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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 PDF

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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
pure
rosin
type polyurethane
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CN109265727B (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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    • C08J9/00—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
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    • 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
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • 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
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    • 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
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • 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
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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

A kind of preparation method of abietyl HDI type polyurethane molecular engram microsphere
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)

1.一种松香基HDI型聚氨酯分子印迹微球的制备方法，其特征在于具体步骤为：A method for preparing a rosin-based HDI type polyurethane molecularly imprinted microsphere, characterized in that the specific steps are: 将40.00质量份的去离子水和0.80~1.20质量份化学纯聚乙烯醇加入至反应釜中，在N2存在下以400~700 r·min-1搅拌速度水浴加热至75~90℃；将3.00质量份松香基HDI型聚氨酯、0.90~2.60质量份分析纯苯乙烯、20.00质量份分析纯甲苯、0.20~0.25质量份分析纯甲基丙烯酸、0.05质量份分析纯偶氮二异丁腈和0.09~0.16质量份化学纯双酚A在50℃下超声分散均匀，加入到上述反应釜中，反应3小时后升高5℃熟化2小时，停止反应，将产物用40℃蒸馏水洗涤3~5次，再用体积比为1:9的分析纯乙酸-分析纯甲醇混合液于78℃抽提48小时，除去模板分子双酚A，最后用蒸馏水洗涤至中性，自然晾干，得到松香基HDI型聚氨酯分子印迹微球；40.00 parts by mass of deionized water and 0.80~1.20 parts by mass of chemically pure polyvinyl alcohol are added to the reaction kettle, and heated in a water bath at a stirring speed of 400-700 r·min -1 in the presence of N 2 to 75-90 ° C; 3.00 parts by mass of rosin-based HDI type polyurethane, 0.90 to 2.60 parts by mass of analytically pure styrene, 20.00 parts by mass of analytically pure toluene, 0.20 to 0.25 parts by mass of analytically pure methacrylic acid, 0.05 parts by mass of analytically pure azobisisobutyronitrile and 0.09 ~0.16 parts by mass of chemically pure bisphenol A was uniformly dispersed by ultrasonication at 50 ° C, added to the above reaction vessel, and after 3 hours of reaction, the mixture was aged at 5 ° C for 2 hours, the reaction was stopped, and the product was washed 3 to 5 times with 40 ° C distilled water. Then, the analytical pure acetic acid-analytical pure methanol mixture having a volume ratio of 1:9 was extracted at 78 ° C for 48 hours to remove the template molecule bisphenol A, and finally washed with distilled water until neutral, and naturally dried to obtain rosin-based HDI. Type polyurethane molecularly imprinted microspheres; 所述松香基HDI型聚氨酯的制备方法为：The preparation method of the rosin-based HDI type polyurethane is: （1）将100.0质量份松香加入到装有搅拌棒、回流冷凝管、温度计、氮气保护装置的反应釜中，加热熔化后在400 r·min-1下进行搅拌，加热至230℃后，开始缓慢滴加28.60质量份化学纯丙烯酸，持续1小时，滴加完毕后使其在230℃下继续反应2小时，待温度降至200℃出料，得到丙烯酸松香加成物；(1) Adding 100.0 parts by mass of rosin to a reaction vessel equipped with a stir bar, a reflux condenser, a thermometer, and a nitrogen protection device, heating and melting, stirring at 400 r·min -1 , heating to 230 ° C, and starting 28.60 parts by mass of chemically pure acrylic acid was slowly added dropwise for 1 hour, and after the completion of the dropwise addition, the reaction was continued at 230 ° C for 2 hours, and the temperature was lowered to 200 ° C to discharge, thereby obtaining an acrylic rosin adduct; （2）在反应釜中将108.51质量份步骤（1）所得丙烯酸松香加成物溶解于191.86质量份分析纯甲苯中，加入82.40质量份纯度97%甲基丙烯酸缩水甘油酯，0.54质量份分析纯三乙胺和0.41质量份分析纯1,4-对苯二酚，升温至120℃，反应4小时，测酸值为2.40mgKOH/g，即得到松香基多元醇的甲苯溶液，测固体质量百分比为50.52 %；(2) 108.51 parts by mass of the acrylic rosin adduct obtained in the step (1) was dissolved in 191.86 parts by mass of analytically pure toluene in the reaction vessel, and 82.40 parts by mass of pure 97% glycidyl methacrylate was added, and 0.54 parts by mass of analytical pure Triethylamine and 0.41 parts by mass of analytically pure 1,4-hydroquinone, heated to 120 ° C, reacted for 4 hours, and the acid value was 2.40 mg KOH / g, that is, a toluene solution of rosin-based polyol was obtained, and the solid mass percentage was measured. 50.52%; （3）将30.91质量份步骤（2）所得松香基多元醇和0.11质量份化学纯二丁基二月桂酸锡用18.54质量份分析纯甲苯溶解后加入反应釜中，在N2保护下加热至55℃，加入6.00质量份纯度99%的六亚甲基二异氰酸酯，设置转速400 r·min-1，进行反应，待-NCO含量降至理论值，加入1.41质量份分析纯1,6-己二醇进行扩链，反应至-NCO含量降为0，得到松香基HDI型聚氨酯，测固体质量百分比为50.23 %。(3) 30.91 parts by mass of the rosin-based polyol obtained in the step (2) and 0.11 part by mass of chemically pure dibutyltin dilaurate dissolved in 18.54 parts by mass of analytically pure toluene, added to the reaction vessel, and heated to 55 under N 2 protection. °C, adding 6.00 parts by mass of 99% pure hexamethylene diisocyanate, set the rotation speed of 400 r·min -1 , carry out the reaction, wait until the -NCO content drops to the theoretical value, add 1.41 parts by mass of analytical pure 1,6-hexane The alcohol was subjected to chain extension, and the reaction was carried out until the -NCO content was lowered to 0 to obtain a rosin-based HDI type polyurethane, and the solid mass percentage was determined to be 50.23%.
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