CN114085427A - Preparation method of phosphorus-containing flame retardant for decorative plate - Google Patents
Preparation method of phosphorus-containing flame retardant for decorative plate Download PDFInfo
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- CN114085427A CN114085427A CN202111183722.1A CN202111183722A CN114085427A CN 114085427 A CN114085427 A CN 114085427A CN 202111183722 A CN202111183722 A CN 202111183722A CN 114085427 A CN114085427 A CN 114085427A
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 44
- 239000011574 phosphorus Substances 0.000 title claims abstract description 44
- 239000003063 flame retardant Substances 0.000 title claims abstract description 40
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 47
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229960004029 silicic acid Drugs 0.000 claims abstract description 19
- 239000012796 inorganic flame retardant Substances 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 30
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 239000010703 silicon Substances 0.000 claims description 15
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 14
- 229960001866 silicon dioxide Drugs 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 235000012239 silicon dioxide Nutrition 0.000 claims description 13
- 238000010521 absorption reaction Methods 0.000 claims description 12
- 239000003929 acidic solution Substances 0.000 claims description 12
- 239000004115 Sodium Silicate Substances 0.000 claims description 11
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 239000012488 sample solution Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 231100000357 carcinogen Toxicity 0.000 abstract description 2
- 239000003183 carcinogenic agent Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 2
- 229910052704 radon Inorganic materials 0.000 abstract description 2
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 abstract description 2
- 230000036632 reaction speed Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 150000003017 phosphorus Chemical class 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000002650 laminated plastic Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of a phosphorus-containing flame retardant for a decorative plate, which comprises the steps of respectively preparing an inorganic flame retardant and a phosphorus-containing mixing agent, and then adding water and a catalyst into the inorganic flame retardant and the phosphorus-containing flame retardant for chemical combination to obtain the phosphorus-containing flame retardant; in the steps of the invention, the flame retardant and the phosphorus series mixing agent are separately prepared, the mixing stability of respective compounds is improved, and then the phosphorus-containing flame retardant with strong stability is obtained by catalytic mixing; the inorganic flame retardant is prepared from easily available raw materials, diatomite and hydrated silica are added in the preparation of the inorganic flame retardant, and the diatomite and the hydrated silica with small particle size are obtained after further grinding and impurity removal, so that the reaction speed of dissolving in an acid solution is improved, the phosphorus-containing flame retardant not only has good flame retardance, but also the decorative plate prepared from the phosphorus-containing flame retardant can decompose harmful carcinogens such as formaldehyde, benzene, radon and the like, and the effect of environmental protection is achieved.
Description
Technical Field
The invention belongs to the technical field of building decorative plate preparation, and particularly relates to a preparation method of a phosphorus-containing flame retardant for a decorative plate.
Background
The decorative board is an artificial board, it is a thermosetting laminated plastic made of high-temperature high-pressure adhesive after chemical treatment with many kinds of special paper, the board has various wood grains or patterns, it is bright and flat, the color is bright and beautiful, at the same time it has higher wear-resisting, heat-resisting, cold-resisting, fire-resisting good physical properties, etc., the walls and roofs of many high-grade houses, the cabinet, table, bed made of the special teaching, the working table of the precise instrument, the laboratory table, the television, the radio and other broadcasting telecommunication equipment's shell, most adopt this kind of new decorative board.
The flame retardant is a functional auxiliary agent for endowing flammable polymers with flame retardancy, is mainly designed aiming at the flame retardancy of high polymer materials, is also one of important raw materials of decorative boards, and although the most commonly used halogen flame retardant in the flame retardant has incomparable high efficiency of other flame retardant series, the harm to the environment and people is not negligible.
Therefore, the flame retardant which is high in safety, green and environment-friendly and good in flame retardance is also needed by the industry, and the phosphorus-containing flame retardant has the advantages of low smoke, no toxicity, low halogen, no halogen and the like, accords with the development direction of the flame retardant, and has a good development prospect. The phosphorus-containing flame retardant in the prior art is a phosphorus flame retardant, most of the phosphorus-containing flame retardants are organic flame retardants, the preparation cost is high, and particularly, when the phosphorus-containing flame retardant is used in public environments or industries, the dosage is large, so that the cost is increased, and the construction cost of the industrial and public environments is increased.
Disclosure of Invention
In view of the problems raised by the background art, the technical scheme adopted by the invention is as follows:
a method of preparing a phosphorus-containing flame retardant for use in a trim panel, the method comprising the steps of:
1) preparing an inorganic flame retardant:
(a) pulverizing diatomite and hydrated silica by a ball mill, soaking in water to remove impurities, dehydrating, drying, and grinding into a powder mixture;
(b) adding an acidic solution into the powder mixture, stirring for 2.5h, filtering, removing precipitates, retaining the acidic solution, and adjusting the pH value to 6-6.5 to obtain a weakly acidic mixed liquid;
(c) adding aluminum hydroxide particles and silicon dioxide particles into the weakly acidic mixed liquid, and continuously stirring for 25-40 min to obtain a silicon mixed liquid;
(d) adding absolute ethyl alcohol into sodium silicate, uniformly stirring, dropwise adding an acidic solution, heating in a water bath for 1h to enable the pH value to be 6-6.3, and obtaining a sol containing silicon;
(e) adding the sol containing silicon and the silicon solution into a reaction kettle, stirring for 45-60 min until the sol and the silicon solution are uniformly mixed, and filtering to obtain a solidified mixture;
(f) adding deionized water into the cured mixture, washing until the pH value is neutral, and continuously drying in a drying oven at 100-110 ℃ for 3-5 h to obtain inorganic flame retardant particles;
2) preparing a phosphorus mixed agent:
(h) taking a proper amount of phosphorus oxychloride into a reaction barrel, cooling the reaction barrel by water, adding absolute ethyl alcohol into the reaction barrel while stirring, keeping the reaction for 1.5-2 h, and carrying out primary esterification reaction at the temperature of 10-12 ℃ to obtain an esterified liquid;
(i) distilling esterified liquid in a distillation flask under vacuum and reduced pressure, absorbing the distilled liquid with phosphorus oxychloride, cooling an absorption flask with ice water to keep the temperature of the absorption liquid at-5 ℃, and stopping distillation when the boiling point of the distilled liquid is suddenly changed to obtain absorption liquid;
(j) repeatedly adding absolute ethyl alcohol into the absorption liquid, carrying out secondary esterification reaction according to the step (h), and carrying out secondary reduced pressure distillation through the step (i) to obtain a phosphotriester solution;
(k) adding finished phosphate and water into a phosphotriester solution, placing the mixture in an anaerobic environment, stirring the mixture for 30min, adding an alkoxy radical catalyst, mixing the mixture, heating the mixture to 40-60 ℃ under an anaerobic condition, uniformly stirring the mixture, dropwise adding ethylene oxide, heating the mixture to 60-80 ℃ after reaction and feeding are finished until the measured acid value of an aged sample solution is lower than 0.2mgKOH/g, and obtaining a phosphorus-based mixing agent;
3) preparing a phosphorus-containing flame retardant:
(m) placing the inorganic flame retardant particles into a reaction kettle, injecting the phosphorus-based mixing agent under an oxygen-free condition, heating to 60 ℃, preserving heat, adding water, continuously stirring for 30min, dropwise adding a catalyst, heating to 100-120 ℃, and stirring for 3-5 h to obtain a finished product mixed solution;
(n) adding the finished product mixed solution into deionized water, stirring for 20min, filtering, and continuously drying in a drying oven at 100-110 ℃ for 6-8 h to obtain the phosphorus-containing flame retardant.
Preferably, the method comprises the following components in parts by weight:
15-25 parts of hydrated silica, 20-28 parts of diatomite, 5-10 parts of aluminum hydroxide particles, 6-11 parts of silicon dioxide particles and 45-55 parts of sodium silicate;
5-8 parts of phosphorus oxychloride and 8-12 parts of absolute ethyl alcohol.
Preferably, the particle size of the hydrated silica powder in the step (a) is 5 μm to 8 μm, and the particle size of the diatomite is 5 μm to 6 μm.
Preferably, in step (c), the particle size of the aluminum hydroxide particles is 8 μm to 10 μm, and the particle size of the silica particles is 8 μm to 10 μm.
Preferably, the acidic solution in step (d) is a hydrochloric acid solution.
Preferably, the temperature of the water bath in step (d) is 55 ℃ to 62 ℃.
Preferably, the vacuum in step (i) is required to be 3.5kpa to 4 kpa.
Preferably, the catalyst in step (i) is a phosphoric acid catalyst.
By adopting the technical scheme of the invention, the following beneficial effects are obtained:
1. the phosphorus-containing flame retardant is obtained by respectively preparing an inorganic flame retardant and a phosphorus-containing mixing agent, and then combining the inorganic flame retardant and the phosphorus-containing flame retardant by adding water and a catalyst;
2. the inorganic flame retardant has the advantages that the inorganic flame retardant is prepared at a local cost, raw materials are easy to obtain, in the preparation process of the inorganic flame retardant, the diatomite and the hydrated silica are added, after further grinding and impurity removal, the diatomite and the hydrated silica with small particle size are obtained, the reaction speed of dissolving in an acid solution is improved, the phosphorus-containing flame retardant not only has good flame retardance, but also can decompose harmful carcinogens such as formaldehyde, benzene, radon and the like through the decorative plate prepared from the phosphorus-containing flame retardant, and the effect of environmental protection is achieved.
Detailed Description
In order that those skilled in the art can better understand the present invention, the following embodiments are provided to further illustrate the present invention.
A method of preparing a phosphorus-containing flame retardant for use in a trim panel, the method comprising the steps of:
1) preparing an inorganic flame retardant:
(a) pulverizing diatomite and hydrated silica by a ball mill, soaking in water to remove impurities, dehydrating, drying, and grinding into a powder mixture;
(b) adding an acidic solution into the powder mixture, stirring for 2.5h, filtering, removing precipitates, retaining the acidic solution, and adjusting the pH value to 6-6.5 to obtain a weakly acidic mixed liquid;
(c) adding aluminum hydroxide particles and silicon dioxide particles into the weakly acidic mixed liquid, and continuously stirring for 25-40 min to obtain a silicon mixed liquid;
(d) adding absolute ethyl alcohol into sodium silicate, uniformly stirring, dropwise adding an acidic solution, heating in a water bath for 1h to enable the pH value to be 6-6.3, and obtaining a sol containing silicon;
(e) adding the sol containing silicon and the silicon solution into a reaction kettle, stirring for 45-60 min until the sol and the silicon solution are uniformly mixed, and filtering to obtain a solidified mixture;
(f) adding deionized water into the cured mixture, washing until the pH value is neutral, and continuously drying in a drying oven at 100-110 ℃ for 3-5 h to obtain inorganic flame retardant particles;
2) preparing a phosphorus mixed agent:
(h) taking a proper amount of phosphorus oxychloride into a reaction barrel, cooling the reaction barrel by water, adding absolute ethyl alcohol into the reaction barrel while stirring, keeping the reaction for 1.5-2 h, and carrying out primary esterification reaction at the temperature of 10-12 ℃ to obtain an esterified liquid;
(i) distilling esterified liquid in a distillation flask under vacuum and reduced pressure, absorbing the distilled liquid with phosphorus oxychloride, cooling an absorption flask with ice water to keep the temperature of the absorption liquid at-5 ℃, and stopping distillation when the boiling point of the distilled liquid is suddenly changed to obtain absorption liquid;
(j) repeatedly adding absolute ethyl alcohol into the absorption liquid, carrying out secondary esterification reaction according to the step (h), and carrying out secondary reduced pressure distillation through the step (i) to obtain a phosphotriester solution;
(k) adding finished phosphate and water into a phosphotriester solution, placing the mixture in an anaerobic environment, stirring the mixture for 30min, adding an alkoxy radical catalyst, mixing the mixture, heating the mixture to 40-60 ℃ under an anaerobic condition, uniformly stirring the mixture, dropwise adding ethylene oxide, heating the mixture to 60-80 ℃ after reaction and feeding are finished until the measured acid value of an aged sample solution is lower than 0.2mgKOH/g, and obtaining a phosphorus-based mixing agent;
3) preparing a phosphorus-containing flame retardant:
(m) placing the inorganic flame retardant particles into a reaction kettle, injecting the phosphorus-based mixing agent under an oxygen-free condition, heating to 60 ℃, preserving heat, adding water, continuously stirring for 30min, dropwise adding a catalyst, heating to 100-120 ℃, and stirring for 3-5 h to obtain a finished product mixed solution;
(n) adding the finished product mixed solution into deionized water, stirring for 20min, filtering, and continuously drying in a drying oven at 100-110 ℃ for 6-8 h to obtain the phosphorus-containing flame retardant.
The method comprises the following components in parts by weight:
15-25 parts of hydrated silica, 20-28 parts of diatomite, 5-10 parts of aluminum hydroxide particles, 6-11 parts of silicon dioxide particles and 45-55 parts of sodium silicate;
5-8 parts of phosphorus oxychloride and 8-12 parts of absolute ethyl alcohol.
The particle diameter of the hydrated silica powder in the step (a) is 5-8 μm, and the particle diameter of the diatomite is 5-6 μm.
In the step (c), the particle size of the aluminum hydroxide particles is 8-10 μm, and the particle size of the silicon dioxide particles is 8-10 μm.
The acidic solution in step (d) is a hydrochloric acid solution.
The temperature of the water bath in the step (d) is 55-62 ℃.
The vacuum in step (i) is required to be 3.5-4 kpa.
The catalyst in step (i) is a phosphoric acid catalyst.
Example 1
15 parts of hydrated silica, 20 parts of diatomite, 7 parts of aluminum hydroxide particles, 8 parts of silicon dioxide particles and 50 parts of sodium silicate;
5 parts of phosphorus oxychloride and 8 parts of absolute ethyl alcohol;
the phosphorus-containing flame retardant is obtained by respectively preparing the components according to the methods.
Example 2
10 parts of hydrated silica, 25 parts of diatomite, 7 parts of aluminum hydroxide particles, 8 parts of silicon dioxide particles and 50 parts of sodium silicate;
7 parts of phosphorus oxychloride and 10 parts of absolute ethyl alcohol;
the phosphorus-containing flame retardant is obtained by respectively preparing the components according to the methods.
Example 3
25 parts of hydrated silica, 28 parts of diatomite, 7 parts of aluminum hydroxide particles, 8 parts of silicon dioxide particles and 50 parts of sodium silicate;
8 parts of phosphorus oxychloride and 12 parts of absolute ethyl alcohol;
the phosphorus-containing flame retardant is obtained by respectively preparing the components according to the methods.
Example 4
10 parts of hydrated silica, 15 parts of diatomite, 7 parts of aluminum hydroxide particles, 8 parts of silicon dioxide particles and 50 parts of sodium silicate;
2 parts of phosphorus oxychloride and 6 parts of absolute ethyl alcohol;
the phosphorus-containing flame retardant is obtained by respectively preparing the components according to the methods.
Example 5
30 parts of hydrated silica, 35 parts of diatomite, 7 parts of aluminum hydroxide particles, 8 parts of silicon dioxide particles and 50 parts of sodium silicate;
10 parts of phosphorus oxychloride and 15 parts of absolute ethyl alcohol;
the phosphorus-containing flame retardant is obtained by respectively preparing the components according to the methods.
The phosphorus-containing flame retardant prepared in different examples, the decorative plate prepared according to the raw materials with the same components and the performance table obtained by combustion are as follows:
the above table shows that the larger the specific gravity of the hydrated silica and diatomaceous earth according to the method and composition of the present invention, the more phosphorus oxychloride increases, the longer the ignition time, and the longer the duration of continuous combustion per square, the better the flame retardancy.
The foregoing embodiments are merely illustrative of the principles of the present invention and its efficacy, and are not to be construed as limiting the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (8)
1. A method for preparing a phosphorus-containing flame retardant for a decorative board, the method comprising the steps of:
1) preparing an inorganic flame retardant:
(a) pulverizing diatomite and hydrated silica by a ball mill, soaking in water to remove impurities, dehydrating, drying, and grinding into a powder mixture;
(b) adding an acidic solution into the powder mixture, stirring for 2.5h, filtering, removing precipitates, retaining the acidic solution, and adjusting the pH value to 6-6.5 to obtain a weakly acidic mixed liquid;
(c) adding aluminum hydroxide particles and silicon dioxide particles into the weakly acidic mixed liquid, and continuously stirring for 25-40 min to obtain a silicon mixed liquid;
(d) adding absolute ethyl alcohol into sodium silicate, uniformly stirring, dropwise adding an acidic solution, heating in a water bath for 1h to enable the pH value to be 6-6.3, and obtaining a sol containing silicon;
(e) adding the sol containing silicon and the silicon solution into a reaction kettle, stirring for 45-60 min until the sol and the silicon solution are uniformly mixed, and filtering to obtain a solidified mixture;
(f) adding deionized water into the cured mixture, washing until the pH value is neutral, and continuously drying in a drying oven at 100-110 ℃ for 3-5 h to obtain inorganic flame retardant particles;
2) preparing a phosphorus mixed agent:
(h) taking a proper amount of phosphorus oxychloride into a reaction barrel, cooling the reaction barrel by water, adding absolute ethyl alcohol into the reaction barrel while stirring, keeping the reaction for 1.5-2 h, and carrying out primary esterification reaction at the temperature of 10-12 ℃ to obtain an esterified liquid;
(i) distilling esterified liquid in a distillation flask under vacuum and reduced pressure, absorbing the distilled liquid with phosphorus oxychloride, cooling an absorption flask with ice water to keep the temperature of the absorption liquid at-5 ℃, and stopping distillation when the boiling point of the distilled liquid is suddenly changed to obtain absorption liquid;
(j) repeatedly adding absolute ethyl alcohol into the absorption liquid, carrying out secondary esterification reaction according to the step (h), and carrying out secondary reduced pressure distillation through the step (i) to obtain a phosphotriester solution;
(k) adding finished phosphate and water into a phosphotriester solution, placing the mixture in an anaerobic environment, stirring the mixture for 30min, adding an alkoxy radical catalyst, mixing the mixture, heating the mixture to 40-60 ℃ under an anaerobic condition, uniformly stirring the mixture, dropwise adding ethylene oxide, heating the mixture to 60-80 ℃ after reaction and feeding are finished until the measured acid value of an aged sample solution is lower than 0.2mgKOH/g, and obtaining a phosphorus-based mixing agent;
3) preparing a phosphorus-containing flame retardant:
(m) placing the inorganic flame retardant particles into a reaction kettle, injecting the phosphorus-based mixing agent under an oxygen-free condition, heating to 60 ℃, preserving heat, adding water, continuously stirring for 30min, dropwise adding a catalyst, heating to 100-120 ℃, and stirring for 3-5 h to obtain a finished product mixed solution;
(n) adding the finished product mixed solution into deionized water, stirring for 20min, filtering, and continuously drying in a drying oven at 100-110 ℃ for 6-8 h to obtain the phosphorus-containing flame retardant.
2. The preparation method according to claim 1, wherein the method comprises the following components in parts by weight:
15-25 parts of hydrated silica, 20-28 parts of diatomite, 5-10 parts of aluminum hydroxide particles, 6-11 parts of silicon dioxide particles and 45-55 parts of sodium silicate;
5-8 parts of phosphorus oxychloride and 8-12 parts of absolute ethyl alcohol.
3. The method of claim 1, wherein: the particle diameter of the hydrated silica powder in the step (a) is 5-8 μm, and the particle diameter of the diatomite is 5-6 μm.
4. The method of claim 1, wherein: in the step (c), the particle size of the aluminum hydroxide particles is 8-10 μm, and the particle size of the silicon dioxide particles is 8-10 μm.
5. The method of claim 1, wherein: the acidic solution in step (d) is a hydrochloric acid solution.
6. The method of claim 1, wherein: the temperature of the water bath in the step (d) is 55-62 ℃.
7. The method of claim 1, wherein: the vacuum in step (i) is required to be 3.5-4 kpa.
8. The method of claim 1, wherein: the catalyst in step (i) is a phosphoric acid catalyst.
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| CN115257094A (en) * | 2022-07-20 | 2022-11-01 | 上海靓目新材料科技发展有限公司 | Decorative plate and manufacturing method thereof |
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