CN109225083B - Preparation method of self-crosslinking rosin-based polyurethane microspheres - Google Patents
Preparation method of self-crosslinking rosin-based polyurethane microspheres 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 89
- 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 89
- 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 89
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 44
- 239000004814 polyurethane Substances 0.000 title claims abstract description 44
- 239000004005 microsphere Substances 0.000 title claims abstract description 24
- 238000004132 cross linking Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 100
- 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 abstract description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004088 foaming agent Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 238000010438 heat treatment Methods 0.000 claims description 28
- 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 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 229920005862 polyol Polymers 0.000 claims description 12
- 150000003077 polyols Chemical class 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- 108010010803 Gelatin Proteins 0.000 claims description 6
- 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 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 229920000159 gelatin Polymers 0.000 claims description 6
- 239000008273 gelatin Substances 0.000 claims description 6
- 235000019322 gelatine Nutrition 0.000 claims description 6
- 235000011852 gelatine desserts Nutrition 0.000 claims description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 6
- 238000010907 mechanical stirring Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000011160 research Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000010558 suspension polymerization method Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000003999 initiator Substances 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 238000004587 chromatography analysis Methods 0.000 abstract description 2
- 230000000149 penetrating effect Effects 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- -1 coatings Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical group NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 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
- 238000004043 dyeing Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
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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
- C08G18/28—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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/6705—Unsaturated polymers not provided for in the groups C08G18/671, C08G18/6795, C08G18/68 or C08G18/69
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method of self-crosslinking rosin-based polyurethane microspheres. Rosin is used as a raw material, modification research is carried out to obtain rosin-based TDI polyurethane, and then toluene, toluene/ethyl acetate, toluene/acetonitrile or toluene/dimethyl sulfoxide is used as a pore-foaming agent and azodiisobutyronitrile is used as an initiator to synthesize the self-crosslinking rosin-based polyurethane microsphere by a suspension polymerization method. The most remarkable characteristic of the invention is that rosin is used as raw material, the prepared polyurethane microsphere has good sphericity and rigidity, and has a pore structure penetrating through the interior of the microsphere, which not only improves the added value of rosin and polyurethane, but also can be applied to the fields of industrial production, chromatographic analysis, biomedicine, adsorption separation technology, wastewater treatment and the like.
Description
Technical Field
The invention relates to a preparation method of self-crosslinking rosin-based polyurethane microspheres.
Background
Rosin is a non-volatile natural resin obtained by processing pine rosin in different modes, is a natural renewable forest resource which is abundant in nature and is an indispensable chemical raw material in national production, and is widely applied to the fields of coatings, electrical appliances, adhesives, papermaking, printing and dyeing, printing ink, plastics, pesticides, rubber, spices, cosmetics and the like due to excellent performances of softening, insulation, moisture prevention, corrosion prevention, adhesion and the like. However, rosin has O which is liable to be in the air2Oxidation, easy crystallization, low softening point and the like, which limits the wider application of the material. Two chemical reaction active centers, namely carboxyl and double bond, existing in the molecular structure of the rosin can be used for modification researches such as addition, isomerization, hydrogenation, dehydrogenation and esterification, and further the application range of the rosin in industrial production is expanded.
The polyurethane microsphere is a novel polyurethane product, contains polar groups such as carbamate and the like and a microphase separation structure, has the characteristics of good adsorption, ion exchange, chelation, biocompatibility, high elasticity, high strength and the like due to more folds and pores on the surface and inside of the microsphere, and has wide application prospects 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-emulsification method, a suspension polymerization method, a dispersion polymerization method, an SPG membrane emulsification 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 invention takes rosin and the like as raw materials, obtains rosin-based TDI polyurethane through modification research, and then synthesizes the self-crosslinking rosin-based polyurethane microsphere by using a suspension polymerization method under the action of an initiator and a pore-foaming agent. The invention provides a new application approach for reasonably developing and utilizing rosin resources, widens the added value of polyurethane, and the microspheres prepared by a series of reactions can be applied to the fields of industrial production, chromatographic analysis, biomedicine, separation technology, wastewater treatment and the like.
Disclosure of Invention
The invention aims to provide a preparation method of self-crosslinking rosin-based polyurethane microspheres.
The method comprises the following specific steps:
adding 40-80 parts by mass of distilled water and 0.36 part by mass of analytically pure gelatin into a reaction kettle, and introducing N2Heating the mixture to 70-85 ℃ in a water bath under the action of mechanical stirring, adding a mixed solution of 6.00 parts by mass of rosin-based TDI polyurethane, 9.00-18.00 parts by mass of a pore-forming agent and 0.06 part by mass of analytically pure azobisisobutyronitrile, reacting for 3 hours, finishing, washing the product with distilled water for 3-5 times, filtering and drying to obtain the self-crosslinking rosin-based polyurethane microsphere with the average particle size of 65-110 um;
the pore-foaming agent is toluene, toluene/ethyl acetate, toluene/acetonitrile or toluene/dimethyl sulfoxide, and the purity of the pore-foaming agent is analytically pure.
The preparation method of the rosin-based TDI 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, 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 raised to 120 ℃, the reaction is carried out for 4 hours, the measured acid value is 2.40mgKOH/g, and the toluene solution of rosin-based polyol is obtained, and the measured solid mass percentage is 50.52%.
(3) Dissolving 30.48 parts by mass of the rosin-based polyol obtained in the step (2) and 0.10 part by mass of chemically pure dibutyltin dilaurate with 22.02 parts by mass of analytically pure toluene, adding the mixture into a reaction kettle, and adding the mixture into the reaction kettle under the condition of N2Heating to 30 ℃ under protection, adding 4.76 parts by mass of experimental reagent toluene-2, 4-diisocyanate (TDI), and setting the rotating speed to 400 r.min-1Reacting, adding 0.41 part by mass of analytically pure 1, 4-butanediol for chain extension when the-NCO content is reduced to a theoretical value, and reacting until the-NCO content is reduced to 0 to obtain the rosin-based TDI type polyurethane, wherein the measured solid mass percentage is 40.00%.
Compared with other related technologies, the invention has the most remarkable characteristics that natural renewable forest resource rosin and the like are used as raw materials, rosin-based TDI polyurethane is obtained through modification research, and then self-crosslinking rosin-based polyurethane microspheres are synthesized by using a suspension polymerization method under the action of an initiator and a pore-foaming agent. The invention not only obtains the polyurethane microspheres which have better spherical shape and rigidity and a pore passage structure penetrating through the interior of the microspheres, but also endows the rosin with wider application.
Detailed Description
Example 1:
adding 40.00 parts by mass of distilled water and 0.36 part by mass of analytically pure gelatin into a reaction kettle, and introducing N2At a rotation speed of 400 r.min-1Heating the water bath to 80 ℃ under the mechanical stirring action, adding a mixed solution of 6.00 parts by mass of rosin-based TDI polyurethane, 18.00 parts by mass of analytically pure toluene and 0.06 part by mass of analytically pure azobisisobutyronitrile, reacting for 3 hours, finishing, washing for 5 times with distilled water, filtering and drying the product to obtain the self-crosslinking rosin-based polyurethane microsphere with the average particle size of 69.40 mu m;
the preparation method of the rosin-based TDI 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, 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 raised to 120 ℃, the reaction is carried out for 4 hours, the measured acid value is 2.40mgKOH/g, and the toluene solution of rosin-based polyol is obtained, and the measured solid mass percentage is 50.52%.
(3) Dissolving 30.48 parts by mass of the rosin-based polyol obtained in the step (2) and 0.10 part by mass of chemically pure dibutyltin dilaurate with 22.02 parts by mass of analytically pure toluene, adding the mixture into a reaction kettle, and adding the mixture into the reaction kettle under the condition of N2Heating to 30 ℃ under protection, adding 4.76 parts by mass of experimental reagent toluene-2, 4-diisocyanate (TDI), and setting the rotating speed to 400 r.min-1Reacting, adding 0.41 part by mass of analytically pure 1, 4-butanediol for chain extension when the-NCO content is reduced to a theoretical value, and reacting until the-NCO content is reduced to 0 to obtain the rosin-based TDI type polyurethane, wherein the measured solid mass percentage is 40.00%.
Example 2:
adding 40.00 parts by mass of distilled water and 0.36 part by mass of analytically pure gelatin into a reaction kettle, and introducing N2At a rotation speed of 400 r.min-1The water bath is heated to 80 ℃ under the mechanical stirring action, then mixed liquid of 6.00 mass parts of rosin-based TDI polyurethane, 15.00 mass parts of analytically pure toluene, 3.00 mass parts of analytically pure ethyl acetate and 0.06 mass part of analytically pure azobisisobutyronitrile is added into the mixed liquid, the reaction is finished after 3 hours, finally, distilled water is used for washing for 5 times, and products are filtered and dried to obtain the self-crosslinking rosin-based polyurethane microspheres with the average particle size of 73.80 um.
The preparation method of the rosin-based TDI 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, 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 raised to 120 ℃, the reaction is carried out for 4 hours, the measured acid value is 2.40mgKOH/g, and the toluene solution of rosin-based polyol is obtained, and the measured solid mass percentage is 50.52%.
(3) Dissolving 30.48 parts by mass of the rosin-based polyol obtained in the step (2) and 0.10 part by mass of chemically pure dibutyltin dilaurate with 22.02 parts by mass of analytically pure toluene, adding the mixture into a reaction kettle, and adding the mixture into the reaction kettle under the condition of N2Heating to 30 ℃ under protection, adding 4.76 parts by mass of experimental reagent toluene-2, 4-diisocyanate (TDI), and setting the rotating speed to 400 r.min-1Reacting, adding 0.41 part by mass of analytically pure 1, 4-butanediol for chain extension when the-NCO content is reduced to a theoretical value, and reacting until the-NCO content is reduced to 0 to obtain the rosin-based TDI type polyurethane, wherein the measured solid mass percentage is 40.00%.
Example 3:
adding 40.00 parts by mass of distilled water and 0.36 part by mass of analytically pure gelatin into a reaction kettle, and introducing N2At a rotation speed of 400 r.min-1Heating the water bath to 80 ℃ under the mechanical stirring action, adding a mixed solution of 6.00 parts by mass of rosin-based TDI polyurethane, 15.00 parts by mass of analytically pure toluene, 3.00 parts by mass of analytically pure acetonitrile and 0.06 part by mass of analytically pure azobisisobutyronitrile, reacting for 3 hours, washing for 5 times by using distilled water, filtering and drying a product to obtain the self-crosslinking pinosyl with the average particle size of 86.40umFragrant polyurethane microsphere.
The preparation method of the rosin-based TDI 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, 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 raised to 120 ℃, the reaction is carried out for 4 hours, the measured acid value is 2.40mgKOH/g, and the toluene solution of rosin-based polyol is obtained, and the measured solid mass percentage is 50.52%.
(3) Dissolving 30.48 parts by mass of the rosin-based polyol obtained in the step (2) and 0.10 part by mass of chemically pure dibutyltin dilaurate with 22.02 parts by mass of analytically pure toluene, adding the mixture into a reaction kettle, and adding the mixture into the reaction kettle under the condition of N2Heating to 30 ℃ under protection, adding 4.76 parts by mass of experimental reagent toluene-2, 4-diisocyanate (TDI), and setting the rotating speed to 400 r.min-1Reacting, adding 0.41 part by mass of analytically pure 1, 4-butanediol for chain extension when the-NCO content is reduced to a theoretical value, and reacting until the-NCO content is reduced to 0 to obtain the rosin-based TDI type polyurethane, wherein the measured solid mass percentage is 40.00%.
Example 4:
adding 40.00 parts by mass of distilled water and 0.36 part by mass of analytically pure gelatin into a reaction kettle, and introducing N2At a rotation speed of 400 r.min-1The water bath is heated to 80 ℃ under the mechanical stirring action, then mixed liquid of 6.00 mass parts of rosin-based TDI type polyurethane, 15.00 mass parts of analytically pure toluene, 3.00 mass parts of analytically pure dimethyl sulfoxide and 0.06 mass part of analytically pure azobisisobutyronitrile is added into the mixed liquid, the reaction is finished after 3 hours, finally, distilled water is used for 5 times, and the mixture is filtered,The product was dried to obtain self-crosslinking rosin-based polyurethane microspheres having an average particle diameter of 108.70 um.
The preparation method of the rosin-based TDI 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, 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 raised to 120 ℃, the reaction is carried out for 4 hours, the measured acid value is 2.40mgKOH/g, and the toluene solution of rosin-based polyol is obtained, and the measured solid mass percentage is 50.52%.
(3) Dissolving 30.48 parts by mass of the rosin-based polyol obtained in the step (2) and 0.10 part by mass of chemically pure dibutyltin dilaurate with 22.02 parts by mass of analytically pure toluene, adding the mixture into a reaction kettle, and adding the mixture into the reaction kettle under the condition of N2Heating to 30 ℃ under protection, adding 4.76 parts by mass of experimental reagent toluene-2, 4-diisocyanate (TDI), and setting the rotating speed to 400 r.min-1Reacting, adding 0.41 part by mass of analytically pure 1, 4-butanediol for chain extension when the-NCO content is reduced to a theoretical value, and reacting until the-NCO content is reduced to 0 to obtain the rosin-based TDI type polyurethane, wherein the measured solid mass percentage is 40.00%.
Claims (1)
1. A preparation method of self-crosslinking rosin-based polyurethane microspheres is characterized by comprising the following specific steps:
adding 40-80 parts by mass of distilled water and 0.36 part by mass of analytically pure gelatin into a reaction kettle, and introducing N2Heating the mixture to 70-85 ℃ in a water bath under the action of mechanical stirring, and adding 6.00 parts by mass of rosin-based TDI polyurethane, 9.00-18.00 parts by mass of pore-foaming agent and 0.06 parts by mass of a mixed solution of analytically pure azobisisobutyronitrile, ending the reaction after the reaction lasts for 3 hours, washing the product with distilled water for 3-5 times, filtering and drying to obtain the self-crosslinking rosin-based polyurethane microspheres with the average particle size of 65-110 um;
the pore-foaming agent is toluene, toluene/ethyl acetate, toluene/acetonitrile or toluene/dimethyl sulfoxide, and the purity of the pore-foaming agent is analytically pure;
the preparation method of the rosin-based TDI 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 measured acid value is 2.40mgKOH/g, and the toluene solution of rosin-based polyol is obtained, the measured solid mass percentage is 50.52%;
(3) dissolving 30.48 parts by mass of the rosin-based polyol obtained in the step (2) and 0.10 part by mass of chemically pure dibutyltin dilaurate with 22.02 parts by mass of analytically pure toluene, adding the mixture into a reaction kettle, and adding the mixture into the reaction kettle under the condition of N2Heating to 30 ℃ under protection, adding 4.76 parts by mass of experimental reagent toluene-2, 4-diisocyanate, and setting the rotating speed to 400 r.min-1Reacting, adding 0.41 part by mass of analytically pure 1, 4-butanediol for chain extension when the-NCO content is reduced to a stable value, and reacting until the-NCO content is reduced to 0 to obtain the rosin-based TDI type polyurethane, wherein the measured solid mass percentage is 40.00%.
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Application publication date: 20190118 Assignee: Guangxi Aigui Intelligent Technology Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2023980044282 Denomination of invention: A preparation method of self crosslinking rosin based polyurethane microspheres Granted publication date: 20210409 License type: Common License Record date: 20231025 |
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