CN109369951A - A kind of preparation method of rosin-based IPDI type polyurethane molecularly imprinted microspheres - Google Patents
A kind of preparation method of rosin-based IPDI type polyurethane molecularly imprinted microspheres Download PDFInfo
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- 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
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Abstract
本发明公开了一种松香基IPDI型聚氨酯分子印迹微球的制备方法。以松香等为原料经改性得到松香基IPDI型聚氨酯,以含有不饱和双键的聚氨酯为交联剂，甲基丙烯酸为功能单体、双酚A为模板分子、偶氮二异丁腈为引发剂、聚乙烯醇为分散剂、甲苯为致孔剂，采用悬浮聚合法制备了一种对双酚A具有特异性结合能力的功能型分子印迹微球。制备的印迹微球球形规则、颗粒均匀，并对双酚A具有特性吸附。本发明最显著的特点是以天然可再生资源松香为原料，不仅赋予了松香更为广泛的应用前景，而且提供了一种制备双酚A分子印迹微球的有效方法。The invention discloses a preparation method of a rosin-based IPDI type polyurethane molecularly imprinted microsphere. Rosin-based IPDI polyurethane is obtained by modification with rosin and other raw materials. Polyurethane containing unsaturated double bonds is used as cross-linking agent, methacrylic acid is used as functional monomer, bisphenol A is used as template molecule, and azobisisobutyronitrile is used as Initiator, polyvinyl alcohol as dispersant and toluene as porogen, a functional molecularly imprinted microsphere with specific binding ability to bisphenol A was prepared by suspension polymerization method. The prepared imprinted microspheres have regular spherical shape and uniform particles, and have characteristic adsorption to bisphenol A. The most notable feature of the present invention is that the natural renewable resource rosin is used as the raw material, which not only gives the rosin a wider application prospect, but also provides an effective method for preparing bisphenol A molecularly imprinted microspheres.
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 %.
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