CN109280137B - Preparation method of rosin-based TDI (toluene diisocynate) type waterborne polyurethane microsphere - Google Patents
Preparation method of rosin-based TDI (toluene diisocynate) type waterborne polyurethane microsphere Download PDFInfo
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims abstract description 82
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 title claims abstract description 82
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 43
- 239000004814 polyurethane Substances 0.000 title claims abstract description 43
- 239000004005 microsphere Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title claims description 48
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 16
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 44
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 10
- 229920005862 polyol Polymers 0.000 claims description 10
- 150000003077 polyols Chemical class 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 230000001804 emulsifying effect Effects 0.000 claims description 5
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 5
- 238000010907 mechanical stirring Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 239000003999 initiator Substances 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract 1
- 239000010865 sewage Substances 0.000 abstract 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical group NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- -1 coatings Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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- 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
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
-
- 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
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- 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
- C08G18/67—Unsaturated compounds having active hydrogen
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method of rosin-based TDI type waterborne polyurethane microspheres. Rosin and the like are used as raw materials, modified to obtain rosin-based TDI (toluene diisocyanate) waterborne polyurethane, and then copolymerized with styrene under the action of polyvinylpyrrolidone and an initiator to obtain the rosin-based TDI waterborne polyurethane microsphere. The most remarkable characteristic of the invention is that the ionic waterborne polyurethane microspheres with smaller particle size and better monodispersity and sphericity are prepared by taking rosin and the like as raw materials. The rosin and the polyurethane are endowed with wider application, and the synthesized waterborne polyurethane microspheres can be applied to the fields of drug loading and release, metal ion adsorption, sewage treatment and the like.
Description
Technical Field
The invention relates to a preparation method of rosin-based TDI type waterborne polyurethane microspheres.
Background
With the increasing exhaustion of non-renewable fossil energy sources and the increasing awareness of environmental protection, the research of replacing fossil energy sources partially or completely with natural renewable resources to alleviate the energy crisis has become one of the main tasks of chemical workers. Rosin is an extremely abundant natural renewable resource in nature, and has the defects of high acid value and easy oxidation although the yield is rich, so that the application of the rosin in a plurality of industrial production is limited. The double bond and carboxyl in the rosin structure are utilized to modify the rosin, so that the purpose of expanding the application range of the rosin can be achieved. The application of rosin in polymer synthesis is mainly to introduce the rosin into a polymer chain through carboxyl and double bonds. The functional polymer synthesized by using rosin as a raw material is non-toxic and harmless to human bodies, and can be safely used in the fields of medicines and foods.
The polyurethane microsphere is a novel polyurethane product, contains polar groups such as carbamate and the like and a microphase separation structure, has more folds and pore channels on the surface and inside, has smaller particle size and larger specific surface area, has better stability when being dispersed in a solution, has the characteristics of good adsorption, ion exchange, chelation, biocompatibility, high elasticity, high strength and the like, and shows wide application prospect in the aspects of separation and purification, biochemical diagnosis, drug carriers, coatings, adhesives, printing ink and the like. The preparation method of the polyurethane microspheres mainly comprises a self-emulsifying method, a suspension polymerization method, a dispersion polymerization method and the like. By designing, synthesizing and modifying the polyurethane resin, the polyurethane microspheres with controllable particle size, good appearance, good mechanical property, good water resistance and good stability can be obtained.
The rosin-based TDI waterborne polyurethane microsphere is prepared by taking rosin as a raw material, modifying to obtain rosin-based TDI waterborne polyurethane, and copolymerizing the rosin-based TDI waterborne polyurethane and styrene. The invention provides a new application approach for reasonably developing and utilizing rosin resources, and the prepared polyurethane microspheres can be applied to the fields of chromatographic analysis, adsorption separation technology, wastewater treatment and the like.
Disclosure of Invention
The invention aims to provide a preparation method of rosin-based TDI type waterborne polyurethane microspheres.
The method comprises the following specific steps:
3.20 to 1.60 parts by mass of rosin-based TDI type waterborne polyurethane, 0.80 to 2.40 parts by mass of chemically pure styrene, 0.08 to 0.32 part by mass of chemically pure polyvinylpyrrolidone and 0.02 to E0.08 part by mass of analytically pure azobisisobutyronitrile is placed in a beaker, 40-60 parts by mass of distilled water is added, the mixture is uniformly mixed after ultrasonic dispersion for 10 minutes, and then the mixed solution is added into a reaction kettle and stirred in a reactor with N2Heating to 80-100 ℃ under the protection action, and setting the rotating speed to be 200 r.min-1The reaction lasts for 4-10 hours and finally is carried out at 10000 r.min-1And (3) carrying out centrifugal separation for 15 minutes at a rotating speed, washing with distilled water for 3-5 times, carrying out centrifugal separation, and naturally airing to obtain the rosin-based TDI type waterborne polyurethane microsphere with the average particle size of 85-200 nm.
The preparation method of the rosin-based TDI type waterborne polyurethane comprises the following steps:
(1) adding 100.0 parts by mass of rosin into a reaction kettle provided with a stirring rod, a reflux condenser tube, a thermometer and a nitrogen protection device, heating and melting the rosin, and then heating and melting the rosin at 400 r.min-1Stirring, heating to 230 ℃, slowly dropwise adding 28.60 parts by mass of chemically pure acrylic acid for 1 hour, continuously reacting at 230 ℃ for 2 hours after dropwise adding, and discharging when the temperature is reduced to 200 ℃ to obtain the acrylic rosin adduct.
(2) 108.51 parts by mass of the acrylic rosin adduct obtained in the step (1) is dissolved in 191.86 parts by mass of analytically pure toluene in a reaction kettle, 82.40 parts by mass of methacrylic glycidyl methacrylate with purity of 97%, 0.54 part by mass of analytically pure triethylamine and 0.41 part by mass of analytically pure 1, 4-hydroquinone are added, the temperature is increased to 120 ℃, the reaction is carried out for 4 hours, the acid value is measured to be 2.40mgKOH/g, and toluene is removed by rotary evaporation, thus obtaining the rosin-based polyol.
(3) Adding 30.00 parts by mass of rosin-based polyol obtained in the step (2), 0.21 part by mass of chemically pure dibutyl tin dilaurate and 100.00 parts by mass of analytically pure acetone into a reaction kettle, and reacting in the presence of N2Heating to 30 ℃ under protection, adding 11.89 parts by mass of experimental reagent toluene-2, 4-diisocyanate (TDI), and setting the rotating speed at 400 r.min-1When the-NCO content is reduced to a theoretical value, 4.61 parts by mass of analytically pure 2, 2-dimethylolpropionic acid is added, the temperature is raised to 55 ℃, the reaction is carried out until the-NCO content is reduced to 0, the temperature is reduced to 18 ℃, 3.48 parts by mass of analytically pure triethylamine is added for neutralization for 10 minutes, and the reaction is carried out at 1300 r.min-1Adding 200mL of deionized water under mechanical stirring for emulsifying and dispersing for 30 minutes, and distilling under reduced pressureRemoving acetone to obtain rosin-based TDI type waterborne polyurethane, wherein the measured solid mass percentage is 18.20%.
Compared with other related technologies, the invention has the most remarkable characteristic that rosin and the like which are natural renewable forest resources are used as raw materials, the rosin-based TDI type waterborne polyurethane is obtained through modification, and then the rosin-based TDI type waterborne polyurethane is copolymerized with styrene under the action of an initiator to synthesize the rosin-based TDI type waterborne polyurethane microsphere. Not only the submicron polyurethane microsphere with better monodispersity and sphericity is obtained, but also the rosin is endowed with wider application.
Detailed Description
Example 1:
putting 2.80 parts by mass of rosin-based TDI type waterborne polyurethane, 1.20 parts by mass of chemically pure styrene, 0.24 part by mass of chemically pure polyvinylpyrrolidone and 0.04 part by mass of analytically pure azobisisobutyronitrile into a beaker, adding 46 parts by mass of distilled water, ultrasonically dispersing for 10 minutes, uniformly mixing, adding the mixed solution into a reaction kettle, and adding N into the reaction kettle2Heating to 85 deg.C under protection, and setting rotation speed at 200r min-1The reaction lasts for 8 hours and finally at 10000 r.min-1Centrifugally separating for 15 minutes at a rotating speed, washing with distilled water for 4 times, centrifugally separating, and naturally airing to obtain the rosin-based TDI type waterborne polyurethane microspheres with the average particle size of 187.10 nm.
The preparation method of the rosin-based TDI type waterborne polyurethane comprises the following steps:
(1) adding 100.0 parts by mass of rosin into a reaction kettle provided with a stirring rod, a reflux condenser tube, a thermometer and a nitrogen protection device, heating and melting the rosin, and then heating and melting the rosin at 400 r.min-1Stirring, heating to 230 ℃, slowly dropwise adding 28.60 parts by mass of chemically pure acrylic acid for 1 hour, continuously reacting at 230 ℃ for 2 hours after dropwise adding, and discharging when the temperature is reduced to 200 ℃ to obtain the acrylic rosin adduct.
(2) 108.51 parts by mass of the acrylic rosin adduct obtained in the step (1) is dissolved in 191.86 parts by mass of analytically pure toluene in a reaction kettle, 82.40 parts by mass of methacrylic glycidyl methacrylate with purity of 97%, 0.54 part by mass of analytically pure triethylamine and 0.41 part by mass of analytically pure 1, 4-hydroquinone are added, the temperature is increased to 120 ℃, the reaction is carried out for 4 hours, the acid value is measured to be 2.40mgKOH/g, and toluene is removed by rotary evaporation, thus obtaining the rosin-based polyol.
(3) Adding 30.00 parts by mass of rosin-based polyol obtained in the step (2), 0.21 part by mass of chemically pure dibutyl tin dilaurate and 100.00 parts by mass of analytically pure acetone into a reaction kettle, and reacting in the presence of N2Heating to 30 ℃ under protection, adding 11.89 parts by mass of experimental reagent toluene-2, 4-diisocyanate (TDI), and setting the rotating speed at 400 r.min-1When the-NCO content is reduced to a theoretical value, 4.61 parts by mass of analytically pure 2, 2-dimethylolpropionic acid is added, the temperature is raised to 55 ℃, the reaction is carried out until the-NCO content is reduced to 0, the temperature is reduced to 18 ℃, 3.48 parts by mass of analytically pure triethylamine is added for neutralization for 10 minutes, and the reaction is carried out at 1300 r.min-1And adding 200mL of deionized water under mechanical stirring for emulsifying and dispersing for 30 minutes, and removing acetone through reduced pressure distillation to obtain the rosin-based TDI type waterborne polyurethane, wherein the measured solid mass percentage is 18.20%.
Example 2:
2.40 parts by mass of rosin-based TDI (toluene diisocynate) type waterborne polyurethane, 1.60 parts by mass of chemically pure styrene, 0.24 part by mass of chemically pure polyvinylpyrrolidone and 0.04 part by mass of analytically pure azobisisobutyronitrile are placed in a beaker, 46 parts by mass of distilled water is added, ultrasonic dispersion is carried out for 10 minutes, the mixture is uniformly mixed, then the mixed solution is added into a reaction kettle, and N is added into the reaction kettle2Heating to 85 deg.C under protection, and setting rotation speed at 200r min-1The reaction lasts for 8 hours and finally at 10000 r.min-1Centrifugally separating for 15 minutes at a rotating speed, washing with distilled water for 4 times, centrifugally separating, and naturally airing to obtain the rosin-based TDI type waterborne polyurethane microspheres with the average particle size of 160.80 nm.
The preparation method of the rosin-based TDI type waterborne polyurethane comprises the following steps:
(1) adding 100.0 parts by mass of rosin into a reaction kettle provided with a stirring rod, a reflux condenser tube, a thermometer and a nitrogen protection device, heating and melting the rosin, and then heating and melting the rosin at 400 r.min-1Stirring, heating to 230 ℃, slowly dropwise adding 28.60 parts by mass of chemically pure acrylic acid for 1 hour, continuously reacting at 230 ℃ for 2 hours after dropwise adding, and discharging when the temperature is reduced to 200 ℃ to obtain the acrylic rosin adduct.
(2) 108.51 parts by mass of the acrylic rosin adduct obtained in the step (1) is dissolved in 191.86 parts by mass of analytically pure toluene in a reaction kettle, 82.40 parts by mass of methacrylic glycidyl methacrylate with purity of 97%, 0.54 part by mass of analytically pure triethylamine and 0.41 part by mass of analytically pure 1, 4-hydroquinone are added, the temperature is increased to 120 ℃, the reaction is carried out for 4 hours, the acid value is measured to be 2.40mgKOH/g, and toluene is removed by rotary evaporation, thus obtaining the rosin-based polyol.
(3) Adding 30.00 parts by mass of rosin-based polyol obtained in the step (2), 0.21 part by mass of chemically pure dibutyl tin dilaurate and 100.00 parts by mass of analytically pure acetone into a reaction kettle, and reacting in the presence of N2Heating to 30 ℃ under protection, adding 11.89 parts by mass of experimental reagent toluene-2, 4-diisocyanate (TDI), and setting the rotating speed at 400 r.min-1When the-NCO content is reduced to a theoretical value, 4.61 parts by mass of analytically pure 2, 2-dimethylolpropionic acid is added, the temperature is raised to 55 ℃, the reaction is carried out until the-NCO content is reduced to 0, the temperature is reduced to 18 ℃, 3.48 parts by mass of analytically pure triethylamine is added for neutralization for 10 minutes, and the reaction is carried out at 1300 r.min-1And adding 200mL of deionized water under mechanical stirring for emulsifying and dispersing for 30 minutes, and removing acetone through reduced pressure distillation to obtain the rosin-based TDI type waterborne polyurethane, wherein the measured solid mass percentage is 18.20%.
Example 3:
2.40 parts by mass of rosin-based TDI (toluene diisocynate) type waterborne polyurethane, 1.60 parts by mass of chemically pure styrene, 0.32 part by mass of chemically pure polyvinylpyrrolidone and 0.04 part by mass of analytically pure azobisisobutyronitrile are placed in a beaker, 46 parts by mass of distilled water is added, ultrasonic dispersion is carried out for 10 minutes, the mixture is uniformly mixed, then the mixed solution is added into a reaction kettle, and N is added into the reaction kettle2Heating to 80 deg.C under protection, and setting rotation speed at 200r min-1The reaction lasts for 8 hours and finally at 10000 r.min-1Centrifugally separating for 15 minutes at a rotating speed, washing for 5 times by using distilled water, centrifugally separating, and naturally airing to obtain the rosin-based TDI type waterborne polyurethane microsphere with the average particle size of 120.00 nm.
The preparation method of the rosin-based TDI type waterborne polyurethane comprises the following steps:
(1) adding 100.0 parts by mass of rosin into a stirring rod, a reflux condenser tube, a thermometer and a nitrogen protection deviceIn the reaction kettle, heating and melting the mixture at 400 r.min-1Stirring, heating to 230 ℃, slowly dropwise adding 28.60 parts by mass of chemically pure acrylic acid for 1 hour, continuously reacting at 230 ℃ for 2 hours after dropwise adding, and discharging when the temperature is reduced to 200 ℃ to obtain the acrylic rosin adduct.
(2) 108.51 parts by mass of the acrylic rosin adduct obtained in the step (1) is dissolved in 191.86 parts by mass of analytically pure toluene in a reaction kettle, 82.40 parts by mass of methacrylic glycidyl methacrylate with purity of 97%, 0.54 part by mass of analytically pure triethylamine and 0.41 part by mass of analytically pure 1, 4-hydroquinone are added, the temperature is increased to 120 ℃, the reaction is carried out for 4 hours, the acid value is measured to be 2.40mgKOH/g, and toluene is removed by rotary evaporation, thus obtaining the rosin-based polyol.
(3) Adding 30.00 parts by mass of rosin-based polyol obtained in the step (2), 0.21 part by mass of chemically pure dibutyl tin dilaurate and 100.00 parts by mass of analytically pure acetone into a reaction kettle, and reacting in the presence of N2Heating to 30 ℃ under protection, adding 11.89 parts by mass of experimental reagent toluene-2, 4-diisocyanate (TDI), and setting the rotating speed at 400 r.min-1When the-NCO content is reduced to a theoretical value, 4.61 parts by mass of analytically pure 2, 2-dimethylolpropionic acid is added, the temperature is raised to 55 ℃, the reaction is carried out until the-NCO content is reduced to 0, the temperature is reduced to 18 ℃, 3.48 parts by mass of analytically pure triethylamine is added for neutralization for 10 minutes, and the reaction is carried out at 1300 r.min-1And adding 200mL of deionized water under mechanical stirring for emulsifying and dispersing for 30 minutes, and removing acetone through reduced pressure distillation to obtain the rosin-based TDI type waterborne polyurethane, wherein the measured solid mass percentage is 18.20%.
Claims (1)
1. A preparation method of rosin-based TDI type waterborne polyurethane microspheres is characterized by comprising the following specific steps:
3.20-1.60 parts by mass of rosin-based TDI (toluene diisocynate) waterborne polyurethane, 0.80-2.40 parts by mass of chemically pure styrene, 0.08-0.32 part by mass of chemically pure polyvinylpyrrolidone and 0.02-0.08 part by mass of analytically pure azodiisobutyronitrile are placed in a beaker, 40-60 parts by mass of distilled water is added, ultrasonic dispersion is carried out for 10 minutes, the mixture is uniformly mixed, then the mixed solution is added into a reaction kettle, and the mixture is subjected to reaction under the condition of N2Heating to 80-100 ℃ under the protection action, and setting the rotating speed to be 200 r·min-1The reaction lasts for 4-10 hours and finally is carried out at 10000 r.min-1Carrying out centrifugal separation for 15 minutes at a rotating speed, washing with distilled water for 3-5 times, carrying out centrifugal separation, and naturally airing to obtain rosin-based TDI (toluene diisocynate) type waterborne polyurethane microspheres with the average particle size of 85-200 nm;
the preparation method of the rosin-based TDI type waterborne polyurethane comprises the following steps:
(1) adding 100.0 parts by mass of rosin into a reaction kettle provided with a stirring rod, a reflux condenser tube, a thermometer and a nitrogen protection device, heating and melting the rosin, and then heating and melting the rosin at 400 r.min-1Stirring, heating to 230 ℃, slowly dropwise adding 28.60 parts by mass of chemically pure acrylic acid for 1 hour, continuously reacting at 230 ℃ for 2 hours after dropwise adding, and discharging when the temperature is reduced to 200 ℃ to obtain an acrylic rosin adduct;
(2) 108.51 parts by mass of the acrylic rosin adduct obtained in the step (1) is dissolved in 191.86 parts by mass of analytically pure toluene in a reaction kettle, 82.40 parts by mass of glycidyl methacrylate with purity of 97%, 0.54 part by mass of analytically pure triethylamine and 0.41 part by mass of analytically pure 1, 4-hydroquinone are added, the temperature is increased to 120 ℃, the reaction is carried out for 4 hours, the acid value is measured to be 2.40mgKOH/g, and toluene is removed by rotary evaporation, thus obtaining the rosin-based polyol;
(3) adding 30.00 parts by mass of rosin-based polyol obtained in the step (2), 0.21 part by mass of chemically pure dibutyl tin dilaurate and 100.00 parts by mass of analytically pure acetone into a reaction kettle, and reacting in the presence of N2Heating to 30 ℃ under protection, adding 11.89 parts by mass of experimental reagent toluene-2, 4-diisocyanate, and setting the rotating speed at 400 r.min-1When the-NCO content is reduced to a theoretical value, 4.61 parts by mass of analytically pure 2, 2-dimethylolpropionic acid is added, the temperature is raised to 55 ℃, the reaction is carried out until the-NCO content is reduced to 0, the temperature is reduced to 18 ℃, 3.48 parts by mass of analytically pure triethylamine is added for neutralization for 10 minutes, and the reaction is carried out at 1300 r.min-1And adding 200mL of deionized water under mechanical stirring for emulsifying and dispersing for 30 minutes, and removing acetone through reduced pressure distillation to obtain the rosin-based TDI type waterborne polyurethane, wherein the measured solid mass percentage is 18.20%.
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Application publication date: 20190129 Assignee: Guangxi manjin Energy Saving Technology Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2022450000619 Denomination of invention: A preparation method of rosin-based TDI waterborne polyurethane microspheres Granted publication date: 20210112 License type: Common License Record date: 20221230 Application publication date: 20190129 Assignee: Nanning Richong Technology Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2022450000635 Denomination of invention: A preparation method of rosin-based TDI waterborne polyurethane microspheres Granted publication date: 20210112 License type: Common License Record date: 20221230 |