CN104829846A - Comb-shaped self-emulsifying nonionic type water-borne epoxy resin, water-borne epoxy resin emulsion and water-borne epoxy resin preparation method - Google Patents
Comb-shaped self-emulsifying nonionic type water-borne epoxy resin, water-borne epoxy resin emulsion and water-borne epoxy resin preparation method Download PDFInfo
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Abstract
The invention discloses a comb-shaped self-emulsifying nonionic type water-borne epoxy resin, a water-borne epoxy resin emulsion and a water-borne epoxy resin preparation method. According to the water-borne epoxy resin preparation method, bisphenol-A or bisphenol-F type epoxy resin low in molecular weight is subjected to chain extension, and comb-shaped hydrophilic nonionic chain segments are introduced into the structure of the bisphenol-A or bisphenol-F type epoxy resin through chemical modification to obtain the comb-shaped self-emulsifying nonionic type water-borne epoxy resin. Self-emulsifying capability of the water-borne epoxy resin is enhanced greatly through the comb-shaped structure, and the emulsion comprising the water-borne epoxy resin can be stored for more than six months and can be used as a basic material of water-borne epoxy resin paint.
Description
Technical field
The present invention relates to water-borne modification of epoxy resin field, be specifically related to a kind of pectination self-emulsifiable non-ionic water-borne epoxy resin and emulsion thereof and preparation method.
Background technology
Epoxy resin has physics, the chemical property of excellent metal adhesion, erosion resistance and excellence, and being widely used in the fields such as electronics, machinery, building, aviation and traffic, is the most widely used resin in current protective system.Most of epoxy resin is only soluble in the organic such as aromatic hydrocarbon and ketone solvent, and water insoluble.But organic solvent has many shortcomings, comprise contaminate environment, poisonous, explosive, inflammable etc., bring very large inconvenience to accumulating and construction.
Along with the common people are to the pay attention to day by day of environmental protection, using water as the epoxy resin of dispersion medium or solvent, namely aqueous epoxy resins more and more receives an acclaim.It is the stable dispersion obtained in the dispersion medium of external phase that aqueous epoxy resins refers to that epoxy resin is dispersed in the form of particulate or drop with water; it has a lot of advantages; as lower to environmental hazard; be convenient to accumulating; use safety; and can construct on the body surface of humidity, easy to clean.On the other hand, there is a large amount of ehter bonds in aqueous epoxy resins makes it have very strong alkaline resistance properties.
According to the difference of preparation method, water-borne modification of epoxy resin mainly contains mechanical process, phase inversion and chemic modified method 3 kinds of methods.Can obtain Self-Emulsified Epoxy emulsion with chemic modified method, without the need to additional emulsifying agent, the dispersed phase particle sizes of obtained emulsion arrives between hundreds of nanometer about tens greatly, excellent storage stability; Can according to demand, make epoxy resin obtain the performance of certain uniqueness with different properties-correcting agent, it is incomparable that this prepares aqueous epoxy resin emulsion with mechanical process and phase inversion simultaneously.Zhu Fang etc. utilize chemic modified method that diethanolamine is made epoxy resin portion open loop, and carry out chain extension with polyether polyamine, prepare cationic aqueous epoxy resin emulsion (Zhu Fang etc., the development of self-emulsification aqueous epoxy resin emulsion, polymer is circulated a notice of, 05 phase in 2008, P45-P49); Vinylformic acid and the vinylbenzene such as Hui Yunzhen carry out graft reaction to epoxy resin, then use in alkali and obtained anion-type water-thinned epoxy resin latex, its dispersed phase size reaches nano level, good (the Hui Yunzhen etc. of package stability, the synthesis of aqueous epoxy resin emulsion and performance study, bonding, 02 phase in 2008, P14-P18).But the change adaptability of the ionic water-borne epoxy systems prepared with chemic modified method to pH is poor, and the snappiness of film and water tolerance are also undesirable.
The non-ionic self-emulsifying aqueous epoxy resin emulsion prepared of chemic modified method is due to only containing hydrophilic segment, and not containing zwitterion group, therefore emulsion is to the change strong adaptability of pH, and the snappiness of film and water tolerance also have larger lifting simultaneously.Patent CN102977376A discloses non-ionic self-emulsifying aqueous epoxy resin and preparation method thereof, it utilizes poly glycol monomethyl ether and di-isocyanate reaction to prepare one end containing-NCO functional group, the other end, containing the wetting ability intermediate of polyether segment, utilizes the hydroxyl reaction in this wetting ability intermediate and epoxy resin to prepare non-ionic self-emulsifying aqueous epoxy resin.Due to Hydrophilicrto polyether side chain limited emulsifying capacity in resin structure, when emulsion polarity changes or temperature is fluctuated, the self-emulsifying ability of emulsion can be caused not enough, and emulsion intercalation method also can be affected.
Summary of the invention
The invention provides a kind of pectination self-emulsifiable non-ionic water-borne epoxy resin, in its resin structure, Hydrophilic nonionic segment is pectination distribution, solve in prior art because of the distribution of hydrophilic segment and quantity single, the emulsion self-emulsifying ability caused and the problem of stability deficiency.The present invention provides the preparation method of above-mentioned pectination self-emulsifiable non-ionic water-borne epoxy resin simultaneously.
Another object of the present invention is that providing a kind of comprises aqueous epoxy resin emulsion of above-mentioned aqueous epoxy resins and preparation method thereof.
In order to realize foregoing invention object, aqueous epoxy resins of the present invention by the following technical solutions: namely aqueous epoxy resins has structure shown in general formula 1:
R in general formula 1
1there is structure shown in general formula 2:
R in general formula 1
2for containing two hydrocarbyl substituents replacing positions or the hydrocarbyl substituent connected by Sauerstoffatom, described two carbon chain lengths replaced between positions are not less than 2;
In general formula 1 and general formula 2, X is 0 or 1, when X is 0, and R
3for replacing the hydrocarbyl substituent of position containing two, described two carbon chain lengths replaced between position are not less than 4; When X is 1, R
3for replacing the hydrocarbyl substituent of position containing three, wherein any two carbon chain lengths replaced between position are not less than 4;
R in general formula 2
4for methyl or hydrogen;
Described in general formula 1 and general formula 2
number-average molecular weight is 400 ~ 6000.
In the formula of above-mentioned aqueous epoxy resins, R
2the hydrocarbyl substituent referred to is made up of hydrocarbon atom, and two replace between positions can be a carbochain can be also many carbochains, is as the criterion with shorter carbon chain lengths when calculating carbon chain lengths.R
2when being chosen as hydrocarbyl substituent, be preferably 2-9 carbon chain lengths, wherein the hydrocarbyl substituent of 2 carbon chain lengths is as ethylidene, and the hydrocarbyl substituent of 3 carbon chain lengths is as m-phenylcnc, the hydrocarbyl substituent of 4 carbon chain lengths as para-orientation phenyl, the hydrocarbyl substituent of 8 carbon chain lengths as
the hydrocarbyl substituent of 9 carbon chain lengths as
or
r
2the hydrocarbyl substituent connected by Sauerstoffatom can also be adopted, if number-average molecular weight is 400 ~ 6000 polyoxyethylene glycol, when calculating carbon chain lengths, do not comprise Sauerstoffatom.
R
3the same R of implication of the carbon chain lengths between the hydrocarbyl substituent of statement and two replacement positions
2identical, general formula 1 and general formula 2 are when X=1, and any two carbon chain lengths replaced between positions are not less than 4, and preferred carbon chain lengths is not less than 9, further the R of preferred 9 carbon chain lengths
3, its structure is
when X=0, R
3the preferred 4-9 of the hydrocarbyl substituent a referred to carbon chain lengths, two replace carbon chain lengths between positions is 4 have
two replace carbon chain lengths between positions is 5 have
two replace carbon chain lengths between positions is 6 have
two replace carbon chain lengths between positions is 9 have
Aqueous epoxy resins of the present invention is by increasing to the main chain of the epoxy resin containing ethylene oxide group, active reactive group (-OH) is introduced in main chain, thus by introducing many hydrophilic non-ionic type side chains with the reaction of-NCO group, thus the self-emulsifying ability of aqueous epoxy resins is strengthened.On the other hand, R
3three hydrocarbyl substituents replacing position can be adopted, the number of nonionic side chain will be increased further, further optimize the self-emulsifying ability of aqueous epoxy resins.
Aqueous epoxy resins of the present invention is adopted and is prepared from the following method:
1) polyethylene oxide monomethyl ether and triisocyanate or vulcabond are in a heated condition, and the addition reaction of hydroxyl and isocyanate group occurs, and obtain the adduct containing an isocyanate group;
2) epoxy resin containing ethylene oxide group and dibasic alcohol or dihydric phenol, heating and reacting under catalysts conditions, obtain Epoxy resin chain extension product;
3) according to step 2) in chain extension product contained hydroxyl moles get the step 1 of identical mole number) described adduct, adduct and chain extension product are obtained by reacting aqueous epoxy resins in a heated condition.
In above-mentioned preparation method, the triisocyanate adopted or vulcabond refer to R in general formula 1 and general formula 2
3substituent replacement position connects isocyanate group, i.e.-NCO, form triisocyanate or vulcabond.When getting 0 as X in general formula 1 and general formula 2, preparation method's step 1) in corresponding employing vulcabond, when X gets 1, preparation method's step 1) in adopt triisocyanate accordingly.Preferred scheme: triisocyanate is triphenylmethane triisocyanate; Vulcabond is tolylene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, naphthalene diisocyanate, PPDI, 1,4-cyclohexyl diisocyanate, xylylene diisocyanate, cyclohexanedimethyleterephthalate vulcabond, trimethylammonium-1,6-hexamethylene diisocyanate or tetramethyl-m-xylylene diisocyanate.
In above-mentioned preparation method, step 1) in the polyethylene oxide monomethyl ether that adopts be a kind of conventional polymer, be namely methyl ether base in polyethylene oxide one end, the other end is hydroxyl.The number-average molecular weight selecting polyethylene oxide monomethyl ether is 400 ~ 6000.Because isocyanate groups is easy and water reacts, through processed, preferably vacuum hydro-extraction to be adopted before polyethylene oxide monomethyl ether uses.
Step 1) addition reaction that occurs is that oh group (-OH) on polyethylene oxide monomethyl ether reacts with the isocyanate groups (-NCO) on triisocyanate or vulcabond, obtain-NHCOO-linking group, this addition reaction is one to be needed to heat the popular response carried out, and in the present invention, the concrete temperature of reaction adopted selects 50-120 DEG C, reaction 1-24h.
Step 1) in isocyanic ester type when being triisocyanate, the mol ratio of polyethylene oxide monomethyl ether and triisocyanate is 2:1; When isocyanic ester type is vulcabond, the mol ratio of polyethylene oxide monomethyl ether and vulcabond is 1:1.Adopt this ratio to carry out reacting reaction raw materials can be made to use more abundant, thus obtain the product of more simple function group (-NCO), as active reaction sites formation hydrophilic nonionic type side chain.
Step 2) temperature of reaction be 40 ~ 120 DEG C, the reaction times is 1-24h.Catalyzer is dibutyl tin laurate, boron trifluoride diethyl etherate, stannous octoate or dibutyltin diacetate.Catalyst levels is 0.1 ~ 1% of reactant total mass.
Step 2) described in be bisphenol A-type or bisphenol f type epoxy resin containing the epoxy resin of ethylene oxide group, its Mn≤700.
Step 2) in dibasic alcohol or dihydric phenol there is no particular requirement, conventional chain extending reaction can be there is with the epoxy resin containing ethylene oxide group, dibasic alcohol can be ethylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol or number-average molecular weight are the polyoxyethylene glycol of 400 ~ 6000, dihydric phenol can be 4,4 '-'-biphenyl diphenol, dihydroxyphenyl propane, Bisphenol F, Resorcinol or Resorcinol.
Step 2) in dibasic alcohol or dihydric phenol be 1:2 ~ 2.5 with the mol ratio of the epoxy resin containing ethylene oxide group.
Step 3) in the mol ratio of adduct and chain extension product be 4:1.
Adopt an aqueous epoxy resin emulsion for above-mentioned aqueous epoxy resins, it is characterized in that: each component comprising following weight part: aqueous epoxy resins 20 ~ 50 parts, deionized water 80 ~ 50 parts.
Aqueous epoxy resin emulsion preparation technology of the present invention is simple, and product containing organic solvent, does not meet environmental requirement; Aqueous epoxy resin emulsion dispersion particle is little, and lower 6 months of room temperature is not stratified, and stability is high.
Embodiment
Embodiments of the present invention are described in detail below in conjunction with embodiment.
Embodiment 1
1. the pectination self-emulsifiable non-ionic water-borne epoxy resin of the present embodiment is as shown in structural formula 1:
Wherein R
1there is following structure:
Be 1, R relative to the general formula 1 of summary of the invention and general formula 2, X
2for ethylidene, R
3for
r
4for methyl, structure is
number-average molecular weight be 1000.
2. the preparation method of aqueous epoxy resins shown in the present embodiment structural formula 1 is:
1) under the condition of 50 DEG C, be that the polyethylene oxide monomethyl ether of 1000 joins in triphenylmethane triisocyanate and reacts after 24 hours by number-average molecular weight, obtain adduct.Wherein, the mol ratio of polyethylene oxide monomethyl ether and triphenylmethane triisocyanate is 2:1.Reaction signal formula is as follows:
Wherein
for the oxyethane monomethyl ether of number-average molecular weight 1000,
2) under the condition of 80 DEG C, add catalyst dibutyltin dilaurylate, ethylene glycol is joined in bisphenol A type epoxy resin E44 and react after 12 hours, obtain Epoxy resin chain extension product.Wherein, the mol ratio of ethylene glycol and bisphenol A type epoxy resin E44 is 1:2, and the consumption of dibutyl tin laurate is 0.1% of reactant total mass.
Wherein HO-R
2be ethylene glycol in-OH the present embodiment,
for bisphenol A-type or bisphenol f type epoxy resin (the present embodiment is bisphenol A type epoxy resin), its structure is as follows:
Bisphenol A-type:
Bisphenol-f type:
Bisphenol A-type or bisphenol f type epoxy resin meet: Mn≤700, n=1.
3) under the condition of 80 DEG C, adduct is joined reaction in chain extension product and namely obtain pectination self-emulsifiable non-ionic water-borne epoxy resin after 12 hours, wherein the mol ratio of adduct and chain extension product is 4:1.In reaction process, in chain extension product, on two dihydroxyphenyl propanes or Bisphenol F unit respectively with 1 hydroxyl and chain extension after 2 hydroxyls (totally 4 hydroxyls) of producing and the isocyanic ester radical reaction in adduct, form pectination.
3. emulsion adopting the present embodiment aqueous epoxy resins and preparation method thereof
At room temperature, the pectination self-emulsifiable non-ionic water-borne epoxy resin be prepared from by the present embodiment joins in a certain amount of deionized water, mix with high speed homogenizer and obtain aqueous epoxy resin emulsion, wherein the mass ratio of aqueous epoxy resins and deionized water is 34:50.Performance sees attached list 4.
Embodiment 2-9
1. the structure of the pectination self-emulsifiable non-ionic water-borne epoxy resin of embodiment 2-9
Embodiment 2-9 sets forth 8 kinds of concrete pectination self-emulsifiable non-ionic water-borne epoxy resin, with reference to general formula 1 and general formula 2, and can determine the concrete structure of described aqueous epoxy resins in conjunction with following table 1.
The structure of the aqueous epoxy resins of table 1 embodiment 2-9
2. the preparation method of aqueous epoxy resins shown in embodiment 2-9
The preparation method of the aqueous epoxy resins shown in embodiment 2-9 is substantially the same manner as Example 1, and difference is to employ vulcabond, and have employed different reaction conditionss, and its concrete distinctive points is listed in table 2:
The preparation of the aqueous epoxy resins shown in table 2 embodiment 2-9
In embodiment 2-9, step 1) Raw polyethylene oxide monomethyl ether adopts in table 1 in corresponding embodiment
the number-average molecular weight of group, as in embodiment 2, the number-average molecular weight of polyethylene oxide monomethyl ether is 1000; Vulcabond adopts R in table 1 accordingly
3the two ends substituting group of shown structure is the vulcabond of isocyanate groups, and the vulcabond as adopted in embodiment 2 is
In embodiment 2-9, step 2) Raw dibasic alcohol or dihydric phenol adopt R in table 1 accordingly
2shown structure two ends substituting group is dibasic alcohol or the dihydric phenol of hydroxyl, and the dibasic alcohol as implemented to adopt in 2 is BDO; For the epoxy resin in raw material, R
4during for-H, as embodiment 2, embodiment 7, epoxy resin adopts bisphenol f type epoxy resin, R
4for-CH
3time, as in embodiment 3-6, embodiment 8-9, epoxy resin adopts bisphenol A type epoxy resin.
3. emulsion adopting embodiment 2-9 aqueous epoxy resins and preparation method thereof
Adopt the preparation method of the emulsion of embodiment 2-9 aqueous epoxy resins identical with embodiment 1, its distinctive points is as shown in table 3:
The emulsion of the aqueous epoxy resins of table 3 embodiment 2-9
Detect the emulsion property of embodiment 1 to 9, its performance is in table 4.
Table 4
Claims (10)
1. a pectination self-emulsifiable non-ionic water-borne epoxy resin, is characterized in that: have structure shown in general formula 1:
R in general formula 1
1adopt structure shown in general formula 2:
R in general formula 1
2for containing two hydrocarbyl substituents replacing positions or the hydrocarbyl substituent connected by Sauerstoffatom, described two carbon chain lengths replaced between positions are not less than 2;
In general formula 1 and general formula 2, X is 0 or 1, when X is 0, and R
3for replacing the hydrocarbyl substituent of position containing two, described two carbon chain lengths replaced between position are not less than 4; When X is 1, R
3for replacing the hydrocarbyl substituent of position containing three, wherein any two carbon chain lengths replaced between position are not less than 4;
R in general formula 2
4for methyl or hydrogen;
Described in general formula 1 and general formula 2
number-average molecular weight is 400 ~ 6000.
2. aqueous epoxy resins according to claim 1, is characterized in that: R in general formula 1
2be selected from the alkyl of carbonatoms 2 ~ 6, or para-orientation phenyl, or m-phenylcnc, or number-average molecular weight is the polyoxyethylene glycol that 400 ~ 6000 terminal hydroxy group are substituted,
3. aqueous epoxy resins according to claim 1, is characterized in that: in general formula 1 and general formula 2 when X=1, R
3for
when X=0, R
3be selected from
4. a preparation method for aqueous epoxy resins as claimed in claim 1, is characterized in that: be prepared from by following steps:
1) polyethylene oxide monomethyl ether and triisocyanate or vulcabond are in a heated condition, and the addition reaction of hydroxyl and isocyanate group occurs, and obtain the adduct containing an isocyanate group;
2) epoxy resin containing ethylene oxide group and dibasic alcohol or dihydric phenol catalyzed reaction in a heated condition, obtain Epoxy resin chain extension product;
3) according to step 2) in chain extension product contained hydroxyl moles get the step 1 of identical mole number) described adduct, adduct and chain extension product are obtained by reacting aqueous epoxy resins in a heated condition.
5. the preparation method of aqueous epoxy resins according to claim 4, is characterized in that: step 1) temperature of reaction 50 ~ 120 DEG C, the reaction times is 1 ~ 24h.
6. the preparation method of aqueous epoxy resins according to claim 4, is characterized in that: step 1) in isocyanic ester type when being triisocyanate, the mol ratio of polyethylene oxide monomethyl ether and triisocyanate is 2:1; When isocyanic ester type is vulcabond, the mol ratio of polyethylene oxide monomethyl ether and vulcabond is 1:1.
7. the preparation method of aqueous epoxy resins according to claim 4, it is characterized in that: step 2) temperature of reaction be 40 ~ 120 DEG C, described catalytic reaction catalyst is dibutyl tin laurate, boron trifluoride diethyl etherate, stannous octoate or dibutyltin diacetate.
8. the preparation method of aqueous epoxy resins according to claim 4, it is characterized in that: step 2) described in dibasic alcohol be ethylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol or number-average molecular weight are the polyoxyethylene glycol of 400 ~ 6000, described dihydric phenol is 4,4 '-'-biphenyl diphenol, dihydroxyphenyl propane, Bisphenol F, Resorcinol or Resorcinol.
9. the preparation method of aqueous epoxy resins according to claim 4, is characterized in that: step 3) in the mol ratio of adduct and chain extension product be 4:1.
10. comprise an aqueous epoxy resin emulsion for the aqueous epoxy resins described in any one of claims 1 to 3, it is characterized in that: each material comprising following weight part: aqueous epoxy resins 20 ~ 50 parts, deionized water 80 ~ 50 parts.
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| CN109913109A (en) * | 2019-01-23 | 2019-06-21 | 河北晨阳工贸集团有限公司 | A kind of water-fast high pressure resistant water paint and preparation method thereof |
| CN110951082A (en) * | 2019-12-06 | 2020-04-03 | 万华化学集团股份有限公司 | Preparation method of comb-shaped anionic-nonionic active epoxy emulsifier and preparation method of epoxy resin emulsion |
| CN112898594A (en) * | 2021-01-11 | 2021-06-04 | 广东锐涂精细化工有限公司 | Epoxy resin emulsion and preparation method thereof |
| CN113278346A (en) * | 2021-06-03 | 2021-08-20 | 武汉工程大学 | Water-based epoxy resin emulsion for heavy-duty anticorrosive paint and preparation method and application thereof |
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| CN102977376A (en) * | 2012-11-29 | 2013-03-20 | 西安交通大学 | Nonionic self-emulsifying waterborne epoxy resin and preparation method and application thereof |
| CN104558524A (en) * | 2013-10-21 | 2015-04-29 | 北京化工大学 | Preparation method for non-ionic reactive water-borne epoxy resin emulsion |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113278346A (en) * | 2021-06-03 | 2021-08-20 | 武汉工程大学 | Water-based epoxy resin emulsion for heavy-duty anticorrosive paint and preparation method and application thereof |
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Application publication date: 20150812 |