CN114316372A - Smoke suppressant and preparation method thereof - Google Patents
Smoke suppressant and preparation method thereof Download PDFInfo
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- CN114316372A CN114316372A CN202111661378.2A CN202111661378A CN114316372A CN 114316372 A CN114316372 A CN 114316372A CN 202111661378 A CN202111661378 A CN 202111661378A CN 114316372 A CN114316372 A CN 114316372A
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Abstract
The invention discloses a smoke suppressant and a preparation method thereof, and relates to the technical field of multielement flame retardance, wherein the smoke suppressant comprises iron molybdate and zinc borate, and the iron molybdate is coated on the zinc borate; compared with the direct use of iron molybdate as a smoke suppressant, the iron molybdate coated zinc borate prepared by the invention has the advantages that the content of rare metal element molybdenum in the iron molybdate coated zinc borate with the same quality is less, the cost can be reduced, and simultaneously compared with the direct blending of iron molybdate and zinc borate in PVC, the smoke suppression effect of the iron molybdate coated zinc borate in PVC is better, and compared with the independent synthesis of iron molybdate, the particle size is obviously smaller, and the mechanical property is better.
Description
The technical field is as follows:
the invention relates to the technical field of multielement flame retardance, and particularly relates to a smoke suppressant and a preparation method thereof.
Background art:
with the development of social science and technology and the improvement of living standard, organic polymer materials are rapidly developed, and the yield of the organic polymer materials is improved year by year. Polymer materials have been widely used in the fields of building materials, decorative materials, electric wires and cables, electronic and electric appliances, information, transportation, and the like. Until now, PVC is still a general-purpose high polymer material with wide application, and has the advantages of low price, excellent processing performance, excellent service performance, excellent decorative performance and the like. Common PVC materials such as plastic floor blocks, plastic doors and windows and ABS/PVC composite materials. PVC itself has good flame resistance and a Limiting Oxygen Index (LOI) as high as 45%, and although rigid PVC has a reduced limiting oxygen index by adding certain amounts of flammable processing aids, lubricants and modifiers, it still has a higher limiting oxygen index.
Because a large amount of plasticizer such as diisooctyl phthalate (DOP) is added into the soft PVC, the plasticizer is very easy to burn, so that the limited oxygen index of the material is greatly reduced, even the limited oxygen index is reduced to below 21 percent, and the material becomes a combustible material. When the PVC is combusted in a fire, not only a certain amount of heat is generated, but also a large amount of black smoke and corrosive gas are generated more seriously. Therefore, the smoke suppression and flame retardance of PVC, particularly the smoke suppression, have been developed into one of the key problems in the scientific research and research of flame retardance, and have very important economic significance, social benefit and theoretical research value for solving the problem.
The invention content is as follows:
the invention aims to solve the technical problem of providing a smoke suppressant and a preparation method thereof, and the smoke suppressant is applied to PVC, so that the use amount of rare metal elements can be effectively reduced, and the smoke suppression efficiency is higher.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
one object of the present invention is to provide a smoke suppressant comprising iron molybdate and zinc borate, wherein the iron molybdate is coated on the zinc borate.
The particle size of the smoke suppressant is 0.1-3 mu m.
The iron molybdate accounts for 5-30% of the smoke suppressant by mass.
The iron molybdate is nano-scale.
The second purpose of the invention is to provide a preparation method of the smoke suppressant, which comprises the following steps:
1) adding soluble ferric salt and zinc borate into water to form a solution A;
2) dissolving soluble molybdenum salt and a surfactant in water to form a solution B;
3) dropwise adding the solution B into the solution A while stirring to obtain a solution C:
4) adding a pH regulator into the solution C, and performing ultrasonic dispersion to obtain a mixed solution;
5) reacting the mixed solution at 90-150 ℃ for 3-8 h;
6) cooling the reactant to normal temperature, filtering, washing and drying;
7) grinding and sieving the dried powder to obtain Fe2(MoO4)3A smoke suppressant coated with zinc borate.
The soluble ferric salt is at least one of ferric nitrate, ferric chloride and ferric sulfate.
The soluble molybdenum salt is at least one of ammonium octamolybdate and sodium molybdate.
The surfactant is at least one of polyvinylpyrrolidone (PVP) and glucose.
The mass ratio of the soluble ferric salt to the soluble molybdenum salt to the zinc borate is (0.5-3) to (0.5-4) to (5-15).
The dripping time is 15-45 min.
The pH regulator is at least one of nitric acid, sulfuric acid and hydrochloric acid, and the pH is regulated to 9-10.
The invention has the beneficial effects that:
(1) compared with the direct use of iron molybdate as a smoke suppressant, the smoke suppressant of the invention with the same quality contains less rare metal element molybdenum, and can reduce the cost.
(2) Compared with the direct blending of iron molybdate and zinc borate in PVC, the smoke suppressant (zinc borate coated by iron molybdate) has better smoke suppression effect in PVC.
Description of the drawings:
FIG. 1 is a graph showing a particle size distribution test of a product obtained in example 1;
FIG. 2 is a graph showing a particle size distribution test of a product obtained in comparative example 1;
FIG. 3 is a smoke density test chart of the product obtained in example 1;
FIG. 4 is an SEM photograph of the product obtained in example 1.
The specific implementation mode is as follows:
in order to make the technical means, the original characteristics, the achieved purposes and the effects of the invention easy to understand, the invention is further explained by combining the specific embodiments and the drawings.
The zinc borate is provided by Anhui Shitong materials science and technology Co., Ltd, D502-3 mu m, and the ignition weight loss is 13.5%.
PVP is available from Aladdin reagent, Inc. and has a molecular weight of 3500.
Example 1
First, 0.601g of ferric nitrate and 6.80g of zinc borate were weighed into 150ml of water, and stirred by a magnetic stirring apparatus until the solid raw materials were completely dissolved to form a solution a.
Next, 0.88g of ammonium octamolybdate and 0.1g of a surfactant PVP were weighed out and dissolved in 150ml of water, and stirred by a magnetic stirring apparatus until the solid raw material was completely dissolved to form a solution B.
Dropwise adding the solution B into the solution A under the condition that the solution A is continuously stirred, wherein the dropwise adding speed is 200ml/30min, and obtaining a solution C.
And (3) taking dilute nitric acid as a pH regulator, adding the pH regulator into the solution C to regulate the pH to 9.2, and performing ultrasonic dispersion for 30min to obtain a mixed solution.
And putting the mixed solution into a three-neck flask, reacting for 5 hours at 110 ℃ in an oil bath, and arranging a condensation reflux device and a stirring device in an auxiliary manner.
Cooling the reactant to normal temperature, filtering, washing with deionized water for 2 times, and drying in a vacuum oven at 60 ℃.
Grinding the dried powder, and sieving with a 150-mesh sieve to obtain Fe2(MoO4)3A smoke suppressant coated with zinc borate.
Weighing the prepared Fe2(MoO4)3Coated zinc borate, added in comparative example 4In the flame-retardant PVC formula D, the mass percentage is 5%, an internal mixer is used for processing and blending, sample pieces are prepared, and performance test is carried out.
Example 2
First, 1.02g of ferric nitrate and 6.80g of zinc borate were weighed into 150ml of water, and stirred by a magnetic stirring apparatus until the solid raw materials were completely dissolved to form a solution a.
Next, 1.76g of ammonium octamolybdate and 0.1g of a surfactant PVP were weighed and dissolved in 150ml of water, and stirred by a magnetic stirring apparatus until the solid raw material was completely dissolved to form a solution B.
Dropwise adding the solution B into the solution A under the condition that the solution A is continuously stirred, wherein the dropwise adding speed is 200ml/30min, and obtaining a solution C.
And (3) adopting dilute nitric acid as a pH regulator, adding the pH regulator into the solution C to regulate the pH to 10, and performing ultrasonic dispersion for 30min to obtain a mixed solution.
And putting the mixed solution into a three-neck flask, reacting for 5 hours at 110 ℃ in an oil bath, and arranging a condensation reflux device and a stirring device in an auxiliary manner.
Cooling the reactant to normal temperature, filtering, washing with deionized water for 2 times, placing in a vacuum oven for drying at 60 ℃, grinding the dried powder, and sieving with a 150-mesh sieve to obtain Fe2(MoO4)3A smoke suppressant coated with zinc borate.
Weighing the prepared Fe2(MoO4)3And (3) coating zinc borate, adding the zinc borate into the flame-retardant PVC formula D in the comparative example 4, wherein the mass percentage is 5%, processing and blending by using an internal mixer to prepare a sample sheet, and performing performance test.
Example 3
First, 1.53g of ferric nitrate and 6.80g of zinc borate were weighed into 150ml of water, and stirred by a magnetic stirring apparatus until the solid raw material was completely dissolved to form a solution a.
Next, 2.64g of ammonium octamolybdate and 0.1g of a surfactant PVP were weighed and dissolved in 150ml of water, and stirred by a magnetic stirring apparatus until the solid raw material was completely dissolved to form a solution B.
Dropwise adding the solution B into the solution A under the condition that the solution A is continuously stirred, wherein the dropwise adding speed is 300ml/30min, and obtaining a solution C.
And (3) adopting dilute nitric acid as a pH regulator, adding the pH regulator into the solution C to regulate the pH to 9.6, and performing ultrasonic dispersion for 30min to obtain a mixed solution.
And (3) putting the mixed solution into a three-neck flask, carrying out reaction for 3h at 150 ℃ in an oil bath, and arranging a condensation reflux device and a stirring device in an auxiliary manner.
Cooling the reactant to normal temperature, filtering, washing with deionized water for 2 times, and drying in a vacuum oven at 60 ℃.
Grinding the dried powder, and sieving with a 150-mesh sieve to obtain Fe2(MoO4)3A smoke suppressant coated with zinc borate.
Weighing the prepared Fe2(MoO4)3And (3) coating zinc borate, adding the zinc borate into the flame-retardant PVC formula D in the comparative example 4, wherein the mass percentage is 5%, processing and blending by using an internal mixer to prepare a sample sheet, and performing performance test.
Example 4
First, 0.401g of ferric chloride hexahydrate and 6.80g of zinc borate were weighed into 150ml of water, and stirred by a magnetic stirring apparatus until the solid raw materials were completely dissolved to form a solution a.
Then, 0.919g of sodium molybdate and 0.1g of surfactant PVP are weighed and dissolved in 150ml of water, and stirred by a magnetic stirring device until the solid raw materials are completely dissolved to form solution B.
Dropwise adding the solution B into the solution A under the condition that the solution A is continuously stirred, wherein the dropwise adding speed is 100ml/30min, and obtaining a solution C.
And (3) adopting dilute hydrochloric acid as a pH regulator, adding the pH regulator into the solution C to regulate the pH to 9.2, and performing ultrasonic dispersion for 30min to obtain a mixed solution.
And (3) putting the mixed solution into a three-neck flask, carrying out reaction for 8h at 90 ℃ in an oil bath, and arranging a condensation reflux device and a stirring device in an auxiliary manner.
Cooling the reactant to normal temperature, filtering, washing with deionized water for 2 times, and drying in a vacuum oven at 60 ℃.
Grinding the dried powder, and sieving with a 150-mesh sieve to obtain Fe2(MoO4)3A smoke suppressant coated with zinc borate.
Weighing the prepared Fe2(MoO4)3And (3) coating zinc borate, adding the zinc borate into the flame-retardant PVC formula D in the comparative example 4, wherein the mass percentage is 5%, processing and blending the zinc borate by using an internal mixer to prepare a sample sheet, and performing performance test.
Comparative example 1
First, 0.601g of ferric nitrate was weighed into 150ml of water and stirred with a magnetic stirring apparatus until the solid raw material was completely dissolved to form a solution A.
Next, 0.88g of ammonium octamolybdate and 1g of a surfactant PVP were weighed and dissolved in 150ml of water, and stirred by a magnetic stirring apparatus until the solid raw material was completely dissolved to form a solution B.
Dropwise adding the solution B into the solution A under the condition that the solution A is continuously stirred, wherein the dropwise adding speed is 100ml/30min, and obtaining a solution C.
And (3) adopting dilute nitric acid as a pH regulator, adding the pH regulator into the solution C to regulate the pH to 9.5, and performing ultrasonic dispersion for 30min to obtain a mixed solution.
And putting the mixed solution into a three-neck flask, reacting for 5 hours at 110 ℃ in an oil bath, and arranging a condensation reflux device and a stirring device in an auxiliary manner.
Cooling the reactant to normal temperature, filtering, washing with deionized water for 2 times, placing in a vacuum oven for drying at 60 ℃, grinding the dried powder, and sieving with a 150-mesh sieve to obtain Fe2(MoO4)3A smoke suppressant.
Weighing the prepared Fe2(MoO4)3And the flame-retardant PVC is added into the flame-retardant PVC formula D in the comparative example 4, the mass percentage is 5%, and an internal mixer is used for processing and blending to prepare a sample piece and carry out performance test.
Comparative example 2
Weighing iron molybdate and zinc borate in a mass ratio of 1:10, adding the iron molybdate and the zinc borate into the flame-retardant PVC formula D in the comparative example 4, wherein the mass ratio is 5%, processing and blending by using an internal mixer, preparing a sample wafer, and carrying out performance test.
Comparative example 3
Weighing molybdenum oxide, iron oxide and zinc borate in a mass ratio of 1:1:10, adding the molybdenum oxide, iron oxide and zinc borate into the flame-retardant PVC formula D in the comparative example 4, wherein the mass ratio is 5%, processing and blending the mixture by using an internal mixer to prepare a sample sheet, and performing performance test.
Comparative example 4
According to the flame-retardant PVC formula D, an internal mixer is used for processing and blending to prepare a sample wafer, and performance test is carried out.
The preparation steps of the flame-retardant PVC formula D and the sample wafer are as follows: weighing 100 parts of PVC resin, 26 parts of dioctyl terephthalate (DOTP), 5 parts of TXIB (2, 2, 4-trimethyl-1, 3-pentanediol diisobutyrate), 12 parts of aluminum hydroxide ATH (aluminum hydroxide) and 3 parts of calcium-zinc stabilizer, all putting into an internal mixer for blending, and when the mixing temperature is raised to 150 ℃, mixing for 15min and then discharging; and (3) after discharging, vulcanizing by using a flat vulcanizing machine, wherein the vulcanizing temperature is 150 ℃, the vulcanizing time is 10min, and the pressure is 10-15 Mpa, so as to obtain the molding material. The tensile property of the molding material is measured according to the national standard GB/T1040.3, the smoke density is measured by a GB/T8323.2 single chamber method, and the oxygen index is measured by GB/T24093.
The smoke suppression efficiency is (1-smoke density after improvement/smoke density before improvement) multiplied by 100%
The test results are shown in Table 1.
TABLE 1
The mass ratios of iron molybdate to zinc borate in examples 1-3 were 0.12:1, 0.24:1, and 0.36:1, respectively, wherein the increase in iron molybdate-coated zinc borate content compared to comparative example 4 yielded test data: the mechanical property is basically not changed, the oxygen index is slightly improved to 28.0-28.4, the smoke density is obviously reduced, and the smoke suppression efficiency is 42-48%.
Example 4 is a zinc borate surface coated by adopting other iron salt and molybdate synthesis, and the test performances of the zinc borate surface coated by the iron salt and the molybdate are basically the same as those of example 1.
Comparative example 1 for the synthesis of iron molybdate alone, test data were obtained in comparison with example 1: comparative example 1 synthetic Material D, determined by particle size analysis50About 7.6 μm, the particle size distribution of the synthetic material of example 1 is bimodal, D50It was 2.9 μm. The iron molybdate of the comparative example 1 is used in PVC, the mechanical property is obviously reduced, and the smoke suppression efficiency is reduced compared with that of the example 1The lower is 14%.
The comparison between the example 1 and the comparative examples 2 to 3 shows that the coating effect prepared by adopting the synthesis process is superior to the coating effect prepared by adopting uncoated iron molybdate and zinc borate which are blended in PVC in 31 percent and uncoated molybdenum oxide, iron oxide and zinc borate which are blended in PVC in 35 percent, the mechanical properties of the coating effect are basically the same in tensile strength and elongation at break, and the coating effect is slightly excellent in the oxygen index test.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A smoke suppressant is characterized in that: the zinc borate iron molybdate powder comprises iron molybdate and zinc borate, wherein the zinc borate is coated with the iron molybdate.
2. The smoke suppressant of claim 1, wherein: the particle size of the smoke suppressant is 0.1-3 mu m.
3. The smoke suppressant of claim 1, wherein: the weight percentage of the iron molybdate is 5-30%.
4. The smoke suppressant of claim 1, wherein: the iron molybdate is nano-scale.
5. A process for preparing a smoke suppressant according to any of claims 1-4, comprising the steps of:
1) adding soluble ferric salt and zinc borate into water to form a solution A;
2) dissolving soluble molybdenum salt and a surfactant in water to form a solution B;
3) dropwise adding the solution B into the solution A while stirring to obtain a solution C:
4) adding a pH regulator into the solution C, and performing ultrasonic dispersion to obtain a mixed solution;
5) reacting the mixed solution at 90-150 ℃ for 3-8 h;
6) cooling the reactant to normal temperature, filtering, washing and drying;
7) grinding and sieving the dried powder to obtain Fe2(MoO4)3A smoke suppressant coated with zinc borate.
6. The method of producing a smoke suppressant according to claim 5, characterized in that: the soluble ferric salt is at least one of ferric nitrate, ferric chloride and ferric sulfate; the soluble molybdenum salt is at least one of ammonium octamolybdate and sodium molybdate.
7. The method of producing a smoke suppressant according to claim 5, characterized in that: the surfactant is at least one of polyvinylpyrrolidone (PVP) and glucose.
8. The method of producing a smoke suppressant according to claim 5, characterized in that: the mass ratio of the soluble ferric salt to the soluble molybdenum salt to the zinc borate is (0.5-3) to (0.5-4) to (5-15).
9. The method of producing a smoke suppressant according to claim 5, characterized in that: the dripping time of the solution B is 15-45 min.
10. The method of producing a smoke suppressant according to claim 5, characterized in that: the pH regulator is at least one of nitric acid, sulfuric acid and hydrochloric acid, and the pH is regulated to 9-10.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60179442A (en) * | 1984-02-24 | 1985-09-13 | Plus Teku Kk | Flame-retardant resin composition |
| JP2004027062A (en) * | 2002-06-26 | 2004-01-29 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semicondcutor device |
| US20110031454A1 (en) * | 2006-11-03 | 2011-02-10 | The Sherwin-Williams Company | Smoke suppressants |
| JP2013142136A (en) * | 2012-01-12 | 2013-07-22 | Shin-Etsu Chemical Co Ltd | Flame-retardant liquid epoxy resin composition for encapsulating semiconductor and semiconductor device |
| CN112457527A (en) * | 2020-11-10 | 2021-03-09 | 佛山金戈新材料股份有限公司 | Bimetal compound complex flame-retardant smoke suppressant |
| CN112745525A (en) * | 2019-10-29 | 2021-05-04 | 合肥杰事杰新材料股份有限公司 | Flame-retardant filler and preparation method thereof |
-
2021
- 2021-12-30 CN CN202111661378.2A patent/CN114316372A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60179442A (en) * | 1984-02-24 | 1985-09-13 | Plus Teku Kk | Flame-retardant resin composition |
| JP2004027062A (en) * | 2002-06-26 | 2004-01-29 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semicondcutor device |
| US20110031454A1 (en) * | 2006-11-03 | 2011-02-10 | The Sherwin-Williams Company | Smoke suppressants |
| JP2013142136A (en) * | 2012-01-12 | 2013-07-22 | Shin-Etsu Chemical Co Ltd | Flame-retardant liquid epoxy resin composition for encapsulating semiconductor and semiconductor device |
| CN112745525A (en) * | 2019-10-29 | 2021-05-04 | 合肥杰事杰新材料股份有限公司 | Flame-retardant filler and preparation method thereof |
| CN112457527A (en) * | 2020-11-10 | 2021-03-09 | 佛山金戈新材料股份有限公司 | Bimetal compound complex flame-retardant smoke suppressant |
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