CN110294954A - A kind of preparation method of the inorganic fire-retarded packing material for PVC coating - Google Patents
A kind of preparation method of the inorganic fire-retarded packing material for PVC coating Download PDFInfo
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- CN110294954A CN110294954A CN201910585613.9A CN201910585613A CN110294954A CN 110294954 A CN110294954 A CN 110294954A CN 201910585613 A CN201910585613 A CN 201910585613A CN 110294954 A CN110294954 A CN 110294954A
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- retarded
- inorganic fire
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- packing material
- pvc coating
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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
-
- 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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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Fireproofing Substances (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention relates to a kind of preparation methods of inorganic fire-retarded packing material for PVC coating, and micro-nano brucite powder raw material is added to 20~80min of stirring in three-neck flask；It is misty after (dioctylphyrophosphoric acid acyloxy) the ethylene titanate esters of isopropyl three are dispersed with a small amount of solvent again to spray into micro-nano brucite powder, heating stirring, then collection material, obtain the inorganic fire-retarded packing material for PVC coating, the activation index of the inorganic fire-retarded packing material reaches 99.85%, oil factor is not higher than 25.65%, sedimentation time 52h.The present invention carries out surface to shepardite using (dioctylphyrophosphoric acid acyloxy) the ethylene titanate esters of isopropyl three and is modified, the micro-nano shepardite material surface of modification obtained is containing there are many non-polarization groups, dispersibility of the material in PVC coating can be greatly improved, the promotion of PVC coating flame retardant property is realized under big fill conditions.
Description
Technical field
It is especially a kind of to be filled out for the inorganic fire-retarded of PVC coating the present invention relates to inorganic fire-retarded packing material technical field
Fill the preparation method of material, the preparation method and application of specifically a kind of functionality shepardite base flame resistant filler material.
Background technique
PVC coating has good decorative and resistance to corrosive chemicals.In recent years, PVC coating has been widely used
In fields such as mobile phone, television set, computer, automobile, motorcycle accessories, such as automobile external-use component and interior component is used.As China passes through
The high speed development of Ji, the range that PVC coating uses is more and more common, while also bringing some safety problems, therefore, to PVC
Coating flame retardant property requires also higher and higher.In order to meet the needs of PVC coating flame retardant property, often it is filled and is changed
Property, to achieve the desired purpose.
It is filling-modified refer to inorganic or organic filler is added during plastics processing, plastics can not only be substantially reduced
The price of product promotes the popularization and application of plastic products, and can significantly improve the crocking resistance of plastics, thermal property, resistance to
Ageing properties etc..The country is in PVC coating material production at present, and calcium carbonate is common inorganic fill modifying agent, but calcium carbonate sheet
Body does not simultaneously have flame retardant property.Shepardite also known as brucite are made of natural magnesium hydroxide, contain H2O30.88%, point
Solving temperature is 450 DEG C.Micro-nano shepardite is a kind of novel inorganic functional stuffing, can decompose generate MgO at high temperature, is absorbed big
The heat of amount, while the MgO generated can cover comburant surface, completely cut off air, good flame retardant effect is played, in macromolecule
The filling-modified aspect of material has broad application prospects.But micro-nano shepardite surface polarity is larger, activation energy is high, with
Nonpolar PVC media compatibility is poor, is not easy to disperse, and there is serious product reunion, stability difference and loading in use
The deficiencies of small, this greatly limits application of the micro-nano brucite powder in the filling-modified field of PVC coating.Therefore, lead to
It is modified to micro-nano shepardite progress surface to cross chemical action, improves the hydrophobic oleophilic oil of material, preparation can be simultaneous with PVC coating
Hold, and the novel micro nanometer rice shepardite material with good stability is one of the research hotspot of the current technical field.
Summary of the invention
The present invention is directed to micro-nano brucite powder surface hydrophilic oleophobic, be not easy to disperse in PVC coating, stability is poor,
The small feature of loading provides a kind of preparation method for being modified micro-nano shepardite filler, using the higher isopropyl of hydrophobicity
(dioctylphyrophosphoric acid acyloxy) the ethylene titanate esters of base three carry out surface to it and are modified, the micro-nano shepardite material of modification obtained
Surface non-polar hydrophobic alkyl chain chemical group containing there are many, can be greatly improved micro-nano brucite powder in PVC coating
Dispersibility, under big fill conditions realize PVC coating flame retardant property promotion, improve coating property.
The present invention solves its technical problem and adopts the following technical solutions to realize, a kind of use proposed according to the present invention
It is to be obtained to micro-nano brucite powder by dry method modification in the preparation method of the inorganic fire-retarded packing material of PVC coating, tool
Body the following steps are included:
(1) micro-nano brucite powder raw material is taken to be added to 20~80min of stirring in three-neck flask；
(2) misty after dispersing (dioctylphyrophosphoric acid acyloxy) the ethylene titanate esters of isopropyl three with a small amount of solvent to spray into
It states in micro-nano brucite powder, heating stirring, then collection material is used for the inorganic fire-retarded of PVC coating to get to described
Packing material, the activation index of the flame resistant filler material reach 99.85%, and oil factor is not higher than 25.65%, and the sedimentation time is
52h。
Preferably, the partial size of brucite powder raw material is 300~8000 mesh in step (1), and additional amount is 20~100g.
Preferably, the stirring in step (1) and step (2) is mechanical stirring, and the temperature of heating stirring is 20 in step (2)
~130 DEG C.
Preferably, in step (2) isopropyl three (dioctylphyrophosphoric acid acyloxy) ethylene titanate esters additional amount be 0.1~
5g, solvent used are that toluene or dimethylbenzene or isopropanol or the mixing of one or more of acetonitrile or atoleine, solvent are used
Amount is 2~40mL.
The activation index refers to that in glycerine solvent, oil factor refers to that, to castor oil, the sedimentation time refers to third
In triol, infrared spectroscopy refers to KBr pressed disc method.
Compared with prior art, the invention has the following advantages that
(1), chelating type modifying agent isopropyl three (dioctylphyrophosphoric acid acyloxy) ethylene titanate esters selected by the present invention
Containing a large amount of non-polar functional groups, the hydrophobicity of material can be improved, and then improves loading of the modified material in PVC coating；Its
Secondary, the modifying agent of chelating type water resistance with higher can be directly used in the modification of high-moisture brucite powder, without pair
Brucite powder is dried, and can reduce production cost；Finally, selected modifying agent inherently has flame retardant property,
It can be further improved the flame retardant property of modified material.
(2), the micro-nano brucite powder of modification of the invention is by isopropyl three (dioctylphyrophosphoric acid acyloxy) ethylene titanium
Isopropyl three (dioctylphyrophosphoric acid acyloxy) ethylene is made by covalent bonding junction to micro-nano brucite powder surface in acid esters
The ester modified micro-nano brucite powder of metatitanic acid, material has preferable stability, not easily to fall off in production process modifying agent；This hair
Modified technique used by bright is dry method modification, and consumption of organic solvent is few, is not necessarily to subsequent liquid waste processing, environmentally protective, meets ring
Border benefit.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of shepardite before modified；
Fig. 2 is the modified infrared spectrogram of 3 shepardite of embodiment；
Fig. 3 is the scanning electron microscope (SEM) photograph of shepardite before modified；
Fig. 4 is the modified scanning electron microscope (SEM) photograph of 3 shepardite of embodiment.
Specific embodiment
The technological means and technical effect taken for the present invention is further explained, with reference to embodiments, to the present invention one
Preparation method of the kind for the inorganic fire-retarded packing material of PVC coating is described in detail.
Embodiment 1
One, the micro-nano brucite powder of 400 mesh of 20g is added to stirring at normal temperature 20min in three-necked bottle.
Two, (dioctylphyrophosphoric acid acyloxy) the ethylene titanate esters of 0.1g isopropyl three 10mL isopropanol is dispersed, it is misty
It sprays into above-mentioned micro-nano brucite powder, is warming up to 50 DEG C and continues to stir 20min, then collection material；Described in obtaining
Inorganic fire-retarded packing material for PVC coating.
Activation index, oil factor, sedimentation time test and infrared spectroscopy are carried out to the inorganic fire-retarded packing material of gained and swept
Electronic Speculum characterization is retouched, infrared spectrogram shows that there is isopropyl three (dioctylphyrophosphoric acid acyloxy) ethylene titanium on modified shepardite surface
The characteristic absorption peak of acid esters.
Activation index is used to detect and characterize surface modification effect, and the general relative density of inorganic filler powder is larger, and
Surface is in polarization state, the natural subsidence in polar solvent.And organic surface modifying agent is nonpolar coupling agent, and therefore, warp
Inorganic particle after surface modification treatment, surface become nonpolarity.Activation index measures in accordance with the following methods: weighing a certain amount of obtain
The micro-nano brucite powder of the modification arrived, is placed in the container for filling certain volume polar solvent, with certain revolving speed stirring 1~
2min is then allowed to stand, and after waiting solution to clarify, is stood, is scraped off the powder stuffing of solution surface, and the powder that will sink to beaker bottom
Filtering, drying, weighing.Activation index is calculated according to formula, it may be assumed that
Oil factor is one of modified most important direct characterizing method of inorganic particle, and size will have a direct impact on composite material
The processing performance and loading of processing.When filler is used in combination simultaneously with plasticizer, if filler oil factor height will adsorb plasticising
Agent reduces plasticizer to the plasticization effect of resin, or need to increase the dosage of plasticizer.Oil factor measures in accordance with the following methods:
The micro-nano brucite powder material of the modification weighed up is put into area not less than on the glass of 20cm × 20cm cleaning, is dripped with acid
Determine pipe and contain castor oil, castor oil is slowly added dropwise into sample, while constantly being stirred with glass bar, keeps sample and castor oil abundant
It is uniformly mixed, when sample and castor oil bonding are agglomerating, as terminal when without the drying sample to dissociate.Calculation formula:
Sedimentation time is used to characterize and evaluate the dispersion stabilization of powder in the solution, and dispersibility is better, and sinking speed is got over
Slowly, the sedimentation time is also longer.Sedimentation time measures in accordance with the following methods: first taking a certain amount of micro-nano shepardite of obtained modification
Powder body material is configured to certain density glycerine suspension, then this suspension is moved into the sedimentation pipe for having certain scale,
Particle is deposited to the time of assigned scale in record suspension.
After tested, activation index of the modified micro-nano brucite powder packing material of gained in glycerine reaches
99.85%, oil factor 25.65%, sedimentation time 52h, infrared spectrogram shows Mg-O-Ti key and dioctylphyrophosphoric acid
Acyloxy absorption peak.
Embodiment 2
One, the micro-nano brucite powder of 900 mesh of 40g is added to stirring at normal temperature 40min in three-necked bottle.
Two, (dioctylphyrophosphoric acid acyloxy) the ethylene titanate esters of 1.5g isopropyl three 20mL dimethylbenzene is dispersed, it is misty
It sprays into above-mentioned micro-nano brucite powder, is warming up to 70 DEG C and continues to stir 40min, then collection material is described to get arriving
Inorganic fire-retarded packing material for PVC coating.Its activation index in glycerine reaches 99.55%, and oil factor is
24.63%, sedimentation time 50h, infrared spectrogram show isopropyl three (dioctylphyrophosphoric acid acyloxy) ethylene titanate esters
Characteristic absorption peak.
Embodiment 3
One, the micro-nano brucite powder of 1200 mesh of 60g is added to stirring at normal temperature 60min in three-necked bottle.
Two, (dioctylphyrophosphoric acid acyloxy) the ethylene titanate esters of 2.5g isopropyl three 30mL acetonitrile is dispersed, mist spray
Enter in above-mentioned micro-nano brucite powder, be warming up to 90 DEG C continue stir 70min, then collection material to get arrive the use
In the inorganic fire-retarded packing material of PVC coating.Its activation index in glycerine reaches 98.79%, and oil factor is
24.27%, sedimentation time 48h, infrared spectrogram show isopropyl three (dioctylphyrophosphoric acid acyloxy) ethylene titanate esters
Characteristic absorption peak.
Embodiment 4
One, the micro-nano brucite powder of 2000 mesh of 80g is added to stirring at normal temperature 80min in three-necked bottle.
Two, (dioctylphyrophosphoric acid acyloxy) the ethylene titanate esters of 5.0g isopropyl three 40mL toluene is dispersed, mist spray
Enter in above-mentioned micro-nano brucite powder, be warming up to 130 DEG C continue stir 90min, then collection material to get arrive the use
In the inorganic fire-retarded packing material of PVC coating.Its activation index in glycerine reaches 98.25%, and oil factor is
24.33%, sedimentation time 49h, infrared spectrogram show isopropyl three (dioctylphyrophosphoric acid acyloxy) ethylene titanate esters
Characteristic absorption peak.
Embodiment 5
One, the micro-nano brucite powder of 7000 mesh of 100g is added to stirring at normal temperature 20min in three-necked bottle.
Two, (dioctylphyrophosphoric acid acyloxy) the ethylene titanate esters of 5.0g isopropyl three 40mL atoleine is dispersed, mist
Shape sprays into above-mentioned micro-nano brucite powder, is warming up to 130 DEG C and continues to stir 90min, then collection material is to get described in
The inorganic fire-retarded packing material for PVC coating.Its activation index in glycerine reaches 97.25%, and oil factor is
23.33%, sedimentation time 47h, infrared spectrogram show isopropyl three (dioctylphyrophosphoric acid acyloxy) ethylene titanate esters
Characteristic absorption peak.
The above is only the embodiment of the present invention, is not intended to limit the present invention in any form, the present invention may be used also
To have the embodiment of other forms with function according to the above structure, will not enumerate.Therefore, any skill for being familiar with this profession
Art personnel, without departing from the scope of the present invention, to the above embodiments according to the technical essence of the invention
What simple modification, equivalent change and modification, all of which are still within the scope of the technical scheme of the invention.
Claims (5)
1. a kind of preparation method of the inorganic fire-retarded packing material for PVC coating, it is characterised in that micro-nano brucite powder
Body is obtained by dry method modification, specifically includes the following steps:
(1) micro-nano brucite powder raw material is taken to be added to 20~80min of stirring in three-neck flask；
(2) misty penetrating is above-mentioned micro- after dispersing (dioctylphyrophosphoric acid acyloxy) the ethylene titanate esters of isopropyl three with a small amount of solvent
Nanometer brucite powder in, heating stirring, then collection material to get arrive the inorganic fire-retarded filling for PVC coating
Material, the activation index of the flame resistant filler material reach 99.85%, and oil factor is not higher than 25.65%, sedimentation time 52h.
2. the preparation method of inorganic fire-retarded packing material as described in claim 1, it is characterised in that brucite powder in step (1)
The partial size of body raw material is 300~8000 mesh, and additional amount is 20~100g.
3. the preparation method of inorganic fire-retarded packing material as described in claim 1, it is characterised in that heating stirring in step (2)
Temperature be 20~130 DEG C.
4. the preparation method of inorganic fire-retarded packing material as described in claim 1, it is characterised in that isopropyl three in step (2)
The additional amount of (dioctylphyrophosphoric acid acyloxy) ethylene titanate esters is 0.1~5g, and solvent used is toluene or dimethylbenzene or different
Propyl alcohol or the mixing of one or more of acetonitrile or atoleine, solvent usage are 2~40mL.
5. the preparation method of inorganic fire-retarded packing material as described in claim 1, it is characterised in that the activation index is
Refer in glycerine solvent, oil factor refers to that, to castor oil, the sedimentation time refers in glycerine.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910585613.9A CN110294954B (en) | 2019-07-01 | 2019-07-01 | Preparation method of inorganic flame-retardant filling material for PVC (polyvinyl chloride) coating |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910585613.9A CN110294954B (en) | 2019-07-01 | 2019-07-01 | Preparation method of inorganic flame-retardant filling material for PVC (polyvinyl chloride) coating |
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| CN110294954A true CN110294954A (en) | 2019-10-01 |
| CN110294954B CN110294954B (en) | 2021-04-27 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538419A (en) * | 2009-04-09 | 2009-09-23 | 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 |
| CN106746718A (en) * | 2016-11-16 | 2017-05-31 | 杭州之江有机硅化工有限公司 | 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 |
| CN108192403A (en) * | 2018-01-23 | 2018-06-22 | 永星化工(上海)有限公司 | A kind of solvent type zinc-aluminum paint |
-
2019
- 2019-07-01 CN CN201910585613.9A patent/CN110294954B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538419A (en) * | 2009-04-09 | 2009-09-23 | 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 |
| CN106746718A (en) * | 2016-11-16 | 2017-05-31 | 杭州之江有机硅化工有限公司 | 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 |
| CN108192403A (en) * | 2018-01-23 | 2018-06-22 | 永星化工(上海)有限公司 | A kind of solvent type zinc-aluminum paint |
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