CN107304244B - Modified polyisocyanate composition and preparation method thereof - Google Patents
Modified polyisocyanate composition and preparation method thereof Download PDFInfo
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- CN107304244B CN107304244B CN201610244850.5A CN201610244850A CN107304244B CN 107304244 B CN107304244 B CN 107304244B CN 201610244850 A CN201610244850 A CN 201610244850A CN 107304244 B CN107304244 B CN 107304244B
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- 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
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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
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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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
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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
- C08G18/77—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
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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
- C08G18/81—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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Abstract
The invention provides a modified polyisocyanate composition and a preparation method thereof, wherein the preparation method comprises the following steps: 1) reacting monohydric alcohol with polyisocyanate under heating condition, and heating while stirring; 2) continuously adding polyisocyanate, and carrying out secondary reaction under the conditions of catalyst and heating to generate a polyisocyanate composition; wherein, the catalyst is selected from one or two of organic zinc compound, organic tin compound, organic alkali metal salt, tertiary amine and salt compound thereof. The invention adopts the monol modified polyisocyanate with special functional groups to prepare the polyisocyanate composition with a certain allophanate content, and the polyurethane resin prepared by using the polyisocyanate composition can show the special functionality of the monol, simultaneously increases the rebound resilience of the polyurethane resin, and also has the characteristics of high hydrophobicity, photocurability and the like.
Description
Technical Field
The invention relates to the field of polyisocyanates, and particularly discloses a modified polyisocyanate composition and a preparation method thereof.
Background
The polyisocyanate has various modification methods, so that various isocyanate derivatives such as isocyanate homopolymer mainly comprising diisocyanate trimer, polyol adduct, biuret and blocked isocyanate are obtained, the derivatives are mostly used for curing agents of two-component adhesives or coatings, except that part of HDI derivatives are liquid, most of the HDI derivatives are solid, the use is inconvenient, the HDI derivatives are not suitable for environment-friendly water-based or solvent-free systems after being diluted by a solvent, and the environmental pollution and the health hazard are brought.
In the allophanate modified polyisocyanate technology, a blocked or unblocked polyisocyanate composition with an average functionality of more than 2 is modified by using a polyfunctional alcohol compound as a raw material, the method is not easy to control the degree of polymerization, the obtained product has high viscosity, the product can be used only by diluting with an organic solvent, and the molecular structure of the product is uncertain. The prior art focuses on the utilization of the high polarity of allophanate groups, which can further increase the properties such as rigidity of resin coating films when used as a curing agent. However, since the leather prepared by the polyisocyanate composition in the prior art has no resilience, the modified polyisocyanate composition cannot be applied to the field of leather, resulting in the single performance of the modified polyisocyanate composition in the prior art. Therefore, the research and development of modified polyisocyanate compositions with simple preparation and multiple performances have important practical significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a modified polyisocyanate composition and a preparation method thereof, wherein the preparation method comprises the steps of introducing a single special functional group on the basis of introducing an allophanate key group, and preparing allophanate modified polyisocyanate by using an alcohol compound containing the single special functional group as a raw material; the obtained modified polyisocyanate composition has multiple performances and can be applied to multiple fields of coatings, synthetic leather bass, fabrics and the like.
In order to achieve the above objects and other objects, the present invention includes the following technical solutions: a process for preparing a modified polyisocyanate composition comprising the steps of: 1) reacting monohydric alcohol with polyisocyanate under the heating condition, wherein heating and stirring are required during the reaction process; 2) continuously adding polyisocyanate, carrying out secondary reaction under the conditions of catalyst and heating, wherein heating and stirring are required in the reaction process to generate a polyisocyanate composition; wherein the catalyst is selected from any one or two of organic zinc compound, organic tin compound, organic alkali metal salt, tertiary amine and salt compound thereof, and the polyisocyanate composition comprises polyisocyanate, allophanate and isocyanurate.
Preferably, the polyisocyanate is any one or more of isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, and 4,4' -dicyclohexylmethane diisocyanate.
Preferably, the polyisocyanate is any one or more of isophorone diisocyanate, hexamethylene diisocyanate and toluene diisocyanate.
Preferably, the monohydric alcohol contains a linear, branched or cyclic divalent aliphatic hydrocarbon group or a monovalent aliphatic hydrocarbon group of 12 to 36 carbon atoms, but no aromatic hydrocarbon groups.
Preferably, the monohydric alcohol is selected from any one of perfluoroalkyl alcohol, hydroxy acrylate or hydroxy methacrylate.
Preferably, the organozinc compound in the step 2) is selected from any one of zinc isooctanoate, zinc octanoate and zinc acetylacetonate; the organic tin compound is selected from any one of dibutyl tin laurate and stannous octoate; the organic alkali metal salt is sodium acetate.
Preferably, the molar ratio of the polyisocyanate to the monohydric alcohol in step 1) is (1-1.5): 1; the reaction temperature is 70-90 ℃, and the reaction time is 1-4 h.
Preferably, the molar ratio of the polyisocyanate to the monohydric alcohol in step 1) is 1: 1; the reaction temperature is 75-85 ℃, and the reaction time is 2-3 h.
Preferably, the molar ratio of polyisocyanate to the monohydric alcohol added in step 2) is in the range of (2-14): 1; the temperature of the secondary reaction is 100-150 ℃, and the time of the secondary reaction is 1-5 h.
Preferably, the molar ratio of polyisocyanate to the monohydric alcohol added in step 2) is in the range of (4-8): 1; the temperature of the secondary reaction is 120-140 ℃, and the time of the secondary reaction is 3-4 h.
Preferably, the polyisocyanate composition has an NCO group content of 10 to 30% by weight.
The polyisocyanate composition prepared by the preparation method comprises 50-80% by weight of polyisocyanate, 5-40% by weight of allophanate and 3-25% by weight of isocyanurate, and the viscosity of the polyisocyanate composition is in the range of 100-2000 mPa/s.
In summary, the present invention provides a modified polyisocyanate composition and a preparation method thereof, and the modified polyisocyanate composition has the following beneficial effects:
the invention adopts the monol modified polyisocyanate with single special functional group to prepare the polyisocyanate composition with a certain allophanate content, and the polyurethane resin prepared by using the polyisocyanate composition can show the special functionality of the monol, simultaneously increases the rebound resilience of the polyurethane resin, has high rebound resilience, and is applied to the synthesis of structural foams such as resin for Beth; the water-proof fabric has high hydrophobicity and is applied to the synthesis of water-proof fabric resin; has photocurability, is applied to the synthesis of photocureable coating, has high drying speed and high spraying efficiency.
Furthermore, the invention uses monofunctional monohydric alcohol as raw material, which is easier to control molecular structure, and makes the reaction easy to control, and the product viscosity is not large and can be used without dilution.
Furthermore, the invention increases the types of polyisocyanates and provides more raw material choices for polyurethane resin synthesis.
Furthermore, the reaction process of the invention does not use organic solvent, thereby reducing environmental pollution, improving working environment and reducing personal injury of working personnel caused by organic solvent.
Furthermore, the process provided by the invention is simple to operate, improves the working efficiency, is low in cost and is suitable for industrial production.
Detailed Description
The invention provides a preparation method of a modified polyisocyanate composition, which comprises the following steps:
1) reacting monohydric alcohol with polyisocyanate under the heating condition, and stirring and heating to obtain carbamate;
2) continuously adding polyisocyanate, and carrying out secondary reaction under the heating condition of 100-150 ℃ in the presence of a catalyst to obtain the polyisocyanate composition.
First, step 1) is performed: the monohydric alcohol and the polyisocyanate are reacted under heating conditions, and are heated while stirring.
The polyisocyanate is one of the main raw materials of the polyurethane resin, and examples of the polyisocyanate for producing the polyurethane resin include diisocyanate, triisocyanate and modified products thereof. The polyisocyanate has two or more active sites in its molecule, and thus can be extended in two or three directions to form a linear or crosslinked (bulk) polymer when polymerization occurs. The most common of these is a diisocyanate, and preferably, the polyisocyanate is any one of isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and 4,4' -dicyclohexylmethane diisocyanate (HMDI).
In one embodiment of the present invention, the monohydric alcohol contains a linear, branched or cyclic divalent aliphatic hydrocarbon group or a monovalent aliphatic hydrocarbon group of 12 to 36 carbon atoms, but does not contain an aromatic hydrocarbon group, since the aromatic hydrocarbon group enhances the hardness of the polyurethane resin prepared from the composition. The carbon number of the monohydric alcohol is not less than 12, which increases the hydrophobicity of the polyurethane resin prepared from the composition.
In another embodiment of the present invention, the monol has a single C ═ C double bond, which is not reacted with NCO groups, and the C ═ C double bond is introduced into the polyisocyanate composition through step 1), which is advantageous for the photocuring properties of the polyurethane resin prepared from the composition. The photo-curing property refers to that polymerization and cross-linking reaction between low-molecular prepolymer or oligomer in the coating and monomer molecules as active diluent are initiated by light energy to obtain a hardened coating, namely, chemical drying is realized by forming chemical bonds. After the C ═ C double bond is introduced into the coating, polymerization of the C ═ C double bond can be achieved by illumination when the coating is used, and apparently, rapid drying of the coating is exhibited. Preferably, the monohydric alcohol is hydroxy acrylate or hydroxy methacrylate, a C ═ C double bond is introduced into the polyisocyanate composition, and the polyurethane resin prepared from the polyisocyanate composition has photocuring characteristics, so that a film can be rapidly cured. Compared with other thermosetting single-component coatings, the coating can be cured at room temperature without high-temperature treatment, and energy is saved. Compared with other single-component coatings dried at room temperature, the coating saves drying time, is self-crosslinked, and has high coating strength.
In another embodiment of the present invention, the monohydric alcohol is a perfluoroalkyl alcohol. The monol is perfluoroalkyl alcohol to introduce fluorine groups into the polyisocyanate composition, and the introduction of the fluorine groups can greatly reduce the surface tension reduction of water, and the greatly reduced tendency is the same in both water and organic solvent, so that the obtained polyisocyanate composition has excellent hydrophobicity and oleophobicity; and exhibits stability in both strong acids and strong bases, and does not decompose, so that it can be used in various environments. In conclusion, the polyisocyanate composition is used for preparing the fabric, and the obtained fabric has incomparable advantages in the aspects of water repellency, oil repellency, dirt repellency, washing resistance, corrosion resistance and the like.
In step 1), the reaction of the isocyanate with the monol, which may be considered as a chain extender or curing agent, allows the molecular chain to grow and form carbamates. The reaction can be carried out under the heating condition of 70-90 ℃ without catalyst and solvent in the step.
Then, step 2) is performed: continuously adding polyisocyanate, and carrying out secondary reaction under the conditions of catalyst and heating, wherein stirring is required in the reaction process.
In the step 2), the reaction of the carbamate compound with the excessive polyisocyanate is the key of the whole preparation method, and because the activity of the N atom in the carbamate is low, the reaction is not easy to occur and the proceeding speed is low, the addition of a proper catalyst and the selection of a proper temperature are particularly important. Preferably, in the step 2), 0.01 to 0.5 weight percent of catalyst is added, and a diluent is added according to the viscosity, wherein the catalyst is selected from any one or two of organozinc compounds, organotin compounds, organic alkali metal salts, tertiary amines and salt compounds thereof. Preferably, the reaction temperature of step 2) is from 100 ℃ to 150 ℃, more preferably, the reaction temperature is from 120 ℃ to 140 ℃.
Reacting carbamate with NCO groups of polyisocyanate to generate allophanate; an isocyanate trimer, i.e., isocyanurate, is inevitably formed in this reaction. The isocyanurate, allophanate and isocyanate constitute the modified polyisocyanate composition of the present invention, and are viscous liquids which can be used without purification.
The synthesis reaction formulas related to the step 1) and the step 2) are as follows:
the present invention also provides a polyisocyanate composition prepared by the above process comprising, by weight, 50% to 80% polyisocyanate, 5% to 40% allophanate and 3% to 25% isocyanurate, which polyisocyanate composition is generally a viscous liquid that does not require purification and can be used directly, reducing process steps.
In one embodiment of the invention, the modified polyisocyanate composition has a viscosity (bulk viscosensitivity) of at least 100mPa/s measured at 25 ℃ and a viscosity of up to 2000mPa/s, in some cases less than or equal to 800mPa/s, and in other cases up to 1000 mPa/s. The viscosity of the modified polyisocyanate composition can be any value between or vary within a range between any of the values recited above.
The modified polyisocyanate composition prepared by the invention can be used as a synthetic raw material of polyurethane resin. As a synthetic raw material of polyurethane resin, the polyurethane resin has some special functions: such as high resilience, for structural foams such as bayes; such as high hydrophobicity, for waterproof fabric resins, etc.; such as photocuring properties, for synthesizing photocured coatings, and the like.
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Example 1
62g (about 0.33mol) of analytically pure dodecanol were weighed into a reactor, 75g (about 0.34mol) of isophorone diisocyanate (IPDI) was weighed out, slowly warmed to 80 ℃ with stirring, and then kept at 80 ℃ for reaction for 2 h. Adding 0.5g of zinc isooctanoate, weighing 296g (about 1.33mol) of IPDI, slowly adding into the reaction system, adding for about 30min, heating while adding IPDI, heating to 130 ℃ after adding, and keeping the temperature at 130 ℃ for reaction for 4 h. After the reaction is finished, the temperature is immediately reduced, and the polyisocyanate composition can be obtained after the material is discharged at the temperature of about 60 ℃.
The polyisocyanate composition contained 21.4% by weight of NCO groups, 52% by weight of IPDI monomers, 28% by weight of allophanate and 20% by weight of isocyanurate. Polyisocyanate composition at 25 ℃ and 200 seconds-1Has a viscosity of 675mPa/s at shear rate.
Example 2
62g (about 0.33mol) of dodecanol, 58g (about 0.33mol) of Toluene Diisocyanate (TDI) were weighed in a reactor, slowly heated to 70 ℃ with stirring, and then kept at 70 ℃ for reaction for 3 hours. 0.35g of dibutyltin dilaurate is added, the temperature is raised to 120 ℃, 348g (about 2.00mol) of TDI is weighed and slowly added into a reaction system for about 30min, and the reaction is kept at 120 ℃ for 4h after the addition is finished. After the reaction is finished, the temperature is immediately reduced, and the polyisocyanate composition liquid can be obtained after discharging at about 80 ℃.
Polyisocyanate composition 100% liquid product contains 17.6% by weightContains 58% by weight of TDI monomer, 26% by weight of allophanate and 16% by weight of isocyanurate. Polyisocyanate composition at 25 ℃ and 200 seconds-1Has a viscosity of 890mPa/s at shear rate.
Example 3
50g (about 0.43mol) of hydroxyethyl acrylate and 78g (about 0.45mol) of Toluene Diisocyanate (TDI) were weighed out in a reactor, slowly heated to 70 ℃ with stirring, and then kept at 70 ℃ for reaction for 3 hours. Adding 0.4g of sodium acetate, heating to 120 ℃, weighing 300g (about 1.72mol) of TDI, slowly adding into the reaction system for about 30min, and keeping the temperature of 120 ℃ for reaction for 4 h. After the reaction is finished, the temperature is immediately reduced, and the polyisocyanate composition liquid can be obtained after discharging at about 80 ℃.
Polyisocyanate composition 100% liquid product contained 19.2% by weight of NCO groups, 53% by weight of TDI monomer, 26% by weight of allophanate and 22% by weight of isocyanurate. Polyisocyanate composition at 25 ℃ and 200 seconds-1Has a viscosity at shear rate of 1250 mPa/s.
Example 4
39g (about 0.34mol) of hydroxyethyl acrylate and 90g (about 0.40mol) of isophorone diisocyanate (IPDI) were weighed out in a reactor, slowly warmed to 70 ℃ with stirring, and then kept at 70 ℃ for reaction for 3 hours. Adding 0.4g of sodium acetate, heating to 120 ℃, weighing 300g (about 1.35mol) of IPDI, slowly adding into the reaction system for about 30min, and keeping the temperature of 120 ℃ for reaction for 4 h. After the reaction is finished, the temperature is immediately reduced, and the polyisocyanate composition liquid can be obtained after discharging at about 80 ℃.
Polyisocyanate composition 100% liquid product contains 21.6% by weight of NCO groups, 50% by weight of IPDI monomers, 32% by weight of allophanate and 18% by weight of isocyanurate. Polyisocyanate composition at 25 ℃ and 200 seconds-1The viscosity at shear rate of (3) is 1050 mPa/s.
Example 5
50g (about 0.43mol) of hydroxyethyl acrylate and 75g (about 0.45mol) of Hexamethylene Diisocyanate (HDI) were weighed out in a reactor, slowly warmed to 70 ℃ with stirring and then kept at 70 ℃ for reaction for 4 hours. Adding 0.8g of sodium acetate, heating to 120 ℃, weighing 600g (about 1.79mol) of HDI, slowly adding into a reaction system, adding for about 30min, keeping the temperature of 120 ℃ for reaction for 1H, heating to 140 ℃, keeping the temperature for reaction for 3H, immediately cooling after the reaction is finished, and discharging at about 80 ℃ to obtain the polyisocyanate composition liquid.
Polyisocyanate composition 100% liquid product contained 22.7% by weight of NCO groups, 61% by weight of HDI monomer, 25% by weight of allophanate and 14% by weight of isocyanurate. Polyisocyanate composition at 25 ℃ and 200 seconds-1The viscosity at shear rate of (a) was 565 mPa/s.
Example 6
57g (about 0.43mol) of hydroxyethyl methacrylate and 76g (about 0.45mol) of Hexamethylene Diisocyanate (HDI) were weighed out in a reactor, slowly warmed to 70 ℃ with stirring and then kept at 70 ℃ for reaction for 4 hours. Adding 0.8g of triethylene diamine, heating to 120 ℃, weighing 600g (about 3.6mol) of HDI, slowly adding into a reaction system, adding for about 30min, keeping the temperature of 120 ℃ for reaction for 1h, heating to 140 ℃, keeping the temperature for reaction for 3h, immediately cooling after the reaction is finished, and discharging at about 80 ℃ to obtain the polyisocyanate composition liquid.
Polyisocyanate composition 100% liquid product contained 22.3% by weight of NCO groups, 65% by weight of HDI monomer, 24% by weight of allophanate and 11% by weight of isocyanurate. Polyisocyanate composition at 25 ℃ and 200 seconds-1Has a viscosity at shear rate of 676 mPa/s.
Example 7
57g (about 0.43mol) of hydroxyethyl methacrylate and 96g (about 0.43mol) of isophorone diisocyanate (IPDI) were weighed out in a reactor, slowly warmed to 70 ℃ with stirring and then kept at 70 ℃ for reaction for 4 hours. Adding 0.5g of triethylene diamine, heating to 120 ℃, weighing 300g (about 1.350mol) of IPDI, slowly adding into a reaction system, adding for about 30min, keeping the temperature of 120 ℃ for reaction for 1h, heating to 140 ℃, keeping the temperature for reaction for 3h, immediately cooling after the reaction is finished, and discharging at about 80 ℃ to obtain the polyisocyanate composition liquid.
Polyisocyanate composition 100% liquid product containing 18.4% by weight of NCO groups containing 52% by weight of IPDI monomer, 28% by weight of allophanate and 20% by weight of isocyanurate. Polyisocyanate composition at 25 ℃ and 200 seconds-1Has a viscosity at shear rate of 1500 mPa/s.
Example 8
100g (about 0.24mol) of 6-perfluorohexylhexanol and 40g (about 0.24mol) of Hexamethylene Diisocyanate (HDI) were weighed in a reactor, slowly warmed to 90 ℃ with stirring, and then kept at 90 ℃ for reaction for 2 hours. Adding 0.5g of dibutyltin dilaurate, heating to 120 ℃, weighing 312g (about 1.85mol) of HDI, slowly adding into a reaction system, adding for about 30min, keeping the temperature of 120 ℃ for reaction for 2h, heating to 140 ℃, carrying out heat preservation reaction for 3h, immediately cooling after the reaction is finished, and discharging at about 70 ℃ to obtain the polyisocyanate composition.
The 100% solids product of the polyisocyanate composition contained 19.5% by weight of NCO groups, 50% by weight of HDI monomer, 33% by weight of allophanate and 17% by weight of isocyanurate. Polyisocyanate composition at 25 ℃ and 200 seconds-1Has a viscosity of 1325mPa/s at shear rate.
Example 9
100g (about 0.24mol) of 6-perfluorohexylhexanol and about 42g (about 0.24mol) of Toluene Diisocyanate (TDI) were weighed in a reactor, slowly heated to 80 ℃ with stirring, and then kept at 80 ℃ for reaction for 2 hours. Adding 0.5g of zinc isooctanoate, heating to 140 ℃, weighing 312g (about 1.79mol) of TDI, slowly adding into a reaction system, adding for about 30min, keeping the temperature of 140 ℃ for reaction for 4h after adding, immediately cooling after the reaction is finished, and discharging at about 70 ℃ to obtain the polyisocyanate composition.
Polyisocyanate composition 100% liquid product contains 16.4% by weight NCO groups, 51% by weight TDI monomer, 33% by weight allophanate and 16% by weight isocyanurate. Polyisocyanate composition at 25 ℃ and 200 seconds-1Has a viscosity of 1025mPa/s at a shear rate.
And (3) detection results:
the polyisocyanate compositions obtained in examples 1 and 2 were used as raw materials for producing a base leather, and the produced base leather was tested by a rebound resilience meter, and the base leather had high rebound resilience, which was 50 to 300%, and had excellent oil resistance.
The polyisocyanate composition obtained in examples 3-7 is used as a synthetic raw material of a photocureable coating, the drying time of the synthesized coating is shortened compared with that of the conventional coating, the drying time can be controlled within 30-60 min at room temperature according to the thickness of a coating and the requirements of customers, and the time of secondary coating is less than 60-90 min. The thorough drying time is 8-24 hours. The construction of staff is facilitated, and the working efficiency is improved.
The polyisocyanate composition obtained in examples 8 to 9 is used as a synthetic raw material of a fabric, the prepared fabric shows excellent hydrophobicity (hydrophobicity refers to the capability of the fabric for preventing the fabric from being wetted by water), the hydrophobicity is usually expressed by a value of 0 to 100, and the hydrophobicity of the fabric can reach 80 to 90 through a spray test.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention. Those skilled in the art can make various changes, modifications and equivalent arrangements, which are equivalent to the embodiments of the present invention, without departing from the spirit and scope of the present invention, and which may be made by utilizing the techniques disclosed above; meanwhile, any changes, modifications and variations of the above-described embodiments, which are equivalent to those of the technical spirit of the present invention, are within the scope of the technical solution of the present invention.
Claims (5)
1. A process for the preparation of a modified polyisocyanate composition comprising the steps of:
1) reacting monohydric alcohol with polyisocyanate under the heating condition, wherein heating and stirring are required during the reaction process;
2) continuously adding polyisocyanate, carrying out secondary reaction under the conditions of catalyst and heating, wherein heating and stirring are required in the reaction process to generate a polyisocyanate composition; wherein the catalyst is selected from any one or two of organic zinc compound, organic tin compound, organic alkali metal salt, tertiary amine and salt compound thereof, the polyisocyanate composition comprises polyisocyanate, allophanate and isocyanurate; the monohydric alcohol is internally provided with a single C ═ C double bond or is perfluoroalkyl alcohol; the polyisocyanate composition comprises, by weight, 50% to 80% polyisocyanate, 5% to 40% allophanate and 3% to 25% isocyanurate; the molar ratio of the polyisocyanate to the monohydric alcohol in step 1) is (1-1.5): 1; the polyisocyanate composition has an NCO group content of 10 to 30% by weight;
the synthetic reaction formulas related to the step 1) and the step 2) are as follows:
2. the process for preparing a modified polyisocyanate composition of claim 1 wherein: the polyisocyanate is any one or more of isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate and 4,4' -dicyclohexylmethane diisocyanate.
3. The process for preparing a modified polyisocyanate composition of claim 1 wherein: the organic zinc compound in the step 2) is selected from any one of zinc isooctanoate, zinc octoate and zinc acetylacetonate; the organic tin compound is selected from any one of dibutyl tin laurate and stannous octoate; the organic alkali metal salt is sodium acetate.
4. The process for preparing a modified polyisocyanate composition of claim 1 wherein: the molar ratio of the polyisocyanate to the monohydric alcohol added in the step 2) is (2-14): 1; the temperature of the secondary reaction is 100-150 ℃, and the time of the secondary reaction is 1-5 h.
5. The process for preparing a modified polyisocyanate composition of claim 1 wherein: the molar ratio of the polyisocyanate to the monohydric alcohol added in the step 2) is (4-8): 1; the temperature of the secondary reaction is 120-140 ℃, and the time of the secondary reaction is 3-4 h.
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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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| 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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