CN101302416A - Synthetic method of aqueous polyurethane adhesive - Google Patents
Synthetic method of aqueous polyurethane adhesive Download PDFInfo
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- CN101302416A CN101302416A CNA200810055356XA CN200810055356A CN101302416A CN 101302416 A CN101302416 A CN 101302416A CN A200810055356X A CNA200810055356X A CN A200810055356XA CN 200810055356 A CN200810055356 A CN 200810055356A CN 101302416 A CN101302416 A CN 101302416A
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Abstract
The invention relates to a method for synthesizing aqueous polyurethane adhesives. The method is as follows: firstly, monomer polymer, castor oil, polyester glycol and initiator are uniformly mixed, and modified polyester glycol is prepared after heating reaction and decompression; secondly, the modified polyester glycol is uniformly mixed with acetone, dimethylol propionic acid, diphenylmethane vulcabond and aliphatic vulcabond; after the mixture is heated to the acetone reflux temperature and reacted for 2 to 4 hours, micromolecular glycol is added; reaction is continued at the acetone reflux temperature; after the temperature is reduced to the room temperature, triethyl ammonia is added into the mixture to neutralize the dimethylol propionic acid; after the mixture is stirred for 10 to 30 minutes at the room temperature, deionized water and ethylenediamine are added; after the mixture is strongly stirred for 30 to 60 minutes, the mixture is heated to the acetone reflux temperature for reaction, and the product is obtained after temperature rise, decompression and acetone removal. The product prepared has the advantages of high initial bonding strength and good water resistance.
Description
Technical field
The invention belongs to a kind of method of synthetic water-based polyurethane adhesive, what be specifically related to is polyester glycol, the small molecules glycol prepared in reaction water-based polyurethane adhesive of using isocyanic ester and modification.
Technical background
Aqueous polyurethane is a kind of macromolecular material of excellent property, have solvent-free, no stink, pollution-free, do not fire, performance controllability such as its soft durometer reaches well and the easy blending of other polymkeric substance especially emulsion polymer, helps advantages such as modification.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 aqueous polyurethane has accounted for significant proportion in tackiness agent, also existing some problems needs to solve:
1. in water-based polyurethane adhesive, the use of expensive aliphatic isocyanates has improved the production cost of tackiness agent.
2. when the preparation water-based polyurethane adhesive, the use that contains the hydrophilic radical compound has reduced the water tolerance of tackiness agent, has shortened work-ing life.
3, the high reactivity of aromatic isocyanate has caused water-based polyurethane adhesive preparation technology's complicacy, has limited its extensive popularization in industry and life.
Though the preparation water-based polyurethane adhesive has become traditional, a fixed pattern, the effort that people seek modified aqueous adhesion agent of polyurethane never stopped, and this also becomes one of direction of polyurethane adhesive industry Future Development.
In general, the performance that improves water-based polyurethane adhesive generally adopts the method for improving raw material.People such as Murat, Furukawa and Kim have the particular polyesters polyvalent alcohol of ethyl or methyl comes modified aqueous adhesion agent of polyurethane as raw material performance by preparation.People such as Yoon have reported a kind of water-based polyurethane adhesive, and they adopt the polyacrylonitrile-butadienecopolymer of hydroxyl terminated poly-butadiene and modification to make feedstock production high bond strength and water-proof aqueous adhesive.But these method of modifying are difficult to be used aborning because cost is higher.
At present, adopt vinyl polymer or epoxy compounds also to become the research focus as the method for properties-correcting agent, its preparation technology is simple, operational safety, and its cost is lower.People such as Guo Junjie adopt Resins, epoxy to carry out modification, have prepared the tackiness agent that has than strong cohesive property energy and stripping strength.People such as Hirose and Masakazu adopts acrylate monomer to pass through the polymeric modification aqueous polyurethane respectively, obtains result of study preferably., above-mentioned these method of modifying all inevitably with unreacted properties-correcting agent monomer residue in aqueous polyurethane, the existence of unreacted monomer causes the reduction of final performance, simultaneously contaminate environment.
Summary of the invention
The purpose of this invention is to provide a kind of pollution-free, initial adhesive strength height, the preparation method of the water-based polyurethane adhesive of water-tolerant.
Preparation method of the present invention is as follows:
(1) under stirring at room, polymerization single polymerization monomer, Viscotrol C, polyester glycol and initiator Diisopropyl azodicarboxylate are mixed, behind 80～150 ℃ of reaction 5～10h, decompression makes the polyester glycol of modification;
(2) acetone, dimethylol propionic acid (DMPA), '-diphenylmethane diisocyanate and aliphatic isocyanates are added simultaneously in the polyester glycol of modification and mix; Mix post-heating to the acetone reflux temperature, under refluxad react 2～4h after, add the small molecules glycol, 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, drip quadrol simultaneously, behind stirring 10～30min, be heated to acetone reflux temperature reaction 30～60min, after reaction finished, the decompression that heats up removed acetone and promptly gets product;
The mass ratio of described polymerization single polymerization monomer and polyester glycol is 1～5: 10, and the mass ratio of Viscotrol C and polyester glycol is 1～5: 100, and the mass ratio of Diisopropyl azodicarboxylate and polymerization single polymerization monomer is 0.1～10: 100; Polyester glycol and dimethylol propionic acid (DMPA) mol ratio is 1: 1.5～3, the mol ratio of '-diphenylmethane diisocyanate and aliphatic isocyanates is 1: 1～3, the isocyanic ester total mole number is 1.5～5: 1 with polyester glycol and dimethylol propionic acid total mole number ratio, the acetone add-on is '-diphenylmethane diisocyanate and aliphatic isocyanates and DMPA and polyester glycol total mole number 5～10 times, the total mole number of small molecules two pure and mild quadrols is 33～80: 100 with isocyanic ester total mole number ratio, the mol ratio of small molecules glycol and quadrol is 1～10: 1, and the add-on of deionized water is 1000～1300 times of polyester glycol mole number.
Polymerization single polymerization monomer is vinylbenzene, vinyl cyanide, methyl acrylate, methyl methacrylate etc. as mentioned above.
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. as mentioned above.
Aforesaid aliphatic isocyanates comprises isophorone diisocyanate (IPDI), dicyclohexyl methane diisocyanate (H
12MDI), hexamethylene diisocyanate (HDI), tetramethyl-benzene dimethyl vulcabond (TXMDI) etc.
The small molecules glycol is ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol or glycol ether etc. as mentioned above.
Advantage of the present invention:
The present invention introduces reaction system by rational reaction process with the polyester glycol of modification, utilizes characteristics such as the high mechanical strength of modified poly ester glycol and enhanced water resistance, has improved product performance, has reduced raw materials cost.
The present invention utilizes the polyester glycol of modification to prepare water-based polyurethane adhesive.This be a green, cleaning, the production route of water-based polyurethane adhesive efficiently, method is simple, product initial adhesive strength height, water-tolerant.
Embodiment
Embodiment one
Under stirring at room, vinylbenzene, Viscotrol C, poly adipate succinic acid ester (molecular weight 2000) and initiator Diisopropyl azodicarboxylate are mixed, the mass ratio of vinylbenzene and polyester glycol is 1: 8, the mass ratio of Viscotrol C and polyester glycol is 1: 100, the mass ratio of Diisopropyl azodicarboxylate and polymerization single polymerization monomer is 0.1: 100, behind 80 ℃ of reaction 10h, decompression makes the polyester glycol of polystyrene modification;
The 0.02mol poly adipate succinic acid ester that will contain the polystyrene modification joins in the three-necked flask that fills 0.04mol DMPA and 0.9mol acetone; Add 0.05molMDI and 0.07mol IPDI under the stirring at room; Be heated to the acetone reflux temperature, behind the reaction 3h, add 0.048mol1, ammediol; Continue reaction 2h, after reduce to room temperature, add in the 0.04mol triethylamine and carboxyl; Behind the 20min, drip 20mol deionized water and 0.012mol quadrol under the violent stirring; After dripping off continuation violent stirring 10min, be heated to acetone reflux temperature reaction 30min.At last, decompression removes acetone and promptly gets the water-based polyurethane adhesive that viscosity is 700mPa.s.
Embodiment two
Under stirring at room, vinylbenzene, Viscotrol C, polypropylene adipate (PPA) (molecular weight 2000) and initiator Diisopropyl azodicarboxylate are mixed, the mass ratio of vinylbenzene and polyester glycol is 5: 8, the mass ratio of Viscotrol C and polyester glycol is 5: 100, the mass ratio of Diisopropyl azodicarboxylate and polymerization single polymerization monomer is 1: 100, behind 130 ℃ of reaction 8h, decompression makes the polyester glycol of polystyrene modification;
The 0.02mol polypropylene adipate (PPA) that will contain the polystyrene modification joins in the three-necked flask that fills 0.03mol DMPA and 0.9mol acetone; Add 0.03molMDI under the stirring at room, 0.09mol HDI and 0.9mol solvent acetone; Be heated to the acetone reflux temperature, behind the reaction 2h, add 0.052mol ethylene glycol; After continuing reaction 2 under the reflux temperature of acetone, reduce to room temperature, add in the 0.03mol triethylamine and carboxyl, after stirring 30min under the room temperature, drip the 10mol deionized water, drip the 0.018mol quadrol simultaneously, behind the violent stirring 20min, be heated to acetone reflux temperature reaction 40min.After the decompression that heats up removed acetone, getting viscosity was the water-based polyurethane adhesive of 800mPa.s.
Embodiment three
Under stirring at room, vinylbenzene, vinyl cyanide, Viscotrol C, poly-hexanodioic acid hexylene glycol ester (molecular weight 2000) and initiator Diisopropyl azodicarboxylate are mixed, the total mass of vinylbenzene and vinyl cyanide and the mass ratio of polyester glycol are 5: 8, the mass ratio of Viscotrol C and polyester glycol is 2: 100, the mass ratio of Diisopropyl azodicarboxylate and polymerization single polymerization monomer is 5: 100, behind 100 ℃ of reaction 10h, decompression makes the polyester glycol of polystyrene-vinyl cyanide modification;
To contain the poly-hexanodioic acid hexylene glycol ester of 0.02mol of polystyrene-vinyl cyanide modification, join in the three-necked flask that fills 0.06mol DMPA and 1.5mol acetone; Add 0.06mol MDI and 0.06mol H under the stirring at room
12MDI; Be heated to the acetone reflux temperature, behind the reaction 4h, add 0.028mol 1, the 4-butyleneglycol; After continuing reaction 3h under the reflux temperature of acetone, reduce to room temperature, add in the 0.06mol triethylamine and carboxyl; After stirring 5min under the room temperature, drip the 13mol deionized water, drip the 0.012mol quadrol simultaneously, behind the violent stirring 30min, be heated to acetone reflux temperature reaction 60min.At last, decompression removes acetone and promptly gets the water-based polyurethane adhesive that viscosity is 900mPa.s.
Embodiment four
Under stirring at room, methyl acrylate, Viscotrol C, polycaprolactone (molecular weight 2000) and initiator Diisopropyl azodicarboxylate are mixed, the mass ratio of methyl acrylate and polyester glycol is 3: 8, the mass ratio of Viscotrol C and polyester glycol is 5: 100, the mass ratio of Diisopropyl azodicarboxylate and polymerization single polymerization monomer is 3: 100, behind 90 ℃ of reaction 9h, decompression makes the polyester glycol of polymethyl acrylate modification;
The 0.02mol polycaprolactone that will contain the polymethyl acrylate modification joins in the three-necked flask that fills 0.06mol DMPA and 1.28mol acetone; Add 0.05mol MDI and 0.07mol IPDI under the stirring at room; Be heated to the acetone reflux temperature, behind the reaction 3h, add 0.022mol 1, the 4-butyleneglycol; After continuing reaction 4h under the reflux temperature of acetone, reduce to room temperature, add in the 0.06mol triethylamine and carboxyl; After stirring 10min under the room temperature, drip the 12mol deionized water, drip the 0.018mol quadrol simultaneously, behind the violent stirring 10min, be heated to acetone reflux temperature reaction 50min.At last, decompression removes acetone promptly to get viscosity is the 850mPa.s water-based polyurethane adhesive.
Embodiment five
Under stirring at room, vinylbenzene, Viscotrol C, poly adipate succinic acid ester (molecular weight 2000) and initiator Diisopropyl azodicarboxylate are mixed, the mass ratio of vinylbenzene and polyester glycol is 1: 10, the mass ratio of Viscotrol C and polyester glycol is 1: 100, the mass ratio of Diisopropyl azodicarboxylate and polymerization single polymerization monomer is 10: 100, behind 150 ℃ of reaction 5h, decompression makes the polyester glycol of polystyrene modification;
The 0.01mol poly adipate succinic acid ester that will contain the polystyrene modification joins in the three-necked flask that fills 0.05mol DMPA and 1.5mol acetone; Add 0.03molMDI and 0.09mol HDI under the stirring at room; Be heated to the acetone reflux temperature, behind the reaction 2h, add 0.042mol1, the 4-hexylene glycol; 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 quadrol simultaneously, behind the violent stirring 20min, be heated to acetone reflux temperature reaction 40min.At last, decompression removes acetone promptly to get viscosity is the 500mPa.s water-based polyurethane adhesive.
Embodiment six
Under stirring at room, vinylbenzene, Viscotrol C, poly adipate succinic acid ester (molecular weight 2000) and initiator Diisopropyl azodicarboxylate are mixed, the mass ratio of vinylbenzene and polyester glycol is 5: 10, the mass ratio of Viscotrol C and polyester glycol is 5: 100, the mass ratio of Diisopropyl azodicarboxylate and polymerization single polymerization monomer is 4: 100, behind 140 ℃ of reaction 7h, decompression makes the polyester glycol of polystyrene modification;
The 0.03mol poly adipate succinic acid ester that will contain the polystyrene modification joins in the three-necked flask that fills 0.05mol DMPA and 1.5mol acetone; Add 0.03molMDI and 0.09mol TXMDI under the stirring at room; Be heated to the acetone reflux temperature, behind the reaction 2h, add 0.022mol 1, 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 12mol deionized water, drip the 0.018mol quadrol simultaneously, behind the violent stirring 20min, be heated to acetone reflux temperature reaction 50min.At last, decompression removes acetone promptly to get viscosity is the 1100mPa.s water-based polyurethane adhesive.
Claims (5)
1, a kind of synthetic method of water-based polyurethane adhesive is characterized in that comprising the steps:
(1) under stirring at room, polymerization single polymerization monomer, Viscotrol C, polyester glycol and initiator Diisopropyl azodicarboxylate are mixed, behind 80～150 ℃ of reaction 5～10h, decompression makes the polyester glycol of modification;
(2) acetone, dimethylol propionic acid (DMPA), '-diphenylmethane diisocyanate and aliphatic isocyanates are added simultaneously in the polyester glycol of modification and mix; Mix post-heating to the acetone reflux temperature, under refluxad react 2～4h after, add the small molecules glycol, 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, drip quadrol simultaneously, behind stirring 10～30min, be heated to acetone reflux temperature reaction 30～60min, after reaction finished, the decompression that heats up removed acetone and promptly gets product;
The mass ratio of described polymerization single polymerization monomer and polyester glycol is 1～5: 10, and the mass ratio of Viscotrol C and polyester glycol is 1～5: 100, and the mass ratio of Diisopropyl azodicarboxylate and polymerization single polymerization monomer is 0.1～10: 100; Polyester glycol and dimethylol propionic acid (DMPA) mol ratio is 1: 1.5～3, the mol ratio of '-diphenylmethane diisocyanate and aliphatic isocyanates is 1: 1～3, the isocyanic ester total mole number is 1.5～5: 1 with polyester glycol and dimethylol propionic acid total mole number ratio, the acetone add-on is '-diphenylmethane diisocyanate and aliphatic isocyanates and DMPA and polyester glycol total mole number 5～10 times, the total mole number of small molecules two pure and mild quadrols is 33～80: 100 with isocyanic ester total mole number ratio, the mol ratio of small molecules glycol and quadrol is 1～10: 1, and the add-on of deionized water is 1000～1300 times of polyester glycol mole number.
2, the synthetic method of a kind of water-based polyurethane adhesive as claimed in claim 1 is characterized in that described polymerization single polymerization monomer is vinylbenzene, vinyl cyanide, methyl acrylate or methyl methacrylate.
3, the synthetic method of a kind of water-based polyurethane adhesive 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.
4, the synthetic method of a kind of water-based polyurethane adhesive as claimed in claim 1 is characterized in that described aliphatic isocyanates is isophorone diisocyanate, dicyclohexyl methane diisocyanate, hexamethylene diisocyanate or tetramethyl-benzene dimethyl vulcabond.
5, the synthetic method of a kind of water-based polyurethane adhesive as claimed in claim 1 is characterized in that described small molecules glycol is ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol or glycol ether.
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| CN200810055356XA CN101302416B (en) | 2008-07-04 | 2008-07-04 | Synthetic method of aqueous polyurethane adhesive |
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| CN200810055356XA CN101302416B (en) | 2008-07-04 | 2008-07-04 | Synthetic method of aqueous polyurethane adhesive |
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| CN101302416B CN101302416B (en) | 2011-12-14 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101962524A (en) * | 2010-09-29 | 2011-02-02 | 江苏力合粘合剂有限公司 | Waterborne polyurethane adhesive and preparation method thereof |
| CN101736278B (en) * | 2008-11-21 | 2011-06-22 | 北京有色金属研究总院 | Method for preparing compound powder used for hot spraying |
| CN102336881A (en) * | 2011-07-08 | 2012-02-01 | 华南理工大学 | Polyurethane ionic polymer and preparation method of dispersoid adhesive thereof |
| CN105367743A (en) * | 2015-12-21 | 2016-03-02 | 中国科学院山西煤炭化学研究所 | Synthetic method of waterborne polyurethane emulsion |
| CN106589291A (en) * | 2016-12-29 | 2017-04-26 | 合众（佛山）化工有限公司 | Castor oil terminated polyurethane water-based ink resin and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1189527C (en) * | 2002-12-30 | 2005-02-16 | 华南理工大学 | Polyurethane water dispersion and its preparing method |
| CN1218981C (en) * | 2003-03-06 | 2005-09-14 | 华南理工大学 | Acrylic polyurethane copolymer emulsion, its preparation method and use |
-
2008
- 2008-07-04 CN CN200810055356XA patent/CN101302416B/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101736278B (en) * | 2008-11-21 | 2011-06-22 | 北京有色金属研究总院 | Method for preparing compound powder used for hot spraying |
| CN101962524A (en) * | 2010-09-29 | 2011-02-02 | 江苏力合粘合剂有限公司 | Waterborne polyurethane adhesive and preparation method thereof |
| CN102336881A (en) * | 2011-07-08 | 2012-02-01 | 华南理工大学 | Polyurethane ionic polymer and preparation method of dispersoid adhesive thereof |
| CN105367743A (en) * | 2015-12-21 | 2016-03-02 | 中国科学院山西煤炭化学研究所 | Synthetic method of waterborne polyurethane emulsion |
| CN105367743B (en) * | 2015-12-21 | 2018-01-23 | 中国科学院山西煤炭化学研究所 | A kind of synthetic method of aqueous polyurethane emulsion |
| CN106589291A (en) * | 2016-12-29 | 2017-04-26 | 合众（佛山）化工有限公司 | Castor oil terminated polyurethane water-based ink resin and preparation method thereof |
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| CN101302416B (en) | 2011-12-14 |
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