CN110294954B - Preparation method of inorganic flame-retardant filling material for PVC (polyvinyl chloride) coating - Google Patents
Preparation method of inorganic flame-retardant filling material for PVC (polyvinyl chloride) coating Download PDFInfo
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- CN110294954B CN110294954B CN201910585613.9A CN201910585613A CN110294954B CN 110294954 B CN110294954 B CN 110294954B CN 201910585613 A CN201910585613 A CN 201910585613A CN 110294954 B CN110294954 B CN 110294954B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/04—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C09D127/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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Abstract
The invention relates to a preparation method of an inorganic flame-retardant filling material for PVC (polyvinyl chloride) coating, which comprises the steps of adding a micro-nano brucite powder raw material into a three-neck flask, and stirring for 20-80 min; dispersing isopropyl tri (dioctyl pyrophosphato acyloxy) ethylene titanate by using a small amount of solvent, spraying the dispersed isopropyl tri (dioctyl pyrophosphato acyloxy) ethylene titanate into micro-nano brucite powder in a mist manner, heating and stirring the mixture, and collecting the material to obtain the inorganic flame-retardant filling material for the PVC coating, wherein the activation index of the inorganic flame-retardant filling material reaches 99.85 percent, the oil absorption value is not higher than 25.65 percent, and the settling time is 52 hours. According to the invention, isopropyl tri (dioctyl pyrophosphato acyloxy) ethylene titanate is adopted to carry out surface modification on brucite, and the surface of the prepared modified micro-nano brucite material contains various nonpolar chemical groups, so that the dispersibility of the material in PVC paint can be greatly improved, and the flame retardant property of the PVC paint can be improved under the condition of large filling.
Description
Technical Field
The invention relates to the technical field of inorganic flame-retardant filling materials, in particular to a preparation method of an inorganic flame-retardant filling material for PVC (polyvinyl chloride) coating, and specifically relates to a preparation method and application of a functional brucite-based flame-retardant filling material.
Background
The PVC coating has good decoration and chemical corrosion resistance. In recent years, PVC coatings have been widely used in the fields of mobile phones, televisions, computers, automobiles, motorcycle accessories, and the like, such as automobile exterior parts and interior parts. With the rapid development of economy in China, the application range of PVC coatings is more and more common, and meanwhile, some safety problems are brought, so that the requirement on the flame retardant property of the PVC coatings is higher and higher. In order to meet the requirement of flame retardant property of PVC coating, the PVC coating is often subjected to filling modification to achieve the expected purpose.
The filling modification means that inorganic or organic fillers are added in the plastic molding processing process, so that the price of the plastic product can be greatly reduced, the popularization and the application of the plastic product are promoted, and the friction resistance, the thermal property, the aging resistance and the like of the plastic can be obviously improved. At present, calcium carbonate is a commonly used inorganic filling modifier in PVC coating production in China, but the calcium carbonate does not have flame retardant property per se. Brucite, also known as brucite, is composed of natural magnesium hydroxide containing H2O30.88% and the decomposition temperature is 450 ℃. The micro-nano brucite is a novel inorganic functional filler, can be decomposed at high temperature to generate MgO, absorbs a large amount of heat, can cover the surface of a combustion object to isolate air, has a good flame retardant effect, and has a wide application prospect in the aspect of filling and modifying high polymer materials. However, the micro-nano brucite has large surface polarity, high activation energy, poor compatibility with non-polar PVC media, difficult dispersion, and the defects of serious product agglomeration, poor stability, small filling amount and the like in the using process, thereby greatly limiting the application of the micro-nano brucite powder in the field of PVC coating filling modification. Therefore, the surface modification of the micro-nano brucite is carried out through chemical action, the hydrophobicity and lipophilicity of the material are improved, and the preparation of the novel micro-nano brucite material which is compatible with PVC coating and has good stability is one of the research hotspots in the technical field at present.
Disclosure of Invention
The invention provides a preparation method of a modified micro-nano brucite filler aiming at the characteristics of hydrophilic and oleophobic surfaces of micro-nano brucite powder, difficult dispersion in PVC coating, poor stability and small filling amount.
The technical problem is solved by adopting the following technical scheme, and the preparation method of the inorganic flame-retardant filling material for the PVC coating, which is provided by the invention, is obtained by modifying micro-nano brucite powder by a dry method, and specifically comprises the following steps:
(1) adding the micro-nano brucite powder raw material into a three-neck flask, and stirring for 20-80 min;
(2) dispersing isopropyl tri (dioctyl pyrophosphato acyloxy) ethylene titanate by using a small amount of solvent, spraying the dispersed isopropyl tri (dioctyl pyrophosphato acyloxy) ethylene titanate into the micro-nano brucite powder in a mist manner, heating and stirring the mixture, and collecting the material to obtain the inorganic flame-retardant filling material for the PVC coating, wherein the activation index of the flame-retardant filling material reaches 99.85 percent, the oil absorption value is not higher than 25.65 percent, and the settling time is 52 hours.
Preferably, the particle size of the brucite powder raw material in the step (1) is 300-8000 meshes, and the adding amount is 20-100 g.
Preferably, the stirring in the step (1) and the step (2) is mechanical stirring, and the heating and stirring temperature in the step (2) is 20-130 ℃.
Preferably, the addition amount of the isopropyl tri (dioctyl pyrophosphato acyloxy) ethylene titanate in the step (2) is 0.1-5 g, the used solvent is one or a mixture of toluene, xylene, isopropanol, acetonitrile or liquid paraffin, and the dosage of the solvent is 2-40 mL.
The activation index refers to that in a glycerol solvent, the oil absorption value refers to that of castor oil, the sedimentation time refers to that in glycerol, and the infrared spectrum refers to a KBr tabletting method.
Compared with the prior art, the invention has the following advantages:
(1) the selected chelating modifier isopropyl tri (dioctyl pyrophosphato acyloxy) ethylene titanate contains a large amount of nonpolar functional groups, so that the hydrophobicity of the material can be improved, and the filling amount of the modified material in the PVC coating is further improved; secondly, the chelating modifier has higher water resistance, can be directly used for modifying the brucite powder with high water content, does not need to dry the brucite powder, and can reduce the production cost; finally, the selected modifier has the flame retardant property, so that the flame retardant property of the modified material can be further improved.
(2) The modified micro-nano brucite powder disclosed by the invention is prepared by coupling isopropyl tri (dioctyl pyrophosphato acyloxy) ethylene titanate to the surface of the micro-nano brucite powder through a covalent bond, so that the isopropyl tri (dioctyl pyrophosphato acyloxy) ethylene titanate modified micro-nano brucite powder is prepared, the material has good stability, and a modifier is not easy to fall off in the production process; the modification process adopted by the invention is dry modification, the consumption of organic solvent is less, the subsequent waste liquid treatment is not needed, the environment is protected, and the environmental benefit is met.
Drawings
FIG. 1 is a graph of the infrared spectrum of brucite before modification;
FIG. 2 is a graph of the infrared spectrum of modified brucite of example 3;
FIG. 3 is a scanning electron micrograph of brucite before modification;
FIG. 4 is a scanning electron micrograph of brucite modified in example 3.
Detailed Description
In order to further illustrate the technical means and technical effects adopted by the present invention, the following will explain in detail the preparation method of an inorganic flame retardant filler material for PVC coating in accordance with the embodiments.
Example 1
Firstly, adding 20g of 400-mesh micro-nano brucite powder into a three-necked bottle, and stirring for 20min at normal temperature.
Secondly, dispersing 0.1g of isopropyl tri (dioctyl pyrophosphato acyloxy) ethylene titanate by 10mL of isopropanol, spraying the mixture into the micro-nano brucite powder in a mist manner, heating to 50 ℃, continuing stirring for 20min, and then collecting the material; thus obtaining the inorganic flame-retardant filling material for the PVC coating.
And (3) carrying out activation index, oil absorption value and sedimentation time tests and infrared spectrum and scanning electron microscope characterization on the obtained inorganic flame-retardant filling material, wherein an infrared spectrogram shows that the modified brucite surface has a characteristic absorption peak of isopropyl tri (dioctyl pyrophosphato acyloxy) ethylene titanate.
The activation index is used for detecting and characterizing the surface modification effect, and the inorganic filler powder generally has higher relative density and a polar surface and naturally settles in a polar solvent. The organic surface modifier is a non-polar coupling agent, so that the surface of the inorganic powder after surface modification treatment is non-polar. The activation index was determined as follows: weighing a certain amount of the obtained modified micro-nano brucite powder, placing the modified micro-nano brucite powder in a container filled with a certain volume of polar solvent, stirring at a certain rotating speed for 1-2 min, standing, scraping powder fillers on the surface of the solution after the solution is clarified, filtering, drying and weighing the powder which is deposited at the bottom of a beaker. The activation index was calculated according to the formula, i.e.:
the oil absorption value is one of the most main direct characterization methods for modifying inorganic powder, and the size of the oil absorption value directly influences the processing performance and the filling amount of composite material processing. When the filler is used together with the plasticizer, the plasticizer is adsorbed if the oil absorption value of the filler is high, the plasticizing effect of the plasticizer on the resin is reduced, or the amount of the plasticizer needs to be increased. The oil absorption value was determined as follows: the weighed modified micro-nano brucite powder material is placed on clean glass with the area not less than 20cm multiplied by 20cm, an acid burette is used for containing castor oil, the castor oil is slowly dripped into the sample, and the stirring is continuously carried out by a glass rod, so that the sample and the castor oil are fully and uniformly mixed, and the end point is obtained when the sample and the castor oil are bonded into a mass and free dry samples do not exist. Calculating the formula:
the settling time is used for characterizing and evaluating the dispersion stability of the powder in the solution, and the better the dispersibility is, the slower the settling speed is, and the longer the settling time is. The settling time was determined as follows: firstly, preparing a certain amount of the obtained modified micro-nano brucite powder material into glycerol suspension with a certain concentration, then transferring the suspension into a settling tube with a certain scale, and recording the time when the particles in the suspension settle to the specified scale.
Tests prove that the activation index of the obtained modified micro-nano brucite powder filling material in glycerol reaches 99.85%, the oil absorption value is 25.65%, the settling time is 52h, and an infrared spectrogram shows an Mg-O-Ti bond and a dioctyl pyrophosphato acyloxy absorption peak.
Example 2
Firstly, adding 40g of 900-mesh micro-nano brucite powder into a three-necked bottle, and stirring for 40min at normal temperature.
Secondly, dispersing 1.5g of isopropyl tri (dioctyl pyrophosphato acyloxy) ethylene titanate by 20mL of dimethylbenzene, spraying the mixture into the micro-nano brucite powder in a mist manner, heating to 70 ℃, continuing stirring for 40min, and collecting materials to obtain the inorganic flame-retardant filling material for the PVC coating. The activation index of the compound in glycerol reaches 99.55%, the oil absorption value is 24.63%, the settling time is 50h, and an infrared spectrogram shows a characteristic absorption peak of isopropyl tri (dioctyl pyrophosphato acyloxy) ethylene titanate.
Example 3
Firstly, adding 60g of 1200-mesh micro-nano brucite powder into a three-necked bottle, and stirring for 60min at normal temperature.
Dispersing 2.5g of isopropyl tri (dioctyl pyrophosphato acyloxy) ethylene titanate by using 30mL of acetonitrile, spraying the mixture into the micro-nano brucite powder in a mist manner, heating to 90 ℃, continuing stirring for 70min, and collecting the material to obtain the inorganic flame-retardant filling material for the PVC coating. The activation index of the compound in glycerol reaches 98.79 percent, the oil absorption value is 24.27 percent, the settling time is 48 hours, and an infrared spectrogram shows a characteristic absorption peak of isopropyl tri (dioctyl pyrophosphato acyloxy) ethylene titanate.
Example 4
Firstly, adding 80g of 2000-mesh micro-nano brucite powder into a three-necked bottle, and stirring for 80min at normal temperature.
Dispersing 5.0g of isopropyl tri (dioctyl pyrophosphato acyloxy) ethylene titanate by 40mL of toluene, spraying the obtained product into the micro-nano brucite powder in a mist manner, heating to 130 ℃, continuing stirring for 90min, and collecting the material to obtain the inorganic flame-retardant filling material for the PVC coating. The activation index of the compound in glycerol reaches 98.25%, the oil absorption value is 24.33%, the settling time is 49h, and an infrared spectrogram shows a characteristic absorption peak of isopropyl tri (dioctyl pyrophosphato acyloxy) ethylene titanate.
Example 5
Firstly, 100g of 7000-mesh micro-nano brucite powder is added into a three-necked bottle and stirred for 20min at normal temperature.
Dispersing 5.0g of isopropyl tri (dioctyl pyrophosphato acyloxy) ethylene titanate by using 40mL of liquid paraffin, spraying the dispersed liquid paraffin into the micro-nano brucite powder in a mist manner, heating to 130 ℃, continuing stirring for 90min, and collecting materials to obtain the inorganic flame-retardant filling material for the PVC coating. The activation index of the catalyst in glycerol reaches 97.25%, the oil absorption value is 23.33%, the settling time is 47h, and an infrared spectrogram shows a characteristic absorption peak of isopropyl tri (dioctyl pyrophosphato acyloxy) ethylene titanate.
The above description is only an embodiment of the present invention, and is not intended to limit the present invention in any way, and the present invention may also have other embodiments according to the above structures and functions, and is not listed again. Therefore, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention by those skilled in the art can be made within the technical scope of the present invention.
Claims (4)
1. A preparation method of an inorganic flame-retardant filling material for PVC coating is characterized in that micro-nano brucite powder is obtained by dry modification, and the preparation method specifically comprises the following steps:
(1) adding the micro-nano brucite powder raw material into a three-neck flask, and stirring for 20-80 min, wherein the particle size of the brucite powder raw material is 300-2000 meshes, and the addition amount is 20-100 g;
(2) dispersing isopropyl tri (dioctyl pyrophosphato acyloxy) ethylene titanate by using a small amount of solvent, spraying the dispersed isopropyl tri (dioctyl pyrophosphato acyloxy) ethylene titanate into the micro-nano brucite powder in a mist manner, heating and stirring the mixture, and collecting the material to obtain the inorganic flame-retardant filling material for the PVC coating, wherein the activation index of the flame-retardant filling material reaches 99.85 percent, the oil absorption value is not higher than 25.65 percent, and the settling time is 52 hours.
2. The method for preparing the inorganic flame-retardant filling material according to claim 1, wherein the heating and stirring temperature in the step (2) is 20 to 130 ℃.
3. The method for preparing the inorganic flame-retardant filling material according to claim 1, wherein the amount of the isopropyltris (dioctylpyrophosphate) ethylenetitanate added in the step (2) is 0.1 to 5g, the solvent used is one or a mixture of toluene, xylene, isopropanol, acetonitrile or liquid paraffin, and the amount of the solvent used is 2 to 40 mL.
4. The method for preparing an inorganic flame-retardant filler according to claim 1, wherein the activation index is in a glycerol solvent, the oil absorption value is for castor oil, and the settling time is in glycerol.
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| CN101538419B (en) * | 2009-04-09 | 2012-07-04 | 池州灵芝化建材料科技有限公司 | Process for preparing brucite inorganic flame retardant |
| CN102653599A (en) * | 2012-05-08 | 2012-09-05 | 大连盖特科技发展有限公司 | Active magnesium flame retardant with high-molecule coupling agent and preparation method of active magnesium flame retardant |
| CN103044710A (en) * | 2012-12-28 | 2013-04-17 | 大连亚泰科技新材料股份有限公司 | Method for preparing flame retardant from natural brucite and application of flame retardant in cable compound |
| CN106746718B (en) * | 2016-11-16 | 2019-04-09 | 杭州之江新材料有限公司 | A kind of activator and preparation method thereof |
| CN107418419A (en) * | 2017-06-13 | 2017-12-01 | 杭州之江新材料有限公司 | A kind of quick-dry type silane coupling agent, its preparation method and its application |
| CN108192403B (en) * | 2018-01-23 | 2020-04-17 | 永星化工(上海)有限公司 | Solvent type zinc-aluminum coating |
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