also provides the applications that polyurethane resin is prepared using organo-metallic catalyst made from the above method, answer
With method following steps:
1. reaction temperature is 60-80 DEG C by oligomer polyol and diisocyanate hybrid reaction, the reaction time is 3~4
Hour, obtain product I；
The parts by weight of each ingredient in component are as follows:
Oligomer polyol: 30-90 parts
Diisocyanate: 10-100 parts
Wherein:
Oligomer polyol is the polyether polyol that molecular weight is 400-5000 or molecular weight is 1000-3000 polyester polyols
Alcohol or the mixture of both, polyether polyol are selected from polytetrahydrofuran diol or polyoxypropyleneglycol；
Polyester polyol is that polycaprolactone glycol, polyadipate ethylene glycol, polyadipate hexylene glycol and polyadipate one contract
One of diethylene glycol or more than one mixture；
Diisocyanate is toluene di-isocyanate(TDI) (TDI), 4,4 ' (or 2,4)-ditolyl methane diisocyanate
(MDI), Carbodiimide-Modified MDI, polymeric MDI (PAPI), hexamethylene diisocyanate (HDI), two isocyanide of isophorone
Acid esters (IPDI), dicyclohexyl methyl hydride diisocyanate (HMDI), 1,5- how one of diisocyanate NDI or more than one
Mixture.
2. oligomer polyol, chain extender, the catalyst are mixed, as P component；
The parts by weight of each ingredient in component are as follows:
Oligomer polyol: 30-90 parts
Chain extender: 10-100 parts
Catalyst: 0.1-0.5 parts
A) oligomer polyol is polyether polyol that molecular weight is 400-5000 or molecular weight is 1000-3000 poly-
Ester polyol and its mixture；
B) polyether polyol is selected from polytetrahydrofuran diol or polyoxypropyleneglycol；
C) polyester polyol is selected from polycaprolactone glycol, polyadipate ethylene glycol, polyadipate hexylene glycol or gathers oneself
Diacid diglycol；
D) chain extender described in is two adjacent chlorodiphenyl amine methane (MOCA), diethyl toluene diamine (DETDA), dimethyl sulphur-based
One of toluenediamine (DMTDA), 1,4 butanediols or 1,6 hexylene glycols or a variety of mixtures.
The present invention also provides the polyurethane resin comprising oligomeric coordination heterozygosis organo-metallic catalyst of the invention is prefabricated
Component, which is characterized in that including independent I component and P component:
I component obtains as follows: by oligomer polyol (30-90 parts) and diisocyanate (10-100 parts) hybrid reaction,
Reaction temperature is 60-80 DEG C, and the reaction time is 3~4 hours, and the oligomer polyol is the polyethers that molecular weight is 400-5000
Or molecular weight is 1000-3000 polyester polyol or the mixture of both；The polyether polyol is selected from polytetrahydrofuran
Glycol or polyoxypropyleneglycol；The polyester polyol be polycaprolactone glycol, polyadipate ethylene glycol, polyadipate oneself two
One of alcohol, polyadipate diglycol or more than one mixture；The diisocyanate is that toluene two is different
Cyanate TDI, 4,4 ' (or 2,4)-ditolyl methane diisocyanate MDI, Carbodiimide-Modified MDI, polymeric MDI
(PAPI), hexamethylene diisocyanate HDI, isoflurane chalcone diisocyanate IPDI, dicyclohexyl methyl hydride diisocyanate
HMDI, 1,5- how one of diisocyanate NDI or more than one mixture.
P component obtains as follows: by oligomer polyol (30-90 parts), chain extender (10-100 parts), catalyst of the invention
(0.1-0.5 parts) mixing；The oligomer polyol is the polyethers that molecular weight is 400-5000 or molecular weight is 1000-3000 poly-
Ester polyol or the mixture of both；The polyether polyol is selected from polytetrahydrofuran diol or polyoxypropyleneglycol；
The polyester polyol is selected from polycaprolactone glycol, polyadipate ethylene glycol, polyadipate hexylene glycol or the contracting of polyadipate one two
Ethylene glycol；The chain extender is two adjacent chlorodiphenyl amine methane (MOCA), diethyl toluene diamine (DETDA), dimethyl sulphur-based first
One of phenylenediamine (DMTDA), 1,4 butanediols or 1,6 hexylene glycols or more than one mixture.
I component and P combination are used in mixed way according to required ratio using preceding.In some preferred embodiments,
The weight ratio of catalyst is 0.2-0.3 parts, 0.3-0.4 parts or 0.4-0.5 parts.
Compared with prior art, the beneficial effects of the invention are as follows environmentally protective characteristic is possessed, without hypertoxic heavy metal, simultaneously
It is very low to the catalytic reaction activity of moisture and isocyanates with very strong targeting catalysis characteristics, polyurethane can be better solved
Product occur bubble, scale, bulge phenomena such as, greatly reduce rejection rate.
Specific embodiment
The present invention is specifically described below by example, is served only for that invention is further explained, it cannot
It is interpreted as limiting the scope of the present invention.Implementation condition used in the examples can be done according to specific condition and requirement
Some nonessential modifications and adaptations.
Embodiment 1
The present embodiment provides a kind of oligomeric coordination heterozygosis metallic catalysts.It weighs NaOH 80g to be dissolved in 300g water, weigh
Cyclopentadiene 132.2g, which is dissolved in 300gTHF, to be placed in three-necked flask, and magnetic stirring apparatus is started, and NaOH solution is gradually added dropwise
Enter in THF solution, after reaction 1-2 hours, 129.6g NiCl is added2, temperature keep 70-80 DEG C reaction 2-3 hours, will react
Mixture is stood, and solution layering, lower layer is green crystal, filters off upper solution, and lower layer is washed with deionized and crystallizes 2-3 times
Afterwards, remaining water is removed with vacuum rotary steam device, obtains dicyclopentadienyl nickel.Being cooled to 50 DEG C makes gained dicyclopentadienyl nickel dissolution hereinafter, THF is added,
And 60g butyl lithium is added and is stirred to react, and is passed through CO into reaction system2It is small to maintain the temperature at 70-80 DEG C of reaction 1-2 for gas
When or so bottle green liquid, stop logical CO2Gas, and solution is cooled to 50 DEG C hereinafter, continuing to stir；Weigh 80g ZnSO4
Being added in 200-300g water makes to dissolve, this solution is gradually added dropwise in the liquid in reaction flask, and reaction temperature is controlled in 70-
80 DEG C stop reaction after reaction 1-2 hours, stand, solution layering, filter off upper solution, and with pure water washing lower layer solution 2-
After 3 times, the moisture in sub-cloud solution is removed with the dry mode of reduced vacuum, obtaining a kind of oligomeric coordination heterozygosis of the invention has
Organic metal catalyst C-1.
Embodiment 2
The present embodiment provides a kind of oligomeric coordination heterozygosis metallic catalysts.It weighs NaOH 80g to be dissolved in 300g water, weigh
Cyclopentadiene 132.2g, which is dissolved in 300gTHF, to be placed in three-necked flask, and magnetic stirring apparatus is started, and NaOH solution is gradually added dropwise
Enter in THF solution, react 1-2 hours, 129.6g NiCl is added2, temperature is kept for 70-80 DEG C reaction 2-3 hours, and reaction is mixed
It closes object to stand, solution layering, lower layer is green crystal, filters off upper solution, washs lower layer crystallization 2-3 after with aqueous solution, uses
Vacuum rotary steam device removes remaining water, obtains dicyclopentadienyl nickel.It is cooled to 50 DEG C to make it dissolve hereinafter, THF is added, and 60g butyl is added
Lithium is stirred to react, and is passed through CO2Gas maintains the temperature at 70-80 DEG C of reaction 1-2 hours or so to obtain bottle green liquid, stops logical
CO2Gas, and solution is cooled to 50 DEG C hereinafter, continuing to stir；Weigh 130gBi (NO3)3Make in addition 200-300g glycerol molten
Solution, this solution is gradually added dropwise in the liquid in reaction flask, and reaction temperature control stops after reaction 1-2 hours at 70-80 DEG C
It only reacts, cool down and pure water is added, stand, solution layering filters off upper solution, and with pure water washing lower layer solution 2-3
After secondary, remove the moisture in sub-cloud solution with the dry mode of reduced vacuum, both another oligomeric coordination heterozygosis organic metal
Catalyst C-2.
Embodiment 3
The present embodiment provides a kind of oligomeric coordination heterozygosis metallic catalysts.It weighs NaOH 80g to be dissolved in 300g water, weigh
Cyclopentadiene 132.2g, which is dissolved in 300gTHF, to be placed in three-necked flask, and magnetic stirring apparatus is started, and NaOH solution is gradually added dropwise
Enter in THF solution, react 1-2 hours, 126.7g FeCl is added2, temperature is kept for 70-80 DEG C reaction 2-3 hours, and reaction is mixed
It closes object to stand, solution layering, lower layer is orange crystal, filters off upper solution, washs lower layer crystallization 2-3 after with aqueous solution, uses
Vacuum rotary steam device removes remaining water, obtains ferrocene.It is cooled to 50 DEG C to make it dissolve hereinafter, THF is added, and 60g butyl is added
Lithium is stirred to react, and is passed through CO2Gas maintains the temperature at 70-80 DEG C of reaction 1-2 hours or so to obtain brown liquid, stops logical CO2
Gas, and solution is cooled to 50 DEG C hereinafter, continuing to stir；Weigh 80gZnSO4Being added in 200-300g water makes to dissolve, by this
Solution is gradually added dropwise in the liquid in reaction flask, and reaction temperature control is reacted in 70-80 DEG C of stopping after reaction 1-2 hour,
It stands, solution layering, filters off upper solution, and with the mode after pure water washing lower layer solution 2-3 times, dried with reduced vacuum
Except the moisture in sub-cloud solution, both another oligomeric coordination heterozygosis organo-metallic catalyst C-3.
Embodiment 4
The present embodiment provides a kind of oligomeric coordination heterozygosis metallic catalysts.It weighs NaOH 80g to be dissolved in 300g water, weigh
Cyclopentadiene 132.2g, which is dissolved in 300gTHF, to be placed in three-necked flask, and magnetic stirring apparatus is started, and NaOH solution is gradually added dropwise
Enter in THF solution, react 1-2 hours, 126.7g FeCl is added2, temperature is kept for 70-80 DEG C reaction 2-3 hours, and reaction is mixed
It closes object to stand, solution layering, lower layer is orange crystal, filters off upper solution, washs lower layer crystallization 2-3 after with aqueous solution, uses
Vacuum rotary steam device removes remaining water, obtains ferrocene.It is cooled to 50 DEG C to make it dissolve hereinafter, THF is added, and 60g butyl is added
Lithium is stirred to react, and is passed through CO2Gas maintains the temperature at 70-80 DEG C of reaction 1-2 hours or so to obtain brown liquid, stops logical CO2
Gas, and solution is cooled to 50 DEG C hereinafter, continuing to stir；Weigh 134.8gCe2(SO4)3Make in addition 200-300g water molten
Solution, this solution is gradually added dropwise in the liquid in reaction flask, and reaction temperature control stops after reaction 1-2 hours at 70-80 DEG C
It only reacts, stands, solution layering filters off upper solution, and with after pure water washing lower layer solution 2-3 times, is done with reduced vacuum
Dry mode except the moisture in sub-cloud solution, both the oligomeric coordination heterozygosis organo-metallic catalyst C-4 of another of the invention.
Embodiment 5
The present embodiment provides a kind of applications of oligomeric coordination heterozygosis metallic catalyst.(1) by 23.26g toluene diisocynate
Ester (TDI-80), 76.74g molecular weight are the polyether polyol hybrid reaction that 2000 degrees of functionality are 2, and control reaction temperature is 85
DEG C, after 2 hours reaction time, as polyurethane resin I-1 component.(2) by 42.1g molecular weight be 3000 degrees of functionality be 3 it is poly-
The oligomeric coordination heterozygosis metallic catalyst X-1 of ethoxylated polyhydric alcohol, 18.04g MOCA, 0.18g is uniformly mixed, as polyurethane resin P-1
Component.
Embodiment 6
The present embodiment provides a kind of applications of oligomeric coordination heterozygosis metallic catalyst.(1) by two isocyanide of 30g diphenyl methane
Acid esters (MDI50), 70g molecular weight are the polyether polyol hybrid reaction that 2000 degrees of functionality are 2, and control reaction temperature is 75 DEG C,
After 2 hours reaction time, as polyurethane resin I-2 component.It (2) is polyethers that 3000 degrees of functionality are 3 by 37.54g molecular weight
The oligomeric coordination heterozygosis metallic catalyst X-2 of polyalcohol, 16.09g MOCA, 0.16g is uniformly mixed, as polyurethane resin P-2 group
Point.
Embodiment 7
The present embodiment provides a kind of applications of oligomeric coordination heterozygosis metallic catalyst.(1) by 23.26g toluene diisocynate
Ester (TDI-80), 76.74g molecular weight are the polyether polyol hybrid reaction that 2000 degrees of functionality are 2, and control reaction temperature is 85
DEG C, after 2 hours reaction time, as polyurethane resin I-3 component.(2) by 53.7g molecular weight be 3000 degrees of functionality be 3 it is poly-
The oligomeric coordination heterozygosis metallic catalyst X-3 of ethoxylated polyhydric alcohol, 11g DETDA, 0.07g is uniformly mixed, as polyurethane resin P-3 group
Point.
Embodiment 8
The present embodiment provides a kind of applications of oligomeric coordination heterozygosis metallic catalyst.(1) by two isocyanide of 15.5g isophorone
Polyether polyol that the degree of functionality that acid esters (IPDI), 36g molecular weight are 5000 is 3,48.5g molecular weight are that 2000 degrees of functionality are 2
Polyether polyol hybrid reaction, control reaction temperature is 90 DEG C, after 2 hours reaction time, as polyurethane resin I-4 group
Point.(2) by 55.03g molecular weight be 3000 degrees of functionality be 3 polyether polyol, 13.76g MOCA, the oligomeric coordination heterozygosis of 0.2g
Metallic catalyst X-4 is uniformly mixed, as polyurethane resin P-4 component.
Embodiment 9
The present embodiment provides a kind of applications of oligomeric coordination heterozygosis metallic catalyst.(1) by 10g Carbodiimide-Modified
MDI is as polyurethane resin I-5 component.(2) by 113.9g molecular weight be 5000 degrees of functionality be 3 polyether polyol, 0.5g it is low
Poly- coordination heterozygosis metallic catalyst X-1 is uniformly mixed, as polyurethane resin P-5 component.
Embodiment 10
The present embodiment provides a kind of applications of oligomeric coordination heterozygosis metallic catalyst.(1) by 20.5g toluene di-isocyanate(TDI)
(TDI-80), 79.5g molecular weight is the polytetrahydrofuran ethoxylated polyhydric alcohol hybrid reaction that 2000 degrees of functionality are 2, controls reaction temperature
It is 80-85 DEG C, after 2 hours reaction time, as polyurethane resin I-6 component.It (2) is 2000 degrees of functionality by 56.1g molecular weight
It is uniformly mixed, makees for the 2 oligomeric coordination heterozygosis metallic catalyst X-2 of polytetrahydrofuran ethoxylated polyhydric alcohol, 12.32g MOCA, 0.2g
For polyurethane resin P-6 component.
Embodiment 11
The present embodiment provides a kind of applications of oligomeric coordination heterozygosis metallic catalyst.(1) by two isocyanide of 30g diphenyl methane
Acid esters (MDI50), 70g molecular weight are the polytetrahydrofuran ethoxylated polyhydric alcohol hybrid reaction that 2000 degrees of functionality are 2, control reaction temperature
It is 75 DEG C, after 2 hours reaction time, as polyurethane resin I-7 component.It (2) be molecular weight by 42.34g molecular weight is 2000
The oligomeric coordination heterozygosis metallic catalyst X-3 mixing of the polytetrahydrofuran ethoxylated polyhydric alcohol, 9.29g DETDA, 0.15g that degree of functionality is 2
Uniformly, as polyurethane resin P-7 component.
Embodiment 12
The present embodiment provides a kind of applications of oligomeric coordination heterozygosis metallic catalyst.(1) by 35.06g toluene diisocynate
Ester (TDI-80), 19.48g molecular weight be 400 degrees of functionality be 2 polyether polyol, 45.45g molecular weight be that 1000 degrees of functionality are 2
Polyether polyol hybrid reaction, control reaction temperature is 80-85 DEG C, after 2 hours reaction time, as polyurethane resin I-8
Component.(2) by 36.85g molecular weight be 5000 degrees of functionality be 3 polyether polyol, 10.84g DETDA, the white MOCA of 6.5g,
The oligomeric coordination heterozygosis metallic catalyst X-4 of 0.1g is uniformly mixed, as polyurethane resin P-8 component.
Comparative example 1
The present embodiment provides a kind of applications of oligomeric coordination heterozygosis metallic catalyst.(1) by 23.26g toluene diisocynate
Ester (TDI-80), 76.74g molecular weight are the polyether polyol hybrid reaction that 2000 degrees of functionality are 2, and control reaction temperature is 85
DEG C, after 2 hours reaction time, as polyurethane resin component A.It (2) is polyethers that 3000 degrees of functionality are 3 by 42.1g molecular weight
Polyalcohol, 18.04g MOCA are uniformly mixed, as polyurethane resin B component.(3) by the oligomeric coordination heterozygosis organic metal of 0.18g
Catalyst X-1 is as C1 component；It regard 0.18g bismuth neodecanoate catalyst (tenor 20%) as C2 component；By 0.18g50%
The bismuth neodecanoate catalyst (tenor 20%) of (mass ratio) and 50% (mass ratio) zinc neodecanoate catalyst (tenor
16%) mixture is as C3 component；It regard 0.18g isooctyl acid lead catalyst (tenor 20%) as C4 component.
| 80 DEG C of gel times | 80 DEG C of curing times | The transparency | Shore hardness (A) | |
| A+B+C1 | 16min | 1h 5min | It is transparent | 85-87 |
| A+B+C2 | 10min 30sec | 2h 10min | Foaming, scale | 75-78 |
| A+B+C3 | 13min | 1h 55min | Fretting map, scale | 75-80 |
| A+B+C4 | 13min 35sec | 1h 35min | Send out mist | 82-83 |
As can be seen from the above results bismuth neodecanoate catalyst targeting catalysis characteristics are insufficient, catalysis hydroxyl is reacted with isocyanates
While also catalytic water reacted with isocyanates, easily cause product foaming, the defects such as the transparency is poor, hardness is low.Organo-bismuth zinc is urged
Curing rate after agent compounding can accelerate, but still not can avoid moisture and participate in reaction, product easily foams.The targeting of lead catalyst is urged
It is good to change effect, but product is easily caused to send out mist, influences the transparency.Oligomeric coordination heterozygosis organo-metallic catalyst targeting catalytic effect is aobvious
It writes, product is transparent, does not foam, hardness height.
Comparative example 2
It is following quadruplicate to prepare component A and B component: and then by component A and B component and corresponding oligomeric coordination heterozygosis
Metallic catalyst (0.18g X-1,0.16g X-2,0.07g X-3,0.2g X-4) mixes, described in the following table of concrete outcome,
It (1) is that the polyethers that 2000 degrees of functionality are 2 is more by 23.26g toluene di-isocyanate(TDI) (TDI-80), 76.74g molecular weight
First alcohol hybrid reaction, control reaction temperature are 85 DEG C, after 2 hours reaction time, as polyurethane resin component A.
(2) by 42.1g molecular weight be 3000 degrees of functionality be 3 polyether polyol, 18.04gMOCA be uniformly mixed, as poly-
Urethane resin B component.
| 80 DEG C of gel times | 80 DEG C of curing times | The transparency | Shore hardness (A) | |
| A+B+X1 | 16min | 1h 5min | It is transparent | 85-87 |
| A+B+X2 | 15min 30sec | 1h 10min | It is transparent | 76-78 |
| A+B+X3 | 15min | 1h 5min | It is transparent | 77-80 |
| A+B+X4 | 15min 35sec | 1h 15min | It is transparent | 82-85 |
It can be seen that the catalyst of the present invention containing different metal ions all has close catalytic effect.
Comparative example 3
This comparative example, which is in example, proves that catalyst of the invention can be used for the reactant of separate sources, i.e. embodiment 5-12
Obtained different component I is mixed with component P.Concrete outcome is as follows
| 80 DEG C of gel times | 80 DEG C of curing times | The transparency | Shore hardness (A) | |
| I-1+P-1 | 16min | 1h 5min | It is transparent | 85-87 |
| I-2+P-2 | 16min 30sec | 1h 15min | It is transparent | 76-82 |
| I-3+P-3 | 17min | 1h 10min | It is transparent | 77-83 |
| I-4+P-4 | 15min 35sec | 1h 5min | It is transparent | 85-87 |
| I-5+P-5 | 15min 30sec | 1h 10min | It is transparent, fretting map | 76-80 |
| I-6+P-6 | 16min 15sec | 1h 5min | It is transparent | 66-73 |
| I-7+P-7 | 15min 55sec | 1h25min | It is transparent, micro- hair mist | 65-70 |
| I-8+P-8 | 16min 35sec | 1h 15min | It is transparent | 81-85 |
It can be seen that being directed to different raw materials, catalyst examples of the invention are all able to achieve more satisfactory expection substantially
Effect.To which those skilled in the art can according to need, and when not paying more creative work, experiment is obtained
Other suitable metals and ratio.These results are also contained in protection scope of the present invention.
Claims (10)
1. a kind of oligomeric coordination heterozygosis organo-metallic catalyst, it is characterised in that have the structure shown by the following formula:
[A-Me1-A-B-Me2]n；
Wherein:
A is penta alkyl C of ring5H5-；
Me1、Me2It is metal ion selected from the following: Ca, Ce, Fe, Ni, Ti, Bi, Zn respectively；
N is greater than 1；
B is-RCOO—。
2. oligomeric coordination heterozygosis organo-metallic catalyst according to claim 1, it is characterised in that have a structure that
Wherein: Me1、Me2It is metal ion selected from the following: Ca, Ce, Fe, Ni, Ti, Bi, Zn respectively；The nature that n is 2 to 50
Number.
3. the preparation method of oligomeric coordination heterozygosis organo-metallic catalyst described in claim 1, which is characterized in that including following
Step:
A, with ring penta 2 is dilute and metal chloride synthesizes metallocene；
B, metallocene acid is made by indirect method；
C, with metal salt carry out metathesis reaction be made metallocene acid soap, collect product both the oligomeric coordination heterozygosis is organic
Metallic catalyst.
4. preparation method according to claim 3, which is characterized in that
The synthesis metallocene carries out as follows: with cyclopentadiene and sodium hydroxide, reaction 1 to 2 is small in tetrahydrofuran (THF)
When, sodium cyclopentadiene is generated, metal chloride is added and carries out displacement reaction, 70 to 80 DEG C of reactions must both react intermediate for 2 hours
Body metallocene compound；
The obtained metallocene acid is following to carry out: gained reaction intermediate metallocene compound is reacted with butyl lithium, and
It is passed through carbon dioxide gas to reaction system, is reacted 2 to 3 hours under counterflow condition, temperature is kept for 70 to 80 DEG C, and products therefrom exists
It is hydrolyzed in water and both obtains metallocene acid；
The obtained metallocene acid soap carries out as follows: inorganic metal salt is added into obtained metallocene acid, keeps carrying 60
After reacting 1 to 2 hour under the conditions of to 70 DEG C, collect product and in 105 DEG C or so removing moisture, both the oligomeric coordination heterozygosis
Organo-metallic catalyst.
5. the preparation method according to claim 4, which is characterized in that each step reaction is designed to equivalent reaction.
6. preparation method according to claim 5, which is characterized in that collect reaction intermediate from the reaction product
Method, include the following steps:
1) it under the conditions of 68 to 72 DEG C, is kept for 2 to 3 hours, removes THF with vacuum rotary steam device, obtain metallocene compound；
2) water-phase product is removed with the method for stratification, collects metallic compound；
3) the repeated multiple times washing reaction product of deionized water is used, to remove remaining soluble inorganic metallic salt；
4) it under the conditions of 105 DEG C, is kept for 2 to 3 hours, the moisture in product is removed with the mode of vacuum dehydration.
7. the oligomeric coordination heterozygosis organo-metallic catalyst of method preparation according to any one of claim 3 to 6.
8. the application of oligomeric coordination heterozygosis organo-metallic catalyst according to claim 1, which is characterized in that be used to prepare
Polyurethane resin.
9. the application of oligomeric coordination heterozygosis organo-metallic catalyst according to claim 8, which is characterized in that including as follows
Step:
1) by oligomer polyol and diisocyanate hybrid reaction, reaction temperature is 60-80 DEG C,
Reaction time is 3~4 hours, obtains I component；
The parts by weight of each ingredient in reaction system are as follows:
Oligomer polyol: 30-90 parts
Diisocyanate: 10-100 parts
A) oligomer polyol be polyethers that molecular weight is 400-5000 or molecular weight be 1000-3000 polyester polyol or
The mixture of both；
B) polyether polyol is selected from polytetrahydrofuran diol or polyoxypropyleneglycol；
C) polyester polyol is polycaprolactone glycol, polyadipate ethylene glycol, polyadipate hexylene glycol, the contracting of polyadipate one
One of diethylene glycol or more than one mixture；
D) diisocyanate described in is toluene di-isocyanate(TDI) TDI, 4,4 ' (or 2,4)-ditolyl methane diisocyanate
MDI, Carbodiimide-Modified MDI, polymeric MDI (PAPI), hexamethylene diisocyanate HDI, isoflurane chalcone diisocyanate
IPDI, dicyclohexyl methyl hydride diisocyanate HMDI, 1,5- how one of diisocyanate NDI or more than one mixing
Object.
2) oligomer polyol, chain extender, catalyst of the invention are mixed, obtains P component；The weight of each ingredient in reaction system
Measure number are as follows:
Oligomer polyol: 30-90 parts
Chain extender: 10-100 parts
Catalyst: 0.1-0.5 parts
A) oligomer polyol be polyethers that molecular weight is 400-5000 or molecular weight be 1000-3000 polyester polyol or
The mixture of both；
B) polyether polyol is selected from polytetrahydrofuran diol or polyoxypropyleneglycol；
C) polyester polyol is selected from polycaprolactone glycol, polyadipate ethylene glycol, polyadipate hexylene glycol or polyadipate
Diglycol；
D) chain extender described in is two adjacent chlorodiphenyl amine methane (MOCA), diethyl toluene diamine (DETDA), dimethyl sulphur-based toluene
One of diamines (DMTDA), 1,4 butanediols or 1,6 hexylene glycols or more than one mixture.
10. the polyurethane resin pre-formed component comprising oligomeric coordination heterozygosis organo-metallic catalyst according to claim 1,
It is characterised in that it includes independent I component and P component:
I component obtains as follows: by oligomer polyol (30-90 parts) and diisocyanate (10-100 parts) hybrid reaction, reaction
Temperature is 60-80 DEG C, and the reaction time is 3~4 hours, and the oligomer polyol is the polyethers that molecular weight is 400-5000 or divides
Son amount is 1000-3000 polyester polyol or the mixture of both；The polyether polyol is selected from polytetrahydrofuran diol
Or polyoxypropyleneglycol；The polyester polyol be polycaprolactone glycol, polyadipate ethylene glycol, polyadipate hexylene glycol,
One of polyadipate diglycol or more than one mixture；The diisocyanate is toluene diisocynate
Ester TDI, 4,4 ' (or 2,4)-ditolyl methane diisocyanate MDI, Carbodiimide-Modified MDI, polymeric MDI (PAPI), six
Methylene diisocyanate HDI, isoflurane chalcone diisocyanate IPDI, dicyclohexyl methyl hydride diisocyanate HMDI, 1,5- how
One of diisocyanate NDI or more than one mixture.
P component obtains as follows: by oligomer polyol (30-90 parts), chain extender (10-100 parts), catalyst of the invention
(0.1-0.5 parts) mixing；The oligomer polyol is the polyethers that molecular weight is 400-5000 or molecular weight is 1000-3000 poly-
Ester polyol or the mixture of both；The polyether polyol is selected from polytetrahydrofuran diol or polyoxypropyleneglycol；
The polyester polyol is selected from polycaprolactone glycol, polyadipate ethylene glycol, polyadipate hexylene glycol or the contracting of polyadipate one two
Ethylene glycol；The chain extender is two adjacent chlorodiphenyl amine methane (MOCA), diethyl toluene diamine (DETDA), dimethyl sulphur-based first
One of phenylenediamine (DMTDA), 1,4 butanediols or 1,6 hexylene glycols or more than one mixture.
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| CN113292692A (en) * | 2021-05-26 | 2021-08-24 | 广州优润合成材料有限公司 | Polyurethane reaction type organic metal catalyst and preparation method and application thereof |
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