CN101497737B - Preparation of aqueous epoxy resin - Google Patents
Preparation of aqueous epoxy resin Download PDFInfo
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- CN101497737B CN101497737B CN2008100306204A CN200810030620A CN101497737B CN 101497737 B CN101497737 B CN 101497737B CN 2008100306204 A CN2008100306204 A CN 2008100306204A CN 200810030620 A CN200810030620 A CN 200810030620A CN 101497737 B CN101497737 B CN 101497737B
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Abstract
The invention provides a preparation method of water-dilutable epoxide resin, comprising two steps as follows: epoxide resin and polyether dihydric alcohol react under the action of Lewis acid catalyst to prepare a reactivity emulsifier which is a polymerized substance with terminal groups of an epoxy group and a hydroxyl group; and then different epoxide resins react with the reactivity emulsifier prepared in the first step to obtain the water-dilutable epoxide resin. The water-dilutable epoxide resin can be applied to the fields of dope, cement enhancement, terrace, and the like through mixing with matched a firming agent and taking water as a diluting agent.
Description
Technical field
The present invention relates to a kind of preparation method of water-dilutable epoxide resin.
Background technology
Resins, epoxy has excellent chemical stability, erosion resistance, good, the physical strength advantages of higher of its gluing performance, thereby use widely in industrial acquisition.In a lot of fields that Resins, epoxy is used; paint field aspect particularly; although Resins, epoxy has the performance of many excellences; but its traditional applying portion is to add organic solvent; thereby be subjected to the challenge of aspects such as environmental pollution, construction safety; particularly along with world economy and science and technology development, the reinforcement of global environmental protection consciousness, national governments more and more pay attention to volatile organic matter in the coating (VOC) and the HAP pollution to environment.The application and development of Resins, epoxy environment-friendly type more and more is subject to people's attention.China has come into effect the water-borne coatings national standard on July 1st, 2004.
Aqueous epoxy resins more and more comes into one's own, and has become popular research direction in recent years.
Aqueous epoxy resins first-generation product is directly to carry out emulsification with emulsifying agent to make emulsion.Its emulsion particle particle is big, and poor stability, emulsifying agent do not participate in curing reaction, and the product water tolerance is relative with mechanical property relatively poor.
S-generation water-borne epoxy systems is to adopt water soluble solid agent oil in water emulsion dissolubility Resins, epoxy.Resin is hydrophobic, and solidifying agent is hydrophilic aminated compounds.Like this, there are very big difference in resin and solidifying agent aspect wetting ability and the hydrophobicity, and solubility parameters mismatches, and the surface is solidified easily, become harder, finally make resin and solidifying agent skewness in the paint film, have influence on the performance of paint film.
The Resins, epoxy of third generation water-borne epoxy systems has connected nonionic surface active agent, and hydrophilic nonionogenic tenside is connected on the resin.Can meet or exceed the paint film property index of solvent based coating by its coatings formulated paint film.The prepared particle of this method is thinner, is generally nano level, and the system stability of preparation improves greatly than first kind, guarantee is provided for the stability and the film performance of product emulsion, is more conducive to the practical application of aqueous epoxy resins.
Learn by literature search, " a kind of aqueous epoxide resin paint and preparation method thereof " patent application (application number is 02137607.7) that the applicant proposed on October 24th, 2002, a kind of preparation method of water-dilutable epoxide resin is provided, and 1. its reactive emulsifier is mixed with the aqueous solution that solid content is 40-50% with water dissolution.Just because of this material has obtained dilution, thus with the reaction process of resin in reaction be difficult to carry out even not reaction.The existence of free emulsifying agent that is to say that this reactive emulsifier reality has only played simple emulsifying agent effect, owing to will have influence on the performance of cured article.2. the add-on of its solvent: the solvent that low-molecular-weight epoxy resin has been added 25～35% weight; The solvent that high molecular expoxy resin has been added 50～60% weight.Solvent ratios is too big, has increased the VOC value.
Summary of the invention
The object of the present invention is to provide a kind of reactive emulsifier and resin reaction can embedded resin in the chain, the relatively low aqueous epoxy resins of VOC value.
A kind of preparation method of water-dilutable epoxide resin provided by the invention comprises 2 steps:
First step: by bisphenol A type epoxy resin with have surface-active polyoxyethylene glycol prepared in reaction under the lewis acid catalyst effect and obtain reactive emulsifier, this reactive emulsifier is the aggretion type material that end group is respectively epoxy group(ing) and hydroxyl;
Second step: the reactive emulsifier reaction that different Resins, epoxy and the first step are made obtains aqueous epoxy resins.
Concrete technical scheme of the present invention is as follows:
(1) bisphenol A type epoxy resin and polyoxyethylene glycol are dissolved under the condition of heating, the mol ratio of bisphenol A type epoxy resin and polyoxyethylene glycol is: 0.90: 1.0～1.20: 1.0, the lewis acid catalyst that adds total mass 0.15%～0.3% again, under 65 ℃～110 ℃, reacted the formation reaction emulsifying agent 1 hour～5 hours;
(2) with bisphenol A type epoxy resin or o-cresol formaldehyde type Resins, epoxy, add dissolution with solvents, the add-on of solvent is 2%～10% of a weight epoxy, adds above-mentioned reactive emulsifier again, and the add-on of reactive emulsifier is 10%～20% of a weight epoxy, 80 ℃～150 ℃ reactions down, realize phase reversion, under agitation condition, add water and carry out emulsification, make the aqueous epoxy resins of different solid contents, the add-on of water is determined according to the product solid content.
Lewis acid catalyst of the present invention is boron trifluoride diethyl etherate or tin tetrachloride.
Solvent of the present invention can adopt alcoholic solvent: phenylcarbinol, phenylethyl alcohol, ethylene glycol or ether solvent: ethylene glycol ethyl ether, butyl glycol ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, propylene glycol butyl ether.
Because the polarity of bisphenol A type epoxy resin and the polarity of water differ greatly, simple water can't be with its emulsification.And the affiliation that adds that adds emulsifying agent remains in the filming after the curing, influences its condensate performance.The present invention introduces nonionic surface active agent by chemical process in the structural chain of bisphenol A type epoxy resin, its hydrophile-lipophile balance value increases, and makes it have good self-emulsifying function.Simultaneously because reactive emulsifier is a non-ionic type, the aqueous dispersion of Xing Chenging has good stability thus, disperses particle diameter little, when being used with aqueous epoxy curing agent, filler and various additive, be subjected to the influence of system acid-basicity less, mixed time limit of service is also longer relatively.
The consumption of reactive emulsifier is too low, and hydrophilic segment is too short in the resin structure, and demulsifying phenomenon takes place the aqueous epoxy resins poor stability that makes easily.The consumption of reactive emulsifier is generally 10%～20% of resin, is 12%～16% preferably.
Solvent plays 3 effects in system, 1. in order to reduce the viscosity of aqueous epoxy resins; 2. in order to increase the intermiscibility of aqueous epoxy resins and water; 3. when curing of coating, help resin particle to evaporate the back and assemble film forming at water.Choice of Solvent is followed 3 principles: 1. polar phase seemingly; 2. similar mixing; 3. nontoxic or toxic side effect is very little, and consumption is less.When selective solvent, except using single solvent, also can use mixed solvent.It is all good when mixed solvent is with the dissolving power of polymkeric substance even than any solvent of independent use sometimes.The viscosity of resin solution determined by the interaction force between various kinds of resin-solvent, also is subjected to the influence of the hydrogen bond between molecular weight, solvent and the molecular resin of non-crimping degree, resin of viscosity, the molecular resin of solvent itself, the hydrogen bond between the solvent molecule etc.The add-on of solvent is generally 2%～10% of Resins, epoxy.
The aqueous epoxy resins of the present invention's preparation is a kind of macromolecular compound of hydrophilic-lipophilic balance; This resin used water is made thinner, by mixing with supporting solidifying agent, can be used for fields such as coating, cement enhancing, terrace.
In order better to understand the present invention, the present invention is described in further detail below in conjunction with embodiment, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment 1: the condensation reaction of bisphenol A type epoxy resin and polyoxyethylene glycol.
Embodiment
In the 500ml four-hole boiling flask of being furnished with whipping appts, condensing works, thermometer and drying nitrogen system, dropping into the 15.3g epoxy equivalent (weight) is bisphenol A type epoxy resin and the 237.1g polyoxyethylene glycol (molecular weight is 2000～6000) of 188g/eq.Feeding drying nitrogen 10min drives the air in the system away, and heating for dissolving divides to add boron trifluoride diethyl etherate 3 times in 30min, is warming up to 100 ℃, reaction 3h, and obtaining the white extremely little yellow solid matter of 252.4g is reactive emulsifier.
Embodiment 2: the condensation reaction of bisphenol A type epoxy resin and polyether Glycols.
In the 500ml four-hole boiling flask of being furnished with whipping appts, condensing works, thermometer and drying nitrogen system, dropping into the 60.2g epoxy equivalent (weight) is bisphenol A type epoxy resin and the 282.2g polyoxyethylene glycol (molecular weight is 2000～6000) of 640g/eq.Feeding drying nitrogen 10min drives the air in the system away, and heating for dissolving divides to add SnCl 3 times in 30min
4, be warming up to 100 ℃, reaction 3.5h, obtaining 342.4g white to little yellow solid matter is reactive emulsifier.
Embodiment 3: in the 500ml four-hole boiling flask of being furnished with whipping appts, condensing works, thermometer and drying nitrogen system, dropping into the 230g epoxy equivalent (weight) is the bisphenol A type epoxy resin of 188g/eq, be warming up to 150 ℃, add 32.5g embodiment 2 gained reactive emulsifiers, react 2h down at 140～150 ℃, add 8g phenylcarbinol and 6g butyl glycol ether, mix, in 2L emulsification still, add emulsifying water, make aqueous epoxy resins.Its solid content is 49.3%.
Embodiment 4: in the 500ml four-hole boiling flask of being furnished with whipping appts, condensing works, thermometer and drying nitrogen system, dropping into the 230g epoxy equivalent (weight) is the 220g/eq novolac epoxy, add 9.3g phenylcarbinol and 25.9g butyl glycol ether, rising temperature for dissolving, add 33.8g embodiment 1 gained reactive emulsifier, react 40min down at 100～110 ℃, in 2L emulsification still, add emulsifying water, make aqueous epoxy resins.Its solid content is 50.2%.
Embodiment 5: in the 500ml four-hole boiling flask of being furnished with whipping appts, condensing works, thermometer and drying nitrogen system, dropping into the 230g epoxy equivalent (weight) is the 951g/eq bisphenol A type epoxy resin, add 13.3g phenylcarbinol and 20.7g butyl glycol ether, rising temperature for dissolving, add 34.5g embodiment 1 gained reactive emulsifier, react 1h down at 120～130 ℃, in 2L emulsification still, add emulsifying water, make aqueous epoxy resins.Its solid content is 48.8%.
Embodiment 6: in the 500ml four-hole boiling flask of being furnished with whipping appts, condensing works, thermometer and drying nitrogen system, dropping into the 180g epoxy equivalent (weight) is bisphenol A epoxide resin and the 62.2g dihydroxyphenyl propane of 188g/eq, after the heating for dissolving, under catalyst action, react 1h, add 36g embodiment 1 gained reactive emulsifier, react 1h down at 120～150 ℃, add 30g propylene glycol butyl ether, mix, in 2L emulsification still, add emulsifying water, make aqueous epoxy resins.Its solid content is 49.6%.
Embodiment 7: in the 500ml four-hole boiling flask of being furnished with whipping appts, condensing works, thermometer and drying nitrogen system, dropping into the 180g epoxy equivalent (weight) is the o-cresol formaldehyde epoxy resin of 197g/eq, after the heating for dissolving, add 36g embodiment 1 gained prepolymer, 120～150 ℃ of reaction 1h add the dissolving of 18.3g phenylcarbinol and 11.5g butyl glycol ether under catalyst action, mix, in 2L emulsification still, add emulsifying water, make aqueous epoxy resins.Its solid content is 51.2%.
Claims (3)
1. preparation method of water-dilutable epoxide resin is characterized in that:
(1) bisphenol A type epoxy resin and polyoxyethylene glycol are dissolved under the condition of heating, the mol ratio of bisphenol A type epoxy resin and polyoxyethylene glycol is: 0.90: 1.0～1.20: 1.0, the lewis acid catalyst that adds total mass 0.15%～0.3% again, under 65 ℃～110 ℃, reacted the formation reaction emulsifying agent 1 hour～5 hours;
(2) with bisphenol A type epoxy resin or o-cresol formaldehyde type Resins, epoxy, add dissolution with solvents, the add-on of solvent is 2%～10% of a weight epoxy, adds above-mentioned reactive emulsifier again, and the add-on of reactive emulsifier is 10%～20% of a weight epoxy, 80 ℃～150 ℃ reactions down, realize phase reversion, under agitation condition, add water and carry out emulsification, make the aqueous epoxy resins of different solid contents, the add-on of water is determined according to the product solid content.
2. method according to claim 1 is characterized in that: lewis acid catalyst is boron trifluoride diethyl etherate or tin tetrachloride.
3. method according to claim 1 and 2 is characterized in that: solvent is phenylcarbinol or phenylethyl alcohol or ethylene glycol or ethylene glycol ethyl ether or butyl glycol ether or propylene glycol monomethyl ether or propylene-glycol ethyl ether or propylene glycol butyl ether.
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| CN2008100306204A CN101497737B (en) | 2008-02-02 | 2008-02-02 | Preparation of aqueous epoxy resin |
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| CN2008100306204A CN101497737B (en) | 2008-02-02 | 2008-02-02 | Preparation of aqueous epoxy resin |
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| CN101497737B true CN101497737B (en) | 2011-12-07 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504282B (en) * | 2011-09-28 | 2013-11-06 | 武汉工程大学 | Preparation method of waterborne epoxy resin emulsion |
| CN103450448A (en) * | 2012-05-31 | 2013-12-18 | 中国石油化工股份有限公司 | Preparation method of compound aqueous curing agent |
| CN103554386B (en) * | 2013-10-22 | 2016-06-01 | 北京金汇利应用化工制品有限公司 | The preparation method of a kind of self-emulsifying bicomponent epoxy resin |
| CN103755966B (en) * | 2014-01-08 | 2016-12-07 | 天津大学 | Emulsifying agent that aqueous solid epoxy resin latex is special and the preparation method of emulsion |
| CN107523179B (en) * | 2017-07-21 | 2019-07-12 | 华南理工大学 | A kind of water-base epoxy insulated paint and the preparation method and application thereof |
| CN109575236B (en) * | 2017-09-28 | 2021-10-12 | 中国石油化工股份有限公司 | Water-based epoxy resin, preparation method thereof and application of water-based epoxy polyurethane ink binder |
| CN108003325B (en) * | 2017-12-14 | 2020-09-15 | 江苏钟山化工有限公司 | Preparation method of high-molecular water-based epoxy resin, resin prepared by preparation method and application of resin |
| CN109021254A (en) * | 2018-08-28 | 2018-12-18 | 江苏扬农锦湖化工有限公司 | A kind of aqueous epoxy resin emulsion and preparation method thereof |
| CN110951358A (en) * | 2019-11-19 | 2020-04-03 | 广东海特高新材料有限公司 | Double-component water-based tile crack beautifying agent and preparation method thereof |
| CN113136039A (en) * | 2020-11-25 | 2021-07-20 | 广州御达电子科技有限公司 | Preparation method of single-component water-based epoxy ester emulsion |
| CN113337182B (en) * | 2021-04-30 | 2022-04-15 | 中车青岛四方机车车辆股份有限公司 | Water-based two-component anticorrosive paint and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1415680A (en) * | 2002-10-24 | 2003-05-07 | 同济大学 | Paint of aqueous epoxy resin and its preparation method |
| CN1752163A (en) * | 2005-10-20 | 2006-03-29 | 同济大学 | A kind of aqueous epoxide resin paint and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1415680A (en) * | 2002-10-24 | 2003-05-07 | 同济大学 | Paint of aqueous epoxy resin and its preparation method |
| CN1752163A (en) * | 2005-10-20 | 2006-03-29 | 同济大学 | A kind of aqueous epoxide resin paint and preparation method thereof |
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