CN110982118A - Synergistic flame retardant and preparation method of synergistic flame retardant master batch - Google Patents
Synergistic flame retardant and preparation method of synergistic flame retardant master batch Download PDFInfo
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- CN110982118A CN110982118A CN201911347687.5A CN201911347687A CN110982118A CN 110982118 A CN110982118 A CN 110982118A CN 201911347687 A CN201911347687 A CN 201911347687A CN 110982118 A CN110982118 A CN 110982118A
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
- C08K2003/321—Phosphates
- C08K2003/325—Calcium, strontium or barium phosphate
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a synergistic flame retardant and a preparation method of a synergistic flame retardant master batch. The synergistic flame retardant obtained by the scheme is mainly used for partially replacing antimony trioxide to be applied to the polymer flame-retardant material, so that the production cost of the polymer flame-retardant material is reduced on the basis of not influencing the performance of the flame-retardant polymer, and the flame-retardant efficiency of the material is improved. The phosphorus component in the synergistic flame retardant can be used as a dehydrating agent of a flame retardant material and promotes carbon formation, the heat conduction from flame to a condensed phase is reduced by the generation of carbon, and a formed carbon layer can effectively isolate oxygen in the air, thereby being beneficial to improving the flame retardant effect.
Description
Technical Field
The invention belongs to the field of flame retardant manufacturing, and particularly relates to a synergistic flame retardant and a preparation method of master batches thereof.
Background
With the continuous improvement of the awareness of fire safety, the flame retardant material occupies a larger proportion in production and life, but the high price of the flame retardant material limits the use of the flame retardant material in some fields, so that the price reduction of the flame retardant material becomes very important.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a method for preparing a low-cost synergistic flame retardant and master batches.
In order to realize the purpose, the following technical scheme is adopted: a preparation method of a synergistic flame retardant comprises the following steps:
s1, mixing phosphoric acid or soluble metal phosphate and water according to the weight ratio of 1: 1-6, heating the reaction kettle to 30-90 ℃, adding a metal hydroxide or a metal oxide or a metal salt into the reaction kettle, stirring while adding, and releasing heat; wherein the mass ratio of the input amount of the metal hydroxide, the metal oxide or the metal salt to the phosphoric acid or the soluble metal phosphate is 1: 0.2 to 5;
and S2, after the corresponding metal hydroxide or metal oxide or metal salt is added, stirring for 10-20 minutes at the temperature of 30-90 ℃, then cooling, when the temperature is reduced to 0-30 ℃, performing suction filtration, performing solid-liquid separation by using a centrifuge to obtain a filter cake, and drying and crushing the filter cake to obtain the synergistic flame retardant.
In the above technical solution, preferably, the metal hydroxide is one or more of barium hydroxide, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, lanthanum hydroxide and cerium hydroxide.
In the above technical scheme, preferably, the soluble metal phosphate is one or more of sodium phosphate, sodium hypophosphite, magnesium hypophosphite and aluminum hypophosphite.
In the above technical solution, preferably, the phosphoric acid is 85% phosphoric acid.
In the above technical solution, preferably, the metal oxide is one or more of magnesium oxide, calcium oxide, barium oxide, aluminum oxide, lanthanum oxide, and cerium oxide.
In the above technical solution, preferably, the metal salt is Cl-containing-,SO4 2-，NO3 -,CO3 2-Or HCO3 -One or more soluble metal salts of ions.
In the preparation method of the scheme, when an insoluble metal reactant, namely metal hydroxide or metal oxide, is put into a reaction kettle
Or metal salts, the reaction principle is different, and specifically, the method comprises the following steps:
principle of reaction 1:
reaction of Metal (M) hydroxide with phosphoric acid
Reaction principle 2:
the metal salt (for example, a metal salt containing a chloride ion) is reacted with the metal (A) phosphate compound
Principle of reaction 3:
reaction of Metal (M) oxide with phosphoric acid
The preparation and flame-retardant principle of the invention is that metal hydroxide, metal oxide or metal salt reacts with phosphoric acid or soluble metal phosphate in proper solvent to generate insoluble metal phosphorus-containing compound and other products, and the product is coprecipitated, solid-liquid separated by a centrifuge to obtain filter cake, and the filter cake is dried by airflow and crushed to obtain the synergistic flame retardant. Wherein the insoluble metal phosphorus-containing compound is the main and effective component of the synergistic flame retardant; the phosphorus component can be used as a dehydrating agent of the flame retardant material and promotes carbon formation, the heat conduction from flame to a condensed phase is reduced by the generation of carbon, and a formed carbon layer can effectively isolate oxygen in the air and is beneficial to improving the flame retardant effect.
The invention also discloses a preparation method of the synergistic flame retardant master batch, which comprises the steps of putting the synergistic flame retardant prepared by the method and resin into a twin-screw extruder, carrying out high-temperature melt extrusion, and granulating by using a granulator to obtain the synergistic flame retardant master batch.
In the scheme, the length-diameter ratio of the screw of the double-screw extruder is preferably 30-64.
The synthesized synergistic flame retardant powder and proper resin are extruded and granulated to obtain the synergistic flame retardant master batch.
The preparation method can reduce the production cost of the flame-retardant polymer material and improve the flame-retardant efficiency of the material on the basis of not influencing the performance of the flame-retardant polymer; the synergistic flame retardant and the master batch material thereof obtained by the preparation method can be used for partially replacing antimony trioxide to be applied to polymer flame retardant materials, such as flame retardant materials of electronic appliances, automobiles and the like.
Detailed Description
The invention will now be further illustrated with reference to specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes and modifications can be made by those skilled in the art after reading the disclosure of the present invention, and equivalents also fall within the scope of the invention defined by the claims.
The test equipment used in the tests of the various examples described below is shown in Table one
Watch 1
| Name (R) | Model number | Manufacturer of the product |
| TGA thermogravimetric analyzer | TGA2(LF) | Mettler toledo |
| Laser particle size analyzer | WINNER 2018 | Micro-nano particle |
| PH value tester | LP—160A | Tin-free lever environmental protection technology |
| Density tester | JW—M100 | Medicine for treating high blood pressure |
| Water content tester | LXT-200 | Shenzhen laixite |
| Total phosphorus on-line automatic monitor | GTP-5 | Shanghai bath source environment-friendly science and technology |
Example 1:
10 kg of 85% strength phosphoric acid and 40 kg of water are introduced into a 0.2m3 reaction vessel. After the reaction kettle is heated until the liquid in the reaction kettle is in a slightly boiling state, 25 kg of barium hydroxide octahydrate is added, and the reaction is exothermic while stirring. Stirring for 10min under slightly boiling state after the addition is finished, and then cooling. And when the temperature is reduced to 10 ℃, suction filtration is started, and the filter cake is subjected to air flow drying and crushing to obtain the synergistic flame retardant powder.
The performance of the prepared synergistic flame retardant is detected, and the performance of the obtained synergistic flame retardant is shown in the following table II.
Watch two
| 1% thermal decomposition temperature | 430℃ |
| Average particle diameter | 1.5μm |
| pH value | 6 |
| Density of | 3.1g/cm3 |
| Phosphorus content | 13.8％ |
| Water content ratio | 0.2％ |
Example 2:
10 kg of sodium phosphate and 30 kg of water were added to a 0.2m3 reaction kettle. Heating the reaction kettle until the liquid in the reaction kettle is slightly boiled, adding 18 kg of barium chloride while stirring, and discharging heat. Stirring for 10min under slightly boiling state after the addition is finished, and then cooling. And when the temperature is reduced to 10 ℃, suction filtration is started, and the filter cake is subjected to air flow drying and crushing to obtain the synergistic flame retardant powder.
The performance of the prepared synergistic flame retardant is detected, and the performance of the obtained synergistic flame retardant is shown in the third table.
Watch III
| 1% thermal decomposition temperature | 432℃ |
| Average particle diameter | 1.7μm |
| pH value | 6.2 |
| Density of | 3.0g/cm3 |
| Phosphorus content | 13.2％ |
| Water content ratio | 0.2％ |
Example 3:
10 kg of sodium phosphate and 20 kg of water were added to 0.2m3In a reaction kettle. After the reaction kettle is heated until the liquid in the reaction kettle is in a slightly boiling state, 9 kg of calcium oxide is added, and the reaction kettle is stirred while adding, so that the heat is released. Stirring for 10min under slightly boiling state after the addition is finished, and then cooling. And when the temperature is reduced to 10 ℃, suction filtration is started, and the filter cake is subjected to air flow drying and crushing to obtain the synergistic flame retardant powder.
The performance of the prepared synergistic flame retardant is detected, and the performance of the obtained synergistic flame retardant is shown in the following table four.
Watch four
| 1% thermal decomposition temperature | 423℃ |
| Average particle diameter | 1.6μm |
| pH value | 6.4 |
| Density of | 2.8g/cm3 |
| Phosphorus content | 13.9％ |
| Water content ratio | 0.2％ |
Example 4
The synergistic flame retardant prepared in the example 1 is added into PA6 resin, and the weight ratio of the synergistic flame retardant to PA6 is 3: 1. adding into a double-screw extruder, and extruding and granulating.
Wherein the length-diameter ratio of a screw of the double-screw extruder is 44, and the diameter of the screw is 35 mm; the working temperature (unit ℃) of each working section in the double-screw extruder is shown in the table five below, the rotating speed of the screw is 350 r/min, and the yield is 30 kg/h.
Watch five
| A segment of | Two segment | Three sections | Four sections | Five sections | Six sections | Seven segments | Eight sections | Nine sections | Machine head |
| 160℃ | 200 | 220 | 220 | 210 | 200 | 200 | 200 | 210 | 220 |
And carrying out twin-screw extrusion granulation according to two formulas of the sixth table to produce two groups of flame-retardant PA6GF30, wherein the synergistic flame-retardant master batch prepared in the example 1 is added in the second formula.
Watch six
| Raw materials | Formulation I | Formulation II |
| PA6(2500A) | 54 | 53.46 |
| Glass fiber (988A) | 30 | 30 |
| Decabromodiphenylethane | 12 | 12 |
| Antimony trioxide | 4 | 2.4 |
| Synergistic flame retardant masterbatch (example 1) | 2.14 | |
| 1098/168 | 0.2/0.2 | 0.2/0.2 |
The two groups of flame retardant PA6GF30 were compared for performance test, and the main difference between the two schemes was that the dual-purpose synergistic flame retardant in the formula was substituted for 40% of antimony trioxide in the formula I, and the results are as shown in the following seven:
watch seven
| Detecting items | Test standard | Formulation I | Formulation II |
| Tensile strength MPa | ISO 527-2 | 130 | 132 |
| Bending strength MPa | ISO 178 | 172 | 175 |
| Flexural modulus MPa | ISO 178 | 8500 | 8650 |
| Impact strength KJ/square meter | ISO 179 | 9 | 9 |
| Density g/cm3 | ISO 1183 | 1.53 | 1.54 |
| Flame retardancy (1.6mm) | UL94 | V0 | V0 |
Example 5
The synergistic flame retardant prepared in the example 2 is added into PBT resin, and the weight ratio of the synergistic flame retardant to the PBT is 3: 1. adding the mixture into a double-screw extruder, and extruding and granulating, wherein the working temperature (unit ℃) of each working section in the double-screw extruder is shown in the table eight, the rotating speed of a screw is 350 revolutions per minute, and the yield is 30 kilograms per hour.
Table eight
| A segment of | Two segment | Three sections | Four sections | Five sections | Six sections | Seven segments | Eight sections | Nine sections | Machine head |
| 160 | 230 | 240 | 220 | 220 | 210 | 210 | 220 | 230 | 240 |
And carrying out twin-screw extrusion granulation according to the two formulas of the nine groups in the following table to produce two groups of flame-retardant PBTGF30, wherein the synergistic flame-retardant master batch prepared in the example 2 is added into the formula IV.
Watch nine
| Raw materials | Formulation III | Formulation IV |
| PBT(1100) | 54 | 53.46 |
| GF(988A) | 30 | 30 |
| Decabromodiphenylethane | 12 | 12 |
| Antimony trioxide | 4 | 2.4 |
| Synergistic flame-retardant master batchEXAMPLE 2) | 2.14 | |
| 1076/168 | 0.2/0.2 | 0.2/0.2 |
The two groups of flame retardant PBTGF30 are compared in performance detection, and the main difference between the two schemes is that the formula IV uses the synergistic flame retardant to replace 40 percent of antimony trioxide in the formula powder, and the results are shown in the following table ten:
watch ten
The detection data show that the synergistic flame retardant can replace antimony trioxide to play a role under the condition of not influencing flame retardance and material physical properties, so that the cost of the flame retardant material is reduced.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (8)
1. A preparation method of a synergistic flame retardant is characterized in that: the method comprises the following steps:
s1, mixing phosphoric acid or soluble metal phosphate and water according to the weight ratio of 1: 1-6, heating the reaction kettle to 30-90 ℃, adding a metal hydroxide or a metal oxide or a metal salt into the reaction kettle, stirring while adding, and releasing heat; wherein the mass ratio of the input amount of the metal hydroxide, the metal oxide or the metal salt to the phosphoric acid or the soluble metal phosphate is 1: 0.2 to 5;
and S2, after the corresponding metal hydroxide or metal oxide or metal salt is added, stirring for 10-20 minutes at the temperature of 30-90 ℃, then cooling, when the temperature is reduced to 0-30 ℃, performing suction filtration, performing solid-liquid separation by using a centrifuge to obtain a filter cake, and drying and crushing the filter cake to obtain the synergistic flame retardant.
2. The method for preparing the synergistic flame retardant of claim 1, wherein the metal hydroxide is one or more of barium hydroxide, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, lanthanum hydroxide and cerium hydroxide.
3. The method for preparing the synergistic flame retardant of claim 1, wherein the soluble metal phosphate is one or more of sodium phosphate, sodium hypophosphite, magnesium hypophosphite and aluminum hypophosphite.
4. The method of claim 1, wherein the phosphoric acid at step S1 is 85% phosphoric acid.
5. The method for preparing the synergistic flame retardant of claim 1, wherein the metal oxide is one or more of magnesium oxide, calcium oxide, barium oxide, aluminum oxide, lanthanum oxide and cerium oxide.
6. The method for preparing the synergistic flame retardant of claim 1, wherein the metal salt is Cl-containing-，SO4 2-，NO3 -，CO3 2-Or HCO3 -One or more soluble metal salts of ions.
7. A preparation method of the synergistic flame retardant master batch is characterized by comprising the steps of putting the synergistic flame retardant prepared by the method of any one of claims 1 to 6 and resin into a twin-screw extruder, carrying out high-temperature melt extrusion, and granulating by using a granulator to obtain the synergistic flame retardant master batch.
8. The preparation method of the synergistic flame retardant masterbatch according to claim 7, wherein the length-diameter ratio of the screws of the twin-screw extruder is 30-64.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114585671A (en) * | 2019-10-15 | 2022-06-03 | 特莱巴赫工业有限公司 | Heat stabilizer for polyester |
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| CN102838098A (en) * | 2011-06-24 | 2012-12-26 | 中国科学技术大学苏州研究院 | Rare earth metal hypophosphite and preparation method and application of rare earth metal hypophosphite |
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2019
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114585671A (en) * | 2019-10-15 | 2022-06-03 | 特莱巴赫工业有限公司 | Heat stabilizer for polyester |
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