CN104841358A - Preparation method for hydrotalcite acid absorption agent used for polyolefin - Google Patents
Preparation method for hydrotalcite acid absorption agent used for polyolefin Download PDFInfo
- Publication number
- CN104841358A CN104841358A CN201510226827.9A CN201510226827A CN104841358A CN 104841358 A CN104841358 A CN 104841358A CN 201510226827 A CN201510226827 A CN 201510226827A CN 104841358 A CN104841358 A CN 104841358A
- Authority
- CN
- China
- Prior art keywords
- hydrotalcite
- polyolefin
- acid
- preparation
- organic solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method for more excellent performance of hydrotalcite acid absorption agent used for polyolefin, which belongs to the field of polyolefin additives preparative techniques. The preparation method comprises the following steps of adding soluble divalent metal salt, soluble trivalent metal salt and urea into organic solvent or mixed solvent of water and organic solvent and moving into a high pressure reactor for crystallizing at a certain temperature, centrifugal washing and drying after reacting, and obtaining the hydrotalcite acid absorption agent used for polyolefin. According to the method provided by the invention, the organic solvent is added when hydrotalcite is synthesized, and hydrotalcite crystal growth is affected by the factors that solubilities of metal ions are different in the organic solvent, solvent viscosity is increased and the like, and eventually, the hydrotalcite crystal structure growth is not complete, the surface of hydrotalcite crystal has more acid adsorption sites, and chemical adsorption capacity of the hydrotalcite on chloridion is greatly improved; thus the hydrotalcite has better acid absorption effect when the polyolefin is synthesized, and the stability is improved; meanwhile, the hydrotalcite is not easy to precipitate in resin, and the corrosion of production equipment caused by residual metal stearic acid salt type acid absorption agent is eliminated.
Description
Technical field
The invention belongs to polyolefin auxiliary agent preparing technical field, be specifically related to the preparation method of the more excellent polyolefin hydrotalcite acid-acceptor of a kind of performance.
Background technology
The Ziegler-Natta catalyst that polyolefin synthesis uses and radical initiator can reduce side reaction and obtain the less product of side chain better, but are deposited on CaCl mainly with the chloride of titanium due to Ziegler-Natta catalyst
2crystallization or SiO
2on carrier, this can cause residual a small amount of chlorine-containing compound in product, in addition other additives (mainly brominated flame-retardant) also can remain other acid impurities in process of production, also variable color and damage can be there is in the product that these residues can make polymer make in long-term use procedure, chlorion or common corrosive ion simultaneously, easily cause stainless corrosion, production equipment and pipeline are worked the mischief.The removal of conventional metal stearate salt acid-acceptor can cause a small amount of calcium stearate to remain on the inwall of process equipment, and calcium stearate can generate stearic acid steam under the condition of being heated, and causes the corrosion of equipment inner wall.
Summary of the invention
For solving above-mentioned the problems of the prior art, polyolefin hydrotalcite acid-acceptor that the invention provides a kind of excellent performance and preparation method thereof.The acid-acceptor that the present invention obtains can provide better inhales acid energy, makes polyolefin stability more lasting, and reduces corrosion and the destruction of production equipment and pipeline caused by residues of chloride.
Technical scheme of the present invention is: solvable divalent metal salt, solvable trivalent metal salt, urea are added organic solvent, or in the mixed solvent of water and organic solvent, to move in autoclave crystallization at a certain temperature, reacted rear centrifuge washing, be drying to obtain polyolefin hydrotalcite acid-acceptor.
The preparation method of hydrotalcite acid-acceptor of the present invention is: add in the mixed solvent of organic solvent or water and organic solvent by solvable divalent metal salt, solvable trivalent metal salt, urea, wherein the ratio of the amount of substance of bivalent metal ion and trivalent metal ion is 1:1-5:1, the concentration of bivalent metal ion is 0.0001-2mol/L, and the addition of urea is 2-5 times of the molal quantity sum of bivalent metal ion and trivalent metal ion; Reaction temperature is 90 DEG C-200 DEG C; Reaction time is 1-108h; React rear centrifuge washing, be drying to obtain hydrotalcite acid-acceptor.
Described solvable divalent metal salt and solvable trivalent metal salt are villaumite, nitrate or sulfate.
Described bivalent metal ion is selected from Mg
2+, Zn
2+, Ca
2+, Cu
2+, Ni
2+, Co
2+, Fe
2+, Mn
2+, Cd
2+, Be
2+in one or both, preferred Mg
2+, Zn
2+, Ca
2+, Ni
2+in one or both; Trivalent metal ion is selected from Al
3+, Ni
3+, Co
3+, Fe
3+, Mn
3+, Cr
3+, V
3+, Ti
3+, In
3+, Ga
3+in one or both, preferred Al
3+, Ni
3+, Fe
3+in one or both.
Described organic solvent is selected from one or more in methyl alcohol, ethanol, ethylene glycol, glycerine, acetone, ether.
The above-mentioned hydrotalcite acid-acceptor prepared is applied in polyolefin synthesis.
Described polyolefin is polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, vinyl-acrylate copolymer, propylene acrylic acid copolymer, poly 1-butene, poly(4-methyl-1-pentene), cyclic olefin polymer.
The present invention adds organic solvent when hydrotalcite synthesizes, the metal ion in organic solvent factor such as different solubility, the increase of solvent viscosity affects hydrotalcite crystal growth, final hydrotalcite crystalline structure growth is imperfect, surface has more polyacid adsorption potential, greatly improves hydrotalcite to the chemical adsorption capacity of chlorion.Thus make having when polyolefin synthesizes of hydrotalcite better inhale sour effect, improve its stability.The organic solvent that the present invention adopts mostly is nontoxic or low toxicity, to environment without crossing major injury.
The present invention cleans polyolefin acid-acceptor using hydrotalcite as one, the layer structure of hydrotalcite and loose structure can acidic materials that effectively absorbing catalyst is residual, particularly residual chlorion, improve polyolefin stability, compared with obtaining hydrotalcite with common synthetic methods, the method has the acid energy of stronger suction and long-time stability.Simultaneously hydrotalcite is not easily separated out in resin, eliminates metal stearate salt form acid-acceptor and remains corrosion for production equipment, and this acid-acceptor low toxic and environment-friendly, meet the requirement that current green is produced.Preparation method of the present invention is simple, and raw material sources are extensive, technological process and simple, and inhales acidity and can significantly improve.
Detailed description of the invention
Embodiment 1
Organic solvent/water mixed solvent synthesis Mg-Al hydrotalcite is as polyolefin acid-acceptor:
By Mg (NO
3)
2, Al (NO
3)
3with urea according to Mg
2+/ Al
3+mol ratio is 2:1, Urea/ (Mg
2++ Al
3+the molar ratio of)=2 is made into ethanol/water mixed solution, and wherein the ratio of the amount of substance of ethanol/water is 1:3; , Mg
2+concentration is 0.6mol/L.Moved into by mixed solution in closed reactor, next at 90 DEG C, crystallization 24h obtains CO
3-LDHs slurries, naturally cool to room temperature, by slurries through washing centrifugal be neutrality to supernatant liquor after obtain LDHs filter cake, and by filter cake dry 10h in the baking oven of 60 DEG C, obtain for polyolefinic magnalium hydrotalcite acid-acceptor after grinding, its structural formula is [Mg
0.66al
0.33(OH)
2] (CO
3)
0.16h
2o.
The magnalium hydrotalcite acid-acceptor of preparation is joined in polypropylene powder, the addition of magnalium hydrotalcite acid-acceptor is 500ppm, extrude at double screw extruder, screw temperature set is TS1:180 DEG C, TS2-TS10:200 DEG C, extrude through three times, the polypropylene yellow colour index extruding test for three times is respectively 1.7,3.8 and 6.3.
Comparative example 1
Water is that solvent synthesizes Mg-Al hydrotalcite as polyolefin acid-acceptor:
By Mg (NO
3)
2, Al (NO
3)
3with urea according to Mg
2+/ Al
3+mol ratio is 2:1, Urea/ (Mg
2++ Al
3+the molar ratio obtained aqueous solution of)=2, wherein, Mg
2+concentration is 0.6mol/L.Moved into by solution in closed reactor, next at 90 DEG C, crystallization 24h obtains CO
3-LDHs slurries, naturally cool to room temperature, by slurries through washing centrifugal be neutrality to supernatant liquor after obtain LDHs filter cake, and by filter cake dry 10h in the baking oven of 60 DEG C, obtain for polyolefinic magnalium hydrotalcite acid-acceptor after grinding, its structural formula is [Mg
0.66al
0.33(OH)
2] (CO
3)
0.16h
2o.
The magnalium hydrotalcite acid-acceptor of preparation is joined in polypropylene powder, the addition of magnalium hydrotalcite acid-acceptor is 500ppm, extrude at double screw extruder, screw temperature set is TS1:180 DEG C, TS2-TS10:200 DEG C, extrude through three times, the polypropylene yellow colour index extruding test for three times is respectively 2.3,4.8 and 8.1.
Embodiment 2
Organic solvent/water mixed solvent synthesis Zn-Al hydrotalcite is as polyolefin acid-acceptor:
By Zn (NO
3)
2, Al (NO
3)
3with urea according to Zn
2+/ Al
3+mol ratio is 2:1, Urea/ (Zn
2++ Al
3+the molar ratio preparation ether/aqueous solution of)=5, wherein the ratio of the amount of substance of ether/water is 1:3, Zn
2+concentration is 0.6mol/L.Moved into by solution in closed reactor, next at 90 DEG C, crystallization 24h obtains CO
3-LDHs slurries, naturally cool to room temperature, by slurries through washing centrifugal be neutrality to supernatant liquor after obtain LDHs filter cake, and by filter cake dry 10h in the baking oven of 60 DEG C, obtain for polyolefinic zinc-aluminum hydrotalcite acid-acceptor after grinding, its structural formula is [Zn
0.66al
0.33(OH)
2] (CO
3)
0.16h
2o.
The zinc-aluminum hydrotalcite acid-acceptor of preparation is joined in polypropylene powder, the addition of zinc-aluminum hydrotalcite acid-acceptor is 500ppm, extrude at double screw extruder, screw temperature set is TS1:180 DEG C, TS2-TS10:200 DEG C, extrude through three times, the polypropylene yellow colour index extruding test for three times is respectively 1.2,3.0 and 5.8.
Comparative example 2
Water is that solvent synthesizes Zn-Al hydrotalcite as polyolefin acid-acceptor:
By Zn (NO
3)
2, Al (NO
3)
3with urea according to Zn
2+/ Al
3+mol ratio is 2:1, Urea/ (Zn
2++ Al
3+the molar ratio obtained aqueous solution of)=5, wherein, Zn
2+concentration is 0.6mol/L.Moved into by solution in closed reactor, next at 90 DEG C, crystallization 24h obtains CO
3-LDHs slurries, naturally cool to room temperature, by slurries through washing centrifugal be neutrality to supernatant liquor after obtain LDHs filter cake, and by filter cake dry 10h in the baking oven of 60 DEG C, obtain for polyolefinic zinc-aluminum hydrotalcite acid-acceptor after grinding, its structural formula is [Zn
0.66al
0.33(OH)
2] (CO
3)
0.16h
2o.
The zinc-aluminum hydrotalcite acid-acceptor of preparation is joined in polypropylene powder, the addition of zinc-aluminum hydrotalcite acid-acceptor is 500ppm, extrude at double screw extruder, screw temperature set is TS1:180 DEG C, TS2-TS10:200 DEG C, extrude through three times, the polypropylene yellow colour index extruding test for three times is respectively 2.5,4.6 and 7.7.
Drawn by above-mentioned contrast test, organic solvent/water mixed solvent synthetic hydrotalcite, can acidic materials that effectively absorbing catalyst is residual as acid-acceptor, improve polyolefinic stability.Embodiment 1 and embodiment 2 using mixed solvent synthetic hydrotalcite as the effect of acid-acceptor all than only using water as the effect of solvent synthetic hydrotalcite as acid-acceptor is improved significantly.
Claims (6)
1. the preparation method of a hydrotalcite acid-acceptor, it is characterized in that, its concrete operation step is: add in the mixed solvent of organic solvent or water and organic solvent by solvable divalent metal salt, solvable trivalent metal salt, urea, wherein the ratio of the amount of substance of bivalent metal ion and trivalent metal ion is 1:1-5:1, the concentration of bivalent metal ion is 0.0001-2mol/L, and the addition of urea is 2-5 times of the molal quantity sum of bivalent metal ion and trivalent metal ion; Reaction temperature is 90 DEG C-200 DEG C; Reaction time is 1-108h; React rear centrifuge washing, be drying to obtain hydrotalcite acid-acceptor.
2. preparation method according to claim 1, is characterized in that, described solvable divalent metal salt and solvable trivalent metal salt are villaumite, nitrate or sulfate.
3. preparation method according to claim 1, is characterized in that, described bivalent metal ion is selected from Mg
2+, Zn
2+, Ca
2+, Cu
2+, Ni
2+, Co
2+, Fe
2+, Mn
2+, Cd
2+, Be
2+in one or both, preferred Mg
2+, Zn
2+, Ca
2+, Ni
2+in one or both; Trivalent metal ion is selected from Al
3+, Ni
3+, Co
3+, Fe
3+, Mn
3+, Cr
3+, V
3+, Ti
3+, In
3+, Ga
3+in one or both, preferred Al
3+, Ni
3+, Fe
3+in one or both.
4. preparation method according to claim 1, is characterized in that, described organic solvent is selected from one or more in methyl alcohol, ethanol, ethylene glycol, glycerine, acetone, ether.
5. according to the application of hydrotalcite acid-acceptor in polyolefin synthesis that the arbitrary described method of claim 1-4 prepares.
6. application according to claim 5, it is characterized in that, described polyolefin is polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, vinyl-acrylate copolymer, propylene acrylic acid copolymer, poly 1-butene, poly(4-methyl-1-pentene), cyclic olefin polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510226827.9A CN104841358B (en) | 2015-05-06 | 2015-05-06 | A kind of preparation method of polyolefin hydrotalcite acid-acceptor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510226827.9A CN104841358B (en) | 2015-05-06 | 2015-05-06 | A kind of preparation method of polyolefin hydrotalcite acid-acceptor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104841358A true CN104841358A (en) | 2015-08-19 |
| CN104841358B CN104841358B (en) | 2018-03-30 |
Family
ID=53841571
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510226827.9A Active CN104841358B (en) | 2015-05-06 | 2015-05-06 | A kind of preparation method of polyolefin hydrotalcite acid-acceptor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104841358B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106433010A (en) * | 2016-10-10 | 2017-02-22 | 珠海格力电器股份有限公司 | Flame-retardant ABS material and preparation method thereof |
| CN116081679A (en) * | 2023-02-22 | 2023-05-09 | 西尼尔(山东)新材料科技有限公司 | Novel acid absorber and application thereof in polymer system |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58214338A (en) * | 1982-06-04 | 1983-12-13 | Kyowa Chem Ind Co Ltd | Composite adsorbent |
| CN104558775A (en) * | 2015-01-12 | 2015-04-29 | 北京化工大学 | Hydrotalcite acid acceptor for polyolefin |
-
2015
- 2015-05-06 CN CN201510226827.9A patent/CN104841358B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58214338A (en) * | 1982-06-04 | 1983-12-13 | Kyowa Chem Ind Co Ltd | Composite adsorbent |
| CN104558775A (en) * | 2015-01-12 | 2015-04-29 | 北京化工大学 | Hydrotalcite acid acceptor for polyolefin |
Non-Patent Citations (1)
| Title |
|---|
| 贺娟等: "混合溶剂制备Mg/Al水滑石", 《硅酸盐学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106433010A (en) * | 2016-10-10 | 2017-02-22 | 珠海格力电器股份有限公司 | Flame-retardant ABS material and preparation method thereof |
| CN116081679A (en) * | 2023-02-22 | 2023-05-09 | 西尼尔(山东)新材料科技有限公司 | Novel acid absorber and application thereof in polymer system |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104841358B (en) | 2018-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101228880B1 (en) | Hydrotalcite with extremely low content of sodium, process for preparing it and synthetic resin composition comprising it | |
| EP3497060B1 (en) | Synthetic hydrotalcite | |
| AU649761B2 (en) | Polymeric materials | |
| CN104558775B (en) | Hydrotalcite acid acceptor for polyolefin | |
| CN104841358A (en) | Preparation method for hydrotalcite acid absorption agent used for polyolefin | |
| CN107629310B (en) | Supermolecule intercalation structure light stabilizer and preparation method thereof | |
| RU2017117662A (en) | DEPOSITED CALCIUM CARBONATE WITH REDUCED PORTLANDITIS CONTENT | |
| EP3068728A1 (en) | Doped copper-ii-hydroxide phosphate, method for producing same, and use thereof | |
| EP3354621B1 (en) | Hydrotalcite and method for producing same | |
| CN104194111B (en) | Polyolefine resin composition containing nucleator and preparation method thereof | |
| WO1981001712A1 (en) | Process for preparing polyoxymethylene | |
| CN108359164A (en) | It is a kind of to build special drainage pipe and preparation method thereof | |
| CN104163938A (en) | Nucleating agent and preparation method thereof | |
| CN104211985B (en) | Aluminum hydroxide-containing nucleating agent and preparation method thereof | |
| JP2014129202A (en) | Method for manufacturing layered double hydroxide | |
| CN107602925B (en) | A kind of supermolecular intercalation structure anti-light aging material and preparation method thereof | |
| CN109438692A (en) | A kind of synthetic method of phosphonitrile polyethers | |
| CN104163984A (en) | Polyolefin resin composition and preparation method thereof | |
| CN107513179B (en) | One kind ultraviolet absorber of supermolecular intercalation structure containing auxiliary agent and preparation method thereof | |
| Yamauchi et al. | Studies on imidazole derivatives as chelating agents—IV: Stability constants of the metal chelates of azoimidazoles | |
| JP2008280486A (en) | Al-Li TYPE INFRARED RAY ABSORBER, ITS MANUFACTURING METHOD, FILM FOR AGRICULTURE AND MASTERBATCH PELLETS FOR AGRICULTURAL FILM | |
| EP1311605A1 (en) | Use of amphiphilic polymers or copolymers for surface modification of reactive inorganic fillers | |
| CN109679208A (en) | A kind of environment-friendly high-efficiency anti-flaming polypropylene composite and preparation method thereof | |
| EP1088872A2 (en) | Near infrared absorbing compound | |
| CN116854120A (en) | High acid absorption talcum, preparation method and PVC material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |