CN115650880A - Recycling method of MDI with over-shelf life, method for preparing carbodiimide modified isocyanate from MDI with over-shelf life and product - Google Patents
Recycling method of MDI with over-shelf life, method for preparing carbodiimide modified isocyanate from MDI with over-shelf life and product Download PDFInfo
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- CN115650880A CN115650880A CN202211374581.6A CN202211374581A CN115650880A CN 115650880 A CN115650880 A CN 115650880A CN 202211374581 A CN202211374581 A CN 202211374581A CN 115650880 A CN115650880 A CN 115650880A
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- 238000000034 method Methods 0.000 title claims abstract description 45
- 150000001718 carbodiimides Chemical class 0.000 title claims abstract description 38
- 239000012948 isocyanate Substances 0.000 title claims abstract description 29
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 29
- 238000004064 recycling Methods 0.000 title claims abstract description 23
- 239000000539 dimer Substances 0.000 claims abstract description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 12
- 239000011574 phosphorus Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 83
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 12
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 10
- -1 phosphorus compound Chemical class 0.000 claims description 10
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 8
- SVABQOITNJTVNJ-UHFFFAOYSA-N diphenyl-2-pyridylphosphine Chemical compound C1=CC=CC=C1P(C=1N=CC=CC=1)C1=CC=CC=C1 SVABQOITNJTVNJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- BHMCETZNSRSQAO-UHFFFAOYSA-N 2h-pyrrolo[3,2-c]pyridine Chemical compound C1=NC=CC2=NCC=C21 BHMCETZNSRSQAO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 claims description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 2
- UVECLJDRPFNRRQ-UHFFFAOYSA-N ethyl trifluoromethanesulfonate Chemical compound CCOS(=O)(=O)C(F)(F)F UVECLJDRPFNRRQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 2
- HOBCFUWDNJPFHB-UHFFFAOYSA-N indolizine Chemical compound C1=CC=CN2C=CC=C21 HOBCFUWDNJPFHB-UHFFFAOYSA-N 0.000 claims description 2
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- GRJHONXDTNBDTC-UHFFFAOYSA-N phenyl trifluoromethanesulfonate Chemical compound FC(F)(F)S(=O)(=O)OC1=CC=CC=C1 GRJHONXDTNBDTC-UHFFFAOYSA-N 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- MJYCCJGURLWLGE-UHFFFAOYSA-N propyl trifluoromethanesulfonate Chemical compound CCCOS(=O)(=O)C(F)(F)F MJYCCJGURLWLGE-UHFFFAOYSA-N 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims description 2
- IIOSDXGZLBPOHD-UHFFFAOYSA-N tris(2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P(C=1C(=CC=CC=1)OC)C1=CC=CC=C1OC IIOSDXGZLBPOHD-UHFFFAOYSA-N 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims 1
- 239000000047 product Substances 0.000 description 25
- 238000003756 stirring Methods 0.000 description 15
- 238000002156 mixing Methods 0.000 description 11
- 238000011056 performance test Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- HJSPBGHQCVGOEZ-UHFFFAOYSA-N P.C1=CCCC1 Chemical group P.C1=CCCC1 HJSPBGHQCVGOEZ-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 2
- KOFDMTFGDBPZFS-UHFFFAOYSA-N C1=CC=C(C=C1)C2=CC(=C(C(=C2C3=CC=CC=C3)C4=CC=CC=C4)C5=CC=CC=C5)PC6=CC=CC=C6 Chemical compound C1=CC=C(C=C1)C2=CC(=C(C(=C2C3=CC=CC=C3)C4=CC=CC=C4)C5=CC=CC=C5)PC6=CC=CC=C6 KOFDMTFGDBPZFS-UHFFFAOYSA-N 0.000 description 1
- BXLBIJUFCJJTEL-UHFFFAOYSA-N [PH3]=O.C1=CCCC1 Chemical compound [PH3]=O.C1=CCCC1 BXLBIJUFCJJTEL-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- DFGMXHGIJKCSMQ-UHFFFAOYSA-N phospholan-2-one Chemical compound O=C1CCCP1 DFGMXHGIJKCSMQ-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a recycling method of MDI with a shelf life, a method for preparing carbodiimide modified isocyanate by using the recycling method and a product. Firstly, adding nitrogen and/or phosphorus-containing compounds into MDI with the over-shelf life at high temperature to decompose supersaturated dimer in the MDI; and then carrying out carbodiimide reaction under the action of a phosphorus heterocyclic catalyst to prepare carbodiimide modified isocyanate with low color number and stable storage, thereby realizing the reutilization of MDI with over shelf life.
Description
Technical Field
The invention belongs to the technical field of isocyanate, and provides a recycling method of MDI with an over-shelf life, a method for preparing carbodiimide modified isocyanate by using the recycling method and a product.
Technical Field
Diphenylmethane diisocyanate (MDI) is an important raw material for preparing polyurethane materials, and because the reactivity of isocyanate groups is higher and has strong self-polymerization tendency, the MDI is easy to form a ring by self-polymerization at room temperature, namely a dimer is generated, so that the effective components are reduced, the activity is reduced, the product turbidity is increased after the dimer is separated out, the quality of a polyurethane product is obviously influenced, and the downstream application is possibly influenced because the requirement on the dimer content of the isocyanate in more fields in the downstream application is strict.
Diphenylmethane diisocyanate (MDI) has 3 isomers, i.e., 2'-MDI, 2,4' -MDI and 4,4'-MDI, more than 98% of 4,4' -MDI being MDI-100, i.e., pure MDI; MDI-50 is composed of 2,4'-MDI and 4,4' -MDI, each 50% by mass. The activity of the three isomers is different, the dimer growth rate is different in the storage process at the same temperature, MDI-50 is liquid at room temperature, and the shelf life is usually 6 months at 15-30 ℃ due to low activity and high solubility of the dimer; the crystallization temperature of MDI-100 is 38.6 ℃, MDI-100 is solid at room temperature, in order to ensure the liquid state, MDI-100 is generally stored at 40-45 ℃, the storage shelf life of MDI-100 at 45 ℃ in the prior industry is about two weeks due to higher activity and lower dimer solubility, and the storage period of only liquid material of the Dow MDI-100 reaches 45 days.
At present, the existing method for controlling the formation of MDI series product dimer mainly comprises the control of the temperature in the storage process and the mode of a rectification crystallization process, but has complex operation and does not have a method for obviously prolonging the shelf life aiming at the storage period of liquid 4, 4-diphenylmethane diisocyanate. When the MDI has over-shelf life and the dimer is separated out, the MDI with over-shelf life is mainly used for the field of back mixing PM or supplying to low-end paving filling materials, and the utilization value is greatly reduced.
Therefore, there is a need for the development of a method for recycling MDI with an over-shelf life to ensure the long-term utility value of MDI.
Disclosure of Invention
In view of the above-mentioned deficiencies of the prior art, it is an object of the present invention to provide a method for recycling MDI with an excessive shelf life by decomposing supersaturated dimers in MDI by adding a phosphorane compound under high temperature conditions.
The invention also aims to provide a method and a product for preparing carbodiimide modified isocyanate by using the MDI after the dimer decomposition, so that the recycling of MDI with over shelf life is realized.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention firstly provides a recycling treatment method of MDI with over-shelf life, which comprises the steps of heating MDI with over-shelf life to 180-220 ℃, preferably 200-205 ℃, then adding nitrogen and/or phosphorus compounds to be uniformly mixed, and carrying out heat preservation reaction for 2-5h, preferably 2-3h until the content of dimer is reduced to below 2000ppm to obtain recycled MDI.
In the invention, the MDI with the over-shelf life comprises separated MDI dimer, namely, the dimer is saturated and separated out at the storage temperature of the liquid product;
the dimer content in the MDI with over-shelf life is more than 2500ppm, preferably 2500-20000ppm, more preferably 5000-18000ppm, and further preferably 10000-15000ppm.
In the invention, the over-shelf-life MDI has no specific requirement on the MDI type, and can be MDI-50 or MDI-100, preferably MDI-100;
preferably, the MDI comprises the following components in percentage by weight: 96-100wt% of 4,4' -MDI, 0-1wt% of 2,2' -MDI and 0.1-4wt% of 2,4' -MDI.
In the present invention, the nitrogen-and/or phosphorus-containing compound, preferably a nitrogen-containing heterocyclic ring and/or phosphine compound such as indolizine, 4-azopyridine, quinoline, isoquinoline, indole, 2H-pyrrolo [3,2-c ] pyridine, diphenyl-2-pyridylphosphine, 1' -binaphthyl-2, 2' -bisdiphenylphosphine, tris (2-methoxyphenyl) phosphine, tetraphenyliminophosphine, methyldiphenylphosphine, 2-dicyclohexylphosphine-2 ',6' -diisopropoxy-1, 1' -biphenyl, isopropylbiphenylphosphine, trioctylphosphine, and the like, preferably at least one selected from quinoline, isoquinoline, diphenyl-2-pyridylphosphine, 1' -binaphthyl-2, 2' -bisdiphenylphosphine, tetraphenyldiphenylphosphine, and more preferably diphenyl-2-pyridylphosphine;
preferably, the nitrogen and/or phosphorus containing compound is used in an amount of 1 to 100ppm, preferably 2 to 50ppm, more preferably 5 to 20ppm, based on the mass of the over-shelf MDI.
In the present invention, the reaction is carried out in an inert gas atmosphere, preferably a nitrogen atmosphere.
The invention also provides a method for preparing carbodiimide modified isocyanate by adopting MDI with the over-shelf life, which takes the recycled MDI as a raw material (namely the recycled MDI with the over-shelf life is obtained by the recycling treatment method), and the carbodiimide modified isocyanate is prepared by carrying out carbodiimide reaction under the action of the phosphorus heterocyclic catalyst.
In the method, the phosphorus heterocyclic catalyst is cyclopentene phosphine, preferably cyclopentene phosphine oxide;
preferably, the oxypentene phosphine is selected from at least one of 1-methyl-3-phosphole-1-oxide, 1-methyl-1-oxyphosphole, 3-methyl-1-phenyl-3-phosphole, 2-methyl-2, 5-dioxo-1, 2-oxyphosphole;
preferably, the phosphorus heterocyclic catalyst is used in an amount of 0.5 to 50ppm, preferably 1 to 30ppm, more preferably 2 to 10ppm, based on the weight of the recycled MDI.
In the method, the carbodiimide reacts at the temperature of 150-220 ℃, preferably 180-210 ℃, and more preferably 200-205 ℃; for a period of time of 0.5-2.5h, preferably 1-2h, more preferably 1-1.5h;
preferably, after the carbodiimide reaction is finished, a cooling curing process is further included, and the temperature is preferably reduced to 60-70 ℃ for constant-temperature curing for 4-5h;
the carbodiimide reaction is carried out in an inert gas environment, preferably a nitrogen environment.
In the method, after the carbodiimide reaction is finished, preferably, a terminator is added after the temperature reduction and the aging are finished to finish the reaction, wherein the terminator is an acid terminator, and is preferably selected from at least one of trifluoromethanesulfonic anhydride, ethyl trifluoromethanesulfonate, propyl trifluoromethanesulfonate, phenyl trifluoromethanesulfonate, adipoyl chloride and benzoyl chloride;
preferably, the amount of the terminating agent is 10-100ppm of the mass of the recycled MDI;
preferably, the terminator is added and stirred for 1-2h, and then the temperature is reduced to 45-50 ℃ to obtain the product.
According to the method provided by the invention, MDI with a shelf life being over can be recycled and reused, and is applied to producing carbodiimide modified isocyanate with qualified dimer content.
The carbodiimide modified isocyanate prepared by the invention also has the advantage of low color number, and the color number can be reduced to 10-30APHA, preferably 10-20APHA from 40-110APHA of MDI with over-shelf life.
The carbodiimide-modified isocyanate of the invention has an isocyanate group content of 24 to 32wt%, preferably 26 to 31wt%; the dimer content is 6000ppm or less, preferably 3000ppm or less.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
the invention adds the nitrogen phosphine compound into MDI with over quality guarantee period to carry out recovery treatment, and reduces the saturated dimer content in isocyanate by catalytically decomposing MDI dimer four-membered ring in the MDI with high temperature. The invention further carries out carbodiimidization reaction on the isocyanate to obtain a modified isocyanate product, thereby achieving the purpose of recycling MDI (diphenylmethane diisocyanate) after the shelf life is over;
in the invention, during the modification reaction of the carbodiimide, the generation of color development substances in the process of modifying the isocyanate by the carbodiimide can be reduced through the synergistic action of the nitrogen phosphine compound and the cyclopentene phosphine catalyst, so that the carbodiimide modified isocyanate with low color number and stability is prepared.
Detailed Description
Specific embodiments of the process are further illustrated below with reference to examples. The invention is not limited to the embodiments listed but also comprises any other known variations within the scope of the invention as claimed.
In each of the examples and comparative examples of the present invention, the main raw material sources were as follows, and other raw materials and reagents were obtained by ordinary commercial routes unless otherwise specified:
over shelf life MDI: the Wanhua chemical MDI-100 is obtained after being stored for more than 48 hours at the high temperature of 80 ℃;
4, 4-azopyridine: gede chemical, 98%;
isoquinoline: 97% of Aladdin;
tetraphenylphosphonium imine: gede chemical, 99%;
1,1 '-binaphthyl-2, 2' -bisdiphenylphosphine: geder chemical, 97%;
diphenyl-2-pyridylphosphine: 97% of Aladdin;
3-methyl-1-phenyl-3-phosphole: mcrine, 99.5%;
1-methyl-1-oxaphosphole: 99% of Beijing Vocko Biotech, inc.;
2-methyl-2, 5-dioxo-1, 2-oxophospholane: honghu Yitai science and technology, inc., 99%;
triethylene diamine: 98% of Aladdin;
triphenylphosphine: 95% of Aladdin;
triethyl phosphate: 99.5 percent of Aladdin;
trifluoromethanesulfonic anhydride: geder chemical, 98%.
The main performance in the examples of the invention was tested by the following method:
content of dimer: testing instrument near infrared;
product color/haze: test instrument BYK LCS iii.
Example 1
1) Recycling the treated shelf-life MDI:
1000g of diphenylmethane diisocyanate having a shelf-life dimer content of 10000ppm in N 2 Stirring in the atmosphere, quickly heating to 200 ℃, adding 1ppm 4, 4-azopyridine, uniformly mixing, keeping the temperature at 200 ℃, stirring and reacting for 2 hours until the dimer content is reduced to 1985ppm, and obtaining the recycled MDI.
2) Modification of carbodiimide:
adding 30ppm of 3-methyl-1-phenyl-3-phosphole into the recycled MDI, uniformly mixing, rapidly heating to 200 ℃, reacting for 60min, cooling to 70 ℃, curing at constant temperature for 4h, adding 30ppm of trifluoromethanesulfonic anhydride, stirring for 1h, and cooling to 45 ℃ to obtain a carbodiimide modified isocyanate product, wherein performance test results are shown in Table 1.
Example 2
1) Recycling of the treated shelf-life MDI:
1000g of diphenylmethane diisocyanate having an overdue dimer content of 20000ppm in N 2 Stirring in the atmosphere, quickly heating to 205 ℃, adding 100ppm isoquinoline, uniformly mixing, keeping the temperature of 205 ℃, stirring and reacting for 5 hours until the dimer content is reduced to 1500ppm, and obtaining the recycled MDI.
2) Modification of carbodiimide:
adding 2ppm of 1-methyl-1-oxyphospholene into the recycled MDI, uniformly mixing, quickly heating to 210 ℃, reacting for 150min, then cooling to 70 ℃, curing at constant temperature for 4h, then adding 10ppm of trifluoromethanesulfonic anhydride, stirring for 1h, and cooling to 45 ℃ to obtain a carbodiimide modified isocyanate product, wherein performance test results are shown in Table 1.
Example 3
1) Recycling of the treated shelf-life MDI:
1000g of diphenylmethane diisocyanate having an over-shelf life dimer content of 20000ppm in N 2 Stirring in the atmosphere, quickly heating to 200 ℃, adding 50ppm tetraphenyl imine phosphine, uniformly mixing, keeping the temperature at 205 ℃ and stirring for reaction for 2 hours until the dimer content is reduced to 1800ppm, thus obtaining the recycled MDI.
2) Modification of carbodiimide:
adding 10ppm of 2-methyl-2, 5-dioxo-1, 2-oxyphospholane into the recycled MDI, uniformly mixing, quickly heating to 205 ℃, reacting for 60min, then cooling to 70 ℃, curing at constant temperature for 4h, then adding 30ppm of trifluoromethanesulfonic anhydride, stirring for 1h, and cooling to 45 ℃ to obtain a carbodiimide modified isocyanate product, wherein performance test results are shown in Table 1.
Example 4
1) Recycling of the treated shelf-life MDI:
1000g of diphenylmethane diisocyanate having a dimer content of 10000ppm over the shelf life in N 2 Stirring in atmosphere, rapidly heating to 200 deg.C, adding 20ppm1,1 '-binaphthyl-2, 2' -bis-diphenylphosphine, uniformly mixing, keeping the temperature at 205 ℃, stirring and reacting for 2 hours until the dimer content is reduced to 1400ppm, and obtaining the recycled MDI.
2) Modification of carbodiimide:
and (2) adding 30ppm of 2-methyl-2, 5-dioxo-1, 2-oxyphospholane into the recovered MDI, uniformly mixing, quickly heating to 205 ℃, reacting for 60min, cooling to 70 ℃, curing at constant temperature for 4h, adding 30ppm of trifluoromethanesulfonic anhydride, stirring for 1h, and cooling to 45 ℃ to obtain a carbodiimide modified isocyanate product, wherein performance test results are shown in Table 1.
Example 5:
1) Recycling of the treated shelf-life MDI:
1000g of diphenylmethane diisocyanate having a dimer content of 10000ppm over the shelf life in N 2 Stirring in the atmosphere, quickly heating to 200 ℃, adding 20ppm diphenyl-2-pyridine phosphine, uniformly mixing, keeping the temperature at 205 ℃, stirring and reacting for 2 hours until the dimer content is reduced to 1100ppm, and obtaining the recycled MDI.
2) Modification of carbodiimide:
adding 30ppm of 2-methyl-2, 5-dioxo-1, 2-oxyphospholane into the recycled MDI, uniformly mixing, quickly heating to 205 ℃, reacting for 60min, then cooling to 70 ℃, curing at constant temperature for 4h, then adding 30ppm of trifluoromethanesulfonic anhydride, stirring for 1h, and cooling to 45 ℃ to obtain a carbodiimide modified isocyanate product, wherein performance test results are shown in Table 1.
Comparative example 1
The process of example 1 is referred to with the only difference that: when MDI with the shelf life is recycled in the step 1), 4-azopyridine is not added, other parameters and operations are not changed, and the product performance test results are shown in table 1.
Comparative example 2
The process of example 1 is referred to with the only difference that: step 1) when the MDI with the shelf life is recycled, replacing 4, 4-azopyridine with 10ppm triethylene diamine, keeping other parameters and operation unchanged, and showing the product performance test result in table 1.
Comparative example 3
The process referred to in example 1 differs only in that: step 1) when the quality guarantee period MDI is recycled, 4-azopyridine is replaced by 10ppm triphenylphosphine, other parameters and operations are unchanged, and the product performance test results are shown in Table 1.
Comparative example 4
The process referred to in example 1 differs only in that: and 2) replacing 3-methyl-1-phenyl-3-phosphole with 100ppm triethyl phosphate when carbodiimide modifies MDI, and keeping other parameters and operations unchanged, wherein the product performance test results are shown in Table 1.
Comparative example 5
The process referred to in example 1 differs only in that: and 2) when the carbodiimide is used for modifying the MDI, no terminator trifluoromethanesulfonic anhydride is added, other parameters and operation are unchanged, and the product performance test results are shown in Table 1.
TABLE 1 results of performance test of examples and comparative examples
The experimental results shown in table 1 show that the nitrogen phosphine compound is added under the high temperature condition to decompose the supersaturated dimer in MDI, so that the purpose of recycling MDI with the over-shelf life is achieved, the carbodiimide modified isocyanate is prepared by using the recycled MDI after the dimer decomposition, the color number of the modified organic isocyanate product is remarkably reduced to 10-30APHA under the condition of ensuring that the viscosity of the modified organic isocyanate product is not obviously different, the modified organic isocyanate product can be stably stored for a long time, the color number of the product is not changed after being stored for two months, the color number of the product is not remarkably changed after being stored for six months, and the color number of the product is still lower than that of the commercial product.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. 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 by the claims.
Claims (10)
1. The recycling treatment method of MDI with the over-shelf life is characterized by comprising the steps of heating MDI with the over-shelf life to 180-220 ℃, preferably 200-205 ℃, then adding a nitrogen and/or phosphorus compound to be uniformly mixed, and carrying out heat preservation reaction for 2-5 hours, preferably 2-3 hours until the dimer content is reduced to below 2000ppm to obtain the recycled MDI.
2. The recycling process according to claim 1, wherein the over-shelf MDI contains precipitated MDI dimers;
the dimer content in the MDI with over-shelf life is more than 2500ppm, preferably 2500-20000ppm, more preferably 5000-18000ppm, and further preferably 10000-15000ppm.
3. The recycling process according to claim 1 or 2, wherein the over-shelf MDI is MDI-50 or MDI-100, preferably MDI-100;
preferably, the MDI comprises 96-100wt% 4,4' -MDI, 0-1wt% 2,2' -MDI and 0.1-4wt% 2,4' -MDI.
4. The recovery processing method according to any one of claims 1 to 3, characterized in that the nitrogen-and/or phosphorus-containing compound, preferably a nitrogen-containing heterocyclic ring and/or phosphine compound such as indolizine, 4-azopyridine, quinoline, isoquinoline, indole, 2H-pyrrolo [3,2-c ] pyridine, diphenyl-2-pyridylphosphine, 1' -binaphthyl-2, 2' -bisdiphenylphosphine, tris (2-methoxyphenyl) phosphine, tetraphenyliminophosphine, methyldiphenylphosphine, 2-dicyclohexylphosphine-2 ',6' -diisopropoxy-1, 1' -biphenyl, isopropylbiphenylphosphine, trioctylphosphine and the like, preferably at least one selected from quinoline, isoquinoline, diphenyl-2-pyridylphosphine, 1' -binaphthyl-2, 2' -bisdiphenylphosphine, tetraphenyliminophosphine, more preferably diphenyl-2-pyridylphosphine;
preferably, the nitrogen and/or phosphorus containing compound is used in an amount of 1 to 100ppm, preferably 2 to 50ppm, more preferably 5 to 20ppm, based on the mass of the over-shelf MDI.
5. A recycling treatment process according to any one of claims 1 to 4, characterized in that the reaction is carried out in an inert gas environment, preferably a nitrogen environment.
6. A method for preparing carbodiimide modified isocyanate by MDI with over shelf life, which is characterized in that the carbodiimide modified isocyanate is prepared by taking the recycled MDI obtained by the recycling treatment method of any one of claims 1 to 5 as a raw material and carrying out carbodiimide reaction under the action of a phosphorus heterocyclic catalyst.
7. The process according to claim 6, characterized in that the phosphoheterocyclic catalyst is a cyclopentenophosphine, preferably a cyclopentenophosphine oxide;
preferably, the oxypentene phosphine is selected from at least one of 1-methyl-3-phosphole-1-oxide, 1-methyl-1-oxyphosphole, 3-methyl-1-phenyl-3-phosphole, 2-methyl-2, 5-dioxo-1, 2-oxyphospholane;
preferably, the phosphorus heterocyclic catalyst is used in an amount of 0.5 to 50ppm, preferably 1 to 30ppm, more preferably 2 to 10ppm, based on the weight of the recycled MDI.
8. The process according to claim 6 or 7, characterized in that the carbodiimide is reacted at a temperature of 150-220 ℃, preferably 180-210 ℃, more preferably 200-205 ℃; for a period of time of 0.5-2.5h, preferably 1-2h, more preferably 1-1.5h;
the carbodiimide reaction is carried out in an inert gas environment, preferably a nitrogen environment.
9. The method according to any one of claims 6 to 8, wherein after the carbodiimide reaction is completed, a cooling curing process is included, and preferably, the temperature is reduced to 60 to 70 ℃ for constant-temperature curing for 4 to 5 hours.
10. The method according to any one of claims 6 to 9, characterized in that the reaction is finished by adding a terminating agent after the cooling and curing are finished, wherein the terminating agent is an acid terminating agent, preferably at least one selected from trifluoromethanesulfonic anhydride, ethyl trifluoromethanesulfonate, propyl trifluoromethanesulfonate, phenyl trifluoromethanesulfonate, adipoyl chloride and benzoyl chloride;
preferably, the amount of the terminating agent is 10-100ppm of the mass of the recycled MDI; preferably, the terminator is added and stirred for 1-2h, and then cooled to 45-50 ℃.
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