WO2019076099A1 - 一种浅色改性异氰酸酯混合物及其制备方法 - Google Patents

一种浅色改性异氰酸酯混合物及其制备方法 Download PDF

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WO2019076099A1
WO2019076099A1 PCT/CN2018/098253 CN2018098253W WO2019076099A1 WO 2019076099 A1 WO2019076099 A1 WO 2019076099A1 CN 2018098253 W CN2018098253 W CN 2018098253W WO 2019076099 A1 WO2019076099 A1 WO 2019076099A1
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group
terminator
isocyanate
ppm
catalyst
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PCT/CN2018/098253
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English (en)
French (fr)
Inventor
周也
王文博
夏以禄
张宏科
刘小高
牛桂英
王会会
刘雪婷
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万华化学集团股份有限公司
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Priority to ES18867976T priority Critical patent/ES2956043T3/es
Priority to SG11202002749QA priority patent/SG11202002749QA/en
Priority to EP18867976.5A priority patent/EP3699169B1/en
Priority to US16/645,612 priority patent/US11034651B2/en
Priority to JP2020540662A priority patent/JP7060697B2/ja
Publication of WO2019076099A1 publication Critical patent/WO2019076099A1/zh

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    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C263/00—Preparation of derivatives of isocyanic acid
    • C07C263/18—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C267/00—Carbodiimides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D229/00—Heterocyclic compounds containing rings of less than five members having two nitrogen atoms as the only ring hetero atoms

Definitions

  • the present invention relates to a light-colored modified isocyanate mixture containing carbodiimide (CDI) and/or uretonimine (UTI) derivatives, which is liquid at room temperature and low in color. No., with good room temperature storage and high temperature stability.
  • CDI carbodiimide
  • UTI uretonimine
  • the isocyanate can be subjected to polycondensation to release CO 2 under certain conditions to form a carbodiimide derivative, and the carbodiimide group can be reacted with an isocyanate to form a uretonimine group.
  • the inclusion of CDI and UTI substances in the isocyanate can lower the melting point of the isocyanate, make it liquid at normal temperature, and form a stable low-viscosity liquid for transportation, and have good storage stability;
  • the isocyanate-prepared articles are somewhat improved in terms of light resistance, flame resistance, hydrolysis resistance, and increased initial strength.
  • the isocyanate group can be simply used as a high-efficiency catalyst for the phospholene, especially a high-efficiency catalyst for the oxidation of the phospholene, under certain reaction conditions, heating the isocyanate to partially convert it into carbodiimide and / or uretonimine derivatives, the preparation method can be produced by the method of US-A-6120699, US-A-2853473 and EP-A-515933.
  • a phospholene catalyst particularly a phosphine oxide catalyst
  • the catalyst remains at room temperature. It has sufficient activity to affect the storage stability of products containing free NCO groups, and the NCO group continues to be consumed during the process, so that the viscosity is continuously increased, so it needs to be deactivated by other methods such as chemical or physical.
  • a limited amount of terminator may be added to the reaction liquid to deactivate the high-efficiency catalyst.
  • Suitable terminators are mentioned in the patent specifications EP-A-515933, CN-A-1721395, US-A-4,120,884, CN-A-1, 789, 241, and CN-A-102, 718, 683, including Lewis acids, acid chlorides, A chloroformic acid, an aromatic sulfonic acid/ester, a methylsilylated acid, an alkyl sulfate, and a halide of a main group element.
  • Catalytic termination with an acid is not effective, wherein the acid can also be present in the form of an acid chloride.
  • a CDI/UTI group-containing isocyanate mixture prepared from a phospholene catalyst terminates the catalyst activity by at least an equimolar amount with the catalyst, preferably 1-2.
  • a molar amount of, for example, trimethylsilyl trifluoromethanesulfonate (TMST) is used to terminate.
  • TMST trimethylsilyl trifluoromethanesulfonate
  • the modified isocyanate prepared by this method has problems such as incomplete termination, poor storage stability, and the like, especially in the environment where the outdoor temperature is low in winter, the process of using the water bath and the chemical in the process of using the product. Gas is generated in the middle, resulting in high pressure in the storage container, and the product NCO drops significantly and the viscosity rises significantly.
  • a methylsilylated acid such as trimethylsilyl trifluoromethanesulfonate
  • the color number rises rapidly.
  • the patent uses trimethylsilyl trifluoromethanesulfonate to compound non-silylated acid, acid chloride and sulfonate to improve the termination effect of the terminator and improve the stability of the product. It can reach 50-60APHA, but in the current technical field, the appearance color still can not meet our needs, and the viscosity rises significantly during the high-temperature heating process.
  • the alkylation reagent such as trifluoromethanesulfonate is used to terminate the reaction, and the stability can be terminated by increasing the molar equivalent ratio of the terminator and the catalyst, but the product color number is not satisfactory.
  • CN-A-102718683 is optimized for the use of an acid anhydride terminator to terminate the phospholene or phosphine oxide catalyst, preferably a terminator of trifluoromethanesulfonic anhydride and/or p-toluene Anhydride.
  • an acid anhydride terminator to terminate the phospholene or phosphine oxide catalyst, preferably a terminator of trifluoromethanesulfonic anhydride and/or p-toluene Anhydride.
  • the present invention relates to a light-colored modified isocyanate mixture containing carbodiimide (CDI) and/or uretonimine (UTI) derivatives, which is liquid at room temperature and low in color. No., with good room temperature storage and high temperature stability.
  • CDI carbodiimide
  • UTI uretonimine
  • the invention finds in the research that the halogenated silane organic substance and the sulfonic acid anhydride substance have better termination effect because they do not contain -OH or active hydrogen atom, and are superior to acid substances, alkylating agents and single acid anhydrides. And the prepared modified isocyanate containing CDI and/or UTI groups is stable, and the viscosity does not increase even during high temperature deterioration.
  • a process for the preparation of a light colored modified isocyanate mixture comprising a carbodiimide (CDI) and/or a uretonimine (UTI) derivative, the method comprising the steps of:
  • the terminator is a halogenated silane-based organic compound compounded with a sulfonic anhydride.
  • the reaction of the step a) can be carried out at a temperature of from 40 to 210 ° C, preferably from 100 ° C to 200 ° C, more preferably from 150 to 200 ° C, still more preferably from 190 to 200 ° C.
  • halosilane-based organic compound has the chemical formula of the following formula (I),
  • R 1 , R 2 and R 3 independently of each other represent an aliphatic, aromatic, araliphatic and alicyclic group optionally containing a hetero atom, wherein “optional” means With or without heteroatoms.
  • R 1 , R 2 and R 3 independently of each other represent an aliphatic group (for example, a C1-C10 hydrocarbon group, preferably a C1-C6 hydrocarbon group such as methyl group, ethyl group, n-propyl group, isopropyl group, or n-butyl group).
  • Base isobutyl, tert-butyl, etc.
  • aromatic for example, C6-C15 aromatic group, specifically, for example, phenyl, tolyl, ethylphenyl, etc.
  • araliphatic for example, C7-C15 aryl aliphatic group
  • a group such as a benzyl group, a phenethyl group or the like, an alicyclic group (for example, a C3-C12 alicyclic group, specifically, for example, a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, a cyclopentyl group, etc.),
  • R 1 , R 2 and R 3 may be the same or different; two of R 1 , R 2 and R 3 may be bonded to each other to form a ring structure, ie, for R 1 In the case of R 2 X 2 Si, R
  • the groups may be bonded to each other to form a ring structure or not to form a ring structure;
  • X represents a halogen element and may be represented by elements such as fluorine, chlorine and bromine.
  • the subscript numbers 1 , 2, and 3 in X 1 , X 2 , and X 3 all refer to the number of Xs in the formula; for R 1 X 3 Si or R 1 R 2 X 2 Si, two of them Or the three Xs may be the same or different; and the subscript numbers of the R groups such as R 1 , R 2 and R 3 are only for convenience to distinguish each R group, not a numerical meaning, and other similarities of the present invention. The meaning is the same.
  • the halosilane-based organic substance is preferably one or two or more of diphenyldifluorosilane, diphenyldichlorosilane, tritylfluorosilane, and tert-butyltrichlorosilane.
  • sulfonic anhydride type substance has the following structural formula (II):
  • R 4 and R 5 independently of each other represent an aliphatic, aromatic, araliphatic or alicyclic group optionally containing a hetero atom and/or other functional group, wherein “optional” It means that it may or may not contain heteroatoms and/or other functional groups. Further, R 4 and R 5 independently of each other represent aliphatic (for example, a C1-C10 hydrocarbon group, preferably a C1-C6 hydrocarbon group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert.
  • an aromatic for example, a C6-C15 aromatic group, specifically, for example, a phenyl group, a tolyl group, an ethylphenyl group, etc.
  • an araliphatic group for example, a C7-C15 araliphatic group, specifically, for example, a benzyl group
  • a group such as a phenethyl group or an alicyclic group (for example, a C3-C12 alicyclic group, specifically, for example, a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, a cyclopentyl group, etc.), which may contain a hetero atom and/or Or other functional group
  • R 4 and R 5 may be the same or different, and two groups of R 4 and R 5 may be optionally bonded to each other to form a ring structure, wherein "optionally" means that they may be bonded to each other to
  • the sulfonic anhydride-based substance is preferably one or two or more of p-toluenesulfonic anhydride, methanesulfonic anhydride, ethylsulfonic anhydride, and trifluoromethanesulfonic anhydride.
  • a preferred terminator is diphenyldifluorosilane complexed with toluenesulfonic anhydride.
  • the compounding type terminator is used in an amount of from 50 to 2000 ppm, preferably from 100 to 600 ppm, most preferably from 100 to 200 ppm, based on the weight of the raw material isocyanate;
  • the terminator is used in an amount of from 10 to 200 ppm, preferably from 10 to 100 ppm, most preferably from 10 to 50 ppm.
  • the compounding ratio (mass ratio) of the halogenated silane-based terminator and the sulfonic acid anhydride is preferably 2 to 6:1, more preferably 3-5:1, still more preferably 4:1.
  • the catalyst for preparing the isocyanate containing a carbodiimide and/or a uretonimine derivative is a phospholane catalyst and/or a phospholene catalyst and an oxo thereof, preferably a phosphorus A cyclopentene or a phosphine oxide heterocyclic catalyst.
  • Catalysts are known, for example, as described in EP-A-515,933 and US-A-2,663,737, the disclosure of which are hereby incorporated by reference.
  • a preferred catalyst is 1-methyl-3-methyl-3-phospholene-1-oxide or 1-phenyl-3-methyl-3-phospholene.
  • the isocyanate polycondensation reaction is carried out in the presence of the above catalyst in an amount of from 0.1 to 10 ppm, preferably from 0.2 to 2 ppm, and most preferably from 0.5 ppm, based on the weight of the starting material isocyanate.
  • any suitable isocyanate can be used as the starting material isocyanate in the process of the invention.
  • the process of the present invention is preferably a diisocyanate such as one or more selected from the group consisting of aromatic, araliphatic, aliphatic and alicyclic diisocyanates, particularly preferably diphenylmethane diisocyanate for carbodiimidation. reaction.
  • the starting material isocyanate is diphenylmethane diisocyanate, wherein the diphenylmethane diisocyanate contains 97-100 wt% 4,4-isomer, 0-1 wt% 2,2-isomer, and 0.5- 1.8 wt% 2,4-isomer.
  • the carbodiimide reaction is carried out in the presence of a high-efficiency catalyst, and the reaction is carried out at a temperature of 40 to 210 ° C, preferably between 190 and 200 ° C.
  • the reaction can also be carried out at a mild ambient temperature, but this is required
  • the amount of catalyst is large, and the amount of terminator added causes the product color number to be unsatisfactory. The small amount of catalyst will cause the reaction rate to be slow, which is not conducive to industrial production.
  • the carbodiimide reaction is an NCO polycondensation reaction accompanied by the production of CO 2
  • the reaction process can be monitored by measuring the amount of CO 2 released; or the NCO content can be reacted by continuously measuring the change in the refractive index of the reaction solution. Variety.
  • the carbodiimidation reaction time reaches between 10 min and 24 h, preferably between 1 h and 4 h, the reaction is terminated by the addition of a compound terminator.
  • the step b) adding a complex terminator to terminate the carbodiimidation reaction is carried out at a temperature of 40-70 ° C, further preferably 40-60 ° C, more preferably 50-60 ° C, such as 60 ° C. .
  • 5-20%, preferably 10-15%, of the NCO groups of the starting isocyanate are converted to CDI groups by carbodiimidation, followed by CDI groups and unreacted NCO groups
  • the reaction forms a UTI group, so that the UTI group can be easily introduced into the isocyanate system. Since the conversion of the CDI group to the UTI group is a reversible process, there is also a small amount of residual CDI groups in the product.
  • the appropriate amount of isocyanate raw material can be reversed.
  • this step can also be carried out without reverse-reacting operation, and the reverse-isocyanate raw material can mainly accelerate the cooling process; after adding the terminator, it can be again
  • the amount of the isocyanate raw material may be reversed, and the reversed isocyanate may be added to adjust the target NCO value; the total amount of the reversed isocyanate raw material is determined according to the NCO value to be adjusted.
  • the positive effects of the present invention are as follows: a) The modified isocyanate product obtained by the invention has very good storage stability at room temperature, and does not undergo polycondensation reaction in the process of high-temperature chemical conversion, even in a high-temperature environment, the NCO group of the product during storage The group content is not lowered, and the viscosity change is very small; b) The modified isocyanate prepared by the present invention has a lower color number and is generally stable at 20-30 APHA, and the color number is significantly reduced as compared with the prior art.
  • the invention further relates to a liquid modified isocyanate mixture containing CDI and/or UTI groups obtained by the above process, having an NCO content of from 20 to 32% by weight, preferably from 28 to 30% by weight; a viscosity of from 10 to 200 cp, preferably from 20 to 60 cp, color
  • the number is in the range of 20-40 APHA; preferably, the initial value of the product Hasen color number is 20-30, and the value after 2 months is 25-35.
  • diphenylmethane diisocyanate wherein diphenylmethane diisocyanate contains 97-100% by weight of 4,4-isomer, 0-1% by weight of 2,2-isomer and 0.5-1.8% by weight of 2,4-
  • the isomer had an NCO content of 33.6 wt%.
  • the catalyst is: 1-methyl-3-methyl-3-phospholene-1-oxide or 1-phenyl-3-methyl-3-phospholene-1-oxide solution, Using dichloromethane as a solvent, the catalyst concentration was 1%, relative to the mass of the solvent dichloromethane; both the catalyst and the solvent were purchased and purchased from the Chinese medicine.
  • Diphenyldifluorosilane purity 96%, color No. 10#, from Suzhou Yake Technology Co., Ltd.
  • Tritylfluorosilane 96% pure, can be purchased from Chinese medicine.
  • P-toluenesulfonic anhydride purity 95%, can be purchased from Chinese medicine.
  • Trifluoromethanesulfonic anhydride purity 98%, can be purchased from Chinese medicine.
  • Trimethylsilyl trifluoromethanesulfonate 95% pure, can be purchased from Chinese medicine.
  • Dibutyl phosphate 98% pure, can be purchased from Chinese medicine.
  • the comparative example can also be carried out as follows: 500 g of diphenylmethane diisocyanate is heated to about 50 ° C while stirring under N 2 , and a catalyst amount of 0.025 g of 1-phenyl-3-methyl-3-phosphorus is added.
  • the heterocyclic pentene high-efficiency catalyst solution is rapidly heated to 200 ° C after mixing, and after reacting for 90 min, 400 g of diphenylmethane diisocyanate is reacted, and after quenching the temperature to 60 ° C, 0.1 g of a terminator diphenyldifluorosilane is added.
  • the mixture was stirred for 30 min, then warmed to between 70-80 ° C and stirred for 120 min to give the final product. There was no significant change in the performance of the product and the performance of the product prepared according to the previous procedure.
  • This embodiment can also be carried out as follows: 500 g of diphenylmethane diisocyanate is heated to about 50 ° C while stirring under N 2 , and a catalyst amount of 0.05 g of 1-phenyl-3-methyl-3-phosphonium is added.
  • Cyclopentene-1-oxide high-efficiency catalyst solution ie, 1-phenyl-3-methyl-3-phospholene-1-oxide solution
  • the temperature was quenched to 60 ° C, 0.1 g of the terminator tritylfluorosilane and 0.025 g of the terminator p-toluenesulfonic anhydride were added, and the mixture was stirred for 30 minutes and then heated to 70-
  • the final product was obtained by stirring at 80 ° C for 120 min. There was no significant change in the performance of the product and the performance of the product prepared according to the previous procedure.
  • This embodiment can also be carried out as follows: 500 g of diphenylmethane diisocyanate is heated to about 50 ° C while stirring under N 2 , and a catalyst amount of 0.025 g of 1-phenyl-3-methyl-3-phosphorus is added.
  • Heterocyclic pentene-1-oxide high-efficiency catalyst solution (1-phenyl-3-methyl-3-phospholene-1-oxide solution), heated rapidly to 200 ° C after mixing, reacted for 90 min
  • the temperature was quenched to 60 ° C, 0.05 g of the terminator diphenyldifluorosilane and 0.01 g of the terminator trifluoromethanesulfonic anhydride were added, and the mixture was stirred for 30 minutes and then heated to 70.
  • the mixture was stirred at -80 ° C for 120 min to give the final product. There was no significant change in the performance of the product and the performance of the product prepared according to the previous procedure.
  • the comparative example can also be carried out as follows: 500 g of diphenylmethane diisocyanate is heated to about 50 ° C while stirring under N 2 , and a catalyst amount of 0.025 g of 1-phenyl-3-methyl-3-phosphorus is added.
  • the heterocyclic pentene high-efficiency catalyst solution is rapidly heated to 200 ° C after mixing, and after reacting for 90 min, 400 g of diphenylmethane diisocyanate is reversed, the temperature is quenched to 60 ° C, and 0.025 g of terminator trimethylsilyl III is added.
  • the fluoromethane sulfonate was stirred for 30 min, then warmed to between 70-80 ° C and stirred for 120 min to give the final product. There was no significant change in the performance of the product and the performance of the product prepared according to the previous procedure.
  • the comparative example can also be carried out as follows: 500 g of diphenylmethane diisocyanate is heated to about 50 ° C while stirring under N 2 , and a catalyst amount of 0.025 g of 1-phenyl-3-methyl-3-phosphorus is added.
  • the heterocyclic pentene high-efficiency catalyst solution is rapidly heated to 200 ° C after mixing, and after reacting for 90 min, 400 g of diphenylmethane diisocyanate is reversed, the temperature is quenched to 60 ° C, and 0.005 g of the terminator trimethylsilyl III is added.
  • the fluoromethanesulfonate was compounded with 0.1 g of dibutyl phosphate, and the mixture was stirred for 30 minutes, and then heated to 70-80 ° C, and stirred for 120 minutes to obtain a final product. There was no significant change in the performance of the product and the performance of the product prepared according to the previous procedure.
  • the comparative example can also be carried out as follows: 500 g of diphenylmethane diisocyanate is heated to about 50 ° C while stirring under N 2 , and a catalyst amount of 0.025 g of 1-phenyl-3-methyl-3-phosphorus is added.
  • the heterocyclic pentene high-efficiency catalyst solution is rapidly heated to 200 ° C after mixing, and after reacting for 90 min, 400 g of diphenylmethane diisocyanate is reversed, the temperature is quenched to 60 ° C, and 0.025 g of the terminator p-toluenesulfonic anhydride is added. The mixture was stirred for 30 min, then warmed to between 70-80 ° C and stirred for 120 min to give the final product. There was no significant change in the performance of the product and the performance of the product prepared according to the previous procedure.
  • the comparative example can also be carried out as follows: 500 g of diphenylmethane diisocyanate is heated to about 50 ° C while stirring under N 2 , and a catalyst amount of 0.025 g of 1-phenyl-3-methyl-3-phosphorus is added.
  • the heterocyclic pentene high-efficiency catalyst solution is rapidly heated to 200 ° C after mixing, and after reacting for 90 min, 400 g of diphenylmethane diisocyanate is reversed, the temperature is quenched to 60 ° C, and 0.025 g of the terminator trifluoromethanesulfonic acid is added.
  • the mixture was stirred for 30 min and then warmed to between 70-80 ° C and stirred for 120 min to give the final product. There was no significant change in the performance of the product and the performance of the product prepared according to the previous procedure.
  • the viscosity is determined by reference to the third part of the viscosity of the polymethylidene polyphenyl isocyanate GB/T 12009.3-2009.
  • the NCO determination refers to the determination of the fourth part of the isocyanate content of the aromatic isocyanate for polyurethane production according to the national standard GB/T 12009.4-2016 of the People's Republic of China.
  • the color number is measured by a color meter, and the color meter model BYK-LCSIII.
  • the appearance color number is high and the high temperature stability is not ideal.
  • the comparative example 3-5 modified isocyanate product has good storage stability at room temperature, but the high temperature stability is not ideal, the NCO decreases obviously and the viscosity rises greatly.
  • diphenyldifluorosilane is used alone, and the high temperature stability is not good.
  • Examples 1-4 show that the halosilane organic compound is ideally matched to the toluenesulfonic anhydride, and the temperature is high and the stability is high. It is also lower than other embodiments.

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Abstract

本发明涉及一种浅色改性异氰酸酯混合物及其制备方法。该方法包括以下步骤：a)使原料异氰酸酯的异氰酸酯基团在磷杂环类催化剂的作用下进行反应，最终得到含有碳化二亚胺和/或脲酮亚胺类衍生物的改性异氰酸酯反应液；b)向步骤a得到的反应液中加入卤代硅烷类有机物和磺酸酐类复配的终止剂用以终止碳化二亚胺化反应，该方法制备的改性异氰酸酯具有常温液态、常温和高温存储稳定且低色号的特征。

Description

一种浅色改性异氰酸酯混合物及其制备方法 技术领域
本发明涉及一种浅色改性异氰酸酯混合物及其制备方法，该改性异氰酸酯混合物含有碳化二亚胺(CDI)和/或脲酮亚胺(UTI)类衍生物，常温下为液态且低色号，具有良好的常温储存和高温稳定性。
背景技术
异氰酸酯可以在一定的条件下，缩聚释放出CO 2后生成碳化二亚胺类衍生物，碳化二亚胺基团可以同异氰酸酯进行加合反应形成脲酮亚胺基团。通过此方法使异氰酸酯中含有CDI和UTI类物质可以降低异氰酸酯的熔点，使其在常温下呈液态，并形成稳定的低粘度液体便于运输，同时具有良好的储存稳定性；而且由这种改性异氰酸酯制备的制品在耐光、耐燃、耐水解、增加初始强度等性能方面得到一定的改善。
异氰酸酯基团可以简单的使用磷杂环戊烯类的高效催化剂，特别是氧化磷杂环戊烯类的高效催化剂，在一定的反应条件下，加热异氰酸酯，使之部分转化成碳化二亚胺和/或脲酮亚胺类衍生物，制备方法可以参考US-A-6120699、US-A-2853473和EP-A-515933中的方法来生产。
磷杂环戊烯类催化剂特别是氧化磷杂环戊烯类催化剂具有高的活性是人们所期望的，以便能够在温和的温度条件下使碳化二亚胺化反应活化，但是在室温下催化剂仍具有充分的活性从而影响含有游离NCO基团产品的储存稳定性，过程中继续消耗NCO基团，使粘度不断增加，因此需要通过化学或者物理等其他方法使其失活。
为了终止形成NCO继续生产CDI和UTI类基团的反应，可以向反应液中加入限量的终止剂，从而使高效催化剂失活。合适的终止剂在专利说明书EP-A-515933、CN-A-1721395、US-A-4120884、CN-A-1789241以及CN-A-102718683中都有提及，其中包括路易斯酸、酰氯类、氯甲酸类、芳香磺酸/酯类、甲基硅烷基化酸、烷基硫酸盐类和主族元素的卤化物。用酸终止催化作用不够有效，其中酸也可以以酰氯的形式存在。
参考专利说明书EP-A-515933的公开文本，由磷杂环戊烯类催化剂制备的含有CDI/UTI基团的异氰酸酯混合物，终止催化剂活性至少用与催化剂等摩尔量、较佳的是1-2倍摩尔量的，例如三甲基甲硅烷基三氟甲烷磺酸酯(TMST)来终止。然而实践中证明，通过此方法制备的改性异氰酸酯存在终止不完全，存储稳定性不佳等问题，特别是冬季室外温度较低的环境下，产品使用过程中需要水浴化料，化料的过程中会产生气体，导致储存容器内压力高，并且产品NCO下降明显及粘度上涨显著。
参考专利说明CN-A-1721395的公开文本，使用甲基硅烷基化酸，诸如三甲基甲硅烷基三氟甲烷磺酸酯终止催化剂活性，可以通过终止剂用量来达到预期目的，但产品外观色号上涨迅速，专利通过三甲基甲硅烷基三氟甲烷磺酸酯复配非甲硅烷基化酸、 酰氯和磺酸脂来提高终止剂的终止效果，提升产品的稳定性，产品色号可以达到50-60APHA，但在现在的技术领域，外观颜色仍不能满足我们的需求，且产品高温加热过程中，粘度上涨显著。
参考专利说明书US-A-4120884的公开文本，使用硫酸二甲酯来终止氧化磷杂环戊烯类催化剂，储存稳定性相比使用TMST有一定的提升，但化料的过程粘度上涨显著。
根据CN-A-1789241的说明，采用三氟甲基磺酸酯类等烷基化试剂来终止反应，稳定性可以通过提高终止剂和催化剂摩尔当量比来实现终止完全，但产品色号不理想。
CN-A-102718683对此进行了优化，采用酸酐类终止剂来终止磷杂环戊烯或氧化磷杂环戊烯类催化剂，优选的终止剂为三氟甲基磺酸酐和/或对甲苯磺酸酐。实践中证明，常温储存稳定性得到一定的提高，高温稳定性不是很理想，NCO下降明显，产品色号上涨较快，三氟甲基磺酸酐和/或对甲苯磺酸酐终止剂是目前现有技术中效果最优的终止剂。
现有的制备含有CDI和/或UTI基团的液体异氰酸酯的方法难以克服上述缺陷。
发明内容
本发明涉及一种浅色改性异氰酸酯混合物及其制备方法，该改性异氰酸酯混合物含有碳化二亚胺(CDI)和/或脲酮亚胺(UTI)类衍生物，常温下为液态且低色号，具有良好的常温储存和高温稳定性。
本发明在研究中发现，卤代硅烷类有机物和磺酸酐类物质由于不含有-OH或活泼氢原子，具有较好的终止效果，优于酸类物质、烷基化剂以及单一的酸酐类终止剂，并且所制备的含有CDI和/或UTI基团的改性异氰酸酯稳定性好，即使在高温劣化过程中粘度也不会增加。
具体技术方案如下：
一种浅色改性异氰酸酯混合物的制备方法，该改性异氰酸酯混合物含有碳化二亚胺(CDI)和/或脲酮亚胺(UTI)类衍生物，该方法包括以下步骤：
a)使原料异氰酸酯的异氰酸酯基团在膦杂环类催化剂的作用下进行碳化二亚胺化反应，得到含有碳化二亚胺和\或脲酮亚胺类衍生物的改性异氰酸酯反应液；
b)向步骤a)得到的反应液中加入复配的终止剂用以终止碳化二亚胺化反应；
所述终止剂为卤代硅烷类有机物复配磺酸酐类物质。
步骤a)的反应可以在40-210℃的温度下进行，优选100℃-200℃，更优选150-200℃，更进一步优选190-200℃下进行。
进一步地，所述卤代硅烷类有机物具有以下式(Ⅰ)的化学式，
R 1X 3Si或R 1R 2X 2Si或R 1R 2R 3X 1Si
(Ⅰ)
在分子式(Ⅰ)中，R 1、R 2和R 3相互独立的表示任选含有杂原子的脂肪族、芳 香族、芳脂族和脂环族基团，其中“任选”的含义是可含有或不含有杂原子。在分子式(Ⅰ)中，R 1、R 2和R 3相互独立的表示脂肪族(例如C1-C10烃基，优选C1-C6烃基例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基等)、芳香族(例如C6-C15芳香族基团，具体例如苯基、甲苯基、乙苯基等)、芳脂族(例如C7-C15芳脂族基团，具体例如苯甲基、苯乙基等)、脂环族(例如C3-C12脂环族基团，具体例如环丙基、环丁基、环己基、环戊基等)等基团，其可含有杂原子和/或其它官能团，其中R 1、R 2和R 3可以相同或不同；R 1、R 2和R 3其中两个基团可以相互连接形成环结构，即，对于R 1R 2X 2Si而言，R 1、R 2可以相互连接形成环结构或不形成环结构，对于R 1R 2R 3X 1Si而言，R 1、R 2和R 3中的任意两个基团可以相互连接形成环结构或不形成环结构；X代表卤族元素，可以表示为氟、氯和溴等元素。具体的，X 1、X 2和X 3中的下标数字1、2和3均指分子式中含有所述X的数目；对于R 1X 3Si或R 1R 2X 2Si，其中的两个或三个X之间可以相同或不同；而R 1、R 2和R 3等R基团的下标数字仅为方便区分各个R基团，并非数目的含义，本发明其他类似之处的含义均为同此。所述的卤代硅烷类有机物优选二苯基二氟硅烷、二苯基二氯硅烷、三苯甲基氟硅烷和叔丁基三氯硅烷中的一种或两种或多种。
进一步地，所述磺酸酐类物质具有以下结构式(Ⅱ)：
Figure PCTCN2018098253-appb-000001
在结构式(Ⅱ)中，R 4和R 5相互独立的表示任选含有杂原子和/或其他官能团的脂肪族、芳香族、芳脂族或脂环族等基团，其中“任选”的含义是可以含有也可以不含有杂原子和/其他官能团。进一步的，R 4和R 5相互独立的表示脂肪族(例如C1-C10烃基，优选C1-C6烃基例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基等)、芳香族(例如C6-C15芳香族基团，具体例如苯基、甲苯基、乙苯基等)、芳脂族(例如C7-C15芳脂族基团，具体例如苯甲基、苯乙基等)或脂环族(例如C3-C12脂环族基团，具体例如环丙基、环丁基、环己基、环戊基等)等基团，其可含有杂原子和/或其它官能团，其中R 4和R 5可以相同或不同，R 4和R 5两个基团可任选地相互连接形成环结构，其中“任选地”的含义为可相互连接形成环结构或不形成环结构。所述磺酸酐类物质优选对甲苯磺酸酐、甲基磺酸酐、乙基磺酸酐和三氟甲基磺酸酐中的一种或两种或多种。
优选的终止剂为二苯基二氟硅烷复配对甲苯磺酸酐。
复配型终止剂的用量以原料异氰酸酯的重量为基准计，有机硅烷类终止剂(卤代硅烷类有机物终止剂)用量为50-2000ppm，优选100-600ppm，最优选为100-200ppm； 磺酸酐类终止剂用量为10-200ppm，优选10-100ppm，最优选为10-50ppm。卤代硅烷类终止剂与磺酸酐类的复配比例(质量比)优选为2-6:1，进一步优选3-5:1，更优选4:1。
用于制备所述含有碳化二亚胺和/或脲酮亚胺类衍生物的异氰酸酯的催化剂为磷杂环戊烷类催化剂和/或磷杂环戊烯类催化剂及其氧代物，优选磷杂环戊烯类或氧化磷杂环戊烯类催化剂。催化剂都是已知的，例如EP-A-515933和US-A-2663737中均有所描述，这些催化剂的典型例子在本领域是已知的。
优选的催化剂为1-甲基-3-甲基-3-磷杂环戊烯-1-氧化物或1-苯基-3-甲基-3-磷杂环戊烯。
异氰酸酯缩聚反应是在上述催化剂存在下进行，催化剂用量0.1-10ppm，优选0.2-2ppm，最优使用量为0.5ppm，相对于原料异氰酸酯重量。
任何合适的异氰酸酯都可以作为本发明方法的原料异氰酸酯。但是，本发明的方法优选二异氰酸酯，例如选自芳香族、芳脂族、脂肪族和脂环族二异氰酸酯中的一种或多种，特别优选二苯基甲烷二异氰酸酯进行碳化二亚胺化反应。
在一些实施方式中，原料异氰酸酯为二苯基甲烷二异氰酸酯，其中二苯基甲烷二异氰酸酯含有97-100wt％4,4-异构体、0-1wt％2,2-异构体以及0.5-1.8wt％2,4-异构体。
碳化二亚胺反应在高效催化剂存在的条件下，反应在40-210℃的温度下进行，优选190-200℃之间进行，当然，反应也可以在温和的环境温度下进行反应，但这样需要催化剂用量较大，终止剂添加量大会导致产品色号不理想，催化剂用量小会造成反应速率慢，不利于工业化生产。
由于碳化二亚胺反应是NCO缩聚反应，过程伴随有CO 2的产生，所以该反应过程可以通过测量CO 2释放量来进行监控；或者可以通过连续测定反应液的折光率变化来反应NCO含量的变化。当碳化二亚胺化反应时间达到10min-24h，优选1h-4h之间，加入复配终止剂终止反应。
在一些具体实施方式中，步骤b)添加复配型终止剂进行终止碳化二亚胺化反应的温度条件为40-70℃，进一步优选40-60℃，更优选50-60℃，例如60℃。
根据本发明的一些实施方案，将原料异氰酸酯的NCO基团的5-20％，优选10-15％通过碳化二亚胺化反应转化为CDI基团，之后CDI基团与未反应的NCO基团反应形成UTI基团，从而很容易的将UTI基团引入到该异氰酸酯的体系中，由于CDI基团往UTI基团转化是可逆过程，产物中还会有少量CDI基团的残留。
在步骤a)反应之后，添加终止剂之前，可以反兑适量异氰酸酯原料，当然此步骤也可以不进行反兑操作，反兑异氰酸酯原料主要是可加速降温过程；在添加终止剂后，也可以再次反兑适量异氰酸酯原料，也可以不进行反兑，添加终止剂后反兑异氰酸酯主要是为了调整目标NCO值；总的反兑异氰酸酯原料量根据所需调整的NCO值而确定。
本发明的积极效果在于：a)本发明得到的改性异氰酸酯产品常温存储稳定性非常好，且在高温化料过程中也不会出现缩聚反应，即使在高温环境下产品在储存过程中NCO基团含量不会降低，粘度变化非常小；b)本发明制得的改性异氰酸酯具有较低的色号，一般稳定在20-30APHA，与现有技术相比，色号降低明显。
本发明进一步涉及通过上述方法得到的含有CDI和/或UTI基团的液态改性异氰酸酯混合物，NCO含量为20-32wt％，优选28-30wt％；粘度为10-200cp，优选20-60cp，色数在20-40APHA；优选地，产品哈森色数初始值为20-30，2个月后的值为25-35。依据本发明的方法的优点是显而易见的，由于使用的是卤代硅烷类有机物复配磺酸酐类终止剂，含有CDI和/或UTI基团的异氰酸酯基本是浅色的，具有常温和高温的储存稳定性。本发明的这些和其它优点和益处会从以下的本发明的具体实施方式中明了。
具体实施方式
本发明通过以下的实施例进一步阐述，但本发明的范围并非局限于以下实施例。
原料：二苯基甲烷二异氰酸酯，其中二苯基甲烷二异氰酸酯含有97-100wt％4,4-异构体、0-1wt％2,2-异构体以及0.5-1.8wt％2,4-异构体，NCO含量为33.6wt％。
催化剂为：1-甲基-3-甲基-3-磷杂环戊烯-1-氧化物或1-苯基-3-甲基-3-磷杂环戊烯-1-氧化物溶液，使用二氯甲烷作为溶剂，催化剂浓度为1％，相对于溶剂二氯甲烷的质量；催化剂和溶剂均购买获得，可购自国药。
二苯基二氟硅烷，纯度96％，色号10#，出自苏州亚科科技有限公司。
三苯甲基氟硅烷，纯度96％，可购自国药。
对甲苯磺酸酐，纯度95％，可购自国药。
三氟甲基磺酸酐，纯度98％，可购自国药。
三甲基甲硅烷基三氟甲烷磺酸酯，纯度95％，可购自国药。
磷酸二丁脂，纯度98％，可购自国药。
对比例1
将500g二苯基甲烷二异氰酸酯在N 2保护下边搅拌边加热至50℃左右，添加催化剂用量0.5ppm(0.025g)的磷杂环戊烯高效催化剂溶液(即，1-苯基-3-甲基-3-磷杂环戊烯-1-氧化物溶液)，混合后迅速加热至200℃，反应90min后反兑二苯基甲烷二异氰酸酯200g后，加入200ppm(0.1g)终止剂二苯基二氟硅烷，将温度急冷降至60℃，再将混合物搅拌30min后二次反兑200g二苯基甲烷二异氰酸酯，之后升温至70-80℃之间，搅拌120min得到最终产品。最终产品的检测结果见表1-2。
该对比例也可按照如下步骤进行：将500g二苯基甲烷二异氰酸酯在N 2保护下边搅拌边加热至50℃左右，添加催化剂用量0.025g的1-苯基-3-甲基-3-磷杂环戊烯高效催化剂溶液，混合后迅速加热至200℃，反应90min后反兑二苯基甲烷二异氰酸酯400g，将温度急冷降至60℃后，加入0.1g终止剂二苯基二氟硅烷，将混合物搅拌30min 后升温至70-80℃之间，搅拌120min得到最终产品。该产品性能和按照前面的步骤制备获得的产品性能没有明显变化。
实施例1
将500g二苯基甲烷二异氰酸酯在N 2保护下边搅拌边加热至50℃左右，添加催化剂用量0.5ppm(0.025g)的1-苯基-3-甲基-3-磷杂环戊烯高效催化剂溶液(即，1-苯基-3-甲基-3-磷杂环戊烯-1-氧化物溶液)，混合后迅速加热至200℃，反应90min后反兑二苯基甲烷二异氰酸酯200g后，加入200ppm(0.1g)终止剂二苯基二氟硅烷和50ppm(0.025g)终止剂对甲苯磺酸酐，将温度急冷降至60℃，再将混合物搅拌30min后二次反兑200g二苯基甲烷二异氰酸酯，升温至70-80℃之间，搅拌120min得到最终产品。最终产品的检测结果见表1-2。
该实施例也可按照如下步骤进行：
将500g二苯基甲烷二异氰酸酯在N 2保护下边搅拌边加热至50℃左右，添加催化剂用量0.025g的1-苯基-3-甲基-3-磷杂环戊烯高效催化剂溶液，混合后迅速加热至200℃，反应90min后反兑二苯基甲烷二异氰酸酯400g，将温度急冷降至60℃，加入0.1g终止剂二苯基二氟硅烷和0.025g终止剂对甲苯磺酸酐，再将混合物搅拌30min后升温至70-80℃之间，搅拌120min得到最终产品。该产品性能和按照前面的步骤制备获得的产品性能没有明显变化。
实施例2
将500g二苯基甲烷二异氰酸酯在N 2保护下边搅拌边加热至50℃左右，添加催化剂用量0.5ppm(0.025g)的1-苯基-3-甲基-3-磷杂环戊烯高效催化剂溶液(为1-苯基-3-甲基-3-磷杂环戊烯-1-氧化物溶液)，混合后迅速加热至200℃，反应90min后反兑二苯基甲烷二异氰酸酯200g后，加入200ppm(0.1g)终止剂二苯基二氯硅烷和50ppm(0.025g)终止剂三氟甲基磺酸酐，将温度急冷降至60℃，再将混合物搅拌30min后二次反兑200g二苯基甲烷二异氰酸酯，后升温至70-80℃之间，搅拌120min得到最终产品。最终产品的检测结果见表1-2。
该实施例也可按照如下步骤进行：
将500g二苯基甲烷二异氰酸酯在N 2保护下边搅拌边加热至50℃左右，添加催化剂用量0.025g的1-苯基-3-甲基-3-磷杂环戊烯高效催化剂溶液，混合后迅速加热至200℃，反应90min后反兑二苯基甲烷二异氰酸酯400g，将温度急冷降至60℃，加入0.1g终止剂二苯基二氯硅烷和0.025g终止剂三氟甲基磺酸酐，再将混合物搅拌30min后升温至70-80℃之间，搅拌120min得到最终产品。该产品性能和按照前面的步骤制备获得的产品性能没有明显变化。
实施例3
将500g二苯基甲烷二异氰酸酯在N 2保护下边搅拌边加热至50℃左右，添加催化剂用量1ppm(0.05g)的1-甲基-3-甲基-3-磷杂环戊烯-1-氧化物高效催化剂溶液(即1-甲基-3-甲基-3-磷杂环戊烯-1-氧化物溶液)，混合后迅速加热至120℃，反应200min后反兑二苯基甲烷二异氰酸酯200g后，加入200ppm(0.1g)终止剂三苯甲基氟硅烷和50ppm(0.025g)终止剂对甲苯磺酸酐，将温度急冷降至60℃，再将混合物搅拌30min后二次反兑200g二苯基甲烷二异氰酸酯，随后再升温至70-80℃之间，搅拌120min得到最终产品。最终产品的检测结果见表1-2。
该实施例也可按照如下步骤进行：将500g二苯基甲烷二异氰酸酯在N 2保护下边搅拌边加热至50℃左右，添加催化剂用量0.05g 1-苯基-3-甲基-3-磷杂环戊烯-1-氧化物高效催化剂溶液(即，1-苯基-3-甲基-3-磷杂环戊烯-1-氧化物溶液)，混合后迅速加热至120℃，反应200min后反兑二苯基甲烷二异氰酸酯400g后，将温度急冷降至60℃，加入0.1g终止剂三苯甲基氟硅烷和0.025g终止剂对甲苯磺酸酐，再将混合物搅拌30min后升温至70-80℃之间，搅拌120min得到最终产品。该产品性能和按照前面的步骤制备获得的产品性能没有明显变化。
实施例4
将500g二苯基甲烷二异氰酸酯在N 2保护下边搅拌边加热至50℃左右，添加催化剂用量0.5ppm(0.025g)的1-甲基-3-甲基-3-磷杂环戊烯-1-氧化物高效催化剂溶液(为1-甲基-3-甲基-3-磷杂环戊烯-1-氧化物溶液)，混合后迅速加热至200℃，反应90min后反兑二苯基甲烷二异氰酸酯200g后，加入100ppm(0.05g)终止剂二苯基二氟硅烷和20ppm(0.01g)终止剂三氟甲基磺酸酐，将温度急冷降至60℃，再将混合物搅拌30min后二次反兑200g二苯基甲烷二异氰酸酯，随后再升温至70-80℃之间，搅拌120min得到最终产品。最终产品的检测结果见表1-2。
该实施例也可按照如下步骤进行：将500g二苯基甲烷二异氰酸酯在N 2保护下边搅拌边加热至50℃左右，添加催化剂用量0.025g的1-苯基-3-甲基-3-磷杂环戊烯-1-氧化物高效催化剂溶液(1-苯基-3-甲基-3-磷杂环戊烯-1-氧化物溶液)，混合后迅速加热至200℃，反应90min后反兑二苯基甲烷二异氰酸酯400g后，将温度急冷降至60℃，加入0.05g终止剂二苯基二氟硅烷和0.01g终止剂三氟甲基磺酸酐，再将混合物搅拌30min后升温至70-80℃之间，搅拌120min得到最终产品。该产品性能和按照前面的步骤制备获得的产品性能没有明显变化。
对比例2
将500g二苯基甲烷二异氰酸酯在N 2保护下边搅拌边加热至50℃左右，添加催化剂用量0.5ppm(0.025g)的1-苯基-3-甲基-3-磷杂环戊烯高效催化剂溶液(即1-苯基-3-甲基-3-磷杂环戊烯-1-氧化物溶液)，混合后迅速加热至200℃，反应90min后反兑二苯基甲烷二异氰酸酯200g后，加入10ppm(0.025g)终止剂三甲基甲硅烷基三 氟甲烷磺酸酯，将温度急冷降至60℃，再将混合物搅拌30min后二次反兑200g，随后再升温至70-80℃之间，搅拌120min得到最终产品。最终产品的检测结果见表1-2。
该对比例也可按照如下步骤进行：将500g二苯基甲烷二异氰酸酯在N 2保护下边搅拌边加热至50℃左右，添加催化剂用量0.025g的1-苯基-3-甲基-3-磷杂环戊烯高效催化剂溶液，混合后迅速加热至200℃，反应90min后反兑二苯基甲烷二异氰酸酯400g后，将温度急冷降至60℃，加入0.025g终止剂三甲基甲硅烷基三氟甲烷磺酸酯，再将混合物搅拌30min后升温至70-80℃之间，搅拌120min得到最终产品。该产品性能和按照前面的步骤制备获得的产品性能没有明显变化。
对比例3
将500g二苯基甲烷二异氰酸酯在N 2保护下边搅拌边加热至50℃左右，添加催化剂用量0.5ppm(0.025g)的1-苯基-3-甲基-3-磷杂环戊烯高效催化剂溶液(即，1-苯基-3-甲基-3-磷杂环戊烯-1-氧化物溶液)，混合后迅速加热至200℃，反应90min后反兑二苯基甲烷二异氰酸酯200g后，加入10ppm(0.005g)终止剂三甲基甲硅烷基三氟甲烷磺酸酯复配200ppm(0.1g)磷酸二丁脂，将温度急冷降至60℃，再将混合物搅拌30min后二次反兑200g，随后再升温至70-80℃之间，搅拌120min得到最终产品。最终产品的检测结果见表1-2。
该对比例也可按照如下步骤进行：将500g二苯基甲烷二异氰酸酯在N 2保护下边搅拌边加热至50℃左右，添加催化剂用量0.025g的1-苯基-3-甲基-3-磷杂环戊烯高效催化剂溶液，混合后迅速加热至200℃，反应90min后反兑二苯基甲烷二异氰酸酯400g后，将温度急冷降至60℃，加入0.005g终止剂三甲基甲硅烷基三氟甲烷磺酸酯复配0.1g磷酸二丁脂，再将混合物搅拌30min后升温至70-80℃之间，搅拌120min得到最终产品。该产品性能和按照前面的步骤制备获得的产品性能没有明显变化。
对比例4
将500g二苯基甲烷二异氰酸酯在N 2保护下边搅拌边加热至50℃左右，添加催化剂用量0.5ppm(0.025g)的1-苯基-3-甲基-3-磷杂环戊烯高效催化剂溶液(即，1-苯基-3-甲基-3-磷杂环戊烯-1-氧化物溶液)，混合后迅速加热至200℃，反应90min后反兑二苯基甲烷二异氰酸酯200g后，加入50ppm(0.025g)终止剂对甲苯磺酸酐，将温度急冷降至60℃，再将混合物搅拌30min后二次反兑200g，随后再升温至70-80℃之间，搅拌120min得到最终产品。最终产品的检测结果见表1-2。
该对比例也可按照如下步骤进行：将500g二苯基甲烷二异氰酸酯在N 2保护下边搅拌边加热至50℃左右，添加催化剂用量0.025g的1-苯基-3-甲基-3-磷杂环戊烯高效催化剂溶液，混合后迅速加热至200℃，反应90min后反兑二苯基甲烷二异氰酸酯400g后，将温度急冷降至60℃，加入0.025g终止剂对甲苯磺酸酐，再将混合物搅拌30min后升温至70-80℃之间，搅拌120min得到最终产品。该产品性能和按照前面的 步骤制备获得的产品性能没有明显变化。
对比例5
将500g二苯基甲烷二异氰酸酯在N 2保护下边搅拌边加热至50℃左右，添加催化剂用量0.5ppm(0.025g)的1-苯基-3-甲基-3-磷杂环戊烯高效催化剂溶液(即，1-苯基-3-甲基-3-磷杂环戊烯-1-氧化物溶液)，混合后迅速加热至200℃，反应90min后反兑二苯基甲烷二异氰酸酯200g后，加入50ppm(0.025g)终止剂三氟甲基磺酸甲酯，将温度急冷降至60℃，再将混合物搅拌30min后二次反兑200g，随后再升温至70-80℃之间，搅拌120min得到最终产品。最终产品的检测结果见表1-2。
该对比例也可按照如下步骤进行：将500g二苯基甲烷二异氰酸酯在N 2保护下边搅拌边加热至50℃左右，添加催化剂用量0.025g的1-苯基-3-甲基-3-磷杂环戊烯高效催化剂溶液，混合后迅速加热至200℃，反应90min后反兑二苯基甲烷二异氰酸酯400g后，将温度急冷降至60℃，加入0.025g终止剂三氟甲基磺酸甲酯，再将混合物搅拌30min后升温至70-80℃之间，搅拌120min得到最终产品。该产品性能和按照前面的步骤制备获得的产品性能没有明显变化。
各产物的储存稳定性和色号对比见表1-2。
其中，粘度参考中华人民共和国国家标准GB/T 12009.3-2009多亚甲基多苯基异氰酸酯第三部分粘度的测定。
NCO测定参考中华人民共和国国家标准GB/T 12009.4-2016聚氨酯生产用芳香族异氰酸酯第四部分异氰酸酯含量的测定。
色号采用色号仪测量，色号仪型号BYK-LCSⅢ。
表1：各例产物储存稳定性和色数对比表
Figure PCTCN2018098253-appb-000002
Figure PCTCN2018098253-appb-000003
表2：各例产物储存稳定性和色数对比表
Figure PCTCN2018098253-appb-000004
参考对比例2改性异氰酸酯产品外观色号偏高且高温稳定性不理想，对比例3-5改性异氰酸酯产品常温储存稳定性理想，但高温稳定性不理想，NCO下降明显和粘度上涨较大，对比例1可以看出单独使用二苯基二氟硅烷，高温稳定性欠佳，实施例1-4表明卤代硅烷类有机物复配对甲苯磺酸酐后常温和高温稳定性均理想，且色号相比其他实施例而言也有所降低。

Claims (11)

  1. 一种浅色改性异氰酸酯混合物的制备方法，该方法包括以下步骤：
    a)使原料异氰酸酯的异氰酸酯基团在磷杂环类催化剂的作用下进行碳化二亚胺化反应，得到含有碳化二亚胺和\或脲酮亚胺类衍生物的改性异氰酸酯反应液；
    b)向步骤a)得到的反应液中加入复配的终止剂用以终止碳化二亚胺化反应；
    所述终止剂为卤代硅烷类有机物复配磺酸酐类物质。
  2. 根据权利要求1所述的制备方法，其中，步骤a)的反应在40-210℃的温度下进行，优选190-200℃下进行。
  3. 根据权利要求1或2所述的制备方法，其中，所述卤代硅烷类有机物具有以下式(Ⅰ)的化学式：
    R 1X 3Si或R 1R 2X 2Si或R 1R 2R 3X 1Si
    (Ⅰ)
    在分子式(Ⅰ)中，R 1、R 2和R 3相互独立的表示任选含有杂原子的脂肪族(例如C1-C10烃基)、芳香族(例如C6-C15芳香族基团，进一步例如苯基、甲苯基、乙苯基)、芳脂族(例如C7-C15芳脂族基团，进一步例如苯甲基、苯乙基等)、脂环族(例如C3-C12脂环族基团)基团，其中R 1、R 2和R 3可相同或不同，并且R 1、R 2和R 3中的两个基团可任选地相互连接形成环结构；
    X代表选自氟、氯、溴和碘中的卤素元素；
    优选的，所述卤代硅烷类有机物选自二苯基二氟硅烷、二苯基二氯硅烷、三苯甲基氟硅烷和叔丁基三氯硅烷中的一种或多种。
  4. 根据权利要求1-3中任一项所述的制备方法，其中，所述磺酸酐类物质具有以下结构式(Ⅱ)：
    Figure PCTCN2018098253-appb-100001
    在结构式(Ⅱ)中，R 4和R 5相互独立的表示任选含有杂原子和/或其它官能团的脂肪族(例如C1-C10烃基)、芳香族(例如C6-C15芳香族基团，进一步例如苯基、甲苯基、乙苯基)、芳脂族(例如C7-C15芳脂族基团，进一步例如苯甲基、苯乙基等)或脂环族(例如C3-C12脂环族基团，进一步例如环丙基、环丁基、环己基、环戊基等)基团，其中R 4和R 5可相同或不同，R 4和R 5两个基团可任选地相互连接形成环结构；优选所述磺酸酐类物质是选自对甲苯磺酸酐、甲基磺酸酐、乙基磺酸酐和三氟甲基磺酸酐中的一种或多种。
  5. 根据权利要求1-4中任一项所述的制备方法，其中，优选终止剂为二苯基二氟硅烷复配对甲苯磺酸酐。
  6. 根据权利要求1-5中任一项所述的制备方法，其中，步骤b)添加复配型终止剂进行终止碳化二亚胺化反应的温度条件为40-70℃，进一步优选40-60℃，更优选50-60℃。
  7. 根据权利要求1-6中任一项所述的制备方法，其中，复配型终止剂的用量以原料异氰酸酯的重量为基准计，卤代硅烷类有机物终止剂用量为50-2000ppm，优选100-600ppm，更优选为100-200ppm；磺酸酐类终止剂用量为10-200ppm，优选10-100ppm，更优选10-50ppm；
    优选的，卤代硅烷类有机物与磺酸酐类的复配质量比为2-6:1，进一步优选3-5:1，更优选4:1。
  8. 根据权利要求1-7中任一项所述的制备方法，其中，用于制备含有碳化二亚胺和/或脲酮亚胺类衍生物的异氰酸酯的催化剂为磷杂环戊烷类催化剂和/或磷杂环戊烯类催化剂及其氧代物，催化剂用量0.1-10ppm，优选0.2-2ppm，最优使用量为0.5ppm，相对于原料异氰酸酯重量。
  9. 根据权利要求1-8中任一项所述的制备方法，其中，原料异氰酸酯是选自芳香族、芳脂族、脂肪族和脂环族二异氰酸酯中的一种或多种，优选二苯基甲烷二异氰酸酯。
  10. 根据权利要求1-9中任一项所述的制备方法，其中，当碳化二亚胺化反应时间达到10min-24h，优选1h-4h之间，加入复配终止剂终止反应；
  11. 通过权利要求1-10中任一项所述的制备方法得到的含有碳化二亚胺和/或脲酮亚胺基团的浅色改性异氰酸酯混合物，其NCO含量为20-32wt％，优选28-30wt％，粘度为10-200cp，优选20-60cp，色数在20-40APHA。
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CN103797633B (zh) * 2012-02-28 2016-09-07 长野自动机械株式会社 制造电极体的装置以及方法
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CN115650880B (zh) * 2022-11-03 2024-08-20 万华化学（宁波）有限公司 一种过保质期mdi的回收处理方法及由其制备碳化二亚胺改性异氰酸酯的方法和产品
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Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2663737A (en) 1951-08-07 1953-12-22 Du Pont Substituted phosphacyclopentene oxides and process of preparing them
US2853473A (en) 1956-08-27 1958-09-23 Du Pont Production of carbodiimides
US4088665A (en) * 1975-08-23 1978-05-09 Bayer Aktiengesellschaft Process for the partial carbodiimidization of organic isocyanates
US4120884A (en) 1976-02-18 1978-10-17 Basf Aktiengesellschaft Storage-stable, liquid polyisocyanates possessing carbodiimide groups, and process for their manufacture
EP0515933A2 (de) 1991-05-28 1992-12-02 Bayer Ag Verfahren zur Herstellung flüssiger, lagerstabiler Carbodiimid- und/oder Uretonimingruppen aufweisender organischer Isocyanate und ihre Verwendung zur Herstellung von Polyurethankunststoffen
US6120699A (en) 1998-09-21 2000-09-19 Basf Corporation Storage stable methylene bis(phenylisocyanate) compositions
CN1502605A (zh) * 2002-11-25 2004-06-09 含有脲二酮基团的多异氰酸酯的制备
US20050282993A1 (en) * 2004-06-17 2005-12-22 Rosthauser James W Process for the production of carbodiimide modified organic isocyanates
CN1721395A (zh) 2004-07-13 2006-01-18 拜尔材料科学股份公司 低色数、含有碳二亚胺和/或脲酮亚胺基团、储存稳定的液体有机异氰酸酯的制备方法
CN1789241A (zh) 2005-12-12 2006-06-21 拜尔材料科学股份公司 液态、储存稳定、色指数低、含有碳二亚胺和/或脲酮亚胺基团的有机异氰酸酯的制备方法
WO2007006622A1 (en) * 2005-07-07 2007-01-18 Huntsman International Llc Method for producing a storage-stable and colorless liquid polyisocyanate composition possessing carbodiimide and/or uretonimine groups
WO2007076998A1 (de) * 2006-01-05 2007-07-12 Bayer Materialscience Ag Verfahren zur herstellung flüssiger, lagerstabiler carbodiimid- und/oder uretonimingruppen aufweisender organischer isocyanate
CN101003496A (zh) * 2006-01-17 2007-07-25 拜尔材料科学股份公司 液态、储存稳定、含有碳二亚胺和/或脲酮亚胺基团的有机异氰酸酯的制备方法
WO2008009669A1 (en) * 2006-07-21 2008-01-24 Basf Se Method of producing a uretonimine-modified isocyanate composition
CN101553517A (zh) * 2006-12-07 2009-10-07 拜尔材料科学股份公司 制备改性多异氰酸酯的方法
CN102718683A (zh) 2012-06-05 2012-10-10 烟台万华聚氨酯股份有限公司 一种制备低色数异氰酸酯的方法及由其制得的异氰酸酯
CN102858747A (zh) * 2010-03-30 2013-01-02 亨茨曼国际有限公司 制备脲酮亚胺改性的异氰酸酯组合物的方法
CN102964566A (zh) * 2012-11-08 2013-03-13 烟台万华聚氨酯股份有限公司 一种制备含亚氨代噁二嗪二酮的多异氰酸酯的方法
CN107879951A (zh) * 2017-10-20 2018-04-06 万华化学集团股份有限公司 一种浅色改性异氰酸酯混合物及其制备方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6054951B2 (ja) 1978-01-25 1985-12-03 日本ポリウレタン工業株式会社 有機イソシアネ−トのイソシアネ−ト基の部分カルボジイミド化法
CN106604944B (zh) * 2014-09-04 2019-03-15 旭化成株式会社 多异氰酸酯组合物、涂料组合物、涂膜及其制造方法、以及潮湿稳定化方法

Patent Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2663737A (en) 1951-08-07 1953-12-22 Du Pont Substituted phosphacyclopentene oxides and process of preparing them
US2853473A (en) 1956-08-27 1958-09-23 Du Pont Production of carbodiimides
US4088665A (en) * 1975-08-23 1978-05-09 Bayer Aktiengesellschaft Process for the partial carbodiimidization of organic isocyanates
US4120884A (en) 1976-02-18 1978-10-17 Basf Aktiengesellschaft Storage-stable, liquid polyisocyanates possessing carbodiimide groups, and process for their manufacture
EP0515933A2 (de) 1991-05-28 1992-12-02 Bayer Ag Verfahren zur Herstellung flüssiger, lagerstabiler Carbodiimid- und/oder Uretonimingruppen aufweisender organischer Isocyanate und ihre Verwendung zur Herstellung von Polyurethankunststoffen
US6120699A (en) 1998-09-21 2000-09-19 Basf Corporation Storage stable methylene bis(phenylisocyanate) compositions
CN1502605A (zh) * 2002-11-25 2004-06-09 含有脲二酮基团的多异氰酸酯的制备
US20050282993A1 (en) * 2004-06-17 2005-12-22 Rosthauser James W Process for the production of carbodiimide modified organic isocyanates
CN1721395A (zh) 2004-07-13 2006-01-18 拜尔材料科学股份公司 低色数、含有碳二亚胺和/或脲酮亚胺基团、储存稳定的液体有机异氰酸酯的制备方法
WO2007006622A1 (en) * 2005-07-07 2007-01-18 Huntsman International Llc Method for producing a storage-stable and colorless liquid polyisocyanate composition possessing carbodiimide and/or uretonimine groups
CN1789241A (zh) 2005-12-12 2006-06-21 拜尔材料科学股份公司 液态、储存稳定、色指数低、含有碳二亚胺和/或脲酮亚胺基团的有机异氰酸酯的制备方法
WO2007076998A1 (de) * 2006-01-05 2007-07-12 Bayer Materialscience Ag Verfahren zur herstellung flüssiger, lagerstabiler carbodiimid- und/oder uretonimingruppen aufweisender organischer isocyanate
CN101003496A (zh) * 2006-01-17 2007-07-25 拜尔材料科学股份公司 液态、储存稳定、含有碳二亚胺和/或脲酮亚胺基团的有机异氰酸酯的制备方法
WO2008009669A1 (en) * 2006-07-21 2008-01-24 Basf Se Method of producing a uretonimine-modified isocyanate composition
CN101553517A (zh) * 2006-12-07 2009-10-07 拜尔材料科学股份公司 制备改性多异氰酸酯的方法
CN102858747A (zh) * 2010-03-30 2013-01-02 亨茨曼国际有限公司 制备脲酮亚胺改性的异氰酸酯组合物的方法
CN102718683A (zh) 2012-06-05 2012-10-10 烟台万华聚氨酯股份有限公司 一种制备低色数异氰酸酯的方法及由其制得的异氰酸酯
CN102964566A (zh) * 2012-11-08 2013-03-13 烟台万华聚氨酯股份有限公司 一种制备含亚氨代噁二嗪二酮的多异氰酸酯的方法
CN107879951A (zh) * 2017-10-20 2018-04-06 万华化学集团股份有限公司 一种浅色改性异氰酸酯混合物及其制备方法

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