CN116813878B - Method for continuously preparing 1,5 naphthalene diisocyanate prepolymer - Google Patents
Method for continuously preparing 1,5 naphthalene diisocyanate prepolymer Download PDFInfo
- Publication number
- CN116813878B CN116813878B CN202311090889.2A CN202311090889A CN116813878B CN 116813878 B CN116813878 B CN 116813878B CN 202311090889 A CN202311090889 A CN 202311090889A CN 116813878 B CN116813878 B CN 116813878B
- Authority
- CN
- China
- Prior art keywords
- naphthalene diisocyanate
- prepolymer
- ndi
- reaction
- diisocyanate prepolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 18
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- 230000035484 reaction time Effects 0.000 claims description 16
- 229920005862 polyol Polymers 0.000 claims description 15
- 150000003077 polyols Chemical class 0.000 claims description 15
- 239000003995 emulsifying agent Substances 0.000 claims description 12
- 239000000839 emulsion Substances 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000010408 film Substances 0.000 claims description 5
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical group [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 5
- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- 239000010409 thin film Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 239000004632 polycaprolactone Substances 0.000 claims description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- LAXBNTIAOJWAOP-UHFFFAOYSA-N 2-chlorobiphenyl Chemical group ClC1=CC=CC=C1C1=CC=CC=C1 LAXBNTIAOJWAOP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 230000004907 flux Effects 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000199 molecular distillation Methods 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 abstract description 6
- 238000002844 melting Methods 0.000 abstract description 4
- 230000008018 melting Effects 0.000 abstract description 4
- 229920002635 polyurethane Polymers 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 125000001624 naphthyl group Chemical group 0.000 abstract description 3
- 230000000704 physical effect Effects 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000004806 packaging method and process Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 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 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920003225 polyurethane elastomer Polymers 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 238000007790 scraping Methods 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- -1 polybutylene adipate Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7678—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing condensed aromatic rings
-
- 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
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the field of chemical synthesis, in particular to a method for continuously preparing 1,5 Naphthalene Diisocyanate (NDI) prepolymer. 1, 5-Naphthalene Diisocyanate (NDI) has a symmetrical rigid aromatic naphthalene ring structure, and Polyurethane (PU) synthesized from it has more excellent mechanical and physical properties than other polyurethanes. Because NDI has high melting point and extremely active chemical property, the NDI prepolymer prepared by the prior art has the technical problem of poor stability. The invention discloses a method for preparing an NDI prepolymer, which is characterized in that NDI is emulsified and then introduced into a microchannel reactor for reaction, so that the technical problem of side reaction influence caused by chemical property and activity of NDI at high temperature is solved by improving heat exchange efficiency, and the stability and production efficiency of the NDI prepolymer are improved.
Description
Technical Field
The invention relates to the field of chemical synthesis, in particular to a method for continuously preparing a 1,5 naphthalene diisocyanate prepolymer.
Background
The polyurethane elastomer has unique properties, is an emerging organic polymer material, is widely applied to various fields of national life such as light industry, chemical industry, electronics, construction, automobiles, spinning, medical treatment, national defense, aerospace and the like, and becomes a special organic synthetic material with the largest variety, the largest application and the fastest development in the current polymer materials.
The polyurethane elastomer is divided into TDI type, MDI type, PPD type, NDI type and other prepolymers according to the different isocyanate, wherein 1,5 Naphthalene Diisocyanate (NDI) has a higher melting point than diphenylmethane diisocyanate (MDI) and Toluene Diisocyanate (TDI), and NDI has an aromatic naphthalene ring structure, and NDI has a larger steric hindrance effect, so that the synthesized polyurethane has the characteristics of high hardness, good rebound resilience and heat resistance, excellent dynamic performance, good wear resistance and the like, and can be suitable for high dynamic load scenes.
1,5 Naphthalene Diisocyanate (NDI) has a symmetrical rigid aromatic naphthalene ring structure, and Polyurethane (PU) synthesized from it has more excellent mechanical and physical properties than other polyurethanes. For example, excellent dynamic properties, extremely high mechanical properties, outstanding cutting resistance, wear resistance, temperature resistance and the like, and are widely applied to the fields of automobile shock absorbers, forklift load-bearing wheels, printing and dyeing textile rubber rollers and rubber scrapes, bridge building buffer blocks, military industry and the like. However, NDI has a high melting point and extremely active chemical properties, and the NDI prepolymer prepared from the NDI has poor stability, and the chain extension reaction needs to be completed immediately within a few hours after the prepolymer is synthesized, otherwise, the NDI prepolymer can be seriously deteriorated and cannot be used. It follows that the stability problem of NDI prepolymers limits the application of NDI-based polyurethane materials.
The current method for preparing NDI prepolymer generally comprises adding dissolved liquid polyol and NDI particles into a reaction kettle, heating to dissolve NDI, and then cooling to control the reaction degree. The heat transfer area of the reaction kettle is limited, and particularly when the reaction kettle is used for large-scale production, the heat exchange efficiency is difficult to improve, so that the reaction completeness and quality of the NDI prepolymer are difficult to control by the method.
NDI prepolymers prepared by conventional methods often contain a large amount of free NDI monomers which gradually precipitate from the prepolymer during storage to form crystals; in the subsequent use process, when the prepolymer is preheated, the monomers are difficult to integrate with the prepolymer, and can be melted only by a method of increasing the temperature, so that the crosslinking side reaction can be initiated, the free NDI content is reduced, the viscosity of the prepolymer is increased, and the convenience and the product quality of the subsequent product synthesis process of the prepolymer are affected; therefore, how to fundamentally solve the problem of stability of NDI prepolymer, prevent the increase of viscosity of prepolymer and the decrease of NCO group number is the problem to be solved at present.
Disclosure of Invention
The invention aims to provide a method for continuously preparing 1,5 naphthalene diisocyanate prepolymer.
In order to achieve the above purpose, the invention adopts the technical scheme that:
a process for continuously preparing a 1,5 naphthalene diisocyanate prepolymer:
1) Adding 1,5 naphthalene diisocyanate particles, polyalcohol, solvent and emulsifier into an emulsifier, and mixing at the temperature of 25-40 ℃ for 10-30 min; the rotating speed is 600-12000 rpm, and 1,5 naphthalene diisocyanate/polyol emulsion with the particle size distribution of 10-50 mu m is prepared;
2) Introducing the 1, 5-naphthalene diisocyanate/polyol emulsion prepared in the step 1) into a microchannel reactor for reaction, wherein the reaction temperature of the first stage is 130-150 ℃, the reaction time of the first stage is 2-6 min, the reaction temperature of the second stage is 100 ℃, the reaction time of the third stage is 10-30 min, the reaction temperature of the third stage is 70 ℃, and the reaction time of the third stage is 30-60 min, so as to obtain a 1, 5-naphthalene diisocyanate prepolymer;
3) And (2) adding the 1,5 naphthalene diisocyanate prepolymer prepared in the step (2) into a vacuum molecular distillation system to serve as a thin film evaporator, wherein the distillation temperature is 140-180 ℃, the residence time is 1-5 minutes, the system vacuum degree is 10-30 pa, the thickness of the scratch film is 0.05-0.5mm, and the 1,5 naphthalene diisocyanate prepolymer is obtained through separation.
The 1,5 naphthalene diisocyanate is flake or powder, and the particle size and the thickness are smaller than 0.5mm; reactive isocyanate groups of the 1,5 naphthalene diisocyanate and reactive hydroxyl content NCO of the polyol: the OH is controlled to be in an equivalent ratio of 2:1-2.5:1; the dosage of the emulsifier is 0.1-0.5% of the mass of the polyol; the solvent consumption is 300-1500% of the mass of 1.5 naphthalene diisocyanate.
The polyol is one or a mixture of a plurality of polytetrahydrofuran ether glycol, polycaprolactone glycol and polycarbonate glycol according to any ratio, and the molecular weight range is 300-5000.
The solvent is one or a mixture of more than one of sulfolane, 1, 2-dichloroethane, carbon tetrachloride, chlorobenzene, o-dichlorobenzene, p-dichlorobenzene, monochlorobiphenyl, methyl ethyl ketone and acetonitrile according to any ratio.
The emulsifier is sodium dodecyl sulfonate.
The technological parameters of the microchannel reactor are as follows: the reaction modules are not less than three, and the specific surface area is as follows: 1000-5000 m 2 m -3 Microchannel aperture: 1-1.4 mm, flux of 0.2-20 mL/min, and heat conduction coefficient: not less than 100W/mK; residence time: 3 sec-1 h; working side pressure range: 0-25 bar; heat exchange side pressure range: 0-5 bar.
The invention uses solvent and emulsifier to disperse NDI particles and polyalcohol into uniform emulsion through a high shear emulsifying machine at low temperature, then the emulsion is sent into a micro-channel reactor to react rapidly at a temperature higher than the melting point of NDI, and then the temperature is reduced rapidly and gradually, so that the prepolymerization reaction is completed. Avoiding unnecessary side reactions caused by long-time high temperature. The preparation method can continuously prepare the 1,5 naphthalene diisocyanate prepolymer, is simple, low in cost and safe and environment-friendly in preparation process.
The 1,5 naphthalene diisocyanate prepolymer prepared by the method can be stored for a long time at room temperature, and the processing and using problems of the NDI prepolymer are effectively solved; and polyurethane elastomer products prepared by using the 1,5 naphthalene diisocyanate prepolymer of the invention have excellent physical properties.
Detailed Description
The following description of the embodiments of the present invention is further provided in connection with the accompanying examples, and it should be noted that the embodiments described herein are for the purpose of illustration and explanation only, and are not limiting of the invention.
The following examples were made with the addition of materials in parts by weight, with all the raw materials being commercially available products.
Example 1
1) 100 parts of 1,5 naphthalene diisocyanate, 130 parts of polytetrahydrofuran ether glycol with the average molecular weight of 650g/mol, 0.15 part of emulsifier sodium dodecyl sulfonate and 750 parts of chlorobenzene are mixed at the temperature of 25 ℃ at the speed of 12000rpm for 25min; preparing 1,5 naphthalene diisocyanate/polyol emulsion;
2) Pumping the 1,5 naphthalene diisocyanate/polyol emulsion prepared in the step 1 into a microchannel reactor through a metering pump to react, wherein the reaction temperature of the first stage is 135 ℃, the reaction time is 8min, the reaction temperature of the second stage is 100 ℃, the reaction time is 30min, and the reaction temperature of the third stage is 70 ℃ and the reaction time is 45min; preparing a 1,5 naphthalene diisocyanate prepolymer;
3) And (2) adding the 1, 5-naphthalene diisocyanate prepolymer prepared in the step (2) into a thin film evaporator, wherein the evaporation temperature is 160 ℃, the residence time is 4 minutes, the vacuum degree of the system is 13pa, the thickness of the scraping film is 0.05mm, separating to obtain the prepolymer, and packaging the prepolymer in a packaging barrel by nitrogen.
Example 2
1) 100 parts of 1,5 naphthalene diisocyanate, 220 parts of polybutylene adipate glycol with the average molecular weight of 1000g/mol, 0.5 part of sodium dodecyl sulfonate as an emulsifier and 900 parts of sulfolane are mixed at the temperature of 40 ℃ at the speed of 10000rpm for 30min; preparing 1,5 naphthalene diisocyanate/polyol emulsion;
2) Pumping the 1,5 naphthalene diisocyanate/polyol emulsion prepared in the step 1 into a microchannel reactor through a metering pump to react, wherein the reaction temperature of the first stage is 150 ℃, the reaction time is 5min, the reaction temperature of the second stage is 100 ℃, the reaction time is 45min, and the reaction temperature of the third stage is 70 ℃ and the reaction time is 30min; preparing a 1,5 naphthalene diisocyanate prepolymer;
3) And (2) adding the 1, 5-naphthalene diisocyanate prepolymer prepared in the step (2) into a thin film evaporator, wherein the evaporation temperature is 140 ℃, the residence time is 2 minutes, the vacuum degree of the system is 20pa, the thickness of the scraping film is 0.1mm, separating to obtain the prepolymer, and packaging the prepolymer in a packaging barrel by nitrogen.
Example 3
1) 100 parts of 1,5 naphthalene diisocyanate, 450 parts of polycaprolactone dihydric alcohol with the average molecular weight of 2000g/mol, 2 parts of emulsifier sodium dodecyl sulfonate and 550 parts of o-dichlorobenzene are mixed at the temperature of 30 ℃ at the speed of 1000rpm for 10min; preparing 1,5 naphthalene diisocyanate/polyol emulsion;
2) Pumping the 1,5 naphthalene diisocyanate/polyol emulsion prepared in the step 1 into a microchannel reactor through a metering pump to react, wherein the reaction temperature of the first stage is 130 ℃, the reaction time is 6min, the reaction temperature of the second stage is 100 ℃, the reaction time is 15min, and the reaction temperature of the third stage is 70 ℃ and the reaction time is 60min; preparing a 1,5 naphthalene diisocyanate prepolymer;
3) And (2) adding the 1, 5-naphthalene diisocyanate prepolymer prepared in the step (2) into a thin film evaporator, wherein the evaporation temperature is 150 ℃, the residence time is 1 minute, the vacuum degree of the system is 30pa, the thickness of the scraping film is 0.15mm, separating to obtain the prepolymer, and packaging the prepolymer in a packaging barrel by nitrogen.
Comparative example
The prepolymer was prepared by heating and emulsifying the same raw materials in the same proportions as in example 1 under the protection of nitrogen, except that the prepolymer was prepared by heating and emulsifying in a reaction kettle, the dissolution temperature of the materials was 130 ℃, the dissolution time was 60min, the reaction temperature was 100 ℃, and the reaction time was 2.5h.
The performance indexes such as NCO group percentage of the polyurethane prepolymer obtained in each of the above examples and after 24 hours of standing after the control preparation were compared, and the viscosity performance thereof was examined at 80℃by using an NDJ type rotational viscometer with 8 viscosity, see Table 1.
TABLE 1
| NCO% | Viscosity cps | Appearance of | |
| Example 1 | 6.98 | 686 | Clear and transparent |
| Example 2 | 5.02 | 1218 | Clear and clear |
| Example 3 | 3.32 | 1370 | Clear and transparent |
| Comparative example | 5.13 | 6012 | Milky white liquid |
The NDI prepolymers prepared in example 1 and comparative examples were left for 24, 48, 72, 96 hours and the viscosity properties were measured at 80℃using an NDJ type rotational viscometer with 8 viscosities, and the comparison is shown in Table 2.
TABLE 2
| Time/h | 0 | 24 | 48 | 72 | 96 |
| EXAMPLE 1/cps | 542 | 686 | 720 | 776 | 796 |
| EXAMPLE 2/cps | 807 | 1218 | 1380 | 1440 | 1480 |
| EXAMPLE 3/cps | 908 | 1370 | 1450 | 1580 | 1610 |
| Comparative example/cps | 5433 | 6012 | 6804 | 8843 | 11100 |
Claims (5)
1. A process for the continuous preparation of a 1,5 naphthalene diisocyanate prepolymer characterized by:
1) Adding 1,5 naphthalene diisocyanate particles, polyalcohol, solvent and emulsifier into an emulsifier, mixing at 25-40 ℃ for 10-30 min at 600-12000 rpm to obtain 1,5 naphthalene diisocyanate/polyalcohol emulsion with particle size distribution of 10-50 mu m, wherein the active isocyanate group of 1,5 naphthalene diisocyanate and the active hydroxyl content NCO of polyalcohol are: the OH is controlled to be in an equivalent ratio of 2:1-2.5:1;
2) Introducing the 1, 5-naphthalene diisocyanate/polyol emulsion prepared in the step 1) into a microchannel reactor for reaction, wherein the reaction temperature of one stage is 130-150 ℃, the reaction time of one stage is 2-6 min, the reaction temperature of two stages is 100 ℃, the reaction time of three stages is 10-30 min, the reaction temperature of three stages is 70 ℃, and the reaction time of three stages is 30-60 min, so as to obtain the 1, 5-naphthalene diisocyanate prepolymer, and the microchannel reactor meets the following technological parameters: the technological parameters are in accordance with at least three reaction modules, and the specific surface area is as follows: 1000-5000 m2m-3, micro-channel aperture: 1-1.4 mm, flux of 0.2-20 mL/min, heat conduction coefficient: not less than 100W/mK, residence time: 3 sec-1 h, working side pressure range: 0-25 bar, heat exchange side pressure range: 0-5 bar;
3) And (2) adding the 1,5 naphthalene diisocyanate prepolymer prepared in the step (2) into a vacuum molecular distillation system to serve as a thin film evaporator, wherein the distillation temperature is 140-180 ℃, the residence time is 1-5 minutes, the system vacuum degree is 10-30 pa, the thickness of the scratch film is 0.05-0.5mm, and the 1,5 naphthalene diisocyanate prepolymer is obtained through separation.
2. The process for continuously preparing 1, 5-naphthalene diisocyanate prepolymer according to claim 1, wherein: the 1,5 naphthalene diisocyanate is flake or powder, and the particle size and the thickness are smaller than 0.5mm; the dosage of the emulsifier is 0.1-0.5% of the mass of the polyol; the solvent consumption is 300-1500% of the mass of 1.5 naphthalene diisocyanate.
3. The process for continuously preparing 1, 5-naphthalene diisocyanate prepolymer according to claim 1, wherein: the polyol is one or a mixture of more than one of polytetrahydrofuran ether glycol, polycaprolactone glycol and polycarbonate glycol according to any ratio, and the molecular weight range is 300-5000.
4. The process for continuously preparing 1, 5-naphthalene diisocyanate prepolymer according to claim 1, wherein: the solvent is one or a mixture of more than one of sulfolane, 1, 2-dichloroethane, carbon tetrachloride, chlorobenzene, o-dichlorobenzene, p-dichlorobenzene, monochlorobiphenyl, methyl ethyl ketone and acetonitrile according to any ratio.
5. The process for continuously preparing 1, 5-naphthalene diisocyanate prepolymer according to claim 1, wherein: the emulsifier is sodium dodecyl sulfonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311090889.2A CN116813878B (en) | 2023-08-29 | 2023-08-29 | Method for continuously preparing 1,5 naphthalene diisocyanate prepolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311090889.2A CN116813878B (en) | 2023-08-29 | 2023-08-29 | Method for continuously preparing 1,5 naphthalene diisocyanate prepolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116813878A CN116813878A (en) | 2023-09-29 |
| CN116813878B true CN116813878B (en) | 2023-11-10 |
Family
ID=88127758
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311090889.2A Active CN116813878B (en) | 2023-08-29 | 2023-08-29 | Method for continuously preparing 1,5 naphthalene diisocyanate prepolymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116813878B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119192523A (en) * | 2024-09-20 | 2024-12-27 | 广东工业大学 | A method for continuously preparing waterborne polyurethane dispersion by microreactor |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805304A (en) * | 2010-04-07 | 2010-08-18 | 烟台万华聚氨酯股份有限公司 | Method for preparing aliphatic polyisocyanurate by using microreactor |
| CN101861346A (en) * | 2007-11-17 | 2010-10-13 | 拜尔材料科学股份公司 | Method for producing cellular Polyurethane (PUR) cast elastomers from storage-stable 1, 5-Naphthalene Diisocyanate (NDI) prepolymers |
| CN102391468A (en) * | 2011-09-30 | 2012-03-28 | 南京金三力橡塑有限公司 | Preparation method of prepolymer based on 1, 5-naphthyl diisocyanate and stably stored |
| KR20140123702A (en) * | 2013-04-15 | 2014-10-23 | (주) 동양이화 | Method of preparing 1,5-naphthalene diisocyanate prepolymer comprising high-content NCO and storage stable NDI prepolymer comprising high-content NCO thereof |
| CN112409215A (en) * | 2020-11-16 | 2021-02-26 | 中海油常州涂料化工研究院有限公司 | Method for synthesizing biuret polyisocyanate by using microchannel reactor and application thereof |
| CN113429542A (en) * | 2021-05-31 | 2021-09-24 | 吉林中科优锐科技有限公司 | Preparation method of 1, 5-naphthalene diisocyanate polyurethane prepolymer |
| CN114008101A (en) * | 2019-07-11 | 2022-02-01 | 朗盛公司 | Process for producing NDI prepolymers |
| CN114015009A (en) * | 2021-12-09 | 2022-02-08 | 上海汇得科技股份有限公司 | 1, 5-naphthalene diisocyanate prepolymer and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007031546A1 (en) * | 2007-06-01 | 2008-12-04 | Bayer Materialscience Ag | Process for the preparation of thermoplastic polyurethanes based on 1,5-naphthalene diisocyanate |
-
2023
- 2023-08-29 CN CN202311090889.2A patent/CN116813878B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101861346A (en) * | 2007-11-17 | 2010-10-13 | 拜尔材料科学股份公司 | Method for producing cellular Polyurethane (PUR) cast elastomers from storage-stable 1, 5-Naphthalene Diisocyanate (NDI) prepolymers |
| CN101805304A (en) * | 2010-04-07 | 2010-08-18 | 烟台万华聚氨酯股份有限公司 | Method for preparing aliphatic polyisocyanurate by using microreactor |
| CN102391468A (en) * | 2011-09-30 | 2012-03-28 | 南京金三力橡塑有限公司 | Preparation method of prepolymer based on 1, 5-naphthyl diisocyanate and stably stored |
| KR20140123702A (en) * | 2013-04-15 | 2014-10-23 | (주) 동양이화 | Method of preparing 1,5-naphthalene diisocyanate prepolymer comprising high-content NCO and storage stable NDI prepolymer comprising high-content NCO thereof |
| CN114008101A (en) * | 2019-07-11 | 2022-02-01 | 朗盛公司 | Process for producing NDI prepolymers |
| CN112409215A (en) * | 2020-11-16 | 2021-02-26 | 中海油常州涂料化工研究院有限公司 | Method for synthesizing biuret polyisocyanate by using microchannel reactor and application thereof |
| CN113429542A (en) * | 2021-05-31 | 2021-09-24 | 吉林中科优锐科技有限公司 | Preparation method of 1, 5-naphthalene diisocyanate polyurethane prepolymer |
| CN114015009A (en) * | 2021-12-09 | 2022-02-08 | 上海汇得科技股份有限公司 | 1, 5-naphthalene diisocyanate prepolymer and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116813878A (en) | 2023-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6046297A (en) | Polyurethanes cured with 4,4'-methylene-bis-(3-chloro-2,6-diethylaniline-methylene | |
| CN116813878B (en) | Method for continuously preparing 1,5 naphthalene diisocyanate prepolymer | |
| CN106700029B (en) | Polyurethane resin for shoe sole and preparation method and application thereof | |
| CN105175678A (en) | High-transparency polyurethane elastomer and preparation method thereof | |
| CN106832203B (en) | Polyurethane resin for tire and preparation method thereof | |
| CN105131569A (en) | A kind of calendering grade thermoplastic polyurethane elastomer and preparation method thereof | |
| CN109322008B (en) | Method for improving performance stability of spandex product | |
| DE3233384C2 (en) | ||
| CN112625248A (en) | Organic silicon nylon elastomer and preparation method thereof | |
| CN114790275A (en) | High-temperature-resistant melt-spun spandex slice with excellent mechanical properties and preparation method thereof | |
| KR101601782B1 (en) | Fiber reinforced tpu composites | |
| CN112876649B (en) | Preparation method and application of 1,5-naphthalene diisocyanate prepolymer | |
| CN106674465B (en) | Polyurethane resin for shoe sole and preparation method and application thereof | |
| CN110982042A (en) | Preparation method of polyurethane elastomer with adjustable hardness | |
| CN112457467B (en) | High-damping thermoplastic polyurethane elastomer and preparation method thereof | |
| CN106008898A (en) | High-moisture-resistance cold/heat-resistant thermoplastic polyurethane elastomer and preparation method thereof | |
| CN106810668B (en) | Polyurethane resin for shoe sole and preparation method and application thereof | |
| US2852483A (en) | Method of plasticizing a polyurethane-polyether and composition thereby obtained | |
| CN109021195B (en) | High-performance polyurethane elastomer for table tennis ball preparation and preparation method thereof | |
| CN110437422B (en) | Preparation method and application of stable NDI prepolymer | |
| CN114605612A (en) | Double-component reactive polyurethane resin for safety shoes, preparation method of double-component reactive polyurethane resin and safety shoes | |
| CN110951034B (en) | High-load-bearing low-endogenous heat polyurethane elastomer and preparation method thereof | |
| CN111393609A (en) | Pouring type polyurethane elastomer and preparation method thereof | |
| KR101784442B1 (en) | Thermoplastic Polyurethane Resin Composition For T-die Extrusion Molding, Method For Preparing The Same and Molded Product Thereof | |
| CN113214509A (en) | Preparation method of yellowing-resistant TPU master batch |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |