CN106519572B - A kind of aqueous epoxy resin emulsion and preparation method thereof - Google Patents
A kind of aqueous epoxy resin emulsion and preparation method thereof Download PDFInfo
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- CN106519572B CN106519572B CN201610986032.2A CN201610986032A CN106519572B CN 106519572 B CN106519572 B CN 106519572B CN 201610986032 A CN201610986032 A CN 201610986032A CN 106519572 B CN106519572 B CN 106519572B
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- epoxy resin
- nonionic emulsifier
- acid anhydrides
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- resin emulsion
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Paints Or Removers (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a kind of aqueous epoxy resin emulsions and preparation method thereof, belong to epoxy resin water paint field, nonionic emulsifier intermediate is synthesized with acid anhydrides by polyethylene glycol, it reacts to obtain nonionic emulsifier with epoxy resin by the intermediate again, the nonionic emulsifier that weight percent is 5%-20% is mixed with the epoxy resin of 20%-55% again, and the deionized water of 40%-60% is instilled, stirring heating obtains aqueous epoxy resin emulsion.Aqueous epoxy resin emulsion adhesion property provided by the invention, excellent anti-corrosion performance；Entire reaction system is solvent-free system, safe and non-toxic, environmental-friendly；It can solidify in room temperature 11h-12h, 1h solidifies at 80 DEG C, and condition of cure is mild, construction is simple.
Description
Technical field
The invention belongs to epoxy resin water paint fields, it particularly relates to epoxy resin latex and preparation method thereof.
Background technique
Epoxy resin has excellent caking property, adhesive force, stability, resist chemical, insulation and mechanical strength properties,
It is widely used in the fields such as coating, adhesive and composite material.China in 1956 starts to develop epoxy resin, and in 1958 year's harvest
Function produces epoxy resin.Epoxy coating is that a kind of widely used protective paint kind, epoxy coating can shield corruption
Medium is lost, passivating metallic surfaces form electrochemical effect to protect metal.Therefore, epoxy coating is widely used always
In paint field.Possess good physics, chemical property after epoxy resin cure, has excellent glue in metal and nonmetallic surface
Performance and antiseptic property are connect, high temperature strength is high, and thermal stability is good.Traditional epoxy resin is soluble in many solvents therefore one
As be solvent epoxy varnish, but solvent is volatile, and toxicity is big, causes environmental pollution, and it is essential to bring to production and life
Harm.
It in recent years, is the requirement for meeting environmental protection, aqueous epoxy resins have obtained broad development, although aqueous epoxy resins
VOC content is lower, but appoints and so contain toxic and volatile solvent, still threatens the health of the mankind.Such as patent
CN104497320A (applying date 2015.01.20) discloses a kind of preparation method of epoxy resin latex, including with poly- second two
Alcohol, binary isocyanic acid and epoxy alcohol prepare the preparation of emulsifier and epoxy resin latex, the addition when preparing epoxy resin latex
0-5 parts of organic solvent propylene glycol monomethyl ether, the solvent is volatile and toxic, be detrimental to health.
Summary of the invention
Object of the present invention is to be intended to provide it is a kind of using water as decentralized medium, it is solvent-free volatilize, it is safe and nontoxic, can be very
Good protection environment and adhesion property and the mild aqueous epoxy resin emulsion of excellent anti-corrosion performance, condition of cure and this
The preparation method of kind aqueous epoxy resin emulsion.
To realize the above-mentioned technical purpose, The technical solution adopted by the invention is as follows:
A kind of aqueous epoxy resin emulsion only includes nonionic emulsifier, the 20%- of 5%-20% by weight percentage
The deionized water of 55% epoxy resin, 40%-60%, the preparation component of the nonionic emulsifier include polyethylene glycol,
Acid anhydrides, epoxy resin.
Invention by adopting the above technical scheme, aqueous epoxy resin emulsion only include by polyethylene glycol, acid anhydrides, epoxy resin
Nonionic emulsifier obtained, epoxy resin, deionized water, only using water as decentralized medium, solvent-free volatilization, safety, nothing
Poison can protect environment well；And learn that the adhesion property of the aqueous epoxy resins and that corrosive nature are excellent after tested, energy
It effectively is attached to automobile metal surface, and protects metallic paint shell；It can solidify within 12 hours at normal temperature, 1-2h can consolidate at 70-80 DEG C
Change, condition of cure is mild.
Preferably, the polyethylene glycol, acid anhydrides, epoxy resin are 1:1-3:1-3 by the ratio between amount of substance.
Preferably, the acid anhydrides be along succinic acid acid anhydrides, adjacent two butyric acid acid anhydrides of benzene, along one of butadienoic acid acid anhydrides or
Several mixtures.
Preferably, the molecular weight polyethylene glycol is 200, one of 400,2000,4000,6000,10000 or its is several
Kind mixing.
Using the polyethylene glycol of different molecular quality, the stability of epoxy resin latex can be influenced, is learnt after tested, poly- second
When glycol molecules quality is 10000, obtained epoxy resin latex average grain diameter is 700nm, and stability is 9000r/min's
30min is not stratified under revolving speed, and dilution stability 72h hours not stratified.
Preferably, the epoxy resin is selected from one of E20, E44, E51, CYD115 or its several mixing.
A kind of preparation method of aqueous epoxy resin emulsion, including
Step 1, the synthesis of nonionic emulsifier intermediate
Taking polyethylene glycol and acid anhydrides are in reactor, after mixing by above-mentioned substance, are warming up to 80-120 DEG C under stirring,
Cooling discharge after keeping the temperature 5-6 hour, products obtained therefrom is nonionic emulsifier intermediate；
Step 2, the synthesis of nonionic emulsifier
It takes nonionic emulsifier intermediate and epoxy resin in step 1 to be placed in reactor, is warming up under stirring
80-120 DEG C, cooling discharge is nonionic emulsifier to get product after keeping the temperature 5-6 hour；
Step 3, the preparation of aqueous epoxy resin emulsion
It takes nonionic emulsifier made in step 2, epoxy resin in reactor, is warming up to 40-80 DEG C, turning
Speed be under 300-600r/min by above-mentioned substance after mixing, be slowly added dropwise deionized water, deionized water drips finish after,
Revolving speed is stir about 2h under 1200-1500r/min, and cooling discharge obtains aqueous epoxy resin emulsion.
The aqueous epoxy resin emulsion average grain diameter as made from the above method is 700-900nm, stability 9000r/
30min is not stratified under the revolving speed of min.
Above-mentioned entire reaction system is solvent-free reaction system, and solvent-free volatilization, safety is nontoxic, can good protection ring
Border.
Preferably, the rate of addition of the deionized water is 1-5d/s.
Aqueous epoxy resin emulsion provided by the invention and preparation method thereof has as follows a little compared with prior art:
(1) aqueous epoxy resins of this method preparation have good adhesion and corrosion resistance, can effectively be attached to
Automobile metal surface, and protect metallic paint shell；
(2) aqueous epoxy resins prepared using this method, entire reaction system are solvent-free reaction system, are not volatilized
Property solvent exist, only using water as decentralized medium, can be well protected environment, it is safe and non-toxic, can be safe to use.
(3) aqueous epoxy resins prepared using this method, can be long placed in solidification at normal temperature, also can at high temperature quickly
Solidification, condition of cure is mild, construction is simple.
Detailed description of the invention
The present invention can be further illustrated by the nonlimiting examples that attached drawing provides；
Fig. 1 is the infrared spectrum of the nonionic emulsifier intermediate synthesized in the embodiment of the present invention 1 to 4；
Fig. 2 is the nuclear magnetic spectrogram of the nonionic emulsifier intermediate synthesized in the embodiment of the present invention 1 to 4；
Fig. 3 is the infrared spectrum of the nonionic emulsifier synthesized in the embodiment of the present invention 1 to 4；
Fig. 4 is the nuclear magnetic spectrogram of the nonionic emulsifier synthesized in the embodiment of the present invention 1 to 4.
Specific embodiment
In order to make those skilled in the art that the present invention may be better understood, with reference to the accompanying drawings and examples to this hair
Bright technical solution further illustrates.
Embodiment 1, with molecular weight polyethylene glycol for 4000, epoxy resin model is E44, and emulsifier weight percent is
For 10%:
Step 1, the synthesis of nonionic emulsifier intermediate
Take the polyethylene glycol and suitable succinic acid acid anhydrides that molecular weight is 4000 in reactor, wherein polyethylene glycol and suitable fourth two
The ratio between amount of acid anhydrides substance is 1:1, after mixing by above-mentioned substance, 95 DEG C is warming up under stirring, after keeping the temperature 5-6 hour
Cooling discharge, this reaction is solvent-free reaction, and products obtained therefrom is nonionic emulsifier intermediate；
Step 2, the synthesis of nonionic emulsifier
Nonionic emulsifier intermediate and epoxy resin E44 prepared in step 1 are placed in reactor, wherein
The ratio between amount of substance of nonionic emulsifier intermediate and epoxy resin is that 1:1 after mixing by above-mentioned substance rises under stirring
Temperature is condensed back cooling discharge after 5-6 hour, products obtained therefrom is nonionic emulsifier to 120 DEG C；
Step 3, the preparation of aqueous epoxy resin emulsion
Take by weight percentage nonionic emulsifier obtained in 10% step 2,40% epoxy resin E44 in anti-
It answers in device, stirring is warming up to 75 DEG C, revolving speed 500r/min；After mixing by above-mentioned substance, it is slowly dripped with the speed of 1d/s
Add 50% deionized water, deionized water drips finish after, revolving speed is risen into 1500r/min, insulated and stirred 2h, cooling discharge.
It should be noted that 40% epoxy resin is not include to be used to prepare emulsifier in step 2 in step 3
Epoxy resin.
Embodiment 2 to 7
Aqueous epoxy resin emulsion is prepared using the identical technique of embodiment 1, wherein difference such as the following table 1, table 2, table 3
It is shown.
Step 1, the synthesis of nonionic emulsifier intermediate
Table 1
Step 2, the synthesis of nonionic emulsifier
Table 2
Step 3, the preparation of aqueous epoxy resin emulsion
Table 3
To nonionic emulsifier intermediate obtained in embodiment 1 to 4 carry out FTIR and1H NMR test, such as Fig. 1 institute
Show, FTIR spectrum figure is shown in the hydroxyl peak at 3450cm-1 and is remarkably reinforced, and ester carbonyl group occurs in 1740cm-1
Stretching vibration peak shows to introduce ester group and new hydroxyl on product；As shown in Fig. 2, nonionic emulsifier intermediate1There is the unimodal of carboxylic hydroxyl near δ=8 in H NMR spectra, occurs the division of methylene near ester group near δ=4.5
Peak, it is indicated above that reaction has synthesized the nonionic emulsifier intermediate of required structure.
To nonionic emulsifier obtained in embodiment 1 to 4 carry out FTIR and1H NMR test, as shown in figure 3, in Fu
Leaf infrared spectrogram shows that the stretching vibration peak of the epoxy group at 1038cm-1 and 917cm-1 significantly reduces, in 3793cm-1
With the stretching vibration peak for introducing hydroxyl and ester group at 1727cm-1；As shown in figure 4, reaction product1H NMR spectra is in δ=8
Nearby there is not the unimodal of carboxylic hydroxyl, occurs the division peak of methylene near ester group near δ=4.5, thus prove ring
Oxygen resin portion open loop, is reacted with intermediate, has synthesized required nonionic emulsifier.
The nonionic emulsifier as made from this method introduces polar oxyethylene group and connects section from the above, makes its tool
Standby hydrophily, only can be made aqueous epoxy resin emulsion using water as decentralized medium, so that this method is safe and nontoxic, environmentally friendly.
Aqueous epoxy resin emulsion obtained in embodiment 1 to 7 is tested for the property, test result is as follows:
Table 4
As seen from the above table, the aqueous epoxy resin emulsion as made from this method, adhesive force and excellent anti-corrosion performance can have
Effect is attached to automobile metal surface, and protects metallic paint shell；11h-12h it can solidify at normal temperature, 1-1.5h is at 80 DEG C of high temperature
Curable, condition of cure is mild, easy for construction；And entire reaction system is solvent-free reaction system, without volatile solvent
In the presence of, only using water as decentralized medium, it can be well protected environment, it is safe and non-toxic, it can be safe to use.
A kind of aqueous epoxy resin emulsion provided by the invention and preparation method thereof is described in detail above.Specifically
The explanation of embodiment is merely used to help understand method and its core concept of the invention.It should be pointed out that for the art
Those of ordinary skill for, without departing from the principle of the present invention, can also to the present invention carry out it is several improvement and repair
Decorations, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
Claims (5)
1. a kind of aqueous epoxy resin emulsion, it is characterised in that: only include the non-ionic cream of 5%-20% by weight percentage
The preparation component of the deionized water of agent, the epoxy resin of 20%-55%, 40%-60%, the nonionic emulsifier contains only
There are polyethylene glycol, acid anhydrides, epoxy resin；
The acid anhydrides is along succinic acid acid anhydrides, two butyric acid acid anhydrides of adjacent benzene, along the mixing of one or more of butadienoic acid acid anhydrides
Object；
The polyethylene glycol, acid anhydrides, epoxy resin are 1:1-3:1-3 by the ratio between amount of substance；
In nonionic emulsifier preparation process, polyethylene glycol and acid anhydrides is first allowed to be mixed to prepare among nonionic emulsifier
Body: taking polyethylene glycol and acid anhydrides are in reactor, after mixing by above-mentioned substance, 80-120 DEG C are warming up under stirring, heat preservation
Cooling discharge after 5-6 hour, products obtained therefrom are nonionic emulsifier intermediate；
Nonionic emulsifier intermediate and epoxy resin are reacted again, nonionic emulsifier are made: take it is obtained above it is non-from
Subtype emulsifier intermediate and epoxy resin are placed in reactor, and 80-120 DEG C is warming up under stirring, are dropped after keeping the temperature 5-6 hour
Temperature discharging is nonionic emulsifier to get product.
2. a kind of aqueous epoxy resin emulsion according to claim 1, it is characterised in that: the molecular weight polyethylene glycol is
One of 200,400,2000,4000,6000,10000 or its several mixing.
3. a kind of aqueous epoxy resin emulsion according to claim 1, it is characterised in that: the epoxy resin be selected from E20,
One of E44, E51, CYD115 or its several mixing.
4. a kind of preparation method of aqueous epoxy resin emulsion according to any of the above-described claim, it is characterised in that:
Including
Step 1, the synthesis of nonionic emulsifier intermediate
Taking polyethylene glycol and acid anhydrides are in reactor, after mixing by above-mentioned substance, 80-120 DEG C are warming up under stirring, heat preservation
Cooling discharge after 5-6 hour, products obtained therefrom are nonionic emulsifier intermediate；
Step 2, the synthesis of nonionic emulsifier
It takes nonionic emulsifier intermediate and epoxy resin in step 1 to be placed in reactor, is warming up to 80-120 under stirring
DEG C, cooling discharge is nonionic emulsifier to get product after keeping the temperature 5-6 hour；
Step 3, the preparation of aqueous epoxy resin emulsion
It takes nonionic emulsifier made in step 2, epoxy resin in reactor, is warming up to 40-80 DEG C, be in revolving speed
Under 300-600r/min after mixing by above-mentioned substance, be slowly added dropwise deionized water, deionized water drips finish after, in revolving speed
Aqueous epoxy resin emulsion is obtained for stir about 2h, cooling discharge under 1200-1500r/min.
5. a kind of preparation method of aqueous epoxy resin emulsion according to claim 4, it is characterised in that: the deionization
The rate of addition of water is 1-5d/s.
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| CN107033739B (en) * | 2017-05-09 | 2020-03-10 | 重庆交通大学 | Nonionic water-based epoxy emulsion with adjustable coating flexibility and preparation method thereof |
| CN107083071B (en) * | 2017-05-09 | 2020-01-07 | 重庆交通大学 | Normal-temperature asphalt pavement maintenance repair material and preparation method thereof |
| CN107556492B (en) * | 2017-09-28 | 2020-02-14 | 厦门凯纳石墨烯技术股份有限公司 | Graphene-containing waterborne epoxy resin emulsion and preparation method thereof |
| CN107603410A (en) * | 2017-10-13 | 2018-01-19 | 武汉工程大学 | Floor coatings aqueous epoxy resin emulsion and preparation method thereof |
| CN107903405A (en) * | 2017-12-26 | 2018-04-13 | 大余松瀛化工有限公司 | A kind of preparation process of self-emulsified aqueous epoxy synthetic emulsion |
| CN108047431A (en) * | 2017-12-28 | 2018-05-18 | 中科院广州化学有限公司 | A kind of aqueous epoxy emulsion, aqueous epoxide resin paint and preparation method thereof |
| CN108503846B (en) * | 2018-05-02 | 2021-04-02 | 北京化工大学 | Method for synthesizing nonionic emulsifier by solid acid catalysis and application thereof |
| CN109456674B (en) * | 2018-10-23 | 2021-01-26 | 湖北大学 | Water-based epoxy resin coating and application thereof in automobile corrosion prevention |
| CN111378095B (en) * | 2018-12-29 | 2023-05-26 | 万华化学集团股份有限公司 | Emulsifier preparation method, emulsifier, epoxy resin water dispersion and preparation method |
| CN109810243B (en) * | 2019-01-28 | 2021-12-14 | 上海骁鹏新材料科技有限公司 | Reactive emulsifier for epoxy resin and preparation method and application thereof |
| CN110577652A (en) * | 2019-09-03 | 2019-12-17 | 江苏扬农锦湖化工有限公司 | Preparation method of low-viscosity water-based epoxy emulsion |
| CN112794967B (en) * | 2019-11-13 | 2022-11-25 | 万华化学集团股份有限公司 | Radiation-curable water-based resin and preparation method and application thereof |
| CN113956489A (en) * | 2021-11-25 | 2022-01-21 | 重庆国际复合材料股份有限公司 | Modified epoxy emulsifier, preparation method thereof and self-modified epoxy emulsion |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102229701A (en) * | 2011-05-13 | 2011-11-02 | 湖南大学 | Non-ionic aqueous epoxy resin emulsion and its preparation method |
| CN102627752A (en) * | 2012-04-23 | 2012-08-08 | 吴江市太湖绝缘材料有限公司 | Preparation method for waterborne epoxy resin emulsion |
| CN105801868A (en) * | 2016-03-22 | 2016-07-27 | 常州大学 | Preparing method of bifunctionality epoxy resin emulsifier and emulsion |
-
2016
- 2016-11-09 CN CN201610986032.2A patent/CN106519572B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102229701A (en) * | 2011-05-13 | 2011-11-02 | 湖南大学 | Non-ionic aqueous epoxy resin emulsion and its preparation method |
| CN102627752A (en) * | 2012-04-23 | 2012-08-08 | 吴江市太湖绝缘材料有限公司 | Preparation method for waterborne epoxy resin emulsion |
| CN105801868A (en) * | 2016-03-22 | 2016-07-27 | 常州大学 | Preparing method of bifunctionality epoxy resin emulsifier and emulsion |
Non-Patent Citations (2)
| Title |
|---|
| 《水性环氧树脂乳液的制备及其应用》;李晴，等;《涂料工业》;20150331;第45卷(第3期);第41-45页 * |
| 相反转法制备水性环氧树脂及其固化动力学;张雪芳，等;《高分子材料科学与工程》;20120731;第28卷(第7期);第128-131页 * |
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