CN101597307A - A kind of uV curable phosphorus-nitrogen-containing halogen-free flame retardant and preparation method thereof - Google Patents
A kind of uV curable phosphorus-nitrogen-containing halogen-free flame retardant and preparation method thereof Download PDFInfo
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Abstract
The invention discloses phosphorus-nitrogen-containing halogen-free flame retardant of a kind of uV curable and preparation method thereof, feature is to be the polyvalent alcohol or the polyphenol reaction of response matrix and part propylene acidifying or part methyl acrylated with the phosphorus dichloride acid phenenyl ester, again with the nitrogenous compound reaction that has two reactive amino groups, the phosphorous nitride of resultant thickness yellow transparent liquid is for having the uV curable monomer molecule of activity double key and phosphorus nitrogen ignition-proof element simultaneously, add to it in resin matrix of uV curable as reactive flame retardant, can form Clear coating at fast setting under the ultraviolet light irradiation, have high flame retardant efficient.Flame retardant coating behind this uv radiation curing residual massfraction 34.0% under the air conditions in the time of 600 ℃ is 26.3% under the condition of nitrogen gas; Its maximum heat rate of release is 146.6W/g.UV curable halogen-free phosphorus-containing nitrogen combustion inhibitor of the present invention can be applicable to the fire-retardant of timber, fabric, plastics, metal or circuit card.
Description
Technical field
The invention belongs to the fire retardant technical field, be specifically related to phosphorus-nitrogen-containing halogen-free flame retardant of uV curable and preparation method thereof.
Background technology
Ultraviolet light cross-linking solidified resin is applied to fields such as coating industry, graphic art industry and microelectronic industry more and more widely, and it has replaced the coating and the tackiness agent of traditional thermal-initiated polymerization gradually.But similar with traditional synthetic resins, the major defect of existing ultraviolet light cross-linking cured resin is exactly their inflammableness.And existing conventional fire retardant generally is low-molecular-weight organic or inorganic additive, and add-on is very big usually, and needs when construction and the base-material blend, and bad owing to itself and macromolecular consistency, the blend effect is undesirable; Blend has not only brought very big labor capacity and numerous and diverse step to construction, and can cause crosslinked difficulty and serious degraded after adding high-load filler, and particularly this problem seems especially outstanding in the ultraviolet light cross-linking system.
Obtained good flame-retardant effect though adopt Halogen monomer or oligopolymer as the fire retardant of ultraviolet light cross-linking system, but owing to there is halogen fire retardant when burning, can produce toxic gas, environment is polluted, harm humans health, and possible damage equipment, therefore, reduce or limit the use of halogen flame, the halogen-free flame retardants of development low-smoke low-toxicity gaseous emission, become the research focus of current flame retardant area.
A kind of expansive water transparant fire-proof paint of Chinese patent publication number CN1043516A report; by membrane-forming agent (melamine formaldehyde resin etc.), whipping agent (urea, trimeric cyanamide etc.), carbided catalyst (Secondary ammonium phosphate, ammonium polyphosphate etc.) with become four kinds of base stocks of charcoal material (ethylene glycol, tetramethylolmethane, dextrin etc.) to form, can be widely used in the timber structure flameproof protection of Highrise buildings, surface facility etc.Its shortcoming is can emit formaldehyde gas and organic solvent small molecules in construction and the use, can cause health threat to workmen and user.
International monopoly WO9952971A1 has reported that curing of coating is as the fire-resisting protection layer of material after radiation-curable resin and the fire retardant blend; But in order to reach the fire-retardant purpose of ideal, the add-on of fire retardant generally accounts for 5～95wt% of total protective layer.This requires high especially to the cohesive force of curable resin and base material on the one hand; On the other hand the consistency of curable resin and fire retardant is required also very highly, be separated when avoiding blend; Moreover a large amount of existence that can not the cured flame-retardant agent can make the intensity of material reduce greatly.
A kind of fire retardant type UV light solidifying polyurethane acrylic acid paint of Chinese patent publication number CN1718657A report and preparation method thereof, with modified diphenylmethane diisocyanate, the two keys of band contain trimeric cyanamide-STUDY ON THE MODIFICATION OF PENOLIC RESIN polyvalent alcohol, catalyzer and reactive thinner are with 200～500: 80～120: 0.1～2: 10～30 part by weight mixes, obtain containing the polyurethane acroleic acid prepolymer of trimeric cyanamide-resol through certain chemical reaction, again itself and light trigger and some other auxiliary agent are stirred, promptly get the flame-retardant polyurethane acrylate paint of uV curable.This method technology is simple, and cost is low, is widely used.Its shortcoming is that flame retardant effect is not so good as the effective of phosphorus phosphorus-nitrogen coordinated fire-retardant agent, and the resol of using can discharge obnoxious flavoures such as formaldehyde in coating application and use.
Chinese patent publication number CN1382739A has reported a kind of Phosphorus contained ultra-branched polyurethane acrylate as fire retarding agent solidified by radiation and its preparing process, the phosphoric acid ester trivalent alcohol that forms with phosphoric acid and epoxy compounds reaction is a response matrix, the monohydroxy end-caps that adds vulcabond and radiation-curable by " pre-polymerization method " or " single stage method ", but thereby resulting phosphorus contained ultra-branched polyurethane acrylate as fire retarding agent solidified by radiation fast setting under ultraviolet light irradiation obtains transparent hard cured film, and its body oxygen index is 27.But it is not high that its shortcoming is a flame retarding efficiency, and preparation process is numerous and diverse.
Summary of the invention
The purpose of this invention is to provide phosphorus-nitrogen-containing halogen-free flame retardant of a kind of uV curable and preparation method thereof, to overcome the above-mentioned defective that exists in the existing photocuring Clear paint.
The preparation method of the phosphorus-nitrogen-containing halogen-free flame retardant of uV curable of the present invention, it is characterized in that: with the phosphorus dichloride acid phenenyl ester is response matrix, the polyvalent alcohol or the polyphenol that add part propylene acidifying or part methyl acrylated by reaction mole proportioning, add attached sour agent, ice bath is stirred to and no longer includes the hydrogenchloride generation in solvent; Add the nitrogenous compound that has two reactive amino groups according to the reaction mol ratio then, under condition of ice bath, stirred 8～12 hours, decompress filter is removed attached sour agent salt, underpressure distillation removes and desolvates, and resulting thickness transparent yellow liquid is the phosphorus-nitrogen-containing halogen-free flame retardant of uV curable of the present invention.
The polyvalent alcohol or the polyphenol of described part propylene acidifying or part methyl acrylated, its chemical structural formula can be expressed as HOR
1[O (C=O) CR
2=CH
2]
m, R in the formula
1For containing the alkyl or aryl of 1-12 carbon, R
2Be CH
3Or H, m is 1,2 or 3; The polyvalent alcohol of this part propylene acidifying or part methyl acrylated or polyphenol comprise methacrylic acid-beta-hydroxy ethyl ester, senecioate-hydroxyl ethyl ester, 2-hydroxyl dimethyl allene acid glyceride, 2-hydroxyl glycerol diacrylate, 1-methylol-3,5-dimethyl allene acid phenenyl ester or 1-methylol-3,5-diacrylate phenyl ester.
Described attached sour agent is selected from triethylamine or pyridine.
The temperature that described ice bath stirs is-5 ℃～5 ℃.
Described solvent can be selected from tetrahydrofuran (THF), methylene dichloride, chloroform, ether or dioxane.
The described nitrogenate that has two reactive amino groups can be selected from Piperazine anhydrous, mphenylenediamine, O-Phenylene Diamine, Ursol D, quadrol or propylene diamine.
Adopt the phosphorus-nitrogen-containing halogen-free flame retardant of the uV curable of the present invention of method for preparing, for having the monomer molecule of activity double key and phosphorus nitrogen ignition-proof element simultaneously, its chemical structural formula can be expressed as:
In the formula, R is the functional group of part propylene acidifying or part methyl acrylated; R ' is for having the nitrogen-containing functional group of two tertiary amines or secondary amine.
The inventive method is the polyvalent alcohol or polyphenol reaction acquisition half affixture of response matrix and part propylene acidifying or part methyl acrylated with the phosphorus dichloride acid phenenyl ester, again with the nitrogenous compound reaction that has two reactive amino groups, the phosphorous nitride of resultant thickness yellow transparent liquid is for having the uV curable monomer molecule of activity double key and phosphorus nitrogen ignition-proof element simultaneously, add to it in resin matrix of uV curable as reactive flame retardant, can form Clear coating at fast setting under the ultraviolet light irradiation, have high flame retardant efficient.Compare with existing additive flame retardant, the phosphorus-nitrogen-containing halogen-free flame retardant of the uV curable of the present invention's preparation is owing to participated in the ultraviolet light polymerization film process of coating directly, and better with the consistency of resin matrix, cure shrinkage is little; Compare with traditional inorganic transparent anti-flaming dope, the fire retardant that employing the inventive method prepares can form the charcoal layer that expands preferably owing to utilized phosphorus nitrogen element cooperative flame retardant principle in the molecule, and base material is had better flameproof protection effect; And, improves greatly the transparent yellow liquid that adopts the inventive method to prepare because comparing the transparency with existing additive flame retardant, can reach 90%, after making employing transparent phosphorus-nitrogen-containing halogen-free flame retardant of the present invention add the resin matrix of uV curable to, can be at room temperature with the ultraviolet light irradiation fast filming, save energy not only, the production efficiency height, and raw material sources are extensive, are easy to suitability for industrialized production; Can be applicable to the flame retardant area of a lot of aspects such as timber, fabric, plastics, metal or circuit card, have wide prospect in industrial application.
Embodiment
Embodiment 1:
One, the preparation of the phosphorus-nitrogen-containing halogen-free flame retardant of uV curable
In the 250ml three-necked bottle of mechanical stirring and constant pressure funnel is housed, add 21.1g (0.1mol) phosphorus dichloride acid phenenyl ester and 80ml tetrahydrofuran (THF), ice bath stirs, after 10 minutes, add 21.2g (0.21mol) triethylamine, again under continue stirring in 2 hours the slow mixing solutions of dropwise addition of acrylic acid hydroxyl ethyl ester 11.6g (0.1mol) and 20ml tetrahydrofuran (THF), continue reaction 4 hours.Then piperazine 4.307g (0.05mol) is dissolved in the 80ml tetrahydrofuran (THF), under continuing stirring, slowly splashes in the above-mentioned reaction system, reacted 8 hours.Decompress filter is removed triethylamine salt, and underpressure distillation removes and desolvates, and the pale brown look thickness transparent liquid that obtains is product of the present invention.Productive rate is 90%.
Products therefrom is through nmr analysis, the peak position of chemical shift at 7.13～7.38ppm place is the phenyl ring peak position, three identical peaks of integral area that chemical shift occurs at 5.8ppm, 6.1ppm, 6.4ppm place are respectively three hydrogen peak positions on two keys of Hydroxyethyl acrylate, chemical shift is respectively the peak position of hydrogen on two methylene radical of (0-CH2-CH2-) on the Hydroxyethyl acrylate at two peaks at 4.28ppm, 4.38ppm place, and the peak that appears on the 3.15ppm is-N (CH2)
2The peak position of last four hydrogen.
Explanation thus, but the phosphorus-nitrogen-containing halogen-free flame retardant of the uv radiation curing of the present invention that the employing method for preparing obtains are for having the monomer molecule of activity double key and phosphorus nitrogen ignition-proof element simultaneously.
Two, the uv radiation curing of radiation-curable transparent flame-retardant coating
But get phosphorus-nitrogen-containing halogen-free flame retardant 5 grams of the uv radiation curing of above-mentioned preparation, with light trigger α, alpha-alpha-dimethyl-Alpha-hydroxy methyl phenyl ketone (Darocur 1173) 0.15 gram (3wt%) mixes at 60 ℃.On sheet glass, paint 100 microns film then, on uv cure machine, be cured under the room temperature condition with spreader, set time 10s, double bond conversion rate surpasses 80%.Explanation thus, the material that adopts the inventive method to prepare can be at room temperature with the ultraviolet radiation fast filming, and production efficiency height and save energy are easy to suitability for industrialized production.
Three, the mensuration of the transparency of uv radiation curing transparent flame-retardant coating, thermogravimetic analysis (TGA) and heat release rate
But get phosphorus-nitrogen-containing halogen-free flame retardant 5 grams of the uv radiation curing of above-mentioned preparation, with light trigger α, alpha-alpha-dimethyl-Alpha-hydroxy methyl phenyl ketone (Darocur 1173) 0.15 gram (3wt%), under 60 ℃ of conditions, mix, on sheet glass, paint 100 microns film then with spreader, on uv cure machine, carry out self-vulcanizing, obtain transparent flame-retardant coating.With uv-vis spectra it is carried out the transparency and measure, its visible light transmissivity is greater than 90%.
But get phosphorus-nitrogen-containing halogen-free flame retardant 2 grams of the uv radiation curing of above-mentioned preparation, with light trigger α, alpha-alpha-dimethyl-Alpha-hydroxy methyl phenyl ketone (Darocur 1173) 0.06 gram (3wt%), under 60 ℃ of conditions, mix, be cast to fold with rubber sheet paper in advance and be of a size of 30 * 30 * 10mm
3Box in, on uv cure machine, be cured.With thermogravimetric analyzer solidified coating is tested as can be known, in air atmosphere, the initial heat decomposition temperature of coating is 185 ℃, residual massfraction 34.0% in the time of 600 ℃; In nitrogen atmosphere, the initial heat decomposition temperature of coating is 185 ℃, residual massfraction 26.3% in the time of 600 ℃.Through the heat release rate of miniature calorimeter mensuration solidified coating, the maximum heat rate of release of coating is 146.6W/g.
Embodiment 2:
In the 250ml three-necked bottle of mechanical stirring and constant pressure funnel is housed, add 21.1g (0.1mol) phosphorus dichloride acid phenenyl ester and 80ml methylene dichloride, ice bath stirs, after 10 minutes, add 21.2g (0.21mol) triethylamine, again under continue stirring in 2 hours the slow mixing solutions of dropwise addition of acrylic acid hydroxyl ethyl ester 11.6g (0.1mol) and 20ml methylene dichloride, continue reaction 4 hours.Then piperazine 4.307g (0.05mol) is dissolved in the 60ml methylene dichloride, under continuing stirring, slowly splashes in the above-mentioned reaction system, reacted 8 hours.Decompress filter is removed triethylamine salt, and underpressure distillation removes and desolvates, and the thickness transparent liquid that obtains is product of the present invention.Productive rate is 88%.
Products therefrom is through nmr analysis, the peak position of chemical shift at 7.13～7.38ppm place is the phenyl ring peak position, three identical peaks of integral area that chemical shift occurs at 5.8ppm, 6.1ppm, 6.4ppm place are respectively three hydrogen peak positions on two keys of Hydroxyethyl acrylate, chemical shift is respectively the peak position of hydrogen on two methylene radical of (O-CH2-CH2-) on the Hydroxyethyl acrylate at two peaks at 4.28ppm, 4.38ppm place, and the peak that appears on the 3.15ppm is-N (CH2)
2The peak position of last four hydrogen.
But the phosphorus-nitrogen-containing halogen-free flame retardant of getting the uv radiation curing of above-mentioned preparation carries out uv radiation curing, obtains transparent flame-retardant coating.With uv-vis spectra it is carried out the transparency and measure, its visible light transmissivity is greater than 90%.With thermogravimetric analyzer solidified coating is tested as can be known, in air atmosphere, the initial heat decomposition temperature of coating is 185 ℃, residual massfraction 34.1% in the time of 600 ℃; In nitrogen atmosphere, the initial heat decomposition temperature of coating is 185 ℃, residual massfraction 26.0% in the time of 600 ℃.Through the heat release rate of miniature calorimeter mensuration solidified coating, the maximum heat rate of release of coating is 146.5W/g.
Embodiment 3:
In the 250ml three-necked bottle of mechanical stirring and constant pressure funnel is housed, add 21.1g (0.1mol) phosphorus dichloride acid phenenyl ester and 80ml tetrahydrofuran (THF), ice bath stirs, after 10 minutes, add 21.2g (0.21mol) triethylamine, again under continue stirring in 2 hours the slow mixing solutions of dropwise addition of acrylic acid hydroxyl ethyl ester 11.6g (0.1mol) and 20ml tetrahydrofuran (THF), continue reaction 4 hours.Then mphenylenediamine 5.407g (0.05mol) is dissolved in the 80ml tetrahydrofuran (THF), under continuing stirring, slowly splashes in the above-mentioned reaction system, reacted 8 hours.Decompress filter is removed pyridinium salt, and underpressure distillation removes and desolvates, and the brown thickness transparent liquid that obtains is product of the present invention.Productive rate is 85%.
Products therefrom is through nmr analysis, the peak position of chemical shift at 7.13～7.38ppm place is the phenyl ring peak position, chemical shift is at 5.8ppm, 6.0ppm, 6.4ppm three identical peaks of integral area locating to occur are respectively three hydrogen peak positions on two keys of Hydroxyethyl acrylate, chemical shift is at 4.28ppm, 4.38ppm two peaks of locating are respectively the peak position of hydrogen on two methylene radical of (O-CH2-CH2-) on the Hydroxyethyl acrylate, appearing at 6.0ppm has overlapping to the several peaks on the 6.7ppm with two key hydrogen peak positions, be the peak position of four hydrogen on a benzene two ammoniums, and the 4.0ppm place is (the hydrogen peak position NH-).
But the phosphorus-nitrogen-containing halogen-free flame retardant of getting the uv radiation curing of above-mentioned preparation carries out uv radiation curing, obtains transparent flame-retardant coating.With uv-vis spectra it is carried out the transparency and measure, its visible light transmissivity is greater than 90%.With thermogravimetric analyzer solidified coating is tested as can be known, in air atmosphere, the initial heat decomposition temperature of coating is 185 ℃, residual massfraction 33.5% in the time of 600 ℃; In nitrogen atmosphere, the initial heat decomposition temperature of coating is 184 ℃, residual massfraction 25.6% in the time of 600 ℃.Through the heat release rate of miniature calorimeter mensuration solidified coating, the maximum heat rate of release of coating is 148.6W/g.
Hence one can see that, and the phosphorus-nitrogen-containing halogen-free compound of the uV curable that employing the inventive method prepares can be used as fire retardant and is applied to the fire-retardant of timber, fabric, also can be used for the fire-retardant of plastics, metal or circuit card.
Claims (7)
1, a kind of preparation method of phosphorus-nitrogen-containing halogen-free flame retardant of uV curable, it is characterized in that: with the phosphorus dichloride acid phenenyl ester is response matrix, the polyvalent alcohol or the polyphenol that add part propylene acidifying or part methyl acrylated by the reaction mol ratio, add attached sour agent, ice bath is stirred to and no longer includes the hydrogenchloride generation in solvent; Add the nitrogenous compound that has two reactive amino groups by the reaction mol ratio then, under condition of ice bath, stirred 8～12 hours, decompress filter is removed attached sour agent salt, and underpressure distillation removes and desolvates, and resulting thickness transparent yellow liquid is the phosphorus-nitrogen-containing halogen-free flame retardant of uV curable.
2, the preparation method of the phosphorus-nitrogen-containing halogen-free flame retardant of uV curable according to claim 1 is characterised in that the polyvalent alcohol or the polyphenol of described part propylene acidifying or part methyl acrylated, and its chemical structural formula is HOR
1[O (C=O) CR
2=CH
2]
m, in the formula, R1 is the alkyl or aryl that contains 1-12 carbon, R
2Be CH
3Or H, m is 1,2 or 3; The polyvalent alcohol of this part propylene acidifying or part methyl acrylated or polyphenol are methacrylic acid-beta-hydroxy ethyl ester, senecioate-hydroxyl ethyl ester, 2-hydroxyl dimethyl allene acid glyceride, 2-hydroxyl glycerol diacrylate, 1-methylol-3,5-dimethyl allene acid phenenyl ester, 1-methylol-3,5-diacrylate phenyl ester.
3, the preparation method of the phosphorus-nitrogen-containing halogen-free flame retardant of uV curable according to claim 1 is characterised in that described attached sour agent is selected from triethylamine or pyridine.
4, the preparation method of the phosphorus-nitrogen-containing halogen-free flame retardant of uV curable according to claim 1 is characterised in that the temperature that described ice bath stirs is-5 ℃～5 ℃.
5, the preparation method of the phosphorus-nitrogen-containing halogen-free flame retardant of uV curable according to claim 1 is characterised in that described solvent is selected from tetrahydrofuran (THF), methylene dichloride, chloroform, ether or dioxane.
6, the preparation method of the phosphorus-nitrogen-containing halogen-free flame retardant of uV curable according to claim 1 is characterised in that the described nitrogenate that has two reactive amino groups is selected from Piperazine anhydrous, mphenylenediamine, O-Phenylene Diamine, Ursol D, quadrol or propylene diamine.
7, the phosphorus-nitrogen-containing halogen-free flame retardant of the uV curable of the described method preparation of claim 1 is characterised in that it is the monomer molecule that has activity double key and phosphorus nitrogen ignition-proof element simultaneously, and chemical structural formula is:
In the formula, R is the functional group of part propylene acidifying or part methyl acrylated; R ' is for having the nitrogen-containing functional group of two tertiary amines or secondary amine.
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| CN103382393A (en) * | 2013-06-20 | 2013-11-06 | 佛山科学技术学院 | Liquid reactive flame retardant agent containing nitrogen and phosphorus and preparation method thereof |
| CN104558039A (en) * | 2013-10-24 | 2015-04-29 | 中国石油化工股份有限公司 | Phosphorus-nitrogen intumescent flame retardant and preparation method thereof |
| CN105112074A (en) * | 2015-09-23 | 2015-12-02 | 浙江工业职业技术学院(浙江工业高级技术学校) | Preparation method for expansive flame retardant |
| CN105733376A (en) * | 2016-02-23 | 2016-07-06 | 广东四方威凯新材料有限公司 | Weather-proof, halogen-free, flame-retardant, anti-corrosion and insulating fluorine-carbon coating |
| CN108948424A (en) * | 2017-05-19 | 2018-12-07 | 四川大学 | A kind of response type phosphonium flame retardant and its preparation method and application |
| CN109735222A (en) * | 2018-11-29 | 2019-05-10 | 安徽开林新材料股份有限公司 | A kind of fire-retardant corrosion-resistant polyurethane coating |
| CN110330828A (en) * | 2019-07-12 | 2019-10-15 | 顺德职业技术学院 | Novel UV anti-flaming dope and preparation method thereof |
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| US6277988B1 (en) * | 1999-08-27 | 2001-08-21 | General Electric Company | Solvent-free method for preparing sterically hindered phosphoramidates |
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| CN103382393A (en) * | 2013-06-20 | 2013-11-06 | 佛山科学技术学院 | Liquid reactive flame retardant agent containing nitrogen and phosphorus and preparation method thereof |
| CN104558039A (en) * | 2013-10-24 | 2015-04-29 | 中国石油化工股份有限公司 | Phosphorus-nitrogen intumescent flame retardant and preparation method thereof |
| CN104558039B (en) * | 2013-10-24 | 2017-12-15 | 中国石油化工股份有限公司 | A kind of phosphorus nitrogen expansion type combustion inhibitor and preparation method thereof |
| CN105112074A (en) * | 2015-09-23 | 2015-12-02 | 浙江工业职业技术学院(浙江工业高级技术学校) | Preparation method for expansive flame retardant |
| CN105733376A (en) * | 2016-02-23 | 2016-07-06 | 广东四方威凯新材料有限公司 | Weather-proof, halogen-free, flame-retardant, anti-corrosion and insulating fluorine-carbon coating |
| CN105733376B (en) * | 2016-02-23 | 2018-10-30 | 广东四方威凯新材料有限公司 | Weather resistant halogen-free flame retardant anti-corrosion insulation fluorocarbon coating |
| CN108948424A (en) * | 2017-05-19 | 2018-12-07 | 四川大学 | A kind of response type phosphonium flame retardant and its preparation method and application |
| CN108948424B (en) * | 2017-05-19 | 2020-12-11 | 四川大学 | Reactive phosphorus-containing flame retardant and preparation method and application thereof |
| CN109735222A (en) * | 2018-11-29 | 2019-05-10 | 安徽开林新材料股份有限公司 | A kind of fire-retardant corrosion-resistant polyurethane coating |
| CN110330828A (en) * | 2019-07-12 | 2019-10-15 | 顺德职业技术学院 | Novel UV anti-flaming dope and preparation method thereof |
| CN111116989A (en) * | 2019-12-25 | 2020-05-08 | 苏州和塑美科技有限公司 | Reactive flame retardant and preparation method and application thereof |
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