CN105482498A - Organophosphorus hybrid alpha-ZrP flame-retardant material and preparation method thereof - Google Patents

Organophosphorus hybrid alpha-ZrP flame-retardant material and preparation method thereof Download PDF

Info

Publication number
CN105482498A
CN105482498A CN201510860016.4A CN201510860016A CN105482498A CN 105482498 A CN105482498 A CN 105482498A CN 201510860016 A CN201510860016 A CN 201510860016A CN 105482498 A CN105482498 A CN 105482498A
Authority
CN
China
Prior art keywords
zrp
organophosphorus
hydridization
retardant material
fire retardant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201510860016.4A
Other languages
Chinese (zh)
Inventor
朱美芳
周家良
孙宾
江晓泽
相恒学
胡泽旭
麻伍军
王斌
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Donghua University
National Dong Hwa University
Original Assignee
Donghua University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Donghua University filed Critical Donghua University
Priority to CN201510860016.4A priority Critical patent/CN105482498A/en
Publication of CN105482498A publication Critical patent/CN105482498A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • 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
    • C08K3/32—Phosphorus-containing compounds
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)

Abstract

The present invention relates to an organophosphorus hybrid alpha-ZrP flame-retardant material and a preparation method thereof, alpha-ZrP is used as a substrate, a small molecule amine is used for supporting in advance to reduce alpha-ZrP inter-laminate force and increase interlayer spacing, then a silane coupling agent is inserted between layers, the small molecule amine for supporting in advance is removed by heat treatment, and the organophosphorus hybrid alpha-ZrP flame-retardant material can be prepared by the effect of formation of chemical bonding of a terminal group of the silane coupling agent and organophosphorus, wherein the initial decomposition temperature of the organophosphorus hybrid alpha-ZrP is 340-450 DEG C, the interlayer spacing is 1.60-2.50nm, the grafting ratio of the silane coupling agent is 6 to 18%, and the organophosphorus content is 1 to 15%. The organophosphorus hybrid alpha-ZrP flame-retardant material has high thermal stability, grafting ratio, interlayer spacing and organophosphorus content, has stronger nonpolar organic substance affinity, can be uniformly dispersed in a hydrophobic organic polymer material, may be added into most polymer materials (PET, PBT, PP, and the like) processed by melting for e preparation of flame-retardant materials, and has excellent flame retardant properties.

Description

A kind of organophosphorus hydridization α-ZrP fire retardant material and preparation method thereof
Technical field
The invention belongs to technical field of material modification, relate to a kind of organophosphorus hydridization α-ZrP fire retardant material and preparation method thereof.
Background technology
Alpha zirconium phosphate (α-ZrP) is a kind of layered phosphates; there is outstanding feature; as macroion switching performance (7meq/g; MMT is 1meq/g), controlled area ratio, heat and chemical stability be high; compared with other laminar nano weighting agent; easier in polymeric matrix by intercalation or stripping, it is widely used in the fields such as catalyzer, fuel cell, photochemistry, environment protection, fire retardant.α-ZrP is as a kind of novel inorganic combustion inhibitor with nano level laminate structure, when introducing polymeric system, due to the iris action of inorganic nano lamella, " life-span " of the free radical that decomposition can be made to produce between inorganic sheet extends, delay the degradation process of polymkeric substance, recombinate through sufficient free radical, obtain more degraded product, increase neat coal amout, improve flame retardant effect, meanwhile, α-ZrP is also a kind of excellent anti-dripping agent in polymkeric substance, can effectively prevent its melting from dripping.
But, the same with most of inorganic nanometer powder, α-ZrP is owing to containing a large amount of oh groups in surface, wetting ability is stronger, incompatible with most hydrophobic thermoplastic polymer hot in nature, be difficult to be evenly dispersed in polymeric matrix, thus affect α-ZrP to the fire-retardant of high molecular polymer and the effect of raising mechanical property.Therefore to α-ZrP organically-modified be prepare polymer inorganic composite materials before key one step.To this, scientist has carried out various trial, wherein surface modification becomes a kind of key method, mainly be divided into organic cation intercalation modifying and covalence graft modification, organic cation intercalation modifying is effectively fairly simple, α-ZrP surface is mainly utilized to have the feature of a large amount of slightly acidic group P-OH, alkaline small amine, ketones etc. are easy to insert in α-ZrP lamella and P-OH surperficial with it sets up ionic linkage, if want that the interlayer at α-ZrP introduces the amine of long chain molecule, micromolecular amine first need be used to carry out pre-support to α-ZrP and to increase its interlamellar spacing, CN101829544A utilizes methylamine to support reduction α-ZrP interlaminar action power in advance, and then by between tensio-active agent cetyl trimethylammonium bromide interposed layer (CTAB), prepare CTAB intercalation modifying zirconium phosphate material.But product binding strength prepared by this method is lower, thermal stability is poor, the processing temperature that hydrophobic thermoplastic polymer is higher cannot be adapted to, be applied to polymer modification, its spinning process at polymkeric substance decomposes the small molecules amine produced can affect the spinning property of polymkeric substance and mechanical property etc., makes fibroblast processing difficulties.
Covalence graft modification then requires that properties-correcting agent has reactive functional as isocyanic ester, acyl chlorides key etc., chemical reaction can be there is and set up the higher covalent linkage of thermostability in these groups with α-ZrP surface P-OH, thus go for further processing, wherein silane coupling agent class formation is more special, containing two or more different reactive groups on each molecule, one of them reactive group is methoxy or ethoxy, it can be combined with inorganic materials, as glass, metal, silica sand etc., another reactive group is vinyl, epoxy group(ing), amino, methacryloxypropyl or sulfydryl etc., chemical bonding can be formed with organic materials, silane coupling agent class properties-correcting agent can play good function served as bridge preparing in organic/inorganic composite material, at present, research silane coupling agent being applied to zirconium phosphate modification is less, KevinDalPont has carried out preliminary trial, utilize γ-aminopropyltrimethoxysilane modified alpha-ZrP, and itself and styrene-butadiene rubber(SBR) (SBR) compound have been prepared a kind of novel nano composite material (PontKD, GerardJ.MicrostructureandPropertiesofStyrene-ButadieneRu bberBasedNanocompositesPreparedfromanAminosilaneModified SyntheticLamellarNanofiller [J] .POLYMERPHYSICS, 2013 (51): 1051-1059.), but, the same with other covalence graft properties-correcting agent, silane coupling agent due to molecule larger, often be difficult to direct intercalation and enter α-ZrP lamella inside, only instead give birth to lamella outside surface P-OH and react, make the properties-correcting agent quantity being grafted on α-ZrP surface less, little (MosbyBM is changed to its hydrophilicity, Agust í nD í az.SurfaceFunctionalizationofZirconiumPhosphateNanoplate letsfortheDesignofPolymerFillers [J] .Appl.Mater.Interfaces, 2014 (6): 585-592.).
α-ZrP is a kind of well inorganic combustion inhibitor, research at present about α-ZrP dispersion and organophosphorus one cooperative flame retardant is less, CharlesA etc. utilize cetalkonium chloride modified alpha-ZrP, and by the α-ZrP of modification respectively and EVA, PS melt blending, find that being used alone α-ZrP there is no and play fire-retardant effect, but in time using together with other fire retardants, but can show the effect of fire retarding synergist.(HongdianLu, CharlesA.Wilkie.Theinfluenceofa-zirconiumphosphateonfire performanceofEVAandPScomposites [J] .Polym.Adv.Technol.2011,22:1123-1130.) JennyAlongi, AlbertoFrache utilizes the method for melt blending to prepare PA6 respectively, PP, EVA, PET, with the blend of α-ZrP.And have studied mechanical property and the flame retardant properties of blend, find that α-ZrP shows the effect of cooperative flame retardant with zinc phosphate and ammonium phosphate type fire retardant, find that the deployment conditions of α-ZrP has important association with the performance such as fire-retardant simultaneously.(JennyAlongi,AlbertoFrache.Flameretardancypropertiesofa-zirconiumphosphatebasedcomposites[J].PolymerDegradationandStability,2010,(95):1928-1933.)
Summary of the invention
Primary and foremost purpose of the present invention is that the shortcoming overcoming prior art is with not enough, provides a kind of organophosphorus hydridization α-ZrP fire retardant material.
Organophosphorus hydridization α-ZrP fire retardant material of the present invention, outward appearance is white powder, and described organophosphorus hydridization α-ZrP fire retardant material is lamellar compound, and interlamellar spacing is 1.60 ~ 2.50nm; Described organophosphorus hydridization α-ZrP fire retardant material is made up of α-ZrP, silane coupling agent and organophosphorus, and silane coupling agent is inserted into α-ZrP interlayer, and the percentage of grafting of silane coupling agent on α-ZrP is 6 ~ 18%; Organophosphorus is connected with chemical bond with silane coupling agent, and organophosphorus exists surface and the interlayer of α-ZrP; Described organophosphorus hydridization α-ZrP fire retardant material initial decomposition temperature is 340 ~ 450 DEG C; Described organophosphorus hydridization α-ZrP fire retardant material can be dispersed in non-polar organic solvent normal hexane.
Another object of the present invention is to provide a kind of preparation method of organophosphorus hydridization α-ZrP fire retardant material, and step is:
1) be scattered in solvent by α-ZrP, α-ZrP surface is containing great amount of hydroxy group group, and wetting ability is strong, can be scattered in solvent preferably, acts on the dispersion that can promote α-ZrP by ultrasonic grade;
2) add small molecule amine reaction, small molecule amine, in alkalescence, can react with weakly acidic α-ZrP and set up ionic linkage, simultaneously because himself molecular chain is shorter, easy insertion stratiform α-ZrP is inner, increases α-ZrP interlamellar spacing, is conducive to the insertion of next step reactant;
3) drip silane coupling agent again and continue reaction, silica group in silane coupling agent is met water and is hydrolyzed, the active higher silanol key Si-OH of formation reaction, dehydration condensation can be there is in Si-OH with P-OH on α-ZrP lamella, at the P-O-Si covalent linkage that α-ZrP sheet surfaces Heat of Formation stability is higher, simultaneously owing to containing hydrophobic chain segment in silane coupled agent molecule, when percentage of grafting reaches certain value, α-ZrP can be become hydrophobic material from hydrophilic material, increase the consistency between itself and hydrophobic polymer;
4) add organophosphorus and continue reaction, the amino of silane coupling agent end group or isocyanate group and the organophosphorus containing the group such as hydroxyl, carboxyl is utilized to form chemical bond, organophosphorus is guided to lamella and the interlayer of α-ZrP, the sheet interlayer spacing of further expansion α-ZrP, can form the effect that a kind of organic-inorganic synergistic is fire-retardant;
5) solid product is through being separated, washing and drying the α-ZrP organophosphorus hybrid material that can obtain modification, and this step main purpose removes reaction solvent and unreacted monomer etc.;
6) α-ZrP organophosphorus hybrid material of described modification processes under 250 ~ 320 DEG C of conditions, namely organophosphorus hydridization α-ZrP is obtained, heat treated object removes the heat-labile small molecule amine of pre-intercalation in organophosphorus hydridization α-ZrP molecule, improve the thermostability of organophosphorus hydridization α-ZrP, be conducive to being applied to great majority by the macromolecular material of melt-processed.
As preferred technical scheme:
The preparation method of a kind of organophosphorus hydridization α-ZrP fire retardant material as above, step 1) in, described solvent is trichloromethane, tetrahydrofuran (THF), DMF; α-ZrP is through stirring ultrasonic being easily scattered in solvent, and after dispersion, the concentration of α-ZrP is that 0.005 ~ 0.02g/ml, α-ZrP concentration is suitable for, and is conducive to forming stable dispersion system in follow-up small molecule amine interposed layer, and the excessive System forming that easily causes of concentration precipitates.
The preparation method of a kind of organophosphorus hydridization α-ZrP fire retardant material as above, step 1) in, described dispersion refers at ambient temperature, ultrasonic and mechanical stirring; Churned mechanically rotating speed is 200 ~ 800r/min, and the time is 20 ~ 50min; Describedly ultrasonicly refer at ambient temperature, ultrasonic power is 50 ~ 90W, and the time is 20 ~ 50min, and this dispersion condition can be avoided mutually reuniting between α-ZrP, reaches optimum dispersion state, increases the specific surface area of α-ZrP, is conducive to and modifying agent.
The preparation method of a kind of organophosphorus hydridization α-ZrP fire retardant material as above, the mol ratio of small molecule amine and α-ZrP is 1:2.0 ~ 1:4.0, this ratio is too small, easily cause α-ZrP intercalation incomplete, be unfavorable for entering of follow-up silane coupling agent, excessive, make α-ZrP surface hydrophobicity organic substance too much, wetting ability declines, middle water molecule is expelled out of, and laminate recovers non-intercalation configuration.
The preparation method of a kind of organophosphorus hydridization α-ZrP fire retardant material as above, step 2) in, the time adding small molecule amine reaction is 0.6 ~ 1.8h, and the reaction times is short, and amine intercalation is incomplete, longly causes energy dissipation; Described small molecule amine is methylamine, ethamine or Tri N-Propyl Amine.
The preparation method of a kind of organophosphorus hydridization α-ZrP fire retardant material as above, the general formula of molecular structure of described silane coupling agent is YRSiX 3, wherein R is alkyl, and the essential characteristic of described silane coupling agent is that wherein X is hydrolization group containing two kinds of reactive group X and Y of different nature in same a part, Y be can with the organo-functional group of polymer reaction; The dripping quantity of silane coupling agent and the mass ratio of α-ZrP are 0.5:1 ~ 2.0:1; Drop rate is 0.1 ~ 1.5ml/min; The described time of continuing reaction is 3 ~ 8h.
The preparation method of a kind of organophosphorus hydridization α-ZrP fire retardant material as above, described X is alkoxyl group; Described Y is amino or isocyanate group.
The preparation method of a kind of organophosphorus hydridization α-ZrP fire retardant material as above; step 4) in; described organophosphorus is phosphoric acid, phosphorous acid, phospho acid, phenyl phosphinic acid, phosphenylic acid, 2-(diphenylphosphino)-1; 4-dihydroxy-benzene, diphenyl phosphonic acid, phenoxy group phosphonyl dichloride, methyl-phosphorous acid, methyl phosphonyl dichloride, 2-carboxyethyl phenyl phosphinic acid or hydroxymethyl phenyl phospho acid; the mol ratio of described organophosphorus and silane coupling agent is 0.2:1 ~ 2:1, and the time of described reaction is 2 ~ 8h.
The preparation method of a kind of organophosphorus hydridization α-ZrP fire retardant material as above, step 5) in, solid product and separated from solvent adopt Rotary Evaporators; Described washing is first is that the acetone of 90 ~ 98% and the mixing solutions of water soak 24 ~ 36h in concentration, and a large amount of acetone soln of rear use cleans 3 ~ 5 times until the reaction raw materials of noresidue in product; Described oven dry, for being placed in vacuum drying oven, 60 ~ 80 DEG C, dries 24 ~ 36h under vacuum tightness 0.05 ~ 0.1MPa condition.
The preparation method of a kind of organophosphorus hydridization α-ZrP fire retardant material as above, step 6) in, described process refers to cures 3 ~ 10min by the α-ZrP of modification under 250 ~ 320 DEG C of conditions.
The preparation method of a kind of organophosphorus hydridization α-ZrP fire retardant material as above, described organophosphorus hydridization α-ZrP outward appearance is white powder; Described organophosphorus hydridization α-ZrP is lamellar compound, and interlamellar spacing is 1.60 ~ 2.50nm; Described organophosphorus hydridization α-ZrP is made up of α-ZrP, silane coupling agent and organophosphorus, silane coupling agent is inserted in α-ZrP interlayer, organophosphorus is at the lamella of α-ZrP and interlayer, and the percentage of grafting of silane coupling agent on α-ZrP is 6 ~ 18%, and organic phosphorous content is 1 ~ 15%; Described organophosphorus hydridization α-ZrP initial decomposition temperature is 340 ~ 450 DEG C; Described organophosphorus hydridization α-ZrP can be dispersed in non-polar organic solvent normal hexane, and described organophosphorus hydridization α-ZrP can play good fire retardation.
Beneficial effect
The present invention compared with prior art has following advantages:
1, heat resisting temperature is higher, thermal stability is good: with α-ZrP for carrier, small molecule amine is for support agent in advance, silane coupling agent is properties-correcting agent, organophosphorus is that organophosphorus hydridization α-ZrP prepared by twice-modified dose and synergistic flame retardant has the higher heat resisting temperature of the modified alpha-ZrP for preparing than quaternary ammonium salt properties-correcting agent, its initial decomposition temperature is 340 ~ 450 DEG C, overcome modified alpha-ZrP heat resisting temperature prepared by current quaternary ammonium salt properties-correcting agent lower than the shortcoming of 300 DEG C, be conducive to being added on great majority by the macromolecular material of melt-processed.Quaternary ammonium salt properties-correcting agent is combined with ionic linkage with α-ZrP, and silane coupling agent can with α-ZrP with covalent bonds, and organophosphorus can with silane coupling agent with covalent bonds, and research finds, the thermostability of covalent linkage is generally higher than ionic linkage.
2, percentage of grafting is higher: high thermal stability organophosphorus hydridization α-ZrP prepared by the method has the higher percentage of grafting of the organically-modified α of the high thermal stability-ZrP for preparing than additive method, its percentage of grafting is 6 ~ 18%, the organic substance overcoming the organically-modified α of current high thermal stability-ZrP combination is less, with the problem of organic substance poor compatibility, be conducive to being dispersed in most hydrophobic organic polymer material.Other prepare the organically-modified α of high thermal stability-ZrP method is exactly the properties-correcting agent directly utilizing epoxy compounds etc. to contain active group, without the pre-intercalation of small molecule amine and heat treatment step, only there is covalent reaction with the P-OH of α-ZrP outside surface, interlayer can not be entered by intercalation, therefore the organic substance being grafted on its surface is fewer, in the present invention, properties-correcting agent can enter layer inside, so relative to additive method, percentage of grafting significantly improves.
3, interlamellar spacing is larger: high thermal stability organophosphorus hydridization α-ZrP prepared by the method has the higher interlamellar spacing of the organically-modified α of the high thermal stability-ZrP for preparing than additive method, principle is the same, its interlamellar spacing is 1.60 ~ 2.50nm, overcome and prepare the organically-modified α of high thermal stability-ZrP properties-correcting agent at present and be difficult to intercalation and enter α-ZrP, interlamellar spacing is still the problem of original 0.76nm, be conducive to polymer segment intercalation to enter in organic modified alpha-ZrP layer, realize dispersed in hydrophobic polymer material of organophosphorus hydridization α-ZrP.
4, synergistic fire retardation: high thermal stability organophosphorus hydridization α-ZrP prepared by the method has the advantage of structure-function integration.Compare other fire retardant materials, organophosphorus and inorganic nano-particle are divided into two kinds of components to add playing synergistic fire retardation simultaneously, organophosphorus hydridization α-ZrP fire retardant material prepared by the present invention, only need a kind of component, by the effect of chemical bonding between component, one step completes dispersion, synergistic is fire-retardant, a step can realize fire-retardant, dispersion.
Accompanying drawing explanation
Fig. 1 is the process schematic that embodiment 1 prepares organophosphorus hydridization α-ZrP fire retardant material, wherein α-ZrP is first through the pre-intercalation of Tri N-Propyl Amine (n-propylamine), graft reaction is there is again with 3-aminopropyl-triethoxyl silane (APTES), organophosphorus (diphenyl phosphonic acid DPPO) forms chemical bond with APTES again, eventually passes thermal treatment (heat-treatment) and namely obtains organophosphorus hydridization α-ZrP fire retardant material.
Fig. 2 is that (ordinate zou is relative intensity to the X-ray diffractogram of organophosphorus hydridization α-ZrP fire retardant material prepared of the embodiment of the present invention 1, X-coordinate is 2 θ angles), wherein α-ZrP-PA-APTES-OP-HT is after the propylamine (PA) after process in advance support and 3-aminopropyl-triethoxyl silane (APTES) graft reaction and diphenylphosphoric acid and APRES occur to react the α-ZrP after forming secondary intercalation grafting.
Fig. 3 is that (ordinate zou is quality to the thermogravimetric curve of organophosphorus hydridization α-ZrP fire retardant material prepared of the embodiment of the present invention 1, X-coordinate is temperature), α-ZrP-PA-APTES be propylamine (PA) in advance after support and 3-aminopropyl-triethoxyl silane (APTES) there is the α-ZrP of graft reaction, α-ZrP-PA-APTES-HT is the α-ZrP-PA-APTES after process, α-ZrP-PA-APTES-OP-HT.
Embodiment
Below in conjunction with embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
In embodiments of the invention:
The calculation formula of interlamellar spacing is: d=λ/2sin θ; λ is the wavelength of X-ray, and θ is the angle of incident X-rays and corresponding crystal face.
The interlamellar spacing of the α-ZrP that modification adopts is 0.76nm (2 θ=10.8 °).
The calculation formula of percentage of grafting is as follows:
The quality of the quality/unmodified α-ZrP of percentage of grafting (%)=organic constituent.
The quality of organic phosphorous content (%)=(total weight loss-organic constituent weight loss)/unmodified α-ZrP.
Embodiment 1
A kind of preparation method of organophosphorus hydridization α-ZrP fire retardant material, as shown in Figure 1, for preparing the process schematic of organically-modified α-ZrP, wherein α-ZrP is first through the pre-intercalation of Tri N-Propyl Amine (n-propylamine), graft reaction is being there is with 3-aminopropyl-triethoxyl silane (APTES), then the end group of the silane coupling agent of diphenylphosphine and α-ZrP surface and interlayer reacts, eventually pass thermal treatment (heat-treatment) and namely obtain organophosphorus hydridization α-ZrP fire retardant material, step is:
1) by α-ZrP at ambient temperature, ultrasonic and mechanical stirring, ultrasonic power is 50W, and the time is 20min; Churned mechanically rotating speed is 200r/min, and the time is that 20min is scattered in tetrahydrofuran solution, and after dispersion, the concentration of α-ZrP is 0.005g/ml;
2) add the reaction of small molecules Tri N-Propyl Amine, the mol ratio of Tri N-Propyl Amine and α-ZrP is 1:2.0, and the time adding Tri N-Propyl Amine reaction is 0.6h;
3) drip silane coupling agent 3-aminopropyl-triethoxyl silane (APTES) and continue reaction; The dripping quantity of APTES and the mass ratio of α-ZrP are 0.5:1; Drop rate is 0.1ml/min; The time of continuing reaction is 3h;
4) add diphenyl phosphonic acid and continue reaction; The dripping quantity of diphenyl phosphonic acid and the mol ratio of APTES are 1:1; Raised temperature to 80 DEG C, continues reaction 6h;
5) solid product is through being separated, washing and drying the α-ZrP organophosphorus hybrid material that can obtain modification, and solid product and separated from solvent adopt Rotary Evaporators; Washing is first is that the acetone of 90% and the mixing solutions of water soak 24h in concentration, and a large amount of acetone soln of rear use cleans 3 times until the reaction raw materials of noresidue in product; Drying as being placed in vacuum drying oven, 60 DEG C, under vacuum tightness 0.05MPa condition, drying 24h;
6) α-ZrP of organophosphorus hydridization cures 3min under 250 DEG C of conditions, namely organophosphorus hydridization α-ZrP fire retardant material is obtained, this organophosphorus hydridization α-ZrP fire retardant material outward appearance is white powder, and be lamellar compound, as shown in Figure 2, the interlamellar spacing of this organophosphorus hydridization α-ZrP fire retardant material is 1.74nm (2 θ=5.06 °); This organophosphorus hydridization α-ZrP fire retardant material is made up of α-ZrP, silane coupling agent 3-aminopropyl-triethoxyl silane (APTES) and organophosphorus diphenyl phosphonic acid (DPPO), APTES is inserted in α-ZrP interlayer, DPPO and α-ZrP reacts with the end group of the APTES of interlayer on surface, as shown in Figure 3, the percentage of grafting of APTES on α-ZrP is 13.78%, organic phosphorous content is about 10%, and the initial decomposition temperature of this organophosphorus hydridization α-ZrP fire retardant material is 368 DEG C; Organophosphorus hydridization α-ZrP fire retardant material can be dispersed in non-polar organic solvent normal hexane.
Embodiment 2
A preparation method for organophosphorus hydridization α-ZrP fire retardant material, step is:
1) by α-ZrP at ambient temperature, ultrasonic and mechanical stirring, ultrasonic power is 90W, and the time is 50min; Churned mechanically rotating speed is 800r/min, and the time is that 50min is scattered in trichloromethane, and after dispersion, the concentration of α-ZrP is 0.02g/ml;
2) add the reaction of small molecules ethamine, the mol ratio of ethamine and α-ZrP is 1:4.0, and the time adding ethamine reaction is 1.8h;
3) drip silane coupling agent 3-aminopropyl-Trimethoxy silane (APTMS) and continue reaction; The dripping quantity of APTMS and the mass ratio of α-ZrP are 2:1; Drop rate is 1.5ml/min; The time of continuing reaction is 8h;
4) add methyl-phosphorous acid and continue reaction; The dripping quantity of methyl-phosphorous acid and the mol ratio of APTMS are 1.5:1; Temperature of reaction is 60 DEG C, continues reaction times 5h;
5) solid product is through being separated, washing and drying the α-ZrP organophosphorus hybrid material that can obtain modification, and solid product and separated from solvent adopt Rotary Evaporators; Washing is first is that the acetone of 98% and the mixing solutions of water soak 36h in concentration, and a large amount of acetone soln of rear use cleans 5 times until the reaction raw materials of noresidue in product; Drying as being placed in vacuum drying oven, 80 DEG C, under vacuum tightness 0.1MPa condition, drying 36h;
6) α-ZrP organophosphorus hybrid material of modification cures 10min under 320 DEG C of conditions, namely organophosphorus hydridization α-ZrP fire retardant material is obtained, this organophosphorus hydridization α-ZrP fire retardant material outward appearance is white powder, and be lamellar compound, the interlamellar spacing of this organophosphorus hydridization α-ZrP fire retardant material is 1.84nm (2 θ=4.80 °); This organophosphorus hydridization α-ZrP fire retardant material is made up of α-ZrP, silane coupling agent 3-aminopropyl-Trimethoxy silane (APTMS) and methyl-phosphorous acid, APTMS is inserted in α-ZrP interlayer, methyl-phosphorous acid reacts with the APTMS end group being distributed in α-ZrP interlayer and surface, the percentage of grafting of APTMS on α-ZrP is 9.62%, organic phosphorous content is 7%, and organophosphorus hydridization α-ZrP fire retardant material initial decomposition temperature is 365 DEG C; Organophosphorus hydridization α-ZrP fire retardant material can be dispersed in non-polar organic solvent normal hexane.
Embodiment 3
A preparation method for organophosphorus hydridization α-ZrP fire retardant material, step is:
1) by α-ZrP at ambient temperature, ultrasonic and mechanical stirring, ultrasonic power is 60W, and the time is 30min; Churned mechanically rotating speed is 500r/min, and the time is that 30min is scattered in DMF, and after dispersion, the concentration of α-ZrP is 0.008g/ml;
2) add the reaction of small molecules Tri N-Propyl Amine, the mol ratio of Tri N-Propyl Amine and α-ZrP is 1:2.2, and the time adding Tri N-Propyl Amine reaction is 0.9h;
3) drip silane coupling agent 3-aminopropyl-triethoxyl silane (APTES) and continue reaction; The dripping quantity of APTES and the mass ratio of α-ZrP are 1.0:1; Drop rate is 1.2ml/min; The time of continuing reaction is 5h;
4) add methyl phosphonyl dichloride and continue reaction; The dripping quantity of methyl phosphonyl dichloride and the mol ratio of APTES are 2:1; Temperature of reaction is 40 DEG C, continues reaction times 4h;
5) solid product is through being separated, washing and drying the α-ZrP organophosphorus hybrid material that can obtain modification, and solid product and separated from solvent adopt Rotary Evaporators; Washing is first is that the acetone of 92% and the mixing solutions of water soak 28h in concentration, and a large amount of acetone soln of rear use cleans 4 times until the reaction raw materials of noresidue in product; Drying as being placed in vacuum drying oven, 65 DEG C, under vacuum tightness 0.06MPa condition, drying 28h;
6) α-ZrP organophosphorus hybrid material of modification cures 5min under 260 DEG C of conditions, namely organophosphorus hydridization α-ZrP fire retardant material is obtained, this organophosphorus hydridization α-ZrP fire retardant material outward appearance is white powder, and be lamellar compound, the interlamellar spacing 1.81nm (2 θ=4.86 °) of this organophosphorus hydridization α-ZrP fire retardant material; This organophosphorus hydridization α-ZrP fire retardant material is made up of α-ZrP, silane coupling agent 3-aminopropyl-triethoxyl silane (APTES) and methyl phosphonyl dichloride, APTES is inserted in α-ZrP interlayer, methyl phosphonyl dichloride forms chemical bond with the MPMS end group being distributed in α-ZrP surface and interlayer, the percentage of grafting of APTES on α-ZrP is 10.28%, organic phosphorous content is 8.5%, and organophosphorus hydridization α-ZrP fire retardant material initial decomposition temperature is 374 DEG C; Organophosphorus hydridization α-ZrP fire retardant material can be dispersed in non-polar organic solvent normal hexane.
Embodiment 4
A preparation method for organophosphorus hydridization α-ZrP fire retardant material, step is:
1) by α-ZrP at ambient temperature, ultrasonic and mechanical stirring, ultrasonic power is 60W, and the time is 25min; Churned mechanically rotating speed is 500r/min, and the time is that 30min is scattered in tetrahydrofuran (THF), and after dispersion, the concentration of α-ZrP is 0.01g/ml;
2) add the reaction of small molecules methylamine, the mol ratio of methylamine and α-ZrP is 1:3.0, and the time adding methylamine reaction is 1.5h;
3) drip silane coupling agent 3-aminopropyl-Trimethoxy silane (APTMS) and continue reaction; The dripping quantity of APTMS and the mass ratio of α-ZrP are 1.5:1; Drop rate is 1.1ml/min; The time of continuing reaction is 5h;
4) add phosphenylic acid and continue reaction; The dripping quantity of phosphenylic acid and the mol ratio of APTMS are 2:1; Temperature of reaction is 70 DEG C, continues reaction times 6h;
5) solid product is through being separated, washing and drying the α-ZrP organophosphorus hybrid material that can obtain modification, and solid product and separated from solvent adopt Rotary Evaporators; Washing is first is that the acetone of 92% and the mixing solutions of water soak 30h in concentration, and a large amount of acetone soln of rear use cleans 4 times until the reaction raw materials of noresidue in product; Drying as being placed in vacuum drying oven, 66 DEG C, under vacuum tightness 0.08MPa condition, drying 30h;
6) α-ZrP organophosphorus hybrid material of modification cures 6min under 300 DEG C of conditions, namely organophosphorus hydridization α-ZrP fire retardant material is obtained, this organophosphorus hydridization α-ZrP fire retardant material outward appearance is white powder, and be lamellar compound, the interlamellar spacing of this organophosphorus hydridization α-ZrP fire retardant material is 1.76nm (2 θ=5.00 °); This organophosphorus hydridization α-ZrP fire retardant material is made up of α-ZrP, silane coupling agent 3-aminopropyl-Trimethoxy silane (APTMS) and phenyl-phosphonic acid, APTMS is inserted in α-ZrP interlayer, phenyl-phosphonic acid forms chemical bond with the APTMS end group being distributed in α-ZrP surface and interlayer, the percentage of grafting of APTMS on α-ZrP is 11.26%, organic phosphorous content is 9.8%, and organophosphorus hydridization α-ZrP fire retardant material initial decomposition temperature is 366 DEG C; Organophosphorus hydridization α-ZrP fire retardant material can be dispersed in non-polar organic solvent normal hexane.
Embodiment 5
A preparation method for organophosphorus hydridization α-ZrP fire retardant material, step is:
1) by α-ZrP at ambient temperature, ultrasonic and mechanical stirring, ultrasonic power is 60W, and the time is 35min; Churned mechanically rotating speed is 650r/min, and the time is that 25min is scattered in trichloromethane, and after dispersion, the concentration of α-ZrP is 0.009g/ml;
2) add the reaction of small molecules ethamine, the mol ratio of ethamine and α-ZrP is 1:2.5, and the time adding ethamine reaction is 0.9h;
3) drip silane coupling agent isocyanic ester propyl-triethoxysilicane (IPTS) again and continue reaction; The dripping quantity of IPTS and the mass ratio of α-ZrP are 1.2:1; Drop rate is 0.6ml/min; The time of continuing reaction is 7h;
4) add phosphoric acid and continue reaction; The dripping quantity of phosphoric acid and the mol ratio of IPTS are 1.5:1; Temperature of reaction is 60 DEG C, continues reaction times 3h;
5) solid product is through being separated, washing and drying the α-ZrP organophosphorus hybrid material that can obtain modification, and solid product and separated from solvent adopt Rotary Evaporators; Washing is first is that the acetone of 96% and the mixing solutions of water soak 26h in concentration, and a large amount of acetone soln of rear use cleans 5 times until the reaction raw materials of noresidue in product; Drying as being placed in vacuum drying oven, 66 DEG C, under vacuum tightness 0.07MPa condition, drying 32h;
6) α-ZrP organophosphorus hybrid material of modification cures 5min under 280 DEG C of conditions, namely organophosphorus hydridization α-ZrP fire retardant material is obtained, this organophosphorus hydridization α-ZrP fire retardant material outward appearance is white powder, and be lamellar compound, the interlamellar spacing of this organophosphorus hydridization α-ZrP fire retardant material is 1.65nm (2 θ=5.34 °); This organophosphorus hydridization α-ZrP fire retardant material is made up of α-ZrP, silane coupling agent isocyanic ester propyl-triethoxysilicane (IPTS) and phenyl-phosphonic acid dimethyl ester, IPTS is inserted in α-ZrP interlayer, it is 12.19% that phenyl-phosphonic acid dimethyl ester forms the percentage of grafting of chemical bond IPTS on α-ZrP with the IPTS end group being distributed in α-ZrP surface and interlayer, organic phosphorous content is 10.5%, and organophosphorus hydridization α-ZrP fire retardant material initial decomposition temperature is 380 DEG C; Organophosphorus hydridization α-ZrP fire retardant material can be dispersed in non-polar organic solvent normal hexane.
Embodiment 6
A preparation method for organophosphorus hydridization α-ZrP fire retardant material, step is:
1) by α-ZrP at ambient temperature, ultrasonic and mechanical stirring, ultrasonic power is 50W, and the time is 20min; Churned mechanically rotating speed is 200r/min, and the time is that 20min is scattered in tetrahydrofuran solution, and after dispersion, the concentration of α-ZrP is 0.005g/ml;
2) add the reaction of small molecules Tri N-Propyl Amine, the mol ratio of Tri N-Propyl Amine and α-ZrP is 1:2.0, and the time adding Tri N-Propyl Amine reaction is 0.6h;
3) drip silane coupling agent 3-aminopropyl-triethoxyl silane (APTES) and continue reaction; The dripping quantity of APTES and the mass ratio of α-ZrP are 0.5:1; Drop rate is 0.1ml/min; The time of continuing reaction is 3h;
4) add phosphorous acid and continue reaction; The dripping quantity of phosphorous acid and the mol ratio of APTES are 1:1; Raised temperature to 80 DEG C, continues reaction 6h;
5) solid product is through being separated, washing and drying the α-ZrP organophosphorus hybrid material that can obtain modification, and solid product and separated from solvent adopt Rotary Evaporators; Washing is first is that the acetone of 90% and the mixing solutions of water soak 24h in concentration, and a large amount of acetone soln of rear use cleans 3 times until the reaction raw materials of noresidue in product; Drying as being placed in vacuum drying oven, under 60C, vacuum tightness 0.05MPa condition, drying 24h;
6) α-ZrP of organophosphorus hydridization cures 3min under 250 DEG C of conditions, namely organophosphorus hydridization α-ZrP fire retardant material is obtained, this organophosphorus hydridization α-ZrP fire retardant material outward appearance is white powder, and be lamellar compound, the interlamellar spacing of this organophosphorus hydridization α-ZrP fire retardant material is 1.60nm (2 θ=5.51 °); This organophosphorus hydridization α-ZrP fire retardant material is made up of α-ZrP, silane coupling agent 3-aminopropyl-triethoxyl silane (APTES) and organophosphorus phosphorous acid, APTES is inserted in α-ZrP interlayer, phosphorous acid and α-ZrP surface are reacted with the end group of the APTES of interlayer, the percentage of grafting of APTES on α-ZrP is 15.78%, organic phosphorous content is about 12%, and the initial decomposition temperature of this organophosphorus hydridization α-ZrP fire retardant material is 375 DEG C; Organophosphorus hydridization α-ZrP fire retardant material can be dispersed in non-polar organic solvent normal hexane.
Embodiment 7
A preparation method for organophosphorus hydridization α-ZrP fire retardant material, step is:
1) by α-ZrP at ambient temperature, ultrasonic and mechanical stirring, ultrasonic power is 90W, and the time is 50min; Churned mechanically rotating speed is 800r/min, and the time is that 50min is scattered in trichloromethane, and after dispersion, the concentration of α-ZrP is 0.02g/ml;
2) add the reaction of small molecules ethamine, the mol ratio of ethamine and α-ZrP is 1:4.0, and the time adding ethamine reaction is 1.8h;
3) drip silane coupling agent 3-aminopropyl-Trimethoxy silane (APTMS) and continue reaction; The dripping quantity of APTMS and the mass ratio of α-ZrP are 2:1; Drop rate is 1.5ml/min; The time of continuing reaction is 8h;
4) add phospho acid and continue reaction; The dripping quantity of phospho acid and the mol ratio of APTMS are 1.5:1; Temperature of reaction is 60 DEG C, continues reaction times 5h;
5) solid product is through being separated, washing and drying the α-ZrP organophosphorus hybrid material that can obtain modification, and solid product and separated from solvent adopt Rotary Evaporators; Washing is first is that the acetone of 98% and the mixing solutions of water soak 36h in concentration, and a large amount of acetone soln of rear use cleans 5 times until the reaction raw materials of noresidue in product; Drying as being placed in vacuum drying oven, under 80C, vacuum tightness 0.1MPa condition, drying 36h;
6) α-ZrP organophosphorus hybrid material of modification cures 10min under 320 DEG C of conditions, namely organophosphorus hydridization α-ZrP fire retardant material is obtained, this organophosphorus hydridization α-ZrP fire retardant material outward appearance is white powder, and be lamellar compound, the interlamellar spacing of this organophosphorus hydridization α-ZrP fire retardant material is 1.68nm (2 θ=5.51 °); This organophosphorus hydridization α-ZrP fire retardant material is made up of α-ZrP, silane coupling agent 3-aminopropyl-Trimethoxy silane (APTMS) and phospho acid, APTMS is inserted in α-ZrP interlayer, phospho acid react with the APTMS end group being distributed in α-ZrP interlayer and surface, the percentage of grafting of APTMS on α-ZrP is 9.78%, organic phosphorous content is 7.36%, and organophosphorus hydridization α-ZrP fire retardant material initial decomposition temperature is 362 DEG C; Organophosphorus hydridization α-ZrP fire retardant material can be dispersed in non-polar organic solvent normal hexane.
Embodiment 8
A preparation method for organophosphorus hydridization α-ZrP fire retardant material, step is:
1) by α-ZrP at ambient temperature, ultrasonic and mechanical stirring, ultrasonic power is 60W, and the time is 25min; Churned mechanically rotating speed is 500r/min, and the time is that 30min is scattered in tetrahydrofuran (THF), and after dispersion, the concentration of α-ZrP is 0.01g/ml;
2) add the reaction of small molecules methylamine, the mol ratio of methylamine and α-ZrP is 1:3.0, and the time adding methylamine reaction is 1.5h;
3) drip silane coupling agent 3-aminopropyl-Trimethoxy silane (APTMS) and continue reaction; The dripping quantity of APTMS and the mass ratio of α-ZrP are 1.5:1; Drop rate is 1.1ml/min; The time of continuing reaction is 5h;
4) add phenyl phosphinic acid and continue reaction; The dripping quantity of phenyl phosphinic acid and the mol ratio of APTMS are 2:1; Temperature of reaction is 70 DEG C, continues reaction times 6h;
5) solid product is through being separated, washing and drying the α-ZrP organophosphorus hybrid material that can obtain modification, and solid product and separated from solvent adopt Rotary Evaporators; Washing is first is that the acetone of 92% and the mixing solutions of water soak 30h in concentration, and a large amount of acetone soln of rear use cleans 4 times until the reaction raw materials of noresidue in product; Drying as being placed in vacuum drying oven, 66 DEG C, under vacuum tightness 0.08MPa condition, drying 30h;
6) α-ZrP organophosphorus hybrid material of modification cures 6min under 300 DEG C of conditions, namely organophosphorus hydridization α-ZrP fire retardant material is obtained, this organophosphorus hydridization α-ZrP fire retardant material outward appearance is white powder, and be lamellar compound, the interlamellar spacing of this organophosphorus hydridization α-ZrP fire retardant material is 1.76nm (2 θ=5.01 °); This organophosphorus hydridization α-ZrP fire retardant material is made up of α-ZrP, silane coupling agent 3-aminopropyl-Trimethoxy silane (APTMS) and phenyl phosphinic acid, APTMS is inserted in α-ZrP interlayer, phenyl phosphinic acid forms chemical bond with the APTMS end group being distributed in α-ZrP surface and interlayer, the percentage of grafting of APTMS on α-ZrP is 14.32%, organic phosphorous content is 11.08%, and organophosphorus hydridization α-ZrP fire retardant material initial decomposition temperature is 377 DEG C; Organophosphorus hydridization α-ZrP fire retardant material can be dispersed in non-polar organic solvent normal hexane.
Embodiment 9
A preparation method for organophosphorus hydridization α-ZrP fire retardant material, step is:
1) by α-ZrP at ambient temperature, ultrasonic and mechanical stirring, ultrasonic power is 60W, and the time is 35min; Churned mechanically rotating speed is 650r/min, and the time is that 25min is scattered in trichloromethane, and after dispersion, the concentration of α-ZrP is 0.009g/ml;
2) add the reaction of small molecules ethamine, the mol ratio of ethamine and α-ZrP is 1:2.5, and the time adding ethamine reaction is 0.9h;
3) drip silane coupling agent isocyanic ester propyl-triethoxysilicane (IPTS) again and continue reaction; The dripping quantity of IPTS and the mass ratio of α-ZrP are 1.2:1; Drop rate is 0.6ml/min; The time of continuing reaction is 7h;
4) add 2-(diphenylphosphino)-1, 4-benzenediol and continue reaction; The dripping quantity of 2-(diphenylphosphino)-1, 4-benzenediol and the mol ratio of IPTS are 1.5:1; Temperature of reaction is 60 DEG C, continues reaction times 3h;
5) solid product is through being separated, washing and drying the α-ZrP organophosphorus hybrid material that can obtain modification, and solid product and separated from solvent adopt Rotary Evaporators; Washing is first is that the acetone of 96% and the mixing solutions of water soak 26h in concentration, and a large amount of acetone soln of rear use cleans 5 times until the reaction raw materials of noresidue in product; Drying as being placed in vacuum drying oven, 66 DEG C, under vacuum tightness 0.07MPa condition, drying 32h;
6) α-ZrP organophosphorus hybrid material of modification cures 5min under 280 DEG C of conditions, namely organophosphorus hydridization α-ZrP fire retardant material is obtained, this organophosphorus hydridization α-ZrP fire retardant material outward appearance is white powder, and is lamellar compound, and interlamellar spacing is 2.05nm (2 θ=4.30 °); This organophosphorus hydridization α-ZrP fire retardant material is by α-ZrP, silane coupling agent isocyanic ester propyl-triethoxysilicane (IPTS) and 2-(diphenylphosphino)-1,4-dihydroxy-benzene forms, IPTS is inserted in α-ZrP interlayer, 2-(diphenylphosphino)-1, it is 16.41% that 4-dihydroxy-benzene forms the percentage of grafting of chemical bond IPTS on α-ZrP with the IPTS end group being distributed in α-ZrP surface and interlayer, organic phosphorous content is 12.78%, and organophosphorus hydridization α-ZrP fire retardant material initial decomposition temperature is 387 DEG C; Organophosphorus hydridization α-ZrP fire retardant material can be dispersed in non-polar organic solvent normal hexane.
Embodiment 10
A preparation method for organophosphorus hydridization α-ZrP fire retardant material, step is:
1) by α-ZrP at ambient temperature, ultrasonic and mechanical stirring, ultrasonic power is 50W, and the time is 20min; Churned mechanically rotating speed is 200r/min, and the time is that 20min is scattered in tetrahydrofuran solution, and after dispersion, the concentration of α-ZrP is 0.005g/ml;
2) add the reaction of small molecules Tri N-Propyl Amine, the mol ratio of Tri N-Propyl Amine and α-ZrP is 1:2.0, and the time adding Tri N-Propyl Amine reaction is 0.6h;
3) drip silane coupling agent 3-aminopropyl-triethoxyl silane (APTES) and continue reaction; The dripping quantity of APTES and the mass ratio of α-ZrP are 0.5:1; Drop rate is 0.1ml/min; The time of continuing reaction is 3h;
4) add phenoxy group phosphonyl dichloride and continue reaction; The dripping quantity of phenoxy group phosphonyl dichloride and the mol ratio of APTES are 1:1; Raised temperature to 80 DEG C, continues reaction 6h;
5) solid product is through being separated, washing and drying the α-ZrP organophosphorus hybrid material that can obtain modification, and solid product and separated from solvent adopt Rotary Evaporators; Washing is first is that the acetone of 90% and the mixing solutions of water soak 24h in concentration, and a large amount of acetone soln of rear use cleans 3 times until the reaction raw materials of noresidue in product; Drying as being placed in vacuum drying oven, 60 DEG C, under vacuum tightness 0.05MPa condition, drying 24h;
6) α-ZrP of organophosphorus hydridization cures 3min under 250 DEG C of conditions, namely organophosphorus hydridization α-ZrP fire retardant material is obtained, this organophosphorus hydridization α-ZrP fire retardant material outward appearance is white powder, and be lamellar compound, the interlamellar spacing of this organophosphorus hydridization α-ZrP fire retardant material is 1.82nm (2 θ=4.86 °); This organophosphorus hydridization α-ZrP fire retardant material is made up of α-ZrP, silane coupling agent 3-aminopropyl-triethoxyl silane (APTES) and organophosphorus phenoxy group phosphonyl dichloride, APTES is inserted in α-ZrP interlayer, phenoxy group phosphonyl dichloride and α-ZrP surface are reacted with the end group of the APTES of interlayer, the percentage of grafting of APTES on α-ZrP is 13.56%, organic phosphorous content is about 10.34%, and the initial decomposition temperature of this organophosphorus hydridization α-ZrP fire retardant material is 376 DEG C; Organophosphorus hydridization α-ZrP fire retardant material can be dispersed in non-polar organic solvent normal hexane.
Embodiment 11
A preparation method for organophosphorus hydridization α-ZrP fire retardant material, step is:
1) by α-ZrP at ambient temperature, ultrasonic and mechanical stirring, ultrasonic power is 90W, and the time is 50min; Churned mechanically rotating speed is 800r/min, and the time is that 50min is scattered in trichloromethane, and after dispersion, the concentration of α-ZrP is 0.02g/ml;
2) add the reaction of small molecules ethamine, the mol ratio of ethamine and α-ZrP is 1:4.0, and the time adding ethamine reaction is 1.8h;
3) drip silane coupling agent 3-aminopropyl-Trimethoxy silane (APTMS) and continue reaction; The dripping quantity of APTMS and the mass ratio of α-ZrP are 2:1; Drop rate is 1.5ml/min; The time of continuing reaction is 8h;
4) add 2-carboxyethyl phenyl phosphinic acid and continue reaction; The dripping quantity of 2-carboxyethyl phenyl phosphinic acid and the mol ratio of APTMS are 1.5:1; Temperature of reaction is 60 DEG C, continues reaction times 5h;
5) solid product is through being separated, washing and drying the α-ZrP organophosphorus hybrid material that can obtain modification, and solid product and separated from solvent adopt Rotary Evaporators; Washing is first is that the acetone of 98% and the mixing solutions of water soak 36h in concentration, and a large amount of acetone soln of rear use cleans 5 times until the reaction raw materials of noresidue in product; Drying as being placed in vacuum drying oven, under 80C, vacuum tightness 0.1MPa condition, drying 36h;
6) α-ZrP organophosphorus hybrid material of modification cures 10min under 320 DEG C of conditions, namely organophosphorus hydridization α-ZrP fire retardant material is obtained, this organophosphorus hydridization α-ZrP fire retardant material outward appearance is white powder, and be lamellar compound, the interlamellar spacing of this organophosphorus hydridization α-ZrP fire retardant material is 1.76nm (2 θ=5.01 °); This organophosphorus hydridization α-ZrP fire retardant material is made up of α-ZrP, silane coupling agent 3-aminopropyl-Trimethoxy silane (APTMS) and 2-carboxyethyl phenyl phosphinic acid, APTMS is inserted in α-ZrP interlayer, 2-carboxyethyl phenyl phosphinic acid reacts with the APTMS end group being distributed in α-ZrP interlayer and surface, the percentage of grafting of APTMS on α-ZrP is 12.62%, organic phosphorous content is 9.87%, and organophosphorus hydridization α-ZrP fire retardant material initial decomposition temperature is 373 DEG C; Organophosphorus hydridization α-ZrP fire retardant material can be dispersed in non-polar organic solvent normal hexane.
Embodiment 12
A preparation method for organophosphorus hydridization α-ZrP fire retardant material, step is:
1) by α-ZrP at ambient temperature, ultrasonic and mechanical stirring, ultrasonic power is 60W, and the time is 30min; Churned mechanically rotating speed is 500r/min, and the time is that 30min is scattered in DMF, and after dispersion, the concentration of α-ZrP is 0.008g/ml;
2) add the reaction of small molecules Tri N-Propyl Amine, the mol ratio of Tri N-Propyl Amine and α-ZrP is 1:2.2, and the time adding Tri N-Propyl Amine reaction is 0.9h;
3) drip silane coupling agent 3-aminopropyl-triethoxyl silane (APTES) and continue reaction; The dripping quantity of APTES and the mass ratio of α-ZrP are 1.0:1; Drop rate is 1.2ml/min; The time of continuing reaction is 5h;
4) add hydroxymethyl phenyl phospho acid and continue reaction; The dripping quantity of hydroxymethyl phenyl phospho acid and the mol ratio of APTES are 2:1; Temperature of reaction is 40 DEG C, continues reaction times 4h;
5) solid product is through being separated, washing and drying the α-ZrP organophosphorus hybrid material that can obtain modification, and solid product and separated from solvent adopt Rotary Evaporators; Washing is first is that the acetone of 92% and the mixing solutions of water soak 28h in concentration, and a large amount of acetone soln of rear use cleans 4 times until the reaction raw materials of noresidue in product; Drying as being placed in vacuum drying oven, 65 DEG C, under vacuum tightness 0.06MPa condition, drying 28h;
6) α-ZrP organophosphorus hybrid material of modification cures 5min under 260 DEG C of conditions, namely organophosphorus hydridization α-ZrP fire retardant material is obtained, this organophosphorus hydridization α-ZrP fire retardant material outward appearance is white powder, and be lamellar compound, the interlamellar spacing 1.72nm (2 θ=5.12 °) of this organophosphorus hydridization α-ZrP fire retardant material; This organophosphorus hydridization α-ZrP fire retardant material is made up of α-ZrP, silane coupling agent 3-aminopropyl-triethoxyl silane (APTES) and hydroxymethyl phenyl phospho acid, APTES is inserted in α-ZrP interlayer, hydroxymethyl phenyl phospho acid form chemical bond with the MPMS end group being distributed in α-ZrP surface and interlayer, the percentage of grafting of APTES on α-ZrP is 13.82%, organic phosphorous content is 10.05%, and organophosphorus hydridization α-ZrP fire retardant material initial decomposition temperature is 383 DEG C; Organophosphorus hydridization α-ZrP fire retardant material can be dispersed in non-polar organic solvent normal hexane.

Claims (10)

1. a preparation method for organophosphorus hydridization α-ZrP fire retardant material, is characterized in that, step is:
1) α-ZrP is scattered in solvent;
2) small molecule amine reaction is added;
3) drip silane coupling agent and continue reaction;
4) add organophosphorus and continue reaction;
5) solid product is through being separated, washing and drying the α-ZrP organophosphorus hybrid material that can obtain modification;
6) α-ZrP organophosphorus hybrid material of described modification processes under 250 ~ 320 DEG C of conditions, namely obtains organophosphorus hydridization α-ZrP fire retardant material.
2. the preparation method of a kind of organophosphorus hydridization α-ZrP fire retardant material according to claim 1, it is characterized in that, step 1) in, described solvent is tetrahydrofuran (THF), trichloromethane or N, dinethylformamide, after dispersion, the concentration of α-ZrP is 0.005 ~ 0.02g/ml.
3. the preparation method of a kind of organophosphorus hydridization α-ZrP fire retardant material according to claim 1, is characterized in that, step 1) in, described dispersion refers at ambient temperature, ultrasonic and mechanical stirring; Churned mechanically rotating speed is 200 ~ 800r/min, and the time is 20 ~ 50min; Describedly ultrasonicly refer at ambient temperature, ultrasonic power is 50 ~ 90W, and the time is 20 ~ 50min.
4. the preparation method of a kind of organophosphorus hydridization α-ZrP fire retardant material according to claim 1, it is characterized in that, the mol ratio of small molecule amine and α-ZrP is 1:2.0 ~ 1:4.0, and the time adding small molecule amine reaction is 0.6 ~ 1.8h; Described small molecule amine is methylamine, ethamine or Tri N-Propyl Amine.
5. the preparation method of a kind of organophosphorus hydridization α-ZrP fire retardant material according to claim 1, it is characterized in that, the general formula of molecular structure of described silane coupling agent is YRSiX 3, wherein R is alkyl, and the essential characteristic of described silane coupling agent is that wherein X is hydrolization group, and Y is the organo-functional group that can react with organophosphorus containing two kinds of reactive group X and Y of different nature in same a part; The dripping quantity of silane coupling agent and the mass ratio of α-ZrP are 0.5:1 ~ 2.0:1; Drop rate is 0.1 ~ 1.5ml/min; The described time of continuing reaction is 3 ~ 8h.
6. the preparation method of a kind of organophosphorus hydridization α-ZrP fire retardant material according to claim 1, it is characterized in that, described X is alkoxyl group; Described Y is amino, isocyanate group.
7. the preparation method of a kind of organophosphorus hydridization α-ZrP fire retardant material according to claim 1; it is characterized in that; described organophosphorus is phosphoric acid, phosphorous acid, phospho acid, phenyl phosphinic acid, phosphenylic acid, 2-(diphenylphosphino)-1; 4-dihydroxy-benzene, diphenyl phosphonic acid, phenoxy group phosphonyl dichloride, methyl-phosphorous acid, methyl phosphonyl dichloride, 2-carboxyethyl phenyl phosphinic acid or hydroxymethyl phenyl phospho acid; described organophosphorus and the mol ratio of silane coupling agent are 0.2:1 ~ 2:1, and the time of described reaction is 2 ~ 8h.
8. the preparation method of a kind of organophosphorus hydridization α-ZrP fire retardant material according to claim 1, is characterized in that, step 5) in, solid product and separated from solvent adopt Rotary Evaporators; Described washing is first is that the acetone of 90 ~ 98% and the mixing solutions of water soak 24 ~ 36h in concentration, and a large amount of acetone soln of rear use cleans 3 ~ 5 times until the reaction raw materials of noresidue in product; Described oven dry, for being placed in vacuum drying oven, 60 ~ 80 DEG C, dries 24 ~ 36h under vacuum tightness 0.05 ~ 0.1MPa condition.
9. the preparation method of a kind of organophosphorus hydridization α-ZrP fire retardant material according to claim 1, it is characterized in that, step 6) in, described process refers to cures 3 ~ 10min by the α-ZrP organophosphorus hybrid material of described modification under 250 ~ 320 DEG C of conditions.
10. a kind of organophosphorus hydridization α-ZrP fire retardant material of method of modifying gained according to any one of claim 1 ~ 9, is characterized in that: described organophosphorus hydridization α-ZrP fire retardant material outward appearance is white powder; Described organophosphorus hydridization α-ZrP fire retardant material is lamellar compound, and interlamellar spacing is 1.60 ~ 2.50nm; Described organophosphorus hydridization α-ZrP fire retardant material is made up of α-ZrP, silane coupling agent and organophosphorus, and silane coupling agent is inserted in α-ZrP interlayer, and the percentage of grafting of silane coupling agent on α-ZrP is 6 ~ 18%; End of silane reactive group and organophosphorus are with chemical bond linkage; The content of organophosphorus is 1 ~ 15%; Organophosphorus is present in surface and the interlayer of α-ZrP; Described organophosphorus hydridization α-ZrP fire retardant material initial decomposition temperature is 340 ~ 450 DEG C; Described organophosphorus hydridization α-ZrP fire retardant material can be dispersed in non-polar organic solvent normal hexane.
CN201510860016.4A 2015-11-30 2015-11-30 Organophosphorus hybrid alpha-ZrP flame-retardant material and preparation method thereof Pending CN105482498A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510860016.4A CN105482498A (en) 2015-11-30 2015-11-30 Organophosphorus hybrid alpha-ZrP flame-retardant material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510860016.4A CN105482498A (en) 2015-11-30 2015-11-30 Organophosphorus hybrid alpha-ZrP flame-retardant material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN105482498A true CN105482498A (en) 2016-04-13

Family

ID=55669784

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510860016.4A Pending CN105482498A (en) 2015-11-30 2015-11-30 Organophosphorus hybrid alpha-ZrP flame-retardant material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN105482498A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108752834A (en) * 2018-05-29 2018-11-06 项赛飞 A kind of high intensity charging pile cable thermoplastic elastomer (TPE) and preparation method thereof
CN109438759A (en) * 2018-09-29 2019-03-08 华南理工大学 A kind of compound intercalation modified zirconium phosphate of nitrogen-phosphorus with fire retardation and preparation method

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1067605A (en) * 1996-08-23 1998-03-10 Mitsui Petrochem Ind Ltd Antimicrobial material
CN101275230A (en) * 2008-05-09 2008-10-01 北京化工大学 Zirconium phosphate compound film for surface corrosion resistance of copper or alloy thereof and preparation thereof
CN101503567A (en) * 2009-03-05 2009-08-12 中国科学技术大学 Nano composite expansion flame-retardant polyurethane foam plastic and preparation thereof
US20110039947A1 (en) * 2008-05-08 2011-02-17 3M Innovative Properties Company Surface-modified nanoparticles
CN102210048A (en) * 2008-10-09 2011-10-05 巴茨卡普公司 Electrode comprising a modified complex oxide as active substance
CN102430431A (en) * 2012-01-12 2012-05-02 北京化工大学 Supported organic rhenium catalyst and preparation method thereof
CN102897737A (en) * 2012-09-24 2013-01-30 常州大学 Method for preparation of pillared zirconium phosphate material by self-assembly technology
CN103011118A (en) * 2012-12-10 2013-04-03 常州大学 Method for preparing zirconium phosphate layer column material by guide assembly technology
CN105061761A (en) * 2015-08-14 2015-11-18 华南理工大学 Nano zirconium phosphate-modified triazine macromolecular charring agent, and preparation method and application thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1067605A (en) * 1996-08-23 1998-03-10 Mitsui Petrochem Ind Ltd Antimicrobial material
US20110039947A1 (en) * 2008-05-08 2011-02-17 3M Innovative Properties Company Surface-modified nanoparticles
CN101275230A (en) * 2008-05-09 2008-10-01 北京化工大学 Zirconium phosphate compound film for surface corrosion resistance of copper or alloy thereof and preparation thereof
CN102210048A (en) * 2008-10-09 2011-10-05 巴茨卡普公司 Electrode comprising a modified complex oxide as active substance
CN101503567A (en) * 2009-03-05 2009-08-12 中国科学技术大学 Nano composite expansion flame-retardant polyurethane foam plastic and preparation thereof
CN102430431A (en) * 2012-01-12 2012-05-02 北京化工大学 Supported organic rhenium catalyst and preparation method thereof
CN102897737A (en) * 2012-09-24 2013-01-30 常州大学 Method for preparation of pillared zirconium phosphate material by self-assembly technology
CN103011118A (en) * 2012-12-10 2013-04-03 常州大学 Method for preparing zirconium phosphate layer column material by guide assembly technology
CN105061761A (en) * 2015-08-14 2015-11-18 华南理工大学 Nano zirconium phosphate-modified triazine macromolecular charring agent, and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LILIAN S. BRANDA˜O,ET AL.: "Thermal and Mechanical Properties of Poly(ethylene terephthalate)/Lamellar Zirconium Phosphate Nanocomposites", 《JOURNAL OF APPLIED POLYMER SCIENCE》 *
YA DU ET AL.: "Preparation and performance of lipophilic α-zirconium phosphate with high thermal stability and its application in thermal-plastic polymers", 《PROGRESS IN NATURAL SCIENCE: MATERIALS INTERNATIONAL》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108752834A (en) * 2018-05-29 2018-11-06 项赛飞 A kind of high intensity charging pile cable thermoplastic elastomer (TPE) and preparation method thereof
CN109438759A (en) * 2018-09-29 2019-03-08 华南理工大学 A kind of compound intercalation modified zirconium phosphate of nitrogen-phosphorus with fire retardation and preparation method
CN109438759B (en) * 2018-09-29 2021-03-30 华南理工大学 Nitrogen-phosphorus composite intercalation modified zirconium phosphate with flame retardant effect and preparation method thereof

Similar Documents

Publication Publication Date Title
Aziz et al. Recent progress in silane coupling agent with its emerging applications
CN101760049B (en) Method for preparing core-shell silicon dioxide-coated ammonium polyphosphate (APP)
CN111303665B (en) Modified hydroxyapatite and application thereof in water-based fireproof coating
CN103849165B (en) Functionalized nanometer silica with ultraviolet ray absorption function group grafted on surface, and preparation method thereof
CN104327549B (en) Alumina silica hydrogel double-coating ammonium polyphosphate modifying and the application in polypropylene flame redardant thereof
WO2022160673A1 (en) Phenylboronic acid grafted modified zirconium phosphate-based flame retardant and preparation method therefor
CN109943099B (en) Flame retardant based on modified alpha-zirconium phosphate and preparation method thereof
CN110183730A (en) Organic modified nano basic zirconium phosphate cladded type ammonium polyphosphate and preparation method thereof
Gibertini et al. Silica-encapsulated red phosphorus for flame retardant treatment on textile
CN103387757A (en) Method for preparing supercritical hydrotalcite grafted with flame retardant
CN110804445B (en) Preparation method of bio-based flame-retardant microcapsule
CN106592201A (en) Method for preparing flame retardation-type hydrophobic aerosil composite felt pad under normal pressure
CN105482498A (en) Organophosphorus hybrid alpha-ZrP flame-retardant material and preparation method thereof
CN102504616A (en) Phosphorus-nitrogen clay-based compound flame retardant and method of preparing same
CN105504878A (en) Organically modified alpha-ZrP and modification method thereof
CN105504877A (en) Organically modified and metal ion-loaded anti-microbial alpha-ZrP powder and preparation method thereof
CN102516785A (en) Core-shell urea formaldehyde modified lignin intumescent flame-retardant charring agent and preparation method thereof
CN106832414B (en) A kind of preparation method and applications of nano-silicon dioxide modified ammonium polyphosphate
CN104650432B (en) Modification method of nano white carbon black used as rubber additive
CN104762009B (en) Nano modified polyurethane flame-retardant waterproof coating and preparation method thereof
Ma et al. Construction of green versatile coating integrating fireproof, electric-conduction and self-cleaning performance for cotton fabrics
CN103694742A (en) Method for graft modification of insoluble ammonium polyphosphate through organosilicon, and use of obtained product
Chiou et al. Fine dispersion of phosphazene-amines and silicate platelets in epoxy nanocomposites and the synergistic fire-retarding effect
CA2847994C (en) Nanoclays containing flame retardant chemicals for fire retardant applications
CN104449766A (en) Benzene-ring-containing hydrophobic organic ammonium polyphosphate fire retardant and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20160413