CN110872238B - Isocyanate stabilizer and preparation method thereof - Google Patents
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- C07—ORGANIC CHEMISTRY
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- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/18—Separation; Purification; Stabilisation; Use of additives
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C265/00—Derivatives of isocyanic acid
- C07C265/02—Derivatives of isocyanic acid having isocyanate groups bound to acyclic carbon atoms
- C07C265/04—Derivatives of isocyanic acid having isocyanate groups bound to acyclic carbon atoms of a saturated carbon skeleton
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C265/00—Derivatives of isocyanic acid
- C07C265/02—Derivatives of isocyanic acid having isocyanate groups bound to acyclic carbon atoms
- C07C265/06—Derivatives of isocyanic acid having isocyanate groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
- C07C265/08—Derivatives of isocyanic acid having isocyanate groups bound to acyclic carbon atoms of an unsaturated carbon skeleton the carbon skeleton containing rings
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C265/00—Derivatives of isocyanic acid
- C07C265/12—Derivatives of isocyanic acid having isocyanate groups bound to carbon atoms of six-membered aromatic rings
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C265/00—Derivatives of isocyanic acid
- C07C265/14—Derivatives of isocyanic acid containing at least two isocyanate groups bound to the same carbon skeleton
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/04—Carbamic acid halides
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- 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
- C08G18/71—Monoisocyanates or monoisothiocyanates
- C08G18/712—Monoisocyanates or monoisothiocyanates containing halogens
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- 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
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8083—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/8087—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C2601/14—The ring being saturated
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Abstract
The invention relates to an isocyanate stabilizer and a preparation method thereof. The isocyanate stabilizer has a structure shown as a general formula (I),
Description
Technical Field
The invention belongs to the technical field of isocyanate, and relates to an isocyanate stabilizer and a preparation method thereof.
Background
Among isocyanate compounds, since isocyanate groups have high reactivity and they tend to yellow or self-polymerize during storage, affecting downstream applications, it is essential to suppress the yellowing and self-polymerization of isocyanates by adding a stabilizer.
Currently, isocyanate compound stabilizers are typically hindered phenolic compounds, for example, U.S. Pat. No. 3,182,81 discloses 2, 6-di-tert-butyl-4-methylphenol (BHT) as an isocyanate stabilizer, and Japanese patent publication No. JP33438/1970 reports that phosphite esters such as triphenyl phosphite antioxidants have good effects, and are still widely used at present.
In addition, many other stabilizers are known, such as japanese patent JPS5036546 which discloses substituted ureas as stabilizers that can prevent yellowing of isocyanates due to sunlight or ultraviolet light; german patent DE2837770 discloses acidic substances such as perchloric acid and trifluoromethanesulfonic acid as stabilizers; US3247236 discloses the same stabilization of carbon dioxide and sulphur dioxide; japanese patent JPS 50101344A discloses organic tertiary amines as MDI stabilizers which are effective in preventing color numbers from increasing; also patent CN104718215 discloses that acyl chloride species are used as stabilizers for silicon-containing isocyanates to improve their storage stability.
However, the stability effect of the above stabilizers such as acid stabilizer perchloric acid, trifluoromethanesulfonic acid, carbon dioxide or acid chloride on m-Xylylene Diisocyanate (XDI) is poor, it is known that XDI tends to become turbid by forming a nylon-1 type polymer by self-polymerization, and it is difficult to stably store XDI at room temperature for 1 month or more with the currently used isocyanate stabilizers and the stabilizers disclosed in the above patents.
In the aspect of isocyanate application, the isocyanate compound raw material for preparing the optical resin has strict requirements on stability, and the raw material is required not to have yellowing or turbidity, so that isocyanates such as XDI (X double hydroxides) serving as the raw material of the optical resin have higher requirements on additives.
Therefore, there is an urgent need for a stabilizer capable of suppressing yellowing and clouding of isocyanate compounds, particularly XDI, due to long-term storage.
Disclosure of Invention
The present invention has been made in view of the above-mentioned disadvantages of the prior art, and an object of the present invention is to provide an isocyanate stabilizer which can prevent yellowing and clouding of isocyanate-based compounds during long-term storage and can inhibit self-polymerization of isocyanates, particularly m-Xylylene Diisocyanate (XDI). The isocyanate compound to which the stabilizer of the present invention is added can be used as a raw material for an optical polyurethane resin such as a plastic lens.
It is another object of the present invention to provide a method for preparing the isocyanate stabilizer.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an isocyanate stabilizer having the structure shown in formula (I):
wherein n is more than or equal to 1 and less than or equal to 3; e.g., n can be 1, 2, or 3;
x is chlorine or bromine;
r is selected from C1-C12 alkyl, C3-C12 cycloalkyl, C3-C12 cycloalkyl with substituent, phenyl with substituent, and five-membered or six-membered heterocyclic aromatic group containing at least one atom selected from oxygen, sulfur and nitrogen, preferably C1-C6 alkyl, C5-C6 cycloalkyl, C5-C6 cycloalkyl with substituent, phenyl and phenyl with substituent;
the substituent on the C3-C12 cycloalkyl with substituent and the substituent on the phenyl with substituent are respectively at least one of C1-C12 alkyl, C1-C12 alkoxy, halogen, nitro, ester group and cyano, and preferably at least one of C1-C4 alkyl and C1-C4 alkoxy.
The isocyanate stabilizer is preferably at least one of compounds of the following structures:
the isocyanate stabilizer is added to the isocyanate at a concentration of 1 to 2000ppm, preferably 5 to 500 ppm.
The isocyanate stabilizer is preferably mixed with the existing isocyanate stabilizer for use, and the mixing mass ratio is preferably 1: 1; the prior isocyanate stabilizer is preferably hindered phenol stabilizer, phosphite stabilizer, benzoyl chloride stabilizer, phenol, most preferably phenol.
Suitable isocyanates include monoisocyanates, and diisocyanates having the structure of formula (II)
OCN-R′-NCO
(Ⅱ)
Wherein R' is selected from C2-C18 alkyl, C3-C12 cycloalkyl, C3-C12 cycloalkyl with substituent, phenyl with substituent, naphthyl and naphthyl with substituent;
the substituent on the C3-C12 naphthenic base with the substituent, the substituent on the phenyl with the substituent and the substituent on the naphthyl with the substituent are respectively at least one of C1-C12 alkyl, alkoxy of C1-C12, halogen, nitro, ester group and cyano.
The monoisocyanate is preferably methyl isocyanate, butyl isocyanate, phenyl isocyanate or benzyl isocyanate;
the diisocyanate is preferably toluene diisocyanate, 4 '-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4' -dicyclohexylmethane diisocyanate, or m-xylylene diisocyanate.
The isocyanate is most preferably m-Xylylene Diisocyanate (XDI).
The preparation method of the isocyanate stabilizer comprises the following steps:
a) dissolving a compound of a general formula (III) in an inert organic solvent, and introducing hydrogen chloride or hydrogen bromide gas for reaction;
wherein n and R are the same as formula (I);
b) and a) carrying out filter pressing separation on the reaction system in the step a) by using nitrogen to obtain the isocyanate stabilizer.
The preparation method of the isocyanate stabilizer has the following reaction formula:
The inert organic solvent is at least one of aromatic hydrocarbon, halogenated aromatic hydrocarbon, alkane and halogenated alkane, and preferably at least one of chlorobenzene, dichlorobenzene, toluene and xylene.
The mass ratio of the compound of the general formula (III) to the inert organic solvent is 1: 10-100, preferably 1: 20-50; the molar ratio of the compound of the general formula (III) to hydrogen chloride or hydrogen bromide is 1: 2.2-20, preferably 1: 2.5-10.
The reaction temperature is controlled below 30 ℃, the flow of hydrogen chloride or hydrogen bromide is 1-20L/h per 20g of the compound of the formula (III), preferably 10L/h per 20g of the compound of the formula (III), and the reaction is completed after the hydrogen chloride is introduced.
The isocyanate to which the stabilizer of the present invention is added can inhibit self-polymerization of isocyanate itself, and is useful as a raw material for optical polyurethane resins such as plastic lenses. Effectively solves the yellowing and turbidity phenomena of the isocyanate in the long-term storage process and effectively improves the stability of the isocyanate.
Compared with the prior art, the invention has the following positive effects:
1. the isocyanate stabilizer is a compound with a carbamyl chloride or bromine structure, wherein a hindered amine structure contained in the compound can capture free radicals, so that the stability is improved; meanwhile, the structure reacts in isocyanate to release hydrogen chloride or hydrogen bromide, so that isocyanate polymerization is inhibited, a stabilizing effect is further achieved, and turbidity caused by increase of polymers is prevented.
2. The isocyanate stabilizer disclosed by the invention is simple in preparation method, is suitable for improving the long-term storage stability of isocyanate, particularly XDI, inhibiting a long-chain homopolymerized compound generated by XDI due to free radicals, preventing the isocyanate from becoming turbid after long-term storage, and prolonging the storage time to more than six months. XDI added with the stabilizing agent can obtain lens resin without optical deformation and white turbidity when used for preparing the lens resin.
Detailed Description
The invention will now be further illustrated with reference to the following examples, but is not limited thereto.
The embodiment of the invention and the comparative example have the following main raw material sources:
1. isocyanates such as XDI, MDI, HDI and the like are self-made by a conventional method;
2. the hydrogen chloride or hydrogen bromide gas comes from cigarette-table Shuangfeng gas company;
3. other reagents were obtained from Sigma Aldrich.
The performance test method of the embodiment and the comparative example comprises the following steps:
1. isocyanate color number: measured according to the method of GB/T3143-1982;
2. nuclear magnetic analyses were tested using Bruker 400 MHz.
Preparation of isocyanate stabilizer
Example 1
The preparation method of the isocyanate stabilizer comprises the following steps:
20g of pure MDI is added into a reaction bottle, the pure MDI is dissolved in 400g of chlorobenzene, 29.2g of hydrogen chloride gas (the molar ratio of the MDI to the hydrogen chloride is 1:10) is introduced at the speed of 10L/h, the reaction temperature is controlled below 30 ℃, white solid in reaction liquid is separated out by pressure filtration of 0.3Mpa nitrogen after the reaction is finished, and the fresh chlorobenzene is washed and dried to obtain 25.5g of white solid matter, namely the isocyanate stabilizer shown in the formula (Ia), and the yield is 99.0%.
Nuclear magnetic data of1H NMR(400MHz,DMSO)δ9.15(b,1.2H),7.59-7.50(m,4H),7.25-7.20(m,4H),3.96(s,2H)；13C NMR(100MHz,DMSO):δ133.5,133.4,129.9,127.6,122.1,41.3.
Example 2
The preparation method of the isocyanate stabilizer comprises the following steps:
20g of pure MDI is added into a reaction bottle, the pure MDI is dissolved in 400g of chlorobenzene, 7.30g of hydrogen chloride gas (the molar ratio of the MDI to the hydrogen chloride is 1:2.5) is introduced at the speed of 10L/h, the reaction temperature is controlled to be less than 30 ℃, after the reaction is finished, IIIIV is subjected to pressure filtration by using nitrogen with the pressure of 0.3Mpa to separate white solid from reaction liquid, and fresh chlorobenzene is washed and dried to obtain 12.8g of white solid matter, namely the isocyanate stabilizer shown in the formula (Ia), wherein the yield is 50.0%.
Example 3
The preparation method of the isocyanate stabilizer comprises the following steps:
adding 20g of pure MDI into a reaction bottle, dissolving the pure MDI in 400g of chlorobenzene, introducing 64.7g of hydrogen bromide gas (the molar ratio of the MDI to the hydrogen bromide is 1:10) at the speed of 10L/h, controlling the reaction temperature to be less than 30 ℃, after the reaction is finished, performing pressure filtration by using nitrogen with the pressure of 0.3Mpa to separate white solid in reaction liquid, washing and drying fresh chlorobenzene to obtain 32.3g of white solid matter, namely the isocyanate stabilizer shown in the formula (Ib), wherein the yield is 98.0%.
Nuclear magnetic data of1H NMR(400MHz,DMSO)δ9.17(b,1.2H),7.59-7.51(m,4H),7.26-7.20(m,4H),3.94(s,2H)；13C NMR(100MHz,DMSO):δ133.4,129.9,127.6,125.5,122.1,41.3.
Example 4
The preparation method of the isocyanate stabilizer comprises the following steps:
adding 20g of phenyl isocyanate into a reaction bottle, dissolving the phenyl isocyanate in 400g of chlorobenzene, introducing 30.6g of hydrogen chloride gas (the molar ratio of the phenyl isocyanate to the hydrogen chloride is 1:5) at the speed of 10L/h, controlling the reaction temperature to be less than 30 ℃, after the reaction is finished, performing pressure filtration by using nitrogen with the pressure of 0.3Mpa to separate white solid in a reaction liquid, washing and drying fresh chlorobenzene to obtain 25.8g of white solid matter, namely the isocyanate stabilizer shown in the formula (ic), wherein the yield is 99.0%.
Nuclear magnetic data of1H NMR(400MHz,DMSO)δ9.15(b,0.6H),7.61-7.59(m,2H),7.43-7.19(m,3H)；13C NMR(100MHz,DMSO):δ135.9,133.4,128.9,128.0,121.6.
Example 5
The preparation method of the isocyanate stabilizer comprises the following steps:
20g of triphenylmethane triisocyanate was added into a reaction flask, dissolved in 1000g of chlorobenzene, 19.9g of hydrogen chloride gas was introduced at a rate of 10L/h (molar ratio of triphenylmethane triisocyanate to hydrogen chloride: 1:10), the reaction temperature was controlled at <30 ℃, after the reaction was completed, white solid in the reaction solution was separated by pressure filtration using 0.3Mpa of nitrogen, and 24.6g of white solid, i.e., the isocyanate stabilizer represented by formula (Id), was obtained by washing and drying fresh chlorobenzene with a yield of 95.0%.
Nuclear magnetic data of1H NMR(400MHz,DMSO)δ9.16(b,1.8H),7.61-7.50(m,6H),7.26-7.19(m,6H),5.48(s,1H)；13C NMR(100MHz,DMSO):δ144.9,135.9,133.4,129.8,122.1,55.2.
Example 6
The preparation method of the isocyanate stabilizer comprises the following steps:
20g of HDI was dissolved in 1000g of chlorobenzene in a reaction flask, approximately 43.4g of hydrogen chloride gas (molar ratio 1:10 of HDI to hydrogen chloride) was introduced at a rate of 10L/h, the reaction temperature was controlled at <30 ℃ and the introduction of hydrogen chloride was completed, a white solid in the reaction solution was separated by pressure filtration using 0.3MPa of nitrogen, and the reaction solution was washed with fresh chlorobenzene and dried to obtain 27.5g of a white solid substance, i.e., an isocyanate stabilizer represented by the formula (ie), with a yield of 96.0%.
Nuclear magnetic data of1H NMR(400MHz,DMSO)δ8.03(b,1.2H),3.20-3.16(m,4H),1.54-1.50(m,4H),1.31-1.27(m,4H),13C NMR(100MHz,DMSO):δ136.2,41.8,29.1,26.4。
Example 7
The preparation method of the isocyanate stabilizer comprises the following steps:
20g of XDI was dissolved in 500g of toluene in a reaction flask, and about 23.3g of hydrogen chloride gas (molar ratio of XDI to hydrogen chloride: 1:6) was introduced at a rate of 10L/h to control the reaction temperature<After the reaction is finished at 30 ℃, white solid in the reaction liquid is separated out by using nitrogen of 0.3Mpa through pressure filtration, and the white solid is washed by fresh toluene and dried to obtain 27.4g of white solid matter, namely the isocyanate stabilizer shown in the formula (if), and the yield is 99.0%. . Nuclear magnetic data of1H NMR(400MHz,DMSO)δ8.05(b,1.2H),7.45-7.40(m,1H),7.10-7.04(m,3H),4.25-4.20(m,4H),13C NMR(100MHz,DMSO):δ137.4,136.5,128.3,126.7,124.9,45.4。
The application of the isocyanate stabilizer comprises the following steps:
the XDI preparation method comprises the following steps: in a four-neck flask, 136g of XDA is dissolved in 1564g of o-dichlorobenzene, hydrogen chloride gas is introduced at the rate of 100L/h for salt forming reaction, the temperature is controlled to be less than 30 ℃, milky viscous substance is obtained after salt forming is finished, the temperature is increased to 150 ℃, phosgene is introduced at the rate of 50L/h for photochemical reaction, and unreacted phosgene is condensed and recycled and enters an alkali washing system for destruction. After the reaction solution is clarified and the photochemical reaction is finished, nitrogen is introduced to drive out unreacted phosgene, and after the solvent is subsequently removed, the XDI pure product (the purity is 99.8 percent and the hydrolytic chlorine is 50ppm) is obtained by rectification and separation.
Storage stability test of examples 8 to 17 and comparative examples 1 to 5:
the XDI purified products (purity 99.8%, hydrolysis chlorine 50ppm) were charged with different amounts of the stabilizer, respectively, as shown in Table 1, stored in 1000mL aluminum bottles, stored at 20 ℃ under nitrogen protection, and measured for color number and turbidity every one week, and the test was stopped when the color number was greater than 20hazen or when turbidity was observed visually, as shown in Table 1.
TABLE 1 XDI stability data
As can be seen from Table 1, the stabilizer of the invention has good stability effect under the condition of good protection, when the amount of the XDI added is 5ppm, the storage time can reach more than 24 weeks, and the color number turbidity is not obviously increased. In comparative examples 2 to 4, the conventional hindered phenol BHT, phosphite stabilizer and benzoyl chloride stabilizer were used, which had poor stability to XDI, and were unable to inhibit self-polymerization of isocyanate, and cloudy turbidity was observed in less than two weeks. The comparative example is phenol, which is the better effect, and the stability is higher, but the XDI has turbidity after only 4 weeks of storage, which is still far lower than the stabilizer of the invention.
It is noted that the stabilizer of the present invention may be used in combination with the above-mentioned stabilizer to provide a better stability to XDI.
Claims (17)
1. The use of a compound of formula (I) as an isocyanate stabiliser, the compound of formula (I) having the structure:
wherein n is more than or equal to 1 and less than or equal to 3;
x is chlorine or bromine;
r is selected from C1-C12 alkyl, C3-C12 cycloalkyl, C3-C12 cycloalkyl with substituent, phenyl with substituent, and five-membered or six-membered heterocyclic aromatic group containing at least one atom selected from oxygen, sulfur and nitrogen;
the substituent on the C3-C12 naphthenic base with substituent and the substituent on the phenyl with substituent are respectively at least one of C1-C12 alkyl, C1-C12 alkoxy, halogen, nitro, ester group and cyano;
or, the compound shown in the formula (I) is at least one of the compounds with the following structures:
2. use according to claim 1, characterized in that: in the formula (I), the compound is shown in the specification,
n is 1, 2 or 3;
r is C1-C6 alkyl, C5-C6 cycloalkyl, C5-C6 cycloalkyl with substituent, phenyl and phenyl with substituent.
3. Use according to claim 1, characterized in that: the substituent on the C3-C12 naphthenic base with the substituent and the substituent on the phenyl with the substituent are respectively at least one of C1-C4 alkyl and C1-C4 alkoxy.
4. Use according to claim 1, characterized in that: the compound shown in the formula (I) is at least one of the following compounds:
5. use according to claim 1, characterized in that: the addition concentration of the isocyanate is 1-2000 ppm, wherein 1ppm is not included.
6. Use according to claim 5, characterized in that: the addition concentration of the isocyanate is 5-500 ppm.
7. Use according to claim 1, characterized in that: mixing with isocyanate stabilizer.
8. Use according to claim 7, characterized in that: the mass ratio of the isocyanate stabilizer to the existing isocyanate stabilizer is 1: 1.
9. Use according to claim 7, characterized in that: the existing isocyanate stabilizer is selected from hindered phenol stabilizers, phosphite stabilizers, benzoyl chloride stabilizers or phenol.
10. Use according to claim 1, characterized in that: the isocyanate stabilizer, suitable isocyanate include monoisocyanate, and diisocyanate containing formula (II)
OCN-R′-NCO
(Ⅱ)
Wherein R' is selected from C2-C18 alkyl, C3-C12 cycloalkyl, C3-C12 cycloalkyl with substituent, phenyl with substituent, naphthyl and naphthyl with substituent;
the substituent on the C3-C12 naphthenic base with the substituent, the substituent on the phenyl with the substituent and the substituent on the naphthyl with the substituent are respectively at least one of C1-C12 alkyl, alkoxy of C1-C12, halogen, nitro, ester group and cyano.
11. Use according to claim 10, characterized in that: the monoisocyanate is methyl isocyanate, butyl isocyanate, phenyl isocyanate and benzyl isocyanate; the diisocyanate is toluene diisocyanate, 4 '-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4' -dicyclohexylmethane diisocyanate, and m-xylylene diisocyanate.
12. Use according to claim 10, characterized in that: the isocyanate is m-xylylene diisocyanate.
13. Use according to any one of claims 1 to 12, wherein: the preparation method of the isocyanate stabilizer comprises the following steps:
a) dissolving a compound of a general formula (III) in an inert organic solvent, and introducing hydrogen chloride or hydrogen bromide gas for reaction;
wherein n and R are the same as formula (I);
b) separating the reaction system in the step a) to obtain the isocyanate stabilizer.
14. Use according to claim 13, characterized in that: the inert organic solvent is at least one of aromatic hydrocarbon, halogenated aromatic hydrocarbon, alkane and halogenated alkane.
15. Use according to claim 14, characterized in that: the inert organic solvent is at least one of chlorobenzene, dichlorobenzene, toluene and xylene.
16. Use according to claim 13, characterized in that: the mass ratio of the compound of the general formula (III) to the inert organic solvent is 1: 10-100; the molar ratio of the compound of the general formula (III) to hydrogen chloride or hydrogen bromide is 1: 2.2-20.
17. Use according to claim 16, characterized in that: the mass ratio of the compound of the general formula (III) to the inert organic solvent is 1: 20-50; the molar ratio of the compound of the general formula (III) to hydrogen chloride or hydrogen bromide is 1: 2.5-10.
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| US3640886A (en) * | 1968-09-25 | 1972-02-08 | Basf Wyandotte Corp | Toluene diisocyanate compositions |
| US3715381A (en) * | 1969-06-11 | 1973-02-06 | Allied Chem | Polyisocyanate compositions stabilized against discoloration |
| CN1294575A (en) * | 1998-03-25 | 2001-05-09 | 拜尔公司 | Stabilisation of organic polyisocyanates |
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