CN112940222B - Flocculation-stable polyisocyanate composition and preparation method thereof - Google Patents
Flocculation-stable polyisocyanate composition and preparation method thereof Download PDFInfo
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- CN112940222B CN112940222B CN202110154032.7A CN202110154032A CN112940222B CN 112940222 B CN112940222 B CN 112940222B CN 202110154032 A CN202110154032 A CN 202110154032A CN 112940222 B CN112940222 B CN 112940222B
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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
- 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
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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
- 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
Abstract
The invention discloses a flocculation-stable polyisocyanate composition and a preparation method thereof, wherein the polyisocyanate composition is prepared by reacting alicyclic (cyclo) diisocyanate and monohydric or dihydric alcohol, and the molar ratio of allophanate to allophanate connected with isocyanurate rings is 0.001-0.6:1, preferably 0.001-0.4:1, more preferably 0.001-0.3:1. The present invention can provide a polyisocyanate composition excellent in flocculation stability under moisture conditions, as compared with the prior art, without adding any additives.
Description
Technical Field
The invention relates to a polyisocyanate composition, in particular to a polyisocyanate composition with stable flocculation and a preparation method thereof.
Background
Isocyanates are used for the preparation of polyurethane coatings, in particular aliphatic isocyanate products, which have good weather resistance and chemical stability and are therefore used for a long time in a wide variety of 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 multiple opening and closing processes are the main reasons for flocculation. The prior art mostly solves the flocculation problem of isocyanates by adding additionally water scavengers, such as tetradiphosphate in CN110621712a, trialkyltin chloride in EP2038746 (A1), bis trimethylsilylacetamide or hexamethyldisilazane in US2008257214 (A1) etc., but these compounds have to be added stoichiometrically and the decomposition products formed consume NCO groups, affecting downstream applications. Therefore, it is important to investigate how to obtain a polyisocyanate composition which is excellent in flocculation stability and low in viscosity without using any additives.
Disclosure of Invention
The purpose of the present invention is to provide a polyisocyanate composition that has excellent flocculation stability. The present invention has been completed by unexpectedly finding that by controlling the distribution of an alcohol-derived allophanate in a larger proportion in a small molecule compound during the alcohol modification of a polyisocyanate, a polyisocyanate composition having better compatibility with a large molecule polyurea produced during the opening process can be obtained, and a polyisocyanate composition which can suppress turbidity even under a wet condition and maintain a low level of viscosity can be obtained.
Another object of the present invention is to provide a process for producing a polyisocyanate composition having excellent flocculation stability.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a flocculation stable polyisocyanate composition prepared by reacting an alicyclic diisocyanate with a mono-or dihydric alcohol, wherein the molar ratio of allophanate to allophanate linked to the isocyanurate ring is from 0.001 to 0.6:1, preferably from 0.001 to 0.4:1, more preferably from 0.001 to 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, etc.
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 represented by the formula (1) includes both a small molecule allophanate formed from an isocyanate group of a diisocyanate and a urethane group (represented by the formula (3)) formed from a diisocyanate group and a hydroxyl group of a monohydric or dihydric alcohol, and a large molecule allophanate further linked to an isocyanurate ring represented by the following formulas (4), (5), (6):
the present inventors have surprisingly found that the presence of small allophanate compounds which are not linked to isocyanurate rings gives better compatibility of the polyisocyanate composition with the macromolecular polyureas which are produced during the opening process, which gives better flocculation stability of the polyisocyanate composition.
The molar ratio of allophanate to 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 larger proportion of allophanate groups exists in a small molecule form, which results in good compatibility of the polyisocyanate composition with the macromolecular polyurea produced during the opening process, and thus flocculation stability. 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 allophanate/allophanate molar ratio linked to the isocyanurate ring can be determined by GPC and 13 C-NMR was obtained by combination. First, the polyisocyanate composition is subjected to 13 C-NMR measurement, the ratio was determined by measuring the signal area of the carbon atom of the carbonyl group of allophanate in the vicinity of 154.4ppm and the signal area of the carbon atom of the carbonyl group of the isocyanurate ring in the vicinity of 148.4ppm, to obtain the molar ratio A of allophanate groups to isocyanurate groups.
And secondly, obtaining the mass ratio of each component in the polyisocyanate composition by a gel chromatography method, wherein five molecules and more than five molecules of the polymer stay in the gel chromatography for 15.0-25.2 min to obtain peaks, and collecting mobile phases of the five molecules and more than five molecules of the polymer. Subjecting the collected mobile phase to 13 C-NMR test, the ratio of the signal area of the carbon atom of the carbonyl group of allophanate in the vicinity of 154.4ppm to the signal area of the carbon atom of the carbonyl group of isocyanurate ring in the vicinity of 148.4ppm was determined to obtain allophanate group and isoparaffinate groupCyanurate group molar ratio B. Finally, the allophanate/allophanate molar ratio linked to the isocyanurate ring is B/A.
Further, the molar ratio of allophanate groups to isocyanurate in the composition is from 0.05 to 0.4:1, preferably from 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, etc.
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 becomes good. By the above molar ratio being 0.4 or less, the curability of the composition system becomes good.
Further, the alicyclic 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.
Further, the monohydric or dihydric alcohol is at least one of straight-chain or branched monohydric alcohol or dihydric alcohol with 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 mono-or di-alcohol constituting the polyisocyanate composition of the present invention is not particularly limited, but the molar ratio of the mono-or di-alcohol to the alicyclic diisocyanate is preferably 0.01 to 0.5:1, and the adhesion of the polyisocyanate composition to be described later to the substrate is good and the excellent mechanical properties can be ensured even when the molar ratio of the mono-or di-alcohol to the alicyclic diisocyanate is 0.01 to 0.5:1.
The polyisocyanate composition further comprises one or more of carbamate shown in a formula (3), uretdione structure shown in a formula (7) and iminooxadiazinedione structure shown in a formula (8) which are obtained by trimerization reaction;
the uretdione structure shown in the formula (7) is formed by heating and reacting two isocyanate groups, the iminooxadiazinedione structure shown in the formula (8) is a side reaction in the process of trimerization of diisocyanate, and the content of the iminooxadiazinedione structure is greatly related to the catalyst used.
A process for preparing the aforementioned flocculation-stable polyisocyanate composition comprising the steps of:
the first step: reacting alicyclic diisocyanate with monohydric alcohol or dihydric alcohol as a starting material at 60-120 ℃, preferably 80-110 ℃ to obtain a reaction liquid I;
and a second step of: 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;
and a third step of: after the reaction, unreacted alicyclic diisocyanate was separated by thin film evaporation.
As mentioned above, the allophanate group is formed by reacting a diisocyanate group with a hydroxyl group of a mono-or dihydric alcohol and then reacting with isocyanate to obtain allophanate, and the first reaction step is carried out at a temperature range of 60 to 120 ℃ and preferably 80 to 110 ℃ to promote the formation of small molecule allophanate, and below this temperature range, the reaction is too slow, and the formation of small molecule allophanate is too low, and above this temperature range, the diisocyanate monomer itself is polymerized to form isocyanurate polymer, and the isocyanurate polymer is further reacted with a mono-or dihydric alcohol to form macromolecular allophanate, which is disadvantageous for the intended purpose of the present invention.
Further, under the aforementioned first-step reaction conditions, the progress of the reaction can be further controlled by controlling the conversion of the alcohol, and it is preferable to stop the reaction when the conversion of the monohydric or dihydric alcohol in the reaction liquid I reaches 60 to 90%. By controlling the conversion of the alcohol in the first reaction step within this range, a large portion of the alcohol can be converted to small molecule allophanate groups, which allows it to maintain small molecule allophanate morphology also during the second reaction step; the polyisocyanate composition is then prepared by a second reaction step. The present preparation process allows a greater proportion of the alcohol-derived allophanates to be distributed in 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 lead to a large amount of unreacted monohydric alcohol or dihydric alcohol remained 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 affects the reaction efficiency and the color of the reaction solution becomes poor.
Therefore, the reaction degree of the two reaction means is controlled mainly by controlling the reaction temperature and time, and the reaction progress is judged by combining the conversion rate of the alcohol because the reactivity of the different diisocyanates and the alcohol is different.
Further, the reaction catalyst in the second step is at least one of tetramethyl ammonium acetate, dodecyl trimethyl ammonium octoate, 2-hydroxypropyl trimethyl ammonium iso-octoate and N, N, N-trimethyl-N-hydroxypropyl ammonium formate. Preferably, the catalyst is added in an amount of 30 to 1000ppm, preferably 30 to 500ppm, relative to the mass of the diisocyanate monomer.
Further, the skilled person can determine the reaction temperature in the second step according to the temperature requirements of different catalysts; for the catalyst selection described above, the reaction temperature in the second step is preferably 50 to 100℃and preferably 60 to 90 ℃.
Further, the reaction is ended by adding a terminator, preferably an acid containing phosphorus or sulfur or an acidic ester thereof, more preferably at least one of dibutyl phosphate, dioctyl phosphate, dimethyl sulfate. Preferably, the terminator is added in an amount of 20 to 800ppm, preferably 20 to 400ppm, relative to the mass of the diisocyanate monomer.
Compared with the prior art, the invention has the advantages that: it is possible to provide a polyisocyanate composition excellent in flocculation stability under wet gas conditions without adding any additives; in addition, the increase in the content of small-molecule allophanate compounds in the embodiments of the invention also contributes to the reduction in the viscosity of the polyisocyanate composition, and therefore the viscosity is also at a lower level than in the case of polyisocyanate compositions which are not adjusted in any proportion at the same time, with significant advantages in application.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
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 or more polymers were peaked in the gel chromatography with a residence time of 15.0min to 25.2min, and the mobile phases of the five or more polymers were collected.
The Gel chromatography test method comprises using LC-20AD/RID-10A, and the chromatography column is composed of MZ-Gel SDplus10E3A 5 μm (8.0X100 mm), MZ-Gel SDplus 500A 5 μm (8.0X100 mm), MZ-Gel SDplus100A 5 μm (8.0X100 mm) connected in series, and Shimadzu; mobile phase: tetrahydrofuran; flow rate: 1.0mL/min; analysis time: 40min, column temperature: 35 ℃.
The molar percentage of allophanate structure is denoted by "a", a=allophanate structure/isocyanurate structure;
the mole percent of allophanate structures linked to the isocyanurate ring is denoted by "B", b=allophanate structures linked to the isocyanurate ring/isocyanurate structures;
allophanate structure/allophanate structure mole percent linked to the isocyanurate ring is denoted "C", c=b/a;
A. the test method of B was 13C-NMR. The instrument used was a Bruker400MHz instrument, sample concentration 50% (CDCl 3 solution), test conditions 100MHz, relaxation time: 4s, number of scans 2000 times, δ=77.0ppm CDCl 3 As a displacement reference.
A is a test for collecting a nuclear magnetic resonance spectrum (designated as a spectrum 1) of the composition, and B is a test for collecting a nuclear magnetic resonance spectrum (designated as a spectrum 2) of five molecules and above polymer components collected by gel chromatography, i.e., a material obtained after concentrating a mobile phase of the collected five molecules and above polymer to remove THF.
Isocyanurate structure: an absorption peak around 148.4 ppm;
allophanate structure: 154.4ppm absorption peak;
the calculation mode of A is as follows: in the spectrogram 1, the integrated value around 154.4 ppm/the integrated value around 148.4 ppm;
the calculation mode of B is as follows: in the spectrum 2, a value of a vicinity of 154.4 ppm/a value of a vicinity of 148.4ppm was integrated;
< determination of product viscosity > the viscosities of the products of examples and comparative examples were determined using a Brookfield RC/S rheometer, rotor model CC-40, thermostatic waterbath, and temperature was controlled at 25.+ -. 0.1 ℃. The shear rate is 25S-1 to 250S-1.
< determination of product colorimetry > the colorimetry of the products in the examples and comparative examples was determined using a BYK-Gardner GmbH/USA colorimeter.
< determination of mass concentration of HDI monomer >
The 20mL sample bottle was placed on a digital balance, 1g of sample was precisely weighed and added. Next, 0.04g of nitrobenzene (internal standard solution) was precisely weighed and added to a sample bottle. Finally, 9mL of ethyl acetate was added to the sample bottle, and the bottle was capped. Then, the mixture was sufficiently stirred to prepare a measurement sample. The measurement sample was subjected to a color chromatography under the following conditions, and the amount of HDI monomer was quantified.
The device comprises: "GC-8A" manufactured by Shimadzu corporation "
Column: silicones OV-17, made by Xin and chemical Co., ltd "
Column oven temperature: 120 DEG C
Injection/detector temperature: 160 DEG C
< NCO content (%) >
The NCO content (%) was obtained by neutralizing the isocyanate group in the measurement sample with an excess of 2mol/L amine and then back-titrating with 1mol/L hydrochloric acid.
Generally, the water content in the commercial solvent is low, so the test allows the sample to flocculate more rapidly after dilution by the additional addition of water to the solvent. Application example of the invention the flocculation stability of polyisocyanate compositions was tested by formulating n-butyl acetate with a water content of 600ppm, the water content being measured by Karl-Fischer titration.
< alcohol conversion (%) >
Alcohol conversion (%) was determined by 13C-NMR nuclear magnetic resonance: the ratio of the alcoholic hydroxyl groups in the mixture before the reaction is denoted as M, M=mol of the alcoholic hydroxyl groups/(mol of the alcoholic hydroxyl groups+mol of the isocyanate groups), the total ratio of the allophanate and the carbamate is denoted as N, and the peak area integration is performed on each component in the reaction solution, N= (allophanate integration+carbamate integration)/(allophanate integration+carbamate integration+isocyanurate integration+isocyanate integration+iminooxadiazinedione integration); the alcohol conversion in the reaction solution=n/m×100%.
Flocculation measurement: to measure flocculation, a 30% strength by mass 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% were placed in a 50ml screw cap container, replaced with nitrogen and stored hermetically at 23℃under a sealed atmosphere (ambient humidity: 50% atmospheric humidity). The sample bottle was illuminated with a strong light flashlight and the appearance of flocs was observed how many days (d) in the polyisocyanate solution.
Flocculation scoring:
0: the last day before flocculation was measured, or there was no flocculation throughout the test;
1a: the first day was measured with only very slight cloudiness or fine sediment visible to the naked eye;
1b: the last day of only very slight cloudiness or fine sediment visible to the naked eye was measured;
2: the first day of clearly discernible sediment or flocs was measured;
3: initial gelation;
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 (molar ratio 7:3) are mixed and heated at 120 ℃, and after 1 hour of reaction, the alcohol conversion rate is tested to be 85%; the reaction temperature was lowered to 60℃and 1ml of a 20% n-butanol solution of 2-hydroxypropyl trimethyl isooctanoate (available from Evonik Co.) was added thereto, and when the NCO content in the reaction solution reached 29.3%, 0.19g of di-n-butyl phosphate was added thereto to terminate the reaction. Next, the resultant was purified 2 times at 150℃under 0.2Torr using a thin film evaporator to obtain a polyisocyanate composition having an HDI monomer concentration of 0.16% by mass.
The polyisocyanate composition thus prepared was tested for a color 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 were mixed with 51g of n-hexanol (molar ratio 9:1) and heated at 100℃after 1h of reaction, the alcohol conversion was tested as 82%; the reaction temperature was lowered to 60℃and 1ml of a 20% n-butanol solution of 2-hydroxypropyl trimethyl isooctanoate (available from Evonik Co.) was added thereto, and when the NCO content in the reaction solution reached 38.1%, 0.19g of di-n-butyl phosphate was added thereto to terminate the reaction. Next, the resultant was purified 2 times at 150℃under 0.2Torr using a thin film evaporator to obtain a polyisocyanate composition having an HDI monomer concentration of 0.15% by mass.
The polyisocyanate composition thus prepared was tested for a color of 17Hazen, a viscosity of 2511 mPa.s (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 ]
672g of HDI and 102g of n-hexanol (molar ratio 8:2) were mixed and heated at 100℃and after 2h of reaction, the alcohol conversion was tested to 88%; the reaction temperature was lowered to 60℃and 1ml of a 20% n-butanol solution of 2-hydroxypropyl trimethyl isooctanoate (available from Evonik Co.) was added thereto, and when the NCO content in the reaction solution reached 36.0%, 0.19g of di-n-butyl phosphate was added thereto to terminate the reaction. Next, the resultant was purified 2 times at 150℃under 0.2Torr using a thin film evaporator to obtain a polyisocyanate composition having an HDI monomer concentration of 0.16% by mass.
The polyisocyanate composition thus prepared was tested for a color of 16Hazen, a viscosity of 2452 mPas (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 ]
672g of HDI and 102g of n-hexanol (molar ratio 8:2) were mixed and heated at 80℃and after 1h of reaction, the alcohol conversion was tested to be 77%; the reaction temperature was lowered to 70℃and 1ml of a 20% N-butanol solution of quaternary ammonium N, N, N-trimethyl-N-hydroxypropyl formate (available from Guogui reagent Co.) 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. Next, the resultant was purified 2 times at 150℃under 0.2Torr using a thin film evaporator to obtain a polyisocyanate composition having an HDI monomer concentration of 0.15% by mass.
The polyisocyanate composition thus prepared was tested for a color 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 ]
672g of HDI and 102g of n-hexanol (molar ratio 8:2) were mixed and heated at 70℃and after 1h of reaction, the alcohol conversion was tested as 68%; the reaction temperature was lowered to 60℃and 1ml of a 20% N-butanol solution of quaternary ammonium N, N, N-trimethyl-N-hydroxypropyl formate (available from Guogui reagent Co.) 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. Next, the resultant was purified 2 times at 150℃under 0.2Torr using a thin film evaporator to obtain a polyisocyanate composition having an HDI monomer concentration of 0.15% by mass.
The polyisocyanate composition thus prepared was tested for a color 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 ]
672g of HDI and 102g of n-hexanol (molar ratio 8:2) were mixed and heated at 60℃after 1h of reaction, the alcohol conversion was tested to 62%; the reaction temperature was kept at 60℃and 1ml of a 20% N-butanol solution of quaternary ammonium N, N, N-trimethyl-N-hydroxypropyl formate (available from Guogui reagent Co.) was added thereto, and when the NCO content in the reaction solution reached 37.4%, 0.25g of di-N-butyl phosphate was added thereto to terminate the reaction. Next, the resultant was purified 2 times at 150℃under 0.2Torr using a thin film evaporator to obtain a polyisocyanate composition having an HDI monomer concentration of 0.15% by mass.
The polyisocyanate composition thus prepared was tested for a color 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 ]
888g of IPDI were mixed with 40.8g of n-hexanol (molar ratio 10:1) and heated at 90℃after a reaction time of 1h, the alcohol conversion was tested as 78%; the reaction temperature was lowered to 70℃and 1ml of a 20% N-butanol solution of quaternary ammonium N, N, N-trimethyl-N-hydroxypropyl formate (available from Guogui reagent Co.) 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. Next, the resultant was purified 2 times at 150℃under 0.2Torr using a thin film evaporator to obtain a polyisocyanate composition having an HDI monomer concentration of 0.15% by mass.
The polyisocyanate composition thus prepared was tested for a color 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 ]
888g of IPDI and 40.8g of n-hexanol (molar ratio 10:1) were mixed and heated at 60℃and after 1 hour of reaction, the alcohol conversion was tested to be 63%; the reaction temperature was raised to 70℃and 1ml of a 20% N-butanol solution of quaternary ammonium N, N, N-trimethyl-N-hydroxypropyl formate (available from Guogui reagent Co.) 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. Next, the resultant was purified 2 times at 150℃under 0.2Torr using a thin film evaporator to obtain a polyisocyanate composition having an HDI monomer concentration of 0.15% by mass.
The polyisocyanate composition thus prepared was tested for a color 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) were mixed and heated at 50℃for 1h, after which the alcohol conversion was tested to be 49%; the reaction temperature was adjusted to 60℃and 1ml of a 20% n-butanol solution of 2-hydroxypropyl trimethyl isooctanoate (available from Evonik Co.) was added thereto, and when the NCO content in the reaction solution reached 29.9%, 0.19g of di-n-butyl phosphate was added thereto to terminate the reaction. Next, the resultant was purified 2 times at 150℃under 0.2Torr using a thin film evaporator to obtain a polyisocyanate composition having an HDI monomer concentration of 0.16% by mass.
The polyisocyanate composition thus prepared was tested for 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
672g of HDI and 102g of n-hexanol (molar ratio 8:2) were mixed and heated at 150℃and after 1h of reaction the alcohol conversion was tested as 92%; the reaction temperature was lowered to 60℃and 3ml of a 20% n-butanol solution of 2-hydroxypropyl trimethyl isooctanoate (available from Evonik Co.) was added thereto, and when the NCO content in the reaction solution reached 35.9%, 0.19g of di-n-butyl phosphate was added thereto to terminate the reaction. Next, the resultant was purified 2 times at 150℃under 0.2Torr using a thin film evaporator to obtain a polyisocyanate composition having an HDI monomer concentration of 0.16% by mass.
The polyisocyanate composition thus prepared was found to have a color of 19Hazen, a viscosity of 2592 mPas (25 ℃ C.), an NCO content of 20.3% by mass, an A value of 0.17, a B value of 0.11 and a calculated C value of 0.65.
[ comparative example 3 ]
672g of HDI and 102g of n-hexanol (molar ratio 8:2) were mixed and heated at 150℃and after 2h of reaction the alcohol conversion was tested to 95%; the reaction temperature was lowered to 60℃and 1ml of a 20% n-butanol solution of 2-hydroxypropyl trimethyl isooctanoate (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. Next, the resultant was purified 2 times at 150℃under 0.2Torr using a thin film evaporator to obtain a polyisocyanate composition having an HDI monomer concentration of 0.16% by mass.
The polyisocyanate composition thus obtained was tested for a color of 19Hazen, a viscosity of 2711 mPas (25 ℃ C.), an NCO content of 19.2% by mass, an A value of 0.18, a B value of 0.144 and a calculated C value of 0.8.
[ comparative example 4 ]
888g of IPDI were mixed with 40.8g of n-hexanol (molar ratio 10:1) and heated at 150℃after reaction for 1h, the alcohol conversion was tested as 93%; the reaction temperature was lowered to 70℃and 1ml of a 20% N-butanol solution of quaternary ammonium N, N, N-trimethyl-N-hydroxypropyl formate (available from Guogui reagent Co.) 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. Next, the resultant was purified 2 times at 150℃under 0.2Torr using a thin film evaporator to obtain a polyisocyanate composition having an HDI monomer concentration of 0.15% by mass.
The polyisocyanate composition thus prepared was tested for a color 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 of examples and comparative examples were diluted to 30% by mass respectively using n-butyl acetate having a water content of 600ppm, stored hermetically at room temperature for more than 300 days, and subjected to flocculation/precipitation experiments (in days) with the results shown in Table 1:
TABLE 1 flocculation/precipitation experiment results
Comparing the results of the above table experiments, the polyisocyanate composition of comparative example 3 was significantly inferior to other samples in flocculation stability to open and flocs appeared only after 25 days of storage. The polyisocyanate compositions prepared in comparative examples 1-2 had improved flocculation stability over the polyisocyanate composition of comparative example 3, but still had poorer flocculation stability than the sample of the example of the invention. As can be seen, the flocculation stability of the sample after the dilution of the polyisocyanate composition in examples 1 to 6 is significantly improved over that of the composition in comparative example, and in particular, the flocculation stability is very excellent when the molar ratio of ureido groups to ureido groups linked to the isocyanurate ring in the polyisocyanate composition is less than 0.3:1 (see examples 1 to 5 and 7), and the sample is still normal after storage at room temperature for 300 days.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.
Claims (15)
1. A flocculation-stable polyisocyanate composition prepared by reacting an aliphatic (cyclo) diisocyanate with a monohydric alcohol, wherein the composition has an allophanate/allophanate molar ratio of 0.001 to 0.6:1, and wherein the latter allophanate comprises both small molecule allophanates formed from isocyanate groups and urethane groups of the diisocyanate and allophanate groups linked to the isocyanurate ring;
the molar ratio of allophanate groups to isocyanurate in the composition is 0.05 to 0.4:1.
2. The flocculation-stable polyisocyanate composition according to claim 1, wherein the molar ratio allophanate/allophanate linked to isocyanurate ring in said composition is from 0.001 to 0.4:1.
3. The flocculation-stable polyisocyanate composition according to claim 1, wherein the molar ratio allophanate/allophanate linked to isocyanurate ring in said composition is from 0.001 to 0.3:1.
4. The flocculation-stable polyisocyanate composition according to claim 1, wherein the molar ratio of allophanate groups to isocyanurate in the composition is from 0.05 to 0.3:1.
5. The flocculation-stable polyisocyanate composition according to any one of claims 1 to 4, wherein said alicyclic (cyclo) 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.
6. The flocculation-stable polyisocyanate composition according to claim 5, wherein the alicyclic diisocyanate is at least one of hexamethylene-1, 6-diisocyanate and isophorone diisocyanate.
7. The flocculation-stable polyisocyanate composition according to claim 5, wherein the monohydric alcohol is at least one of a straight chain or branched monohydric alcohol having 1 to 10 carbon atoms.
8. A process for the preparation of a flocculation-stabilised polyisocyanate composition according to any one of claims 1 to 7, comprising the steps of:
the first step: reacting alicyclic diisocyanate with monohydric alcohol as a starting material at 80-110 ℃ to obtain a reaction liquid I; stopping the reaction when the conversion rate of the monohydric alcohol reaches 60-90%;
and a second step of: 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;
and a third step of: after the reaction, unreacted alicyclic diisocyanate was separated by thin film evaporation.
9. The process for preparing flocculation-stable polyisocyanate compositions according to claim 8, wherein in the first step, reaction is carried out at 80 to 110℃to obtain reaction liquid I.
10. The method for preparing a flocculation-stable polyisocyanate composition according to claim 8 or 9, wherein the reaction catalyst in the second step is at least one of tetramethyl ammonium acetate, dodecyl trimethyl ammonium octoate, 2-hydroxypropyl trimethyl ammonium iso-octoate, and N, N-trimethyl-N-hydroxypropyl ammonium formate.
11. The process for preparing flocculation-stabilized polyisocyanate compositions according to claim 10, characterized in that the second reaction temperature is 50 to 100 ℃.
12. The process for the preparation of flocculation-stabilised polyisocyanate compositions according to claim 11, wherein the second reaction temperature is between 60 and 90 ℃.
13. The process for the preparation of a flocculation-stabilised polyisocyanate composition according to claim 11, wherein the reaction is terminated by adding a terminator.
14. A process for the preparation of a flocculation stable polyisocyanate composition according to claim 13, wherein the terminator is a phosphorus or sulphur containing acid or an acidic ester thereof.
15. The method for producing a flocculation-stable polyisocyanate composition according to claim 13, wherein the terminator is at least one of dibutyl phosphate, dioctyl phosphate, and dimethyl sulfate.
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