Note: Descriptions are shown in the official language in which they were submitted.
Preparation for acrylate resin coating and paint of flame-retardant, water-
proof and
water-based core-shell type
Technical field
[01] The present invention relates to a method for preparing an aqueous core-
shell type acrylate
resin, particularly a flame-retardant aqueous core-shell type acrylate resin
coating and a method
for preparing a paint.
Background Arts
[02] Paint, the traditional name in China is paint.The so-called paint is a
continuous film that is
applied to the surface of the object to be protected or decorated and can form
a firm adhesion with
the object to be coated, usually based on resin, oil or emulsion, with or
without adding pigments,
fillers, and additions. A viscous liquid prepared with an organic solvent or
water.
[03] In the 60 years since the founding of the People's Republic of China,
along with the
development of various industries in the national economy, the supporting
coatings industry has
gradually developed from an extremely unobtrusive small industry into an
important industry in
all areas of the national economy.After several generations of hard work and
pioneering efforts,
China has become the world's second largest paint producer and consumer, and
has entered the
mainstream of the world's coatings industry.
[04] Waterborne coatings and powder coatings have become a climate, especially
architectural
coatings based on waterborne paints, which account for about 38% of the total
coatings in China.
Because the chemical properties of water-based paints and oil-based paints are
fundamentally
different, and the properties of water-based paints and oil-based paints are
also very different, it is
unscientific to define water-based paints as a major branch of the paint
industry. .Water-based
paints and oil (sex) paints should be listed as two different series in liquid
paints.
[05] In the early stage of applying acrylic resin to leather finishing agent,
people used the polymer
synthesis technology such as bonding technology and cross-linking to introduce
functional bases
for their shortcomings such as water repellency, heat viscosity, cold
brittleness and solvent
resistance. Modification of styrene, acrylonitrile, etc., to meet the needs of
the innate performance
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of leather finishing, and also established a foundation for the research of
modern
high-performance leather.
[06] The self-crosslinking acrylic resin finishing agent developed by Yang et
al. can be obtained
by introducing N-methylol acrylamide and acrylic acid in a butyl acrylate-
acrylonitrile-methyl
acrylate emulsion polymerization system. A leather finishing agent with better
performance can
improve the problem that the leather finishing agent is not resistant to
organic solvents.
[07] Qi Shifang et al., after halogenating an acrylic monomer with phosphorus
trichloride, reacted
with polyethylene glycol to prepare a monoethylene glycol monoacrylate monomer
containing a
long polar side group, and then the single The acrylic resin emulsion is
prepared by
copolymerization of the body with other acrylates and vinyl compounds. The
resin film has high
tensile strength and elongation at break due to the presence of long, soft
polar side groups;
Significantly improve the solvent and water resistance of the coating. Core-
shell emulsion
polymerization is a new technology developed in the 1980s. It is a new resin
polymerization
technology based on the principle of particle design. The core-shell type
acrylic emulsion
copolymer is heterogeneously coexisted in the latex particles by two or more
kinds of polymers,
that is, one polymer is a core, and the other is a core shell, and an outer
layer is coated with an
emulsion layer. The obtained emulsion has good anti-back tack, low film
forming temperature,
best film forming property, stability and superior mechanical properties, and
the emulsion has the
shell layer or the core layer of the latex particles by selecting different
performance monomers
respectively. Specific properties, the core-shell structure can solve the
problems of resin properties
such as soft and hard, heat and cold resistance. This technology has been
widely used in the
synthesis and modification of acrylic resins.
[08] However, the currently used water-based acrylic resin coatings are also
increasingly showing
their insurmountable disadvantagesI71. For example, in the case of low
temperature and high
humidity, the drying is slow and difficult to form a film; the coating film is
prone to mildew and is
easily contaminated. It is not wear-resistant; the freeze-thaw stability and
mechanical stability are
not good; the dry and wet rubbing resistance of the finishing agent, the film
formation
compactness, the flatness and the glossiness are not good, and the further
improvement of the
performance of the finishing material is limited.
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[09] In addition, there are defects in that the flame retardant performance is
not high and the
emulsifier is relatively cumbersome.
[10] 201610506501.6 The present invention relates to a self-flame-retardant
acrylic emulsion,
characterized in that the self-flame-retardant modified styrene-acrylic
emulsion is a reactive
halogen-containing flame-retardant vinyl monomer which can be used with
acrylic acid. The ester
monomer undergoes emulsion copolymerization, and the flame retardant group is
fixed on the
molecular structure of the resin by chemical bonding, and does not resolve and
fall off. The
synthesized acrylic emulsion has self-flame retarding property, and no
additional resistance is
needed when preparing the coating. The flammable agent can provide long-
lasting flame retardant
properties; the present invention also provides a method for preparing a self-
flame retardant
acrylic emulsion. The self-defining flame-retardant acrylic emulsion prepared
by the invention has
good adhesion, water resistance and durability, and the prepared coating film
has water resistance,
alkali resistance, scrub resistance and long-lasting self-flame retarding
property, and is widely
used indoors. Flame retardant coating for exterior wood, steel structure and
building, which plays
a decorative role and protects
201610645798.4 The invention relates to the field of production and
preparation of polymer
products, in particular to an acrylic resin flame retardant coating, 12-18
parts amino resin, 3-6
parts ethyl acrylate, 3-5 parts of butyl acrylate, 2-10 parts melamine, 1-2
parts defoamer, 2-6 parts
of pigment and filler, 2-3 parts of acrylic acid, 60 to 70 parts by weight of
an anionic aqueous
resin containing a carboxyl group, 5 to 10 parts by weight of a water-
resistant pigment, 7 to 8 parts
by weight of an auxiliary agent, 1 to 2 parts by weight of an interfacial
adhesion promoter, 4-8
parts of charcoal agent, 10-20 parts by weight of deionized water; interface
adhesion promoter is
formed by reacting metal organic compounds, polyisocyanates and hydroxyl
groups-containing
oligomers. The acrylic resin coating of the present invention has excellent
interfacial adhesion
with the substrate and has a good flame retarding effect.
Summary of the invention
[11] The present invention relates to a flame-retardant aqueous core-shell
type acrylate resin
coating and a preparation method of a paint. The main synthetic route is to
improve the
water-based core-shell type acrylate resin coating and paint by flame
retardant functionalization of
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the crosslinking agent. The flame retardancy, that is, the flame retardant
modification from the
viewpoint of the chemical materials required for the acrylate resin, and the
stability of the
acid-base salt is improved due to the anionic and nonionic combination
required in the synthesis
of the acrylate resin. The mechanical stirring stability, the two are combined
into one, and a new
type of emulsifier with both anionic and nonionic properties is prepared. The
emulsifier has the
advantages of convenient operation, stable acid-base salt stability and
mechanical stirring stability.
Advantage.
[12] A method for preparing a flame-retardant aqueous core-shell acrylate
resin coating and a
paint, the preparation method thereof is:
(1) Adding the following weight ratio raw materials to the reaction vessel: 50
to 65 parts of water,
0.4 to 2.3 parts of emulsifier, 0.6 to 3.0 parts of methacrylic acid, and 0.3
to 0.7 parts of acrylic
acid, and the temperature is raised to 45 C, and stirred for 40 minutes.
Adding A monomer, the
emulsification time is 30-70min; the temperature is raised to 65 C and the
reflux water is started.
After the temperature is raised to 77 C, the temperature is kept, and the
initiator A0.3-0.7 parts by
weight is added dropwise. The dropping time lasts for 1-3 hours. After the
reaction, 2-4h, the core
layer emulsion is obtained;
The monomer A is prepared by mixing 2-7 parts by weight of butyl acrylate, 2-5
parts by weight
of methyl methacrylate, 3-3.5 parts by weight of ethyl acrylate, and 2-4 parts
of hydroxyethyl
acrylate;
(2) simultaneously adding B monomer and 0.3 to 0.4 parts by weight of
initiator A to the core
layer emulsion obtained in the step (1), and the dropwise addition time lasts
for 1 to 2 hours, and
after the completion of the dropwise addition, the reaction is stirred at 75
to 85 C for 3 hours.
Then add 0.6-1.1 parts by weight of flame retardant cross-linking agent, heat-
treat 75-95 C for
l-3h, cool down to 50 C, add 0.3 parts by weight of emulsifier, react time for
30min, add
ammonia to adjust pH to 7-8 , the flame retardant, water-repellent water-based
core-shell acrylate
resin coating and paint;
The B monomer is obtained by mixing 1 to 6 parts by weight of butyl acrylate,
3 to 7 parts by
weight of methyl methacrylate, 3 to 5 parts by weight of ethyl acrylate, and 2
to 6 parts of
hydroxyethyl acrylate.
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[13] Initiator A is any one of ammonium persulfate, potassium persulfate, and
potassium hydrogen
persulfate; the emulsifier is prepared by adding 15 g of triethylenetetramine
and 70 g of water to a
three-necked flask, and heating to 30 C. 40 g of ethylene oxide and 1.2 to
2.4 g of substance A
were slowly added, and after reacting at 30 C for 2 h, cooled to 25 C to
obtain an intermediate
product, and then 15 g of dodecylphenol and 1.6 g of pentadecyl group were
added. Phenol and
substance B0.3g, and then increase the temperature to 100 C reflux reaction
for lh, the solvent is
distilled off under reduced pressure, which is an emulsifier; substance A is 2-
bromobutyric acid
ethyl ester, 9-fluorenyl methyl chloroformate, Any one of
trimethylcyclotriborane; the substance
B is any one of ethoxylated amine hydrochloride, methylethylamine and acetic
anhydride; the
flame retardant crosslinking agent is prepared by: 2.1 g of fork diphosphonic
acid, 2.5 g of
phosphorus tetramethylolsulfate and 1.2 g of the substance C1.2 were added to
250 ml of a
three-necked flask, reacted at 70 C for 1 h, and 1.5 g of formamide and 1.6
g of
2,3-pyridinedicarboxylic acid were further added. The reaction is carried out
at 65 C for 1.5 h to
obtain the flame-retardant crosslinking agent; the substance C is any one of
4,41-bipyridine,
aminoacetonitrile or iminodiacetonitrile.
[14] The advantages of the invention are:
(1) The flame retardant function of the cross-linking agent is improved to
improve the flame
retardancy of the aqueous core-shell type acrylate resin coating and the
paint, that is, from the
viewpoint of the chemical materials required for the acrylate resin, At the
same time, due to the
need of anionic and nonionic complexes in the synthesis of acrylate-based
resins to improve the
stability of acid-base salts and the stability of mechanical agitation, the
two are combined into one,
and a new type of anionic and nonionic properties is produced. An emulsifier
which has the
advantages of convenient operation, stability of acid-base salt and stability
of mechanical stirring.
[15] (2) 2-bromobutyric acid ethyl ester, 9-fluorenyl methyl chloroformate,
trimethylcyclotriboroxane as an emulsifier synthesis catalyst, and ethoxylated
amine
hydrochloride, methyl Ethylamine and acetic acid propionic anhydride to
enhance the synergist of
dodecylphenol and m-pentadecylphenol; 4,4'-bipyridine, aminoacetonitrile,
iminodiacetonitrile as
hydroxyethylidene diphosphonic acid, tetrahydroxyl A catalyst for phosphorus
methyl sulfate.
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[16] (3) The mechanism of the present invention is to form a dense film by
using a crosslinking
agent, and a flame retardant group on the surface of the acrylate resin,
thereby reducing the
burning speed of the flame and improving the flame retardancy thereof. .
Embodiments
[17] Example 1
A method for preparing a flame-retardant aqueous core-shell acrylate resin
coating and a paint, the
preparation method thereof is:
(1) Adding the following weight ratio raw materials to the reaction vessel: 50
parts of water, 0.4
parts of emulsifier, 0.6 parts of methacrylic acid and 0.3 parts of acrylic
acid were added to the
reaction vessel, and the temperature was raised to 45 C, stirred for 40
minutes, and added to A.
Monomer, the emulsification time is 30min; the temperature is raised to 65 C,
the reflux water is
started, the temperature is raised to 77 C, the temperature is kept, 0.3
parts by weight of
ammonium persulfate is added dropwise (dissolved with 5 g of water), the
dropping time is
continued for 1 h, and the reaction is completed after the dropwise addition.
2h, obtained a core
layer emulsion;
The A monomer is prepared by mixing 2 parts by weight of butyl acrylate, 2
parts by weight of
methyl methacrylate, 3 parts by weight of ethyl acrylate, and 2 parts of
hydroxyethyl acrylate;
(2) simultaneously adding B monomer and 0.3 parts by weight of ammonium
persulfate (dissolved
with 5 g of water) to the core layer emulsion obtained in the step (1), the
dropwise addition time is
continued for 1 hour, and after the completion of the dropwise addition, the
reaction is stirred at
75 C for 3 hours. Then add 0.6 parts by weight of flame retardant cross-
linking agent, keep the
reaction time of 75 C for 1 h, reduce the temperature to 50 C, add 0.3
parts by weight of
emulsifier, the reaction time is 30 min, add ammonia to adjust the pH value to
7-8, and obtain the
resistance Water-based core-shell acrylate resin coatings and paints;
The B monomer is a mixture of 1 part by weight of butyl acrylate, 3 parts by
weight of methyl
methacrylate, 3 parts by weight of ethyl acrylate, and 2 parts of hydroxyethyl
acrylate.
[18] The emulsifier is prepared by adding 15 g of triethylenetetramine and 70
g of water to a
three-necked flask. After heating to 30 C, 40 g of ethylene oxide and 1.2 g
of ethyl
2-bromobutyrate are slowly added at 30 C. After 2 h of reaction, it was
cooled to 25 C to
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obtain an intermediate product, then 15 g of dodecylphenol, 1.6 g of m-
pentadecylphenol and 0.3
g of ethoxylated amine salt were added, and the temperature was raised to 100
C. The reaction
was refluxed for 1 h, and the solvent was distilled off under reduced pressure
to obtain an
emulsifier;
The flame-retardant cross-linking agent is prepared by adding 2.1 g of
hydroxyethylidene
diphosphonic acid, 2.5 g of tetramethylolsulfate, and 1.2 g of 4,4'-bipyridine
to 250 ml of a
three-necked flask, and reacting at 70 C for 1 h. Further, 1.5 g of
formamide and 1.6 g of
2,3-pyridinedicarboxylic acid were added, and the mixture was reacted at 65
C for 1.5 hours to
obtain a flame-retardant crosslinking agent.
[19] Example 2
A method for preparing a flame-retardant aqueous core-shell acrylate resin
coating and a paint, the
preparation method thereof is:
(1) The following weight ratio raw materials were added to the reaction
vessel: 65 parts of water,
2.3 parts of emulsifier, 3.0 parts of methacrylic acid and 0.7 parts of
acrylic acid, and the
temperature was raised to 45 C, stirred for 40 minutes, and A monomer was
added to
emulsification time. 70min; heating to 65 C began to pass the reflux water,
the temperature was
raised to 77 C after the insulation, dropwise addition of 0.7 parts by
weight of potassium
persulfate (dissolved with 5g of water), the addition time lasted 3h, after
the addition of reaction,
4h, the core layer Emulsion
The A monomer is prepared by mixing 7 parts by weight of butyl acrylate, 5
parts by weight of
methyl methacrylate, 3.5 parts by weight of ethyl acrylate, and 4 parts of
hydroxyethyl acrylate;
(2) simultaneously adding B monomer and 0.4 parts by weight of potassium
persulfate (dissolved
with 5 g of water) to the core layer emulsion obtained in the step (1), the
dropwise addition time is
continued for 2 hours, and after the completion of the dropwise addition, the
mixture is stirred at
85 C for 3 hours. Then add 1.1 parts by weight of flame retardant cross-
linking agent, keep the
reaction time of 95 C for 3 h, reduce the temperature to 50 C, add 0.3
parts by weight of
emulsifier, react time for 30 mm, add ammonia water to adjust the pH value to
7-8, and obtain the
resistance Water-based core-shell acrylate resin coatings and paints;
The B monomer was prepared by mixing 6 parts by weight of butyl acrylate, 7
parts by weight of
methyl methacrylate, 5 parts by weight of ethyl acrylate, and 6 parts of
hydroxyethyl acrylate.
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[20] The emulsifier is prepared by adding 15 g of triethylenetetramine and 70
g of water to a
three-necked flask, and after heating to 30 C, 40 g of ethylene oxide and
2.4 g of
9-fluorenylmethyl chloroformate are slowly added. After reacting at 30 C for
2 h, it was cooled
to 25 C to obtain an intermediate product, and then 15 g of dodecylphenol,
1.6 g of
m-pentadecylphenol and methylethylamine 0.3 g were added, and the temperature
was raised to
100 C to reflux. After reacting for 1 hour, the solvent is distilled off
under reduced pressure to
obtain an emulsifier; the flame-retardant cross-linking agent is prepared by
adding 2.1 g of
hydroxyethylidene diphosphonic acid, 2.5 g of tetramethylolsulfate, and 1.2 g
of aminoacetonitrile
to three. In a 250 ml flask, the reaction was carried out at 70 C for 1 h,
and 1.5 g of formamide
and 1.6 g of 2,3-pyridinedicarboxylic acid were further added, and the mixture
was reacted at 65
C for 1.5 h to obtain a flame-retardant crosslinking agent.
[21] Example 3
A method for preparing a flame-retardant aqueous core-shell acrylate resin
coating and a paint, the
preparation method thereof is:
(1) The following weight-matching raw materials were added to the reaction
vessel: 57 parts of
water, 1.3 parts of emulsifier, 1.8 parts of methacrylic acid and 0.5 parts of
acrylic acid, and the
temperature was raised to 45 C, stirred for 40 minutes, and A monomer was
added to
emulsification time. 50min; heating to 65 C began to pass the reflux water,
the temperature was
raised to 77 C after the incubation, 0.5 parts by weight of potassium
persulfate (dissolved with
5g of water), the addition time lasted 2h, after the addition of reaction, 3h,
obtained nuclear Layer
emulsion
The A monomer is prepared by mixing 4.5 parts by weight of butyl acrylate, 3.5
parts by weight
of methyl methacrylate, 3.3 parts by weight of ethyl acrylate, and 3 parts of
hydroxyethyl acrylate;
(2) simultaneously adding B monomer and 0.3 parts by weight of potassium
persulfate (dissolved
with 5 g of water) to the core layer emulsion obtained in the step (1), the
dropping time is
continued for 1.5 hours, and the mixture is kept at 80 C after the dropwise
addition. 3h, adding
0.8 parts by weight of flame retardant cross-linking agent, keeping the
reaction time of 85 C for
2 h, cooling to 50 C, adding 0.3 parts by weight of emulsifier, reaction
time 30 min, adding
ammonia to adjust pH to 7-8, Flame-retardant water-based core-shell acrylate
resin coatings and
paints;
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The B monomer was prepared by mixing 3.5 parts by weight of butyl acrylate, 5
parts by weight
of methyl methacrylate, 4 parts by weight of ethyl acrylate, and 4 parts of
hydroxyethyl acrylate.
[22] The emulsifier is prepared by adding 15 g of triethylenetetramine and 70
g of water to a
three-necked flask, and after heating to 30 C, 40 g of ethylene oxide and
1.8 g of
trimethylcyclotrioxane are slowly added, at 30 After reacting at C for 2 h,
it was cooled to 25 C
to obtain an intermediate product, and then 15 g of dodecylphenol, 1.6 g of m-
pentadecylphenol
and acetic anhydride (0.3 g) were added, and the temperature was raised to 100
C to reflux for 1
h. The solvent is distilled off under reduced pressure, which is an
emulsifier; the flame-retardant
cross-linking agent is prepared by adding 2.1 g of hydroxyethylidene
diphosphonic acid, 2.5 g of
tetramethylolsulfate, and 1.2 g of iminodiacetonitrile to three. In a 250 ml
flask, the reaction was
carried out at 70 C for 1 h, and 1.5 g of formamide and 1.6 g of 2,3-
pyridinedicarboxylic acid
were further added, and the mixture was reacted at 65 C for 1.5 h to obtain
a flame-retardant
crosslinking agent.
[23] Example 4
A method for preparing a flame-retardant aqueous core-shell acrylate resin
coating and a paint, the
preparation method thereof is:
(1) The following weight ratio raw materials were added to the reaction
vessel: 50 parts of water,
2.3 parts of emulsifier, 3.0 parts of methacrylic acid and 0.3 parts of
acrylic acid, and the
temperature was raised to 45 C, stirred for 40 minutes, and A monomer was
added, and the
emulsification time was 40min; warmed to 65 C began to pass the reflux
water, the temperature
was raised to 77 C after the insulation, dropwise addition of 0.4 parts by
weight of ammonium
persulfate (dissolved with 5g of water), the addition time lasted 1.5h, after
the addition of reaction,
3h, the core layer Emulsion
The A monomer is prepared by mixing 4 parts by weight of butyl acrylate, 3
parts by weight of
methyl methacrylate, 3 parts by weight of ethyl acrylate, and 4 parts of
hydroxyethyl acrylate;
(2) simultaneously adding B monomer and 0.3 parts by weight of ammonium
persulfate (dissolved
with 5 g of water) to the core layer emulsion obtained in the step (1), the
dropwise addition time is
continued for 1 hour, and after the completion of the dropwise addition, the
reaction is stirred at
75 C for 3 hours. Then add 0.7 parts by weight of the flame retardant cross-
linking agent, keep
the reaction time of 80 C for 2 h, cool down to 50 C, add 0.3 parts by
weight of emulsifier, the
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reaction time is 30 min, add ammonia water to adjust the pH value to 7-8, and
obtain the
resistance Water-based core-shell type acrylate resin coating and paint; the B
monomer is
composed of: 3 parts by weight of butyl acrylate, 4 parts by weight of methyl
methacrylate, 4 parts
by weight of ethyl acrylate, and 6 parts by weight of hydroxyethyl acrylate
Mixed.
[24] The emulsifier is prepared by adding 15 g of triethylenetetramine and 70
g of water to a
three-necked flask, and heating to 30 C, and slowly adding 40 g of ethylene
oxide and 1.6 g of
ethyl 2-bromobutyrate at 30 C. After 2 h of reaction, it was cooled to 25
C to obtain an
intermediate product, then 15 g of dodecylphenol, 1.6 g of m-pentadecylphenol
and 0.3 g of
ethoxylated amine salt were added, and the temperature was raised to 100 C.
The reaction was
refluxed for 1 h, and the solvent was distilled off under reduced pressure to
obtain an emulsifier.
The flame-retardant cross-linking agent was prepared by adding 2.1 g of
hydroxyethylidene
diphosphonic acid, 2.5 g of tetramethylolsulfate, and 1.2 g of
aminoacetonitrile. In 250 ml of a
three-necked flask, the reaction was carried out at 70 C for 1 h, and 1.5 g
of formamide and 1.6 g
of 2,3-pyridinedicarboxylic acid were further added, and the mixture was
reacted at 65 C for 1.5
h to obtain a flame-retardant crosslinking agent.
[25] Example 5
A method for preparing a flame-retardant aqueous core-shell acrylate resin
coating and a paint, the
preparation method thereof is:
(1) The following weight ratio raw materials were added to the reaction
vessel: 65 parts of water,
2.3 parts of emulsifier, 3.0 parts of methacrylic acid and 0.7 parts of
acrylic acid, and the
temperature was raised to 45 C, stirred for 40 minutes, and A monomer was
added to
emulsification time. 70min; warming to 65 C began to pass the reflux water,
warmed to 77 C
after the insulation, dropwise addition of 0.7 parts by weight of potassium
persulfate (dissolved
with 5g of water), the addition time lasted for lh, after the completion of
the addition of reaction
for 2h, the nuclear layer Emulsion
The monomer A is prepared by mixing 7 parts by weight of butyl acrylate, 4
parts by weight of
methyl methacrylate, 3 parts by weight of ethyl acrylate, and 2 parts of
hydroxyethyl acrylate;
(2) simultaneously adding B monomer and 0.3 parts by weight of potassium
persulfate (dissolved
with 5 g of water) to the core layer emulsion obtained in the step (1), the
dropwise addition time is
continued for 1 hour, and after the completion of the dropwise addition, the
reaction is stirred at
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75 C for 3 hours. Then add 0.6 parts by weight of flame retardant cross-
linking agent, keep the
reaction time of 75 C for 1 h, reduce the temperature to 50 C, add 0.3
parts by weight of
emulsifier, the reaction time is 30 min, add ammonia to adjust the pH value to
7-8, and obtain the
resistance Water-based core-shell type acrylate resin coating and paint; the B
monomer is
composed of: 6 parts by weight of butyl acrylate, 7 parts by weight of methyl
methacrylate, 5 parts
by weight of ethyl acrylate, and 6 parts by weight of hydroxyethyl acrylate
Mixed.
[26] The preparation method of the emulsifier is to add 15 g of
triethylenetetramine and 70 g of
water to a three-necked flask, and after heating to 30 C, 40 g of ethylene
oxide and 1.6 g of
9-fluorenylmethyl chloroformate are slowly added. After reacting at 30 C for
2 h, it was cooled
to 25 C to obtain an intermediate product, and then 15 g of dodecylphenol,
1.6 g of
m-pentadecylphenol and methylethylamine 0.3 g were added, and the temperature
was raised to
100 C to reflux. After reacting for 1 h, the solvent was distilled off under
reduced pressure to
obtain an emulsifier; the preparation method of the flame-retardant cross-
linking agent was as
follows; 2.1 g of hydroxyethylidene diphosphonic acid, 2.5 g of
tetramethylolsulfate and 1.2 g of
iminodiacetonitrile were added. The mixture was reacted at 250 C for 1 hour
in 250 ml of a
three-necked flask, and 1.5 g of formamide and 1.6 g of 2,3-
pyridinedicarboxylic acid were further
added thereto, and the mixture was reacted at 65 C for 1.5 hours to obtain a
flame-retardant
crosslinking agent.
[27] Flame retardancy is measured by oxygen index and flaming time.
[28] Table 1 Test performance
Example
Example 2 Example 3 Example 4 Example 5
1
Oxygen Index/% 29.4 29.6 30.4 29.8 29.8
Flaming burning
1.1 1.6 0.8 1.2 2.1
time / s
It can be seen from Table 1 that the oxygen index of the flame-retardant
aqueous core-shell type
acrylate resin coating and paint is greatly increased, while the flaming
burning time is greatly
reduced, and the oxygen index and the flaming burning time of Example 1 of
201610506501.6
and 201610645798.4 are compared. They are 22.6, 26.5s and 24.1 and 36.5s
respectively.
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[29] Table 2 Test performance (no flame retardant crosslinker added)
Example 1 Example 2 Example 3 Example 4 Example 5
Oxygen
21.6 22.7 20.4 21.2 21.7
Index/%
Flaming
burning time31.2 32.7 29.4 22.1 25.7
/s
It can be seen from Table 2 that the oxygen index of the flame-retardant water-
based core-shell
type acrylate resin coating and the paint without the flame-retardant cross-
linking agent is greatly
reduced, and the flaming burning time is greatly improved.
[30] Table 3 test performance (add flame retardant crosslinker, no added
material C)
Example 1 Example 2 Example 3 Example 4 Example 5
Oxygen
25.2 24.7 26.4 25.3 27.2
Index/%
Flaming
burning time 11.2 22.7 25.4 16.1 18.2
/s
It can be seen from Table 3 that the flame retardant aqueous core-shell
acrylate resin coating and
the paint have a substantially higher oxygen index than the flame retardant
cross-linking agent
when the flame retardant cross-linking agent is added with no substance C. The
flame burning
time has dropped dramatically.
[31] Table 4 test performance (add flame retardant crosslinker, addition of
substance C, without
addition of 2,3-pyridinedicarboxylic acid)
Example 1 Example 2 Example 3 Example 4 Example 5
Oxygen
26.3 25.8 27.1 26.1 27.3
Index/%
Flaming
burning time 10.3 14.2 18.3 12.0 12.4
/5
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It can be seen from Table 4 that the flame retardant aqueous core-shell
acrylate resin coating and
the paint have no oxygen index when the flame retardant crosslinking agent and
the additive C are
added without adding 2,3-pyridinedicarboxylic acid. The addition of the flame
retardant
cross-linking agent is greatly increased, while the flaming burning time is
greatly reduced.
[32] Chemical resistance stability: The emulsion was mixed with a 5% sodium
chloride solution at
a volume ratio of 1:4, sealed and allowed to stand for 48 hours, and the
amount of precipitation
was observed.
[33] Gel fraction: The percentage of the weight of the gel in the synthesis of
the acrylic resin to
the weight of the theoretically obtained emulsion was measured.
[34] Table 5 Emulsion stability data
Example 1 Example 2 Example 3 Example 4 Example 5
Stable Stable Stable Stable Stable
Chemical
without without without without without
resistance
stratification stratification stratification stratification stratification
Gel filter /% 1.6 2.1 1.7 1.1 0.8
It can be seen from Table 5 that the chemical resistance and gel filtration of
the present invention
are relatively good.The gel filtration of Example 1 of the comparative samples
of 201610506501.6
and 201610645798.4 was 9.7% and 8.3%, respectively.
[35] Table 6 Emulsion stability data (without substance A)
Example 1 Example 2 Example 3 Example 4 Example 5
Stable Stable
Chemical
without Layering without Layering Layering
resistance
stratification stratification
Gel filter /% 7.6 5.8 6.2 4.8 6.6
From Table 6, it can be seen that the chemical resistance and gel filtration
of the present invention
without the substance A are remarkably lowered.
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[36] Table 7 Emulsion stability data (addition A, no addition B)
Example 1 Example 2 Example 3 Example 4 Example 5
Chemical
Layering Layering Layering Layering Layering
resistance
Gel filter /% 7.7 10.3 12.7 8.6 14.3
It can be seen from Table 7 that the gel and chemical resistance of the
unsubstance B of the
present invention are remarkably lowered.
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CA 3028455 2018-12-27
