CN103965247A - Phosphor-containing nitrogen-containing structural type flame retardant polyhydric alcohol as well as preparation method and application thereof - Google Patents
Phosphor-containing nitrogen-containing structural type flame retardant polyhydric alcohol as well as preparation method and application thereof Download PDFInfo
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- CN103965247A CN103965247A CN201410220194.6A CN201410220194A CN103965247A CN 103965247 A CN103965247 A CN 103965247A CN 201410220194 A CN201410220194 A CN 201410220194A CN 103965247 A CN103965247 A CN 103965247A
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Abstract
The invention discloses a phosphor-containing nitrogen-containing structural type flame retardant polyhydric alcohol as well as a preparation method and application thereof, and relates to a flame retardant polymer. The preparation method comprises the following steps of carrying out heat-up reaction on paraformaldehyde and ethanol amine under protection of a nitrogen gas after mixing and reacting, then, adding alcohol liquor of aromatic phenol compounds, and refluxing and reacting to obtain an Mannich polyhydric alcohol intermediate; adding phosphite ester compounds to continuously react with paraformaldehyde after cooling the temperature of the system to 50 DEG C-55 DEG C, removing alcohol and moisture produced by reaction by distilling under reduced pressure to obtain a product. The phosphor-containing nitrogen-containing structural type flame retardant polyhydric alcohol can be applied to manufacturing hard polyurethane foam plastic. A benzene ring structure with good thermal stability and P, N flame-retardant elements are introduced into a PU (poly urethane) structure by virtue of a chemical bond mode by using the polyhydric alcohol without a mobility problem, so that lasting flame resistance is realized on the condition of ensuring material processing performances. A catalyst is not used for synthesizing the flame retardant polyhydric alcohol, materials are cheap and easily available, process is simple; and the retardant polyhydric alcohol is easy for industrial production without producing pollutants, and satisfies environment-friendly requirements.
Description
Technical field
The present invention relates to flame-retardant polymer, especially relate to a kind of phosphorous nitrogenous structure-type flame-proof polyol and preparation method thereof and application.
Background technology
Rigid urethane foam (RPUF), claim again hard polyurethane foam, the advantages such as light weight, heat-insulation and heat-preservation are good owing to having, sound-absorbing and buffering excellent in vibration resistance, and there is good mechanical property and resistance to chemical corrosion, there is very strong cohesive force with multiple material, be therefore widely used as the heat preserving and insulating material of petrochemical pipe, refrigerating plant, transportation equipment and buildings etc.But because PU porous plastics specific surface area is large, gas permeability is good, the hydrocarbon ratio of molecular chain is higher, when burning, can accelerate scattering and disappearing of combustionvelocity and quality, therefore the limiting oxygen index(LOI) (LOI) without the rigid urethane foam of fire-retardant finish is only 17%～19%, belongs to inflammable material; And in combustion processes, emit the toxic gas such as HCN, CO, bring very large difficulty to fire extinguishing and escape from fire, therefore it is carried out to fire-retardant finish extremely important.
At present, the flame retardant properties that improves polyurethane foamed material mainly realizes by add fire retardant in foaming formulation, and main flow fire retardant can be divided into additive flame retardant and the large class of reactive flame retardant two.Compared with additive flame retardant, reactive flame retardant have add-on few, the advantages such as little, the fire-retardant persistence of the Effect on Mechanical Properties of material is good are widely used.Wherein high, the Heat stability is good of the flame retarding efficiency of phosphonium flame retardant, volatility are extremely low, and particularly response type organic phosphorus flame retardant (containing alcoholic extract hydroxyl group or amino), can firmly be combined on macromolecular chain, and flame retardant effect is more lasting.Nitrogenated flame retardant is mainly to emit non-flammable gases in decomposition course, reduces the concentration of inflammable gas or covers the surface of material and bring into play fire retardation.Conventional nitrogenated flame retardant is melamine class, guanidine class and ureas.Because phosphorus flame retardant is mainly condensed phase fire retardant mechanism, and nitrogen is meteorological fire retardant mechanism, and the two has certain synergy, if the two can be used in conjunction with, flame retardant effect is even more ideal.
Application number a kind of preparation method of phosphorus halogen cooperative flame retardant polyether glycol that has been 201210103713.1 Introduction To Cn Patent, and be applied to the preparation of flame-retardant type polyurethane hard bubble, result has significantly improved the flame retardant resistance (LOI is 30.8) of polyurethane rigid foam plastic, but because this flame retardant polyether polyol is owing to containing halogen, in burning, produce poisonous and harmful, have the hydrogen halide of intense stimulus, be difficult to meet environmental requirement.
Application number a kind of preparation method of the response type Mannich polyether glycol with permanent fire retardant effect that has been 201310414097.6 Introduction To Cn Patent, should be by using this polyether glycol that the benzene ring structure of Heat stability is good and ignition-proof element are incorporated in polyurethane structural, but contain ignition-proof element comparatively single (only Nitrogen element) due to this polyether glycol, therefore for the preparation of hard polyurethane foam flame retardant properties improve and not obvious (LOI is up to 26.2), flame retarding efficiency is lower.
Summary of the invention
One of object of the present invention is intended to overcome the deficiencies in the prior art, and a kind of phosphorous nitrogenous structure-type flame-proof polyol and preparation method thereof is provided.
Another object of the present invention is to provide the fire-retardant ethoxylated polyhydric alcohol of described phosphorous nitrogenous structure-type in the application of manufacturing in rigid urethane foam.
The structural formula of described phosphorous nitrogenous structure-type flame-proof polyol is as follows:
Wherein, R " represent
r
xfor C
1-C
4alkyl or phenyl in one.
The method of preparing described phosphorous nitrogenous structure-type flame-proof polyol, comprises the following steps:
1) by temperature reaction under nitrogen protection after paraformaldehyde and thanomin hybrid reaction, then add the ethanolic soln of aromatic series phenolic compound, after back flow reaction, obtain Mannich polyvalent alcohol intermediate;
2) add after system temperature is down to 50～55 DEG C phosphite ester compound and paraformaldehyde to continue reaction, then slough through underpressure distillation the moisture that ethanol and reaction generate, obtain light yellow viscous liquid and be phosphorous nitrogenous structure-type flame-proof polyol.
In step 1) in, described paraformaldehyde and thanomin hybrid reaction can be joined paraformaldehyde and thanomin being equipped with in constant pressure funnel and reflux condensation mode tubular container to 15～20 DEG C of stirring reaction 0.5～1.0h; The temperature of described temperature reaction under nitrogen protection can be 60～80 DEG C, and the time of temperature reaction can be 2～4h; It is the ethanolic soln of 30%～50% aromatic series phenolic compound that the ethanolic soln of described aromatic series phenolic compound can adopt massfraction; The time of described back flow reaction can be 2～4h;
Described aromatic series phenolic compound structural formula is
wherein R represents H or OH or C
1-C
9alkyl in one; Described thanomin, paraformaldehyde and aromatic series phenolic compound three's mol ratio can be 3: (1.5～3.0): (1.0～3.0).
In step 2) in, the time of described continuation reaction can be 2～4h; Described phosphite ester compound can be selected from the one in dimethylphosphite, diethyl phosphite, diisopropyl phosphite, dibutyl phosphite, triethyl-phosphite, tributyl phosphate, triphenyl phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) etc.; Described phosphite ester compound, paraformaldehyde and step 1) in thanomin three's mol ratio can be 1: (0.5～1.0): (2.0～3.0).
The concrete synthetic route of phosphorous nitrogenous structure-type flame-proof polyol of the present invention is:
(1)
(2)
Wherein, in synthetic route (1), R represents H or OH or C
1-C
5alkyl in one, R ' represent
substituent number m=1～3, when R is OH or C
1-C
5alkyl time, R' is not identical with the position of substitution of R;
In synthetic route (2),
be expressed as phosphorous nitrogenous structure-type flame-proof polyol, R " represent
r
xfor C
1-C
4alkyl or phenyl in one, R " the position of substitution on phenyl ring is identical with the R ' in synthetic route (1).
Described phosphorous nitrogenous structure-type flame-proof polyol can be applied in manufacture rigid urethane foam.
Prepared phosphorous nitrogenous structure-type flame-proof polyol part is substituted or the common polyether glycol of replacing whole.Concrete steps are:
The fire-retardant ethoxylated polyhydric alcohol of phosphorous nitrogenous structure-type, polyether glycol, amines catalyst, suds-stabilizing agent, whipping agent and water are mixed to get to combination polyvalent alcohol, again with isocyanic ester mix and blend 10～20s, rotating speed 3000～3500r/min, pour in mould, slaking 48h, obtains flame retardant rigid polyurethane porous plastics.
The mass ratio of the fire-retardant ethoxylated polyhydric alcohol of described phosphorous nitrogenous structure-type, polyether glycol, amines catalyst, suds-stabilizing agent, whipping agent and water can be (50～100): (0～50): (0.1～0.6): (0.5～5): (10～30): (0.01～5); Described isocyanic ester and polyvalent alcohol can be 1.2～2.5 by the mol ratio of NCO/OH;
Described polyether glycol (hydroxyl value 250～450mgKOH/g), preferred, polyethers polyvalent alcohol 403, polyethers 4110;
Described amines catalyst can be selected from N, N ,-dimethylcyclohexylamine, 2,4, at least one in 6-tri-(dimethylamino methyl) phenol, trolamine, α-amino isopropyl alcohol, quaternary amine etc.;
Described whipping agent can be selected from least one in HCFC-141B, HFC-245fa, HFC-365mfc etc.;
Described isocyanic ester can be selected from the one in tolylene diisocyanate, Xylene Diisocyanate, polyphenyl polymethylene polyisocyanates (polymeric MDI) etc.
The present invention, taking thanomin, paraformaldehyde and aromatic series phenolic compound as raw material, is reacted and is obtained Mannich polyvalent alcohol intermediate by Mannich; Then add phosphite ester compound and paraformaldehyde further to react and obtain phosphorous nitrogenous structure-type flame-proof polyol.Preparation by prepared phosphorous nitrogenous structure-type flame-proof polyol for flame retarded rigid polyurethane foams plastics, by using this polyvalent alcohol that the benzene ring structure of Heat stability is good and P, N ignition-proof element are incorporated in PU structure by the mode of chemical bond, there is not transport property problem, under the prerequisite of guarantee materials processing performance, realized lasting fire-retardant.
The invention has the advantages that:
(1) by using this polyvalent alcohol that the benzene ring structure of Heat stability is good and P, N ignition-proof element are incorporated in PU structure by the mode of chemical bond, there is not transport property problem, under the prerequisite that ensures materials processing performance, realized lasting fire-retardant;
(2) the synthetic fire-retardant polyvalent alcohol of the present invention does not use catalyzer, and the raw material that uses is cheap and easy to get, technique is simple, is easy to suitability for industrialized production, and in whole production process, contamination-free produces, and meets environmental requirement, and easily operation, practical.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of the prepared phosphorous nitrogenous structure-type flame-proof polyol of the embodiment of the present invention 1.
Embodiment
The present invention will be further described in connection with accompanying drawing for embodiment below.
Embodiment 1:
On the there-necked flask of 1000mL; load onto constant pressure funnel and reflux condensing tube; 45.00g (1.50mol) paraformaldehyde and 91.68g (1.50mol) thanomin; at 20 DEG C, after stirring reaction 0.5h, under nitrogen protection, be warming up to 60 DEG C of reaction 2h; slowly splash into the phenol ethanolic soln that 94.11g (0.50mol) massfraction is 50%, after backflow 4h reaction, obtaining phenylol Manny is polyvalent alcohol intermediate.
After being down to 50 DEG C, system temperature add successively 207.00g (1.50mol) diethyl phosphite and 45.00g (1.50mol) paraformaldehyde to continue reaction 4h.Slough the moisture that ethanol and reaction generate and obtain light yellow viscous liquid and be phosphorous nitrogenous structure-type flame-proof polyol finally by crossing underpressure distillation.
The infrared spectrogram of the prepared phosphorous nitrogenous structure-type flame-proof polyol of embodiment 1 is referring to Fig. 1.As shown in Figure 1,3271cm
-1the absorption of vibrations that place is-OH; 2935cm
-1, 2873cm
-1place is the stretching vibration absorption peak of upper methyl, methylene radical; 1677cm
-1, 1592cm
-1neighbouring is C=C stretching vibration absorption peak on phenyl ring; 1221cm
-1place is the charateristic avsorption band of P=0; 1025cm
-1for the flexural vibration absorption peak of P-O-C; 967cm
-1place is the P-C absorption peak of (showing that P-H group participates in reaction).
Embodiment 2:
On the there-necked flask of 1000mL; load onto constant pressure funnel and reflux condensing tube; 45.00g (1.50mol) paraformaldehyde and 91.68g (1.50mol) thanomin; at 20 DEG C, after stirring reaction 1.0h, under nitrogen protection, be warming up to 80 DEG C of reaction 2h; slowly splash into the Resorcinol ethanolic soln that 165.15g (0.75mol) massfraction is 50%, after backflow 2h reaction, obtain Mannich polyvalent alcohol intermediate.
After being down to 55 DEG C, system temperature add successively 207.00g (1.50mol) diethyl phosphite and 45.00g (1.50mol) paraformaldehyde to continue reaction 4h.Finally by the flame-proof polyol of crossing underpressure distillation and slough moisture that ethanol and reaction generate and obtain light yellow viscous liquid and be phosphorous nitrogenous structure-type.
Embodiment 3:
On the there-necked flask of 1000mL; load onto constant pressure funnel and reflux condensing tube; 45.00g (1.50mol) paraformaldehyde and 91.68g (1.50mol) thanomin; at 20 DEG C, after stirring reaction 1.0h, under nitrogen protection, be warming up to 70 DEG C of reaction 2h; slowly splash into the phenol ethanolic soln that 297.33g (1.50mol) massfraction is 50%, after backflow 3h reaction, obtain Mannich polyvalent alcohol intermediate.
After being down to 55 DEG C, system temperature add successively 207.00g (1.50mol) diethyl phosphite and 45.00g (1.50mol) paraformaldehyde to continue reaction 4h.Finally by the phosphorous nitrogenous flame-proof polyol of crossing underpressure distillation and slough moisture that ethanol and reaction generate and obtain light yellow viscous liquid and be structure-type.
Embodiment 4:
Flame retarded rigid polyurethane foams plastics is standby: polynary 50 parts, 50 parts polyethers of fire-retardant phosphorous nitrogenous structure-type ethoxylated polyhydric alcohol 403,0.1 part of amines catalyst, 1.6 parts of suds-stabilizing agents, 30 parts of whipping agents, 1.3 parts of high-speed stirring of water are evenly obtained combining polyvalent alcohol, again with 110 parts of polymeric MDI mix and blend 10s, rotating speed 3500r/min, pour in mould, slaking 48h, obtain flame retarded rigid polyurethane foams plastics, the limiting oxygen index(LOI) (LOI) of this material is 26.5%.
Embodiment 5:
Flame retarded rigid polyurethane foams plastics is standby: 100 parts of fire-retardant phosphorous nitrogenous structure-type ethoxylated polyhydric alcohols, 0.1 part of amines catalyst, 1.6 parts of suds-stabilizing agents, 30 parts of whipping agents, 1.3 parts of high-speed stirring of water are evenly obtained combining polyvalent alcohol, again with 100 parts of polymeric MDI mix and blend 10s, rotating speed 3500r/min, pour in mould, slaking 48h, obtain flame retarded rigid polyurethane foams plastics, the limiting oxygen index(LOI) (LOI) of this material is 29.5%.
Claims (10)
1. a phosphorous nitrogenous structure-type flame-proof polyol, is characterized in that its structural formula is as follows:
Wherein, R " represent
r
xfor C
1-C
4alkyl or phenyl in one.
2. synthetic a kind of route of phosphorous nitrogenous structure-type flame-proof polyol is as claimed in claim 1:
(1)
(2)
Wherein, in synthetic route (1), R represents H or OH or C
1-C
5alkyl in one, R ' represent
substituent number m=1～3, when R is OH or C
1-C
5alkyl time, R' is not identical with the position of substitution of R;
In synthetic route (2),
be expressed as phosphorous nitrogenous structure-type flame-proof polyol, R " represent
r
xfor C
1-C
4alkyl or phenyl in one,
r" the position of substitution on phenyl ring is identical with the R ' in synthetic route (1).
3. the preparation method of phosphorous nitrogenous structure-type flame-proof polyol as claimed in claim 1, is characterized in that comprising the following steps:
1) by temperature reaction under nitrogen protection after paraformaldehyde and thanomin hybrid reaction, then add the ethanolic soln of aromatic series phenolic compound, after back flow reaction, obtain Mannich polyvalent alcohol intermediate;
2) add after system temperature is down to 50～55 DEG C phosphite ester compound and paraformaldehyde to continue reaction, then slough through underpressure distillation the moisture that ethanol and reaction generate, obtain light yellow viscous liquid and be phosphorous nitrogenous structure-type flame-proof polyol.
4. method as claimed in claim 3, it is characterized in that in step 1) in, described paraformaldehyde and thanomin hybrid reaction can be joined paraformaldehyde and thanomin being equipped with in constant pressure funnel and reflux condensation mode tubular container to 15～20 DEG C of stirring reaction 0.5～1.0h; The temperature of described temperature reaction under nitrogen protection can be 60～80 DEG C, and the time of temperature reaction can be 2～4h.
5. method as claimed in claim 3, is characterized in that in step 1) in, the ethanolic soln of described aromatic series phenolic compound adopts the ethanolic soln of the aromatic series phenolic compound that massfraction is 30%～50%; Described aromatic series phenolic compound structural formula is
wherein R represents H or OH or C
1-C
9alkyl in one; Described thanomin, paraformaldehyde and aromatic series phenolic compound three's mol ratio is 3: (1.5～3.0): (1.0～3.0).
6. method as claimed in claim 3, is characterized in that in step 1) in, the time of described back flow reaction is 2～4h; In step 2) in, the time of described continuation reaction is 2～4h.
7. method as claimed in claim 3, it is characterized in that in step 2) in, described phosphite ester compound is selected from the one in dimethylphosphite, diethyl phosphite, diisopropyl phosphite, dibutyl phosphite, triethyl-phosphite, tributyl phosphate, triphenyl phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO).
8. method as claimed in claim 3, is characterized in that in step 2) in, described phosphite ester compound, paraformaldehyde and step 1) in thanomin three's mol ratio be 1: (0.5～1.0): (2.0～3.0).
9. a kind of phosphorous nitrogenous structure-type flame-proof polyol is applied in manufacture rigid urethane foam as claimed in claim 1.
10. application as claimed in claim 9, is characterized in that the concrete steps of the method for described manufacture rigid urethane foam are:
The fire-retardant ethoxylated polyhydric alcohol of phosphorous nitrogenous structure-type, polyether glycol, amines catalyst, suds-stabilizing agent, whipping agent and water are mixed to get to combination polyvalent alcohol, again with isocyanic ester mix and blend 10～20s, rotating speed 3000～3500r/min, pour in mould, slaking 48h, obtains flame retardant rigid polyurethane porous plastics;
The mass ratio of the fire-retardant ethoxylated polyhydric alcohol of described phosphorous nitrogenous structure-type, polyether glycol, amines catalyst, suds-stabilizing agent, whipping agent and water is (50～100): (0～50): (0.1～0.6): (0.5～5): (10～30): (0.01～5); Described isocyanic ester and polyvalent alcohol are 1.2～2.5 by the mol ratio of NCO/OH;
Described polyether glycol is selected from polyether glycol 403 or polyethers 4110; The hydroxyl value of polyether glycol is 250～450mgKOH/g;
Described amines catalyst can be selected from N, N ,-dimethylcyclohexylamine, 2,4, at least one in 6-tri-(dimethylamino methyl) phenol, trolamine, α-amino isopropyl alcohol, quaternary amine;
Described whipping agent can be selected from least one in HCFC-141B, HFC-245fa, HFC-365mfc;
Described isocyanic ester can be selected from the one in tolylene diisocyanate, Xylene Diisocyanate, polyphenyl polymethylene polyisocyanates.
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| CN104211900A (en) * | 2014-09-02 | 2014-12-17 | 北京理工大学 | Polyurethane containing DOPO groups and preparation method thereof |
| CN104497268A (en) * | 2014-11-28 | 2015-04-08 | 苏州市安特菲尔新材料有限公司 | Flame-retardant conducting polyurethane material and preparation method thereof |
| CN105367738A (en) * | 2015-12-16 | 2016-03-02 | 佛山科学技术学院 | Rigid polyurethane foam plastic achieving flame retarding through structural flame retardant and preparation method of rigid polyurethane foam plastic |
| CN104193953B (en) * | 2014-09-02 | 2017-01-11 | 北京理工大学 | Polyimide-type polyurethane containing DOPO group and preparation method of polyimide-type polyurethane |
| CN107686547A (en) * | 2017-09-30 | 2018-02-13 | 中国科学院福建物质结构研究所 | flame retardant polyurethane and preparation method thereof |
| CN107955124A (en) * | 2016-10-14 | 2018-04-24 | 南京大学 | High-strength anti-flaming polyurethane hard foam and its preparation method made from the polyether polyol of the more yuan of rings of boracic nitrogen |
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| CN109111558A (en) * | 2018-02-13 | 2019-01-01 | 公安部天津消防研究所 | A kind of low-smoke low-toxicity flame retarded rigid polyurethane foams material and preparation method |
| CN109206573A (en) * | 2018-07-18 | 2019-01-15 | 湖北大学 | A kind of flame-proof polyol and preparation method thereof and the application in polyurethane rigid foam plastic |
| CN109593173A (en) * | 2018-11-20 | 2019-04-09 | 高鼎精细化工(昆山)有限公司 | Have the silicon substrate thermoplastic sulfurized rubber and its synthetic method of anti-flammability |
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| CN111607061A (en) * | 2020-04-15 | 2020-09-01 | 黎明化工研究设计院有限责任公司 | Flame retardant-free high-flame-retardance low-odor full-water self-skinning polyurethane foam and preparation method thereof |
| US10913812B2 (en) | 2018-09-11 | 2021-02-09 | Industrial Technology Research Institute | Secondary amine, radical, and alkoxy amine compound |
| CN113501929A (en) * | 2021-07-27 | 2021-10-15 | 扬州工业职业技术学院 | Flame-retardant wear-resistant polyurethane resin for leather |
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| CN104193953B (en) * | 2014-09-02 | 2017-01-11 | 北京理工大学 | Polyimide-type polyurethane containing DOPO group and preparation method of polyimide-type polyurethane |
| CN104497268A (en) * | 2014-11-28 | 2015-04-08 | 苏州市安特菲尔新材料有限公司 | Flame-retardant conducting polyurethane material and preparation method thereof |
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| CN107686547A (en) * | 2017-09-30 | 2018-02-13 | 中国科学院福建物质结构研究所 | flame retardant polyurethane and preparation method thereof |
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| CN111607061A (en) * | 2020-04-15 | 2020-09-01 | 黎明化工研究设计院有限责任公司 | Flame retardant-free high-flame-retardance low-odor full-water self-skinning polyurethane foam and preparation method thereof |
| CN113501929A (en) * | 2021-07-27 | 2021-10-15 | 扬州工业职业技术学院 | Flame-retardant wear-resistant polyurethane resin for leather |
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