CN108504266A - A kind of preparation method of intumescent unsaturated polyester resin fireproof flame-retardant coating - Google Patents
A kind of preparation method of intumescent unsaturated polyester resin fireproof flame-retardant coating Download PDFInfo
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- CN108504266A CN108504266A CN201810460943.0A CN201810460943A CN108504266A CN 108504266 A CN108504266 A CN 108504266A CN 201810460943 A CN201810460943 A CN 201810460943A CN 108504266 A CN108504266 A CN 108504266A
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- shepardite
- unsaturated polyester
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- intumescent
- polyester resin
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
- C09D5/185—Intumescent paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a kind of preparation methods of intumescent unsaturated polyester resin fireproof flame-retardant coating, select dicyclic pentylene modified unsaturated polyester (UP) for base-material, the unsaturated polyester resin being modified in long-chain endcapped through dicyclopentadiene has good thermal stability and anti-flammability；After stearic acid modified processing shepardite, itself and melamino-formaldehyde prepolymer are interacted, the shepardite particle of Melamino-formaldehyde resin encapsulated is made after in-situ polycondensation, the expanding fire retardant that collection three elements are combined as a whole is can be used as to use, assign coating excellent carbon-forming performance, be conducive to the formation of foamed char, while shepardite particle helps to improve the stability and compactness of layer of charcoal, improve the fire-retardant and smoke suppressing of coating.
Description
Technical field
The present invention relates to unsaturated polyester (UP) fireproof coating technical fields, and in particular to a kind of intumescent unsaturated polyester resin
The preparation method of fireproof flame-retardant coating.
Background technology
The main composition of expanding fire-proof paint by base-material, carbon forming agent, at carbon accelerating agent, foaming agent, pigment etc., when by
When thermal expansion, expanding fire-proof paint foaming can form carbonaceous foam thermal insulation layer and be used for surrounding protected object, for prolonging
The heat between heat and base material is transmitted late.Based on this, prevent under object ignition or intensity caused by due to temperature increases
Drop.
Expansion type flame-retarding technology derived from expanding fire-proof paint clearly proposes acid source（At carbon accelerating agent）, charcoal source（At
Charcoal agent）And air source（Foaming agent）For three basic components of expansion type flame retardant.Wherein common acid source includes ammonium polyphosphate
(APP), ammonium magnesium phosphate, zinc borate etc. can generate phosphoric acid and its derivative when heated, play the role of providing acid source.
Charcoal source is mainly the polyol of high-carbon content, such as：Pentaerythrite (PER), polyamide, starch, carbohydrate etc..Air source
It is commonly called as foaming agent, releasable a large amount of inert gas when heated.It often selects melamine (M), urea, melamine, dicyandiamide, gather
The air source of amino-acid ester, azodiisobutyronitrile, glycine as fire retardant.
Unsaturated polyester resin (UPR, unsaturated polyester resin) is a kind of thermosetting property haveing excellent performance
Resin is obtained by dihydric alcohol, monounsaturated dicarboxylic acid (acid anhydride) and unsaturated acids (acid anhydride) polycondensation, including unsaturated linear polyesters and low molecule
The unsaturated monomer of amount.The oxygen index (OI) of unsaturated polyester resin is only 19.6%, belongs to inflammable product, fire-retardant significant.
Shepardite is non-corrosive when deriving from a wealth of sources, decomposing or noxious material discharges, and is a kind of novel nontoxic flame retardant plastics filler.By
It is high in shepardite surface energy, it is easy to happen reunion, the fire retardant as unsaturated polyester resin needs to carry out table to it when using
Face is modified.
Invention content
The present invention provides a kind of preparation methods of intumescent unsaturated polyester resin fireproof flame-retardant coating, and what is obtained is fire-retardant
Coating has lower thermal weight loss rate and higher neat coal amout, flame retardant effect excellent.
In order to achieve the above objectives, the present invention uses following technical scheme：
A kind of preparation method of intumescent unsaturated polyester resin fireproof flame-retardant coating, using stearic acid as modifying agent to water magnesium
Stone is surface-treated, the shepardite particle coated later using in situ Polycondensation method, obtained melamine formaldehyde resin, then with
It is base-material as expanding fire retardant, dicyclic pentylene modified unsaturated polyester (UP), and it is anti-that intumescent unsaturated polyester (UP) is prepared
Fiery coating；
It is as follows：
（1）The preparation of modified shepardite：
In 60-75 DEG C of water-bath, stearic acid is stirred dilution 20-30min with suitable dispersant, waits being completely dissolved,
At ambient temperature, on spray to shepardite particle after the drying, while 60-90min is disperseed to it using homogenizer,
After taking-up, the dry 20-32h in 105-110 DEG C of electric drying oven with forced convection；
（2）Melamine formaldehyde resin coats shepardite：
According to 1:The molar ratio of 2-3 mixes a certain amount of melamine with formaldehyde, is placed in heating water bath to 65-75 DEG C, is added
10%Na2CO3Solution adjusts pH value of reaction system in 8.0-8.5, and after stirring 20-30min, melamine raw material is completely dissolved, and is obtained
To homogeneous and transparent melamine formaldehyde resin pre-polymer solution；
Modification shepardite after above-mentioned drying is added in the ethanol water of 3-8%, after ultrasonic disperse 20-30min, in addition
Melamine formaldehyde resin pre-polymer solution is stated, with vinegar acid for adjusting pH value in 5.2-6.0, is slowly ramped to 58-63 DEG C, and protect
Temperature stirring 1.5-2.5h, is cooled to room temperature, uses 10%Na after completion of the reaction2CO3Solution adjusts pH value in 8.0-9.0, filters, washing
It is dry, the shepardite particle of melamine formaldehyde resin cladding is obtained, as expanding fire retardant；
（3）The preparation of coating：
Triphenyl phosphate is heated to melting in 55-65 DEG C of constant water bath box, appropriate dicyclopentadiene is then added thereto
The shepardite particle of the melamine formaldehyde resin cladding of modified unsaturated polyester resin and above-mentioned preparation, is stirred at room temperature
After mixing mixing 1-2h, micro accelerating agent methyl ethyl ketone peroxide and catalyst cobalt naphthenate is added, obtains expansion fire-proof resistance
Burning coating material.
Wherein, the shepardite grain size is dried in vacuo for 24 hours using preceding at 105-110 DEG C in 2000-5000 mesh.
Wherein, the stearic mass percentage is 1.0-2.0%, by 1:The ratio of 8-15 uses alcohol dispersant
It is diluted.
Wherein, the mass ratio of the modified shepardite and melamine formaldehyde resin prepolymer is 1:0.2-0.4.
Wherein, the shepardite particle dosage that melamine formaldehyde resin coats in the fireproof flame-retardant coating is in 30-45%.
Beneficial effects of the present invention are as follows：
Dicyclic pentylene modified unsaturated polyester resin is selected in the present invention（UPR）For base-material, through dicyclopentadiene in long-chain
The UPR that endcapped is modified has good thermal stability and anti-flammability, and carbonaceous layer can be quickly formed after burning, hinders it
Inner layer material burns；After stearic acid modified processing shepardite, the hydrophobic oleophilic oil performance of shepardite is improved, shepardite is improved and exists
Dispersibility in coating later interacts itself and melamine-formaldehyde prepolymer, and melamine is made after in-situ polycondensation
The shepardite particle of amine-formaldehyde resin cladding, the melamine formaldehyde resin of layer structure can not only resolve into charcoal when heated
It is used as carbonized agent, and releases ammonia, carbonaceous layer can be blown out porous froth bed, while stearic acid modified rear water
Magnesite decomposes after being heated with triphenyl phosphate, can generate phosphoric acid and its derivative, plays the role of providing acid source, promotes heat drop
In solution preocess at charcoal process, the shepardite particle of melamine formaldehyde resin cladding can be used as collection three elements and be combined as a whole
Expanding fire retardant use, assign coating excellent carbon-forming performance, be conducive to the formation of foamed char, while shepardite particle has
The stability and compactness for helping improve layer of charcoal, improve the fire-retardant and smoke suppressing of coating.
Specific implementation mode
Embodiment 1
A kind of preparation method of intumescent unsaturated polyester resin fireproof flame-retardant coating, using stearic acid as modifying agent to water magnesium
Stone is surface-treated, the shepardite particle coated later using in situ Polycondensation method, obtained melamine formaldehyde resin, then with
It is base-material as expanding fire retardant, dicyclic pentylene modified unsaturated polyester (UP), and it is anti-that intumescent unsaturated polyester (UP) is prepared
Fiery coating；
It is as follows：
（1）The preparation of modified shepardite：
Shepardite grain size is dried in vacuo for 24 hours using preceding at 105 DEG C in 2000-5000 mesh；
In 70 DEG C of water-bath, stearic acid alcohol dispersant is pressed 1:10 ratio is diluted, stearic acid content 1.5%,
Agitation and dilution 30min on spray to shepardite particle after the drying, while utilizing homogenizer pair at ambient temperature
It disperses 80min, after taking-up, is dried for 24 hours in 105 DEG C of electric drying oven with forced convections；
（2）Melamine formaldehyde resin coats shepardite：
According to 1:2.5 molar ratio mixes a certain amount of melamine with formaldehyde, is placed in heating water bath to 70 DEG C, is added 10%
Na2CO3Solution adjusts pH value of reaction system 8.5, and after stirring 30min, melamine raw material is completely dissolved, and obtains transparent and homogeneous
Melamine formaldehyde resin pre-polymer solution；
Modification shepardite after above-mentioned drying is added in 5% ethanol water, after ultrasonic disperse 30min, above-mentioned trimerization is added
The mass ratio of cyanogen amine-formaldehyde resin pre-polymer solution, modified shepardite and melamine formaldehyde resin prepolymer is 1:0.25,
With vinegar acid for adjusting pH value 6.0, it is slowly ramped to 60 DEG C, and insulated and stirred 2h, is cooled to room temperature after completion of the reaction, with 10%
Na2CO3Solution adjusts pH value 8.5, and drying is washed in filtering, obtains the shepardite particle of melamine formaldehyde resin cladding；
（3）The preparation of coating：
Triphenyl phosphate is heated to melting in 60 DEG C of constant water bath box, is then added thereto appropriate dicyclic pentylene modified
Unsaturated polyester resin and above-mentioned preparation melamine formaldehyde resin cladding shepardite particle, be stirred at room temperature mixed
After closing 1h, micro accelerating agent methyl ethyl ketone peroxide and catalyst cobalt naphthenate is added, obtains expansion fire-proof anti-flaming dope.
The shepardite particle dosage that melamine formaldehyde resin coats in the fireproof flame-retardant coating is 35%.
Claims (5)
1. a kind of preparation method of intumescent unsaturated polyester resin fireproof flame-retardant coating, which is characterized in that made using stearic acid
Shepardite is surface-treated for modifying agent, uses in situ Polycondensation method later, the water of melamine formaldehyde resin cladding is made
Magnesite particle, then using it as expanding fire retardant, dicyclic pentylene modified unsaturated polyester (UP) is base-material, and intumescent is prepared
Unsaturated polyester (UP) fireproof coating；
It is as follows：
（1）The preparation of modified shepardite：
In 60-75 DEG C of water-bath, stearic acid is stirred dilution 20-30min with suitable dispersant, waits being completely dissolved,
At ambient temperature, on spray to shepardite particle after the drying, while 60-90min is disperseed to it using homogenizer,
After taking-up, the dry 20-32h in 105-110 DEG C of electric drying oven with forced convection；
（2）Melamine formaldehyde resin coats shepardite：
According to 1:The molar ratio of 2-3 mixes a certain amount of melamine with formaldehyde, is placed in heating water bath to 65-75 DEG C, is added
10%Na2CO3Solution adjusts pH value of reaction system in 8.0-8.5, and after stirring 20-30min, melamine raw material is completely dissolved, and is obtained
To homogeneous and transparent melamine formaldehyde resin pre-polymer solution；
Modification shepardite after above-mentioned drying is added in the ethanol water of 3-8%, after ultrasonic disperse 20-30min, in addition
Melamine formaldehyde resin pre-polymer solution is stated, with vinegar acid for adjusting pH value in 5.2-6.0, is slowly ramped to 58-63 DEG C, and protect
Temperature stirring 1.5-2.5h, is cooled to room temperature, uses 10%Na after completion of the reaction2CO3Solution adjusts pH value in 8.0-9.0, filters, washing
It is dry, the shepardite particle of melamine formaldehyde resin cladding is obtained, as expanding fire retardant；
（3）The preparation of coating：
Triphenyl phosphate is heated to melting in 55-65 DEG C of constant water bath box, appropriate dicyclopentadiene is then added thereto
The shepardite particle of the melamine formaldehyde resin cladding of modified unsaturated polyester resin and above-mentioned preparation, is stirred at room temperature
After mixing mixing 1-2h, micro accelerating agent methyl ethyl ketone peroxide and catalyst cobalt naphthenate is added, obtains expansion fire-proof resistance
Burning coating material.
2. a kind of preparation method of intumescent unsaturated polyester resin fireproof flame-retardant coating according to claim 1, special
Sign is that the shepardite grain size is dried in vacuo for 24 hours using preceding at 105-110 DEG C in 2000-5000 mesh.
3. a kind of preparation method of intumescent unsaturated polyester resin fireproof flame-retardant coating according to claim 1, special
Sign is that the stearic mass percentage is 1.0-2.0%, by 1:The ratio of 8-15 is carried out dilute using alcohol dispersant
It releases.
4. a kind of preparation method of intumescent unsaturated polyester resin fireproof flame-retardant coating according to claim 1, special
Sign is that the mass ratio of the modified shepardite and melamine formaldehyde resin prepolymer is 1:0.2-0.4.
5. a kind of preparation method of intumescent unsaturated polyester resin fireproof flame-retardant coating according to claim 1, special
Sign is that the shepardite particle dosage that melamine formaldehyde resin coats in the fireproof flame-retardant coating is in 30-45%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810460943.0A CN108504266A (en) | 2018-05-15 | 2018-05-15 | A kind of preparation method of intumescent unsaturated polyester resin fireproof flame-retardant coating |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810460943.0A CN108504266A (en) | 2018-05-15 | 2018-05-15 | A kind of preparation method of intumescent unsaturated polyester resin fireproof flame-retardant coating |
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| Publication Number | Publication Date |
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| CN108504266A true CN108504266A (en) | 2018-09-07 |
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| CN201810460943.0A Withdrawn CN108504266A (en) | 2018-05-15 | 2018-05-15 | A kind of preparation method of intumescent unsaturated polyester resin fireproof flame-retardant coating |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110330847A (en) * | 2019-07-12 | 2019-10-15 | 顺德职业技术学院 | Expansible type anti-flaming dope and preparation method thereof |
| CN115368767A (en) * | 2022-08-03 | 2022-11-22 | 中海油常州涂料化工研究院有限公司 | Water-based fireproof coating |
-
2018
- 2018-05-15 CN CN201810460943.0A patent/CN108504266A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110330847A (en) * | 2019-07-12 | 2019-10-15 | 顺德职业技术学院 | Expansible type anti-flaming dope and preparation method thereof |
| CN115368767A (en) * | 2022-08-03 | 2022-11-22 | 中海油常州涂料化工研究院有限公司 | Water-based fireproof coating |
| CN115368767B (en) * | 2022-08-03 | 2023-06-20 | 中海油常州涂料化工研究院有限公司 | Water-based fireproof paint |
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Application publication date: 20180907 |