CN100528925C - Method for preparing dispersion liquid of aqueous polyurethane of diphenyl methane diisocyanate - Google Patents
Method for preparing dispersion liquid of aqueous polyurethane of diphenyl methane diisocyanate Download PDFInfo
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- CN100528925C CN100528925C CNB2006101023129A CN200610102312A CN100528925C CN 100528925 C CN100528925 C CN 100528925C CN B2006101023129 A CNB2006101023129 A CN B2006101023129A CN 200610102312 A CN200610102312 A CN 200610102312A CN 100528925 C CN100528925 C CN 100528925C
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Abstract
This invention relates to a method for preparing diphenylmethane diisocyanate-based aqueous polyurethane dispersion. The method comprises: (1) adding polyester diol, polyether diol or polycarbonate diol, and dihydroxymethyl propionic acid into a reactor; (2) adding diphenylmethane diisocyanate and inert isocyanate at room temperature under stirring; (3) adding acetone, heating to the refluxing temperature of acetone, and reacting; (4) adding 1,4-butylene glycol, and reacting at the refluxing temperature; (5) cooling to room temperature, adding triethylamine and dihydroxymethyl propionic acid, and stirring at room temperature for 5-30 min; (6) dropping deionized water and piperazine, vigorously stirring for 10-30 min, heating to the refluxing temperature of acetone, reacting, heating, and vacuum-distilling to remove acetone and obtain the product. The product has such advantages as high adhesiveness and high hardness.
Description
Technical field
The invention belongs to a kind of method of synthetic dispersion liquid, what be specifically related to is to prepare aqueous polyurethane dispersing liquid with '-diphenylmethane diisocyanate (MDI), inertia isocyanic ester and polyol reaction.
Technical background
The product of organic solvent type polyurethane (PU) preparation is a kind of macromolecular material of excellent property, has wear-resisting wiping, chemicals-resistant, low temperature resistant, flexibility reaches performances such as tackiness is good well.It is widely applied to tackiness agent, coating, paper coating, steel rust prevention, hide finishes, fiber or fabric-treating agent, surface treating agent for glass etc., wherein is most widely used at tackiness agent and paint field.Though the organic solvent type polyurethane accounts for the principal status of public economy always, also existing some problems needs to solve:
1. organic solvent itself has bigger toxicity, and respiratory organs, skin, the eyes to the people have strong impulse in process of production, even the causing death.
2. meeting residual organic solvent in the product of organic solvent type polyurethane preparation bring serious consequence in use can for the mankind and environment.
The use of 3 organic solvents causes the cost of polyurethane products higher, has limited its extensive popularization in industry and life.
Though utilize organic solvent to prepare polyurethane products as dispersion medium, become traditional, a fixed pattern, but people seek the aqueous dispersion medium surrogate comes the effort of synthesis of polyurethane never to stop, and this also becomes one of direction of polyurethane industrial Future Development.Aqueous polyurethane not only has the excellent properties of urethane, and have do not fire, nontoxic, pollution-free, save advantage such as the energy.It is to be the urethane of dispersion medium with water, and its preparation technology is simple, operational safety, and its range of application relates to fields such as tackiness agent, coating, steel rust prevention, hide finishes, fiber or fabric-treating agent gradually.
In this field, carried out a large amount of work abroad, proposed to utilize the thinking of water compositing dispersion medium and obtained good progress.Nineteen forty-three, West German P.Schlack has successfully prepared aqueous polyurethane first, and aqueous polyurethane was realized industrialization first in 1967, and Bayer company took the lead in aqueous polyurethane as hide finishes in 1972.Through the effort in more than 60 years, aqueous polyurethane began to become important commodity.Usually the isocyanic ester that adopts mostly is aliphatic category, as isophorone diisocyanate (IPDI), dicyclohexyl methane diisocyanate (H
12MDI), hexamethylene diisocyanate (HDI), tetramethyl-benzene dimethyl vulcabond (TXMDI) etc.At present, these isocyanic ester mostly are external import, the price comparison costliness.And aromatic isocyanate class aqueous polyurethane is tolylene diisocyanate (TDI) series substantially, and uses the low side field that mainly concentrates on.If adopt '-diphenylmethane diisocyanate (MDI) to make raw material, its polyurethane product has higher mechanical properties.But because the NCO radical reaction activity of MDI is higher, when its performed polymer disperseed in water, Yi Yushui reacted and influences the stability of system.At present, Bum Soo Kim reports that in Journal of Applied Polymer Science (2005) adopting '-diphenylmethane diisocyanate (MDI) is the feedstock production aqueous polyurethane dispersing liquid, and adopt hydroxy-end cappedly, avoid NCO group and the water of MDI to react.But adopt hydroxy-end capped aqueous polyurethane dispersing liquid when preparation tackiness agent and coating, can cause shortcomings such as cohesive strength is low, hardness is little.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of cohesive strength height, dispersion liquid of aqueous polyurethane of diphenyl methane diisocyanate that hardness is big
Preparation method of the present invention is as follows:
(1) with polyester glycol, polyether glycol or polycarbonate diol and dimethylol propionic acid (DMPA) 1: 5 in molar ratio～1: 2, optimum mole ratio 1: 3, join in the reactor, under stirring at room, add '-diphenylmethane diisocyanate and inertia isocyanic ester, add solvent acetone.
(2) be heated to the acetone reflux temperature, behind reaction 2～4h, by 1, the mole number of 4-butyleneglycol is that 60～80% of unreacted NCO group amount adds 1, the 4-butyleneglycol, after continuing reaction 2～4h under the reflux temperature of acetone, reduce to room temperature, add in the triethylamine and dimethylol propionic acid, stir 5～30min under the room temperature after, drip deionized water, its add-on is polyester glycol, polyether glycol or polycarbonate diol mole number 1000～1300 times; Mole number piperazines such as dropping and free NCO behind violent stirring 10～30min, are heated to acetone reflux temperature reaction 5～30min simultaneously.After reaction finished, the decompression that heats up removed acetone and promptly gets product.
Described '-diphenylmethane diisocyanate: the mol ratio of inertia isocyanic ester is 1: 3～1: 1, the total mole number of '-diphenylmethane diisocyanate and inertia isocyanic ester and polyester glycol, polyether glycol or polycarbonate diol and dimethylol propionic acid total mole number ratio are 2: 1～4: 1, and the acetone add-on is '-diphenylmethane diisocyanate and inertia isocyanic ester and DMPA and polyester glycol, polyether glycol or polycarbonate diol total mole number 5～10 times.
Aforesaid polyester glycol is poly-hexanodioic acid hexylene glycol ester, poly adipate succinic acid ester, polyethylene glycol adipate, poly-hexanodioic acid uncle pentadiol ester, polycaprolactone etc.Polyether Glycols is polyoxypropyleneglycol, polypropylene glycol, polyglycol ether, polyoxy fourth-oxygen ethyleneether, PTMG etc.Polycarbonate diol is poly-carbonic acid hexylene glycol ester, polytetramethylene carbonate diol etc.
Aforesaid inertia isocyanic ester comprises isophorone diisocyanate (IPDI), dicyclohexyl methane diisocyanate (H
12MDI), hexamethylene diisocyanate (HDI), tetramethyl-benzene dimethyl vulcabond (TXMDI) etc.React with water when part uses this kind isocyanate can avoid a large amount of MDI water-dispersion in the reaction, influence the stability of dispersion liquid.
Advantage of the present invention:
The present invention introduces reaction system by rational reaction process with MDI, utilizes the torpescence NCO group of inertia isocyanic ester, the product unstable of having avoided the MDI high reactivity to cause.Improve product performance simultaneously, reduced raw materials cost.
The present invention utilizes MDI and inert isocyanic ester to prepare MDI base water polyurethane dispersion liquid.This be a green, cleaning, the production route of aqueous polyurethane dispersing liquid efficiently, method is simple, product cohesive strength height, hardness are big.
Embodiment
Embodiment one
0.01mol poly adipate succinic acid ester (molecular weight 2000) and 0.05mol DMPA are joined in the three-necked flask; Add 0.03mol MDI, 0.09mol HDI and 0.9mol solvent acetone under the stirring at room; Be heated to the acetone reflux temperature, behind the reaction 2h, add 0.042mol1, the 4-butyleneglycol; After continuing reaction 2 under the reflux temperature of acetone, reduce to room temperature, add in the 0.05mol triethylamine and carboxyl, after stirring 30min under the room temperature, drip the 10mol deionized water, drip the 0.018mol piperazine simultaneously, behind the violent stirring 10min, be heated to acetone reflux temperature reaction 5min.After reaction finished, the decompression that heats up removed acetone and promptly gets product.Gained aqueous polyurethane viscosity 1500mPa.s, and the stable emulsion that is translucent.
Embodiment two
Poly-hexanodioic acid hexylene glycol ester (molecular weight 2000) of 0.01mol and 0.02mol DMPA are joined in the three-necked flask; Add 0.06mol MDI, 0.06mol H under the stirring at room
12MDI and 1.5mol solvent acetone; Be heated to the acetone reflux temperature, behind the reaction 4h, add 0.072mol1, the 4-butyleneglycol; After continuing reaction 3h under the reflux temperature of acetone, reduce to room temperature, add in the 0.02mol triethylamine and carboxyl; After stirring 5min under the room temperature, drip the 13mol deionized water, drip piperazine (its mole number equates with free NCO amount) simultaneously, behind the violent stirring 30min, be heated to acetone reflux temperature reaction 20min.After reaction finished, the decompression that heats up removed acetone and promptly gets product.Gained aqueous polyurethane viscosity 80mPa.s, and the unstable emulsion that is white in color.
Embodiment three
0.01mol PTMG (molecular weight 2000) and 0.03mol dimethylol propionic acid are joined in the three-necked flask; Add 0.05mol MDI, 0.07molIPDI and 1.28mol acetone under the stirring at room; Be heated to the acetone reflux temperature, behind the reaction 3h, add 0.056mol 1, the 4-butyleneglycol; After continuing reaction 4h under the reflux temperature of acetone, reduce to room temperature, add in the 0.03mol triethylamine and carboxyl; After stirring 10min under the room temperature, drip the 12mol deionized water, drip the 0.024mol piperazine simultaneously, behind the violent stirring 30min, be heated to acetone reflux temperature reaction 30min.After reaction finished, the decompression that heats up removed acetone and promptly gets product.Gained aqueous polyurethane viscosity 600mPa.s, the stable emulsion that is translucent.
Embodiment four
0.02mol poly adipate succinic acid ester (molecular weight 2000) and 0.04mol DMPA are joined in the three-necked flask; Add 0.05mol MDI, 0.07mol IPDI and 0.9mol acetone under the stirring at room; Be heated to the acetone reflux temperature, behind the reaction 3h, add 0.048mol1, the 4-butyleneglycol; After continuing reaction 2h under the reflux temperature of acetone, reduce to room temperature, add in the 0.04mol triethylamine and carboxyl; After stirring 20min under the room temperature, drip the 20mol deionized water, drip the 0.012mol piperazine simultaneously, behind the violent stirring 30min, be heated to acetone reflux temperature reaction 10min.After reaction finished, the decompression that heats up removed acetone and promptly gets product.Gained aqueous polyurethane viscosity 800mPa.s, the stable emulsion that is translucent.
Embodiment five
Poly-hexanodioic acid hexylene glycol ester (molecular weight 2000) of 0.01mol and 0.05mol DMPA are joined in the three-necked flask; Add 0.03mol MDI, 0.09mol HDI and 0.9mol solvent acetone under the stirring at room; Be heated to the acetone reflux temperature, behind the reaction 2h, add 0.042mol1, the 4-butyleneglycol; After continuing reaction 2 under the reflux temperature of acetone, reduce to room temperature, add in the 0.05mol triethylamine and carboxyl, after stirring 30min under the room temperature, drip the 10mol deionized water, drip the 0.018mol piperazine simultaneously, behind the violent stirring 10min, be heated to acetone reflux temperature reaction 5min.After reaction finished, the decompression that heats up removed acetone and promptly gets product.Gained aqueous polyurethane viscosity 2000mPa.s, and the stable emulsion that is translucent.
Embodiment six
0.01mol polycarbonate hexylene glycol (molecular weight 2000) and 0.05mol DMPA are joined in the three-necked flask; Add 0.03mol MDI, 0.09mol TXMDI and 0.9mol solvent acetone under the stirring at room; Be heated to the acetone reflux temperature, behind the reaction 2h, add 0.042mol1, the 4-butyleneglycol; After continuing reaction 2 under the reflux temperature of acetone, reduce to room temperature, add in the 0.05mol triethylamine and carboxyl, after stirring 30min under the room temperature, drip the 10mol deionized water, drip the 0.018mol piperazine simultaneously, behind the violent stirring 10min, be heated to acetone reflux temperature reaction 5min.After reaction finished, the decompression that heats up removed acetone and promptly gets product.Gained aqueous polyurethane viscosity 2500mPa.s, and the stable emulsion that is translucent.
Claims (5)
1, a kind of preparation method of dispersion liquid of aqueous polyurethane of diphenyl methane diisocyanate is characterized in that comprising the steps:
(1) polyester glycol, polyether glycol or polycarbonate diol and dimethylol propionic acid were joined in the reactor in 1: 5 in molar ratio～1: 2, under stirring at room, add '-diphenylmethane diisocyanate and inertia isocyanic ester, add solvent acetone;
(2) be heated to the acetone reflux temperature, behind reaction 2～4h, by 1, the mole number of 4-butyleneglycol is that 60～80% of unreacted NCO group amount adds 1, the 4-butyleneglycol, after continuing reaction 2～4h under the reflux temperature of acetone, reduce to room temperature, add in the triethylamine and dimethylol propionic acid, stir 5～30min under the room temperature after, drip deionized water, its add-on is polyester glycol, polyether glycol or polycarbonate diol mole number 1000～1300 times; Drip the mole number piperazines with free NCO etc. simultaneously, behind violent stirring 10～30min, be heated to acetone reflux temperature reaction 5～30min, after reaction finished, the decompression that heats up removed acetone and promptly gets product;
Described '-diphenylmethane diisocyanate: the mol ratio of inertia isocyanic ester is 1: 3～1: 1, the total mole number of '-diphenylmethane diisocyanate and inertia isocyanic ester and polyester glycol, polyether glycol or polycarbonate diol and dimethylol propionic acid total mole number ratio are 2: 1～4: 1, and the acetone add-on is '-diphenylmethane diisocyanate and inertia isocyanic ester and dimethylol propionic acid and polyester glycol, polyether glycol or polycarbonate diol total mole number 5～10 times;
Described inertia isocyanic ester is isophorone diisocyanate, dicyclohexyl methane diisocyanate, hexamethylene diisocyanate or tetramethyl-benzene dimethyl vulcabond.
2, the preparation method of a kind of dispersion liquid of aqueous polyurethane of diphenyl methane diisocyanate as claimed in claim 1 is characterized in that described polyester glycol is poly-hexanodioic acid hexylene glycol ester, poly adipate succinic acid ester, polyethylene glycol adipate, poly-hexanodioic acid uncle pentadiol ester or polycaprolactone.
3, the preparation method of a kind of dispersion liquid of aqueous polyurethane of diphenyl methane diisocyanate as claimed in claim 1 is characterized in that described polyether Glycols is polyoxypropyleneglycol, polypropylene glycol, polyglycol ether, polyoxy fourth-oxygen ethyleneether or PTMG.
4, the preparation method of a kind of dispersion liquid of aqueous polyurethane of diphenyl methane diisocyanate as claimed in claim 1 is characterized in that described polycarbonate diol is poly-carbonic acid hexylene glycol ester or polytetramethylene carbonate diol.
5, the preparation method of a kind of dispersion liquid of aqueous polyurethane of diphenyl methane diisocyanate as claimed in claim 1, the mol ratio that it is characterized in that described polyester glycol, polyether glycol or polycarbonate diol and dimethylol propionic acid is 1: 3.
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| CNB2006101023129A CN100528925C (en) | 2006-12-20 | 2006-12-20 | Method for preparing dispersion liquid of aqueous polyurethane of diphenyl methane diisocyanate |
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| CNB2006101023129A CN100528925C (en) | 2006-12-20 | 2006-12-20 | Method for preparing dispersion liquid of aqueous polyurethane of diphenyl methane diisocyanate |
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| CN100528925C true CN100528925C (en) | 2009-08-19 |
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| CN101182681B (en) * | 2007-11-08 | 2010-06-09 | 华明扬 | Preparation method of environment-friendly watersoluble polyurethane textile softening agent |
| CN102850539B (en) * | 2007-11-16 | 2014-07-30 | 旭化成化学株式会社 | Polycarbonate diol with ease of reaction stabilization |
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| CN102070768B (en) * | 2010-12-06 | 2012-10-03 | 安徽好思家涂料有限公司 | Water-soluble polyurethane for wood lacquer and preparation method thereof |
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| CN103113555B (en) * | 2013-02-27 | 2016-08-31 | 东莞市克瑞得环保材料有限公司 | A kind of top coat resin processed for corium surface |
| CN104387548B (en) * | 2014-11-19 | 2017-04-05 | 上海华峰新材料研发科技有限公司 | A kind of mirror face synthetic leather non-yellow stain polyurethane resin and preparation method thereof |
| CN108068176B (en) * | 2017-12-26 | 2020-09-08 | 芜湖市长江起重设备制造有限公司 | Preparation method of high-temperature-resistant polycarbonate type waterborne polyurethane-based plywood |
| CN109053989B (en) * | 2018-07-06 | 2019-12-10 | 兰州科天健康科技股份有限公司 | Preparation method of tear-resistant waterborne polyurethane emulsion for medical waterborne polyurethane film |
| CN112143470B (en) * | 2019-06-28 | 2023-02-03 | 中国石油化工股份有限公司 | Plugging material, preparation method thereof and plugging agent |
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| US4870129A (en) * | 1986-09-04 | 1989-09-26 | Bayer Aktiengesellschaft | Adhesive and use of the adhesive for the formation of bonds |
| CN1418900A (en) * | 2002-12-05 | 2003-05-21 | 武汉大学 | Process for preparing water-based polyurethane powder material |
| WO2006009351A1 (en) * | 2004-07-19 | 2006-01-26 | Hosung Chemex Co., Ltd. | Aqueous polyurethane emulsion composition and polyurethane film using the same |
| CN1729222A (en) * | 2002-12-17 | 2006-02-01 | 帝国化学工业公司 | Aqueous dispersions of polyurethane-addition polymer hybrid particles especially for use in coating compositions |
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2006
- 2006-12-20 CN CNB2006101023129A patent/CN100528925C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4870129A (en) * | 1986-09-04 | 1989-09-26 | Bayer Aktiengesellschaft | Adhesive and use of the adhesive for the formation of bonds |
| CN1418900A (en) * | 2002-12-05 | 2003-05-21 | 武汉大学 | Process for preparing water-based polyurethane powder material |
| CN1729222A (en) * | 2002-12-17 | 2006-02-01 | 帝国化学工业公司 | Aqueous dispersions of polyurethane-addition polymer hybrid particles especially for use in coating compositions |
| WO2006009351A1 (en) * | 2004-07-19 | 2006-01-26 | Hosung Chemex Co., Ltd. | Aqueous polyurethane emulsion composition and polyurethane film using the same |
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