CN107304244A - A kind of polyisocyantates composition of modification and preparation method thereof - Google Patents
A kind of polyisocyantates composition of modification and preparation method thereof Download PDFInfo
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- CN107304244A CN107304244A CN201610244850.5A CN201610244850A CN107304244A CN 107304244 A CN107304244 A CN 107304244A CN 201610244850 A CN201610244850 A CN 201610244850A CN 107304244 A CN107304244 A CN 107304244A
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- polyisocyantates composition
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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
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
-
- 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
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
-
- 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
-
- 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
-
- 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
-
- 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
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
- C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
- C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
- C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention provides a kind of polyisocyantates composition of modification and preparation method thereof, and preparation method comprises the following steps：1) monohydric alcohol is reacted in a heated condition with polyisocyanates, need to be heated while stirring；2) polyisocyanates is continuously added, the secondary response under catalyst, heating condition generates polyisocyantates composition；Wherein, catalyst any one or two kinds in organic zinc compound, organo-tin compound, organic alkali metal salt, tertiary amine and its salt compound.The present invention is using the monohydric alcohol modified polyisocyanate with specific function functional group, prepare the polyisocyantates composition for having certain allophanic acid ester content, the polyurethane resin prepared using the polyisocyantates composition can show the specific functionality of the monohydric alcohol, simultaneously increase polyurethane resin resilience, also with high hydrophobicity, photo-curable the features such as.
Description
Technical field
The present invention relates to polyisocyanates field, a kind of polyisocyantates composition of modification and preparation method thereof is specifically disclosed.
Background technology
Polyisocyanates has a variety of method of modifying, the isocyanate derivates of numerous species is thus obtained, such as with diisocyanate
Isocyanates homopolymer, polyalcohol addition product, biuret, blocked isocyanate based on tripolymer, these derivatives are more
For Bi-component adhesive or the curing agent of coating, and except part HDI derivatives are liquid, other is generally solid-state, using not
It is convenient, it is not suitable for the aqueous or solvent-free system of environment-friendly type after solvent dilution, and bring environmental pollution and health hazard.
In allophanate-modified polyisocyanates technology, many isocyanides of closing or non-close with the average functionality more than 2
Using polyfunctionality alcoholic compound to be modified for raw material acid ester composite, the method is difficult to control the degree of polymerization, obtained product more
Viscosity is big, and product, which needs to be diluted with organic solvent, to be used, and products molecule structure has uncertainty.It is existing
There is technology to concentrate on using the highly polar of allophanate groups, can further increase resin coating film when being used as curing agent
Rigidity etc. performance.But, it is modified because the leather that in the prior art prepared by polyisocyantates composition does not have resilience
Polyisocyantates composition can not be applied to field of leather, cause the property of polyisocyantates composition being modified in the prior art
Can be single.Therefore, the polyisocyantates composition for the modification that research and development prepares simple, many performances has important reality
Meaning.
The content of the invention
It is an object of the invention to the defect for overcoming prior art, there is provided a kind of polyisocyantates composition of modification and its preparation
Method, the preparation method introduces single specific functional groups on the basis of the crucial group of allophanate is introduced, using containing
The alcoholic compound of single specific functional groups is that raw material prepares allophanate-modified polyisocyanates；Many isocyanides of the modification of acquisition
Acid ester composite has multiple performance, can be applied to the multiple fields such as coating, synthetic leather bass, fabric.
In order to realize object above and other purposes, the present invention including following technical scheme by realizing：A kind of modification
The preparation method of polyisocyantates composition, comprises the following steps：1) monohydric alcohol is carried out in a heated condition with polyisocyanates
Need to heat while stirring in reaction, course of reaction；2) polyisocyanates is continuously added, it is secondary under catalyst, heating condition
Need to heat while stirring in reaction, course of reaction, generate polyisocyantates composition；Wherein, the catalyst is selected from organic
Any one in zinc compound, organo-tin compound, organic alkali metal salt, tertiary amine and its salt compound or two kinds are described more
Isocyanate composition includes polyisocyanates, allophanate and isocyanuric acid ester.
Preferably, the polyisocyanates is IPDI, hexamethylene diisocyanate, toluene diisocyanate
Any one or more in acid esters, methyl diphenylene diisocyanate and 4,4'- dicyclohexyl methyl hydride diisocyanates.
Preferably, the polyisocyanates is IPDI, hexamethylene diisocyanate and toluene diisocyanate
Any one or more in acid esters.
Preferably, the monohydric alcohol contains the divalent aliphatic alkyl or one of the straight chain, side chain or ring-type of 12-36 carbon atom
Valency aliphatic hydrocarbyl, but do not contain aromatic hydrocarbyl.
Preferably, the monohydric alcohol be selected from perfluoroalkyl alcohol, acrylic acid hydroxyl ester or hydroxyethyl methacrylate ester any one.
Preferably, the step 2) described in organic zinc compound it is any in zinc Isoocatanoate, zinc octoate and zinc acetylacetonate
It is a kind of；The organo-tin compound in dibutyl tin laurate and stannous octoate any one；The organic alkali metal salt
For sodium acetate.
Preferably, the step 1) described in the mol ratio of polyisocyanates and the monohydric alcohol be (1-1.5):1；It is described anti-
The temperature answered is 70-90 DEG C, and the time of the reaction is 1-4h.
Preferably, the step 1) described in the mol ratio of polyisocyanates and the monohydric alcohol be 1:1；The temperature of the reaction
Spend for 75-85 DEG C, the time of the reaction is 2-3h.
Preferably, the step 2) in the molar ratio of polyisocyanates and the monohydric alcohol that adds at (2-14)：1；
The temperature of the secondary response is 100 DEG C -150 DEG C, and the time of the secondary response is 1-5h.
Preferably, the step 2) in the molar ratio of polyisocyanates and the monohydric alcohol that adds at (4-8)：1；Institute
The temperature for stating secondary response is 120 DEG C -140 DEG C, and the time of the secondary response is 3-4h.
Preferably, the NCO bases content of the polyisocyantates composition is 10-30 weight %.
A kind of polyisocyantates composition prepared by above-mentioned preparation method, the polyisocyantates composition includes components by weight percent
For 50%-80% polyisocyanates, 5%-40% allophanates and 3%-25% isocyanuric acid esters, the polyisocyanates combination
The viscosity scope 100-2000mPa/s of thing.
In summary, the present invention provides a kind of polyisocyantates composition of modification and preparation method thereof, beneficial effect of the invention
Really：
The present invention has certain allophanic acid using the monohydric alcohol modified polyisocyanate with single specific function functional group, preparation
The polyisocyantates composition of ester content, the polyurethane resin prepared using the polyisocyantates composition can show the unitary
The specific functionality of alcohol, while increasing the resilience of polyurethane resin, can have high resilience, applied to structural foam such as shellfish
This uses the synthesis of resin；With high hydrophobicity, the synthesis applied to waterproof fabrics resin；With photo-curable, applied to light
Coating material solidified synthesis, rate of drying is fast, implements spray efficiency high.
Further, the present invention is raw material, molecular structure more easy to control using single functionality monohydric alcohol so that reaction is easily controllable,
And product viscosity less can be used without dilution.
Further, invention increases the species of polyisocyanates, more raw material selections are provided for polyurethane resin synthesis.
Further, environmental pollution is reduced, working environment is improved, subtracted without using organic solvent in course of reaction of the present invention
Few personal injury of the organic solvent to staff.
Further, technological operation of the invention is simple, improves operating efficiency, and cost is relatively low, is adapted to industrialized production.
Embodiment
The present invention provides a kind of preparation method of the polyisocyantates composition of modification, comprises the following steps：
1) monohydric alcohol is reacted in a heated condition with polyisocyanates, heated while stirring, obtain carbamate；
2) polyisocyanates is continuously added, secondary response is carried out under catalyst, 100 DEG C of -150 DEG C of heating conditions, polyisocyanate is generated
Cyanate compositions.
First, step 1 is performed)：Monohydric alcohol is reacted in a heated condition with polyisocyanates, heated while stirring.
Polyisocyanates is one of primary raw material of polyurethane resin, and the polyisocyanates of manufacture polyurethane resin has two isocyanides
Acid esters, triisocyanate and their modified body.Contain two or more active sites in polyisocyanate molecule,
Therefore when occurring polymerisation, can Xiang Erduan or three-dimensional extend into line style or crosslinking (build) polymer.Most common of which is
Diisocyanate, it is preferable that polyisocyanates be IPDI (IPDI), hexamethylene diisocyanate (HDI),
Toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI) and 4,4'- dicyclohexyl methyl hydride diisocyanates (HMDI)
Any one.
In an embodiment of the invention, monohydric alcohol contains the divalence of the straight chain, side chain or ring-type of 12-36 carbon atom
Aliphatic hydrocarbyl or monovalent aliphatic alkyl, but aromatic hydrocarbyl is not contained, prepared because aromatic hydrocarbyl can strengthen by said composition
The hardness of polyurethane resin.No less than 12 meetings of the carbon number of monohydric alcohol are improved prepares polyurethane resin by said composition
Hydrophobicity.
In yet another embodiment of the present invention, carry single C=C double bonds in monohydric alcohol, C=C double bonds not with NCO
Group reacts, by step 1) C=C double bonds are incorporated into the polyisocyantates composition, be conducive to by the combination
The polyurethane resin that thing is prepared has photocuring characteristic, and this polyurethane resin is applied into paint field, and obtaining coating has
Photo-curable.Photo-curable refers to low molecule performed polymer or oligomer in the energy by the use of light triggers coating and is used as activity
Polymerization and cross-linking reaction between the monomer molecule of diluent, obtain hardened coating film, i.e., realize that chemistry is dry by forming chemical bond
It is dry.C=C double bonds are incorporated into after coating, during using coating, illumination achieves that the polymerization of C=C double bonds, apparent upper display
For the rapid draing of coating.It is preferred that, monohydric alcohol is acrylic acid hydroxyl ester or hydroxyethyl methacrylate ester, is polyisocyanates combination
Thing introduces C=C double bonds, and the polyurethane resin prepared by polyisocyantates composition has photocuring characteristic, can be achieved quick
Film-forming.Compared to other heat cure one-component coatings, solidification at room temperature is not required to high-temperature process, saves the energy.With other rooms
Temperature is dried one-component coating and compared, and saves drying time, and film self-crosslinking, coating strength is high.
In yet another embodiment of the present invention, monohydric alcohol is perfluoroalkyl alcohol.Monohydric alcohol is that perfluoroalkyl alcohol draws fluorine-based
Enter into the polyisocyantates composition, fluorine-based introducing then can be such that the reduction in surface tension of water significantly declines, and this
The tendency being greatly lowered is all identical in water or in organic solvent, so that the polyisocyanates combination obtained
Thing shows excellent hydrophobicity and oleophobic property；And stability is shown in strong acid, highly basic, is not decomposed, therefore can be made
For various environment.In a word, polyisocyantates composition is prepared into fabric, the fabric of acquisition in water repellency, oil repellent, refuse
Have the advantages that in terms of dirt, washability and corrosion resistance incomparable.
In step 1) in, the reaction of isocyanates and monohydric alcohol, i.e. monohydric alcohol are considered as a kind of chain extender or curing agent, make
Strand increases, and forms carbamate.Catalyst is not required in the step, without solvent, under 70-90 DEG C of heating condition both
It can be reacted.
Then, step 2 is performed)：Polyisocyanates is continuously added, secondary response is carried out under catalyst, heating condition, instead
Process is answered to need stirring.
This step 2) in, carbamate compounds and key of the excessive polyisocyanates reaction for whole preparation method,
Because N atom actives are smaller in carbamate, reaction is not susceptible to and to carry out speed slower, therefore is added and more suitably urged
Agent and the suitable temperature of selection seem increasingly important.Preferably, step 2) add urging for weight fraction 0.01%-0.5%
Agent, the big I of apparent viscosity adds diluent, and the catalyst is selected from organic zinc compound, organo-tin compound, organic base gold
Belong to any one in salt, tertiary amine and its salt compound or two kinds.Preferably, step 2) reaction temperature be 100 DEG C -150 DEG C,
It is highly preferred that reaction temperature is 120 DEG C -140 DEG C.
The NCO group of carbamate and polyisocyanates is reacted, and generates allophanate；It is inevitable in the reaction
Generation isocyanate trimer be isocyanuric acid ester.Isocyanuric acid ester, allophanate and isocyanates constitute the present invention's
Modified polyisocyantates composition, in thick liquid, without purification, can be used directly.
The step 1 of the present invention) with step 2) the synthetic reaction formula that is related to is：
The present invention also provides the polyisocyantates composition prepared by the above method, and the polyisocyantates composition includes weight
Component is 50%-80% polyisocyanates, 5%-40% allophanates and 3%-25% isocyanuric acid esters, the polyisocyanates group
Compound is general, without purification, to be can be used directly in thick liquid, reduces processing step.
In an embodiment of the invention, the viscosity (bulk viscosity) of modified polyisocyantates composition is at 25 DEG C
At least 100mPa/s during measurement, viscosity is up to 2000mPa/s, in some cases less than or equal to 800mPa/s, at it
It is up to 1000mPa/s in its situation.The viscosity of modified polyisocyantates composition can be between any of the above described two values
Any value, or any of the above described two value between change.
The polyisocyantates composition of modification prepared by the present invention can as polyurethane resin synthesis material.It is used as polyurethane tree
The synthesis material of fat, with some specific functions：Such as high resilience, applied to structural foam such as bass；It is such as high hydrophobic
Property, for waterproof fabrics resin etc.；Such as photocuring characteristic, for synthesizing light solidifying coating etc..
Illustrate embodiments of the present invention below by way of specific instantiation, those skilled in the art can be taken off by this specification
The content of dew understands other advantages and effect of the present invention easily.The present invention can also pass through specific embodiment parties different in addition
Formula is embodied or practiced, and the various details in this specification can also be based on different viewpoints and application, without departing from this hair
Various modifications or alterations are carried out under bright spirit.
Embodiment 1
62g (about 0.33mol) analytically pure lauryl alcohol is weighed in reactor, 75g (about 0.34mol) isophorone is weighed
Diisocyanate (IPDI), is to slowly warm up to 80 DEG C under agitation, then keeps 80 DEG C of reaction 2h.Add 0.5g isooctyl acids
Zinc, weighs 296g (about 1.33mol) IPDI, is slowly added in reaction system, about 30min is added, and adds the same of IPDI
Shi Shengwen, adds rear temperature and rises to 130 DEG C, keeps 130 DEG C of reaction 4h.Reaction cools immediately after terminating, about 60 DEG C of dischargings
Polyisocyantates composition can be obtained.
Polyisocyantates composition contains 21.4 weight % NCO group, IPDI monomers, 28 weights containing 52 weight %
Measure % allophanates and 20 weight % isocyanuric acid esters.Polyisocyantates composition was in 25 DEG C and 200 seconds-1Shearing speed
Viscosity under rate is 675mPa/s.
Embodiment 2
62g (about 0.33mol) lauryl alcohol is weighed in reactor, 58g (about 0.33mol) toluene di-isocyanate(TDI) (TDI) is weighed,
70 DEG C are to slowly warm up under agitation, then keep 70 DEG C of reaction 3h.0.35g dibutyl tin laurates are added, are warming up to
120 DEG C, 348g (about 2.00mol) TDI is weighed, is slowly added in reaction system, about 30min is added, kept after adding
120 DEG C of reaction 4h.Reaction cools immediately after terminating, and about 80 DEG C of dischargings can obtain polyisocyantates composition liquid.
The product liquid of polyisocyantates composition 100% contains 17.6 weight % NCO group, contains 58 weight %'s
TDI monomers, 26 weight % allophanates and 16 weight % isocyanuric acid esters.Polyisocyantates composition is at 25 DEG C and 200
Second-1Shear rate under viscosity be 890mPa/s.
Embodiment 3
50g (about 0.43mol) hydroxy-ethyl acrylate is weighed in reactor, 78g (about 0.45mol) toluene diisocyanate is weighed
Acid esters (TDI), is to slowly warm up to 70 DEG C under agitation, then keeps 70 DEG C of reaction 3h.Add 0.4g sodium acetates, heating
To 120 DEG C, 300g (about 1.72mol) TDI is weighed, is slowly added in reaction system, about 30min is added, protected after adding
Hold 120 DEG C of reaction 4h.Reaction cools immediately after terminating, and about 80 DEG C of dischargings can obtain polyisocyantates composition liquid.
The product liquid of polyisocyantates composition 100% contains 19.2 weight % NCO group, contains 53 weight %'s
TDI monomers, 26 weight % allophanates and 22 weight % isocyanuric acid esters.Polyisocyantates composition is at 25 DEG C and 200
Second-1Shear rate under viscosity be 1250mPa/s.
Embodiment 4
39g (about 0.34mol) hydroxy-ethyl acrylate is weighed in reactor, 90g (about 0.40mol) isophorone two is weighed
Isocyanates (IPDI), is to slowly warm up to 70 DEG C under agitation, then keeps 70 DEG C of reaction 3h.0.4g sodium acetates are added,
120 DEG C are warming up to, 300g (about 1.35mol) IPDI is weighed, is slowly added in reaction system, about 30min is added, plus
120 DEG C of reaction 4h are kept after complete.Reaction cools immediately after terminating, and about 80 DEG C of dischargings can obtain polyisocyantates composition liquid
Body.
The product liquid of polyisocyantates composition 100% contains 21.6 weight % NCO group, contains 50 weight %'s
IPDI monomers, 32 weight % allophanates and 18 weight % isocyanuric acid esters.Polyisocyantates composition is at 25 DEG C and 200
Second-1Shear rate under viscosity be 1050mPa/s.
Embodiment 5
50g (about 0.43mol) hydroxy-ethyl acrylate is weighed in reactor, 75g (about 0.45mol) hexa-methylene two is weighed
Isocyanates (HDI), is to slowly warm up to 70 DEG C under agitation, then keeps 70 DEG C of reaction 4h.0.8g sodium acetates are added,
120 DEG C are warming up to, 600g (about 1.79mol) HDI is weighed, is slowly added in reaction system, about 30min is added, adds
Keep 120 DEG C of reaction 1H afterwards, after be warming up to 140 DEG C of insulation reaction 3h, reaction cools immediately after terminating, and about 80 DEG C of dischargings are
Polyisocyantates composition liquid can be obtained.
The product liquid of polyisocyantates composition 100% contains 22.7 weight % NCO group, contains 61 weight %'s
HDI monomers, 25 weight % allophanates and 14 weight % isocyanuric acid esters.Polyisocyantates composition is at 25 DEG C and 200
Second-1Shear rate under viscosity be 565mPa/s.
Embodiment 6
57g (about 0.43mol) hydroxyethyl methacrylate is weighed in reactor, 76g (about 0.45mol) six methylenes are weighed
Group diisocyanate (HDI), is to slowly warm up to 70 DEG C under agitation, then keeps 70 DEG C of reaction 4h.Add 0.8g Sanyas
Ethyldiamine, is warming up to 120 DEG C, weighs 600g (about 3.6mol) HDI, is slowly added in reaction system, about 30min
Add, 120 DEG C of reaction 1h kept after adding, after be warming up to 140 DEG C of insulation reaction 3h, reaction cools immediately after terminating, about
80 DEG C of dischargings can obtain polyisocyantates composition liquid.
The product liquid of polyisocyantates composition 100% contains 22.3 weight % NCO group, contains 65 weight %'s
HDI monomers, 24 weight % allophanates and 11 weight % isocyanuric acid esters.Polyisocyantates composition is at 25 DEG C and 200
Second-1Shear rate under viscosity be 676mPa/s.
Embodiment 7
57g (about 0.43mol) hydroxyethyl methacrylate is weighed in reactor, 96g (about 0.43mol) different Fo Er is weighed
Ketone diisocyanate (IPDI), is to slowly warm up to 70 DEG C under agitation, then keeps 70 DEG C of reaction 4h.Add 0.5g Sanyas
Ethyldiamine, is warming up to 120 DEG C, weighs 300g (about 1.350mol) IPDI, is slowly added in reaction system, about 30min
Add, 120 DEG C of reaction 1h kept after adding, after be warming up to 140 DEG C of insulation reaction 3h, reaction cools immediately after terminating, about
80 DEG C of dischargings can obtain polyisocyantates composition liquid.
The product liquid of polyisocyantates composition 100% contains 18.4 weight % NCO group, contains 52 weight %'s
IPDI monomers, 28 weight % allophanates and 20 weight % isocyanuric acid esters.Polyisocyantates composition is at 25 DEG C and 200
Second-1Shear rate under viscosity be 1500mPa/s.
Embodiment 8
100g (about 0.24mol) 6- perfluoro hexyl hexanols are weighed in reactor, 40g (about 0.24mol) six methylenes are weighed
Group diisocyanate (HDI), is to slowly warm up to 90 DEG C under agitation, then keeps 90 DEG C of reaction 2h.Add 0.5g February
Cinnamic acid tin dibutyl ester, is warming up to 120 DEG C, weighs 312g (about 1.85mol) HDI, is slowly added in reaction system, about
30min is added, and 120 DEG C of reaction 2h are kept after adding, after be warming up to 140 DEG C of insulation reaction 3h, reaction cools immediately after terminating,
About 70 DEG C of dischargings can obtain polyisocyantates composition.
The solid product of polyisocyantates composition 100% contains 19.5 weight % NCO group, contains 50 weight %'s
HDI monomers, 33 weight % allophanates and 17 weight % isocyanuric acid esters.Polyisocyantates composition is at 25 DEG C and 200
Second-1Shear rate under viscosity be 1325mPa/s.
Embodiment 9
100g (about 0.24mol) 6- perfluoro hexyl hexanols are weighed in reactor, about 42g (about 0.24mol) toluene is weighed
Diisocyanate (TDI), is to slowly warm up to 80 DEG C under agitation, then keeps 80 DEG C of reaction 2h.Add 0.5g isooctyl acids
Zinc, is warming up to 140 DEG C, weighs 312g (about 1.79mol) TDI, is slowly added in reaction system, about 30min is added,
140 DEG C of reaction 4h are kept after adding, reaction cools immediately after terminating, and about 70 DEG C of dischargings can obtain polyisocyantates composition.
The product liquid of polyisocyantates composition 100% contains 16.4 weight % NCO group, contains 51 weight %'s
TDI monomers, 33 weight % allophanates and 16 weight % isocyanuric acid esters.Polyisocyantates composition is at 25 DEG C and 200
Second-1Shear rate under viscosity be 1025mPa/s.
Testing result：
Embodiment 1,2 is obtained into the preparing raw material that polyisocyantates composition is used as bass leather, the bass leather of manufacture passes through
Rebound degree instrument is tested, and leather has high resilience, and rebound degree can reach 50-300%, and with good oil resistivity.
Embodiment 3-7 is obtained into the synthesis material that polyisocyantates composition is used as photocureable coating, the coating of synthesis with it is conventional
Coating is compared to drying time is shortened, and surface drying time can be controlled in 30~60min at room temperature for foundation coating thickness and customer requirement,
The time of secondary film is less than 60-90min.Thorough drying time is 8-24 hours.Facilitate staff to construct, improve work
Efficiency.
Embodiment 8-9 is obtained into the synthesis material that polyisocyantates composition is used as fabric, the fabric of preparation shows excellent
Hydrophobicity (hydrophobicity refers to that fabric prevents the ability being soaked in water), hydrophobicity is generally represented with the value of one 0~100,
The hydrophobicity that can measure the fabric by spray test can reach 80-90.
Described above, only presently preferred embodiments of the present invention, formal and substantial limitation not any to the present invention is answered
When pointing out, for those skilled in the art, on the premise of the inventive method is not departed from, it can also make
Some improvement and supplement, these are improved and supplement also should be regarded as protection scope of the present invention.All those skilled in the art,
Without departing from the spirit and scope of the present invention, when made using disclosed above technology contents it is a little more
Dynamic, modification and the equivalent variations developed, are the equivalent embodiment of the present invention；Meanwhile, all substantial technologicals according to the present invention
The variation, modification and evolution for any equivalent variations made to above-described embodiment, still fall within the model of technical scheme
In enclosing.
Claims (10)
1. a kind of preparation method of the polyisocyantates composition of modification, it is characterised in that comprise the following steps：
1) monohydric alcohol is reacted in a heated condition with polyisocyanates, needs to heat while stirring in course of reaction；
2) polyisocyanates is continuously added, the secondary response under catalyst, heating condition needs in course of reaction to stir in heating
Mix, generate polyisocyantates composition；Wherein, the catalyst be selected from organic zinc compound, it is organo-tin compound, organic
Any one in alkali metal salt, tertiary amine and its salt compound or two kinds, the polyisocyantates composition include polyisocyanates,
Allophanate and isocyanuric acid ester.
2. the preparation method for the polyisocyantates composition being modified as claimed in claim 1, it is characterised in that：The polyisocyanates
For IPDI, hexamethylene diisocyanate, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate
With any one or more in 4,4'- dicyclohexyl methyl hydride diisocyanates.
3. the preparation method for the polyisocyantates composition being modified as claimed in claim 1, it is characterised in that：The monohydric alcohol contains
There are the divalent aliphatic alkyl or monovalent aliphatic alkyl of the straight chain, side chain or ring-type of 12-36 carbon atom, but do not contain aromatics
Alkyl.
4. the preparation method for the polyisocyantates composition being modified as claimed in claim 1, it is characterised in that：The monohydric alcohol is selected from
Any one in perfluoroalkyl alcohol, acrylic acid hydroxyl ester and hydroxyethyl methacrylate ester.
5. the preparation method for the polyisocyantates composition being modified as claimed in claim 1, it is characterised in that：The step 2) in
The organic zinc compound in zinc Isoocatanoate, zinc octoate and zinc acetylacetonate any one；The organo-tin compound choosing
From in dibutyl tin laurate and stannous octoate any one；The organic alkali metal salt is sodium acetate.
6. the preparation method for the polyisocyantates composition being modified as claimed in claim 1, it is characterised in that：The step 1) in
The mol ratio of the polyisocyanates and the monohydric alcohol is (1-1.5):1；The temperature of the reaction is 70-90 DEG C, the reaction
Time be 1-4h.
7. the preparation method for the polyisocyantates composition being modified as claimed in claim 1, it is characterised in that：The step 2) in
The molar ratio of the polyisocyanates of addition and the monohydric alcohol is at (2-14)：1；The temperature of the secondary response is 100 DEG C
- 150 DEG C, the time of the secondary response is 1-5h.
8. the preparation method for the polyisocyantates composition being modified as claimed in claim 1, it is characterised in that：The step 2) in
The molar ratio of the polyisocyanates of addition and the monohydric alcohol is at (4-8)：1；The temperature of the secondary response is 120 DEG C
- 140 DEG C, the time of the secondary response is 3-4h.
9. the preparation method for the polyisocyantates composition being modified as claimed in claim 1, it is characterised in that：The polyisocyanic acid
The NCO bases content of ester composition is 10-30 weight %.
10. polyisocyantates composition made from a kind of preparation method as any one of claim 1 to 9, it is characterised in that
It is 50%-80% polyisocyanates, 5%-40% allophanates and 3%- that the polyisocyantates composition, which includes components by weight percent,
25% isocyanuric acid ester；The viscosity scope 100-2000mPa/s of the polyisocyantates composition.
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| CN109734860A (en) * | 2019-01-10 | 2019-05-10 | 四川东树新材料有限公司 | A kind of urethane composition for vacuum introducing technology |
| WO2019157625A1 (en) * | 2018-02-13 | 2019-08-22 | Covestro Deutschland Ag | Aromatic polyisocyanates with a high solids content |
| CN110423323A (en) * | 2019-08-19 | 2019-11-08 | 佛山市精信汇明科技有限公司 | A kind of water-soluble closed type polyurethane curing agent and its preparation method and application |
| CN111303373A (en) * | 2020-02-25 | 2020-06-19 | 万华化学集团股份有限公司 | Low-chroma allophanate composition and preparation method and application thereof |
| CN111587278A (en) * | 2018-01-10 | 2020-08-25 | 亨茨曼国际有限公司 | Polyurethane comprising a formulation with isocyanate functional groups |
| CN112940222A (en) * | 2021-02-04 | 2021-06-11 | 万华化学（宁波）有限公司 | Flocculation-stable polyisocyanate composition and preparation method thereof |
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| CN102015815A (en) * | 2008-04-24 | 2011-04-13 | 日本聚氨酯工业株式会社 | Polyisocyanate composition and two-package type coating composition using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111587278A (en) * | 2018-01-10 | 2020-08-25 | 亨茨曼国际有限公司 | Polyurethane comprising a formulation with isocyanate functional groups |
| CN111587278B (en) * | 2018-01-10 | 2022-09-23 | 亨茨曼国际有限公司 | Polyurethanes comprising formulations having isocyanate functional groups |
| WO2019157625A1 (en) * | 2018-02-13 | 2019-08-22 | Covestro Deutschland Ag | Aromatic polyisocyanates with a high solids content |
| CN111684031A (en) * | 2018-02-13 | 2020-09-18 | 科思创德国股份有限公司 | Aromatic polyisocyanates having a high solids content |
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| CN110423323A (en) * | 2019-08-19 | 2019-11-08 | 佛山市精信汇明科技有限公司 | A kind of water-soluble closed type polyurethane curing agent and its preparation method and application |
| CN111303373A (en) * | 2020-02-25 | 2020-06-19 | 万华化学集团股份有限公司 | Low-chroma allophanate composition and preparation method and application thereof |
| CN112940222A (en) * | 2021-02-04 | 2021-06-11 | 万华化学（宁波）有限公司 | Flocculation-stable polyisocyanate composition and preparation method thereof |
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