CN112940222A - Flocculation-stable polyisocyanate composition and preparation method thereof - Google Patents
Flocculation-stable polyisocyanate composition and preparation method thereof Download PDFInfo
- Publication number
- CN112940222A CN112940222A CN202110154032.7A CN202110154032A CN112940222A CN 112940222 A CN112940222 A CN 112940222A CN 202110154032 A CN202110154032 A CN 202110154032A CN 112940222 A CN112940222 A CN 112940222A
- Authority
- CN
- China
- Prior art keywords
- polyisocyanate composition
- flocculation
- diisocyanate
- reaction
- allophanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
-
- 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
-
- 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
- C08G18/794—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aromatic isocyanates or isothiocyanates
-
- 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
- C08G18/798—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing urethdione groups
Landscapes
- 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 invention discloses a flocculation-stable polyisocyanate composition and a preparation method thereof, wherein the polyisocyanate composition is prepared by reacting (cyclo) aliphatic diisocyanate and monohydric or dihydric alcohol, and the molar ratio of allophanate/allophanate connected with an isocyanurate ring in the composition is 0.001-0.6: 1, preferably 0.001-0.4: 1, and more preferably 0.001-0.3: 1. Compared with the prior art, the invention can provide the polyisocyanate composition with excellent flocculation stability under moisture condition without adding any additive.
Description
Technical Field
The invention relates to a polyisocyanate composition, in particular to a flocculation-stable polyisocyanate composition and a preparation method thereof.
Background
Isocyanates are used for the production of polyurethane coatings, in particular aliphatic isocyanate products, and have good weathering resistance and chemical stability, and are therefore widely used for a long time in various applications. When the isocyanate is used, an organic solvent is usually added for dilution, and the moisture in the solvent and the moisture in the air introduced in the process of opening and closing for many times are main reasons for the occurrence of flocs. The prior art mostly solves the flocculation problem of isocyanates by adding additional water scavengers, such as tetraphosphate in CN110621712A, trialkyltin chloride in EP2038746(a1), bistrimethylsilylacetamide or hexamethyldisilazane in US2008257214(a1) etc., but these compounds have to be added in stoichiometric amounts and the decomposition products formed consume NCO groups, affecting downstream applications. Therefore, it is of great importance to investigate how to obtain polyisocyanate compositions which are excellent in flocculation stability and have a low viscosity without using any additive.
Disclosure of Invention
The purpose of the present invention is to provide a polyisocyanate composition having excellent flocculation stability. The present inventors have surprisingly found that, in the alcohol modification of a polyisocyanate, by controlling a larger proportion of alcohol-derived allophanates to be distributed in a small-molecular compound, a polyisocyanate composition can be made more compatible with a macromolecular polyurea produced during a thinning process, resulting in a polyisocyanate composition in which clouding is suppressed even under wet conditions and the viscosity is maintained at a low level, and have completed the present invention.
Another object of the present invention is to provide a method for producing a polyisocyanate composition having excellent flocculation stability.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a flocculation-stable polyisocyanate composition prepared by reacting a (cyclo) aliphatic diisocyanate with a monohydric or dihydric alcohol, wherein the molar ratio of allophanate/allophanate linked to the isocyanurate ring in the composition is 0.001-0.6: 1, preferably 0.001-0.4: 1, more preferably 0.001-0.3: 1, and may be, for example, 0.001:1, 0.004:1, 0.007:1, 0.01:1, 0.03:1, 0.05:1, 0.08:1, 0.1:1, 0.15:1, 0.2:1, 0.25:1, 0.3:1, 0.35:1, 0.4:1, 0.45:1, 0.5:1, 0.55:1, or the like.
The polyisocyanate composition of the present invention contains an allophanate group represented by the following formula (1) and an isocyanurate represented by the following formula (2);
wherein, the allophanate group shown in the formula (1) comprises both a small molecule allophanate formed by an isocyanate group of a diisocyanate and a urethane group (shown in the formula (3)) formed by a diisocyanate group and a hydroxyl group of a monohydric or dihydric alcohol, and a large molecule allophanate further connected with an isocyanurate ring shown in the following formulas (4), (5) and (6):
it has been surprisingly found that the presence of small molecule allophanate compounds which are not linked to the isocyanurate ring provides better compatibility of the polyisocyanate composition with the macromolecular polyureas which they produce during the letdown process, which results in better flocculation stability of the polyisocyanate composition.
The molar ratio of allophanate/allophanate linked to the isocyanurate ring is 0.001 to 0.6. The above molar ratio is preferably 0.4 or less, more preferably 0.3 or less. By the above molar ratio of 0.6 or less, a greater proportion of allophanate groups are present in a small molecular manner, which makes the compatibility of the polyisocyanate composition with the macromolecular polyurea produced during the letdown process good, and thus the flocculation stability becomes good. The above molar ratio is preferably 0.001 or more, which makes the adhesion of the polyisocyanate composition to the substrate more excellent.
The above-mentioned and isocyanurate ring phaseThe molar ratio of linked allophanates/allophanates can be determined by GPC with13And C-NMR was used in combination. First of all, the polyisocyanate composition is subjected to13In the C-NMR measurement, the molar ratio A of allophanate groups to isocyanurate groups was determined by measuring the signal area of carbon atoms in the carbonyl group of allophanate groups at about 154.4ppm and the signal area of carbon atoms in the carbonyl group of isocyanurate ring at about 148.4 ppm.
Secondly, obtaining the mass ratio of each component in the polyisocyanate composition by gel chromatography, wherein the retention time of five molecules or more of polymers in the polyisocyanate composition in the gel chromatography is 15.0min-25.2min, and collecting the mobile phase of the five molecules or more of polymers. Subjecting the collected mobile phase to13In the C-NMR measurement, the molar ratio B of allophanate groups to isocyanurate groups was determined by measuring the signal area of carbon atoms in the carbonyl group of allophanate groups at about 154.4ppm and the signal area of carbon atoms in the carbonyl group of isocyanurate ring at about 148.4 ppm. Finally, the molar ratio of allophanate/allophanate linked to the isocyanurate ring is B/A.
Further, the molar ratio of allophanate groups to isocyanurate in the composition is 0.05 to 0.4:1, preferably 0.05 to 0.3:1, and may be, for example, 0.05:1, 0.1:1, 0.15:1, 0.2:1, 0.25:1, 0.3:1, 0.35:1, 0.4:1, and the like.
The molar ratio of the allophanate groups to the isocyanurate groups is 0.1 to 0.4. When the molar ratio is 0.1 or more, the system compatibility is improved. When the molar ratio is 0.4 or less, the curability of the composition system becomes good.
Further, the (cyclo) aliphatic diisocyanate is at least one of tetramethylene-1, 4-diisocyanate, pentamethylene-1, 5-diisocyanate, hexamethylene-1, 6-diisocyanate, lysine diisocyanate, isophorone diisocyanate, trimethylhexyl diisocyanate, dicyclohexylmethane diisocyanate, norbornane dimethylene isocyanate, preferably at least one of hexamethylene-1, 6-diisocyanate and isophorone diisocyanate.
The monohydric or dihydric alcohol is at least one of linear or branched monohydric or dihydric alcohol with the carbon number of 1-10, preferably one or more of n-octanol, n-hexanol, n-butanol, ethanol, n-pentanol, n-heptanol, 1, 3-propanediol, 1, 2-propanediol, 1, 3-butanediol, 1, 3-pentanediol, 1, 4-pentanediol, neopentyl glycol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, and 1, 9-nonanediol.
The amount of the monohydric or dihydric alcohol used to form the polyisocyanate composition of the present invention is not particularly limited, but when the molar ratio of the monohydric or dihydric alcohol to the (cyclo) aliphatic diisocyanate is preferably 0.01 to 0.5:1 and the molar ratio of the monohydric or dihydric alcohol to the (cyclo) aliphatic diisocyanate is 0.01 to 0.5:1, the later-described polyisocyanate composition has good adhesion to a substrate and also has excellent mechanical properties.
The polyisocyanate composition further comprises one or more of a carbamate shown in a formula (3), a uretdione structure shown in a formula (7) and an iminooxadiazinedione structure shown in a formula (8) obtained by trimerization;
wherein, the uretdione structure shown in the formula (7) is formed by heating reaction of two isocyanate groups, the iminooxadiazine dione structure shown in the formula (8) is a side reaction in the trimerization process of diisocyanate, and the content of the iminooxadiazine dione structure is greatly related to the used catalyst.
A process for the preparation of the flocculation-stabilized polyisocyanate composition as described hereinbefore, comprising the steps of:
the first step is as follows: using (cyclo) aliphatic diisocyanate and monohydric or dihydric alcohol as starting materials to react at 60-120 ℃, preferably 80-110 ℃ to obtain a reaction solution I;
the second step is that: taking the reaction liquid I obtained in the first step as a raw material, and continuously reacting in the presence of a catalyst to obtain a reaction liquid II;
the third step: after the reaction, the unreacted (cyclo) aliphatic diisocyanate was separated by thin film evaporation.
As mentioned above, the allophanate group is obtained by reacting a diisocyanate group and a hydroxyl group of a monohydric or dihydric alcohol to form a urethane group, and then reacting the urethane group with an isocyanate to obtain allophanate, wherein the first reaction is carried out at a temperature of 60 to 120 ℃ and preferably 80 to 110 ℃ to promote the formation of small molecular allophanate, the reaction is too slow below the temperature range, the formation of small molecular allophanate is too low, and the reaction is too slow above the temperature range, the diisocyanate monomer itself undergoes a polymerization reaction to form isocyanurate polymer, and the isocyanurate polymer further reacts with the monohydric or dihydric alcohol to form macromolecular allophanate, which is not favorable for the intended purpose of the present invention.
Further, under the first-step reaction conditions, the reaction progress can be further controlled by controlling the conversion rate of the alcohol, and preferably, the reaction is stopped when the conversion rate of the monohydric or dihydric alcohol in the reaction solution I reaches 60 to 90%. By controlling the conversion of the alcohol in the first reaction step within this range, it is possible to convert most of the alcohol into small molecule allophanate groups, which enables it to maintain the small molecule allophanate form also during the second reaction step; and then preparing the polyisocyanate composition through a second reaction step. The present preparation process allows a greater proportion of the alcohol-derived allophanates to be distributed in the small molecule compounds.
In addition, when the first-step reaction meets the requirements of the temperature and the alcohol conversion rate, the reaction time is about 1-3 hours, and too short reaction time can cause a large amount of unreacted monohydric or dihydric alcohol to remain in the reaction liquid I obtained in the first step, so that macromolecular allophanate is formed in the second-step reaction process; too long a reaction time may affect the reaction efficiency and the color of the reaction solution may be deteriorated.
Therefore, because different diisocyanates have different reactivity with alcohols, the first step reaction control means mainly controls the reaction degree of the two by controlling the reaction temperature and time, and judges the reaction progress by combining the conversion rate of the alcohols.
Further, the reaction catalyst in the second step is at least one of tetramethylammonium acetate, dodecyl trimethyl octyl amine, 2-hydroxypropyl trimethyl isooctyl ammonium salt and N, N, N-trimethyl-N-hydroxypropyl quaternary ammonium formate. Preferably, the amount of the catalyst added is 30 to 1000ppm, preferably 30 to 500ppm, based on the mass of the diisocyanate monomer.
Further, the skilled person can determine the reaction temperature in the second step reaction according to the temperature requirements of different catalysts; the catalyst is preferably selected from the above-mentioned types, and the second-step reaction temperature is preferably 50 to 100 ℃, and more preferably 60 to 90 ℃.
Further, the reaction is terminated by adding a terminating agent, preferably an acid containing phosphorus or sulfur or an acid ester thereof, more preferably at least one of dibutyl phosphate, dioctyl phosphate, and dimethyl sulfate. Preferably, the addition amount of the terminator is 20 to 800ppm, preferably 20 to 400ppm, with respect to the mass of the diisocyanate monomer.
Compared with the prior art, the invention has the advantages that: can provide a polyisocyanate composition having excellent flocculation stability under moisture conditions without adding any additive; in addition, the increase of the content of the small molecular allophanate compound in the scheme of the invention also contributes to the reduction of the viscosity of the polyisocyanate composition, so that the viscosity of the polyisocyanate composition is also at a lower level relative to the polyisocyanate composition which is not adjusted in any proportion at the same time, and the application has obvious advantages.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
In the examples and comparative examples of the present invention, the mass ratio of each component in the polyisocyanate composition was obtained by gel chromatography, wherein five molecules or more of the polymers showed peaks at a retention time of 15.0min to 25.2min in the gel chromatography, and simultaneously, mobile phases of five molecules or more of the polymers were collected.
The Gel chromatography test method is implemented by using LC-20AD/RID-10A, and the chromatographic columns are MZ-Gel SDplus10E3A 5 μm (8.0 × 300mm), MZ-Gel SDplus 500A 5 μm (8.0 × 300mm), MZ-Gel SDplus100A 5 μm (8.0 × 300mm) connected in series, Shimadzu; mobile phase: tetrahydrofuran; flow rate: 1.0 mL/min; analysis time: 40min, column temperature: 35 ℃ is carried out.
The molar percentage of allophanate structures is denoted by "a", a ═ allophanate structure/isocyanurate structure;
the molar percentage of allophanate structures linked to the isocyanurate ring is denoted by "B" ═ allophanate/isocyanurate structures linked to the isocyanurate ring;
the mole percent allophanate structure/allophanate structure linked to the isocyanurate ring is represented by "C" ═ B/a;
A. the test method of B adopts a 13C-NMR nuclear magnetic resonance method. The instrument used was a Bruker400MHz instrument, the sample concentration was 50% (CDCl3 solution), the test conditions were 100MHz, the relaxation time: 4s, number of scans 2000 times, with δ 77.0ppm CDCl3As a reference for displacement.
The test of A is to collect the nuclear magnetic resonance spectrum of the composition (denoted as spectrum 1), and the test of B is to collect the nuclear magnetic resonance spectrum of five molecules and more of polymer components (denoted as spectrum 2) collected by gel chromatography, namely, the collected five molecules and more of polymer mobile phase are concentrated to remove THF.
Isocyanurate structure: an absorption peak near 148.4 ppm;
allophanate structure: 154.4ppm absorption peak;
the calculation method of A is as follows: in spectrum 1, an integrated value near 154.4 ppm/an integrated value near 148.4 ppm;
the calculation of B is as follows: in spectrum 2, an integrated value near 154.4 ppm/an integrated value near 148.4 ppm;
< determination of the viscosity of the product > the viscosity of the products in the examples and comparative examples was determined using a Brookfield RC/S rheometer, model CC-40 on a spindle, with a thermostatic water bath, controlled at 25. + -. 0.1 ℃. The shear rate is 25S-1 to 250S-1.
Determination of product chromaticity > the chromaticity of the products in examples and comparative examples was measured using a BYK-Gardner GmbH/USA colorimeter.
< determination of the Mass concentration of HDI monomer >
A 20mL sample vial was placed on a digital balance, and 1g of the sample was precisely weighed and added. Subsequently, 0.04g of nitrobenzene (internal standard solution) was precisely weighed and added to the sample bottle. Finally, 9mL of ethyl acetate was added to the sample bottle, and the cap was closed. Then, the mixture was sufficiently stirred to prepare a measurement sample. The measurement sample was subjected to a hue chromatography under the following conditions to quantify the amount of HDI monomer.
The device comprises the following steps: shimadzu corporation, "GC-8A"
Column: silicone OV-17, product of Xinhe chemical Co., Ltd "
Column oven temperature: 120 deg.C
Injection/detector temperature: 160 deg.C
< NCO content (%) >
The NCO content (%) was determined by neutralizing the isocyanate groups in the test sample with an excess of 2mol/L amine and then back-titrating with 1mol/L hydrochloric acid.
Generally, the water content in commercially available solvents is low, so this test allows the sample to flocculate more rapidly after the dilution by the additional addition of water to the solvent. Examples of the application of the invention the flocculation stability of the polyisocyanate compositions was tested by formulating n-butyl acetate with a water content of 600ppm, measured by Karl-Fischer titration.
< alcohol conversion (%) >
The alcohol conversion (%) was measured by 13C-NMR nuclear magnetic resonance method: taking the alcohol hydroxyl group ratio in the mixture before reaction as M, wherein M is the mole number of the alcohol hydroxyl groups/(mole number of the alcohol hydroxyl groups + mole number of the isocyanate groups), the total ratio of allophanate and carbamate is expressed as N, and peak area integration is carried out on each component in the reaction liquid, wherein N is (allophanate integration + carbamate integration)/(allophanate integration + carbamate integration + isocyanurate integration + isocyanate integration + iminooxadiazinedione integration); the conversion of alcohol in the reaction mixture is 100% N/M.
And (3) flocculation measurement: for the measurement of flocculation, a 30% by weight solution of the polyisocyanate composition was prepared using the above-prepared n-butyl acetate having a water content of 600 ppm. 50g of the polyisocyanate composition having a mass concentration of 30% are placed in a 50ml screw cap container, displaced with nitrogen and stored hermetically sealed at 23 ℃ (ambient humidity 50% atmospheric humidity). The sample bottle was illuminated with a hard light flashlight to observe how many days (d) floes appeared in the polyisocyanate solution.
Flocculation scoring:
0: the last day before flocculation, or no flocculation throughout the test, was measured;
1 a: the first day on which only very slightly turbid or fine precipitates were visible to the naked eye was measured;
1 b: the last day on which only very slightly turbid or fine precipitates were visible to the naked eye was measured;
2: the first day of measuring clearly discernible sediments or flocs;
3: initial gelatinization;
x: no further measurements were made.
The following examples are intended to illustrate the invention, but the invention is not limited to these examples.
[ example 1 ]
588g of HDI and 195g of n-octanol (the molar ratio is 7: 3) are mixed and heated at 120 ℃, and after reaction for 1h, the conversion rate of the test alcohol is 85 percent; the reaction temperature was lowered to 60 ℃ and 1ml of a 20% n-butanol solution of 2-hydroxypropyltrimethylisooctanoic acid ammonium salt (available from Evonik Co.) was added thereto, and when the NCO content in the reaction mixture reached 29.3%, 0.19g of di-n-butyl phosphate was added thereto to terminate the reaction. Then, the mixture was purified 2 times at 150 ℃ and 0.2Torr in a thin film evaporator to obtain a polyisocyanate composition having a HDI monomer mass concentration of 0.16%.
The polyisocyanate composition thus prepared was tested to have a hue of 16Hazen, a viscosity of 2230 mPas (25 ℃ C.), an NCO content of 19.4%, an A value of 0.25, a B value of 0.025 and a calculated C value of 0.1.
[ example 2 ]
756g of HDI and 51g of n-hexanol (the molar ratio is 9: 1) are mixed and heated at 100 ℃, and after reaction for 1h, the conversion rate of the test alcohol is 82%; the reaction temperature was lowered to 60 ℃ and 1ml of a 20% n-butanol solution of 2-hydroxypropyltrimethylisooctanoic acid ammonium salt (available from Evonik Co.) was added thereto, and when the NCO content in the reaction mixture reached 38.1%, 0.19g of di-n-butyl phosphate was added thereto to terminate the reaction. Then, the mixture was purified 2 times at 150 ℃ and 0.2Torr in a thin film evaporator to obtain a polyisocyanate composition having a HDI monomer mass concentration of 0.15%.
The polyisocyanate composition thus prepared was tested to have a chroma of 17Hazen, a viscosity of 2511 mPas (25 ℃ C.), an NCO content of 21.6%, an A value of 0.05, a B value of 0.005 and a calculated C value of 0.1.
[ example 3 ]
Mixing 672g of HDI and 102g of n-hexanol (the molar ratio is 8: 2), heating at 100 ℃, and after reacting for 2 hours, testing the conversion rate of alcohol to be 88%; the reaction temperature was lowered to 60 ℃ and 1ml of a 20% n-butanol solution of 2-hydroxypropyltrimethylisooctanoic acid ammonium salt (available from Evonik Co.) was added thereto, and when the NCO content in the reaction mixture reached 36.0%, 0.19g of di-n-butyl phosphate was added thereto to terminate the reaction. Then, the mixture was purified 2 times at 150 ℃ and 0.2Torr in a thin film evaporator to obtain a polyisocyanate composition having a HDI monomer mass concentration of 0.16%.
The polyisocyanate composition thus prepared was tested to have a hue of 16Hazen, a viscosity of 2452 mPa.s (25 ℃ C.), an NCO content of 20.5%, an A value of 0.16, a B value of 0.008 and a calculated C value of 0.05.
[ example 4 ]
Mixing 672g of HDI and 102g of n-hexanol (the molar ratio is 8: 2), heating at 80 ℃, and testing the conversion rate of alcohol to be 77% after reacting for 1 h; the reaction temperature was lowered to 70 ℃ and 1ml of a 20% N, N-trimethyl-N-hydroxypropyl formic acid quaternary ammonium salt (purchased from national reagent) N-butyl alcohol solution was added, and when the NCO content in the reaction solution reached 36.2%, 0.25g of di-N-butyl phosphate was added to terminate the reaction. Then, the mixture was purified 2 times at 150 ℃ and 0.2Torr in a thin film evaporator to obtain a polyisocyanate composition having a HDI monomer mass concentration of 0.15%.
The polyisocyanate composition thus prepared was tested to have a hue of 16Hazen, a viscosity of 2366 mPas (25 ℃ C.), an NCO content of 20.6%, an A value of 0.14, a B value of 0.028 and a calculated C value of 0.2.
[ example 5 ]
Mixing 672g of HDI and 102g of n-hexanol (the molar ratio is 8: 2), heating at 70 ℃, and testing the alcohol conversion rate to be 68% after reacting for 1 h; the reaction temperature was lowered to 60 ℃ and 1ml of a 20% N, N-trimethyl-N-hydroxypropyl formic acid quaternary ammonium salt (purchased from national reagent) N-butyl alcohol solution was added, and when the NCO content in the reaction solution reached 37.7%, 0.25g of di-N-butyl phosphate was added to terminate the reaction. Then, the mixture was purified 2 times at 150 ℃ and 0.2Torr in a thin film evaporator to obtain a polyisocyanate composition having a HDI monomer mass concentration of 0.15%.
The polyisocyanate composition thus prepared was tested to have a hue of 16Hazen, a viscosity of 2106 mPas (25 ℃ C.), an NCO content of 19.3%, an A value of 0.32, a B value of 0.096 and a calculated C value of 0.3.
[ example 6 ]
Mixing 672g of HDI and 102g of n-hexanol (the molar ratio is 8: 2), heating at 60 ℃, and testing the alcohol conversion rate to be 62% after reacting for 1 h; while maintaining the reaction temperature at 60 ℃, 1ml of a 20% N, N-trimethyl-N-hydroxypropyl formic acid quaternary ammonium salt (purchased from national reagent) N-butyl alcohol solution was added, and when the NCO content in the reaction solution reached 37.4%, 0.25g of di-N-butyl phosphate was added to terminate the reaction. Then, the mixture was purified 2 times at 150 ℃ and 0.2Torr in a thin film evaporator to obtain a polyisocyanate composition having a HDI monomer mass concentration of 0.15%.
The polyisocyanate composition thus prepared was tested to have a hue of 16Hazen, a viscosity of 2106 mPas (25 ℃ C.), an NCO content of 19.3%, an A value of 0.30, a B value of 0.12 and a calculated C value of 0.4.
[ example 7 ]
Mixing 888g IPDI and 40.8g n-hexanol (molar ratio is 10: 1), heating at 90 ℃, and after reacting for 1h, testing the conversion rate of alcohol to be 78%; the reaction temperature was lowered to 70 ℃ and 1ml of a 20% N, N-trimethyl-N-hydroxypropyl quaternary ammonium formate (purchased from national reagent) N-butanol solution was added, and when the NCO content in the reaction solution reached 29.1%, 0.25g of di-N-butyl phosphate was added to terminate the reaction. Then, the mixture was purified 2 times at 150 ℃ and 0.2Torr in a thin film evaporator to obtain a polyisocyanate composition having a HDI monomer mass concentration of 0.15%.
The polyisocyanate composition thus prepared was tested to have a hue of 18Hazen, a viscosity of 7586 mPas (25 ℃ C.), an NCO content of 17.2%, an A value of 0.09, a B value of 0.015 and a calculated C value of 0.17.
[ example 8 ]
Mixing 888g IPDI and 40.8g n-hexanol (molar ratio is 10: 1), heating at 60 ℃, and after reacting for 1h, testing the conversion rate of alcohol to be 63%; the reaction temperature was raised to 70 ℃ and 1ml of a 20% N-butanol solution of N, N, N-trimethyl-N-hydroxypropylformic acid quaternary ammonium salt (purchased from Takara Shuzo Co., Ltd.) was added, and when the NCO content in the reaction solution reached 29.0%, 0.25g of di-N-butyl phosphate was added to terminate the reaction. Then, the mixture was purified 2 times at 150 ℃ and 0.2Torr in a thin film evaporator to obtain a polyisocyanate composition having a HDI monomer mass concentration of 0.15%.
The polyisocyanate composition thus prepared was tested to have a hue of 18Hazen, a viscosity of 7954 mPas (25 ℃ C.), an NCO content of 17.0%, an A value of 0.08, a B value of 0.044 and a calculated C value of 0.55.
Comparative example 1
588g of HDI and 195g of n-octanol (molar ratio 7: 3) are mixed and heated at 50 ℃ for 1h, and the conversion rate of the test alcohol is 49%; the reaction temperature was adjusted to 60 ℃ and 1ml of a 20% n-butanol solution of 2-hydroxypropyltrimethylisooctanoic acid ammonium salt (available from Evonik Co.) was added thereto, and when the NCO content in the reaction mixture reached 29.9%, 0.19g of di-n-butyl phosphate was added thereto to terminate the reaction. Then, the mixture was purified 2 times at 150 ℃ and 0.2Torr in a thin film evaporator to obtain a polyisocyanate composition having a HDI monomer mass concentration of 0.16%.
The polyisocyanate composition thus prepared was tested to have a color of 22Hazen, a viscosity of 2610 mPas (25 ℃ C.), an NCO content of 20.2%, an A value of 0.28, a B value of 0.196 and a calculated C value of 0.7.
Comparative example 2
Mixing 672g of HDI and 102g of n-hexanol (the molar ratio is 8: 2), heating at 150 ℃, and testing the alcohol conversion rate to be 92% after reacting for 1 h; the reaction temperature was lowered to 60 ℃ and 3ml of a 20% n-butanol solution of 2-hydroxypropyltrimethylisooctanoic acid ammonium salt (available from Evonik Co.) was added thereto, and when the NCO content in the reaction mixture reached 35.9%, 0.19g of di-n-butyl phosphate was added thereto to terminate the reaction. Then, the mixture was purified 2 times at 150 ℃ and 0.2Torr in a thin film evaporator to obtain a polyisocyanate composition having a HDI monomer mass concentration of 0.16%.
The polyisocyanate composition thus prepared was tested to have a hue of 19Hazen, a viscosity of 2592 mPas (25 ℃ C.), an NCO content of 20.3 mass%, an A value of 0.17, a B value of 0.11 and a calculated C value of 0.65.
Comparative example 3
Mixing 672g of HDI and 102g of n-hexanol (the molar ratio is 8: 2), heating at 150 ℃, and after reacting for 2 hours, testing the alcohol conversion rate to be 95%; the reaction temperature was lowered to 60 ℃ and 1ml of a 20% n-butanol solution of 2-hydroxypropyltrimethylisooctanoic acid ammonium salt (available from Evonik Co.) was added thereto, and when the NCO content in the reaction solution reached 35.4%, 0.19g of di-n-butyl phosphate was added thereto to terminate the reaction. Then, the mixture was purified 2 times at 150 ℃ and 0.2Torr in a thin film evaporator to obtain a polyisocyanate composition having a HDI monomer mass concentration of 0.16%.
The polyisocyanate composition thus prepared was tested to have a hue of 19Hazen, a viscosity of 2711 mPas (25 ℃ C.), an NCO content of 19.2 mass%, an A value of 0.18, a B value of 0.144 and a calculated C value of 0.8.
Comparative example 4
Mixing 888g IPDI and 40.8g n-hexanol (molar ratio is 10: 1), heating at 150 ℃, and after reacting for 1h, testing the alcohol conversion rate to be 93%; the reaction temperature was lowered to 70 ℃ and 1ml of a 20% N, N-trimethyl-N-hydroxypropyl quaternary ammonium formate (purchased from national reagent) N-butanol solution was added, and when the NCO content in the reaction solution reached 29.1%, 0.25g of di-N-butyl phosphate was added to terminate the reaction. Then, the mixture was purified 2 times at 150 ℃ and 0.2Torr in a thin film evaporator to obtain a polyisocyanate composition having a HDI monomer mass concentration of 0.15%.
The polyisocyanate composition thus prepared was tested to have a hue of 18Hazen, a viscosity of 7844 mPas (25 ℃ C.), an NCO content of 17.3%, an A value of 0.095, a B value of 0.061 and a calculated C value of 0.64.
[ application example ]
Flocculation experiment: the polyisocyanate compositions prepared in each example and comparative example were each diluted to 30% by mass with n-butyl acetate having a water content of 600ppm, stored hermetically at room temperature for more than 300 days, subjected to flocculation/precipitation experiments (in days) and the results are shown in Table 1:
TABLE 1 flocculation/precipitation test results
Comparing the results of the above experiments, the polyisocyanate composition of comparative example 3 showed significantly poorer open flocculation stability than the other samples and showed flocculation after only 25 days of storage. The polyisocyanate compositions prepared in comparative examples 1-2 showed improved flocculation stability compared to the polyisocyanate composition of comparative example 3, but still inferior to the inventive examples. It can be seen that the flocculation stability of the diluted sample of the polyisocyanate compositions of examples 1 to 6 is significantly improved as compared with the comparative example, and in particular, the flocculation stability is excellent when the molar ratio of urea groups/urea groups linked to isocyanurate rings in the polyisocyanate composition is less than 0.3:1 (see examples 1 to 5 and 7), and the sample is stored at room temperature for 300 days.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.
Claims (9)
1. A flocculation-stable polyisocyanate composition prepared by reacting a (cyclo) aliphatic diisocyanate with a mono-or diol, characterized in that the molar ratio allophanate/allophanate linked to the isocyanurate ring in the composition is 0.001 to 0.6:1, preferably 0.001 to 0.4:1, more preferably 0.001 to 0.3: 1.
2. A flocculation-stable polyisocyanate composition according to claim 1, wherein the molar ratio of allophanate groups to isocyanurate groups in the composition is from 0.05 to 0.4:1, preferably from 0.05 to 0.3: 1.
3. A flocculation-stable polyisocyanate composition according to claim 1 or 2, wherein the (cyclo) aliphatic diisocyanate is at least one of tetramethylene-1, 4-diisocyanate, pentamethylene-1, 5-diisocyanate, hexamethylene-1, 6-diisocyanate, lysine diisocyanate, isophorone diisocyanate, trimethylhexyl diisocyanate, dicyclohexylmethane diisocyanate, norbornane dimethylene isocyanate, preferably at least one of hexamethylene-1, 6-diisocyanate and isophorone diisocyanate.
4. A flocculation-stable polyisocyanate composition according to claim 3, wherein the mono-or diol is at least one of a linear or branched mono-or diol having 1 to 10 carbon atoms.
5. A process for the preparation of a flocculation-stabilized polyisocyanate composition according to any one of claims 1 to 4, comprising the steps of:
the first step is as follows: using (cyclo) aliphatic diisocyanate and monohydric or dihydric alcohol as starting materials to react at 60-120 ℃, preferably 80-110 ℃ to obtain a reaction solution I;
the second step is that: taking the reaction liquid I obtained in the first step as a raw material, and continuously reacting in the presence of a catalyst to obtain a reaction liquid II;
the third step: after the reaction, the unreacted (cyclo) aliphatic diisocyanate was separated by thin film evaporation.
6. A process for the preparation of a flocculation-stable polyisocyanate composition according to claim 5, wherein the reaction solution I is stopped at a mono-or diol conversion of 60 to 90%.
7. A process for the preparation of a flocculation-stable polyisocyanate composition according to claim 5 or 6, wherein in the second step the reaction catalyst is at least one of tetramethylammonium acetate, dodecyltrimethyloctylamine, 2-hydroxypropyltrimethylisooctylamine salt, N, N, N-trimethyl-N-hydroxypropylformic acid quaternary ammonium salt.
8. A process for the preparation of a flocculation-stable polyisocyanate composition according to claim 7, wherein the second reaction temperature is 50 to 100 ℃, preferably 60 to 90 ℃.
9. A process for the preparation of a flocculation-stabilized polyisocyanate composition according to claim 8, characterized in that the reaction is terminated by adding a terminating agent, preferably a phosphorus or sulfur containing acid or an acid ester thereof, more preferably at least one of dibutyl phosphate, dioctyl phosphate, dimethyl sulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110154032.7A CN112940222B (en) | 2021-02-04 | 2021-02-04 | Flocculation-stable polyisocyanate composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110154032.7A CN112940222B (en) | 2021-02-04 | 2021-02-04 | Flocculation-stable polyisocyanate composition and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112940222A true CN112940222A (en) | 2021-06-11 |
| CN112940222B CN112940222B (en) | 2023-05-26 |
Family
ID=76243751
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110154032.7A Active CN112940222B (en) | 2021-02-04 | 2021-02-04 | Flocculation-stable polyisocyanate composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112940222B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111094382A (en) * | 2017-09-20 | 2020-05-01 | 巴斯夫欧洲公司 | Process for preparing polyisocyanates of (cyclo) aliphatic diisocyanates which are stable to flocculation in solvents |
| CN115124483A (en) * | 2022-06-02 | 2022-09-30 | 万华化学集团股份有限公司 | Modified isocyanate and polyurea elastomer |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010016623A1 (en) * | 2000-02-05 | 2001-08-23 | Basf Aktiengesellschaft | Storage-stable polyisocyanates |
| CN1469889A (en) * | 2000-10-17 | 2004-01-21 | ������������ʽ���� | Process for preparation of polyisocyanate composition |
| US20130109793A1 (en) * | 2011-10-28 | 2013-05-02 | Harald Schaefer | Process for preparing polyisocyanates which are flocculation-stable in solvents from (cyclo)aliphatic diisocyanates |
| CA2916047A1 (en) * | 2013-06-27 | 2014-12-31 | Asahi Kasei Chemicals Corporation | Polyisocyanate composition and method of manufacturing the same, blocked polyisocyanate composition and method of manufacturing the same, resin composition, curable resin composition and hardened material |
| CN105418886A (en) * | 2014-09-16 | 2016-03-23 | 旭化成化学株式会社 | Polyisocyanates composition, coating composition, and coating method |
| CN106255710A (en) * | 2014-05-02 | 2016-12-21 | 旭化成株式会社 | Polyisocyanates solidfied material and the manufacture method of polyisocyanates solidfied material |
| CN107304244A (en) * | 2016-04-18 | 2017-10-31 | 合肥科天水性科技有限责任公司 | A kind of polyisocyantates composition of modification and preparation method thereof |
| CN111094382A (en) * | 2017-09-20 | 2020-05-01 | 巴斯夫欧洲公司 | Process for preparing polyisocyanates of (cyclo) aliphatic diisocyanates which are stable to flocculation in solvents |
| CN112225857A (en) * | 2020-09-25 | 2021-01-15 | 万华化学集团股份有限公司 | Isocyanurate-containing polyisocyanate composition with stable chromaticity and preparation method thereof |
-
2021
- 2021-02-04 CN CN202110154032.7A patent/CN112940222B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010016623A1 (en) * | 2000-02-05 | 2001-08-23 | Basf Aktiengesellschaft | Storage-stable polyisocyanates |
| CN1469889A (en) * | 2000-10-17 | 2004-01-21 | ������������ʽ���� | Process for preparation of polyisocyanate composition |
| US20130109793A1 (en) * | 2011-10-28 | 2013-05-02 | Harald Schaefer | Process for preparing polyisocyanates which are flocculation-stable in solvents from (cyclo)aliphatic diisocyanates |
| CA2916047A1 (en) * | 2013-06-27 | 2014-12-31 | Asahi Kasei Chemicals Corporation | Polyisocyanate composition and method of manufacturing the same, blocked polyisocyanate composition and method of manufacturing the same, resin composition, curable resin composition and hardened material |
| CN106255710A (en) * | 2014-05-02 | 2016-12-21 | 旭化成株式会社 | Polyisocyanates solidfied material and the manufacture method of polyisocyanates solidfied material |
| CN105418886A (en) * | 2014-09-16 | 2016-03-23 | 旭化成化学株式会社 | Polyisocyanates composition, coating composition, and coating method |
| CN107304244A (en) * | 2016-04-18 | 2017-10-31 | 合肥科天水性科技有限责任公司 | A kind of polyisocyantates composition of modification and preparation method thereof |
| CN111094382A (en) * | 2017-09-20 | 2020-05-01 | 巴斯夫欧洲公司 | Process for preparing polyisocyanates of (cyclo) aliphatic diisocyanates which are stable to flocculation in solvents |
| CN112225857A (en) * | 2020-09-25 | 2021-01-15 | 万华化学集团股份有限公司 | Isocyanurate-containing polyisocyanate composition with stable chromaticity and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111094382A (en) * | 2017-09-20 | 2020-05-01 | 巴斯夫欧洲公司 | Process for preparing polyisocyanates of (cyclo) aliphatic diisocyanates which are stable to flocculation in solvents |
| US11542356B2 (en) | 2017-09-20 | 2023-01-03 | Basf Se | Method for producing polyisocyanates of (cyclo)aliphatic diisocyanates which are flocculation-stable in solvents |
| CN115124483A (en) * | 2022-06-02 | 2022-09-30 | 万华化学集团股份有限公司 | Modified isocyanate and polyurea elastomer |
| CN115124483B (en) * | 2022-06-02 | 2023-08-11 | 万华化学集团股份有限公司 | Modified isocyanate and polyurea elastomer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112940222B (en) | 2023-05-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3115386B1 (en) | Isocyanurate composition | |
| Cakic et al. | The waterborne polyurethane dispersions based on polycarbonate diol: Effect of ionic content | |
| CN112940222B (en) | Flocculation-stable polyisocyanate composition and preparation method thereof | |
| EP3309186A1 (en) | Polyisocyanate composition, polyurethane resin, two-liquid curable polyurethane composition, coating material, and adhesive material | |
| US9988481B2 (en) | Polyisocyanate composition, coating composition, coating film and method for producing same, and humidity stabilization method | |
| CZ301652B6 (en) | Polyurethane solutions having alkoxysilane structural units, process of their preparation, their use, coatings produces therefrom and products including such coatings | |
| TWI679218B (en) | Polyisocyanate composition, polyurethane resin, two-liquid curing type polyurethane composition and coating material | |
| CN107674173B (en) | Waterborne polyurethane crosslinking agent and preparation method thereof | |
| EP3763793A1 (en) | Polyaspartic coating composition, coating film, and coating article | |
| US10189945B2 (en) | Method for producing light-coloured TDI-polyisocyanates | |
| Zhang et al. | Transparent polyester polyol-based polyurethane coatings: the effect of alcohols | |
| US20170130072A1 (en) | Heur thickener | |
| CN110760055B (en) | Polyisocyanate composition and preparation method thereof | |
| CN104892896A (en) | Hyperbranched blocked isocyanate, preparation method therefor and application thereof to coating | |
| CA2502406C (en) | Moisture-curing prepolymers | |
| EP4180441A1 (en) | Alkylene-oxide-added polyol composition, polyurethane using same, and hot-melt adhesive comprising same | |
| EP3981814A1 (en) | Polyol composition comprising anhydrosugar alcohols and anhydrosugar alcohol polymer | |
| CN107207699B (en) | Polyisocyanate composition, method for producing same, coating composition, aqueous coating composition, and coated substrate | |
| CN114085354B (en) | Process for preparing polyisocyanate composition by using recycled monomer | |
| CN100390210C (en) | High weatherability resin, preparation method thereof and coating composition containing the same | |
| CN114276520B (en) | Blocked polyisocyanate composition and preparation method and application thereof | |
| JP5183025B2 (en) | Method for producing polyisocyanate composition | |
| Gogoi et al. | Effect of reaction time on the synthesis and properties of isocyanate terminated polyurethane prepolymer | |
| CN116162223A (en) | Polyisocyanate composition obtained by mixing and polymerizing aliphatic diisocyanate and aromatic diisocyanate | |
| KR20210019036A (en) | Isocyanate prepolymer, moisture-curing polyurethane and eco-friendly adhesive composition comprising the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |