CN105348487A - Preparation method of ricinolic acid based UV cured water-base resin - Google Patents
Preparation method of ricinolic acid based UV cured water-base resin Download PDFInfo
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- CN105348487A CN105348487A CN201510945203.2A CN201510945203A CN105348487A CN 105348487 A CN105348487 A CN 105348487A CN 201510945203 A CN201510945203 A CN 201510945203A CN 105348487 A CN105348487 A CN 105348487A
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- ricinolic acid
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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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a preparation method of ricinolic acid based UV cured water-base resin. Ricinolic acid is used for substituting a conventional hydrophilic chain-extending agent by using structural advantages of the ricinolic acid, is environmentally friendly and is good in performance; and a preparation method of vegetable oleic acid UV curable water-base resin is provided. The water-base polyurethane resin provided by the invention makes use of a polyurethane structure, which is obtained by virtue of reaction between hydroxyl and isocyanate, of ricinolic acid, and free carboxyl at the other end just can be used for neutralizing and emulsifying to be water-based, hexamethylene diisocyanate tripolymer is taken as a core pentaerythritol triacylate is inoculated to introduce double bonds, and polyethylene glycol is taken as a soft segment to finally synthesize dumbbell-structure resin; and a resin system has various good aqueous, photo-curing and biological characteristics at the same time.
Description
Technical field
The invention belongs to the preparation field of bio-based renewable resource material and ultraviolet light curable polyurethane material, be specifically related to a kind of preparation method of vegetable oil acid UV-curable water-base resin.
Background introduction
Along with people are to the pay attention to day by day of material safety and environment protection, be dispersion medium with water and the water-borne UV-curing polyurethane coating adopting UV-curing technology to combine arises at the historic moment.And the hydrophilic chain extender that aqueous polyurethane emulsion uses has substantial connection to emulsion particle diameter and stability thereof, the research mainly carboxylic acid type of current hydrophilic chain extender, sulfonic acid type, non-ionic type and the hydrophilic hydrophilic chain extender of both sexes.These hydrophilic chain extenders have oneself relative merits, just conventional carboxylic acid type hydrophilic chain extender 2,2-dimethylol propionic acid (DMPA), for white powder, indissoluble solution, can be added in system after needing a large amount of acetone or DMF (DMF) to dissolve it in advance, even if adopt expensive 2,2-dimethylolpropionic acids (DMBA) all to need a certain amount of dissolution with solvents.When 20 DEG C, DMBA, DMPA solubleness is in acetone only is 15% and 1%.And ricinolic acid (Ricinoleicacid) can be sent out by ordinary-temp hydrolysis by Viscotrol C, pressurized hydrolysis is sent out, preparation is sent out in saponification acidifying, enzyme process is successfully adopted to obtain high purity ricinolic acid in people such as beautiful Nas in recent years.Ricinolic acid is the processed products of natural biological raw material, environment protection health, be liquid under normal temperature, the NCO of hydroxyl in chain under the electronic effect of double bond easily and on hexamethylene diisocyanate (HDI) tripolymer reacts, and in end carboxyl and triethylamine and after, can stable emulsion particle be formed.
Summary of the invention
The object of the invention is to utilize vegetable oil acid to replace traditional hydrophilic chain extender, synthesize a kind of water borne UV curing resin of health environment-friendly; A kind of preparation method of bio-based UV-curable water-base resin is provided.Utilize the structural advantage of ricinolic acid own successfully to instead of traditional hydrophilic chain extender, both environmental protection in invention, performance is good again.Hydroxyl and the isocyano of ricinolic acid self are obtained by reacting polyurethane structural, and the free carboxyl of the other end just in time can be used for being emulsified into water-based, with hexamethylene diisocyanate (HDI) tripolymer for core, connect pentaerythritol triacrylate (PETA) and introduce double bond, it is soft section with polyoxyethylene glycol, final synthesis dumbbell structure resin, this resin system also has water-based, photocuring, the multiple good characteristic of bio-based simultaneously.
Technical scheme of the present invention is:
A preparation method for ricinolic acid oil base UV-curable waterborne organic silicon urethane resin, comprises the steps:
(1) ricinolic acid polyester diol is warming up to 80-100 DEG C, vacuum hydro-extraction process 30min, obtains the polyester diol after dewatering and ricinolic acid
(2) synthesis of NCO half end capped polyesters type prepolymer: a certain amount of catalyzer, active termination agent, stopper and hexamethylene diisocyanate (HDI) tripolymer are added in 250ml four-hole boiling flask temperature is risen to 47-50 DEG C, react 2-3 hour when NCO reaches theoretical value, obtain just aggressiveness.Controlled by first mer temperature, at 75 DEG C, to add ricinolic acid, whole process acetone hierarchy of control viscosity also leads to nitrogen protection again; react 3 hours after NCO reaches theoretical value; stopped reaction, cools system rapidly with ice-water bath, and seals up for safekeeping stand-by with clean dropping funnel.
(3) synthesis of dumbbell structure prepolymer: separately get the clean four-hole bottle of 250ml, adds metering polyether Glycols and catalyzer, is slowly added drop-wise in four-hole bottle by second step product, terminates to NCO total overall reaction.
(4) formation of emulsion: continue to add metering water and neutralizing agent in system, be stirred to end.
Catalyzer described in step (2) and (3) is at least one in dibutyl tin laurate, stannous octoate;
Active termination agent described in step (2) is at least one in Hydroxyethyl acrylate (HEA), hydroxyethyl methylacrylate (HEMA), Propylene glycol monoacrylate (HPA), Rocryl 410 (HPMA), pentaerythritol triacrylate (PETA);
Stopper described in step (2) is at least one in Resorcinol, p methoxy phenol;
Described in step (4), neutralizing agent is triethylamine;
Polyether Glycols molecular weight described in step (4) can be 400g/mol, 600g/mol, 1000g/mol and 2000g/mol;
The invention has the beneficial effects as follows: by above reaction, synthesis obtains health environment-friendly UV solidified plant oil acidic group aqueous polyurethane coating.This resin can be used for the environment that nail varnish, woodenware and jewellery etc. have higher health requirements.
Embodiment
Embodiment 1
(1) 11.61g hexamethylene diisocyanate (HDI) tripolymer, 0.1g dibutyl tin laurate (DBTDL), 0.05g4-methoxyphenol (MEHQ) and 5ml acetone are added be equipped with in the dry four-hole boiling flask of agitator, prolong, constant pressure funnel and nitrogen conduit; stirring at room temperature is even; logical nitrogen protection; progressively be warming up to 50 DEG C; controlling to drip speed with constant pressure funnel is 1 second/; dropwise drip 5.96gPETA; reaction 3h, terminates when NCO content in system reaches the reaction of the theoretical value the first step.
(2) after the first step terminates, raise system temperature to 65 DEG C continue with 2-3 second/speed of dripping dropwise drips 5.97g ricinolic acid, reaction 2.5h, simultaneously free in titration system-NCO content, after reaching theoretical value, allows system ice bath speed be chilled to room temperature.
(3) system is transferred to another constant pressure funnel; separately get one with agitator; it is 400g/mol polyoxyethylene glycol and 0.1g dibutyl tin laurate (DBTDL) that the four-hole bottle of prolong adds 4g molecular weight; and the product cooled before adding under the protection of nitrogen; reaction 3-4h, complete to NCO reaction.
(4) the 3rd product is cooled to room temperature, adjustment rotating speed is 1000rpm, metering 2.02g triethylamine (TEA) neutralization reaction 1h is added under high-speed stirring, then with 2-3 second/speed of dripping drips 41.3g deionized water emulsification 45min, leave standstill froth breaking, obtain dumbbell shaped aqueous polyurethane emulsion.
Claims (1)
1. a preparation method for Viscotrol C acidic group UV curable water-borne resin, its characterization step is:
(1) ricinolic acid polyester diol is warming up to 80-100 DEG C, vacuum hydro-extraction process 30min, obtains the polyester diol after dewatering and ricinolic acid
(2) synthesis of NCO half end capped polyesters type prepolymer: catalyzer, active termination agent, stopper and hexamethylene diisocyanate (HDI) tripolymer are added in 250ml four-hole boiling flask temperature is risen to 47-50 DEG C, react 2-3 hour when NCO reaches theoretical value, obtain just aggressiveness; Controlled by first mer temperature, at 75 DEG C, to add ricinolic acid, whole process acetone hierarchy of control viscosity also leads to nitrogen protection again, react 3 hours after NCO reaches theoretical value, stopped reaction, cools system rapidly with ice-water bath, and seals up for safekeeping stand-by with clean dropping funnel;
(3) synthesis of dumbbell structure prepolymer: separately get the clean four-hole bottle of 250ml, add polyether Glycols and catalyzer, second step product is slowly added drop-wise in four-hole bottle, terminate to NCO total overall reaction;
(4) formation of emulsion: continue to add water and neutralizing agent in system, be stirred to end.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510945203.2A CN105348487B (en) | 2015-12-16 | 2015-12-16 | A kind of preparation method of castor oil acidic group UV curable water-borne resins |
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|---|---|---|---|
| CN201510945203.2A CN105348487B (en) | 2015-12-16 | 2015-12-16 | A kind of preparation method of castor oil acidic group UV curable water-borne resins |
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| CN105348487A true CN105348487A (en) | 2016-02-24 |
| CN105348487B CN105348487B (en) | 2018-03-20 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105801791A (en) * | 2016-03-22 | 2016-07-27 | 华南农业大学 | Castor oil-based UV-cured polyurethane acrylate and preparation method and application thereof |
| CN106147587A (en) * | 2016-07-12 | 2016-11-23 | 叶有国 | A kind of antimicrobial UV coating containing castor oil-base and its preparation method and application |
| CN106189803A (en) * | 2016-07-12 | 2016-12-07 | 叶有国 | A kind of fingerprint recognition coating and its preparation method and application |
| CN106821796A (en) * | 2016-12-08 | 2017-06-13 | 宝鸡文理学院 | A kind of preparation method of the water-borne UV-curing Environmental-friendnail nail enamel of bio-based |
| CN108236597A (en) * | 2016-12-23 | 2018-07-03 | 张家港康得新光电材料有限公司 | Water-based nail polish |
| CN108912302A (en) * | 2018-05-25 | 2018-11-30 | 南京工业大学 | Waterborne polyurethane and preparation method and application thereof |
| CN109942781A (en) * | 2019-04-01 | 2019-06-28 | 东北林业大学 | A kind of UV solidification castor oil-base aqueous polyurethane dispersion and the preparation method and application thereof |
| CN111040105A (en) * | 2019-12-30 | 2020-04-21 | 珠海华大浩宏化工有限公司 | Soft fluorine-free waterproof agent and preparation method thereof |
| CN113354769A (en) * | 2021-06-07 | 2021-09-07 | 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 |
| CN115716905A (en) * | 2022-11-15 | 2023-02-28 | 广州集泰化工股份有限公司 | Multifunctional bio-based water-based acrylate and preparation method and application thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105801791A (en) * | 2016-03-22 | 2016-07-27 | 华南农业大学 | Castor oil-based UV-cured polyurethane acrylate and preparation method and application thereof |
| CN106147587A (en) * | 2016-07-12 | 2016-11-23 | 叶有国 | A kind of antimicrobial UV coating containing castor oil-base and its preparation method and application |
| CN106189803A (en) * | 2016-07-12 | 2016-12-07 | 叶有国 | A kind of fingerprint recognition coating 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 |
| CN106821796A (en) * | 2016-12-08 | 2017-06-13 | 宝鸡文理学院 | A kind of preparation method of the water-borne UV-curing Environmental-friendnail nail enamel of bio-based |
| CN108236597A (en) * | 2016-12-23 | 2018-07-03 | 张家港康得新光电材料有限公司 | Water-based nail polish |
| CN108912302A (en) * | 2018-05-25 | 2018-11-30 | 南京工业大学 | Waterborne polyurethane and preparation method and application thereof |
| CN109942781A (en) * | 2019-04-01 | 2019-06-28 | 东北林业大学 | A kind of UV solidification castor oil-base aqueous polyurethane dispersion and the preparation method and application thereof |
| CN111040105A (en) * | 2019-12-30 | 2020-04-21 | 珠海华大浩宏化工有限公司 | Soft fluorine-free waterproof agent and preparation method thereof |
| CN113354769A (en) * | 2021-06-07 | 2021-09-07 | 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 |
| CN115716905A (en) * | 2022-11-15 | 2023-02-28 | 广州集泰化工股份有限公司 | Multifunctional bio-based water-based acrylate and preparation method and application thereof |
| CN115716905B (en) * | 2022-11-15 | 2024-07-23 | 广州集泰化工股份有限公司 | Multifunctional bio-based aqueous acrylic ester and preparation method and application thereof |
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| CN105348487B (en) | 2018-03-20 |
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