CN104497051A - Method for preparing reactive type halogen-free flame retardant for coating - Google Patents
Method for preparing reactive type halogen-free flame retardant for coating Download PDFInfo
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- CN104497051A CN104497051A CN201410819947.5A CN201410819947A CN104497051A CN 104497051 A CN104497051 A CN 104497051A CN 201410819947 A CN201410819947 A CN 201410819947A CN 104497051 A CN104497051 A CN 104497051A
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Abstract
The invention provides a method for preparing a reactive type halogen-free flame retardant for a coating, and belongs to the field of flame retardant synthesis. The method is characterized by comprising the following steps: firstly, implementing reaction on neopentyl glycol and phosphorus oxychloride so as to prepare 2-oxo-2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane; implementing condensation reaction on hydroxyethyl methacrylate and 2-oxo-2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane so as to prepare a final product 5,5-dimethyl-2-hydroxyethyl methacrylate-2-oxo-1,3,2-dioxaphosphorinane. The method is simple in process, easy in obtaining of raw materials and high in conversion rate, and the prepared reactive type halogen-free flame retardant is good in flame retardancy, does not affect properties such as the adhesion property and the weather resistance of the coating after being added into the coating, can be widely used for preparing various acrylic acid and acrylic flame-retardant coating emulsions, and can be also applied to flame retardancy of plastic, rubber and textile as a reactive type flame retardant additive.
Description
Technical field
The present invention relates to fire-retardant FRW field, be specifically related to a kind of preparation method of coating response type halogen-free flame retardants.
Background technology
The world today, awareness of safety becomes more and more popular, and frie retardant coating, because can effectively protect wooden structures and steel construction, reduces the occurrence frequency of fire, and receives the concern of people.Because frie retardant coating need add the flame retardant effect that relatively large fire retardant can reach more satisfactory, and there is the problem being added into the performance such as sticking power, weathering resistance that can reduce coating after in coating in the fire retardant of prior art.Therefore, a kind of BACN need be prepared to address this problem.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, there is provided a kind of preparation method of coating response type halogen-free flame retardants, technique is simple, and raw material is easy to get, the response type halogen-free flame retardants flame retardant properties of preparation is good, and is added into the performance such as sticking power, weathering resistance that can not affect coating after in coating.
Task of the present invention is realized by following technology power case, a kind of preparation method of coating response type halogen-free flame retardants, is characterized in adopting hydroxyethyl methylacrylate and 2-oxo-2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane is obtained by condensation reaction, mainly comprises following steps:
(1) 2-oxo-2-chloro-5 is produced, 5-dimethyl-1, 3, 2-dioxaphosphorinane: thermometer is being housed, dropping funnel, nitrogen ingress pipe, in the reactor of reflux exchanger (rear be equipped with Calcium Chloride Powder Anhydrous drying tube is connected with hydrogen chloride absorption bottle), add appropriate neopentyl glycol and solvent, phosphorus oxychloride [neopentyl glycol: solvent: phosphorus oxychloride=(0.1 ~ 0.3mol): 300ml: 0.1mol] is dripped after being stirred and heated to reflux temperature, react at a reflux temperature after dropwising and release without HCl gas to delivery line place, then except desolventizing, obtain white solid 2-oxo-2-chloro-5, 5-dimethyl-1, 3, 2-dioxaphosphorinane,
Reaction formula is:
(2) fire retardant is produced: in the reactor in such as step (1), add 2-oxo-2-chloro-5, 5-dimethyl-1, 3, 2-dioxaphosphorinane and acid binding agent and dispersion medium, after stirring and dissolving, add hydroxyethyl methylacrylate [2-oxo-2-chloro-5 again, 5-dimethyl-1, 3, 2-dioxaphosphorinane: acid binding agent: dispersion medium: hydroxyethyl methylacrylate=(0.2 ~ 0.1mol): 3ml: 300ml: (0.1 ~ 0.2mol)], heating rises to reflux temperature, until substantially release without HCl gas, underpressure distillation is except dispersion medium, dry white solid 5, 5-dimethyl-2-hydroxyethyl methylacrylate-2-oxygen-1, 3, acyl phosphoric acid ester in 2-dioxy phospha is own, i.e. described fire retardant.
Reaction formula is:
Step (1) solvent for use is one in chloroform, tetracol phenixin or its mixture.
Step (2) dispersion medium used is nitrogen dimethylformamide (DMF) or dimethyl sulfoxide (DMSO) (DMSO).
Step (2) acid binding agent used is triethylamine or pyridine.
Step (1) described reflux temperature is the boiling temperature of solvent.
Step (2) described reflux temperature is the boiling temperature of dispersion medium.
In step (2), the feed ratio of chloro-5,5-dimethyl-1,3, the 2-dioxaphosphorinanes of 2-oxo-2-and hydroxyethyl methylacrylate is mol ratio (0.5: 1) ~ (1: 0.5).
Emulsion is chief component and the filmogen of coating, and conventional coating emulsion mainly contains acrylic ester emulsion (generally referring to the ester monomer of acrylic acid or the like or methacrylic), organosilicon crylic acid latex (organosilane monomer containing unsaturated link(age) and acrylic monomer being polymerized), pure-acrylic emulsion (resin be polymerized by acrylic monomer completely) and benzene emulsion (being polymerized by styrene monomer and acrylic monomer) etc.The fire retardant adopting the present invention to prepare comprises esters of acrylic acid functional group, comprise double bond simultaneously, it is the fire-retardant acrylate derivative of a class, when preparing coating emulsion, this fire retardant can be used as a kind of reactant and acrylate generation copolymerization, thus obtained fire-retardant coating emulsion, improve the flame retardant properties of coating, the interpolation of this fire retardant can not affect the performance such as sticking power, weathering resistance of coating.
Positively effect of the present invention is: technique is simple, and raw material is easy to get, and transformation efficiency is high, and the response type halogen-free flame retardants flame retardant properties of preparation is good, and is added into the performance such as sticking power, weathering resistance that can not affect coating after in coating.The response type halogen-free flame retardants of preparation can be widely used in preparing all kinds of vinylformic acid and esters of acrylic acid anti-flaming dope emulsion, in addition, also can be used as reaction-type flame-retarding additive in plastics, rubber and Fire-proof Finishing Agents for Textile.
Embodiment
Below in conjunction with embodiment, comparatively detailed explanation is carried out to technical solution of the present invention.
Embodiment 1:
(1) in the reactor that thermometer, dropping funnel, nitrogen ingress pipe, reflux exchanger (rear be equipped with Calcium Chloride Powder Anhydrous drying tube is connected with hydrogen chloride absorption bottle) are housed, add 0.1mol neopentyl glycol and 300ml chloroform, 0.1mol phosphorus oxychloride is dripped after being stirred and heated to reflux temperature, react at a reflux temperature after dropwising and release without HCl gas to delivery line place, then except desolventizing, obtain white solid 2-oxo-2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane.
(2) in the reactor in such as step (1), 0.1mol 2-oxo-2-chloro-5 is added, 5-dimethyl-1,3,2-dioxaphosphorinane and 3ml acid binding agent and 300ml dimethyl sulfoxide (DMSO), after stirring and dissolving, add 0.1mol hydroxyethyl methylacrylate again, heating rises to reflux temperature, until substantially release without HCl gas.Underpressure distillation is except dispersion medium, and dry white solid 5,5-dimethyl-2-hydroxyethyl methylacrylate-2-oxygen-1,3,2-dioxy phospha is acyl phosphoric acid ester, i.e. described fire retardant in oneself.
Embodiment 2:
(1) in reaction two device that thermometer, dropping funnel, nitrogen ingress pipe, reflux exchanger (rear be equipped with Calcium Chloride Powder Anhydrous drying tube is connected with hydrogen chloride absorption bottle) are housed, add 0.15mol neopentyl glycol and 300ml chloroform, 0.1mol phosphorus oxychloride is dripped after being stirred and heated to reflux temperature, react at a reflux temperature after dropwising and release without HCl gas to delivery line place, then except desolventizing, obtain white solid 2-oxo-2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane.
(2) in the reactor in such as step (1), 0.1mol 2-oxo-2-chloro-5 is added, 5-dimethyl-1,3,2-dioxaphosphorinane and 3ml acid binding agent and 300ml dimethyl sulfoxide (DMSO), after stirring and dissolving, add 0.1mol hydroxyethyl methylacrylate again, heating rises to reflux temperature, until substantially release without HCl gas.Underpressure distillation is except dispersion medium, and dry white solid 5,5-dimethyl-2-hydroxyethyl methylacrylate-2-oxygen-1,3,2-dioxy phospha is acyl phosphoric acid ester, i.e. described fire retardant in oneself.
Embodiment 3:
(1) in the reactor that thermometer, dropping funnel, nitrogen ingress pipe, reflux exchanger (rear be equipped with Calcium Chloride Powder Anhydrous drying tube is connected with hydrogen chloride absorption bottle) are housed, add 0.1mol neopentyl glycol and 300ml chloroform, 0.1mol phosphorus oxychloride is dripped after being stirred and heated to reflux temperature, react at a reflux temperature after dropwising and release without HCl gas to delivery line place, then except desolventizing, obtain white solid 2-oxo-2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane.
(2) in the reactor in such as step (1), 0.1mol 2-oxo-2-chloro-5 is added, 5-dimethyl-1,3,2-dioxaphosphorinane and 3ml acid binding agent and 300ml dimethyl sulfoxide (DMSO), after stirring and dissolving, add 0.15mol hydroxyethyl methylacrylate again, heating rises to reflux temperature, until substantially release without HCl gas.Underpressure distillation is except dispersion medium, and dry white solid 5,5-dimethyl-2-hydroxyethyl methylacrylate-2-oxygen-1,3,2-dioxy phospha is acyl phosphoric acid ester, i.e. described fire retardant in oneself.
Embodiment 4:
(1) in the reactor that thermometer, dropping funnel, nitrogen ingress pipe, reflux exchanger (rear be equipped with Calcium Chloride Powder Anhydrous drying tube is connected with hydrogen chloride absorption bottle) are housed, add 0.1mol neopentyl glycol and 300ml tetracol phenixin, 0.1mol phosphorus oxychloride is dripped after being stirred and heated to reflux temperature, react at a reflux temperature after dropwising and release without HCl gas to delivery line place, then except desolventizing, obtain white solid 2-oxo-2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane.
(2) in the reactor in such as step (1), 0.1mol 2-oxo-2-chloro-5 is added, 5-dimethyl-1,3,2-dioxaphosphorinane and 3ml acid binding agent and 300ml dimethyl sulfoxide (DMSO), after stirring and dissolving, add 0.1mol hydroxyethyl methylacrylate again, heating rises to reflux temperature, until substantially release without HCl gas.Underpressure distillation is except dispersion medium, and dry white solid 5,5-dimethyl-2-hydroxyethyl methylacrylate-2-oxygen-1,3,2-dioxy phospha is acyl phosphoric acid ester, i.e. described fire retardant in oneself.
Embodiment 5:
(1) in the reactor that thermometer, dropping funnel, nitrogen ingress pipe, reflux exchanger (rear be equipped with Calcium Chloride Powder Anhydrous drying tube is connected with hydrogen chloride absorption bottle) are housed, add 0.1mol neopentyl glycol and 300ml chloroform, 0.1mol phosphorus oxychloride is dripped after being stirred and heated to reflux temperature, react at a reflux temperature after dropwising and release without HCl gas to delivery line place, then except desolventizing, obtain white solid 2-oxo-2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane.
(2) in the reactor in such as step (1), 0.1mol 2-oxo-2-chloro-5 is added, 5-dimethyl-1,3,2-dioxaphosphorinane and 3ml acid binding agent and 300ml nitrogen dimethylformamide, after stirring and dissolving, add 0.1mol hydroxyethyl methylacrylate again, heating rises to reflux temperature, until substantially release without HCl gas.Underpressure distillation is except dispersion medium, and dry white solid 5,5-dimethyl-2-hydroxyethyl methylacrylate-2-oxygen-1,3,2-dioxy phospha is acyl phosphoric acid ester, i.e. described fire retardant in oneself.
Claims (7)
1. a coating preparation method for response type halogen-free flame retardants, be is characterized in that adopting hydroxyethyl methylacrylate and chloro-5,5-dimethyl-1,3, the 2-dioxaphosphorinanes of 2-oxo-2-to be obtained by condensation reaction, mainly comprises following steps:
(1) 2-oxo-2-chloro-5 is produced, 5-dimethyl-1, 3, 2-dioxaphosphorinane: thermometer is being housed, dropping funnel, nitrogen ingress pipe, in the reactor of reflux exchanger (rear be equipped with Calcium Chloride Powder Anhydrous drying tube is connected with hydrogen chloride absorption bottle), add appropriate neopentyl glycol and solvent, phosphorus oxychloride [neopentyl glycol: solvent: phosphorus oxychloride=(0.1 ~ 0.3mol): 300ml: 0.1mol] is dripped after being stirred and heated to reflux temperature, react at a reflux temperature after dropwising and release without HCl gas to delivery line place, then except desolventizing, obtain white solid 2-oxo-2-chloro-5, 5-dimethyl-1, 3, 2-dioxaphosphorinane,
Reaction formula is:
(2) fire retardant is produced: in the reactor in such as step (1), add 2-oxo-2-chloro-5, 5-dimethyl-1, 3, 2-dioxaphosphorinane and acid binding agent and dispersion medium, after stirring and dissolving, add hydroxyethyl methylacrylate [2-oxo-2-chloro-5 again, 5-dimethyl-1, 3, 2-dioxaphosphorinane: acid binding agent: dispersion medium: hydroxyethyl methylacrylate=(0.2 ~ 0.1mol): 3ml: 300ml: (0.1 ~ 0.2mol)], heating rises to reflux temperature, until substantially release without HCl gas, underpressure distillation is except dispersion medium, dry white solid 5, 5-dimethyl-2-hydroxyethyl methylacrylate-2-oxygen-1, 3, acyl phosphoric acid ester in 2-dioxy phospha is own, i.e. described fire retardant.
Reaction formula is:
2. the preparation method of a kind of coating response type halogen-free flame retardants according to claim 1, is characterized in that step (1) solvent for use is one in chloroform, tetracol phenixin or its mixture.
3. the preparation method of a kind of coating response type halogen-free flame retardants according to claim 1, is characterized in that step (2) dispersion medium used is nitrogen dimethylformamide (DMF) or dimethyl sulfoxide (DMSO) (DMSO).
4. the preparation method of a kind of coating response type halogen-free flame retardants according to claim 1, is characterized in that step (2) acid binding agent used is triethylamine or pyridine.
5. the preparation method of a kind of coating response type halogen-free flame retardants according to claim 1, is characterized in that step (1) described reflux temperature is the boiling temperature of solvent.
6. the preparation method of a kind of coating response type halogen-free flame retardants according to claim 1, is characterized in that step (2) described reflux temperature is the boiling temperature of dispersion medium.
7. the preparation method of a kind of coating response type halogen-free flame retardants according to claim 1, it is characterized in that 2-oxo-2-chloro-5 in step (2), 5-dimethyl-1, the feed ratio of 3,2-dioxaphosphorinane and hydroxyethyl methylacrylate is mol ratio (0.5: 1) ~ (1: 0.5).
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108559086A (en) * | 2018-05-21 | 2018-09-21 | 武汉工程大学 | A kind of vinyl modified star polyphosphate and its synthetic method |
| CN109897221A (en) * | 2017-12-11 | 2019-06-18 | 广东广山新材料股份有限公司 | A kind of reactive flame retardant and its preparation method and application |
| CN109897220A (en) * | 2017-12-11 | 2019-06-18 | 广东广山新材料股份有限公司 | A kind of reactive flame retardant and its preparation method and application |
| CN111285902A (en) * | 2020-03-12 | 2020-06-16 | 宁波东旭成新材料科技有限公司 | Synthesis method of flame-retardant acrylate monomer and flame-retardant diffusion film thereof |
| WO2021254993A1 (en) | 2020-06-17 | 2021-12-23 | Renolit Se | Flameproof acrylate |
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| CN101302232A (en) * | 2008-05-19 | 2008-11-12 | 江苏利田科技有限公司 | Perfluoro alkyl phosphoester acrylic ester and preparation thereof |
| CN102408513A (en) * | 2011-10-13 | 2012-04-11 | 江苏博特新材料有限公司 | Preparation method of phosphate modified acrylate emulsion |
| CN103193819A (en) * | 2013-03-13 | 2013-07-10 | 苏州蔻美新材料有限公司 | Method for synthesizing MPC using one-pot method |
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Patent Citations (4)
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| CN1958936A (en) * | 2006-11-21 | 2007-05-09 | 苏州大学 | Flame retardant of textile, preparation and application |
| CN101302232A (en) * | 2008-05-19 | 2008-11-12 | 江苏利田科技有限公司 | Perfluoro alkyl phosphoester acrylic ester and preparation thereof |
| CN102408513A (en) * | 2011-10-13 | 2012-04-11 | 江苏博特新材料有限公司 | Preparation method of phosphate modified acrylate emulsion |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109897221A (en) * | 2017-12-11 | 2019-06-18 | 广东广山新材料股份有限公司 | A kind of reactive flame retardant and its preparation method and application |
| CN109897220A (en) * | 2017-12-11 | 2019-06-18 | 广东广山新材料股份有限公司 | A kind of reactive flame retardant and its preparation method and application |
| CN108559086A (en) * | 2018-05-21 | 2018-09-21 | 武汉工程大学 | A kind of vinyl modified star polyphosphate and its synthetic method |
| CN111285902A (en) * | 2020-03-12 | 2020-06-16 | 宁波东旭成新材料科技有限公司 | Synthesis method of flame-retardant acrylate monomer and flame-retardant diffusion film thereof |
| CN111285902B (en) * | 2020-03-12 | 2023-05-12 | 宁波东旭成新材料科技有限公司 | Method for synthesizing flame-retardant acrylic ester monomer and flame-retardant diffusion film thereof |
| WO2021254993A1 (en) | 2020-06-17 | 2021-12-23 | Renolit Se | Flameproof acrylate |
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Application publication date: 20150408 |