CN110066385A - A kind of fire-retardant aqueous epoxy resin curing agent, a kind of extinguishing waterborn epoxy resin latex and preparation method thereof - Google Patents
A kind of fire-retardant aqueous epoxy resin curing agent, a kind of extinguishing waterborn epoxy resin latex and preparation method thereof Download PDFInfo
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- CN110066385A CN110066385A CN201910236170.2A CN201910236170A CN110066385A CN 110066385 A CN110066385 A CN 110066385A CN 201910236170 A CN201910236170 A CN 201910236170A CN 110066385 A CN110066385 A CN 110066385A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/64—Amino alcohols
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- 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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Abstract
The good extinguishing waterborn epoxy resin latex of the stability of the present invention relates to a kind of fire-retardant aqueous epoxy resin curing agent and its preparation with self-emulsifying function.The raw material of the aqueous epoxy resin curing agent includes epoxy resin, DOPO derivative, fatty amine and chain extender containing two or more amidos containing two epoxy groups, is prepared by a method comprising the following steps to obtain: I. contains the epoxy resin of two epoxy groups and DOPO derivative reacts under the effect of the catalyst；II. the fatty amine containing two or more amidos is added in the reaction system obtained to step I, and phosphorous, nitrogen compound is obtained after reaction；III. chain extender is added in the reaction system obtained to step II, and phosphorous, nitrogen epoxy hardener is obtained after reaction；IV. the reaction system that is obtained to step III be added acid-base neutralization agent to get.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of novel fire-retardant with self-emulsifying function
Aqueous epoxy resin curing agent, it is a kind of using the curing agent as the extinguishing waterborn epoxy resin latex of raw material and their preparation
Method.
Background technique
Epoxy resin has the spies such as good strength character, adhesive property, resistance to chemical corrosion and low cure shrinkage
Property, it is widely used in the fields such as coating, adhesive, composite material, laminated material and insulating materials.However, as macromolecule
The epoxy resin of material also belongs to combustible material, and in the field required to flame retardant property, application is just very limited.
In this regard, many researchers have done a large amount of research work in improvement ethoxyline resin antiflaming aspect of performance, passes through and fire retardant is added
Epoxy resin flame retardancy is assigned, to widen the application field of epoxy resin.
Fire retardant can be divided into organic fire-retardant and inorganic fire retardants, halogenated flame retardant (organic chloride from constitutive property
Object and organic bromide) and non-halogen fire retardant.Organic fire-retardant is using bromine system, phosphorus nitrogen system, nitrogen system and red phosphorus and compound as generation
Some fire retardants of table, inorganic fire retardants are mainly the flame-retardant systems such as antimony oxide, magnesium hydroxide, aluminium hydroxide, silicon systems.Out
In environmental requirement, non-halogen fire retardant is generally more favored.From the mode that epoxy resin is added, fire retardant can be divided into additive flame again
Fire agent and reactive flame retardant.As its name suggests, the former is added in epoxy resin by mechanical mix techniques；The latter's then conduct
A kind of monomer participation polymerization reaction, becomes a part of epoxy molecule structure.Additive flame retardant exists and macromolecule material
Material compatibility is poor, transport phenomena is serious and has the shortcomings that different degrees of damage to final products performance.Therefore, non-halogen is anti-
The type fire retardant of answering is the ideal auxiliary agent for improving ethoxyline resin antiflaming performance.
Fire retardant both can be used as the polymerization reaction that monomer directly participates in epoxy resin, can be introduced between curative systems
Connect participation polymerization reaction.
Publication number CN102617829 A (data of publication of application 2012 on August 1) and publication number CN104558528A (application
Date of publication on April 29th, 2015) Chinese invention patent application individually disclose a kind of non-ionic phosphorous, amine self-emulsifying ring
Oxygen resin curing agent, the curing agent is all just prepared by three-step reaction: the first step prepares contain in the presence of an organic
Phosphorus polyamine curing agent；Second step prepares nonionic surface active agent (or self-emulsifier)；Third step is made in second step
Nonionic surface active agent in Phosphorous Containing Polyamines made from the first step are added dropwise so that the curing agent be prepared.Above-mentioned preparation
In method, the phosphorous containing polyamines that the first step is prepared have to pass through the reaction that lower step could be used for after deposition and purification, lead
The pollution and waste of the very complicated and a large amount of organic solvents in preparation process are caused.And the disclosed solidification of the above-mentioned prior art
Agent, the phosphorus group for playing fire retardation are in the side-chain structure of macromolecule network.The general decomposition temperature of the side-chain structure of molecule compared with
It is low, therefore the curing agent heat resistance of the type is poor.And above-mentioned self-emulsifying curative systems are non-ionic, emulsifying capacities
Poor, the aqueous epoxy resins being prepared are not suitable for long-term storage.
Summary of the invention
For overcome the deficiencies in the prior art, the present invention provides a kind of new phosphorous, nitrogen fire-retardant aqueous epoxy resins
Curing agent and the curing agent participate in extinguishing waterborn epoxy resin latex obtained from polymerization.Solidification agent molecule knot of the present invention
In structure, phosphorus-containing groups are in main chain, can make final product --- and extinguishing waterborn epoxy resin latex has higher heat resistance
Energy.The curing agent is cationic system, with excellent emulsifying effectiveness, the epoxy resin partial size fine uniform being prepared, surely
It is qualitative more preferable.In addition, curing agent of the present invention is prepared using one kettle way, intermediate product is without separation and purifying, preparation process
Simply.
In order to achieve the above-mentioned object of the invention, present invention employs the following technical solutions:
A kind of fire-retardant aqueous epoxy resin curing agent with self-emulsifying function, raw material include containing two epoxy groups
Epoxy resin, DOPO derivative, fatty amine and chain extender containing two or more amidos, pass through the side included the following steps
Method is prepared:
I. contain the epoxy resin of two epoxy groups and DOPO derivative reacts under the effect of the catalyst；
II. the fatty amine containing two or more amidos is added in the reaction system obtained to step I, is contained after reaction
Phosphorus, nitrogen compound；
III. chain extender is added in the reaction system obtained to step II, and phosphorous, nitrogen epoxy hardener is obtained after reaction；
IV. the reaction system that is obtained to step III be added acid-base neutralization agent to get.
Preferably, the epoxy resin for containing two epoxy groups is selected from bisphenol A epoxide resin or bisphenol F epoxy resin.
In description of the invention, " DOPO " is the abbreviation of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
(CAS:35948-25-5), molecular formula: C12H9O2P, molecular weight: 216, chemical structural formula are as follows:
Preferably, the DOPO derivative is selected from DOPO-HQ (10- (2,5- dihydroxy phenyl) -10- hydrogen -9- oxa- -10-
Phospho hetero phenanthrene -10- oxide), DOPO-MA (10- (1,4- succinic acid 2 base) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxidation
Object), DOPOBDO (10- (- 2 base of 1,4-butanediol) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxide), DOPO-ITA
(miscellaneous -10- phospho hetero phenanthrene -10- oxide of 10- (2,5- dicarboxypropyl) -9,10- dihydro-9-oxy) and DHP-DOPO (10- (2,5-
One of the miscellaneous -10- phospho hetero phenanthrene -10- oxide of dihydroxy Nai Ji -9,10- dihydro-9-oxy).It is highly preferred that the DOPO spreads out
Biology is DOPO-HQ.
Preferably, the fatty amine containing two or more amidos is selected from diethylenetriamine, triethylene tetramine, tetrem
One of five amine of alkene, pentaethylene hexamine, polyethylene polyamine, ethylenediamine, propane diamine, butanediamine, pentanediamine and hexamethylene diamine are appointed
Meaning ratio it is a variety of.It is highly preferred that the fatty amine containing two or more amidos is selected from triethylene tetramine and four ethylene
Two kinds of one of five amine or arbitrary proportion.
The chain extender is the compound with an epoxy group；More preferably shrink from methyl glycidyl ether, propyl
Glycerin ether, butyl glycidyl ether, allyl glycidyl ether, C8-C18Alkyl glycidyl ether, p-tert-butylphenol shrink sweet
One of oily ether, adjacent phenol glycidyl ethers, ethylene oxide, propylene oxide, epoxy butane and epoxypentane or arbitrary proportion
It is a variety of.
Preferably, the epoxy resin for containing two epoxy groups, DOPO derivative, containing two or more amidos
The molar ratio of fatty amine and chain extender are as follows:
2.0:1.0:2.0:2.0~2.0:1.0:2.4:2.4.
Preferably, in the step I, the catalyst is selected from one of triphenylphosphine, alchlor and triethylamine, more
Preferably triphenyl phosphorus.
It is further preferred that the 0.5 of epoxy resin quality of the additive amount of the catalyst for described in containing two epoxy groups~
3.0wt%.
It is further preferred that reaction temperature is 110 DEG C~140 DEG C in the step I, the reaction time is 2~6h.
It is highly preferred that reaction temperature is 120~130 DEG C in the step I, the reaction time is 3~4h.
In the step I, the boiling point that can be optionally suitable for is higher than 110 DEG C of alcohols or alcohol ethers solvent, preferably ethylene glycol
Methyl ether or butyl glycol ether.
Preferably, in the step II, reaction temperature is 60 DEG C~80 DEG C, and the reaction time is 2~5h.
It is highly preferred that reaction temperature is 65~75 DEG C in the step II, the reaction time is 3~4h.
Preferably, in the step III, reaction temperature is 60 DEG C~80 DEG C, and the reaction time is 2~5h.
It is highly preferred that reaction temperature is 65~75 DEG C in the step III, the reaction time is 3~4h.
Preferably, in the step IV, the acid-base neutralization agent is inorganic acid or organic acid, more preferably organic acid.
As a preferred embodiment, the acid-base neutralization agent is acetic acid.
It is further preferred that in the step IV, amine groups in the acid-base neutralization agent and the epoxy curing agent
Molar ratio is 0.2~0.7:1.0, more preferably 0.3~0.6:1.0.
It is further preferred that reaction temperature is not higher than 60 DEG C, more preferably 40~50 DEG C in the step IV.
The fire-retardant aqueous epoxy resins solidification with self-emulsifying function that it is also an object of the present invention to provide described
Agent is preparing the application in extinguishing waterborn epoxy resin latex.
In addition, there are also thirds to be designed to provide a kind of extinguishing waterborn epoxy resin latex by the present invention, raw material includes upper
Fire-retardant aqueous epoxy resin curing agent, epoxy resin and water with self-emulsifying function are stated, the epoxy curing agent
The epoxide equivalent of active hydrogen equivalent weight and epoxy resin ratio is 0.8:1.0~1.1:1, and the quality of water is the epoxy curing agent
With 1~4 times of the epoxy resin gross mass.
Preferably, the epoxide equivalent of the active hydrogen equivalent weight of the epoxy curing agent and epoxy resin ratio is 1:1.
Preferably, the quality of water is 1.5~2.5 times of the epoxy curing agent and the epoxy resin gross mass.
The epoxy resin can be any type, i.e., contain the polymerization of two or more epoxy groups in molecule
Object.
The present invention also provides the preparation methods of above-mentioned extinguishing waterborn epoxy resin latex, include the following steps:
A. in the container with agitating device, by the fire-retardant water-base epoxy tree of the present invention with self-emulsifying function
Rouge curing agent and epoxy resin are according to the active hydrogen equivalent weight of the aqueous epoxy resin curing agent and the epoxy of the epoxy resin
The ratio of equivalent proportion 0.8:1.0~1.1:1 is uniformly mixed, 100~300rpm of revolving speed；
B. water, 500~1500rpm of revolving speed, the cream being stirred until homogeneous are slowly added in the mixed system obtained to step A
Liquid to get.
Preferably, in the step B, revolving speed is 800~1000rpm.
Fire-retardant aqueous epoxy resin curing agent and extinguishing waterborn asphalt mixtures modified by epoxy resin of the present invention with self-emulsifying function
The preparation of fat liquor, those skilled in the art can be selected from suitable reaction vessel according to actual production scale, for example is equipped with back
Flow condenser pipe, the flask, or the reaction kettle equipped with reflux, temperature control and agitating device of thermometer and agitating device etc..
The fire-retardant aqueous epoxy resin curing agent with self-emulsifying function provided by the invention, to contain two epoxies
Epoxy resin, DOPO derivative, the fatty amine containing two or more amidos and the chain extender of group are primary raw material, through dividing
Step charging-one kettle way is prepared, by taking following scheme as an example, above-mentioned reaction process are as follows:
Wherein,
The method have the benefit that:
(1) the fire-retardant aqueous epoxy resin curing agent provided by the invention with self-emulsifying function, preparation process letter
It is single, without synthesizing the techniques such as different component substances or separation proposition first, but multistep is used to feed, in separation and purifying
Final products can be prepared in mesosome one pot reaction.
(2) the fire-retardant aqueous epoxy resin curing agent with self-emulsifying function that the present invention is prepared, phosphorous list
Member is phospha ring structure, and in the main chain in molecule segment, solidified resin system may make to have higher heat resistance；
(3) the extinguishing waterborn epoxy curing agent with self-emulsifying function that the present invention is prepared belongs to being separated from milk of sun
System has excellent emulsifier effect, and the extinguishing waterborn epoxy resin partial size fine uniform being prepared can be unlimited with water
It is miscible, have excellent storage stability.
Detailed description of the invention
With reference to the accompanying drawing, it elaborates to the present invention.
Shown in fig. 1 is the infrared spectroscopy of the phosphorous reactant feed DOPO-HQ of embodiment 1, step I~III product, wherein
1A is complete infrared spectrogram (4000~400cm-1), 1B is partial enlarged view (1300~650cm of 1A-1)；It is bent in figure
Line a is the infrared absorption spectrum of DOPO-HQ, and curve b is the infrared absorption spectrum for the phosphorus-containing compound that step I is obtained, and curve c is
Phosphorous, nitrogen compound the infrared absorption spectrum that step II is obtained, curve d are phosphorous, the nitrogen flame retardant epoxy tree that step III is obtained
The infrared absorption spectrum of rouge curing agent.
Fig. 2 shows be the extinguishing waterborn epoxy resin latex that embodiment 1 and embodiment 2 are prepared particle size determination knot
Fruit.
Specific embodiment
The present invention is described below with reference to specific embodiments.It will be appreciated by those skilled in the art that these embodiments are only
For illustrating the present invention, do not limit the scope of the invention in any way.
Experimental method in following embodiments is unless otherwise specified conventional method.Original as used in the following examples
Material, reagent material etc. are commercially available products unless otherwise specified.Wherein, equipment component purchase situation is as follows:
Infrared spectrometer: German Brooker Science and Technology Ltd., instrument model Vector 33,
Malvern particle instrument: Malvern Instr Ltd., Britain, instrument model: ZS-Nano-3000.
Embodiment 1A kind of fire-retardant aqueous epoxy resin curing agent and a kind of extinguishing waterborn epoxy with self-emulsifying function
Resin emulsion
The raw material composition of fire-retardant aqueous epoxy resin curing agent described in the present embodiment with self-emulsifying function is shown in Table 1 institute
Show, be prepared via a method which:
I. epoxy resin E-44, phosphorous-containing monomers DOPO-HQ and propandiol butyl ether are added to equipped with reflux condensing tube, temperature
In the flask of meter and agitating device, catalyst triphenylphosphine is then added, after being warming up to 120 DEG C and being stirred at reflux reaction 5h, obtains
To the solution of phosphorus-containing compound；
II. after the obtained solution of step I being cooled to 60 DEG C, triethylene tetramine is added, stirs evenly, is reacted at 70 DEG C
After 4h, phosphorous, nitrogen compound solution is obtained；
III. reaction system keeps temperature, and chain extender n-butyl glycidyl ether is added in the solution obtained to step II,
It stirs evenly, after reacting 3h at 70 DEG C, obtains the solution of phosphorous, nitrogen epoxy hardener；
IV. after the obtained solution of step III being cooled to 50 DEG C, glacial acetic acid is added and product is neutralized to get mesh is arrived
Mark aqueous epoxy resin curing agent (without separation, be directly used in and prepare extinguishing waterborn epoxy resin latex).
DOPO-HQ and step I~III product carry out infrared spectrum measurement respectively, and map is shown in Fig. 1.From infrared spectrum
As can be seen that
Phosphorous reactant feed DOPO-HQ is in 1250cm-1There is absorption peak (curve a), the warp of hydroxyl (C-OH) group in place
After step I and bisphenol A epoxide resin (E-44) react, the phosphorus-containing compound being prepared is in 1250cm-1The absorption peak at place
Disappear (curve b), the C-OH for illustrating phosphorous reactant feed are reacted with the epoxy group of epoxy resin, phosphorus-containing groups into
The main chain of molecule is entered.
By step II, (curve b) is reacted with triethylene tetramine is prepared phosphorous, nitrogen compound (song to phosphorus-containing compound
Line c)；Curve b and curve c are compared, it can be seen that curve c is in 915cm-1The characteristic absorption peak for locating epoxy resin disappears, and
3460cm-1There is the absorption peak of amine groups in place, illustrates that the epoxy group of phosphorus-containing compound has occurred with triethylene tetramine completely
It reacts, introduces amido in molecular structure.
By step III, (curve c) reacts to be prepared with n-butyl glycidyl ether to be contained phosphorous, nitrogen compound
Phosphorus, nitrogen antiflaming epoxy resin curing agent (curve d)；Curve c and curve d are compared, it can be seen that curve is in 722cm-1Occur
New absorption peak, this is that-(CH is introduced by n-butyl glycidyl ether2)4Absorption peak.
The fire-retardant aqueous ring of the present invention with self-emulsifying function can be proved by the parsing of above-mentioned infrared spectroscopy
Oxygen resin curing agent has fire-retardant phosphorus-containing groups and amido and the saturated aliphatic chain with emulsification function, phosphorus-containing groups simultaneously
In molecular backbone.
In the reaction kettle with agitating device, by bisphenol F epoxy resin and the above-mentioned self-emulsifying function being prepared
Fire-retardant aqueous epoxy resin curing agent according to the aqueous epoxy resin curing agent active hydrogen equivalent weight and the epoxy resin
Epoxide equivalent ratio 1:1 mixed, revolving speed 200rpm is stirred evenly；Then it is slowly added into the case where revolving speed is 1000rpm described
Aqueous epoxy resin curing agent and 2 times of epoxy resin gross mass of water, after mixing evenly to get the extinguishing waterborn epoxy resin
Lotion.
By the partial size for the extinguishing waterborn epoxy resin latex that the test of Malvern particle instrument is prepared, Fig. 2 is as a result seen.From
It is 193nm that test result, which can be seen that average grain diameter, and epoxy resin particle size distribution range is 60~250nm, particle diameter distribution index
PDI is only 0.19, illustrates that the extinguishing waterborn epoxy resin partial size of the invention is tiny, distributes very evenly, to ensure that
Epoxy resin latex of the invention has excellent stability.
Embodiment 2A kind of fire-retardant aqueous epoxy resin curing agent and a kind of extinguishing waterborn epoxy with self-emulsifying function
Resin emulsion
The raw material composition of fire-retardant aqueous epoxy resin curing agent described in the present embodiment with self-emulsifying function is shown in Table 1 institute
Show, target product is prepared according to the identical step of embodiment 1 and method, the difference is that:
I. reaction temperature is 130 DEG C, reacts 4h；
II. reaction system is cooled to 65 DEG C, and reacts 4h at such a temperature.
Phosphorous reaction raw materials DOPO-MA and step I~III product carry out infrared spectrum measurement, map and absorption respectively
The variation for changing map corresponding to embodiment 1 and its absorption peak respectively at peak is similar (map summary).
In the reaction kettle with agitating device, by bisphenol F epoxy resin and the above-mentioned self-emulsifying function being prepared
Fire-retardant aqueous epoxy resin curing agent according to the aqueous epoxy resin curing agent active hydrogen equivalent weight and the epoxy resin
Epoxide equivalent ratio 0.8:1.0 mixed, revolving speed 100rpm is slowly added into institute in the case where revolving speed is 1000rpm after mixing evenly
The water of aqueous epoxy resin curing agent and 2.5 times of epoxy resin gross mass is stated, after mixing evenly up to the extinguishing waterborn epoxy
Resin emulsion.
By the partial size for the extinguishing waterborn epoxy resin latex that the test of Malvern particle instrument is prepared, Fig. 2 is as a result seen.With
The test result for the extinguishing waterborn epoxy resin latex that embodiment 1 is prepared is similar, the extinguishing waterborn asphalt mixtures modified by epoxy resin of the present embodiment
Rouge particle size distribution range is 70~310nm, and particle diameter distribution indices P DI is only 0.21, and average grain diameter 232nm illustrates the present invention
The epoxy resin partial size it is tiny, distribute very evenly, to ensure that extinguishing waterborn epoxy resin latex tool of the invention
There is excellent stability.
Embodiment 3~5A kind of fire-retardant aqueous epoxy resin curing agent and a kind of extinguishing waterborn with self-emulsifying function
Epoxy resin latex
The raw material composition of the fire-retardant aqueous epoxy resin curing agent with self-emulsifying function of embodiment 3~5 is shown in Table 1 institute
Show, is prepared substantially according to method and steps described in embodiment 1.
In the reaction kettle with agitating device, by bisphenol F epoxy resin or bisphenol A epoxide resin respectively with above-mentioned implementation
The aqueous epoxy resin curing agent that is prepared of example according to the aqueous epoxy resin curing agent active hydrogen equivalent weight and the ring
Epoxide equivalent ratio 0.8:1.0~1.1:1 of oxygen resin is mixed, and 100~300rpm of revolving speed is in revolving speed after mixing evenly
The water of the aqueous epoxy resin curing agent and 1~4 times of epoxy resin gross mass is slowly added under 1000rpm, after mixing evenly
Up to the extinguishing waterborn epoxy resin latex.
The raw material of aqueous epoxy resin curing agent described in 1 embodiment 1-5 of table forms
Comparative example 1~3A kind of epoxy curing agent and its epoxy resin latex of preparation
The raw material composition of the epoxy curing agent of comparative example 1~3 is shown in Table 2, according to the identical step of embodiment 1
Epoxy curing agent is prepared with method, then prepares epoxy resin latex；But it ends in failure.Wherein, comparative example 1
Fail in the preparation process of curing agent, this is because the ratio of epoxy resin and DOPO-HQ are more than 2:1, epoxy resin is superfluous,
When carrying out second step reaction, curing reaction is had occurred in the triethylene tetramine of superfluous epoxy resin and addition, leads to the failure of an experiment；
Comparative example 2 fails during preparing epoxy resin latex, and reason is that the dosage of DOPO-HQ is much (for epoxy resin E-44
4.5 times), the excessive DOPO not reacted reacts with the chain extender (butyl glycidyl ether) that the later period is added and consumes chain extension
Agent causes there are primary amine group in curing agent product, and primary amine group reacts with epoxy group at room temperature, thus emulsifying
It is cured reaction, emulsification failure in the process；Comparative example 3 also fails in curing agent preparation process, and reason is epoxy resin
There are four epoxy groups for tool in AG-80 molecule, unreacted in AG-80 molecular structure when addition triethylene tetramine is reacted
Epoxy group crosslinks the solidification for reacting and causing system with triethylene tetramine, the failure for causing curing agent to prepare.
The raw material of epoxy curing agent described in 2 comparative example 1~3 of table forms
Test case 1Measurement (1) flame retardant property of the extinguishing waterborn epoxy resin latex performance of preparation of the embodiment of the present invention is surveyed
It is fixed
The extinguishing waterborn epoxy resin latex and commercially available epoxy resin latex product that the embodiment of the present invention is prepared
Flame retardant property tested.
Test sample preparation process: epoxy resin latex to be measured is placed in 60 DEG C of vacuum drying ovens (0.06MPa) dry
Then sample is successively solidified 1h by 72h in 100 DEG C and 140 DEG C of baking ovens, and cooled to room temperature is to prevent sample fracture.
Respectively measure each sample limit oxygen index (LOI) (according to method as defined in GB T 2406.1-2008) and vertically
Combustion method (standard method of test recorded according to UL-94), the results are shown in Table 3.
3 flame retardant property measurement result of table
a: U.S. Hexion Epikote6520-WH-53A.
By data in upper table it is found that the fire-retardant aqueous epoxy resin curing agent with self-emulsifying function of the invention is made
LOI value after standby extinguishing waterborn epoxy resin latex sample solidifies respectively reaches 26.1 to 29.5, hence it is evident that is higher than common non-
The 20.7 of fire-retardant commodity sample, and the UL-94 test highest of extinguishing waterborn epoxy resin latex of the invention can achieve V0 grades.
The above results illustrate that extinguishing waterborn epoxy resin latex prepared by the present invention has preferable flame retardant property.
(II) measurement of epoxy resin latex stability
Dilution stability test method: it in 10ml with 2ml epoxy resin latex to be measured is added in graduated test tube, shakes
It is placed for 24 hours after even, sees whether layering or precipitating, such as nothing, be then denoted as and pass through.
Mechanical stability test method: 300ml epoxy resin latex to be measured is placed in the dispersing head of high speed disperser, is opened
Dynamic stirring, revolving speed are adjusted to 3000rpm, after stirring 0.5h, with 120 mesh net filtrations, see if there is flocculate.Such as nothing, then pass through
Centrifugal stability test method: 50ml epoxy resin latex to be measured is placed in supercentrifuge, revolving speed is adjusted to
3000rpm, taking-up see whether layering or precipitating, such as nothing, are then denoted as and pass through.
Calcium ion stability test method: in 10ml with 5ml epoxy resin latex to be measured is added in graduated test tube,
Then it is slowly added into 1ml calcium chloride solution (concentration 5wt%), is placed after shaking up for 24 hours, sees whether layering or precipitating,
Such as nothing, then it is denoted as and passes through.
Measurement result is shown in Table 4.
4 stability of emulsion test result of table
a: the commodity sample is anion epoxy resin latex, Dow OudraSpers-WB3002 aqueous epoxy resins
Dispersion.
b: the commodity sample is non-ionic epoxy resin emulsion, U.S. Hexion Epikote3510-W-60A.
As can be seen from Table 4, compared with commercially available anion epoxy resin latex and non-ionic epoxy resin emulsion, this
The prepared extinguishing waterborn epoxy resin latex of invention has excellent dilution stability simultaneously, and mechanical stability, centrifugation are stablized
Property and Calcium ion stability.To find out its cause, be that there is excellent emulsifiability because of aqueous epoxy resin curing agent of the invention,
Therefore the aqueous epoxy resin emulsion partial size that is prepared is small, narrowly distributing, thus make lotion that there is excellent stability, it is completely full
The storage and application requirement of sufficient product.
Claims (10)
1. a kind of fire-retardant aqueous epoxy resin curing agent with self-emulsifying function, raw material includes the ring containing two epoxy groups
Oxygen resin, DOPO derivative, fatty amine and chain extender containing two or more amidos, the method by including the following steps
It is prepared:
I. contain the epoxy resin of two epoxy groups and DOPO derivative reacts under the effect of the catalyst；
II. the fatty amine containing two or more amidos is added in the reaction system that obtains to step I, obtained after reaction it is phosphorous,
Nitrogen compound；
III. chain extender is added in the reaction system obtained to step II, and phosphorous, nitrogen epoxy hardener is obtained after reaction；
IV. the reaction system that is obtained to step III be added acid-base neutralization agent to get.
2. aqueous epoxy resin curing agent according to claim 1, which is characterized in that the ring for containing two epoxy groups
Oxygen resin is selected from bisphenol A epoxide resin or bisphenol F epoxy resin；
Preferably, the DOPO derivative in DOPO-HQ, DOPO-MA, DOPOBDO, DOPO-ITA and DHP-DOPO one
Kind；
It is highly preferred that the DOPO derivative is DOPO-HQ；
Preferably, the fatty amine containing two or more amidos is selected from diethylenetriamine, triethylene tetramine, four ethylene five
One of amine, pentaethylene hexamine, polyethylene polyamine, ethylenediamine, propane diamine, butanediamine, pentanediamine and hexamethylene diamine or any ratio
Example it is a variety of；
It is highly preferred that the fatty amine containing two or more amidos in triethylene tetramine and tetraethylenepentamine one
Two kinds of kind or arbitrary proportion；
The chain extender is the compound with an epoxy group；More preferably from methyl glycidyl ether, propylglycidyl
Ether, butyl glycidyl ether, allyl glycidyl ether, C8-C18Alkyl glycidyl ether, p-tert-butylphenol glycidol
One of ether, adjacent phenol glycidyl ethers, ethylene oxide, propylene oxide, epoxy butane and epoxypentane or arbitrary proportion
It is a variety of.
3. aqueous epoxy resin curing agent according to claim 1 or 2, which is characterized in that described to contain two epoxy groups
Epoxy resin, DOPO derivative, the fatty amine containing two or more amidos and chain extender molar ratio are as follows:
2.0:1.0:2.0:2.0~2.0:1.0:2.4:2.4.
4. aqueous epoxy resin curing agent according to any one of claim 1 to 3, which is characterized in that the step I
In, the catalyst is selected from one of triphenylphosphine, alchlor and triethylamine, more preferably triphenyl phosphorus；
It is further preferred that the 0.5 of epoxy resin quality of the additive amount of the catalyst for described in containing two epoxy groups~
3.0wt%；
It is further preferred that reaction temperature is 110 DEG C~140 DEG C in the step I, the reaction time is 2~6h；
It is highly preferred that reaction temperature is 120~130 DEG C in the step I, the reaction time is 3~4h；
In the step I, solvent is optionally the alcohols or alcohol ethers solvent that boiling point is higher than 110 DEG C；More preferably ethylene glycol monomethyl ether
Or butyl glycol ether.
5. aqueous epoxy resin curing agent according to any one of claim 1 to 4, which is characterized in that the step II
In, reaction temperature is 60 DEG C~80 DEG C, and the reaction time is 2~5h；
It is highly preferred that reaction temperature is 65~75 DEG C in the step II, the reaction time is 3~4h.
6. aqueous epoxy resin curing agent according to any one of claim 1 to 5, which is characterized in that the step III
In, reaction temperature is 60 DEG C~80 DEG C, and the reaction time is 2~5h；
Preferably, in the step III, reaction temperature is 65~75 DEG C, and the reaction time is 3~4h.
7. aqueous epoxy resin curing agent according to any one of claim 1 to 6, which is characterized in that the step IV
In, the acid-base neutralization agent is inorganic acid or organic acid；Preferably organic acid；
It is highly preferred that the acid-base neutralization agent is acetic acid；
It is further preferred that in the step IV, mole of amine groups in the acid-base neutralization agent and the epoxy curing agent
Than for 0.2~0.7:1.0, more preferably 0.3~0.6:1.0；
It is further preferred that reaction temperature is not higher than 60 DEG C, more preferably 40~50 DEG C in the step IV.
8. prepared by the fire-retardant aqueous epoxy resin curing agent described in any one of claims 1 to 7 with self-emulsifying function
Application in extinguishing waterborn epoxy resin latex.
9. a kind of extinguishing waterborn epoxy resin latex, raw material includes having self-emulsifying function described in any one of claims 1 to 7
Fire-retardant aqueous epoxy resin curing agent, epoxy resin and the water of energy, the active hydrogen equivalent weight of the aqueous epoxy resin curing agent
It is 0.8:1.0~1.1:1 with the epoxide equivalent ratio of epoxy resin, the quality of water is the aqueous epoxy resin curing agent and described
1~4 times of epoxy resin gross mass；
Preferably, the epoxide equivalent of the active hydrogen equivalent weight of the epoxy curing agent and epoxy resin ratio is 1:1；
Preferably, the quality of water is 1.5~2.5 times of the aqueous epoxy resin curing agent and the epoxy resin gross mass.
10. the preparation method of extinguishing waterborn epoxy resin latex as claimed in claim 9, includes the following steps:
It A., will be fire-retardant with self-emulsifying function described in any one of claims 1 to 7 in the container with agitating device
Aqueous epoxy resin curing agent and epoxy resin according to the aqueous epoxy resin curing agent active hydrogen equivalent weight and the ring
The ratio of epoxide equivalent ratio 0.8:1.0~1.1:1 of oxygen resin is uniformly mixed, 100~300rpm of revolving speed；
B. it is slowly added to water in the mixed system obtained to step A, 500~1500rpm of revolving speed, the lotion being stirred until homogeneous, i.e.,
?；
Preferably, in the step B, revolving speed is 800~1000rpm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111961168A (en) * | 2020-05-20 | 2020-11-20 | 华南理工大学 | Phosphorus-containing acrylic resin polymer and preparation method thereof |
| CN116254033A (en) * | 2023-01-29 | 2023-06-13 | 上海箬宇新材料有限公司 | Flexible low-density ablation heat-resistant coating and preparation method thereof |
-
2019
- 2019-03-27 CN CN201910236170.2A patent/CN110066385A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111961168A (en) * | 2020-05-20 | 2020-11-20 | 华南理工大学 | Phosphorus-containing acrylic resin polymer and preparation method thereof |
| CN116254033A (en) * | 2023-01-29 | 2023-06-13 | 上海箬宇新材料有限公司 | Flexible low-density ablation heat-resistant coating and preparation method thereof |
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Application publication date: 20190730 |