CN109369951A - A kind of preparation method of abietyl IPDI type polyurethane molecular engram microsphere - Google Patents
A kind of preparation method of abietyl IPDI type polyurethane molecular engram microsphere Download PDFInfo
- Publication number
- CN109369951A CN109369951A CN201810921142.XA CN201810921142A CN109369951A CN 109369951 A CN109369951 A CN 109369951A CN 201810921142 A CN201810921142 A CN 201810921142A CN 109369951 A CN109369951 A CN 109369951A
- Authority
- CN
- China
- Prior art keywords
- mass parts
- pure
- abietyl
- rosin
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- C08J9/286—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 the liquid phase being a solvent for the monomers but not for the resulting macromolecular composition, i.e. macroporous or macroreticular polymers
-
- 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
- C08G18/06—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
- C08G18/40—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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- 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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/042—Elimination of an organic solid phase
- C08J2201/0422—Elimination of an organic solid phase containing oxygen atoms, e.g. saccharose
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a kind of preparation methods of abietyl IPDI type polyurethane molecular engram microsphere.Being that raw material is modified with rosin etc. obtains abietyl IPDI type polyurethane, using the polyurethane containing unsaturated double-bond as crosslinking agent, methacrylic acid is 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 molecular engram microsphere 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 IPDI type polyurethane molecular engram microsphere.
Background technique
Bisphenol-A (BPA) is widely used in the plastic industries such as can inner packing, packaging material for food, articles for babies, is commonly present
In water environment；It is it is a kind of can rapidly diffuse into human cell membrane with endocrine disrupting class female hormone,
There is antagonism to lead to the disorder of endocrine system to influence metabolic function, seriously threaten people normocrinic hormone
Class health.Therefore, a kind of method that can accurately identify and adsorb micro BPA in water is developed for ecological environment and human health
Have great importance, wherein removing bisphenol-A using molecular imprinting technology is a kind of feasible method.
Molecular imprinting technology (P-MIP) is to prepare the high molecular material for having specific recognition capability to specific target molecules
Technology.Preparation method is to generate template molecule, function monomer, crosslinking agent, initiator and pore-foaming agent by polymerization reaction to gather
Object is closed, there is the site of specific binding to target molecule using generation after elution.According to the knot of template molecule and function monomer
Method prepared by molecularly imprinted polymer can be divided into 2 kinds by conjunction mode: (1) covalent method is also known as pre-organized method；It is template molecule
Compound is formed in the form of covalent bond with function monomer, and crosslinking agent is added and forms high polymer, then passes through physics or chemical hand
Breaking of covalent bonds is removed the template molecule in polymer, obtains molecular engram material by section.(2) non-covalence method is also known as self assembly
Method；It is, by one or more non-covalent interactions, will to add crosslinking dosage form between function monomer and template molecule
Non-covalent bond is broken at high polymer, then by chemical method, the template molecule in polymer is removed, finally obtains molecular engram
Polymer.Common non-covalent bond effect power includes electric charge transfer, hydrogen bond, metal-chelating effect, electrostatic attraction, hydrophobic effect
Deng wherein being most with hydrogen bond action.The common preparation method of microballoon has: precipitation polymerization, emulsion polymerization and suspension polymerisation etc.,
Middle suspension polymerization can prepare the molecular engram microsphere of large specific surface area, and relative to general indefinite form imprinted polymer, it can
To provide bigger trace space for template molecule.
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 obtains the polyurethane with unsaturated double-bond using rosin as raw material, by modified, with poly- ammonia
Ester is crosslinking agent, and methacrylic acid is function monomer, and bisphenol-A is template molecule, and azodiisobutyronitrile is initiator, and toluene is to cause
Hole agent is prepared for the functional form molecular engram microsphere that a kind of pair of bisphenol-A has specific binding capacity.The present invention is reasonable development
New application approach is provided using rosin resource.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of abietyl IPDI type polyurethane molecular engram microsphere.
Specific steps are as follows:
The deionized water of 40.00 mass parts and the pure polyvinyl alcohol of 0.60~0.70 mass parts chemistry are added to reaction kettle
In, in N2In the presence of with 400~700r/min mixing speed heating water bath to 75~90 DEG C；By 3.00 mass parts abietyl IPDI
Type polyurethane, 20.00 mass parts analysis pure toluene, 0.20~0.25 mass parts analyze pure methacrylic acid, 0.05 mass parts point
It analyses pure azodiisobutyronitrile and the pure bisphenol-A ultrasonic disperse at 50 DEG C of 0.09~0.16 mass parts chemistry is uniform, be added to above-mentioned
In reaction kettle, reaction 3 hours after increase 5 DEG C cure 2 hours, stop reaction, by product with 40 DEG C distillation water washing 3~5 times, then
It is extracted 48 hours with the pure pure methyl alcohol mixed liquor of acetic acid-analysis of analysis that volume ratio is 1:9 in 78 DEG C, removes template molecule bisphenol-A,
It is finally washed with distilled water to neutrality, naturally dry obtains abietyl IPDI type polyurethane molecular engram microsphere.
The preparation method specific steps of the abietyl IPDI type 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 (RA) obtained by 108.51 mass parts steps (1) is dissolved in a kettle
191.86 mass parts are analyzed in pure toluene, and 82.40 mass parts purity, 97% glycidyl methacrylate, 0.54 mass is added
Part analyzes pure triethylamine and 0.41 mass parts analyze pure Isosorbide-5-Nitrae-hydroquinone, is warming up to 120 DEG C, reacts 4 hours, surveys acid value and is
For 2.40mgKOH/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 64.34 mass parts steps (2) and the pure dibutyl tin osmanthus of 0.24 mass parts chemistry
Sour tin is added in reaction kettle after analyzing pure toluene dissolution with 43.27 mass parts, in N2It is heated to 70 DEG C under protection, is added 16.00
Revolving speed 400r/min is arranged in the isophorone diisocyanate of mass parts purity 99%, is down to theoretical value to-NCO content, is added
1.41 mass parts analyze pure 1,6- hexylene glycol and carry out chain extension, react extremely-NCO content and are reduced to 0, obtain the poly- ammonia of abietyl IPDI type
Ester, surveying solid masses percentage is 49.12%.
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 containing unsaturated double-bond by modification, then using polyurethane as crosslinking agent, methacrylic acid is function
Energy monomer, bisphenol-A are template molecule, and azodiisobutyronitrile is initiator, and toluene is that pore-foaming agent is prepared for a kind of pair of bisphenol-A
(BPA) with the functional form molecular engram microsphere (P-MIP) of specific binding capacity.It is more wide that the present invention does not give only rosin
General application 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 0.65 mass parts chemistry are added in reaction kettle, in N2It deposits
With 700rmin under-1Mixing speed heating water bath is to 85 DEG C.By 3.00 mass parts abietyl IPDI type polyurethanes, 20.00 matter
Measure part analysis pure toluene, 0.23 mass parts analyze pure methacrylic acid, 0.05 mass parts analyze pure azodiisobutyronitrile and 0.15
The pure bisphenol-A ultrasonic disperse at 50 DEG C of mass parts chemistry is uniform, is added in aforesaid reaction vessel, and 5 DEG C of raising is ripe after reaction 3 hours
Change 2 hours, stop reaction, by product with 40 DEG C or so distillation water washing 5 times, then the pure acetic acid-point of analysis for being 1:9 with volume ratio
It analyses pure methyl alcohol mixed liquor to extract 48 hours in 78 DEG C, removes template molecule bisphenol-A, be finally washed with distilled water to neutrality, it is natural
It dries, obtains abietyl IPDI type polyurethane molecular engram microsphere (P-MIP), synthesis is without addition template in the same manner
The non-trace microballoon (P-NIP) of molecule BPA is as control.Respectively using P-MIP and P-NIP microballoon as adsorbent, it is in solid-to-liquid ratio
It is 0.25 μm of olmL to concentration under conditions of 1.3g/L, adsorption temp are 25 DEG C, adsorption time is 3 hours-1BPA aqueous solution
Absorption research is carried out, measuring P-MIP microballoon adsorbance is 51.04 μm of ol/g, and P-NIP microballoon adsorbance is 26.93 μm of ol/g.
The preparation method specific steps of the abietyl IPDI type 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/
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 64.34 mass parts steps (2) and the pure dibutyl tin osmanthus of 0.24 mass parts chemistry
Sour tin is added in reaction kettle after analyzing pure toluene dissolution with 43.27 mass parts, in N2It is heated to 70 DEG C under protection, is added 16.00
Revolving speed 400rmin is arranged in the isophorone diisocyanate (IPDI) of mass parts purity 99%-1, reason is down to-NCO content
By 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 abietyl
IPDI type polyurethane, surveying solid masses percentage is 49.12%.
Embodiment 2:
The deionized water of 40.00 mass parts and the pure polyvinyl alcohol of 0.65 mass parts chemistry are added in reaction kettle, in N2It deposits
With 500rmin under-1Mixing speed heating water bath is to 80 DEG C.By 3.00 mass parts abietyl IPDI type polyurethanes, 20.00 matter
Measure part analysis pure toluene, 0.23 mass parts analyze pure methacrylic acid, 0.05 mass parts analyze pure azodiisobutyronitrile and 0.09
The pure bisphenol-A ultrasonic disperse at 50 DEG C of mass parts chemistry is uniform, is added in aforesaid reaction vessel, and 5 DEG C of raising is ripe after reaction 3 hours
Change 2 hours, stop reaction, by product with 40 DEG C or so distillation water washing 5 times, then the pure acetic acid-point of analysis for being 1:9 with volume ratio
It analyses pure methyl alcohol mixed liquor to extract 48 hours in 78 DEG C, removes template molecule bisphenol-A, be finally washed with distilled water to neutrality, it is natural
It dries, obtains abietyl IPDI type polyurethane molecular engram microsphere (P-MIP).Synthesis is without addition template in the same manner
The non-trace microballoon (P-NIP) of molecule BPA, as control.Respectively using P-MIP and P-NIP microballoon as adsorbent, it is in solid-to-liquid ratio
It is 0.25 μm of olmL to concentration under conditions of 1.3g/L, adsorption temp are 25 DEG C, adsorption time is 3 hours-1BPA aqueous solution
Absorption research is carried out, measuring P-MIP microballoon adsorbance is 41.02 μm of ol/g, and P-NIP microballoon adsorbance is 23.30 μm of ol/g.
The preparation method specific steps of the abietyl IPDI type 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/
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 64.34 mass parts steps (2) and the pure dibutyl tin osmanthus of 0.24 mass parts chemistry
Sour tin is added in reaction kettle after analyzing pure toluene dissolution with 43.27 mass parts, in N2It is heated to 70 DEG C under protection, is added 16.00
Revolving speed 400rmin is arranged in the isophorone diisocyanate (IPDI) of mass parts purity 99%-1, reason is down to-NCO content
By 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 abietyl
IPDI type polyurethane, surveying solid masses percentage is 49.12%.
Embodiment 3:
The deionized water of 40.00 mass parts and the pure polyvinyl alcohol of 0.65 mass parts chemistry are added in reaction kettle, in N2It deposits
With 400rmin under-1Mixing speed heating water bath is to 80 DEG C.By 3.0 mass parts abietyl IPDI type polyurethanes, 20.0 mass
Part analysis pure toluene, 0.21 mass parts analyze pure methacrylic acid, 0.05 mass parts analyze pure azodiisobutyronitrile and 0.14 matter
It is uniform to measure the pure bisphenol-A ultrasonic disperse at 50 DEG C of part chemistry, is added in aforesaid reaction vessel, 5 DEG C of curings is increased after reaction 3 hours
2 hours, stop reaction, by product with 40 DEG C or so distillation water washing 5 times, then the pure acetic acid-analysis of analysis for being 1:9 with volume ratio
Pure methyl alcohol mixed liquor extracts 48 hours in 78 DEG C, removes template molecule bisphenol-A, is finally washed with distilled water to neutrality, dries in the air naturally
It is dry, obtain abietyl IPDI type polyurethane molecular engram microsphere (P-MIP).Synthesis is without addition template point in the same manner
The non-trace microballoon (P-NIP) of sub- BPA, as control.Respectively using P-MIP and P-NIP microballoon as adsorbent, it is in solid-to-liquid ratio
It is 0.25 μm of olmL to concentration under conditions of 1.3g/L, adsorption temp are 25 DEG C, adsorption time is 3 hours-1BPA aqueous solution
Absorption research is carried out, measuring P-MIP microballoon adsorbance is 21.09 μm of ol/g, and P-NIP microballoon adsorbance is 15.39 μm of ol/g.
The preparation method specific steps of the abietyl IPDI type 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/
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 64.34 mass parts steps (2) and the pure dibutyl tin osmanthus of 0.24 mass parts chemistry
Sour tin is added in reaction kettle after analyzing pure toluene dissolution with 43.27 mass parts, in N2It is heated to 70 DEG C under protection, is added 16.00
Revolving speed 400rmin is arranged in the isophorone diisocyanate (IPDI) of mass parts purity 99%-1, reason is down to-NCO content
By 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 abietyl
IPDI type polyurethane, surveying solid masses percentage is 49.12%.
Claims (1)
1. a kind of preparation method of abietyl IPDI 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 0.60 ~ 0.70 mass parts chemistry are added into reaction kettle, in N2
In the presence of with 400 ~ 700 r/min mixing speed heating water baths to 75 ~ 90 DEG C；By the 3.00 poly- ammonia of mass parts abietyl IPDI type
Ester, 20.00 mass parts analysis pure toluene, 0.20 ~ 0.25 mass parts analyze pure methacrylic acid, 0.05 mass parts analyze pure azo
Bis-isobutyronitrile and the pure bisphenol-A ultrasonic disperse at 50 DEG C of 0.09 ~ 0.16 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 distillation water washing 3 ~ 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 IPDI type polyurethane molecular engram microsphere；
The preparation method specific steps of the abietyl IPDI type 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 (RA) 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 surveying acid value is 2.40
For mgKOH/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 64.34 mass parts steps (2) and the pure dibutyl tin dilaurate of 0.24 mass parts chemistry
With being added in reaction kettle after the analysis pure toluene dissolution of 43.27 mass parts, in N2It is heated to 70 DEG C under protection, 16.00 mass are added
400 r/min of revolving speed is arranged in the isophorone diisocyanate of part purity 99%, is down to theoretical value to-NCO content, is added 1.41
Mass parts analyze pure 1,6- hexylene glycol and carry out chain extension, react extremely-NCO content and are reduced to 0, obtain abietyl IPDI type polyurethane, survey
Solid masses percentage is 49.12 %.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810921142.XA CN109369951B (en) | 2018-08-14 | 2018-08-14 | Preparation method of rosin-based IPDI polyurethane molecularly imprinted microspheres |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810921142.XA CN109369951B (en) | 2018-08-14 | 2018-08-14 | Preparation method of rosin-based IPDI polyurethane molecularly imprinted microspheres |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109369951A true CN109369951A (en) | 2019-02-22 |
| CN109369951B CN109369951B (en) | 2020-11-24 |
Family
ID=65404320
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810921142.XA Active CN109369951B (en) | 2018-08-14 | 2018-08-14 | Preparation method of rosin-based IPDI polyurethane molecularly imprinted microspheres |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109369951B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110467716A (en) * | 2019-08-01 | 2019-11-19 | 桂林理工大学 | A kind of preparation method of the antibacterial polyurethane of abietyl HDI 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 |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1811411A (en) * | 2006-02-16 | 2006-08-02 | 上海交通大学 | Process for producing chloromycetin molecular engram polymer microsphere |
| CN101092490A (en) * | 2007-06-28 | 2007-12-26 | 上海交通大学 | Method for preparing polymer microballons of molecular engram of nitrogen benzyl penicillin |
| CN101173058A (en) * | 2007-10-11 | 2008-05-07 | 上海交通大学 | Method for producing molecular engram polyalcohol microsphere and method for separating enrofloxacin thereof |
| CN101177500A (en) * | 2007-10-30 | 2008-05-14 | 湖北出入境检验检疫局检验检疫技术中心 | Method for preparing bisphenol A molecular engram polymer |
| CN101497035A (en) * | 2008-12-30 | 2009-08-05 | 安徽农业大学 | Preparation method of solid-phase extraction small column for molecular imprinting of substituted carbamide pesticide |
| CN102702429A (en) * | 2012-06-19 | 2012-10-03 | 苏州市汉微环保科技有限公司 | Method for preparing bisphenol A molecularly imprinted polymer |
| CN105646822A (en) * | 2016-03-13 | 2016-06-08 | 桂林理工大学 | Method for preparing rosin-based IPDI (isophorone diisocyanate)-type polyurethane prepolymers |
| CN106977648A (en) * | 2017-03-13 | 2017-07-25 | 天津科技大学 | The monomer of structure function containing template molecule prepares bisphenol-A molecular engram material method |
-
2018
- 2018-08-14 CN CN201810921142.XA patent/CN109369951B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1811411A (en) * | 2006-02-16 | 2006-08-02 | 上海交通大学 | Process for producing chloromycetin molecular engram polymer microsphere |
| CN101092490A (en) * | 2007-06-28 | 2007-12-26 | 上海交通大学 | Method for preparing polymer microballons of molecular engram of nitrogen benzyl penicillin |
| CN101173058A (en) * | 2007-10-11 | 2008-05-07 | 上海交通大学 | Method for producing molecular engram polyalcohol microsphere and method for separating enrofloxacin thereof |
| CN101177500A (en) * | 2007-10-30 | 2008-05-14 | 湖北出入境检验检疫局检验检疫技术中心 | Method for preparing bisphenol A molecular engram polymer |
| CN101497035A (en) * | 2008-12-30 | 2009-08-05 | 安徽农业大学 | Preparation method of solid-phase extraction small column for molecular imprinting of substituted carbamide pesticide |
| CN102702429A (en) * | 2012-06-19 | 2012-10-03 | 苏州市汉微环保科技有限公司 | Method for preparing bisphenol A molecularly imprinted polymer |
| CN105646822A (en) * | 2016-03-13 | 2016-06-08 | 桂林理工大学 | Method for preparing rosin-based IPDI (isophorone diisocyanate)-type polyurethane prepolymers |
| CN106977648A (en) * | 2017-03-13 | 2017-07-25 | 天津科技大学 | The monomer of structure function containing template molecule prepares bisphenol-A molecular engram material method |
Non-Patent Citations (3)
| Title |
|---|
| 傅强著: "《分子印迹技术与药物分析》", 30 September 2014, 西安交通大学出版社 * |
| 赵丽杰，等: "微球形水杨酸分子印迹聚合物的合成及其结合性质的研究", 《齐齐哈尔大学学报》 * |
| 郑平著: "《分子印迹固相萃取技术及其在食品安全分析中的应用》", 30 November 2011, 合肥工业大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110467716A (en) * | 2019-08-01 | 2019-11-19 | 桂林理工大学 | A kind of preparation method of the antibacterial polyurethane of abietyl HDI 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109369951B (en) | 2020-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tang et al. | Upconversion particles coated with molecularly imprinted polymers as fluorescence probe for detection of clenbuterol | |
| CN101565485B (en) | Method for preparing molecularly imprinted polymers of ethinylestradiol analogue | |
| CN102516326B (en) | Method for synthesizing tannin-based hyperbranched acrylic acid ester | |
| CN109369951A (en) | A kind of preparation method of abietyl IPDI type polyurethane molecular engram microsphere | |
| CN104762077B (en) | The polymer oil-displacing agent of high temperature resistant salt resistance | |
| CN105646800B (en) | A kind of preparation method of abietyl hydroxylated polymer microballoon | |
| Roland et al. | Synthesis and characterization of molecular imprinting polymer microspheres of piperine: extraction of piperine from spiked urine | |
| CN104761692A (en) | Modification method for introducing carbon-carbon double bond to surface of nanometer silicon dioxide | |
| CN104744647B (en) | Modified Nano SiO2The preparation method of graft copolymer | |
| Tang et al. | Preparation of a photoresponsive molecularly imprinted polymer containing fluorine-substituted azobenzene chromophores | |
| Gizawy et al. | Synthesis of chitosan-acrylic acid/multiwalled carbon nanotubes composite for theranostic 47Sc separation from neutron irradiated titanium target | |
| CN104194026A (en) | Visible light triggered material surface graft polymerization based functional modifying method | |
| CN105175652A (en) | Superparamagnetic polymer mono-dispersed microspheres and preparation method thereof | |
| CN106732219A (en) | A kind of preparation method of the CNT/paraffin microcapsule with photo absorption performance | |
| CN109280137A (en) | A kind of preparation method of abietyl TDI type aqueous polyurethane microballoon | |
| CN109232823A (en) | A kind of preparation method of abietyl TDI type polyurethane molecular engram microsphere | |
| CN108558701A (en) | A kind of small molecule AIEE luminescent materials and preparation method thereof with triple stimulating responsives | |
| CN107814867A (en) | A kind of PMMA fluorescent copolymers microballoon and preparation method thereof | |
| CN105403694B (en) | A kind of PS@SiO for detecting paraquat molecule2The preparation method of artificial antibody | |
| CN105542115B (en) | A kind of preparation method of the humic acid modified Waterborne PU Composite of coal base | |
| CN104693363B (en) | Artesunate surface molecule print porous magnetic cellulose microsphere and its preparation method and application | |
| CN107880227B (en) | Method for preparing glycoprotein imprinted fluorescent nanoparticles based on macromolecular self-assembly | |
| CN106977648B (en) | Method for preparing bisphenol A molecularly imprinted material from functional monomer containing template molecular structure | |
| CN105131213A (en) | Glass fibers of grafted temperature-sensitive hydrogel | |
| CN109265727A (en) | A kind of preparation method of abietyl HDI type polyurethane molecular engram microsphere |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20190222 Assignee: GUANGXI JISHUN ENERGY TECHNOLOGY Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2022450000495 Denomination of invention: Preparation of rosin based IPDI polyurethane molecularly imprinted microspheres Granted publication date: 20201124 License type: Common License Record date: 20221229 |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20190222 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 IPDI polyurethane molecularly imprinted microspheres Granted publication date: 20201124 License type: Common License Record date: 20221230 |