CN109265727A - A kind of preparation method of abietyl HDI type polyurethane molecular engram microsphere - Google Patents
A kind of preparation method of abietyl HDI type polyurethane molecular engram microsphere Download PDFInfo
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- CN109265727A CN109265727A CN201810921141.5A CN201810921141A CN109265727A CN 109265727 A CN109265727 A CN 109265727A CN 201810921141 A CN201810921141 A CN 201810921141A CN 109265727 A CN109265727 A CN 109265727A
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- mass parts
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- abietyl
- rosin
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 29
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 29
- 239000004005 microsphere Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 69
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 58
- 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 34
- 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 34
- 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 34
- 229940106691 bisphenol a Drugs 0.000 claims abstract description 27
- 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 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 33
- 238000004458 analytical method Methods 0.000 claims description 28
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 229920005862 polyol Polymers 0.000 claims description 10
- 150000003077 polyols Chemical class 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000004821 distillation Methods 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
- 238000005406 washing Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000006227 byproduct 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
- 238000004090 dissolution Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000008236 heating water Substances 0.000 claims description 5
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000000284 extract Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 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
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 239000012975 dibutyltin dilaurate Substances 0.000 claims 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 239000003431 cross linking reagent Substances 0.000 abstract description 4
- 239000004088 foaming agent Substances 0.000 abstract description 4
- 239000003999 initiator Substances 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 abstract description 4
- 230000009870 specific binding Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000010557 suspension polymerization reaction Methods 0.000 abstract description 2
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 5
- 235000019082 Osmanthus Nutrition 0.000 description 4
- 241000333181 Osmanthus Species 0.000 description 4
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 4
- 235000011613 Pinus brutia Nutrition 0.000 description 4
- 241000018646 Pinus brutia 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
- 238000005516 engineering process Methods 0.000 description 4
- 239000002304 perfume Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000008485 antagonism Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 208000030172 endocrine system disease Diseases 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000003054 hormonal effect Effects 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 210000005260 human cell Anatomy 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 230000000366 juvenile effect Effects 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000007102 metabolic function Effects 0.000 description 1
- 210000002445 nipple Anatomy 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
-
- 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
- C08G18/003—Polymeric products of isocyanates or isothiocyanates with epoxy compounds having no 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
-
- 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
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Dispersion Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a kind of preparation methods of abietyl HDI type polyurethane molecular engram microsphere.Being that raw material is modified with rosin etc. obtains abietyl HDI type polyurethane, using the polyurethane containing unsaturated double-bond as crosslinking agent, methacrylic acid be function monomer, bisphenol-A is template molecule, azodiisobutyronitrile is initiator, polyvinyl alcohol is dispersing agent, toluene is pore-foaming agent, is prepared for the functional form trace microballoon that a kind of pair of bisphenol-A has specific binding capacity using suspension polymerization.The spherical rule of the trace microballoon of preparation, particle are uniform, and have Characteristic Adsorption to bisphenol-A.The most significant feature of the present invention is not give only rosin more broad application prospect using natural reproducible resource rosin as raw material, and provide a kind of effective ways for preparing bisphenol A molecular engram microballoon.
Description
Technical field
The present invention relates to a kind of preparation methods of abietyl HDI type polyurethane molecular engram microsphere.
Background technique
Bisphenol-A (BPA) is a kind of important organic industry raw material, and the amount of annual worldwide production BPA is more than 5,000,000 tons, extensively
It is general to be applied to the plastics-productions industries such as polycarbonate (PC), polysulfone resin (PS) and epoxy resin.But BPA is a kind of again with interior
Interfering class female hormone is secreted, human cell membrane can be rapidly diffused into, there is antagonism to normocrinic hormone
Effect, to influence metabolic function, leads to the disorder of endocrine system, seriously threatens human health.Studies have shown that BPA can be from
It is released in many plastics packages, especially juvenile product, such as baby nipple, can resinous coat, cushion, medical treatment is set
The problems such as standby and food packaging etc., is normally present in water environment, is food safety and environmental protection brings huge hidden danger.Detection
The common method of BPA mainly includes high performance liquid chromatography, gas chromatography-mass spectrum and liquid chromatography mass combination method in environment
Deng.However, these methods not only need expensive instrument and equipment, complicated and multistep sample preparation does not allow real-time, quickly yet
Therefore detection develops a kind of method for fast and accurately separating and detecting micro BPA in water source, for the ecosystem and people
Class health has great importance.Wherein the molecular engram material with molecule distinguishability shows good separation and identification
Performance.
Molecular imprinting technology (MIP) is to prepare the high molecular material for having specific recognition capability to specific target molecules
Technology.Preparation method is that template molecule, function monomer, crosslinking agent, initiator and pore-foaming agent are generated polymerization by polymerization reaction
Object has the site of specific binding using generation after elution to target molecule.Removing bisphenol-A using molecular imprinting technology is one
The feasible method of kind.Common trace method for preparing microsphere has: precipitation polymerization, emulsion polymerization and suspension polymerization etc., wherein hanging
Floating polymerization can prepare the molecular engram microsphere of large specific surface area, and relative to general indefinite form imprinted polymer, it can be
Template molecule provides bigger trace space.
Rosin is led as a kind of natural reproducible forest resources abundant in daily life, industrial production, scientific research etc.
Domain is widely used.The present invention reacts to obtain esters with glycidyl methacrylate using rosin derivative polynary
Alcohol, then reacted with polyisocyanates and prepare polyurethane resin, then using polyurethane resin as crosslinking agent, methacrylic acid is function
Monomer, azodiisobutyronitrile are initiator, and toluene is the function that pore-foaming agent is prepared for that a kind of pair of bisphenol-A has specific binding capacity
It can type molecular engram microsphere.The present invention provides new application approach for rational exploitation and utilization rosin resource.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of abietyl HDI type polyurethane molecular engram microsphere.
Specific steps are as follows:
The deionized water of 40.00 mass parts and the pure polyvinyl alcohol of 0.80~1.20 mass parts chemistry are added to reaction kettle
In, in N2In the presence of with 400~700rmin-1Mixing speed heating water bath is to 75~90 DEG C；By 3.00 mass parts abietyls
HDI type polyurethane, 0.90~2.60 mass parts analysis pure styrene, 20.00 mass parts analyze pure toluene, 0.20~0.25 mass
Part analyzes pure methacrylic acid, 0.05 mass parts analyze pure azodiisobutyronitrile and the pure bisphenol-A of 0.09~0.16 mass parts chemistry
Ultrasonic disperse is uniform at 50 DEG C, is added in aforesaid reaction vessel, increases 5 DEG C after reaction 3 hours and cures 2 hours, stops reaction,
By product with 40 DEG C or so distillation water washing 3~5 times, then the pure pure methyl alcohol mixed liquor of acetic acid-analysis of analysis for being 1:9 with volume ratio
It is extracted 48 hours in 78 DEG C, removes template molecule bisphenol-A, be finally washed with distilled water to neutrality, naturally dry obtains abietyl
HDI type polyurethane molecular engram microsphere.
The abietyl HDI type polyurethane the preparation method comprises the following steps:
(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, 82.40 mass parts purity, 97% glycidyl methacrylate is added, the analysis of 0.54 mass parts is 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/
For g to get the toluene solution for arriving Rosin-based Polyol, surveying solid masses percentage is 50.52%.
(3) by Rosin-based Polyol obtained by 30.91 mass parts steps (2) and the pure dibutyl tin osmanthus of 0.11 mass parts chemistry
Sour tin is added in reaction kettle after analyzing pure toluene dissolution with 18.54 mass parts, in N2It is heated to 55 DEG C under protection, 6.00 matter are added
The hexamethylene diisocyanate (HDI) of part purity 99% is measured, revolving speed 400rmin is set-1, reacted, to-NCO content
It is down to theoretical value, 1.41 mass parts are added and analyze pure 1,6- hexylene glycol progress chain extension, reacts extremely-NCO content and is reduced to 0, obtain pine
Perfume base HDI type polyurethane, surveying solid masses percentage is 50.23%.
For the present invention compared with other the relevant technologies, it is original with natural reproducible forest resources rosin that most significant feature, which is,
Material obtains the rosin based polyurethanes with unsaturated double-bond by modified, then using polyurethane as crosslinking agent, methacrylic acid is function
Energy monomer, bisphenol-A are template molecule, and azodiisobutyronitrile is initiator, and toluene, which is prepared for a kind of pair of bisphenol-A for pore-foaming agent, to be had
The functional form molecular engram microsphere (P-MIP) of specific binding capacity.The present invention does not give only rosin and is more widely applied
Prospect, and provide a kind of effective ways for preparing bisphenol A molecular engram microballoon.
Specific embodiment
Embodiment 1:
The deionized water of 40.00 mass parts and the pure polyvinyl alcohol of 0.91 mass parts chemistry are added in reaction kettle, in N2It deposits
With 700r/min mixing speed heating water bath to 85 DEG C under.By 3.00 mass parts abietyl HDI type polyurethanes, 1.33 mass parts
It analyzes pure styrene, 20.00 mass parts analysis pure toluene, 0.23 mass parts and analyzes pure methacrylic acid, the analysis of 0.05 mass parts
Pure azodiisobutyronitrile and the pure bisphenol-A ultrasonic disperse at 50 DEG C of 0.15 mass parts chemistry are uniform, are added in aforesaid reaction vessel,
Increase 5 DEG C after reaction 3 hours to cure 2 hours, stop reaction, by product with 40 DEG C or so distillation water washing 5 times, then use volume ratio
It is extracted 48 hours for the pure pure methyl alcohol mixed liquor of acetic acid-analysis of analysis of 1:9 in 78 DEG C, removes template molecule bisphenol-A, finally with steaming
Distilled water is washed to neutrality, naturally dry, abietyl HDI type polyurethane molecular engram microsphere (P-MIP) is obtained, according to identical side
Method synthesis is respectively absorption with P-MIP and P-NIP microballoon without the non-trace microballoon (P-NIP) of addition template molecule bisphenol-A
Agent is 0.60 μ to initial concentration under conditions of solid-to-liquid ratio is 1.3g/L, adsorption temp is 30 DEG C, adsorption time is 3 hours
The bisphenol-A aqueous solution of mol/mL carries out absorption research, and measuring P-MIP microballoon adsorbance is 106.93 μm of ol/g, and P-NIP microballoon is inhaled
Attached amount is 37.39 μm of ol/g.
The abietyl HDI type polyurethane the preparation method comprises the following steps:
(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, 82.40 mass parts purity, 97% glycidyl methacrylate is added, the analysis of 0.54 mass parts is 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/
For g to get the toluene solution for arriving Rosin-based Polyol, surveying solid masses percentage is 50.52%.
(3) by Rosin-based Polyol obtained by 30.91 mass parts steps (2) and the pure dibutyl tin osmanthus of 0.11 mass parts chemistry
Sour tin is added in reaction kettle after analyzing pure toluene dissolution with 18.54 mass parts, in N2It is heated to 55 DEG C under protection, 6.00 matter are added
The hexamethylene diisocyanate (HDI) of part purity 99% is measured, revolving speed 400rmin is set-1, reacted, to-NCO content
It is down to theoretical value, 1.41 mass parts are added and analyze pure 1,6- hexylene glycol progress chain extension, reacts extremely-NCO content and is reduced to 0, obtain pine
Perfume base HDI type polyurethane, surveying solid masses percentage is 50.23%.
Embodiment 2:
The deionized water of 40.0 mass parts and the pure polyvinyl alcohol of 0.91 mass parts chemistry are added in reaction kettle, in N2In the presence of
Under with 700r/min mixing speed heating water bath to 85 DEG C.By 3.00 mass parts abietyl HDI type polyurethanes, 1.33 mass parts point
Analyse pure styrene, 20.00 mass parts analyze pure toluene, 0.23 mass parts analyze pure methacrylic acid, the analysis of 0.05 mass parts is pure
Azodiisobutyronitrile and the pure bisphenol-A ultrasonic disperse at 50 DEG C of 0.15 mass parts chemistry are uniform, are added in aforesaid reaction vessel, instead
Increase 5 DEG C after answering 3 hours to cure 2 hours, stop reaction, by product with 40 DEG C or so distillation water washing 5 times, then with volume ratio be
The pure pure methyl alcohol mixed liquor of acetic acid-analysis of the analysis of 1:9 extracts 48 hours in 78 DEG C, removes template molecule bisphenol-A, finally with distillation
Water washing to neutrality, naturally dry obtains abietyl HDI type polyurethane molecular engram microsphere (P-MIP), in the same manner
Non- trace microballoon (P-NIP) of the synthesis without addition template molecule bisphenol-A.Respectively using P-MIP and P-NIP microballoon as adsorbent,
It is 0.30 μm of ol/ to initial concentration under conditions of solid-to-liquid ratio is 1.3g/L, adsorption temp is 30 DEG C, adsorption time is 3 hours
The bisphenol-A aqueous solution of mL carries out absorption research, and measuring P-MIP microballoon adsorbance is 62.93 μm of ol/g, P-NIP microballoon adsorbance
For 23.84 μm of ol/g.
The abietyl HDI type polyurethane the preparation method comprises the following steps:
(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, 82.40 mass parts purity, 97% glycidyl methacrylate is added, the analysis of 0.54 mass parts is 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/
For g to get the toluene solution for arriving Rosin-based Polyol, surveying solid masses percentage is 50.52%.
(3) by Rosin-based Polyol obtained by 30.91 mass parts steps (2) and the pure dibutyl tin osmanthus of 0.11 mass parts chemistry
Sour tin is added in reaction kettle after analyzing pure toluene dissolution with 18.54 mass parts, in N2It is heated to 55 DEG C under protection, 6.00 matter are added
The hexamethylene diisocyanate (HDI) of part purity 99% is measured, revolving speed 400rmin is set-1, reacted, to-NCO content
It is down to theoretical value, 1.41 mass parts are added and analyze pure 1,6- hexylene glycol progress chain extension, reacts extremely-NCO content and is reduced to 0, obtain pine
Perfume base HDI type polyurethane, surveying solid masses percentage is 50.23%.
Embodiment 3:
The deionized water of 40.00 mass parts and the pure polyvinyl alcohol of 0.83 mass parts chemistry are added in reaction kettle, in N2It deposits
With 500r/min mixing speed heating water bath to 80 DEG C under.By 3.00 mass parts abietyl HDI type polyurethanes, 0.90 mass parts
It analyzes pure styrene, 20.00 mass parts analysis pure toluene, 0.23 mass parts and analyzes pure methacrylic acid, the analysis of 0.05 mass parts
Pure azodiisobutyronitrile and the pure bisphenol-A ultrasonic disperse at 50 DEG C of 0.12 mass parts chemistry are uniform, are added in aforesaid reaction vessel,
Increase 5 DEG C after reaction 3 hours to cure 2 hours, stop reaction, by product with 40 DEG C or so distillation water washing 5 times, then use volume ratio
It is extracted 48 hours for the pure pure methyl alcohol mixed liquor of acetic acid-analysis of analysis of 1:9 in 78 DEG C, removes template molecule bisphenol-A, finally with steaming
Distilled water is washed to neutrality, naturally dry, abietyl HDI type polyurethane molecular engram microsphere (P-MIP) is obtained, according to identical side
Non- trace microballoon (P-NIP) of the method synthesis without addition template molecule bisphenol-A.It is respectively absorption with P-MIP and P-NIP microballoon
Agent is 0.25 μ to initial concentration under conditions of solid-to-liquid ratio is 1.3g/L, adsorption temp is 30 DEG C, adsorption time is 3 hours
The bisphenol-A aqueous solution of mol/mL carries out absorption research, and measuring P-MIP microballoon adsorbance is 25.54 μm of ol/g, and P-NIP microballoon is inhaled
Attached amount is 15.29 μm of ol/g.
The abietyl HDI type polyurethane the preparation method comprises the following steps:
(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, 82.40 mass parts purity, 97% glycidyl methacrylate is added, the analysis of 0.54 mass parts is 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/
For g to get the toluene solution for arriving Rosin-based Polyol, surveying solid masses percentage is 50.52%.
(3) by Rosin-based Polyol obtained by 30.91 mass parts steps (2) and the pure dibutyl tin osmanthus of 0.11 mass parts chemistry
Sour tin is added in reaction kettle after analyzing pure toluene dissolution with 18.54 mass parts, in N2It is heated to 55 DEG C under protection, 6.00 matter are added
The hexamethylene diisocyanate (HDI) of part purity 99% is measured, revolving speed 400rmin is set-1, reacted, to-NCO content
It is down to theoretical value, 1.41 mass parts are added and analyze pure 1,6- hexylene glycol progress chain extension, reacts extremely-NCO content and is reduced to 0, obtain pine
Perfume base HDI type polyurethane, surveying solid masses percentage is 50.23%.
Claims (1)
1. a kind of preparation method of abietyl HDI type polyurethane molecular engram microsphere, it is characterised in that specific steps are as follows:
The deionized water of 40.00 mass parts and the pure polyvinyl alcohol of 0.80 ~ 1.20 mass parts chemistry are added into reaction kettle, in N2
In the presence of with 400 ~ 700 rmin-1Mixing speed heating water bath is to 75 ~ 90 DEG C；By the 3.00 poly- ammonia of mass parts abietyl HDI type
Ester, 0.90 ~ 2.60 mass parts analysis pure styrene, 20.00 mass parts analysis pure toluene, 0.20 ~ 0.25 mass parts analyze pure first
Base acrylic acid, 0.05 mass parts analyze pure azodiisobutyronitrile and the pure bisphenol-A of 0.09 ~ 0.16 mass parts chemistry is ultrasonic at 50 DEG C
It is uniformly dispersed, is added in aforesaid reaction vessel, increase 5 DEG C after reaction 3 hours and cure 2 hours, stop reaction, by product with 40 DEG C
Distillation water washing 3 ~ 5 times, then the pure pure methyl alcohol mixed liquor of acetic acid-analysis of analysis for being 1:9 with volume ratio extract 48 hours in 78 DEG C,
Template molecule bisphenol-A is removed, neutrality is finally washed with distilled water to, naturally dry obtains abietyl HDI type polyurethane molecule print
Mark microballoon；
The abietyl HDI type polyurethane the preparation method comprises the following steps:
(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 2.40mgKOH/g, i.e.,
The toluene solution of Rosin-based Polyol is obtained, survey solid masses percentage is 50.52 %；
(3) by Rosin-based Polyol obtained by 30.91 mass parts steps (2) and the pure dibutyl tin dilaurate of 0.11 mass parts chemistry
With being added in reaction kettle after the analysis pure toluene dissolution of 18.54 mass parts, in N2It is heated to 55 DEG C under protection, 6.00 mass parts are added
400 rmin of revolving speed is arranged in the hexamethylene diisocyanate of purity 99%-1, reacted, be down to theory to-NCO content
It is worth, 1.41 mass parts is added and analyze pure 1,6- hexylene glycol progress chain extension, reacts extremely-NCO content and is reduced to 0, obtain abietyl HDI type
Polyurethane, survey solid masses percentage are 50.23 %.
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Application publication date: 20190125 Assignee: GUANGXI JISHUN ENERGY TECHNOLOGY Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2022450000495 Denomination of invention: Preparation of rosin based HDI polyurethane molecularly imprinted microspheres Granted publication date: 20201124 License type: Common License Record date: 20221229 |
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Application publication date: 20190125 Assignee: Guangxi pinri Electronic Technology Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2022450000634 Denomination of invention: A preparation method of rosin-based HDI-type polyurethane molecularly imprinted microspheres Granted publication date: 20201124 License type: Common License Record date: 20221230 |