CN108623766A - The fire-retardant melamine resin of high imino group methyl-etherified and its production method - Google Patents
The fire-retardant melamine resin of high imino group methyl-etherified and its production method Download PDFInfo
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- CN108623766A CN108623766A CN201810498832.9A CN201810498832A CN108623766A CN 108623766 A CN108623766 A CN 108623766A CN 201810498832 A CN201810498832 A CN 201810498832A CN 108623766 A CN108623766 A CN 108623766A
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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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
- C08G12/42—Chemically modified polycondensates by etherifying
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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
- 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
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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
- 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
- C08K3/2279—Oxides; Hydroxides of metals of antimony
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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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
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09D161/32—Modified amine-aldehyde condensates
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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
- C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
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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
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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
- 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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Abstract
The fire-retardant melamine resin of high imino group methyl-etherified and its production method, including：Methyl-etherified trimethylol melamine；Direct adsorption reaction removes formaldehyde under acid condition；And addition synergistic flame retardants.No matter very excellent in content of formaldehyde or flame retardant property etc. fire-retardant melamine resin according to the present invention is, is suitable for oil paint and water paint.
Description
Technical field
The present invention relates to the environmental protection productions of flame-retarded resin.
Background technology
Etherified amino resins are synthesized such as hexamethylolmelamine or trimethylol melamine using melamine
It is known technology in this field, may refer to the patent before applicant or patent application CN 103739563B, CN
103739803B, CN103709111B, CN 105968283A, CN105968281A, CN105968282A and
CN106008870A, herein also to introduce entire contents in a manner of.But these prior art generally existing content of formaldehyde
Higher, the problems such as anti-flammability is insufficient.
Invention content
The object of the present invention is to provide a kind of production methods of flame-retarded resin, can at least overcome the above-mentioned prior art to carry
And certain defect.
The production method of flame-retarded resin according to the present invention, including：
1) methanol and trimethylol melamine is added in etherifying reactor so that trimethylol melamine and methanol
Molar ratio is 1:(4~6)；
2) it is 50 DEG C~70 DEG C by the control of reaction solution temperature, pH value is adjusted to 3~5, reacts 0.5~1 hour；
3) by the reaction solution after etherification reaction by filter, wherein filter is equipped with diatomite, and diatomite is coated with
2,4- dinitrobenzenes；
4) reaction solution pH after filtering is adjusted to 8~9；
5) fire retardant, the wherein quality of fire retardant and the trimethylol melamine of above-mentioned addition are added in reaction solution
Than being 1%~5%；
6) 100 DEG C or so are warming up to, or so half an hour is stirred to react；And
7) to above-mentioned reaction solution dealcoholysis 0.5~3h of dehydration at 75~95 DEG C of temperature and vacuum condition, to obtain
To flame-retarded resin.
According to the present invention, fire retardant group becomes (mass percent)：Silica：55~60%；Magnesium hydroxide：10~
15%；Antimony oxide：25~30%.It can be silica that fire retardant, which preferably constitutes,：60%；Magnesium hydroxide：15%；Three oxygen
Change two antimony：25%.
The fire retardant of the present invention, silica especially contained therein can be with the melamine of a small amount of remaining in raw material
Amine generates synergistic effect, to reach highly effective flame-retardant purpose.In addition, this fire retardant also is compliant with more due to being halogen-free flame retardants
The environmental requirement of kind application scenario.
According to the invention, it is further possible to include：It is added after fire retardant in step 5), continues to add a small amount of melamine
Acid, the mass ratio with the trimethylol melamine of above-mentioned addition are 0.1%~0.5%.By the cyanuric acid being added
Also can react with a small amount of existing melamine in above-mentioned reaction solution and generate melamine cyanurate, thus can be added
Fire retardant form synergy halogen-free flame retardants together so that the flame retardant effect of resin of the invention significantly increases (such as reachable
UL94V-0 grades horizontal).
According to a particular embodiment of the invention, diatomaceous granularity is 60~80 mesh, and bulk density is 0.45~0.5g/
Ml, specific surface area are 4~5m2/g。
According to a preferred embodiment of the invention, every kilogram of diatomite can coat 10~15mg2,4- dinitrobenzenes.It can be with
Diatomite is coated using the dichloromethane saturated solution of 2,4- dinitrobenzenes.
The present invention by complete in acid condition etherificate after directly by reaction solution it is above-mentioned diatomaceous by being filled with
Filter, so as to convert extra formaldehyde to stable formaldehyde hydrazone, to essentially eliminate the free formaldehyde in product.
The present invention also by be added in reaction solution fire retardant and/or cyanuric acid with a small amount of trimerization for wherein containing
Cyanamide generates synergistic effect, to significantly enhance its flame retardant effect.
The present invention, by suitable raw material proportioning and reaction condition, is obtained using trimethylol melamine and methanol as raw material
Obtained methyl-etherified melamine resin (or " amino resins ").This methanol etherification amino resins be especially suitable for oil paint and
Water paint, can be well soluble in alkyd resin and acrylic resin to be made top baking vanish, when solidification have fabulous hardness,
Flexibility and outdoor weathe resistance may be used primarily for coil steel coating and automobile coating etc..
Specific implementation mode
It is further illustrated the present invention with reference to specific embodiment, it will be understood by those skilled in the art that being described below
Embodiment be intended merely to more fully understand and implement the present invention, not be used for any restrictions are made to the present invention.
Etherificate
Methanol and trimethylol melamine is added in etherifying reactor so that trimethylol melamine and methanol rub
You are than being 1:(4~6) left and right.The trimethylol melamine being wherein added be using melamine and equivalent of formaldehyde (such as
The molar ratio of melamine and formaldehyde is 1：3 or so) it is prepared under weak basic condition；Its preparation process also can be found in application
Above-mentioned patent before people or patent application, are not described in detail herein.
It it is 50 DEG C~70 DEG C by the control of reaction solution temperature, preferably 60 DEG C or so, pH value adjusts (such as using hydrochloric acid)
It is 3~5, preferably 4 or so, reacts 30~60 minutes, preferably 50 minutes or so.
Formaldehyde removes
Etherification reaction solution is directly passed through into (tubular type) filter.Diatom of the filling Jing Guo coating processing wherein in filter
Soil.
Diatomaceous granularity is 60~80 mesh, and bulk density is 0.45~0.5g/ml, and specific surface area is 4~5m2/g。
The dissolving of 2,4- dinitrobenzenes is constituted into saturated solution in methylene chloride, is then coated with diatomite, coated weight is every
Kilogram diatomite coats 10~15mg 2,4- dinitrobenzenes.
It is adjusted by means of the acidity of etherification reaction solution, free formaldehyde contained therein is passing through the silicon containing above-mentioned processing
Stable formaldehyde hydrazone can be converted to when the filter of diatomaceous earth, to realize efficient, the economic removal of formaldehyde.
Flame retardant treatment
Reaction solution pH (such as using sodium hydroxide) after filtering is adjusted to 8~9；Resistance is added in reaction solution again
Agent is fired, the mass ratio of wherein fire retardant and the trimethylol melamine of above-mentioned addition is 1%~5%；It is warming up to 100 DEG C of left sides
The right side is stirred to react or so half an hour.
Wherein fire retardant composition is preferably (mass percent)：Silica：60%；Magnesium hydroxide：15%；Three oxidations two
Antimony：25%.
Furthermore it is also possible to it is optionally added cyanuric acid again, the mass ratio with the trimethylol melamine of above-mentioned addition
It is 0.1%~0.5%.
Post-processing
To above-mentioned reaction solution dealcoholysis dehydration 0.5 at temperature 75~95 DEG C (preferably 80 DEG C or so) and vacuum condition
~3h (preferably 2h or so), to obtain flame-retarded resin.
According to the flame-retarded resin that is produced of the present invention, no matter content of formaldehyde (sample detection content is less than 2mg/100g),
Flame retardant property (sample detection reaches UL94V-0 grades of levels) etc. is very excellent；Suitable for oil paint and aqueous painting
Material, can be well soluble in alkyd resin and acrylic resin to be made top baking vanish, and there are fabulous hardness, flexibility in when solidification
And outdoor weathe resistance.
Claims (5)
1. a kind of production method of flame-retarded resin, including：
1) methanol and trimethylol melamine is added in etherifying reactor so that mole of trimethylol melamine and methanol
Than being 1:(4~6)；
2) it is 50 DEG C~70 DEG C by the control of reaction solution temperature, pH value is adjusted to 3~5, reacts 0.5~1 hour；
3) by the reaction solution after etherification reaction by filter, wherein filter is equipped with diatomite, and diatomite is coated with 2,4-
Dinitrobenzene；
4) reaction solution pH after filtering is adjusted to 8~9；
5) fire retardant is added in reaction solution, the mass ratio of wherein fire retardant and the trimethylol melamine of above-mentioned addition is
1%~5%；
6) 100 DEG C or so are warming up to, or so half an hour is stirred to react；And
7) to above-mentioned reaction solution dealcoholysis 0.5~3h of dehydration at 75~95 DEG C of temperature and vacuum condition, to be hindered
Fire resin.
2. production method according to claim 1, wherein fire retardant group become (mass percent)：Silica：55~60%；
Magnesium hydroxide：10~15%；Antimony oxide：25~30%.
3. production method according to claim 1, wherein diatomaceous granularity is 60~80 mesh, bulk density is 0.45~
0.5g/ml, specific surface area are 4~5m2/g。
4. production method according to claim 3, wherein every kilogram of diatomite coats 10~15mg2,4- dinitrobenzenes.
5. a kind of flame-retarded resin is produced according to the method for one of the claims 1-4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810498832.9A CN108623766A (en) | 2018-05-23 | 2018-05-23 | The fire-retardant melamine resin of high imino group methyl-etherified and its production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810498832.9A CN108623766A (en) | 2018-05-23 | 2018-05-23 | The fire-retardant melamine resin of high imino group methyl-etherified and its production method |
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| Publication Number | Publication Date |
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| CN108623766A true CN108623766A (en) | 2018-10-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810498832.9A Pending CN108623766A (en) | 2018-05-23 | 2018-05-23 | The fire-retardant melamine resin of high imino group methyl-etherified and its production method |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4223141A (en) * | 1978-09-13 | 1980-09-16 | Cassella Aktiengesellschaft | Preparation of methoxy-methyl melamines |
| CN102747602A (en) * | 2012-04-05 | 2012-10-24 | 龚䶮 | Formaldehyde removing reagent for treating formaldehyde-containing fabric, and use method thereof |
| CN107540802A (en) * | 2017-10-18 | 2018-01-05 | 重庆建峰浩康化工有限公司 | Pentamethylol melamine synthesizes high Amino resin |
-
2018
- 2018-05-23 CN CN201810498832.9A patent/CN108623766A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4223141A (en) * | 1978-09-13 | 1980-09-16 | Cassella Aktiengesellschaft | Preparation of methoxy-methyl melamines |
| CN102747602A (en) * | 2012-04-05 | 2012-10-24 | 龚䶮 | Formaldehyde removing reagent for treating formaldehyde-containing fabric, and use method thereof |
| CN107540802A (en) * | 2017-10-18 | 2018-01-05 | 重庆建峰浩康化工有限公司 | Pentamethylol melamine synthesizes high Amino resin |
Non-Patent Citations (2)
| Title |
|---|
| 安秋凤等: "《精细化工原材料及中间体手册 橡塑加工助剂》", 30 September 2004 * |
| 王海芳: "《环境监测》", 31 August 2014 * |
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