CN111747867A - Preparation method of low-color-number low-VOC (volatile organic compounds) modified isocyanate - Google Patents
Preparation method of low-color-number low-VOC (volatile organic compounds) modified isocyanate Download PDFInfo
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Abstract
The invention relates to a preparation method of modified isocyanate with low color number and low VOC. The method comprises the following steps: reacting an isocyanate monomer under the action of a phosphorus-containing catalyst to obtain a modified isocyanate reaction solution; adding a boron-containing compound and a phosphorus-containing catalyst into the reaction solution for coordination reaction to obtain modified isocyanate; optionally, a terminating agent is added to terminate the reaction. The modified isocyanate prepared by the method has the advantages of low color number, low VOC, long shelf life, stability under high temperature and the like.
Description
Technical Field
The invention belongs to the field of isocyanate, and particularly relates to a preparation method of low-color-number low-VOC modified isocyanate.
Background
The isocyanate can be condensed under certain conditions to release CO2Then Carbodiimide (CDI) derivatives are generated, carbodiimide groups can be subjected to addition reaction with isocyanate to form Uretonimine (UTI), the isocyanate contains CDI and UTI substances by the method, the modified isocyanate has a reduced freezing point and is liquid at normal temperature, the good storage stability is favorable for long-distance transportation and downstream application, and products prepared from the modified isocyanate are improved to a certain extent in the aspects of light resistance, flame resistance, hydrolysis resistance, initial strength increase and the like.
The isocyanate groups are converted into carbodiimides and uretonimine derivatives by thermal reaction under the action of efficient catalysts of phospholes, especially phospholene oxides, the preparation process being described in detail in patents US6120699, US2853473 and EP 515933.
The phospholene catalyst, especially the phospholene oxide catalyst has higher activity, can activate the carbodiimidization reaction at lower temperature, because the catalyst has high activity, low reaction temperature and short time, the content of dimer formed by self-polymerization of isocyanate is greatly reduced in the reaction process, but the catalyst still has sufficient activity at room temperature so as to influence the storage stability of the product, NCO groups continue to be condensed in the storage process, CO is released2There is a safety risk, and the product viscosity rises and the properties change, so it needs to be deactivated by chemical means or removed by physical means.
In order to terminate the catalyst for further catalyzing the conversion of NCO into CDI and UTI groups, a terminator is added into the reaction liquid to deactivate the catalyst. Suitable terminating agents are described in EP515933, CN1721395. US4120884, CN1789241 and CN102718683 are mentioned, including lewis acids, acid chlorides, chloromethanes, aromatic sulfonic acids/esters, methylsilylated acids, halosilanes, alkyl sulfates and halides of main group elements. The termination of the catalyst with an acid or an anhydride has the following disadvantages: if the acid dosage is too low, the termination effect is poor, and the viscosity of the product continues to rise in the storage process; if the acid dosage is too high, the color of the product is deepened, the acid content is increased, the downstream application activity of the product is seriously influenced, and the VOC of the product is also increased. The product is unstable at the high temperature higher than 100 ℃ by using the silane termination catalyst alone, and NCO continues to react to generate CO2The application field is limited, and the single use of the silane has huge dosage which is generally 300 times of that of the catalyst.
EP515933 discloses isocyanate mixtures containing CDI/UTI groups prepared from phospholene catalysts, the termination catalyst activity being terminated at least with an equimolar, preferably 1-2 times molar amount of catalyst, for example trimethylsilyl trifluoromethanesulfonate (TMST). However, practice proves that the modified isocyanate prepared by the method has the problems of incomplete termination, poor storage stability and the like, particularly, in an environment with low outdoor temperature in winter, a water bath material is needed in the use process of the product, gas is generated in the material dissolving process, so that the pressure in a storage container is high, and the NCO of the product is obviously reduced and the viscosity is obviously increased.
CN1721395 discloses that the catalyst activity is terminated by using a methylsilylated acid, such as trimethylsilyl trifluoromethanesulfonate, the expected purpose can be achieved by using the amount of a terminator, but the appearance color number of the product rises rapidly, the patent improves the termination effect of the terminator by compounding non-silylated acid, acyl chloride and sulfonate through the trimethylsilyl trifluoromethanesulfonate, the stability of the product is improved, the color number of the product can reach 50-60APHA, but in the current technical field, the appearance color still cannot meet the market demand, and the viscosity rises remarkably in the high-temperature heating process of the product.
US4120884 discloses the use of dimethyl sulfate to terminate phospholene catalysts with a certain improvement in storage stability compared to the use of TMST, but with a significant increase in process viscosity of the chemicals.
CN1789241 adopts alkylating reagent such as trifluoromethanesulfonate to terminate the reaction, and stability can be improved by increasing the molar equivalent ratio of the terminating agent to the catalyst to complete the termination, but the color number of the product is not ideal.
CN102718683 optimizes the method, and adopts an acid anhydride terminator to terminate the phosphole or oxidized phosphole catalyst, and the preferred terminator is trifluoromethanesulfonic anhydride and/or p-toluenesulfonic anhydride.
CN107879951 adopts silane organic compound acid anhydride as new terminator, has achieved better effect, but the modified product prepared by this method is still unstable under the condition of more than 100 deg.C, the viscosity rises rapidly, release CO constantly2The application field of the method is limited by the high-temperature instability of the method, and the method has the advantages of large consumption of silane organic matters, easy volatilization of acid anhydride, high final preparation cost and high VOC (volatile organic compounds) of products.
In summary, the existing method for preparing liquid isocyanate containing CDI and/or UTI groups is difficult to overcome the problems of high addition amount of the terminator and high color number and VOC caused by the high addition amount of the terminator.
Disclosure of Invention
The invention provides a preparation method of modified isocyanate with low color number and low VOC (volatile organic compounds), and the modified isocyanate prepared by the method has the advantages of light color, low VOC, long shelf life and good high-temperature stability.
In order to achieve the above purpose, the invention provides the following technical scheme:
a method for preparing a low color number, low VOC modified isocyanate, said method comprising the steps of:
s1: reacting an isocyanate monomer under the action of a phosphorus-containing catalyst to obtain a modified isocyanate reaction solution;
s2: adding a boron-containing compound and a phosphorus-containing catalyst into the reaction solution of S1 for coordination reaction to obtain modified isocyanate;
optionally, adding a terminator in S2 to terminate the catalytic reaction; the addition of a terminating agent is related to the catalyst activity.
The coordination of the boron-containing compound and the catalyst destroys the catalytic effect, and the complex has the following structure:
theoretically, the molar ratio of the catalyst to the boron-containing compound is 1:1 for coordination, but because the concentration of the catalyst is lower, the collision probability between molecules is reduced, and the boron-containing compound needs to be excessive by more than 2 times to achieve better coordination effect.
In one embodiment, the isocyanate monomer is in N2Heating while stirring under protection, adding catalyst, mixing, heating rapidly, reacting, adding isocyanate monomer, quenching, cooling, adding boron-containing compound, and stirring to obtain final product. If the terminator is added, adding the boron-containing compound, stirring for 0.5-4h, adding the terminator, and continuously stirring to obtain the final product.
In the research process of the invention, it is found that if acids or acid anhydrides are used as the terminating agent, the dosage of the terminating agent is larger, generally more than 200ppm, the prepared product has darker color, the acid content of the product is higher, the activity of downstream application is greatly influenced, and the acid anhydrides are volatile, so that the VOC of the final product is higher. The halogenated silane organic matter has large molecular weight and small polarity, the bonding with the catalyst is influenced by steric hindrance and electronic effect, the needed silane amount is 200-300 times of the catalyst amount, and simultaneously the catalyst activity can be reactivated at high temperature, so that the product stability is reduced. If a trace amount of boric acid substances are added to be coordinated with the catalyst before the halogenated silanes are used, the electron density distribution of the catalyst is changed, so that the halogenated silanes are more favorable for attacking the catalyst to react, the method can completely inactivate the catalyst and keep the high-temperature stability, and the consumption of the halogenated silanes is greatly reduced and is superior to acids, acid anhydride substances and silane organic terminating agents. The modified isocyanate containing CDI and UTI groups prepared by the method has light color, low VOC (volatile organic compounds) of products and good stability, and the viscosity of the products can not be obviously increased even at the high temperature of 120 ℃.
In the present invention, the reaction of S1 is a condensation reaction of isocyanate monomers.
In the invention, the condensation reaction is carried out to obtain modified isocyanate containing Carbodiimide (CDI) and Uretonimine (UTI); according to the present invention, it is generally easy to introduce UTI groups into the isocyanate system by converting 5% to 20%, preferably 10% to 15%, of the NCO groups of the starting isocyanate to CDI groups by carbodiimidization, followed by reaction of the CDI groups with unreacted NCO groups to form UTI groups, which usually requires leaving the reaction mixture containing NCO and CDI groups at room temperature for a period of time to allow complete conversion of the CDI groups to UTI groups.
In the invention, the isocyanate monomer in S1 is selected from one or more of aromatic diisocyanate and aliphatic diisocyanate, preferably aromatic diisocyanate, and more preferably diphenylmethane diisocyanate; it is further preferred that the diphenylmethane diisocyanate contains from 97% to 100% by weight of the 4, 4-isomer, from 0% to 1% by weight of the 2, 2-isomer and from 0.5% to 1.8% by weight of the 2, 4-isomer.
In the invention, the temperature of the S1 reaction is 40-210 ℃, preferably 90-120 ℃; the reaction can also be carried out at a mild environmental temperature, but the required catalyst dosage is larger, the addition of a terminator is large, the product color number is not ideal, the cost is increased, the reaction rate is slow due to the small catalyst dosage, the isocyanate is polymerized to form a dimer, the long-term storage of the product is not facilitated, and the industrial production is also not facilitated.
In the present invention, the reaction time of S1 is 0.5 to 10 hours, preferably 1 to 4 hours.
In the present invention, the phosphorus-containing catalyst in S1 is selected from a phospholane catalyst, preferably one or more of a phospholane catalyst, a phospholane oxo catalyst, a phosphole catalyst, and a phosphole oxo catalyst.
In the present invention, the amount of the catalyst used in S1 is 0.3ppm to 15ppm, preferably 1ppm to 9ppm, and most preferably 5ppm, based on the total mass of the isocyanate monomer.
In the present invention, the boron-containing compound of S2 is selected from one or more of boric acid, borate and boron-containing complex, preferably boric acid and/or boron-containing complex.
In the present invention, when a borate is used as the S2, the cation of the borate is one or more of calcium, magnesium and sodium.
In the present invention, the boron-containing compound in S2 is added in an amount of 5ppm to 500ppm, preferably 10ppm to 50ppm, based on the total mass of the isocyanate monomer.
In the invention, the S2 is added with the boron-containing compound and then reacts for 0.5 to 4 hours. During the polycondensation of NCO, CO is generated2So that the reaction process can be measured by CO2The amount of release is monitored; or reflecting the change of the NCO content by continuously measuring the refractive index change of the reaction liquid. When the carbodiimidization reaction is carried out in the above time period, the reaction is terminated by adding no terminator or adding a terminator in portions.
In the present invention, the terminating agent of S2 is one or more of organic acid, inorganic acid and halogenated silane organic substance, wherein the acid is non-boron-containing acid, because the addition amount of the boron-containing compound must be controlled within the aforementioned range, for example, too high boron addition amount may adversely affect the product quality. Preferably, the halosilane organic compound is R1XSi、R1R2XSi and R1R2R3One or more of XSi, wherein R1、R2And R3Independently of each other, is selected from one or more of aliphatic, aromatic and araliphatic radicals containing halogen, nitrogen, phosphorus, oxygen heteroatoms, and X is selected from one or more of fluorine, chlorine, bromine and iodine; more preferably R in the halosilane organic compound1、R2And R3Independently selected from C1-C12 aliphatic hydrocarbon group containing halogen, nitrogen, phosphorus and oxygen heteroatom, C6-C15 aromatic group and C7-C15 araliphatic groupOne or more of; most preferably, the halosilane organic is one or more of tert-butyltrifluorosilane, diphenyldichlorosilane, diphenyldifluorosilane, and tritylfluorosilane.
In the present invention, when the terminator is added to S2, the amount of the terminator to be used is 1ppm to 200ppm, preferably 20ppm to 100ppm, based on the total mass of the isocyanate monomer.
In the invention, when the terminator is added, the S2 reacts for 0.5 to 4 hours after the addition.
In the present invention, an isocyanate monomer is optionally back-blended in S2.
In the invention, the ratio of the isocyanate monomer which is back-blended in S2 to the isocyanate monomer which is added in S1 is 1:3-1: 1.
Another object of the present invention is to provide a modified isocyanate.
A low color number and low VOC modified isocyanate prepared according to the preparation method.
In the invention, the modified isocyanate is modified isocyanate containing carbodiimide and uretonimine groups.
In the present invention, the modified isocyanate has an NCO content of 20 to 32% by weight, preferably 28 to 30% by weight.
In the present invention, the viscosity of the modified isocyanate is 10 to 200cp, preferably 20 to 60 cp.
In the invention, the color number is 20-60APHA, and the initial value of the product hasen color number is preferably 20-30 APHA.
In the invention, the content of the modified isocyanate in online VOC detection is 10ppm to 150ppm, preferably 10ppm to 45 ppm.
The advantages of the process according to the invention are evident, due to the low amounts of boron containing compounds and halosilane type organics used, the isocyanates containing CDI and/or UTI groups are substantially light-colored, the product VOC is low, and the storage stability at normal and high temperatures is provided. These and other advantages and benefits of the present invention are apparent from the detailed description of the invention herein.
The invention has the positive effects that:
a) only a trace amount of terminator or no terminator is used in the process of preparing the modified isocyanate, so that the VOC content of the product is greatly reduced and is less than 150ppm, and generally between 30ppm and 40 ppm.
b) The prepared modified isocyanate has low color number, is generally stable at 20-60APHA, and has obviously reduced color number
c) The prepared modified isocyanate product has good normal temperature storage stability, and does not generate self-polycondensation to release CO in downstream high-temperature application2The stability of the system is ensured by the reaction of the gas; meanwhile, even under a high-temperature environment, the viscosity of the system is changed very little during the storage process of the product.
Detailed Description
The invention is further illustrated by the following examples, but the scope of the invention is not limited thereto.
Raw materials:
diphenylmethane diisocyanate monomer, wherein the diphenylmethane diisocyanate contains 97 wt% to 100 wt% of 4, 4-isomer, 0 wt% to 1 wt% of 2, 2-isomer, and 0.5 wt% to 1.8 wt% of 2, 4-isomer, and has an NCO content of 33.6 wt%;
toluene diisocyanate monomer, wherein the toluene diisocyanate monomer contains 79-81% of 2, 4-isomer and 19-21% of 2, 6-isomer, and the NCO content is 48.3%;
1-methyl-3-phosphole-1-oxide, 1-phenyl-2-phospholene-1-oxide and catalyst to prepare 1 wt% dichloromethane solution;
boronic acid, shanghai future reagent, AR;
sodium borate, Beijing Hengchang Zhongyuan, CR;
boron trifluoride diethyl etherate, shanghai michelin, 98%;
diphenyldifluorosilane, shanghai maireil, 97%;
diphenyldichlorosilane, michelin, 97%;
p-toluenesulfonic acid, Annagiki chemical, 98%.
The testing instrument comprises a DV-79 digital viscometer and a PGM-7360 VOC detector for testing the VOC of the product: 500g of the product was placed in a 1L glass beaker, open at 1m3And (4) sealing the glass space, testing the VOC in the space every 2h, and taking the final stable value as the VOC of the sample. The color number is tested by using a national standard method (standard GB/T605-.
The equipment used for the experiment comprises a conventional four-neck flask, an oil bath kettle, a mechanical stirrer and a rotor flow meter.
Example 1
500g of diphenylmethane diisocyanate in N2Heating to 50 ℃ under protection and stirring, adding 0.5ppm of 1-methyl-3-phosphole-1-oxide efficient catalyst, mixing, rapidly heating to 200 ℃, reacting for 2h, adding 400g of diphenylmethane diisocyanate, rapidly cooling to 75 ℃, adding 20ppm of boron-containing compound sodium borate, and stirring for 4h to obtain the final product.
Example 2
500g of diphenylmethane diisocyanate in N2Heating to 50 ℃ under protection and stirring, adding 12ppm of 1-methyl-3-phosphole-1-oxide efficient catalyst, mixing, rapidly heating to 80 ℃, reacting for 1.5h, then adding 200g of diphenylmethane diisocyanate, rapidly cooling to 75 ℃, adding 500ppm of boron-containing compound sodium borate, and stirring for 4h to obtain the final product.
Example 3
500g of diphenylmethane diisocyanate in N2Heating to 50 ℃ under protection and stirring, adding 5ppm of 1-methyl-3-phosphole-1-oxide efficient catalyst, mixing, rapidly heating to 100 ℃, reacting for 2 hours, then adding 400g of diphenylmethane diisocyanate, rapidly cooling to 75 ℃, adding 10ppm of boron-containing compound boric acid, stirring for 1 hour, then adding 200ppm of p-toluenesulfonic acid, and stirring for 2 hours to obtain the final product.
Example 4
500g of diphenylmethane diisocyanate in N2Heating to 50 deg.C under protection while stirring, adding 2ppm of 1-phenyl-2-phospholene-1-oxide catalyst, mixing, rapidly heating to 90 deg.C, reacting for 10 hr, and adding diphenylAfter 500g of methane diisocyanate, the temperature is cooled down to 75 ℃, 10ppm of boric compound boric acid is added firstly, the mixture is stirred for 1 hour, 50ppm of diphenyl dichlorosilane is added, and the mixture is stirred for 2 hours to obtain the final product.
Example 5
500g of diphenylmethane diisocyanate in N2Heating to 50 ℃ under protection and stirring, adding 5ppm of 1-methyl-3-phosphole-1-oxide efficient catalyst, mixing, rapidly heating to 100 ℃, reacting for 2h, then adding 400g of diphenylmethane diisocyanate, rapidly cooling to 75 ℃, adding 30ppm of boron-containing compound sodium borate, stirring for 2h, then adding 20ppm of hydrogen fluoride, and stirring for 2h to obtain the final product.
Example 6
500g of toluene diisocyanate in N2Heating to 50 ℃ under protection and stirring, adding 5ppm of 1-methyl-3-phosphole-1-oxide efficient catalyst, mixing, rapidly heating to 100 ℃, reacting for 3h, adding 300g of toluene diisocyanate, rapidly cooling to 75 ℃, adding 10ppm of calcium borate, stirring for 2h, adding 50ppm of diphenyl difluorosilane, and stirring for 4h to obtain the final product.
Example 7
500g of diphenylmethane diisocyanate in N2Heating to 50 ℃ under protection and stirring, adding 3ppm of 1-methyl-3-phosphole-1-oxide catalyst, mixing, rapidly heating to 100 ℃, reacting for 2h, adding 300g of diphenylmethane diisocyanate, rapidly cooling to 75 ℃, adding 10ppm of boron-containing compound boron trifluoride diethyl etherate, and stirring for 4h to obtain the final product.
Comparative example 1
500g of diphenylmethane diisocyanate in N2Heating to 50 ℃ under protection and stirring, adding 5ppm of 1-methyl-3-phosphole-1-oxide efficient catalyst, mixing, rapidly heating to 100 ℃, reacting for 2h, adding 400g of diphenylmethane diisocyanate, rapidly cooling to 75 ℃, adding 2000ppm of terminator diphenyldifluorosilane, and stirring for 4h to obtain the final product.
Comparative example 2
500g of diphenylmethane diisocyanate in N2Heating to 50 ℃ under protection and stirring, adding 5ppm of 1-methyl-3-phosphole-1-oxide efficient catalyst, mixing, rapidly heating to 100 ℃, reacting for 2h, then adding 400g of diphenylmethane diisocyanate, rapidly cooling to 75 ℃, adding 500ppm of terminator diphenyl difluorosilane, and stirring for 2h to obtain the final product.
The storage stability and color number of the individual products are compared in Table 1. Comparative examples 1 and 2 show that the use of silane terminating agents has large dosage and VOC problem, and the product viscosity rapidly rises and has poor stability under the high temperature condition of 120 ℃; examples 1 and 2 show that when the addition amount of the boron-containing compound sodium borate is increased, the apparent color number of the modified product is slightly increased, and the high-temperature stability at 120 ℃ is improved; examples 3, 4, 5 and 6 show that the addition amount of the terminating agent can be greatly reduced by using a trace amount of boric acid for coordination with the catalyst and then adding the silane terminating agent, so that the VOC (volatile organic compound) of the product is reduced, and meanwhile, the color number and the high-temperature stability of the product are ideal.
It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
TABLE 1 comparison of the storage stability and color number of the products of the examples
Claims (8)
1. A preparation method of modified isocyanate with low color number and low VOC is characterized by comprising the following steps:
s1: reacting an isocyanate monomer under the action of a phosphorus-containing catalyst to obtain a modified isocyanate reaction solution;
s2: adding a boron-containing compound and a phosphorus-containing catalyst into the reaction solution of S1 for coordination reaction to obtain modified isocyanate;
optionally, a terminating agent is added to S2 to terminate the catalytic reaction.
2. The method according to claim 1, wherein the reaction of S1 is a condensation reaction of isocyanate monomers;
and/or, the condensation reaction yields a modified isocyanate containing Carbodiimide (CDI) and Uretonimine (UTI);
and/or the isocyanate monomer is selected from one or more of aromatic diisocyanate and aliphatic diisocyanate, preferably aromatic diisocyanate, more preferably diphenylmethane diisocyanate;
and/or the temperature of the reaction is 40-210 ℃, preferably 90-120 ℃;
and/or the reaction time is 0.5 to 10 hours, preferably 1 to 4 hours.
3. The method according to claim 1 or 2, wherein the phosphorus-containing catalyst in S1 is selected from the group consisting of phospholane catalysts, preferably one or more of phospholane catalysts, phospholane oxo catalysts, phosphole catalysts, and phosphole oxo catalysts;
and/or the catalyst is used in an amount of 0.3ppm to 15ppm, preferably 1ppm to 9ppm, most preferably 5ppm, based on the total mass of isocyanate monomer.
4. The method according to claim 1, wherein the boron-containing compound of S2 is selected from one or more of boric acid, a borate and a boron-containing complex, preferably boric acid and/or a boron-containing complex;
and/or, when a borate is employed, the cation of the borate is one or more of calcium, magnesium and sodium;
and/or the boron-containing compound is added in an amount of 5ppm to 500ppm, preferably 10ppm to 50ppm, based on the total mass of the isocyanate monomer;
and/or reacting for 0.5-4h after adding the boron-containing compound.
5. The method according to claim 1, wherein the terminating agent of S2 is one or more of an organic acid, an inorganic acid, and a halosilane organic substance, wherein the acid is a boron-free acid;
preferably, the halosilane organic compound is R1XSi、R1R2XSi and R1R2R3One or more of XSi, wherein R1、R2And R3Independently of each other, is selected from one or more of aliphatic, aromatic and araliphatic radicals containing halogen, nitrogen, phosphorus, oxygen heteroatoms, and X is selected from one or more of fluorine, chlorine, bromine and iodine; more preferably R in the halosilane organic compound1、R2And R3One or more of C1-C12 aliphatic hydrocarbon groups containing halogen, nitrogen, phosphorus and oxygen heteroatoms, C6-C15 aromatic groups and C7-C15 aromatic aliphatic groups independently; most preferably, the halogenated silane organic matter is one or more of tert-butyl trifluorosilane, diphenyl dichlorosilane, diphenyl difluorosilane and trityl fluorosilane;
and/or, if a terminator is added, in an amount of from 1ppm to 200ppm, preferably from 20ppm to 100ppm, based on the total mass of the isocyanate monomers;
and/or, if a terminator is added, reacting for 0.5-4h after the addition.
6. The method according to claim 1, wherein an isocyanate monomer is optionally back-blended into S2;
and/or the ratio of the isocyanate monomer which is reversely blended to the isocyanate monomer added in S1 is 1:3-1: 1.
7. A low color number, low VOC modified isocyanate prepared according to the method of any one of claims 1-6.
8. The modified isocyanate according to claim 7, wherein the modified isocyanate is a modified isocyanate containing carbodiimide and uretonimine groups;
and/or the modified isocyanate has an NCO content of 20 to 32 wt.%, preferably 28 to 30 wt.%;
and/or the viscosity of the modified isocyanate is 10-200cp, preferably 20-60 cp;
and/or, the modified isocyanate color number is 20-60 APHA;
and/or the modified isocyanate has an online VOC content of 10ppm to 150ppm, preferably 10ppm to 45 ppm.
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| GB1153815A (en) * | 1966-07-21 | 1969-05-29 | Bayer Ag | Aliphatically Substituted Uretidiones |
| CN101356154A (en) * | 2006-01-05 | 2009-01-28 | 拜尔材料科学股份公司 | Process for preparing liquid, storage-stable organic isocyanates containing carbodiimide and/or uretonimine groups |
| CN102942525A (en) * | 2012-11-01 | 2013-02-27 | 烟台万华聚氨酯股份有限公司 | Method for preparing polyisocyanate containing uretidione group |
| CN103613540A (en) * | 2013-11-26 | 2014-03-05 | 万华化学（宁波）有限公司 | Method for preparing urethodione group-containing diisocyanate homopolymer |
| CN107879951A (en) * | 2017-10-20 | 2018-04-06 | 万华化学集团股份有限公司 | A kind of light modified isocyanate mixture and preparation method thereof |
| CN110183390A (en) * | 2019-06-04 | 2019-08-30 | 中海油常州涂料化工研究院有限公司 | A kind of biology base pentamethylene diisocyanate trimer preparation method |
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