CN109206572B - Preparation method of modified polyurethane resin - Google Patents
Preparation method of modified polyurethane resin Download PDFInfo
- Publication number
- CN109206572B CN109206572B CN201811005822.3A CN201811005822A CN109206572B CN 109206572 B CN109206572 B CN 109206572B CN 201811005822 A CN201811005822 A CN 201811005822A CN 109206572 B CN109206572 B CN 109206572B
- Authority
- CN
- China
- Prior art keywords
- reaction kettle
- gear
- shaft
- parts
- polyurethane resin
- 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
Images
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
- C08G18/28—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
- B01J19/0066—Stirrers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
-
- 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
-
- 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
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- 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
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
- B01J2219/00094—Jackets
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of modified polyurethane resin, in particular to a preparation method of modified polyurethane resin, which adopts an emulsion copolymerization method to realize the industrial production of waterborne polyurethane and comprises the following steps: adding toluene diisocyanate into a reaction kettle, heating to 70-80 ℃, adding a catalyst and dehydrated polyether glycol, heating to 80 ℃, and reacting for 2 hours; adding a micromolecular chain extender to react for 1 hour, and then adding a hydrophilic chain extender to continue to react for 2 hours; adding acetone into the reaction kettle to reduce the viscosity, reducing the temperature of the reaction kettle to 35 ℃, and adding deionized water for emulsification; raising the temperature of the reaction kettle to 75 ℃, slowly adding ethyl acrylate and an initiator, raising the temperature to 82-88 ℃, keeping the temperature, reacting for 3 hours, and finally cooling to obtain a modified polyurethane resin emulsion; the invention adopts a preparation process of chain extension first and then hydrophilicity, has simple process and is easy to realize industrial production.
Description
Technical Field
The invention relates to the technical field of modified polyurethane resin, in particular to a preparation method of modified polyurethane resin.
Background
The waterborne polyurethane resin is an important resin raw material in the basic raw materials of waterborne coatings, and the performance improvement of the waterborne polyurethane plays an important role in the waterborne coatings. The Waterborne Polyurethane (WPU) coating has the advantages of wear resistance, corrosion resistance, high hardness, high elasticity and the like, is flexible in component adjustment, and is widely applied to the fields of furniture coating, metal corrosion resistance, fabric coating, leather coating, building coating, automobile coating, road sign coating and the like.
The research on waterborne polyurethane at home and abroad focuses on modifying the waterborne polyurethane to functionalize the waterborne polyurethane, and the performance indexes of the material, such as water resistance, solvent resistance and the like, are improved through modification. The modification is mainly carried out by two means of physics and chemistry, by grafting, block, internal and external crosslinking other polymer materials, blending or forming interpenetrating polymer networks and the like. The acrylate has better weather resistance and water resistance, but has high hardness and is not resistant to solvents. The acrylate is used for modifying the waterborne polyurethane emulsion, so that the high wear resistance and good mechanical property of polyurethane can be organically combined with the good weather resistance and water resistance of acrylic acid to obtain the modified polyurethane resin with better performance.
At present, when producing the water-based polyurethane resin coating, the main method adopted in industry is to mix the polyurethane and the acrylate, and mechanically stir and disperse the mixture to obtain more uniform emulsion. However, the acrylate modified polyurethane obtained by the method is easy to generate phase separation, and the performance of the coating film can not meet the industrial requirement of rapid development.
Disclosure of Invention
The invention aims to provide a preparation method of modified polyurethane resin, which has simple process and is easy to realize industrial production.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of modified polyurethane resin comprises the following steps:
step 1: filling nitrogen into a reaction kettle, adding toluene diisocyanate, stirring and heating to 70-80 ℃, then adding a catalyst and dehydrated polyether glycol, heating the reaction kettle to 80 ℃, and reacting at constant temperature for 2 hours; adding a micromolecular chain extender to react for 1 hour, and then adding a hydrophilic chain extender to continue to react for 2 hours; stopping heating, adding acetone into the reaction kettle to reduce the viscosity, reducing the temperature of the reaction kettle to 35 ℃, adjusting the pH to 7-8 by using triethylamine, stirring at a high speed for emulsification after the adjustment is finished within three minutes, and finally performing reduced pressure air extraction on the reaction kettle to recover the acetone;
step 2: raising the temperature of the reaction kettle to 75 ℃, starting stirring, filling nitrogen into the reaction kettle, adding a buffering agent triethanolamine and deionized water, slowly adding ethyl acrylate and an initiator, finishing the addition within one hour, then raising the temperature to 82-88 ℃, keeping the temperature for reaction for 3 hours, and cooling to obtain a modified polyurethane resin emulsion;
in the steps, the raw materials comprise, by weight, 20-40 parts of toluene diisocyanate, 30-50 parts of polyether glycol, 1-2 parts of a catalyst, 10-20 parts of a small-molecule chain extender, 3-6 parts of a hydrophilic chain extender, 30-50 parts of acetone, 10-20 parts of a buffering agent, 30-40 parts of ethyl acrylate, 5-8 parts of an initiator, 10-20 parts of deionized water in step 1 and 10-20 parts of deionized water in step 2.
Further, the catalyst is an organotin catalyst.
Further, the micromolecule chain extender is diethylene glycol, and the hydrophilic chain extender is dimethylolpropionic acid.
Further, the initiator is potassium persulfate.
Further, the reaction kettle comprises an upper seal head, a lower seal head, a cylinder body, a rotary selection box and a double-effect stirring paddle, the upper end enclosure is connected with the barrel through a bolt, the lower end enclosure is welded with the barrel, a support is fixedly arranged at the lower part of the lower end enclosure, a heat preservation layer is arranged outside the lower end enclosure, a heat exchange jacket is arranged outside the barrel, the double-effect stirring paddle comprises a turbine stirring paddle and an anchor type stirring paddle, the turbine stirring paddle comprises a turbine stirring paddle blade and a first central shaft, the top of the first central shaft is arranged at the top of the upper seal head, the anchor type stirring paddle comprises an anchor type stirring paddle blade and a second central shaft, the second central shaft is sleeved on the first central shaft, the lower parts of the first central shaft and the second central shaft penetrate through the bottom of the lower end enclosure and are connected with the motor through the stirring selection assembly, the bottom of the first central shaft is provided with a first gear, and the bottom of the second central shaft is provided with a second gear; the stirring selection assembly is arranged in the rotary selection box and comprises a rotary selection shaft, a shifting rod and a sliding gear shaft, the upper end and the lower end of the rotary selection shaft extend out of the rotary selection box respectively, the top end of the rotary selection shaft is movably connected with a clamping block, the clamping block is T-shaped, the bottom of the clamping block is inserted into a cuboid groove formed in the top end of the rotary selection shaft, a plurality of stopping blocks are uniformly distributed at the top of the rotary selection box around the circumferential direction of the rotary selection shaft, the top of the clamping block is clamped between two adjacent stopping blocks, a rotary handle is arranged at the bottom end of the rotary selection shaft, a spiral line guide groove is formed in the middle of the rotary selection shaft, the shifting rod is cross-shaped and comprises a horizontal rod and a vertical rod, the top end and the bottom end of the vertical rod are fixed to the upper bottom surface and the lower bottom surface of the rotary selection box respectively, the horizontal rod is sleeved on the vertical rod, one end of the horizontal rod is a spherical body, The other end of the horizontal rod is a circular ring and the circular ring is sleeved on a groove formed in the middle of a sliding gear shaft, a third gear is fixed on the lower portion of the outer side of the sliding gear shaft, a fourth gear is fixed on the upper portion of the outer side of the sliding gear shaft and meshed with the first gear, the fourth gear is meshed with the second gear, and the sliding gear shaft and an output shaft of a motor are connected through a spline.
Further, the reference circle of the fourth gear is smaller than that of the third gear, and the distance between the third gear and the fourth gear is smaller than that between the first gear and the second gear.
Furthermore, a plurality of baffle plates are uniformly arranged in the heat exchange jacket to form a flow guide channel, the baffle plates are perpendicular to the side wall of the heat exchange jacket and the cylinder body, a baffle plate in an inverted S shape is arranged in the flow guide channel, the baffle plate divides the flow guide channel into a first flow guide channel and a second flow guide channel, and the first flow guide channel and the second flow guide channel are not communicated.
The invention has the beneficial effects that:
the preparation method of the modified polyurethane resin adopts a preparation process of chain extension first and then hydrophilicity, has simple process, can be synthesized at one time, does not need to replace a reaction kettle, is easy to realize industrial production, ensures the stable viscosity of the system, and reduces the using amount of acetone; diethylene glycol reacts with toluene diisocyanate to generate rigid chain segment carbamate, the addition of diethylene glycol can play a role in adjusting the molecular mass of the waterborne polyurethane and the proportion of soft segments and hard segments in the structure, the diethylene glycol molecules contain ether bonds with good hydrophilicity, and the ether bonds have polarity and can increase the bonding strength of the polyurethane resin. In the synthesis process of the dimethylolpropionic acid, a reaction system is acidic, the dimethylolpropionic acid reacts mildly with-OH under an acidic condition, does not participate in the reaction and does not cause gel, and the dimethylolpropionic acid also plays a role of a chain extender so that a hydrophilic group (namely carboxyl) is positioned in a macromolecular chain segment.
The reaction kettle adopts the double-effect stirring paddle, meets the requirements of different stirring speeds in different stages, and can realize different stirring speeds without replacing the reaction kettle; the first flow guide channel and the second flow guide channel in the heat exchange jacket are not communicated, and the two flow guide channels can realize rapid cooling and are more convenient and fast.
Drawings
FIG. 1 is a schematic view of the structure of a reaction vessel in example 4 of the process for producing a modified polyurethane resin according to the present invention.
FIG. 2 is a second schematic view of the structure of a reaction vessel in example 4 of the process for producing a modified polyurethane resin according to the present invention.
FIG. 3 is a third schematic view showing the structure of a reaction vessel in example 4 of the process for producing a modified polyurethane resin according to the present invention.
Fig. 4 is an enlarged sectional view taken at a in fig. 3 according to the present invention.
FIG. 5 is a schematic view showing the structure of a selection shaft, a block and a stopper rotating around the rotation axis in the reaction vessel in example 4 of the process for producing a modified polyurethane resin according to the present invention.
The reference numbers in the drawings are as follows: the heat exchanger comprises an upper end enclosure 1, a lower end enclosure 2, a barrel 3, a rotary selection box 4, a support 5, a heat exchange jacket 6, a turbine stirring paddle blade 7, a first central shaft 8, a first gear 9, an anchor stirring paddle blade 10, a second central shaft 11, a second gear 12, a motor 13, a rotary selection shaft 14, a shifting lever 15, a sliding gear shaft 16, a third gear 17, a fourth gear 18, a rotary handle 19, a clamping block 20, a clamping block 21, a heat insulation layer 22, a baffle 23, a partition plate 24, a first flow guide channel 25 and a second flow guide channel 26.
Detailed Description
The invention is further described with reference to the following figures and detailed description:
example 1
A preparation method of modified polyurethane resin comprises the following steps:
step 1: filling nitrogen into a reaction kettle, adding 40kg of toluene diisocyanate, stirring and heating to 75 ℃, then adding 1kg of organic tin catalyst and 40kg of dehydrated polyether glycol, heating the reaction kettle to 80 ℃, and reacting for 2 hours at constant temperature; adding 13kg of micromolecular chain extender diethylene glycol to react for 1 hour, adding 4kg of hydrophilic chain extender dimethylolpropionic acid to continue to react for 2 hours; stopping heating, adding 50kg of acetone into the reaction kettle to reduce the viscosity, reducing the temperature of the reaction kettle to 35 ℃, adjusting the pH to 7-8 by using triethylamine, stirring at a high speed within three minutes, adding 10kg of deionized water for emulsification, finally performing reduced pressure air extraction on the reaction kettle, and recovering the acetone;
step 2: and (3) raising the temperature of the reaction kettle to 75 ℃, starting stirring, filling nitrogen into the reaction kettle, adding 18kg of triethanolamine as a buffering agent and 13kg of deionized water, slowly adding 30kg of ethyl acrylate and 5kg of potassium persulfate as an initiator, finishing the addition within one hour, raising the temperature to 88 ℃, carrying out heat preservation reaction for 3 hours, and cooling to obtain the modified polyurethane resin emulsion.
Example 2
A preparation method of modified polyurethane resin comprises the following steps:
step 1: filling nitrogen into a reaction kettle, adding 30kg of toluene diisocyanate, stirring and heating to 70 ℃, then adding 2kg of organic tin catalyst and 30kg of dehydrated polyether glycol, heating the reaction kettle to 80 ℃, and reacting for 2 hours at constant temperature; adding 20kg of micromolecular chain extender diethylene glycol to react for 1 hour, adding 6kg of hydrophilic chain extender dimethylolpropionic acid to continue to react for 2 hours; stopping heating, adding 30kg of acetone into the reaction kettle to reduce the viscosity, reducing the temperature of the reaction kettle to 35 ℃, adjusting the pH to 7-8 by using triethylamine, stirring at a high speed within three minutes, adding 15kg of deionized water for emulsification, finally performing reduced pressure air extraction on the reaction kettle, and recovering the acetone;
step 2: and (3) raising the temperature of the reaction kettle to 75 ℃, starting stirring, filling nitrogen into the reaction kettle, adding 10kg of triethanolamine as a buffering agent and 20kg of deionized water, slowly adding 40kg of ethyl acrylate and 8kg of potassium persulfate as an initiator, finishing the addition within one hour, raising the temperature to 85 ℃, carrying out heat preservation reaction for 3 hours, and cooling to obtain the modified polyurethane resin emulsion.
Example 3
A preparation method of modified polyurethane resin comprises the following steps:
step 1: filling nitrogen into a reaction kettle, adding 20kg of toluene diisocyanate, stirring and heating to 78 ℃, then adding 2kg of organic tin catalyst and 50kg of dehydrated polyether glycol, heating the reaction kettle to 80 ℃, and reacting for 2 hours at constant temperature; adding 10kg of micromolecular chain extender diethylene glycol to react for 1 hour, adding 3kg of hydrophilic chain extender dimethylolpropionic acid to continue to react for 2 hours; stopping heating, adding 40kg of acetone into the reaction kettle to reduce the viscosity, reducing the temperature of the reaction kettle to 35 ℃, adjusting the pH to 7-8 by using triethylamine, stirring at a high speed within three minutes, adding 15kg of deionized water for emulsification, finally performing reduced pressure air extraction on the reaction kettle, and recovering the acetone;
step 2: and (3) raising the temperature of the reaction kettle to 75 ℃, starting stirring, filling nitrogen into the reaction kettle, adding 20kg of triethanolamine as a buffering agent and 10kg of deionized water, slowly adding 36kg of ethyl acrylate and 6kg of potassium persulfate as an initiator, finishing the addition within one hour, raising the temperature to 82 ℃, carrying out heat preservation reaction for 3 hours, and cooling to obtain the modified polyurethane resin emulsion.
Example 4
A preparation method of modified polyurethane resin comprises the following steps:
step 1: filling nitrogen into a reaction kettle, adding 28kg of toluene diisocyanate, stirring at a low speed by using an anchor type stirring paddle of the reaction kettle, introducing hot steam or hot water into a first flow guide channel 25 in a heat exchange jacket 6 to heat the reaction kettle to 76 ℃, then adding 1kg of organic tin catalyst and 35kg of dehydrated polyether glycol (the polyether glycol is dehydrated for 24 hours at the temperature of 125 ℃ under the vacuum of 1.061 KPa), heating the reaction kettle to 80 ℃, and reacting at a constant temperature for 2 hours; adding 18kg of micromolecular chain extender diethylene glycol to react for 1 hour, adding 5kg of hydrophilic chain extender dimethylolpropionic acid to continue to react for 2 hours; stopping heating, adding 45kg of acetone into the reaction kettle to reduce the viscosity, stopping introducing hot steam or hot water into the first flow guide channel 25, introducing cooling water into the second flow guide channel 26, reducing the temperature of the reaction kettle to 35 ℃, adjusting the pH value to 7-8 by using triethylamine, switching to a turbine stirring paddle of the reaction kettle for high-speed stirring after the adjustment is completed within three minutes, adding 12kg of deionized water for emulsification, and finally performing reduced pressure air extraction on the reaction kettle to recover the acetone;
step 2: introducing hot steam or hot water into a first diversion channel 25 in a heat exchange jacket 6 to raise the temperature of the reaction kettle to 75 ℃, stirring at a low speed by using an anchor type stirring paddle of the reaction kettle, filling nitrogen into the reaction kettle, adding 13kg of triethanolamine as a buffering agent and 17kg of deionized water, slowly adding 36kg of ethyl acrylate and 7kg of potassium persulfate as an initiator (the dosage of the initiator cannot be too large, otherwise, the reaction is too fast, the reaction heat is not easy to be discharged, the system is difficult to control, the stability of the modified polyurethane resin emulsion is reduced, and the water resistance is also poor), adding within one hour, heating to 83 ℃, keeping the temperature, reacting for 3 hours, introducing cooling water into a second diversion channel 26, and cooling to obtain the modified polyurethane resin emulsion.
As shown in figures 1 to 5, the reaction kettle comprises an upper seal head 1, a lower seal head 2, a cylinder 3, a rotary selection box 4 and a double-effect stirring paddle, the upper seal head 1 is connected with the cylinder 3 through bolts, the top of the upper seal head 1 is provided with a material inlet, the bottom of the lower seal head 2 is provided with a material outlet, the lower end enclosure 2 is welded with the cylinder 3, the lower part of the lower end enclosure 2 is fixedly provided with a support 5, the outer part of the lower end enclosure 2 is provided with a heat preservation layer 22, the outer part of the cylinder 3 is provided with a heat exchange jacket 6, a plurality of baffle plates 23 are uniformly arranged in the heat exchange jacket 6 to separate the space between the heat exchange jacket 6 and the side wall of the cylinder 3 to form a flow guide channel, the baffling baffle 23 is perpendicular to the side wall of the heat exchange jacket 6 and the cylinder 3, a baffle plate 24 in an inverted S shape is arranged in the flow guide channel, the baffle plate 24 divides the flow guide channel into a first flow guide channel 25 and a second flow guide channel 26, and the first flow guide channel 25 is not communicated with the second flow guide channel 26. The double-effect stirring paddle comprises a turbine stirring paddle and an anchor type stirring paddle, the turbine stirring paddle comprises a turbine stirring paddle blade 7 and a first central shaft 8, the top of the first central shaft 8 is arranged at the top of the upper end enclosure 1, the anchor type stirring paddle comprises an anchor type stirring paddle blade 10 and a second central shaft 11, the second central shaft 11 is sleeved on the first central shaft 8, the lower parts of the first central shaft 8 and the second central shaft 11 penetrate through the bottom of the lower end enclosure 2 and are connected with a motor 13 through a stirring selection component, a first gear 9 is arranged at the bottom of the first central shaft 8, and a second gear 12 is arranged at the bottom of the second central shaft 11; the stirring selection assembly is arranged in the rotary selection box 4 and comprises a rotary selection shaft 14, a shifting lever 15 and a sliding gear shaft 16, the upper end and the lower end of the rotary selection shaft 14 respectively extend out of the rotary selection box 4, the top end of the rotary selection shaft 14 is movably connected with a fixture block 20, the fixture block 20 is in a T shape, the bottom of the fixture block 20 is inserted into a cuboid groove arranged at the top end of the rotary selection shaft 14, a plurality of stop blocks 21 are uniformly distributed at the top of the rotary selection box 4 around the circumference of the rotary selection shaft 14, the top of the fixture block 20 is clamped between two adjacent stop blocks 21, the bottom end of the rotary selection shaft 14 is provided with a rotary handle 19, the middle part of the rotary selection shaft 14 is provided with a spiral line guide groove, the shifting lever 15 is in a cross shape, the shifting lever 15 comprises a horizontal rod and a vertical rod, and the top end and the bottom end of the vertical rod are respectively fixed to the upper bottom surface and the lower bottom surface of the rotary selection box 4, the horizontal rod is sleeved on the vertical rod, one end of the horizontal rod is spherical, the spherical body is embedded into the spiral line guide groove of the rotary selection shaft 14 and slides along the spiral line guide groove, the other end of the horizontal rod is annular and sleeved on a groove arranged in the middle of the sliding gear shaft 16, a third gear 17 is fixed on the lower portion of the outer side of the sliding gear shaft 16, a fourth gear 18 is fixed on the upper portion of the outer side of the sliding gear shaft 16, the third gear 17 is meshed with the first gear 9, the fourth gear 18 is meshed with the second gear 12, and the sliding gear shaft 16 is connected with an output shaft of the motor 13 through a spline; the reference circle of the fourth gear 18 is smaller than the reference circle of the third gear 17, and the distance between the third gear 17 and the fourth gear 18 is smaller than the distance between the first gear 9 and the second gear 12.
When the automatic transmission device works, the clamping block 20 is removed, the rotating handle 19 is rotated to drive the rotating selection shaft 14 to rotate, one end of the horizontal rod of the shifting rod 15, which is in the shape of a sphere, slides along the spiral line guide groove of the rotating selection shaft 14 (the highest position of the spiral line guide groove is used for enabling the second gear 12 to be meshed with the fourth gear 18, the lowest position of the spiral line guide groove is used for enabling the first gear 9 to be meshed with the third gear 17), the shifting rod 15 slides up and down, the other end of the horizontal rod of the shifting rod 15, which is in the shape of a circular ring, drives the sliding gear shaft 16 to slide up and down, when one end of the horizontal rod of the shifting rod 15, which is in the shape of a sphere, slides along the spiral line guide groove of the rotating selection shaft 14 to the lowest position of the spiral line guide groove, the third gear 17 is meshed with the first gear 9, when one end of the horizontal rod of the shifting rod 15, which is in the shape of a sphere, slides along the spiral line guide groove of the rotating selection shaft 14 to the highest position of the spiral line guide groove, realize fourth gear 18 and second gear 12 and mesh mutually to realize the rotation of turbine stirring rake or anchor stirring rake, then insert fast 20 bottoms of card to the cuboid recess that rotatory selection axle 14 top set up, the top card of fixture block 20 is to between two adjacent dogs 21, prevents the rotation of rotatory selection axle 14.
The above-mentioned embodiments are only preferred embodiments of the present invention, and not intended to limit the scope of the present invention, so that all equivalent changes and modifications made according to the technical solutions described in the claims of the present invention should be included in the claims of the present invention.
Claims (5)
1. A preparation method of modified polyurethane resin is characterized by comprising the following steps:
step 1: filling nitrogen into a reaction kettle, adding toluene diisocyanate, stirring and heating to 70-80 ℃, then adding a catalyst and dehydrated polyether glycol, heating the reaction kettle to 80 ℃, and reacting at constant temperature for 2 hours; adding a micromolecular chain extender to react for 1 hour, and then adding a hydrophilic chain extender to continue to react for 2 hours; stopping heating, adding acetone into the reaction kettle to reduce the viscosity, reducing the temperature of the reaction kettle to 35 ℃, adjusting the pH to 7-8 by using triethylamine, switching to a turbine stirring paddle of the reaction kettle to stir at a high speed within three minutes, adding deionized water to emulsify, and finally performing reduced pressure air extraction on the reaction kettle to recover the acetone;
step 2: raising the temperature of the reaction kettle to 75 ℃, stirring at a low speed by using an anchor type stirring paddle of the reaction kettle, filling nitrogen into the reaction kettle, adding triethanolamine as a buffering agent and deionized water, slowly adding ethyl acrylate and an initiator, completing the addition within one hour, then raising the temperature to 82-88 ℃, carrying out heat preservation reaction for 3 hours, and cooling to obtain the modified polyurethane resin emulsion;
in the steps, the raw materials comprise, by weight, 20-40 parts of toluene diisocyanate, 30-50 parts of polyether glycol, 1-2 parts of a catalyst, 10-20 parts of a small-molecule chain extender, 3-6 parts of a hydrophilic chain extender, 30-50 parts of acetone, 10-20 parts of a buffering agent, 30-40 parts of ethyl acrylate, 5-8 parts of an initiator, 10-20 parts of deionized water in step 1 and 10-20 parts of deionized water in step 2;
the reaction kettle comprises an upper seal head, a lower seal head, a barrel, a rotary selection box and a double-effect stirring paddle, wherein the upper seal head is connected with the barrel through bolts, the lower seal head is welded with the barrel, a support is fixedly arranged at the lower part of the lower seal head, a heat insulation layer is arranged outside the lower seal head, a heat exchange jacket is arranged outside the barrel, the double-effect stirring paddle comprises a turbine stirring paddle and an anchor stirring paddle, the turbine stirring paddle comprises a turbine stirring paddle blade and a first central shaft, the top of the first central shaft is arranged at the top of the upper seal head, the anchor stirring paddle comprises an anchor stirring paddle blade and a second central shaft, the second central shaft is sleeved on the first central shaft, the lower parts of the first central shaft and the second central shaft penetrate through the bottom of the lower seal head and are connected with a motor through a stirring selection component, a first gear is arranged at the bottom of the first central shaft, and a second gear is arranged at the bottom of the second central shaft; the stirring selection assembly is arranged in the rotary selection box and comprises a rotary selection shaft, a shifting rod and a sliding gear shaft, the upper end and the lower end of the rotary selection shaft extend out of the rotary selection box respectively, the top end of the rotary selection shaft is movably connected with a clamping block, the clamping block is T-shaped, the bottom of the clamping block is inserted into a cuboid groove formed in the top end of the rotary selection shaft, a plurality of stopping blocks are uniformly distributed at the top of the rotary selection box around the circumferential direction of the rotary selection shaft, the top of the clamping block is clamped between two adjacent stopping blocks, a rotary handle is arranged at the bottom end of the rotary selection shaft, a spiral line guide groove is formed in the middle of the rotary selection shaft, the shifting rod is cross-shaped and comprises a horizontal rod and a vertical rod, the top end and the bottom end of the vertical rod are fixed to the upper bottom surface and the lower bottom surface of the rotary selection box respectively, the horizontal rod is sleeved on the vertical rod, one end of the horizontal rod is a sphere, The ball body is embedded into the spiral line guide groove of the rotary selection shaft and slides along the spiral line guide groove, the other end of the horizontal rod is in a circular ring shape, and the circular ring is sleeved on a groove arranged in the middle of the sliding gear shaft;
the reference circle of the fourth gear is smaller than that of the third gear, and the distance between the third gear and the fourth gear is smaller than that between the first gear and the second gear.
2. The method for preparing the modified polyurethane resin as claimed in claim 1, wherein the catalyst is an organotin catalyst.
3. The method for preparing the modified polyurethane resin according to claim 1, wherein the small-molecule chain extender is diethylene glycol, and the hydrophilic chain extender is dimethylolpropionic acid.
4. The method of claim 1, wherein the initiator is potassium persulfate.
5. The method for preparing modified polyurethane resin according to claim 1, wherein a plurality of baffle plates are uniformly arranged in the heat exchange jacket to form a flow guide channel, the baffle plates are perpendicular to the side wall and the cylinder of the heat exchange jacket, an inverted S-shaped partition plate is arranged in the flow guide channel, the partition plate divides the flow guide channel into a first flow guide channel and a second flow guide channel, and the first flow guide channel and the second flow guide channel are not communicated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811005822.3A CN109206572B (en) | 2018-08-30 | 2018-08-30 | Preparation method of modified polyurethane resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811005822.3A CN109206572B (en) | 2018-08-30 | 2018-08-30 | Preparation method of modified polyurethane resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109206572A CN109206572A (en) | 2019-01-15 |
| CN109206572B true CN109206572B (en) | 2021-09-14 |
Family
ID=64987046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811005822.3A Active CN109206572B (en) | 2018-08-30 | 2018-08-30 | Preparation method of modified polyurethane resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109206572B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110026148A (en) * | 2019-04-23 | 2019-07-19 | 广小芳 | A kind of uniformly mixed reaction kettle being used to prepare Corvic |
| CN110038506A (en) * | 2019-05-31 | 2019-07-23 | 金陵科技学院 | A kind of reaction kettle to cool down and its heat preservation, cool-down method |
| CN110358434A (en) * | 2019-07-26 | 2019-10-22 | 帕提古丽·奥布力 | A kind of preparation method of modified polyurethane paint |
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1760619A (en) * | 2005-09-29 | 2006-04-19 | 舒增鳌 | Channel box type evaporator |
| CN101596438A (en) * | 2009-07-10 | 2009-12-09 | 浙江大学 | Be suitable for the adjustable twin shaft reactor that variable physical property medium stirs |
| CN202011851U (en) * | 2011-02-26 | 2011-10-19 | 潍坊中星精细化工有限公司 | Polyurethane resin reaction kettle |
| CN102516465A (en) * | 2011-11-19 | 2012-06-27 | 烟台万华聚氨酯股份有限公司 | High-elasticity waterborne polyurethane-acrylate composite resin, and preparation method and application thereof |
| CN203443430U (en) * | 2013-07-06 | 2014-02-19 | 王金宝 | Detachable curved plate type heat exchanger |
| CN104693368A (en) * | 2015-03-12 | 2015-06-10 | 新疆中泰化学股份有限公司 | Polyurethane/acrylate core-shell emulsion, modified resin powder material and preparation methods thereof |
| CN204768714U (en) * | 2015-07-03 | 2015-11-18 | 宁波大学 | Discrete type ester solubility polyurethane adhesive production reation kettle |
| CN204768704U (en) * | 2015-07-06 | 2015-11-18 | 南通瑞泰电子有限公司 | Novel be convenient for reation kettle that observes |
| CN205599169U (en) * | 2016-04-05 | 2016-09-28 | 上虞颖泰精细化工有限公司 | Interior pipeline reactor who establishes companion's pipe |
| CN206304741U (en) * | 2016-12-20 | 2017-07-07 | 超然(福建)新材料科技有限公司 | A kind of polyurethane resin reactor |
| CN107597010A (en) * | 2017-11-06 | 2018-01-19 | 黄纪春 | A kind of agitating device |
| CN107722187A (en) * | 2017-10-23 | 2018-02-23 | 广东华斓汽车材料研究院 | A kind of preparation method and applications of polymerization of acrylic modified polyurethane aqueous dispersion |
| CN207085896U (en) * | 2017-06-29 | 2018-03-13 | 江苏欣舟化工科技有限公司 | A kind of coaxial double rotating type quick reaction kettle |
| CN207254174U (en) * | 2017-06-06 | 2018-04-20 | 新昌县金瓯新能源科技有限公司 | A kind of new liquid mixer |
| CN108219106A (en) * | 2017-12-26 | 2018-06-29 | 万华化学（宁波）有限公司 | A kind of aqueous polyurethane-acrylate hybrid copolymers and preparation method thereof |
| CN108264614A (en) * | 2017-12-29 | 2018-07-10 | 上海乘鹰新材料有限公司 | Polyurethane-acrylate complex emulsions composition and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100104872A1 (en) * | 2008-09-17 | 2010-04-29 | Archer-Daniels-Midland Company | Biobased waterborne synthetic polyurethane hybrid latexes and films |
| CN108314510A (en) * | 2018-02-01 | 2018-07-24 | 王炜杰 | A kind of high-efficient biological reactor |
-
2018
- 2018-08-30 CN CN201811005822.3A patent/CN109206572B/en active Active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1760619A (en) * | 2005-09-29 | 2006-04-19 | 舒增鳌 | Channel box type evaporator |
| CN101596438A (en) * | 2009-07-10 | 2009-12-09 | 浙江大学 | Be suitable for the adjustable twin shaft reactor that variable physical property medium stirs |
| CN202011851U (en) * | 2011-02-26 | 2011-10-19 | 潍坊中星精细化工有限公司 | Polyurethane resin reaction kettle |
| CN102516465A (en) * | 2011-11-19 | 2012-06-27 | 烟台万华聚氨酯股份有限公司 | High-elasticity waterborne polyurethane-acrylate composite resin, and preparation method and application thereof |
| CN203443430U (en) * | 2013-07-06 | 2014-02-19 | 王金宝 | Detachable curved plate type heat exchanger |
| CN104693368A (en) * | 2015-03-12 | 2015-06-10 | 新疆中泰化学股份有限公司 | Polyurethane/acrylate core-shell emulsion, modified resin powder material and preparation methods thereof |
| CN204768714U (en) * | 2015-07-03 | 2015-11-18 | 宁波大学 | Discrete type ester solubility polyurethane adhesive production reation kettle |
| CN204768704U (en) * | 2015-07-06 | 2015-11-18 | 南通瑞泰电子有限公司 | Novel be convenient for reation kettle that observes |
| CN205599169U (en) * | 2016-04-05 | 2016-09-28 | 上虞颖泰精细化工有限公司 | Interior pipeline reactor who establishes companion's pipe |
| CN206304741U (en) * | 2016-12-20 | 2017-07-07 | 超然(福建)新材料科技有限公司 | A kind of polyurethane resin reactor |
| CN207254174U (en) * | 2017-06-06 | 2018-04-20 | 新昌县金瓯新能源科技有限公司 | A kind of new liquid mixer |
| CN207085896U (en) * | 2017-06-29 | 2018-03-13 | 江苏欣舟化工科技有限公司 | A kind of coaxial double rotating type quick reaction kettle |
| CN107722187A (en) * | 2017-10-23 | 2018-02-23 | 广东华斓汽车材料研究院 | A kind of preparation method and applications of polymerization of acrylic modified polyurethane aqueous dispersion |
| CN107597010A (en) * | 2017-11-06 | 2018-01-19 | 黄纪春 | A kind of agitating device |
| CN108219106A (en) * | 2017-12-26 | 2018-06-29 | 万华化学（宁波）有限公司 | A kind of aqueous polyurethane-acrylate hybrid copolymers and preparation method thereof |
| CN108264614A (en) * | 2017-12-29 | 2018-07-10 | 上海乘鹰新材料有限公司 | Polyurethane-acrylate complex emulsions composition and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Modification of waterborne polyurethane by forming latex interpenetrating polymer networks with acrylate rubber;Byung Kyu Kim，等;《Colloid Polym Sci》;20020424;第280卷(第8期);第716-724页 * |
| 机械搅拌反应釜概述;冯桂江;《橡塑技术与装备（塑料）》;20151115;第41卷(第22期);第56-57页 * |
| 聚氨酯-丙烯酸酯杂化乳液结构与性能的影响;夏骏嵘，等;《功能高分子学报》;20050930;第18卷(第3期);第699-404页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109206572A (en) | 2019-01-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109206572B (en) | Preparation method of modified polyurethane resin | |
| CN102942674B (en) | Three-component polyurethane elastomer composition | |
| CN103540217B (en) | The double-component aqueous car paint of acrylate resin that a kind of aziridine is crosslinked and its preparation method | |
| CN102604368B (en) | NCO replaced crosslinking cured joint filling material for concrete pavement | |
| CN104403547B (en) | Environment-friendly type high performance polyurethane water-proof paint and preparation method thereof | |
| CN110437412B (en) | Polyurethane wood-like material and preparation method thereof | |
| CN114369236B (en) | High-performance polyester ether polyol, and preparation method and application thereof | |
| JP2015500916A (en) | Method for producing polytetrafluoroethylene-containing resin with high fluorine content | |
| CN110305609A (en) | A kind of bi-component flexible compound epoxy resin adhesive | |
| CN104292419B (en) | A kind of preparation method of High-performance green environmental protection coatings for furniture two component polyurethane modified unsaturated polyester | |
| CN114196315B (en) | Wear-resistant floor coating, preparation method thereof and wear-resistant floor coating structure | |
| CN110358055A (en) | The method that one kettle way prepares lignin acid anhydride curable epoxy resin | |
| CN106634476A (en) | Epoxy cured high-flexibility polyester resin used for powdery paint and a preparing method thereof | |
| CN103694637B (en) | A kind of High-tenacity vacuum slow epoxy resin for wind power blade and preparation method thereof | |
| CN106317915B (en) | Vegetable oil based polyurethane modified pitch and mixture containing the modified pitch | |
| CN109306056B (en) | Reactive flame-retardant polyether polyol for OCF joint sealing adhesive and preparation method thereof | |
| CN101967255A (en) | Waterborne resin for plastic film coating and preparation method thereof | |
| CN110963944A (en) | Novel low-free TDI polyurethane curing agent containing fluorocarbon chains and preparation method thereof | |
| CN115612369B (en) | Modified epoxy resin floor coating and preparation method thereof | |
| CN108276939A (en) | A kind of room temperature curing energetic binder and its synthetic method | |
| CN106189194A (en) | The preparation method of a kind of HPU plastic cement and the construction technology in HPU place | |
| Huang et al. | Thermally healable polyurethanes based on furfural-derived monomers via Baylis-Hillman reaction | |
| CN115611554B (en) | Modified epoxy resin anti-abrasion repair mortar and preparation method thereof | |
| CN105778053B (en) | Fry starch of konjak epoxy hardener and preparation method and the floor coatings containing the curing agent | |
| CN114570321A (en) | Polyurethane prepolymer production equipment and production method thereof |
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 |