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 PDF

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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
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mass parts
pure
abietyl
rosin
added
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CN109369951B (en
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余彩莉
陈勇
邵金涛
张发爱
张淑芬
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Guilin University of Technology
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    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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    • C08F283/00Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C08F283/008Macromolecular 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
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    • C08G18/755Polyisocyanates 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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    • C08J2201/00Foams characterised by the foaming process
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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

A kind of preparation method of abietyl IPDI type polyurethane molecular engram microsphere
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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