CN105542144A - Silicon-containing flame retardant polyether surface treating agent as well as preparation method and application thereof - Google Patents

Silicon-containing flame retardant polyether surface treating agent as well as preparation method and application thereof Download PDF

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CN105542144A
CN105542144A CN201610127918.1A CN201610127918A CN105542144A CN 105542144 A CN105542144 A CN 105542144A CN 201610127918 A CN201610127918 A CN 201610127918A CN 105542144 A CN105542144 A CN 105542144A
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polyether
flame retardant
surface treatment
treatment agent
flame retarding
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CN105542144B (en
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陈雅君
钱立军
王伟
岐晓青
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Beijing Technology and Business University
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Abstract

The invention discloses a silicon-containing flame retardant polyether surface treating agent. The silicon-containing flame retardant polyether surface treating agent contains three flame retardant elements including phosphorus, nitrogen and silicon, has the average molecular weight of 1,020-4,720, has the functionality of 6 and is a deep yellow transparent liquid. According to the preparation method, polyether polyol or polyether polyamine reacts with phenyl dichlorophosphate to generate flame retardant polyether, gamma-aminopropyltriethoxysilane is added, and the silicon-containing flame retardant polyether surface treating agent is prepared, wherein the gamma-aminopropyltriethoxysilane chain segment can be combined with a solid inorganic flame retardant through chemical bonds, and the polyether polyol chain segment and a polyether component for preparation of polyurethane resin have good compatibility. The surface treating agent has a flame retardant function, thus, solid inorganic flame retardant particles treated through the silicon-containing flame retardant polyether surface treating agent can be taken as flame retardant master batch and added to a formula material of polyurethane, and polyurethane foam with the solid inorganic flame retardant uniformly dispersed is obtained.

Description

A kind of siliceous flame retarding polyether surface treatment agent and preparation method thereof and application
Technical field
The invention belongs to technical field of polymer materials, relate to surface treatment agent of a kind of fire retardant and its preparation method and application, siliceous flame retarding polyether surface treatment agent being specifically related to a kind of solid inorganic fire retardant for flame retardant polyurethane and preparation method thereof and application.
Background technology
Urethane foam due to lightweight, intensity is high, electrical insulating property is excellent, thermal conductivity is low and be widely used in the industrial circle such as refrigeration, building, automobile.But the porous honeycomb constitutional features due to urethane foam adds the contact area between itself and air, thus makes it very easily burn.In recent years, report more and more by the polyurethane foam fire caused that catches fire, therefore it is fire-retardantly very important.
At present, the fire retardant for polyurethane foam is mainly divided into liquid flame retardant and the large class of solid flame retardant two.The share of market of liquid flame retardant (as TCPP, TEP) is higher, but there is the problem that addition greatly, easily causes polyurethane foam products to shrink.Solid flame retardant (as APP, graphite) is generally added in polyether component material, although polyurethane foam products can not be caused to shrink, due to itself and polyethers consistency bad and in polyethers dispersion effect poor, free settling and reunion.Therefore, need that surface treatment is carried out to solid flame retardant and could obtain good flame retardant effect and higher flame retarding efficiency.
The existing great majority of the surface treatment agent for pressed powder are acrylic block copolymers, although also certain dispersion effect can be played, but the requirement of use cannot be reached, mainly because the consistency of such treatment agent and urethane is bad and do not have anti-flaming function.
Summary of the invention
An object of the present invention is to provide a kind of siliceous functional group flame retarding polyether surface treatment agent.
The structural formula of siliceous functional group of the present invention flame retarding polyether surface treatment agent is:
Wherein R is molecular-weight average is 300 ~ 4000, functionality is 2 polyether glycol or polyether polyamine.This siliceous functional group flame retarding polyether surface treatment agent contains phosphorus, nitrogen, silicon three kinds of ignition-proof elements, molecular-weight average 1020-4720, and functionality 6 is deep yellow transparent liquid.
Second object of the present invention is to provide a kind of method preparing this siliceous functional group flame retarding polyether surface treatment agent.
The method principle uses γ-aminopropyl triethoxysilane end-blocking again after polyether glycol or polyether polyamine and dichloro-phenyl phosphate reaction, and concrete steps are as follows:
Step (1). be 300 ~ 4000 by molecular-weight average, functionality be 2 polyether glycol or polyether polyamine and triethylamine in molar ratio 1:2 mix, in atmosphere of inert gases, stir 0.5 ~ 1 hour at 40-80 DEG C, obtaining functionality is the polyether glycol of 2 or the active hydrogen compounds of polyether polyamine.
Described rare gas element is nitrogen or argon gas;
Step (2). under the condition of Keep agitation, be that the polyether glycol of 2 or the active hydrogen compounds of polyether polyamine are added drop-wise in the non-proton organic solvent of dichloro-phenyl phosphate by functionality in step (1), make the mol ratio of dichloro-phenyl phosphate and polyether glycol (or polyether polyamine) for (2.1 ~ 2.5): 1, time for adding 30-90 minute, reacts 5 ~ 10 hours afterwards at 40-80 DEG C;
In the non-proton organic solvent of dichloro-phenyl phosphate, the concentration of dichloro-phenyl phosphate is 0.1 ~ 1mol/L,
Described non-proton organic solvent is the one in N-Methyl pyrrolidone, N-N dimethyl formamide, N-N N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF), dioxane, acetone, butanone, ethyl acetate;
Step (3). in reaction soln, add γ-aminopropyl triethoxysilane, make the mol ratio of γ-aminopropyl triethoxysilane and polyether glycol or polyether polyamine for (2.1 ~ 2.5): 1, add triethylamine again, make the mol ratio of triethylamine and γ-aminopropyl triethoxysilane for (1 ~ 1.5): 1, keep the temperature of reaction of step (2), reaction 3-7 hour;
Step (4). after reaction terminates, by the triethylamine hydrochloride of product suction filtration removing white, then filter vacuum is revolved steaming, removing non-proton organic solvent and triethylamine, obtaining siliceous flame retarding polyether surface treatment agent, is deep yellow color liquid.
3rd object of the present invention is the application of above-mentioned siliceous functional group flame retarding polyether surface treatment agent, concrete steps are: mixed with polyether glycol by above-mentioned siliceous flame retarding polyether surface treatment agent, then solid inorganic fire retardant is added, emulsification or grind to form underflow material, siliceous flame retarding polyether surface treatment agent is coated on the surface of solid inorganic fire retardant, make solid inorganic fire retardant suspended dispersed in polyether glycol, play the effect preventing the sedimentation of solid inorganic fire retardant.This underflow material can be used as flame-retardant master batch and joins in the polyethers formulation material of hard-foam polyurethane, obtains the finely dispersed hard polyurethane foam of solid inorganic fire retardant.
Described polyether glycol viscosity is 200 ~ 1000cps25 DEG C, and functionality is 2 ~ 4.
Described solid inorganic fire retardant is one or more in ammonium polyphosphate, trimeric cyanamide, trimeric cyanamide urea cyanate, melamine pyrophosphate, hypo-aluminum orthophosphate, zinc borate, magnesium hydroxide, aluminium hydroxide, TDE, decabromodiphynly oxide, nano imvite, graphite, antimonous oxide, zinc oxide.
γ-aminopropyl triethoxysilane and polyether glycol segment to be connected in same molecule by dichloro-phenyl phosphate and to prepare a kind of siliceous flame retarding polyether surface treatment agent by the present invention, wherein, γ-aminopropyl triethoxysilane segment can combine with the mode of solid inorganic fire retardant by chemical bond, polyether glycol segment with prepare urethane resin polyether component used and have good consistency, thus make solid inorganic fire retardant be dispersed in polyethers, play the effect of anti-settling.Meanwhile, this surface treatment agent itself also has anti-flaming function.
Embodiment
Embodiment 1
Step (1). be 300 by molecular-weight average, functionality be 2 polyether glycol and triethylamine in molar ratio 1:2 mix, in nitrogen atmosphere, stir 0.5 hour at 40 DEG C, obtain the active hydrogen compounds that functionality is the polyether glycol of 2;
Step (2). under the condition of Keep agitation, it is in the tetrahydrofuran solvent of 0.1mol/L that the active hydrogen compounds being the polyether glycol of 2 by functionality in step (1) is added drop-wise to dichloro-phenyl phosphate concentration, the mol ratio of dichloro-phenyl phosphate and polyether glycol in solution is made to be 2.1:1, time for adding 30 minutes, reacts 5 hours at 40 DEG C; ;
Step (3). in reaction soln, add γ-aminopropyl triethoxysilane, the mol ratio of γ-aminopropyl triethoxysilane and polyether glycol in solution is made to be 2.1:1, add triethylamine again, the mol ratio of triethylamine and γ-aminopropyl triethoxysilane in solution is made to be 1:1, keep above-mentioned temperature of reaction, react 5 hours;
Step (4). after reaction terminates, by the triethylamine hydrochloride of product suction filtration removing white, then filter vacuum is revolved steaming, removing tetrahydrofuran (THF) and triethylamine, obtaining siliceous flame retarding polyether surface treatment agent, is deep yellow transparent liquid.
Be 1000cps25 DEG C by above-mentioned siliceous flame retarding polyether surface treatment agent and viscosity, functionality is the polyether glycol mixing of 2, then adding ammonium polyphosphate, trimeric cyanamide and nano imvite, emulsification or grind to form underflow material, there is not sedimentation at room temperature static 7 days in this slurry.
Embodiment 2
Step (1). be 4000 by molecular-weight average, functionality be 2 polyether glycol and triethylamine in molar ratio 1:2 mix, in nitrogen, stir 0.5 hour at 80 DEG C, obtain the active hydrogen compounds that functionality is the polyether glycol of 2.
Step (2). under the condition of Keep agitation, it is in the dioxane solvent of 1mol/L that the active hydrogen compounds being the polyether glycol of 2 by functionality in step (1) is added drop-wise to dichloro-phenyl phosphate concentration, the mol ratio of dichloro-phenyl phosphate and polyether glycol is made to be 2.5:1, time for adding 90 minutes, reacts 10 hours at 80 DEG C;
Step (3). in reaction soln, add γ-aminopropyl triethoxysilane, the mol ratio of γ-aminopropyl triethoxysilane and polyether glycol in solution is made to be 2.5:1, add triethylamine again, the mol ratio of triethylamine and γ-aminopropyl triethoxysilane in solution is made to be 1.5:1, keep above-mentioned temperature of reaction, react 7 hours;
Step (4). after reaction terminates, by the triethylamine hydrochloride of product suction filtration removing white, then filter vacuum is revolved steaming, removing dioxane and triethylamine, obtaining siliceous flame retarding polyether surface treatment agent, is deep yellow color liquid.
Be 200cps25 DEG C by above-mentioned siliceous flame retarding polyether surface treatment agent and viscosity, functionality is the polyether glycol mixing of 4, then adds aluminium hydroxide and melamine pyrophosphate, emulsification or grind to form underflow material, and this slurry does not occur sedimentation at room temperature static 7 days.
Embodiment 3
Step (1). be 1000 by molecular-weight average, functionality be 2 polyether polyamine and triethylamine in molar ratio 1:2 mix, in nitrogen atmosphere, stir 0.6 hour at 50 DEG C, obtain the active hydrogen compounds that functionality is the polyether polyamine of 2.
Step (2). under the condition of Keep agitation, it is in 0.5mol/L acetone solvent that the active hydrogen compounds being the polyether polyamine of 2 by functionality in step (1) is added drop-wise to dichloro-phenyl phosphate concentration, makes the mol ratio of dichloro-phenyl phosphate and polyether polyamine be 2.3:1; Time for adding 60 minutes, reacts 7 hours at 50 DEG C;
Step (3). in reaction soln, add γ-aminopropyl triethoxysilane, the mol ratio of γ-aminopropyl triethoxysilane and polyether glycol in solution is made to be 2.3:1, add triethylamine again, the mol ratio of triethylamine and γ-aminopropyl triethoxysilane in solution is made to be 1.2:1, keep above-mentioned temperature of reaction, react 5 hours;
Step (4). after reaction terminates, by the triethylamine hydrochloride of product suction filtration removing white, then filter vacuum is revolved steaming, removing acetone and triethylamine, obtaining siliceous flame retarding polyether surface treatment agent, is deep yellow color liquid.
Be 500cps25 DEG C by above-mentioned siliceous flame retarding polyether surface treatment agent and viscosity, functionality is the polyether glycol mixing of 3, then adds graphite, emulsification or grind to form underflow material, and this slurry does not occur sedimentation at room temperature static 7 days.
Embodiment 4
Step (1). be 3000 by molecular-weight average, functionality be 2 polyether polyamine and triethylamine in molar ratio 1:2 mix, in argon atmosphere, stir 0.8 hour at 70 DEG C, obtain the active hydrogen compounds that functionality is the polyether polyamine of 2.
Step (2). under the condition of Keep agitation, it is in the N-N solvent dimethylformamide of 0.8mol/L that the active hydrogen compounds being the polyether polyamine of 2 by functionality in step (1) is added drop-wise to dichloro-phenyl phosphate concentration, the mol ratio of dichloro-phenyl phosphate and polyether polyamine is made to be 2.2:1, time for adding 70 minutes, reacts 8 hours at 70 DEG C;
Step (3). in reaction soln, add γ-aminopropyl triethoxysilane, the mol ratio of γ-aminopropyl triethoxysilane and polyether glycol in solution is made to be 2.2:1, add triethylamine again, the mol ratio of triethylamine and γ-aminopropyl triethoxysilane in solution is made to be 1.3:1, keep above-mentioned temperature of reaction, react 6 hours;
Step (4). after reaction terminates, by the triethylamine hydrochloride of product suction filtration removing white, then filter vacuum is revolved steaming, removing N-N solvent dimethylformamide and triethylamine, obtaining siliceous flame retarding polyether surface treatment agent, is deep yellow color liquid.
Be 300cps25 DEG C by above-mentioned siliceous flame retarding polyether surface treatment agent and viscosity, functionality is the polyether glycol mixing of 2, then adds decabromodiphynly oxide, emulsification or grind to form underflow material, and this slurry does not occur sedimentation at room temperature static 7 days.

Claims (6)

1. a siliceous functional group flame retarding polyether surface treatment agent, it is characterized in that, its structural formula is
Wherein R is polyether glycol or polyether polyamine, and the molecular-weight average of described polyether glycol or polyether polyamine is 300 ~ 4000, functionality is 2.
2. prepare the method for siliceous functional group as claimed in claim 1 flame retarding polyether surface treatment agent, it is characterized in that, the method comprises the steps:
Step (1). by polyether glycol or polyether polyamine and triethylamine in molar ratio 1:2 mix, in atmosphere of inert gases, stir 0.5 ~ 1 hour at 40-80 DEG C, obtaining functionality is the polyether glycol of 2 or the active hydrogen compounds of polyether polyamine, and described polyether glycol or the molecular-weight average of polyether polyamine are 300 ~ 4000, functionality is 2;
Step (2). under the condition of Keep agitation, be that the polyether glycol of 2 or the active hydrogen compounds of polyether polyamine are added drop-wise in the non-proton organic solvent of dichloro-phenyl phosphate by functionality in step (1), make the mol ratio of dichloro-phenyl phosphate and polyether glycol or polyether polyamine for (2.1 ~ 2.5): 1, time for adding 30-90 minute, reacts 5 ~ 10 hours afterwards at 40-80 DEG C;
In the non-proton organic solvent of described dichloro-phenyl phosphate, the concentration of dichloro-phenyl phosphate is 0.1 ~ 1mol/L;
Step (3). in reaction soln, add γ-aminopropyl triethoxysilane, make the mol ratio of γ-aminopropyl triethoxysilane and polyether glycol or polyether polyamine for (2.1 ~ 2.5): 1, add triethylamine again, make the mol ratio of triethylamine and γ-aminopropyl triethoxysilane for (1 ~ 1.5): 1, keep the temperature of reaction of step (2), reaction 3-7 hour;
Step (4). after reaction terminates, by product suction filtration removing triethylamine hydrochloride, then filter vacuum is revolved steaming, removing non-proton organic solvent and triethylamine, obtain siliceous flame retarding polyether surface treatment agent.
3. the preparation method of siliceous functional group as claimed in claim 2 flame retarding polyether surface treatment agent, is characterized in that: the rare gas element described in step (1) is nitrogen or argon gas.
4. the preparation method of siliceous functional group as claimed in claim 2 flame retarding polyether surface treatment agent, is characterized in that: the non-proton organic solvent described in step (2) is the one in N-Methyl pyrrolidone, N-N dimethyl formamide, N-N N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF), dioxane, acetone, butanone, ethyl acetate.
5. the application of siliceous functional group as claimed in claim 1 flame retarding polyether surface treatment agent, it is characterized in that, siliceous functional group flame retarding polyether surface treatment agent is mixed with polyether glycol, then solid inorganic fire retardant is added, emulsification or grind to form slurry, join in the formulation material of hard-foam polyurethane as flame-retardant master batch, obtain the finely dispersed polyurethane foam of solid inorganic fire retardant; Described polyether glycol viscosity is 200 ~ 1000cps25 DEG C, and functionality is 2 ~ 4.
6. the application of siliceous functional group as claimed in claim 5 flame retarding polyether surface treatment agent, it is characterized in that, described solid inorganic fire retardant is one or more in ammonium polyphosphate, trimeric cyanamide, trimeric cyanamide urea cyanate, melamine pyrophosphate, hypo-aluminum orthophosphate, zinc borate, magnesium hydroxide, aluminium hydroxide, TDE, decabromodiphynly oxide, nano imvite, graphite, antimonous oxide, zinc oxide.
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CN113999365A (en) * 2021-11-20 2022-02-01 扬州工业职业技术学院 Multi-effect synergistic flame-retardant polyol composition

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110157042A (en) * 2019-04-28 2019-08-23 北京工商大学 The application of novel surface inorganic agent, preparation method and the nano particle being processed in resistance combustion polyurethane foam
CN113999365A (en) * 2021-11-20 2022-02-01 扬州工业职业技术学院 Multi-effect synergistic flame-retardant polyol composition

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