CN106243339A - Isocyanuric acid ester polyether polyol and preparation method thereof and the preparation method of coating curing agent - Google Patents
Isocyanuric acid ester polyether polyol and preparation method thereof and the preparation method of coating curing agent Download PDFInfo
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- CN106243339A CN106243339A CN201610620578.6A CN201610620578A CN106243339A CN 106243339 A CN106243339 A CN 106243339A CN 201610620578 A CN201610620578 A CN 201610620578A CN 106243339 A CN106243339 A CN 106243339A
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
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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
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention relates to the preparation method of a kind of isocyanuric acid ester polyether polyol and preparation method thereof and coating curing agent, belong to polyether polyol and polyurethane synthesis technical field.The present invention is using tris(2-hydroxy ethyl)isocyanurate as initiator, under the effect of bimetallic cyanide complex catalyst, makes epoxyalkane compound ring-opening polymerisation obtain isocyanuric acid ester polyether polyol by coordination polymerization.Isocyanuric acid ester polyether polyol carries out prepolymer reaction preparation with isocyanates in organic solvent according to the ratio of mol ratio 1:3 and has the polyether-modified class trimer coating curing agent of isocyanuric acid ester ring structure.This polyether polyol and paint solidification agent producing process are simple, and product yield is high, low cost, safety and environmental protection.
Description
Technical field
The present invention relates to the preparation method of a kind of isocyanuric acid ester polyether polyol and preparation method thereof and coating curing agent,
Belong to polyether polyol and polyurethane synthesis technical field.
Background technology
At present, conventional on market polyurethane coating curing agent includes base polyurethane prepolymer for use as firming agent and trimer curing agent
Two big classes.Mostly base polyurethane prepolymer for use as firming agent is to use trimethylolpropane (TMP) and toluene di-isocyanate(TDI) (TDI) at solvent
The prepolymer solution that middle reaction generates is prepared from.The production of trimer curing agent is under the effect of catalyst for trimerization, three points
Sub-isocyanates generation polyreaction, generates isocyanuric acid ester ring structure, then adds polymerization inhibitor and make catalyst for trimerization be poisoned
Losing catalysis activity, complex manufacturing, product quality is wayward.And trimerization reaction needs special catalyst, adopts
Preparing trimer curing agent with different isocyanates, polymerization yield rate controls also different；Containing substantial amounts of free in polymerizate
Monomer, needs to carry out removing process, and equipment investment is huge, and production cost is high.It addition, pure TDI trimer curing agent is coated with film toughness
Difference, often needs to utilize polyethers to be modified processing to it.And for extraordinary HDI trimer firming agent, in production process, HDI is mono-
When body is only reacted to the 21% of total monomer quality, it is necessary to by techniques such as thin film evaporation, the monomer of a large amount of unreacted monomers is divided
From, product yield is low, and loss of monomer is big, and product cost is high, and this type of firming agent just can be used in only some high-grade fields.City at present
Trimer curing agent on face mainly has TDI trimer, HDI trimer, IPDI trimer, TDI and HDI mixed trimer, TDI
With MDI mixed trimer etc..
It is seen that, base polyurethane prepolymer for use as firming agent production technology is simple, and it is handling good to produce；Trimer curing agent due to
Molecule contains isocyanuric acid ester ring structure and there is the mechanical property of excellence, but complex manufacturing.Contain if prepared
Having the polyether polyol of isocyanurate ring, the coating being prepared class Trimeric structures by the synthetic route of base polyurethane prepolymer for use as is solid
Agent, both can obtain the chemical constitution that trimer coating curing agent is similar, can simplify again production technology manufacturing process, improved
Efficiency and yield, reduce cost, safety and environmental protection；Again trimer is carried out polyether-modified simultaneously, improve firming agent and resin
The compatibility, reduce coating fragility, improve pliability.Change thus by the solution of raw material production and the synchronization of synthesis technique
Enter, it is achieved the simplification of high-end coating curing agent produces, there is society and economic worth greatly.
At present, the polyether polyol containing isocyanurate ring and many with isocyanuric acid ester polyether is not the most also found
Unit's alcohol is the relevant report of coating curing agent prepared by raw material.
Summary of the invention
It is an object of the invention to provide a kind of isocyanuric acid ester polyether polyol, use this polyether polyol can be different with any
Cyanate prepares the similar trimer containing isocyanurate structure by simple base polyurethane prepolymer for use as synthetic technology route
The coating curing agent of firming agent, the most efficiently, safety and environmental protection；Present invention simultaneously provides its preparation method and coating curing agent
Preparation method.
Isocyanuric acid ester polyether polyol of the present invention, using tris(2-hydroxy ethyl)isocyanurate as initiator, double
Under the effect of metal cyanide complex catalyst agent, epoxyalkane compound ring-opening polymerisation is made to obtain isocyanuric acid by coordination polymerization
Ester polyether polyhydric alcohol.
Wherein:
First tris(2-hydroxy ethyl)isocyanurate is carried out pretreatment, then under the effect of bimetallic cyanide complex catalyst,
Epoxyalkane compound ring-opening polymerisation is made by coordination polymerization；
Preprocess method is: after tris(2-hydroxy ethyl)isocyanurate mixes according to mass ratio 1:0.5～1 with distilled water, adds
Account for tris(2-hydroxy ethyl)isocyanurate and distilled water gross mass 10～the acetone of 100%, stir, add and account for trihydroxyethyl isocyanide
Urea acid esters, distilled water and acetone gross mass 0.001～the phosphoric acid of 0.005%, stir, circulating filtration, vacuum abjection moisture
And acetone, it is dried to moisture≤0.05wt.% use.
Described bimetallic cyanide complex catalyst is the one in solid powdery catalyst or emulsion form catalyst
Or two kinds, consumption is initiator and the 0.002～0.05% of epoxyalkane compound weight sum.
The isocyanuric acid ester polyether polyol hydroxyl value that the present invention obtains is 56～445mgKOH/g.
Described epoxyalkane compound is one or more in expoxy propane, oxirane or epoxy butane
Mixture, the polyether polyol obtained blocks with expoxy propane or epoxy butane.
The preparation method of described isocyanuric acid ester polyether polyol, specifically comprises the following steps that first to initiator three hydroxyl second
Base isocyanuric acid ester carries out pretreatment, the tris(2-hydroxy ethyl)isocyanurate after then processing and double metal cyanide complex catalysis
Agent joins in pressure reactor, is warming up to 130 DEG C ± 2 DEG C, is evacuated to-0.095MPa, nitrogen bubble 1h；It has been subsequently adding
Beginning agent weight 10～20% epoxyalkane compound carry out initiation reaction, when question response still pressure drops to 0.01MPa, start
Dropping residual epoxide alkane compound carries out continuous polymerization continuously, and reaction terminates rear evacuation demonomerization 1h, sampling detection isocyanide
Urea acid esters polyether polyol hydroxyl value OHv, cooling discharge preserves.
The method that described isocyanuric acid ester polyether polyol prepares coating curing agent, is first by many for isocyanuric acid ester polyether
Unit's alcohol reacts according to the ratio of mol ratio 1:3 in organic solvent with isocyanates, obtains the polyurethane blocked with-NCO group
Prepolymer, is subsequently adding polymerization inhibitor, obtains the coating curing agent with isocyanuric acid ester ring structure.
Wherein:
Described isocyanates be toluene di-isocyanate(TDI) (TDI), 4,4-methyl diphenylene diisocyanate (pure MDI),
Isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 1,3-Diisocyanatomethylcyclohexane (HTDI) or
One or more mixture in dicyclohexyl methyl hydride diisocyanate (HMDI).
Described organic solvent is selected from some low toxicities or nontoxic esters solvent: ethyl acetate, butyl acetate, acetic acid isopropyl
One or more mixture in ester, isobutyl acetate, ethylene glycol ether acetate or propylene glycol methyl ether acetate；Excellent
Select in ethyl acetate, butyl acetate one or both；Consumption be isocyanuric acid ester polyether polyol and isocyanates reaction institute
Obtain the 25～100% of polyurethane prepolymer quality.
Described polymerization inhibitor is phosphoric acid, sulphuric acid or Benzenecarbonyl chloride.；Preferably phosphoric acid or Benzenecarbonyl chloride.；Consumption is the total matter of firming agent
The 0.002～0.008% of amount.
The method of described coating curing agent specifically includes following steps: organic solvent and isocyanates are put into reactor,
Inflated with nitrogen is protected and stirring is warming up to 40～45 DEG C in 10min, and dropping isocyanuric acid ester polyether polyol, feeds complete continuously
After treating temperature stabilization, in 30min, it is warming up to 65～70 DEG C, insulation reaction 1.5～4h, then it is warming up to 80～85 in 20min
DEG C, insulation reaction 1～3h, sample detection-NCO content, after-NCO content reaches setting value, add polymerization inhibitor, stirring
30min, is cooled to 50 DEG C of dischargings, and nitrogen-sealed preserves.
The method have the advantages that
(1) containing isocyanuric acid ester ring structure in polyethers, thermostability, structural stability and anti-flammability that polyethers is excellent are given
Etc. feature.
(2) firming agent introduces isocyanuric acid ester ring structure by polyethers end, rather than is drawn by the trimerization reaction of isocyanates
Entering, production technology is simple, easy to control, and yield is high, and low cost, Safety and Environmental Protection is good.
(3) firming agent building-up process just introduces polyether segment structure, it is to avoid trimer curing agent uses poly-specially
The tedious steps that ether is modified, the compatibility with resin is good.
(4) preparation can be reacted by isocyanates various with IPDI, HDI, HTDI, HMDI or part TDI, MDI mixture etc.
Various types of coating curing agents, the suitability is wide.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
In 2L autoclave, add 790g tris(2-hydroxy ethyl)isocyanurate under room temperature, add the distilled water of 790g, stir
Mix dissolving, then 300g acetone soln, instill the phosphoric acid of the 85wt.% concentration of 0.05g after stirring, be warming up to 100 DEG C, stir
Mix uniformly and circulating filtration, then evacuation abjection moisture and acetone, be dried to moisture be 0.04wt.%；Nitrogen protection environment
The pressed powder dmc catalyst of lower addition 0.15g, is progressively warming up to 130 ± 2 DEG C, is evacuated to-0.095MPa, nitrogen bubble
1h；The expoxy propane adding 80g carries out initiation reaction, and question response still pressure drops to start to drip continuously during 0.01MPa residue
634g expoxy propane carries out continuous polymerization, and reaction terminates rear evacuation demonomerization 1h, sampling detection OHv=335.9mgKOH/g,
It is cooled to 90 DEG C of dischargings preserve, obtains isocyanuric acid ester polyether polyol A.
Joining in reactor by 550g toluene di-isocyanate(TDI) (TDI) and 284g ethyl acetate, inflated with nitrogen is protected, and starts
Heating and stirring, be warming up to 45 DEG C in 10min, continuously dropping 500g polyether polyol A, feed complete treat temperature stabilization after,
68 DEG C it are to slowly warm up in 30min, insulation reaction 2h, then it is warming up to 83 DEG C of insulation reaction 2h in 20min, samples detection-NCO
Content ,-NCO%=10.5, stopped reaction, add 0.065g phosphoric acid, stir 30min, be cooled to 50 DEG C of dischargings, nitrogen-sealed is protected
Deposit, obtain TDI type coating curing agent.
Embodiment 2
In 2L autoclave, add 395g tris(2-hydroxy ethyl)isocyanurate under room temperature, add the distilled water of 300g, stir
Mix dissolving, then 300g acetone soln, instill the phosphoric acid of the 85wt.% concentration of 0.03g after stirring, be warming up to 100 DEG C, stir
Mix uniformly and circulating filtration, then evacuation abjection moisture and acetone, be dried to moisture be 0.05wt.%；Nitrogen protection environment
The pressed powder dmc catalyst of lower addition 0.05g, is progressively warming up to 130 ± 2 DEG C, is evacuated to-0.095MPa, nitrogen bubble
1h；The expoxy propane adding 40g carries out initiation reaction, and question response still pressure drops to start to drip continuously during 0.01MPa residue
1067g expoxy propane carries out continuous polymerization, and reaction terminates rear evacuation demonomerization 1h, sampling detection OHv=168.5mgKOH/g,
It is cooled to 90 DEG C of dischargings preserve, obtains isocyanuric acid ester polyether polyol B.
By 750g 4,4-methyl diphenylene diisocyanate (pure MDI) and 525g butyl acetate join in reactor, fill
Nitrogen is protected, and starts heating and stirring, is warming up to 40 DEG C in 10min, continuously dropping 1000g polyether polyol B, and feed complete treating
After temperature stabilization, in 30min, it is to slowly warm up to 65 DEG C, insulation reaction 2h, then it is warming up to 80 DEG C of insulation reaction in 20min
1.5h, samples detection-NCO content ,-NCO%=5.54, stopped reaction, adds 0.13g phosphoric acid, stir 30min, be cooled to 50
DEG C discharging, nitrogen-sealed preserves, obtains MDI type coating curing agent.
Embodiment 3
In 2L autoclave, add 786g tris(2-hydroxy ethyl)isocyanurate under room temperature, add the distilled water of 700g, stir
Mix dissolving, then 750g acetone soln, instill the phosphoric acid of the 85wt.% concentration of 0.1g after stirring, be warming up to 100 DEG C, stir
Mix uniformly and circulating filtration, then evacuation abjection moisture and acetone, be dried to moisture be 0.03wt.%；Nitrogen protection environment
The emulsion form dmc catalyst of lower addition 0.23g, is progressively warming up to 130 ± 2 DEG C, is evacuated to-0.095MPa, nitrogen bubble 1h；
The expoxy propane adding 150g carries out initiation reaction, and question response still pressure drops to start to drip continuously during 0.01MPa residue
204g expoxy propane carries out continuous polymerization, and reaction terminates rear evacuation demonomerization 1h, sampling detection OHv=445.1mgKOH/g,
It is cooled to 90 DEG C of dischargings preserve, obtains isocyanuric acid ester polyether polyol C.
Joining in reactor by 505g hexamethylene diisocyanate (HDI) and 800g isobutyl acetate, inflated with nitrogen is protected
Protect, start heating and stirring, in 10min, be warming up to 45 DEG C, continuously dropping 378g polyether polyol C, feed and complete treat that temperature is steady
After Ding, in 30min, it is to slowly warm up to 70 DEG C, insulation reaction 4h, then it is warming up to 85 DEG C of insulation reaction 2h in 20min, sampling
Detection-NCO content ,-NCO%=7.52, stopped reaction, add 0.06g phosphoric acid, stir 30min, be cooled to 50 DEG C of dischargings, nitrogen
Hermetic seal preserves, and obtains color inhibition type HDI coating curing agent.
Claims (10)
1. an isocyanuric acid ester polyether polyol, it is characterised in that: using tris(2-hydroxy ethyl)isocyanurate as initiator, double
Under the effect of metal cyanide complex catalyst agent, epoxyalkane compound ring-opening polymerisation is made to obtain isocyanuric acid by coordination polymerization
Ester polyether polyhydric alcohol.
Isocyanuric acid ester polyether polyol the most according to claim 1, it is characterised in that: first to trihydroxyethyl isocyanuric acid
Ester carries out pretreatment, then under the effect of bimetallic cyanide complex catalyst, makes epoxyalkane compound by coordination polymerization
Ring-opening polymerisation；
Preprocess method is: after tris(2-hydroxy ethyl)isocyanurate mixes according to mass ratio 1:0.5～1 with distilled water, adds and accounts for three
Hydroxyethylisocyanurate and distilled water gross mass 10～the acetone of 100%, stir, and adds and accounts for trihydroxyethyl isocyanuric acid
Ester, distilled water and acetone gross mass 0.001～the phosphoric acid of 0.005%, stir, circulating filtration, vacuum abjection moisture and third
Ketone, is dried to moisture≤0.05wt.% use.
Isocyanuric acid ester polyether polyol the most according to claim 1, it is characterised in that: double metal cyanide complex catalysis
Agent is one or both in solid powdery catalyst or emulsion form catalyst, and consumption is initiator and epoxyalkane compound
The 0.002～0.05% of both weight sums；Isocyanuric acid ester polyether polyol hydroxyl value is 56～445mgKOH/g.
Isocyanuric acid ester polyether polyol the most according to claim 1, it is characterised in that: epoxyalkane compound is epoxy
One or more mixture in propane, oxirane or epoxy butane, the polyether polyol obtained is with expoxy propane
Or epoxy butane end-blocking.
5. the preparation method of the arbitrary described isocyanuric acid ester polyether polyol of Claims 1 to 4, it is characterised in that include
Following steps: first initiator tris(2-hydroxy ethyl)isocyanurate is carried out pretreatment, the trihydroxyethyl isocyanide after then processing
Urea acid esters and bimetallic cyanide complex catalyst join in pressure reactor, are warming up to 130 DEG C ± 2 DEG C, be evacuated to-
0.095MPa, nitrogen bubble 1h；Be subsequently adding initiator weight 10～20% epoxyalkane compound carry out initiation reaction, treat
When reactor pressure drops to 0.01MPa, starting dropping residual epoxide alkane compound continuously and carry out continuous polymerization, reaction terminates
Rear evacuation demonomerization 1h, sampling detection isocyanuric acid ester polyether polyol hydroxyl value OHv, cooling discharge preserves.
6. the method that the arbitrary described isocyanuric acid ester polyether polyol of Claims 1 to 4 prepares coating curing agent, it is special
Levy and be: first isocyanuric acid ester polyether polyol is reacted according to the ratio of mol ratio 1:3 in organic solvent with isocyanates,
Obtain, with the polyurethane prepolymer of-NCO group end-blocking, being subsequently adding polymerization inhibitor, obtaining the painting with isocyanuric acid ester ring structure
Material firming agent.
The method that isocyanuric acid ester polyether polyol the most according to claim 6 prepares coating curing agent, it is characterised in that:
Isocyanates is toluene di-isocyanate(TDI), 4,4-methyl diphenylene diisocyanate, isophorone diisocyanate, hexa-methylene
One or more mixed in diisocyanate, 1,3-Diisocyanatomethylcyclohexane or dicyclohexyl methyl hydride diisocyanate
Compound.
The method that isocyanuric acid ester polyether polyol the most according to claim 6 prepares coating curing agent, it is characterised in that:
Organic solvent is ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, ethylene glycol ether acetate or propylene glycol first
One or more mixture in ether acetate；One or both in ethyl acetate, butyl acetate；Consumption is
Isocyanuric acid ester polyether polyol and the 25～100% of isocyanates reaction gained polyurethane prepolymer quality.
The method that isocyanuric acid ester polyether polyol the most according to claim 6 prepares coating curing agent, it is characterised in that:
Polymerization inhibitor is phosphoric acid, sulphuric acid or Benzenecarbonyl chloride.；Consumption is the 0.002～0.008% of firming agent gross mass.
The method that isocyanuric acid ester polyether polyol the most according to claim 6 prepares coating curing agent, it is characterised in that
Comprising the following steps: organic solvent and isocyanates are put into reactor, inflated with nitrogen is protected and stirring is warming up to 40 in 10min
～45 DEG C, continuously dropping isocyanuric acid ester polyether polyol, feed complete treat temperature stabilization after, be warming up in 30min 65～
70 DEG C, insulation reaction 1.5～4h, then it is warming up to 80～85 DEG C in 20min, insulation reaction 1～3h, sampling detection-NCO contains
Amount, after-NCO content reaches setting value, adds polymerization inhibitor, stirs 30min, be cooled to 50 DEG C of dischargings, and nitrogen-sealed preserves.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610620578.6A CN106243339A (en) | 2016-08-01 | 2016-08-01 | Isocyanuric acid ester polyether polyol and preparation method thereof and the preparation method of coating curing agent |
| PCT/CN2016/099461 WO2018023860A1 (en) | 2016-08-01 | 2016-09-20 | Isocyanurate polyether polyol and preparation method therefor, and preparation method for coating curing agent |
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| CN201610620578.6A CN106243339A (en) | 2016-08-01 | 2016-08-01 | Isocyanuric acid ester polyether polyol and preparation method thereof and the preparation method of coating curing agent |
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| WO (1) | WO2018023860A1 (en) |
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| CN110511372A (en) * | 2019-08-28 | 2019-11-29 | 西安近代化学研究所 | One kind terminal isocyanate group curing agent containing energy and its synthetic method |
| CN111171268A (en) * | 2020-01-22 | 2020-05-19 | 黎明化工研究设计院有限责任公司 | Heat-resistant polyurethane soft foam and preparation method thereof |
| CN114672033A (en) * | 2021-11-24 | 2022-06-28 | 上海交通大学 | Two-dimensional coordination polymer based on isocyano coordination |
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| CN113881033A (en) * | 2021-09-30 | 2022-01-04 | 中国石油化工股份有限公司 | Method for preparing high-toughness high-resilience soft foam polyether polyol based on butylene oxide |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102115525A (en) * | 2010-12-30 | 2011-07-06 | 山东东大一诺威聚氨酯有限公司 | Poly-isocyanurate polyurethane coating curing agent and preparation method thereof |
| CN102844356A (en) * | 2010-04-30 | 2012-12-26 | 旭硝子株式会社 | Polyoxyalkylene polyol, polyol in which polymer is dispersed, flexible polyurethane foam, and processes for production of same |
| CN104403076A (en) * | 2014-11-27 | 2015-03-11 | 山东一诺威新材料有限公司 | Premixed polyether polyol for polyurethane for packaging of precise instrument |
| CN105237759A (en) * | 2015-11-09 | 2016-01-13 | 淄博德信联邦化学工业有限公司 | Polyether polyol for high-tensile elastomer and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2548908A1 (en) * | 2011-07-18 | 2013-01-23 | Bayer MaterialScience AG | Method for manufacturing polyether polyols |
| CN104072745A (en) * | 2014-07-04 | 2014-10-01 | 山东一诺威新材料有限公司 | Method for preparing polyether polyol for aromatic coating |
-
2016
- 2016-08-01 CN CN201610620578.6A patent/CN106243339A/en active Pending
- 2016-09-20 WO PCT/CN2016/099461 patent/WO2018023860A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102844356A (en) * | 2010-04-30 | 2012-12-26 | 旭硝子株式会社 | Polyoxyalkylene polyol, polyol in which polymer is dispersed, flexible polyurethane foam, and processes for production of same |
| CN102115525A (en) * | 2010-12-30 | 2011-07-06 | 山东东大一诺威聚氨酯有限公司 | Poly-isocyanurate polyurethane coating curing agent and preparation method thereof |
| CN104403076A (en) * | 2014-11-27 | 2015-03-11 | 山东一诺威新材料有限公司 | Premixed polyether polyol for polyurethane for packaging of precise instrument |
| CN105237759A (en) * | 2015-11-09 | 2016-01-13 | 淄博德信联邦化学工业有限公司 | Polyether polyol for high-tensile elastomer and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 周冬杰等: "异氰脲酸聚醚多元醇的合成", 《上海塑料》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110396184A (en) * | 2019-06-20 | 2019-11-01 | 佳化化学科技发展（上海）有限公司 | A kind of preparation method of isocyanuric acid ester polyether polyol |
| CN110396184B (en) * | 2019-06-20 | 2022-01-07 | 佳化化学科技发展（上海）有限公司 | Preparation method of isocyanurate polyether polyol |
| CN110511372A (en) * | 2019-08-28 | 2019-11-29 | 西安近代化学研究所 | One kind terminal isocyanate group curing agent containing energy and its synthetic method |
| CN111171268A (en) * | 2020-01-22 | 2020-05-19 | 黎明化工研究设计院有限责任公司 | Heat-resistant polyurethane soft foam and preparation method thereof |
| CN111171268B (en) * | 2020-01-22 | 2022-03-08 | 黎明化工研究设计院有限责任公司 | Heat-resistant polyurethane soft foam and preparation method thereof |
| CN114672033A (en) * | 2021-11-24 | 2022-06-28 | 上海交通大学 | Two-dimensional coordination polymer based on isocyano coordination |
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