CN109280137A - A kind of preparation method of abietyl TDI type aqueous polyurethane microballoon - Google Patents
A kind of preparation method of abietyl TDI type aqueous polyurethane microballoon Download PDFInfo
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- CN109280137A CN109280137A CN201810925532.4A CN201810925532A CN109280137A CN 109280137 A CN109280137 A CN 109280137A CN 201810925532 A CN201810925532 A CN 201810925532A CN 109280137 A CN109280137 A CN 109280137A
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- abietyl
- aqueous polyurethane
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 36
- 239000004814 polyurethane Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 36
- 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 claims abstract description 36
- 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 claims abstract description 36
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 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
- 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 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 28
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- 238000004458 analytical method Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- 229920005862 polyol Polymers 0.000 claims description 10
- 150000003077 polyols Chemical class 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 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 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 238000002474 experimental method Methods 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
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000010907 mechanical stirring Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 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
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000005292 vacuum distillation Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- 239000012975 dibutyltin dilaurate Substances 0.000 claims 1
- 239000008267 milk Substances 0.000 claims 1
- 210000004080 milk Anatomy 0.000 claims 1
- 235000013336 milk Nutrition 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000003999 initiator Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract 1
- 229910021645 metal ion Inorganic materials 0.000 abstract 1
- 239000010865 sewage Substances 0.000 abstract 1
- 238000004821 distillation Methods 0.000 description 6
- 238000004945 emulsification Methods 0.000 description 5
- 239000011806 microball Substances 0.000 description 5
- 235000019082 Osmanthus Nutrition 0.000 description 4
- 241000333181 Osmanthus Species 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000011805 ball Substances 0.000 description 3
- 150000003440 styrenes Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 230000007613 environmental effect Effects 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
- 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
- 229920000642 polymer Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010557 suspension polymerization reaction 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
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- 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 kind of preparation methods of abietyl TDI type aqueous polyurethane microballoon.Being that raw material is modified with rosin etc. obtains abietyl TDI type aqueous polyurethane, then obtains abietyl TDI type aqueous polyurethane microballoon with styrene copolymerized under polyvinylpyrrolidone and initiator effect.It is that smaller partial size, monodispersity and spherical preferable ionic aqueous polyurethane microballoon is prepared in raw material that the most significant feature of the present invention, which is with rosin etc.,.This does not give only rosin and polyurethane is more widely applied, and the aqueous polyurethane microballoon synthesized can be applied in the fields such as drug loading and release, adsorption of metal ions, sewage treatment.
Description
Technical field
The present invention relates to a kind of preparation methods of abietyl TDI type aqueous polyurethane microballoon.
Background technique
With increasingly depleted and people's environmental consciousness the continuous improvement of the non-renewable fossil energy in the whole world, naturally may be used
The research that regenerated resources partly or entirely replace fossil energy to carry out alleviating energy crisis has become mainly appointing for chemist
One of business.Rosin is a kind of natural reproducible resource extremely abundant in nature, although abundance, it is higher that there are acid values
With oxidizable defect, its application in many industrial productions is limited.Using in rosin structure double bond and carboxyl to it
It is modified, can achieve the purpose for expanding its application range.Application of the rosin in Polymer Synthesizing mainly passes through carboxyl
It is introduced into macromolecular chain with double bond.It is non-toxic to humans using rosin as the functional polymer of Material synthesis, it can pacify
Entirely for medicine and field of food.
Polyaminoester microball is a kind of novel polyurethane products, it contains carbamate isopolarity group and microphase-separated
Structure has biggish specific surface since the surface of microballoon and inside have more fold and duct and itself partial size smaller
Product, dispersion in the solution have preferable stability, make it have good absorption, ion exchange, chelating, biocompatibility and
High resiliency and it is high-intensitive the features such as, separating-purifying, biochemical diagnosis, pharmaceutical carrier, coating, adhesive and in terms of show
Wide application prospect out.The preparation method of polyaminoester microball mainly has self-emulsification, suspension polymerization, dispersion copolymerization method etc..
By designing polyurethane resin, synthesize and be modified, can be obtained size tunable, pattern, mechanical property, water resistance and stability compared with
Good polyaminoester microball.
The present invention obtains abietyl TDI type aqueous polyurethane using rosin as raw material, by modification, then carries out with styrene
Copolymerization obtains abietyl TDI type aqueous polyurethane microballoon.The present invention provides new application for rational exploitation and utilization rosin resource
Approach, the polyaminoester microball of preparation can be applied to the fields such as chromatography, adsorption separation technology and wastewater treatment.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of abietyl TDI type aqueous polyurethane microballoon.
Specific steps of the invention are as follows:
By 3.20~1.60 mass parts abietyl TDI type aqueous polyurethanes, 0.80~2.40 mass parts chemistry pure styrene,
The pure polyvinylpyrrolidone of 0.08~0.32 mass parts chemistry and 0.02~0.08 mass parts are analyzed pure azodiisobutyronitrile and are set
In beaker, 40~60 mass parts distilled water are added, is uniformly mixed within ultrasonic disperse 10 minutes, reaction kettle then is added in mixed liquor
In, in N280~100 DEG C are heated under protective effect, setting revolving speed is 200rmin-1, react and continue 4~10 hours, finally
In 10000rmin-1It is centrifugated 15 minutes under revolving speed, is washed with distilled water 3~5 times, centrifuge separation, naturally dry is put down
Equal partial size is 85~200nm abietyl TDI type aqueous polyurethane microballoon.
The preparation method step of the abietyl TDI type aqueous polyurethane are as follows:
(1) 100.0 mass parts rosin are added to equipped with stirring rod, reflux condensing tube, thermometer, nitrogen protection device
In reaction kettle, in 400rmin after heating fusing-1Under be stirred, after being heated to 230 DEG C, start that 28.60 mass are slowly added dropwise
The chemical pure acrylic acid of part, continues 1 hour, it is made after being added dropwise, and the reaction was continued at 230 DEG C 2 hours, is down to 200 DEG C to temperature
Discharging, obtains acrylic acid rosin addition product.
(2) acrylic acid rosin addition product obtained by 108.51 mass parts steps (1) is dissolved in 191.86 matter in a kettle
It measures in part analysis pure toluene, addition 82.40 mass parts purity, 97% glycidyl methacrylate, the analysis of 0.54 mass parts are pure
Triethylamine and 0.41 mass parts analyze pure Isosorbide-5-Nitrae-hydroquinone, are warming up to 120 DEG C, react 4 hours, and survey acid value is 2.40mgKOH/
G, rotary evaporation remove toluene to get Rosin-based Polyol is arrived.
(3) by Rosin-based Polyol obtained by 30.00 mass parts steps (2), the pure dibutyl tin osmanthus of 0.21 mass parts chemistry
Sour tin and 100.00 mass parts analysis pure acetone are added in reaction kettle, in N2It is heated to 30 DEG C under protection, 11.89 mass parts are added
Experiment reagent Toluene-2,4-diisocyanate, 4- diisocyanate (TDI), setting revolving speed are 400rmin-1, it is down to theoretical value to-NCO content, is added
Enter 4.61 mass parts to analyze pure 2,2- dihydromethyl propionic acid and be warming up to 55 DEG C, reaction to-NCO content is reduced to 0, is cooled to 18
DEG C, 3.48 mass parts are added and analyze in pure triethylamine and 10 minutes, in 1300rmin-1Under mechanical stirring be added 200mL go from
Sub- water emulsification disperses 30 minutes, and vacuum distillation removes acetone, obtains abietyl TDI type aqueous polyurethane, surveys solid masses percentage
Than being 18.20%.
For the present invention compared with other the relevant technologies, most significant feature is with natural reproducible forest resources rosin etc. for original
Material, it is modified to obtain abietyl TDI type aqueous polyurethane, then abietyl has been synthesized with styrene copolymerized under initiator effect
TDI type aqueous polyurethane microballoon.Monodispersity and spherical preferable submicron order polyaminoester microball have not only been obtained, but also
Rosin is imparted more to be widely applied.
Specific embodiment
Embodiment 1:
By 2.80 mass parts abietyl TDI type aqueous polyurethanes, 1.20 mass parts chemistry pure styrenes, 0.24 mass parts
It learns pure polyvinylpyrrolidone and 0.04 mass parts is analyzed pure azodiisobutyronitrile and are placed in a beaker, the distillation of 46 mass parts is added
Water is uniformly mixed, then mixed liquor is added in reaction kettle, in N for ultrasonic disperse 10 minutes285 DEG C are heated under protective effect,
Setting revolving speed is 200rmin-1, reaction continues 8 hours, finally in 10000rmin-1It is centrifugated 15 minutes, uses under revolving speed
Distillation water washing 4 times, centrifuge separation, it is that 187.10nm abietyl TDI type aqueous polyurethane is micro- that naturally dry, which obtains average grain diameter,
Ball.
The preparation method step of the abietyl TDI type aqueous polyurethane are as follows:
(1) 100.0 mass parts rosin are added to equipped with stirring rod, reflux condensing tube, thermometer, nitrogen protection device
In reaction kettle, in 400rmin after heating fusing-1Under be stirred, after being heated to 230 DEG C, start that 28.60 mass are slowly added dropwise
The chemical pure acrylic acid of part, continues 1 hour, it is made after being added dropwise, and the reaction was continued at 230 DEG C 2 hours, is down to 200 DEG C to temperature
Discharging, obtains acrylic acid rosin addition product.
(2) acrylic acid rosin addition product obtained by 108.51 mass parts steps (1) is dissolved in 191.86 matter in a kettle
It measures in part analysis pure toluene, addition 82.40 mass parts purity, 97% glycidyl methacrylate, the analysis of 0.54 mass parts are pure
Triethylamine and 0.41 mass parts analyze pure Isosorbide-5-Nitrae-hydroquinone, are warming up to 120 DEG C, react 4 hours, and survey acid value is 2.40mgKOH/
G, rotary evaporation remove toluene to get Rosin-based Polyol is arrived.
(3) by Rosin-based Polyol obtained by 30.00 mass parts steps (2), the pure dibutyl tin osmanthus of 0.21 mass parts chemistry
Sour tin and 100.00 mass parts analysis pure acetone are added in reaction kettle, in N2It is heated to 30 DEG C under protection, 11.89 mass parts are added
Experiment reagent Toluene-2,4-diisocyanate, 4- diisocyanate (TDI), setting revolving speed are 400rmin-1, it is down to theoretical value to-NCO content, is added
Enter 4.61 mass parts to analyze pure 2,2- dihydromethyl propionic acid and be warming up to 55 DEG C, reaction to-NCO content is reduced to 0, is cooled to 18
DEG C, 3.48 mass parts are added and analyze in pure triethylamine and 10 minutes, in 1300rmin-1Under mechanical stirring be added 200mL go from
Sub- water emulsification disperses 30 minutes, and vacuum distillation removes acetone, obtains abietyl TDI type aqueous polyurethane, surveys solid masses percentage
Than being 18.20%.
Embodiment 2:
By 2.40 mass parts abietyl TDI type aqueous polyurethanes, 1.60 mass parts chemistry pure styrenes, 0.24 mass parts
It learns pure polyvinylpyrrolidone and 0.04 mass parts is analyzed pure azodiisobutyronitrile and are placed in a beaker, the distillation of 46 mass parts is added
Water is uniformly mixed, then mixed liquor is added in reaction kettle, in N for ultrasonic disperse 10 minutes285 DEG C are heated under protective effect,
Setting revolving speed is 200rmin-1, reaction continues 8 hours, finally in 10000rmin-1It is centrifugated 15 minutes, uses under revolving speed
Distillation water washing 4 times, centrifuge separation, it is that 160.80nm abietyl TDI type aqueous polyurethane is micro- that naturally dry, which obtains average grain diameter,
Ball.
The preparation method step of the abietyl TDI type aqueous polyurethane are as follows:
(1) 100.0 mass parts rosin are added to equipped with stirring rod, reflux condensing tube, thermometer, nitrogen protection device
In reaction kettle, in 400rmin after heating fusing-1Under be stirred, after being heated to 230 DEG C, start that 28.60 mass are slowly added dropwise
The chemical pure acrylic acid of part, continues 1 hour, it is made after being added dropwise, and the reaction was continued at 230 DEG C 2 hours, is down to 200 DEG C to temperature
Discharging, obtains acrylic acid rosin addition product.
(2) acrylic acid rosin addition product obtained by 108.51 mass parts steps (1) is dissolved in 191.86 matter in a kettle
It measures in part analysis pure toluene, addition 82.40 mass parts purity, 97% glycidyl methacrylate, the analysis of 0.54 mass parts are pure
Triethylamine and 0.41 mass parts analyze pure Isosorbide-5-Nitrae-hydroquinone, are warming up to 120 DEG C, react 4 hours, and survey acid value is 2.40mgKOH/
G, rotary evaporation remove toluene to get Rosin-based Polyol is arrived.
(3) by Rosin-based Polyol obtained by 30.00 mass parts steps (2), the pure dibutyl tin osmanthus of 0.21 mass parts chemistry
Sour tin and 100.00 mass parts analysis pure acetone are added in reaction kettle, in N2It is heated to 30 DEG C under protection, 11.89 mass parts are added
Experiment reagent Toluene-2,4-diisocyanate, 4- diisocyanate (TDI), setting revolving speed are 400rmin-1, it is down to theoretical value to-NCO content, is added
Enter 4.61 mass parts to analyze pure 2,2- dihydromethyl propionic acid and be warming up to 55 DEG C, reaction to-NCO content is reduced to 0, is cooled to 18
DEG C, 3.48 mass parts are added and analyze in pure triethylamine and 10 minutes, in 1300rmin-1Under mechanical stirring be added 200mL go from
Sub- water emulsification disperses 30 minutes, and vacuum distillation removes acetone, obtains abietyl TDI type aqueous polyurethane, surveys solid masses percentage
Than being 18.20%.
Embodiment 3:
By 2.40 mass parts abietyl TDI type aqueous polyurethanes, 1.60 mass parts chemistry pure styrenes, 0.32 mass parts
It learns pure polyvinylpyrrolidone and 0.04 mass parts is analyzed pure azodiisobutyronitrile and are placed in a beaker, the distillation of 46 mass parts is added
Water is uniformly mixed, then mixed liquor is added in reaction kettle, in N for ultrasonic disperse 10 minutes280 DEG C are heated under protective effect,
Setting revolving speed is 200rmin-1, reaction continues 8 hours, finally in 10000rmin-1It is centrifugated 15 minutes, uses under revolving speed
Distillation water washing 5 times, centrifuge separation, it is that 120.00nm abietyl TDI type aqueous polyurethane is micro- that naturally dry, which obtains average grain diameter,
Ball.
The preparation method step of the abietyl TDI type aqueous polyurethane are as follows:
(1) 100.0 mass parts rosin are added to equipped with stirring rod, reflux condensing tube, thermometer, nitrogen protection device
In reaction kettle, in 400rmin after heating fusing-1Under be stirred, after being heated to 230 DEG C, start that 28.60 mass are slowly added dropwise
The chemical pure acrylic acid of part, continues 1 hour, it is made after being added dropwise, and the reaction was continued at 230 DEG C 2 hours, is down to 200 DEG C to temperature
Discharging, obtains acrylic acid rosin addition product.
(2) acrylic acid rosin addition product obtained by 108.51 mass parts steps (1) is dissolved in 191.86 matter in a kettle
It measures in part analysis pure toluene, addition 82.40 mass parts purity, 97% glycidyl methacrylate, the analysis of 0.54 mass parts are pure
Triethylamine and 0.41 mass parts analyze pure Isosorbide-5-Nitrae-hydroquinone, are warming up to 120 DEG C, react 4 hours, and survey acid value is 2.40mgKOH/
G, rotary evaporation remove toluene to get Rosin-based Polyol is arrived.
(3) by Rosin-based Polyol obtained by 30.00 mass parts steps (2), the pure dibutyl tin osmanthus of 0.21 mass parts chemistry
Sour tin and 100.00 mass parts analysis pure acetone are added in reaction kettle, in N2It is heated to 30 DEG C under protection, 11.89 mass parts are added
Experiment reagent Toluene-2,4-diisocyanate, 4- diisocyanate (TDI), setting revolving speed are 400rmin-1, it is down to theoretical value to-NCO content, is added
Enter 4.61 mass parts to analyze pure 2,2- dihydromethyl propionic acid and be warming up to 55 DEG C, reaction to-NCO content is reduced to 0, is cooled to 18
DEG C, 3.48 mass parts are added and analyze in pure triethylamine and 10 minutes, in 1300rmin-1Under mechanical stirring be added 200mL go from
Sub- water emulsification disperses 30 minutes, and vacuum distillation removes acetone, obtains abietyl TDI type aqueous polyurethane, surveys solid masses percentage
Than being 18.20%.
Claims (1)
1. a kind of preparation method of abietyl TDI type aqueous polyurethane microballoon, it is characterised in that specific steps are as follows:
By 3.20~1.60 mass parts abietyl TDI type aqueous polyurethanes, 0.80~2.40 mass parts chemistry pure styrene, 0.08
The pure polyvinylpyrrolidone of~0.32 mass parts chemistry and 0.02~0.08 mass parts analyze pure azodiisobutyronitrile and are placed in burning
In cup, 40~60 mass parts distilled water are added, is uniformly mixed within ultrasonic disperse 10 minutes, then mixed liquor is added in reaction kettle,
In N280~100 DEG C are heated under protective effect, setting revolving speed is 200 rmin-1, react and continue 4~10 hours, finally exist
10000 r·min-1It is centrifugated 15 minutes under revolving speed, is washed with distilled water 3~5 times, centrifuge separation, naturally dry is put down
Equal partial size is 85~200 nm abietyl TDI type aqueous polyurethane microballoons；
The preparation method step of the abietyl TDI type aqueous polyurethane are as follows:
(1) 100.0 mass parts rosin are added to the reaction equipped with stirring rod, reflux condensing tube, thermometer, nitrogen protection device
In kettle, in 400 rmin after heating fusing-1Under be stirred, after being heated to 230 DEG C, start that 28.60 mass parts are slowly added dropwise
Chemical pure acrylic acid continues 1 hour, it is made after being added dropwise, and the reaction was continued at 230 DEG C 2 hours, is down to 200 DEG C to temperature and goes out
Material, obtains acrylic acid rosin addition product；
(2) acrylic acid rosin addition product obtained by 108.51 mass parts steps (1) is dissolved in 191.86 mass parts in a kettle
It analyzes in pure toluene, 82.40 mass parts purity, 97% glycidyl methacrylate is added, 0.54 mass parts analyze pure three second
Amine and 0.41 mass parts analyze pure Isosorbide-5-Nitrae-hydroquinone, are warming up to 120 DEG C, react 4 hours, and survey acid value is 2.40 mgKOH/g,
Rotary evaporation removes toluene to get Rosin-based Polyol is arrived；
(3) by Rosin-based Polyol obtained by 30.00 mass parts steps (2), the pure dibutyl tin dilaurate of 0.21 mass parts chemistry
It is added in reaction kettle with 100.00 mass parts analysis pure acetone, in N2It is heated to 30 DEG C under protection, the experiment of 11.89 mass parts is added
Reagent Toluene-2,4-diisocyanate, 4- diisocyanate, setting revolving speed are 400 rmin-1, it is down to theoretical value to-NCO content, 4.61 matter are added
Amount part analyzes pure 2,2- dihydromethyl propionic acid and is warming up to 55 DEG C, and reaction to-NCO content is reduced to 0, is cooled to 18 DEG C, is added
3.48 mass parts are analyzed in pure triethylamine and 10 minutes, in 1300 rmin-1200 mL deionization water and milk are added under mechanical stirring
Change dispersion 30 minutes, vacuum distillation removes acetone, obtains abietyl TDI type aqueous polyurethane, surveys solid masses percentage and is
18.20 %。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110467719A (en) * | 2019-08-01 | 2019-11-19 | 桂林理工大学 | A kind of preparation method of the antibacterial polyurethane of abietyl TDI type |
| CN110483733A (en) * | 2019-08-01 | 2019-11-22 | 桂林理工大学 | A kind of preparation method of the antibacterial polyurethane of abietyl IPDI type |
| CN114605084A (en) * | 2022-03-29 | 2022-06-10 | 武昌理工学院 | Green energy-saving building glass and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101766981A (en) * | 2010-01-13 | 2010-07-07 | 桂林理工大学 | Method for preparing polymer microsphere by utilizing rosin and crylic acid hydroxy ester |
| CN105778028A (en) * | 2016-03-13 | 2016-07-20 | 桂林理工大学 | Method for preparing rosin-based TDI type polyurethane prepolymer |
-
2018
- 2018-08-14 CN CN201810925532.4A patent/CN109280137B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101766981A (en) * | 2010-01-13 | 2010-07-07 | 桂林理工大学 | Method for preparing polymer microsphere by utilizing rosin and crylic acid hydroxy ester |
| CN105778028A (en) * | 2016-03-13 | 2016-07-20 | 桂林理工大学 | Method for preparing rosin-based TDI type polyurethane prepolymer |
Non-Patent Citations (4)
| Title |
|---|
| 任鹏等: "悬浮聚合法制备含松香GMA 酯的聚合物微球", 《中国化学会第十届全国天然有机化学学术会议论文集》 * |
| 张天鹭: "具有核壳结构的水性聚氨酯/导电聚合物复合纳米弹性微球的制备与表征", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 张鹏等: "分散聚合法制备Fe3O4 /P( St－PU) 磁性微球", 《广州化工》 * |
| 王志强: "药物缓释材料丙烯酸酯改性水性聚氨酯的研究及应用", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110467719A (en) * | 2019-08-01 | 2019-11-19 | 桂林理工大学 | A kind of preparation method of the antibacterial polyurethane of abietyl TDI type |
| CN110483733A (en) * | 2019-08-01 | 2019-11-22 | 桂林理工大学 | A kind of preparation method of the antibacterial polyurethane of abietyl IPDI type |
| CN114605084A (en) * | 2022-03-29 | 2022-06-10 | 武昌理工学院 | Green energy-saving building glass and preparation method thereof |
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