CN105348487B - A kind of preparation method of castor oil acidic group UV curable water-borne resins - Google Patents

A kind of preparation method of castor oil acidic group UV curable water-borne resins Download PDF

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Publication number
CN105348487B
CN105348487B CN201510945203.2A CN201510945203A CN105348487B CN 105348487 B CN105348487 B CN 105348487B CN 201510945203 A CN201510945203 A CN 201510945203A CN 105348487 B CN105348487 B CN 105348487B
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castor oil
water
oil acid
preparation
nco
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CN105348487A (en
Inventor
姚伯龙
赵海平
郑春森
王利魁
李洪萍
孙常青
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Jiangnan University
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Jiangnan University
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    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/675—Low-molecular-weight compounds
    • C08G18/6755—Unsaturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes

Abstract

The present invention relates to a kind of preparation method of castor oil acidic group UV curable water-borne resins；The present invention instead of traditional hydrophilic chain extender using castor oil acid structural advantage itself, both environmentally friendly, and performance is again good；Provide a kind of preparation method of vegetable oil acid UV-curable water-base resin.The waterborne polyurethane resin of the present invention reacts to obtain polyurethane structural using the hydroxyl of castor oil acid itself with isocyanates, and the carboxyl of another end dissociative just can be used for neutralize be emulsified into it is water-based, connected again using hexamethylene diisocyanate trimer as core pentaerythritol triacrylate introducing double bond, polyethylene glycol is soft segment, final synthesis dumbbell structure resin, and the resin system also has a variety of good characteristics of water-based, photocuring, bio-based simultaneously.

Description

A kind of preparation method of castor oil acidic group UV curable water-borne resins
Technical field
The invention belongs to the preparation field of bio-based renewable resource material and ultraviolet light curable polyurethane material, specifically It is related to a kind of preparation method of vegetable oil acid UV-curable water-base resin.
Background introduction
As people are to material safety and the pay attention to day by day of environmental protection, solidify using water as decentralized medium and using ultraviolet light The water-borne UV-curing polyurethane coating that technology is combined arises at the historic moment.And hydrophilic chain extender pair used in aqueous polyurethane emulsion Emulsion particle diameter and its stability have a substantial connection, and the research of current hydrophilic chain extender is mainly carboxylic acid type, sulfonic acid type, nonionic With the hydrophilic hydrophilic chain extender of both sexes.These hydrophilic chain extenders have the advantage and disadvantage of oneself, just conventional carboxylic acid type hydrophilic chain extender 2,2- dihydromethyl propionic acids (DMPA), it is white powder, indissoluble solution, needs a large amount of acetone or DMF (DMF) thing It can be added to after first being dissolved to it in system, even if being required for necessarily using expensive 2,2- dimethylolpropionic acids (DMBA) The solvent dissolving of amount.It is 15% and 1% that the solubility of DMBA at 20 DEG C, DMPA in acetone, which is only,.And castor oil acid (Ricinoleic acid) can be sent out by castor oil by ordinary-temp hydrolysis, pressurized hydrolysis hair, saponification acidifying hair prepare, in recent years in High-purity castor oil acid successfully is made using enzyme process in beautiful Na et al..Castor oil acid is the processing product of natural biological raw material, ring Health care health, is liquid under normal temperature, the hydroxyl in chain under the electronic effect of double bond easily with hexamethylene diisocyanate (HDI) three NCO reactions on aggressiveness, and after end carboxyl neutralizes with triethylamine, stable emulsion particle can be formed.
The content of the invention
It is an object of the invention to substitute traditional hydrophilic chain extender using vegetable oil acid, a kind of the water-based of health environment-friendly is synthesized Light-cured resin；A kind of preparation method of bio-based UV-curable water-base resin is provided.Tied in itself using castor oil acid in invention Structure advantage successfully instead of traditional hydrophilic chain extender, both environmentally friendly, and performance is again good.The hydroxyl of castor oil acid itself and isocyano are anti- Should obtain polyurethane structural, and the carboxyl of another end dissociative can just be used for being emulsified into it is water-based, with the isocyanic acid of hexa-methylene two Ester (HDI) tripolymer is core, connects pentaerythritol triacrylate (PETA) and introduces double bond, using polyethylene glycol as soft segment, finally Dumbbell structure resin is synthesized, the resin system also has a variety of good characteristics of water-based, photocuring, bio-based simultaneously.
The technical scheme is that：
A kind of preparation method of castor oil acid oil base UV-curable waterborne organic silicon polyurethane resin, comprises the following steps：
(1) castor oil acid polyester diol is warming up to 80-100 DEG C, vacuum dehydration processing 30min, after being dehydrated Polyester diol and castor oil acid
(2) synthesis of the end capped polyesters type prepolymers of NCO half：By a certain amount of catalyst, active termination agent, polymerization inhibitor and six Methylene diisocyanate (HDI) tripolymer adds in 250ml four-hole boiling flasks temperature rising to 47-50 DEG C, and reaction 2-3 hours work as When NCO reaches theoretical value, just aggressiveness is obtained.First mer temperature is controlled at 75 DEG C again, adds castor oil acid, whole process is used Acetone control system viscosity and logical nitrogen protection, reaction stop reaction, in 3 hours with ice-water bath rapidly after NCO reaches theoretical value Cooling system, and sealed up for safekeeping with clean dropping funel stand-by.
(3) synthesis of dumbbell structure prepolymer：It is another to take the clean four-hole bottles of 250ml, add metering polyether Glycols and urge Agent, second step product is slowly dropped in four-hole bottle, terminated to NCO total overall reactions.
(4) formation of emulsion：Add metering water and nertralizer in continuing toward system, stirring is to terminating.
Catalyst described in step (2) and (3) is at least one of dibutyl tin laurate, stannous octoate；
Active termination agent described in step (2) is hydroxy-ethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA), third At least one of olefin(e) acid hydroxypropyl acrylate (HPA), hydroxy propyl methacrylate (HPMA), pentaerythritol triacrylate (PETA)；
Polymerization inhibitor described in step (2) is at least one of hydroquinones, p methoxy phenol；
Nertralizer described in step (4) is triethylamine；
Polyether Glycols molecular weight described in step (4) can be 400g/mol, 600g/mol, 1000g/mol and 2000g/mol；
The beneficial effects of the invention are as follows：Reacted more than, it is water-based that synthesis obtains health environment-friendly UV solidified plant oil acidic groups Polyurethane coating.The resin has the environment of higher health requirements available for nail polish, woodenware and jewellery etc..
Embodiment
Embodiment 1
(1) by 11.61g hexamethylene diisocyanates (HDI) tripolymer, 0.1g dibutyl tin laurates (DBTDL), 0.05g4- metoxyphenols (MEHQ) and 5ml acetone, which add, is equipped with agitator, condenser pipe, constant pressure funnel and nitrogen conduit Drying four-hole boiling flask in, be stirred at room temperature uniformly, lead to nitrogen protection, be progressively warming up to 50 DEG C, with constant pressure funnel control drip Speed for 1 second/drop, dropwise be added dropwise 5.96g PETA, react 3h, when in system NCO content reach the theoretical value first step reaction terminate.
After (2) first the end of the step, rise system temperature continues that 5.97g castors are added dropwise dropwise with the speed of 2-3 seconds/drop to 65 DEG C Sesame oil acid, 2.5h is reacted, while dissociate in titration system-NCO content, after reaching theoretical value, system ice bath quickly cooling is allowed to room Temperature.
(3) system is transferred to another constant pressure funnel, separately takes one to carry agitator, the four-hole bottle of condenser pipe adds It is 400g/mol polyethylene glycol and 0.1g dibutyl tin laurates (DBTDL) to enter 4g molecular weight, and is added under the protection of nitrogen The product cooled down before entering, 3-4h is reacted, finished to NCO reactions.
(4) the 3rd product is cooled to room temperature, adjustment rotating speed is 1000rpm, and metering 2.02g tri- is added under high-speed stirred Ethamine (TEA) neutralization reaction 1h, 41.3g deionized waters emulsification 45min is then added dropwise with the speed of 2-3 seconds/drop, stands defoaming, Produce dumbbell shaped aqueous polyurethane emulsion.

Claims (1)

1. a kind of preparation method of castor oil acidic group UV curable water-borne resins, its characterization step are：
(1) castor oil acid and polyether Glycols are warming up to 80-100 DEG C, vacuum dehydration processing 30min, gathering after being dehydrated Ether dihydric alcohol and castor oil acid；
(2) synthesis of the end capped polyesters type prepolymers of NCO half：By catalyst, active termination agent, polymerization inhibitor and the isocyanide of hexa-methylene two Acid esters tripolymer adds in 250ml four-hole boiling flasks temperature rising to 47-50 DEG C, reacts 2-3 hours when NCO reaches theoretical value, Obtain just aggressiveness；Again by first mer temperature control at 75 DEG C, add castor oil acid, whole process with acetone control system viscosity simultaneously Lead to nitrogen protection, reaction stops reaction in 3 hours after NCO reaches theoretical value, and system is rapidly cooled down with ice-water bath, and with totally Dropping funel is sealed up for safekeeping stand-by；The active termination agent is hydroxy-ethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA), third At least one of olefin(e) acid hydroxypropyl acrylate (HPA), hydroxy propyl methacrylate (HPMA), pentaerythritol triacrylate (PETA)；
(3) synthesis of dumbbell structure prepolymer：It is another to take the clean four-hole bottles of 250ml, polyether Glycols and catalyst are added, by second Step product is slowly dropped in four-hole bottle, is terminated to NCO total overall reactions；
(4) formation of emulsion：Add water and nertralizer in continuing toward system, stirring is to terminating.
CN201510945203.2A 2015-12-16 2015-12-16 A kind of preparation method of castor oil acidic group UV curable water-borne resins Active CN105348487B (en)

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CN105801791B (en) * 2016-03-22 2018-07-27 华南农业大学 A kind of castor oil-base UV cured polyurethane acrylates and its preparation method and application
CN106189803B (en) * 2016-07-12 2018-04-24 叶有国 A kind of fingerprint recognition coating and its preparation method and application
CN106147587B (en) * 2016-07-12 2018-04-24 叶有国 A kind of antimicrobial UV coating containing castor oil-base and its preparation method and application
CN106821796B (en) * 2016-12-08 2020-06-16 宝鸡文理学院 Preparation method of bio-based water-based UV-curable environment-friendly nail polish
CN108236597B (en) * 2016-12-23 2021-08-10 张家港康得新光电材料有限公司 Water-based nail polish
CN108912302B (en) * 2018-05-25 2020-11-27 南京工业大学 Waterborne polyurethane and preparation method and application thereof
CN109942781B (en) * 2019-04-01 2020-05-29 东北林业大学 UV-cured castor oil-based aqueous polyurethane dispersion and preparation method and application thereof
CN111040105B (en) * 2019-12-30 2020-10-02 珠海华大浩宏新材料有限公司 Soft fluorine-free waterproof agent and preparation method thereof
CN113354769B (en) * 2021-06-07 2022-08-09 东莞长联新材料科技股份有限公司 Plant oil-based hydrophilic polymer aqueous dispersion and preparation method and application thereof

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