WO2022134122A1 - Preparation method for polymeric pvc heat stabilizer - Google Patents
Preparation method for polymeric pvc heat stabilizer Download PDFInfo
- Publication number
- WO2022134122A1 WO2022134122A1 PCT/CN2020/139766 CN2020139766W WO2022134122A1 WO 2022134122 A1 WO2022134122 A1 WO 2022134122A1 CN 2020139766 W CN2020139766 W CN 2020139766W WO 2022134122 A1 WO2022134122 A1 WO 2022134122A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- heat stabilizer
- parts
- polymer
- preparation
- reaction
- Prior art date
Links
- 239000012760 heat stabilizer Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000004793 Polystyrene Substances 0.000 claims abstract description 23
- 229920002223 polystyrene Polymers 0.000 claims abstract description 23
- 238000006396 nitration reaction Methods 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 47
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 40
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 24
- 229910017604 nitric acid Inorganic materials 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 16
- 239000003638 chemical reducing agent Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000741 silica gel Substances 0.000 claims description 14
- 229910002027 silica gel Inorganic materials 0.000 claims description 14
- 239000011973 solid acid Substances 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 9
- JPTXDWQZDBNNCG-UHFFFAOYSA-N [N+](=O)(O)[O-].NC(CC)C1=NC=CN1C Chemical compound [N+](=O)(O)[O-].NC(CC)C1=NC=CN1C JPTXDWQZDBNNCG-UHFFFAOYSA-N 0.000 claims description 8
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 6
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 5
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- GEMITLJMEMBDKW-UHFFFAOYSA-N hydrogen sulfate;1h-imidazol-3-ium Chemical compound C1=CNC=N1.OS(O)(=O)=O GEMITLJMEMBDKW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 40
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 39
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 150000003384 small molecules Chemical class 0.000 abstract 2
- 230000000802 nitrating effect Effects 0.000 abstract 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- OVTAOJNUBPGPRW-UHFFFAOYSA-N S(=O)(=O)(O)O.C(=O)(O)C(C)C1=NC=CN1C Chemical compound S(=O)(=O)(O)O.C(=O)(O)C(C)C1=NC=CN1C OVTAOJNUBPGPRW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- -1 aromatic 1,3,4 oxadiazole derivative Chemical class 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000003017 thermal stabilizer Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- YFYYRKDBDBILSD-UHFFFAOYSA-N 6-amino-2-sulfanylidene-1h-pyrimidin-4-one Chemical compound NC1=CC(=O)NC(=S)N1 YFYYRKDBDBILSD-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Chemical group 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical group [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- 239000010457 zeolite Chemical group 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of 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; Compositions of derivatives of such polymers
- C08L27/02—Compositions of 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
Definitions
- the present invention is in the field of preparation of plastic auxiliary agents, in particular to a preparation method of a polymer-type PVC heat stabilizer.
- CN103450597B discloses an auxiliary heat stabilizer for PVC processing, which is a system in which organic carboxylic acid is used as a catalyst, and calcium oxide, zinc oxide and glycerin are added to react, and the obtained metal-organic complex is the stabilizer.
- the specific reaction steps are as follows: take Equimolar calcium oxide, zinc oxide, and glycerin were heated to 180°C for 200 minutes in an organic carboxylic acid environment. When the reaction system became colorless and transparent, the temperature was lowered to 120°C, and the total addition amount was added dropwise at a rate of 1 ml per second.
- 6-amino-2-mercapto-pyrimidin-4-ol in an equimolar amount with glycerol was added dropwise and kept at 80° C. for 60 minutes, filtered, dried and pulverized to obtain a stabilizer.
- the invention combines the zinc components that improve the initial effect of thermal stability of PVC processing and the calcium components that inhibit "zinc burning", which not only solves the defect of the stabilizer with poor initial stability, but also can be used as a stabilizer alone Use directly.
- CN104861393A discloses a composite heat stabilizer for PVC.
- the composite heat stabilizer for PVC comprises: (1) aromatic 1,3,4 oxadiazole derivative or aromatic 1,3,4 oxadiazole derivative complex; (2) Ca/Zn heat stabilizer. Since it uses aromatic 1,3,4 oxadiazole derivatives or their complexes as the main stabilizer, it does not contain any heavy metals at all, is non-toxic and environmentally friendly, and can be widely used in food, medical and health care with high safety requirements. and toy products.
- CN103540048A discloses a PVC thermal stabilizer with a long thermal stability time, which is used in PVC products requiring thermal stability time and excellent discoloration resistance.
- the invention is modified with hydrotalcite, hydroxide and zeolite as the main body, and a special antioxidant is added. Solved the current thermal stability time is not long enough, and the phenomenon of poor discoloration. Using this product not only has excellent performance, but also is environmentally friendly, which has won the competitiveness of Chinese enterprises in the European and American markets.
- the present invention provides a preparation method of a polymer-type PVC heat stabilizer.
- a kind of preparation method of polymer type PVC heat stabilizer, its concrete scheme is as follows:
- the imidazole hydrogen sulfate and 100-200 parts of N,N-dimethylformamide are mixed evenly, and the temperature is controlled at -5-5°C and stirred for 30-60min; the addition is completed at 20-60min, and then the temperature is raised to room temperature, The reaction is stirred for 10-18h, the material is precipitated in water after the reaction is completed, the filtrate is washed with ethanol after filtration, and the polymer-type PVC heat stabilizer can be obtained after drying.
- the equation of the partial reaction is shown as:
- Described nitration reaction assistant is a kind of metal-loaded solid acid assistant, and its preparation method is:
- silica gel powder is activated at 300-400 ° C for 30-120 min, cooled to room temperature, and then added to 14-20 parts by mass of 5.4%-7.5% pentachloride Molybdenum aqueous solution, stirred at room temperature for 5-20h, filtered, dried at 80-120°C, put into a muffle furnace at 450-600°C for 3-6h calcination, cooled to room temperature after completion, and dispersed to 60-80 parts of In pure water, 0.5-3 parts of zirconium tetrachloride and 5-10 parts of ethanol are mixed uniformly and then slowly added to the reaction kettle, and the addition is controlled within 30-50 minutes, and then stirred and reacted for 1-5 hours and filtered. After washing with water and drying under vacuum at 100-120 DEG C, the metal-supported solid acid auxiliary can be obtained.
- the particle size of the silica gel powder is 500-800 mesh.
- the ethanol is absolute ethanol.
- the volume ratio of concentrated sulfuric acid and concentrated nitric acid is 1.5-2:1.
- the reducing agent is sodium thiosulfate or sodium sulfite or sodium bisulfite.
- the ultrasonic dispersion power is 1-5kW.
- the polystyrene is firstly nitrated, and then the small molecular heat stabilizer is grafted onto the polystyrene molecular chain after reduction, which can effectively improve the compatibility between the organic heat stabilizer and the polyvinyl chloride, thereby improving the organic heat stabilizer.
- the action efficiency of the stabilizer thereby improving the thermal stability performance of the organic thermal stabilizer.
- a nitration reaction assistant is used, which can significantly improve the nitration rate of polystyrene, provide more grafting reaction sites, improve the graft rate of small molecular heat stabilizers, and obtain polymer PVC with better stabilization effect.
- Heat stabilizers The thermal stability of the PVC of the invention does not contain heavy metal ions at all, and at the same time, it has good compatibility with the PVC resin. A very good PVC heat stabilizer.
- a kind of preparation method of polymer type PVC heat stabilizer, its concrete scheme is as follows:
- Described nitration reaction assistant is a kind of metal-loaded solid acid assistant, and its preparation method is:
- the particle size of the silica gel powder is 500 meshes.
- the ethanol is absolute ethanol.
- the volume ratio of concentrated sulfuric acid and concentrated nitric acid is 1.5:1.
- the reducing agent is sodium thiosulfate.
- the ultrasonic dispersion power is 1kW.
- a kind of preparation method of polymer type PVC heat stabilizer, its concrete scheme is as follows:
- Polystyrene was added to 650kg N,N-dimethylformamide, and then slowly added to the reaction kettle after stirring and mixing; 14kg of ammonium thiocyanate, 16.3kg of 1-carboxyethyl-3 -Methylimidazole hydrogen sulfate and 150kg N,N-dimethylformamide were mixed uniformly, and the temperature was controlled and stirred at 0°C for 40min; the addition was completed in 40min, then the temperature was raised to room temperature, and the reaction was stirred for 14h. After the reaction was completed, the material was placed in Precipitate in water, wash the filtrate with ethanol after filtration, and obtain the polymer-type PVC heat stabilizer after drying.
- Described nitration reaction assistant is a kind of metal-loaded solid acid assistant, and its preparation method is:
- the particle size of the silica gel powder is 600 meshes.
- the ethanol is absolute ethanol.
- the volume ratio of concentrated sulfuric acid and concentrated nitric acid is 1.8:1.
- the reducing agent is sodium sulfite.
- the ultrasonic dispersion power is 3kW.
- a kind of preparation method of polymer type PVC heat stabilizer, its concrete scheme is as follows:
- Styrene was added to 800kg of N,N-dimethylformamide, and then slowly added to the reaction kettle after stirring and mixing; 16kg of ammonium thiocyanate, 20.3kg of 1-carboxyethyl-3- Methylimidazole hydrogen sulfate and 200kg N,N-dimethylformamide were mixed uniformly, and the temperature was controlled and stirred at 5°C for 60min; the addition was completed at 60min, then the temperature was raised to room temperature, and the reaction was stirred for 18h. After the reaction was completed, the material was placed in water After precipitation, the filtrate is washed with ethanol after filtration, and the polymer-type PVC heat stabilizer can be obtained after drying.
- Described nitration reaction assistant is a kind of metal-loaded solid acid assistant, and its preparation method is:
- the particle size of the silica gel powder is 800 meshes.
- the ethanol is absolute ethanol.
- the volume ratio of concentrated sulfuric acid and concentrated nitric acid is 2:1.
- the reducing agent is sodium bisulfite.
- the ultrasonic dispersion power is 5kW.
- a kind of preparation method of polymer type PVC heat stabilizer, its concrete scheme is as follows:
- the volume ratio of concentrated sulfuric acid and concentrated nitric acid is 1.5:1.
- the reducing agent is sodium thiosulfate.
- the ultrasonic dispersion power is 1kW.
- a kind of preparation method of polymer type PVC heat stabilizer, its concrete scheme is as follows:
- Described nitration reaction assistant is a kind of metal-loaded solid acid assistant, and its preparation method is:
- silica gel powder 10kg was activated at 300°C for 30min, cooled to room temperature, then added to 14kg of molybdenum pentachloride aqueous solution with a mass fraction of 5.4%, stirred at room temperature for 5h, filtered, dried at 80°C and put into 450°C.
- the metal-supported solid acid auxiliary can be obtained by calcining in a muffle furnace at °C for 3-6 hours.
- the particle size of the silica gel powder is 500 meshes.
- the ethanol is absolute ethanol.
- the volume ratio of concentrated sulfuric acid and concentrated nitric acid is 1.5:1.
- the reducing agent is sodium thiosulfate.
- the ultrasonic dispersion power is 1kW.
- a kind of preparation method of polymer type PVC heat stabilizer, its concrete scheme is as follows:
- Described nitration reaction assistant is a kind of metal-loaded solid acid assistant, and its preparation method is:
- the particle size of the silica gel powder is 500 meshes.
- the ethanol is absolute ethanol.
- the volume ratio of concentrated sulfuric acid and concentrated nitric acid is 1.5:1.
- the reducing agent is sodium thiosulfate.
- the ultrasonic dispersion power is 1kW.
- the stability effect test adopts the Congo red method: mix 5g of PVC dry powder and 0.1g of stabilizer evenly, pour it into a test tube, and then immerse the test tube in an oil bath at 180°C for heating. The upper surface of the sample is flush with the upper surface of the oil bath. At the same time, place a Congo red test paper above the sample, and the bottom end of the Congo red test paper is 2.5 cm from the upper surface of the sample.
- the time when the sample is immersed in the oil bath until the Congo red test paper above turns blue is the thermal stabilization time of the sample; each sample is measured twice, and the average value is the stabilization time, accurate to half a minute.
- the grafting rate of polystyrene material is calculated according to the weight gain rate.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A preparation method for a polymeric polyvinyl chloride (PVC) heat stabilizer, comprising: first nitrating polystyrene, and carrying out and then grafting a small-molecule heat stabilizer onto a polystyrene molecular chain. The method can effectively improve the compatibility of an organic heat stabilizer and PVC, such that the action efficiency of the organic heat stabilizer is improved, thereby improving the thermal stability of the organic heat stabilizer. By using a nitration reaction promoter, the nitrification rate of polystyrene can be remarkably improved, and more grafting reaction sites can be provided, thereby improving the grafting rate of the small-molecule heat stabilizer and obtaining a polymer PVC heat stabilizer having better thermal stability. The PVC heat stabilizer contains no heavy metal ion, has good compatibility with a PVC resin, has lubricity without affecting the rheological properties of a mixture, and does not affect the plasticization of PVC, and therefore is an excellent PVC heat stabilizer.
Description
本发明塑料助剂制备领域，尤其是一种聚合物型PVC热稳定剂的制备方法。The present invention is in the field of preparation of plastic auxiliary agents, in particular to a preparation method of a polymer-type PVC heat stabilizer.
随着国民经济快速发展，我国对聚氯乙烯的需求量进一步的增加，聚氯乙烯在我国国民经济中的地位将更加重要。但是，由于聚氯乙烯链本身存在的结构缺陷，使得聚氯乙烯在加工过程中受温度、压力作用而易发生脱除氯化氢的反应，致使聚氯乙烯降解颜色发生变化，进而导致性能退化下降。With the rapid development of the national economy, my country's demand for polyvinyl chloride has further increased, and the status of polyvinyl chloride in my country's national economy will become more important. However, due to the structural defects of the polyvinyl chloride chain itself, the polyvinyl chloride is prone to the reaction of removing hydrogen chloride under the action of temperature and pressure during the processing, resulting in a change in the color of the degraded polyvinyl chloride, which in turn leads to a decrease in performance degradation.
CN103450597B公开了PVC加工辅助热稳定剂，它是在有机羧酸为催化剂的体系内，加入氧化钙、氧化锌与甘油反应，得到的金属有机络合物即为稳定剂；具体反应步骤如下：取等摩尔的氧化钙、氧化锌、甘油在有机羧酸环境中，加热到180℃反应200分钟，待反应体系变为无色透明时降温至120℃，以每秒1毫升速度滴加总添加量与甘油等摩尔的6-氨基-2-巯基-嘧啶-4-醇，滴加完全后在80℃保温60分钟，过滤，烘干，粉碎，得稳定剂。该发明将提升PVC加工热稳定初期效果的锌类组分和抑制“锌烧”的钙类组分络合在一起，既解决了初期稳定性不好的稳定剂缺陷，又可单独作为稳定剂直接使用。CN103450597B discloses an auxiliary heat stabilizer for PVC processing, which is a system in which organic carboxylic acid is used as a catalyst, and calcium oxide, zinc oxide and glycerin are added to react, and the obtained metal-organic complex is the stabilizer. The specific reaction steps are as follows: take Equimolar calcium oxide, zinc oxide, and glycerin were heated to 180°C for 200 minutes in an organic carboxylic acid environment. When the reaction system became colorless and transparent, the temperature was lowered to 120°C, and the total addition amount was added dropwise at a rate of 1 ml per second. 6-amino-2-mercapto-pyrimidin-4-ol in an equimolar amount with glycerol was added dropwise and kept at 80° C. for 60 minutes, filtered, dried and pulverized to obtain a stabilizer. The invention combines the zinc components that improve the initial effect of thermal stability of PVC processing and the calcium components that inhibit "zinc burning", which not only solves the defect of the stabilizer with poor initial stability, but also can be used as a stabilizer alone Use directly.
CN104861393A公开了一种PVC用复合热稳定剂。所述的PVC用复合热稳定剂包含：(1)芳香1,3,4恶二唑衍生物或芳香1,3,4恶二唑衍生物配合物；(2)Ca/Zn热稳定剂。由于其以芳香1,3,4恶二唑衍生物或其配合物作为主效稳定剂，完全不含任何重金属，无毒、环保，可广泛用于对安全要求较高的食品类、医疗卫生类和玩具制品类。CN104861393A discloses a composite heat stabilizer for PVC. The composite heat stabilizer for PVC comprises: (1) aromatic 1,3,4 oxadiazole derivative or aromatic 1,3,4 oxadiazole derivative complex; (2) Ca/Zn heat stabilizer. Since it uses aromatic 1,3,4 oxadiazole derivatives or their complexes as the main stabilizer, it does not contain any heavy metals at all, is non-toxic and environmentally friendly, and can be widely used in food, medical and health care with high safety requirements. and toy products.
CN103540048A公开了一种热稳定时间长的PVC热稳定剂，用于PVC要求热稳定时间，耐变色优良的产品中。该发明用水滑石，氢氧化物，沸石为主体改性，加特种抗氧剂。解决了目前热稳定时间不够长，和对变色差的现象。用本产品不但性能优良，而且环保，为中国企业在欧美市场赢得了竞争力。CN103540048A discloses a PVC thermal stabilizer with a long thermal stability time, which is used in PVC products requiring thermal stability time and excellent discoloration resistance. The invention is modified with hydrotalcite, hydroxide and zeolite as the main body, and a special antioxidant is added. Solved the current thermal stability time is not long enough, and the phenomenon of poor discoloration. Using this product not only has excellent performance, but also is environmentally friendly, which has won the competitiveness of Chinese enterprises in the European and American markets.
以上专利以及现有技术制备的热稳定剂种类很多，但是应用最广泛的铅盐类热稳定剂中含有重金属铅，会对环境造成严重污染，因此世界各国均逐步淘汰有毒有害的热稳定剂，选择环保无毒的热稳定剂。有机类辅助热稳定剂虽然多数单独使用时热稳定性不好。There are many types of heat stabilizers prepared by the above patents and the prior art, but the most widely used lead salt heat stabilizers contain heavy metal lead, which will cause serious pollution to the environment. Therefore, all countries in the world are gradually phasing out toxic and harmful heat stabilizers. Choose environmentally friendly and non-toxic heat stabilizers. Although most organic auxiliary heat stabilizers are used alone, the heat stability is not good.
发明内容SUMMARY OF THE INVENTION
为了解决上述问题，本发明提供了一种聚合物型PVC热稳定剂的制备方法。In order to solve the above problems, the present invention provides a preparation method of a polymer-type PVC heat stabilizer.
一种聚合物型PVC热稳定剂的制备方法，其具体方案如下：A kind of preparation method of polymer type PVC heat stabilizer, its concrete scheme is as follows:
按照质量份数，将100-150份的聚苯乙烯粉末和0.2-2份的硝化反应助剂超声分散到300-500份的浓硫酸和浓硝酸混合酸中，在控温35-55℃，搅拌反应60-120min，完成后洗涤、干 燥后将得到1-胺丙基-3-甲基咪唑硝酸盐加入到200-500份的质量份数为5％-10％的还原剂溶液中，控温在60-80℃，搅拌反应4-8h，过滤后洗涤，在60-80℃下真空干燥5-10h，将得到的得到氨基化聚苯乙烯加入到500-800份的N,N-二甲基甲酰胺中，搅拌混合均匀后缓慢的加入到反应釜中；所述的反应釜中预先将12-16份的硫氰酸铵，14.6-20.3份的1-羧乙基-3-甲基咪唑硫酸氢盐和100-200份的N,N-二甲基甲酰胺混合均匀，并控温在-5-5℃搅拌30-60min；控制在20-60min加入完毕，然后升温到室温，搅拌反应10-18h，完成反应后将物料在水中沉析，过滤后用乙醇洗涤滤出物，干燥后即可得到所述的一种聚合物型PVC热稳定剂，部分反应的方程式示意为：According to the parts by mass, ultrasonically disperse 100-150 parts of polystyrene powder and 0.2-2 parts of nitration reaction assistant into 300-500 parts of concentrated sulfuric acid and concentrated nitric acid mixed acid, at a temperature of 35-55 ℃, The reaction is stirred for 60-120min, and after washing and drying, the obtained 1-aminopropyl-3-methylimidazole nitrate is added to 200-500 parts of a reducing agent solution with a mass fraction of 5%-10%, and controlled temperature at 60-80°C, stirring and reacting for 4-8h, washing after filtration, vacuum drying at 60-80°C for 5-10h, and adding the obtained aminated polystyrene to 500-800 parts of N,N-diphenylene In methylformamide, slowly add to the reaction kettle after stirring and mixing evenly; in the reaction kettle, 12-16 parts of ammonium thiocyanate, 14.6-20.3 parts of 1-carboxyethyl-3-methylformamide are preliminarily added. The imidazole hydrogen sulfate and 100-200 parts of N,N-dimethylformamide are mixed evenly, and the temperature is controlled at -5-5°C and stirred for 30-60min; the addition is completed at 20-60min, and then the temperature is raised to room temperature, The reaction is stirred for 10-18h, the material is precipitated in water after the reaction is completed, the filtrate is washed with ethanol after filtration, and the polymer-type PVC heat stabilizer can be obtained after drying. The equation of the partial reaction is shown as:
所述的硝化反应助剂为一种金属负载固体酸助剂，其制备方法为：Described nitration reaction assistant is a kind of metal-loaded solid acid assistant, and its preparation method is:
按照质量份数，将10-15份的硅胶粉在300-400℃下活化处理30-120min后冷却到室温，然后加入到14-20份的质量份数为5.4％-7.5％的五氯化钼水溶液中，室温搅拌5-20h后过滤，在80-120℃下干燥后放入到450-600℃的马弗炉中煅烧3-6h，完成后降温到室温，分散到60-80份的纯水中，将0.5-3份的四氯化锆与5-10份的乙醇混合均匀后缓慢的加入到反应釜中，控制在30-50min加完，然后搅拌反应1-5h后过滤，纯水洗涤后在100-120℃真空干燥后即可得到所述的一种金属负载固体酸助剂。According to the parts by mass, 10-15 parts of silica gel powder is activated at 300-400 ° C for 30-120 min, cooled to room temperature, and then added to 14-20 parts by mass of 5.4%-7.5% pentachloride Molybdenum aqueous solution, stirred at room temperature for 5-20h, filtered, dried at 80-120°C, put into a muffle furnace at 450-600°C for 3-6h calcination, cooled to room temperature after completion, and dispersed to 60-80 parts of In pure water, 0.5-3 parts of zirconium tetrachloride and 5-10 parts of ethanol are mixed uniformly and then slowly added to the reaction kettle, and the addition is controlled within 30-50 minutes, and then stirred and reacted for 1-5 hours and filtered. After washing with water and drying under vacuum at 100-120 DEG C, the metal-supported solid acid auxiliary can be obtained.
所述的硅胶粉的粒径为500-800目。The particle size of the silica gel powder is 500-800 mesh.
所述的乙醇为无水乙醇。The ethanol is absolute ethanol.
所述的浓硫酸和浓硝酸的混合酸中浓硫酸和浓硝酸的体积比为1.5-2:1。In the mixed acid of described concentrated sulfuric acid and concentrated nitric acid, the volume ratio of concentrated sulfuric acid and concentrated nitric acid is 1.5-2:1.
所述的还原剂为硫代硫酸钠或亚硫酸钠或亚硫酸氢钠。The reducing agent is sodium thiosulfate or sodium sulfite or sodium bisulfite.
所述的超声分散功率为1-5kW。The ultrasonic dispersion power is 1-5kW.
本发明首先将聚苯乙烯进行硝化，然后还原后将小分子的热稳定剂接枝到聚苯乙烯分子链上，可以有效地提高有机热稳定剂与聚氯乙烯的兼容性，从而提高有机热稳定剂的作用效 率，进而提高有机热稳定剂的热稳定性能。本文使用一种硝化反应助剂，能够显著提高聚苯乙烯的硝化率，提供更多的接枝反应位点，提高小分子热稳定剂的接枝率，得到人稳定效果更好的高分子PVC热稳定剂。本发明的PVC热稳定完全不含有重金属离子，同时与PVC树脂有很好的相容性，在不影响到配混料的流变性能同时兼具润滑性也不至影响PVC塑化，是一种非常优异的PVC热稳定剂。In the invention, the polystyrene is firstly nitrated, and then the small molecular heat stabilizer is grafted onto the polystyrene molecular chain after reduction, which can effectively improve the compatibility between the organic heat stabilizer and the polyvinyl chloride, thereby improving the organic heat stabilizer. The action efficiency of the stabilizer, thereby improving the thermal stability performance of the organic thermal stabilizer. In this paper, a nitration reaction assistant is used, which can significantly improve the nitration rate of polystyrene, provide more grafting reaction sites, improve the graft rate of small molecular heat stabilizers, and obtain polymer PVC with better stabilization effect. Heat stabilizers. The thermal stability of the PVC of the invention does not contain heavy metal ions at all, and at the same time, it has good compatibility with the PVC resin. A very good PVC heat stabilizer.
下面通过具体实施例对该发明作进一步说明：This invention is further described below by specific embodiment:
实施例1Example 1
一种聚合物型PVC热稳定剂的制备方法，其具体方案如下：A kind of preparation method of polymer type PVC heat stabilizer, its concrete scheme is as follows:
将100kg聚苯乙烯粉末和0.2kg硝化反应助剂超声分散到300kg浓硫酸和浓硝酸混合酸中，在控温35℃，搅拌反应60min，完成后洗涤、干燥后将得到1-胺丙基-3-甲基咪唑硝酸盐加入到200kg质量份数为5％的还原剂溶液中，控温在60℃，搅拌反应4h，过滤后洗涤，在60℃下真空干燥5h，将得到的得到氨基化聚苯乙烯加入到500kgN,N-二甲基甲酰胺中，搅拌混合均匀后缓慢的加入到反应釜中；所述的反应釜中预先将12kg硫氰酸铵，14.6kg1-羧乙基-3-甲基咪唑硫酸氢盐和100kgN,N-二甲基甲酰胺混合均匀，并控温在-5℃搅拌30min；控制在20min加入完毕，然后升温到室温，搅拌反应10h，完成反应后将物料在水中沉析，过滤后用乙醇洗涤滤出物，干燥后即可得到所述的一种聚合物型PVC热稳定剂。Disperse 100kg of polystyrene powder and 0.2kg of nitration reaction auxiliary into 300kg of mixed acid of concentrated sulfuric acid and concentrated nitric acid by ultrasonic, and stir and react for 60min under temperature control at 35°C. After washing and drying, 1-aminopropyl- 3-Methylimidazole nitrate was added to 200kg of reducing agent solution with a mass fraction of 5%, the temperature was controlled at 60°C, the reaction was stirred for 4h, filtered, washed, and dried under vacuum at 60°C for 5h to obtain aminated Polystyrene was added to 500kg of N,N-dimethylformamide, and then slowly added to the reactor after stirring and mixing; 12kg of ammonium thiocyanate, 14.6kg of 1-carboxyethyl-3 -Methylimidazole hydrogen sulfate and 100kg N,N-dimethylformamide were mixed uniformly, and the temperature was controlled at -5°C and stirred for 30min; the addition was completed in 20min, then the temperature was raised to room temperature, and the reaction was stirred for 10h. After the reaction was completed, the material was Precipitate in water, wash the filtrate with ethanol after filtration, and obtain the polymer-type PVC heat stabilizer after drying.
所述的硝化反应助剂为一种金属负载固体酸助剂，其制备方法为：Described nitration reaction assistant is a kind of metal-loaded solid acid assistant, and its preparation method is:
将10kg硅胶粉在300℃下活化处理30min后冷却到室温，然后加入到14kg质量份数为5.4％的五氯化钼水溶液中，室温搅拌5h后过滤，在80℃下干燥后放入到450℃的马弗炉中煅烧3-6h，完成后降温到室温，分散到60kg纯水中，将0.5kg四氯化锆与5kg乙醇混合均匀后缓慢的加入到反应釜中，控制在30min加完，然后搅拌反应1h后过滤，纯水洗涤后在100℃真空干燥后即可得到所述的一种金属负载固体酸助剂。10kg of silica gel powder was activated at 300°C for 30min, cooled to room temperature, then added to 14kg of molybdenum pentachloride aqueous solution with a mass fraction of 5.4%, stirred at room temperature for 5h, filtered, dried at 80°C and put into 450°C. calcined in a muffle furnace at ℃ for 3-6 hours, cooled to room temperature after completion, dispersed into 60kg of pure water, 0.5kg of zirconium tetrachloride and 5kg of ethanol were mixed uniformly and then slowly added to the reaction kettle, and the addition was controlled within 30min. , and then stirred and reacted for 1 h, filtered, washed with pure water, and dried in vacuum at 100° C. to obtain the metal-supported solid acid auxiliary.
所述的硅胶粉的粒径为500目。The particle size of the silica gel powder is 500 meshes.
所述的乙醇为无水乙醇。The ethanol is absolute ethanol.
所述的浓硫酸和浓硝酸的混合酸中浓硫酸和浓硝酸的体积比为1.5:1。In the mixed acid of described concentrated sulfuric acid and concentrated nitric acid, the volume ratio of concentrated sulfuric acid and concentrated nitric acid is 1.5:1.
所述的还原剂为硫代硫酸钠。The reducing agent is sodium thiosulfate.
所述的超声分散功率为1kW。The ultrasonic dispersion power is 1kW.
实施例2Example 2
一种聚合物型PVC热稳定剂的制备方法，其具体方案如下：A kind of preparation method of polymer type PVC heat stabilizer, its concrete scheme is as follows:
将120kg聚苯乙烯粉末和0.8kg硝化反应助剂超声分散到400kg浓硫酸和浓硝酸混合酸 中，在控温45℃，搅拌反应90min，完成后洗涤、干燥后将得到1-胺丙基-3-甲基咪唑硝酸盐加入到300kg质量份数为8％的还原剂溶液中，控温在70℃，搅拌反应6h，过滤后洗涤，在70℃下真空干燥8h，将得到的得到氨基化聚苯乙烯加入到650kgN,N-二甲基甲酰胺中，搅拌混合均匀后缓慢的加入到反应釜中；所述的反应釜中预先将14kg硫氰酸铵，16.3kg1-羧乙基-3-甲基咪唑硫酸氢盐和150kgN,N-二甲基甲酰胺混合均匀，并控温在0℃搅拌40min；控制在40min加入完毕，然后升温到室温，搅拌反应14h，完成反应后将物料在水中沉析，过滤后用乙醇洗涤滤出物，干燥后即可得到所述的一种聚合物型PVC热稳定剂。Disperse 120kg of polystyrene powder and 0.8kg of nitration reaction auxiliary into 400kg of mixed acid of concentrated sulfuric acid and concentrated nitric acid by ultrasonic, and at a temperature of 45 ° C, stirring and reacting for 90 min, after washing and drying, 1-aminopropyl- 3-Methylimidazole nitrate was added to 300kg of reducing agent solution with a mass fraction of 8%, the temperature was controlled at 70°C, stirred and reacted for 6h, filtered, washed, and dried under vacuum at 70°C for 8h, and the obtained amination was obtained. Polystyrene was added to 650kg N,N-dimethylformamide, and then slowly added to the reaction kettle after stirring and mixing; 14kg of ammonium thiocyanate, 16.3kg of 1-carboxyethyl-3 -Methylimidazole hydrogen sulfate and 150kg N,N-dimethylformamide were mixed uniformly, and the temperature was controlled and stirred at 0°C for 40min; the addition was completed in 40min, then the temperature was raised to room temperature, and the reaction was stirred for 14h. After the reaction was completed, the material was placed in Precipitate in water, wash the filtrate with ethanol after filtration, and obtain the polymer-type PVC heat stabilizer after drying.
所述的硝化反应助剂为一种金属负载固体酸助剂，其制备方法为：Described nitration reaction assistant is a kind of metal-loaded solid acid assistant, and its preparation method is:
将13kg硅胶粉在340℃下活化处理60min后冷却到室温，然后加入到17kg质量份数为6.8％的五氯化钼水溶液中，室温搅拌12h后过滤，在100℃下干燥后放入到550℃的马弗炉中煅烧4h，完成后降温到室温，分散到70kg纯水中，将2.2kg四氯化锆与8kg乙醇混合均匀后缓慢的加入到反应釜中，控制在40min加完，然后搅拌反应3h后过滤，纯水洗涤后在110℃真空干燥后即可得到所述的一种金属负载固体酸助剂。13kg of silica gel powder was activated at 340°C for 60min, cooled to room temperature, then added to 17kg of molybdenum pentachloride aqueous solution with a mass fraction of 6.8%, stirred at room temperature for 12h, filtered, dried at 100°C and put into 550°C. calcined in a muffle furnace at a temperature of After stirring and reacting for 3 hours, filtering, washing with pure water, and vacuum drying at 110° C., the metal-supported solid acid auxiliary agent can be obtained.
所述的硅胶粉的粒径为600目。The particle size of the silica gel powder is 600 meshes.
所述的乙醇为无水乙醇。The ethanol is absolute ethanol.
所述的浓硫酸和浓硝酸的混合酸中浓硫酸和浓硝酸的体积比为1.8:1。In the mixed acid of described concentrated sulfuric acid and concentrated nitric acid, the volume ratio of concentrated sulfuric acid and concentrated nitric acid is 1.8:1.
所述的还原剂为亚硫酸钠。The reducing agent is sodium sulfite.
所述的超声分散功率为3kW。The ultrasonic dispersion power is 3kW.
实施例3Example 3
一种聚合物型PVC热稳定剂的制备方法，其具体方案如下：A kind of preparation method of polymer type PVC heat stabilizer, its concrete scheme is as follows:
将150kg聚苯乙烯粉末和2kg硝化反应助剂超声分散到500kg浓硫酸和浓硝酸混合酸中，在控温55℃，搅拌反应120min，完成后洗涤、干燥后将得到1-胺丙基-3-甲基咪唑硝酸盐加入到500kg质量份数为10％的还原剂溶液中，控温在80℃，搅拌反应8h，过滤后洗涤，在80℃下真空干燥10h，将得到的得到氨基化聚苯乙烯加入到800kgN,N-二甲基甲酰胺中，搅拌混合均匀后缓慢的加入到反应釜中；所述的反应釜中预先将16kg硫氰酸铵，20.3kg1-羧乙基-3-甲基咪唑硫酸氢盐和200kgN,N-二甲基甲酰胺混合均匀，并控温在5℃搅拌60min；控制在60min加入完毕，然后升温到室温，搅拌反应18h，完成反应后将物料在水中沉析，过滤后用乙醇洗涤滤出物，干燥后即可得到所述的一种聚合物型PVC热稳定剂。Disperse 150kg of polystyrene powder and 2kg of nitration reaction auxiliary into 500kg of concentrated sulfuric acid and concentrated nitric acid mixed acid by ultrasonic, and stir and react for 120min at a temperature of 55°C. After washing and drying, 1-aminopropyl-3 -Methylimidazole nitrate was added to 500kg of reducing agent solution with a mass fraction of 10%, the temperature was controlled at 80°C, stirred and reacted for 8h, filtered, washed, and dried under vacuum at 80°C for 10h, and the obtained aminated polymer was obtained. Styrene was added to 800kg of N,N-dimethylformamide, and then slowly added to the reaction kettle after stirring and mixing; 16kg of ammonium thiocyanate, 20.3kg of 1-carboxyethyl-3- Methylimidazole hydrogen sulfate and 200kg N,N-dimethylformamide were mixed uniformly, and the temperature was controlled and stirred at 5°C for 60min; the addition was completed at 60min, then the temperature was raised to room temperature, and the reaction was stirred for 18h. After the reaction was completed, the material was placed in water After precipitation, the filtrate is washed with ethanol after filtration, and the polymer-type PVC heat stabilizer can be obtained after drying.
所述的硝化反应助剂为一种金属负载固体酸助剂，其制备方法为：Described nitration reaction assistant is a kind of metal-loaded solid acid assistant, and its preparation method is:
将15kg硅胶粉在400℃下活化处理120min后冷却到室温，然后加入到20kg质量份数为 7.5％的五氯化钼水溶液中，室温搅拌20h后过滤，在120℃下干燥后放入到600℃的马弗炉中煅烧6h，完成后降温到室温，分散到80kg纯水中，将3kg四氯化锆与10kg乙醇混合均匀后缓慢的加入到反应釜中，控制在50min加完，然后搅拌反应5h后过滤，纯水洗涤后在120℃真空干燥后即可得到所述的一种金属负载固体酸助剂。15kg of silica gel powder was activated at 400°C for 120min, cooled to room temperature, then added to 20kg of 7.5% molybdenum pentachloride aqueous solution, stirred at room temperature for 20h, filtered, dried at 120°C and put into 600°C. calcined in a muffle furnace at ℃ for 6h, cooled to room temperature after completion, dispersed into 80kg of pure water, 3kg of zirconium tetrachloride and 10kg of ethanol were mixed uniformly, and then slowly added to the reaction kettle, controlled to be added in 50min, and then stirred After 5 hours of reaction, filtering, washing with pure water, vacuum drying at 120° C., and then obtaining the metal-supported solid acid auxiliary agent.
所述的硅胶粉的粒径为800目。The particle size of the silica gel powder is 800 meshes.
所述的乙醇为无水乙醇。The ethanol is absolute ethanol.
所述的浓硫酸和浓硝酸的混合酸中浓硫酸和浓硝酸的体积比为2:1。In the mixed acid of described concentrated sulfuric acid and concentrated nitric acid, the volume ratio of concentrated sulfuric acid and concentrated nitric acid is 2:1.
所述的还原剂为亚硫酸氢钠。The reducing agent is sodium bisulfite.
所述的超声分散功率为5kW。The ultrasonic dispersion power is 5kW.
对比例1Comparative Example 1
一种聚合物型PVC热稳定剂的制备方法，其具体方案如下：A kind of preparation method of polymer type PVC heat stabilizer, its concrete scheme is as follows:
将100kg聚苯乙烯粉末超声分散到300kg浓硫酸和浓硝酸混合酸中，在控温35℃，搅拌反应60min，完成后洗涤、干燥后将得到1-胺丙基-3-甲基咪唑硝酸盐加入到200kg质量份数为5％的还原剂溶液中，控温在60℃，搅拌反应4h，过滤后洗涤，在60℃下真空干燥5h，将得到的得到氨基化聚苯乙烯加入到500kgN,N-二甲基甲酰胺中，搅拌混合均匀后缓慢的加入到反应釜中；所述的反应釜中预先将12kg硫氰酸铵，14.6kg1-羧乙基-3-甲基咪唑硫酸氢盐和100kgN,N-二甲基甲酰胺混合均匀，并控温在-5℃搅拌30min；控制在20min加入完毕，然后升温到室温，搅拌反应10h，完成反应后将物料在水中沉析，过滤后用乙醇洗涤滤出物，干燥后即可得到所述的一种聚合物型PVC热稳定剂。100kg of polystyrene powder was ultrasonically dispersed into 300kg of concentrated sulfuric acid and concentrated nitric acid mixed acid, the temperature was controlled at 35°C, and the reaction was stirred for 60min. After washing and drying, 1-aminopropyl-3-methylimidazole nitrate was obtained. Add it to 200kg of reducing agent solution with a mass fraction of 5%, control the temperature at 60°C, stir and react for 4h, filter, wash, and vacuum dry at 60°C for 5h, and add the obtained aminated polystyrene to 500kgN, In N-dimethylformamide, slowly add to the reaction kettle after stirring and mixing evenly; in the reaction kettle, 12kg of ammonium thiocyanate, 14.6kg of 1-carboxyethyl-3-methylimidazole hydrogen sulfate are preliminarily prepared. Mix well with 100kg N,N-dimethylformamide, and stir at -5°C for 30min under temperature control; after adding in 20min, the temperature is raised to room temperature, and the reaction is stirred for 10h. After the reaction is completed, the material is precipitated in water and filtered. The filtrate is washed with ethanol and dried to obtain the polymer type PVC heat stabilizer.
所述的浓硫酸和浓硝酸的混合酸中浓硫酸和浓硝酸的体积比为1.5:1。In the mixed acid of described concentrated sulfuric acid and concentrated nitric acid, the volume ratio of concentrated sulfuric acid and concentrated nitric acid is 1.5:1.
所述的还原剂为硫代硫酸钠。The reducing agent is sodium thiosulfate.
所述的超声分散功率为1kW。The ultrasonic dispersion power is 1kW.
对比例2Comparative Example 2
一种聚合物型PVC热稳定剂的制备方法，其具体方案如下：A kind of preparation method of polymer type PVC heat stabilizer, its concrete scheme is as follows:
将100kg聚苯乙烯粉末和0.2kg硝化反应助剂超声分散到300kg浓硫酸和浓硝酸混合酸中，在控温35℃，搅拌反应60min，完成后洗涤、干燥后将得到1-胺丙基-3-甲基咪唑硝酸盐加入到200kg质量份数为5％的还原剂溶液中，控温在60℃，搅拌反应4h，过滤后洗涤，在60℃下真空干燥5h，将得到的得到氨基化聚苯乙烯加入到500kgN,N-二甲基甲酰胺中，搅拌混合均匀后缓慢的加入到反应釜中；所述的反应釜中预先将12kg硫氰酸铵，14.6kg1-羧乙基-3-甲基咪唑硫酸氢盐和100kgN,N-二甲基甲酰胺混合均匀，并控温在-5℃搅拌30min；控制在20min加入完毕，然后升温到室温，搅拌反应10h，完成反应后将物料在水中沉析， 过滤后用乙醇洗涤滤出物，干燥后即可得到所述的一种聚合物型PVC热稳定剂。Disperse 100kg of polystyrene powder and 0.2kg of nitration reaction auxiliary into 300kg of mixed acid of concentrated sulfuric acid and concentrated nitric acid by ultrasonic, and stir and react for 60min under temperature control at 35°C. After washing and drying, 1-aminopropyl- 3-Methylimidazole nitrate was added to 200kg of reducing agent solution with a mass fraction of 5%, the temperature was controlled at 60°C, the reaction was stirred for 4h, filtered, washed, and dried under vacuum at 60°C for 5h to obtain aminated Polystyrene was added to 500kg of N,N-dimethylformamide, and then slowly added to the reactor after stirring and mixing; 12kg of ammonium thiocyanate, 14.6kg of 1-carboxyethyl-3 -Methylimidazole hydrogen sulfate and 100kg N,N-dimethylformamide were mixed uniformly, and the temperature was controlled at -5°C and stirred for 30min; the addition was completed in 20min, then the temperature was raised to room temperature, and the reaction was stirred for 10h. After the reaction was completed, the material was Precipitate in water, wash the filtrate with ethanol after filtration, and dry to obtain the polymer-type PVC heat stabilizer.
所述的硝化反应助剂为一种金属负载固体酸助剂，其制备方法为：Described nitration reaction assistant is a kind of metal-loaded solid acid assistant, and its preparation method is:
将10kg硅胶粉在300℃下活化处理30min后冷却到室温，然后加入到14kg质量份数为5.4％的五氯化钼水溶液中，室温搅拌5h后过滤，在80℃下干燥后放入到450℃的马弗炉中煅烧3-6h，即可得到所述的一种金属负载固体酸助剂。10kg of silica gel powder was activated at 300°C for 30min, cooled to room temperature, then added to 14kg of molybdenum pentachloride aqueous solution with a mass fraction of 5.4%, stirred at room temperature for 5h, filtered, dried at 80°C and put into 450°C. The metal-supported solid acid auxiliary can be obtained by calcining in a muffle furnace at ℃ for 3-6 hours.
所述的硅胶粉的粒径为500目。The particle size of the silica gel powder is 500 meshes.
所述的乙醇为无水乙醇。The ethanol is absolute ethanol.
所述的浓硫酸和浓硝酸的混合酸中浓硫酸和浓硝酸的体积比为1.5:1。In the mixed acid of described concentrated sulfuric acid and concentrated nitric acid, the volume ratio of concentrated sulfuric acid and concentrated nitric acid is 1.5:1.
所述的还原剂为硫代硫酸钠。The reducing agent is sodium thiosulfate.
所述的超声分散功率为1kW。The ultrasonic dispersion power is 1kW.
对比例3Comparative Example 3
一种聚合物型PVC热稳定剂的制备方法，其具体方案如下：A kind of preparation method of polymer type PVC heat stabilizer, its concrete scheme is as follows:
将100kg聚苯乙烯粉末和0.2kg硝化反应助剂超声分散到300kg浓硫酸和浓硝酸混合酸中，在控温35℃，搅拌反应60min，完成后洗涤、干燥后将得到1-胺丙基-3-甲基咪唑硝酸盐加入到200kg质量份数为5％的还原剂溶液中，控温在60℃，搅拌反应4h，过滤后洗涤，在60℃下真空干燥5h，将得到的得到氨基化聚苯乙烯加入到500kgN,N-二甲基甲酰胺中，搅拌混合均匀后缓慢的加入到反应釜中；所述的反应釜中预先将12kg硫氰酸铵，14.6kg1-羧乙基-3-甲基咪唑硫酸氢盐和100kgN,N-二甲基甲酰胺混合均匀，并控温在-5℃搅拌30min；控制在20min加入完毕，然后升温到室温，搅拌反应10h，完成反应后将物料在水中沉析，过滤后用乙醇洗涤滤出物，干燥后即可得到所述的一种聚合物型PVC热稳定剂。Disperse 100kg of polystyrene powder and 0.2kg of nitration reaction auxiliary into 300kg of mixed acid of concentrated sulfuric acid and concentrated nitric acid by ultrasonic, and stir and react for 60min under temperature control at 35°C. After washing and drying, 1-aminopropyl- 3-Methylimidazole nitrate was added to 200kg of reducing agent solution with a mass fraction of 5%, the temperature was controlled at 60°C, the reaction was stirred for 4h, filtered, washed, and dried under vacuum at 60°C for 5h to obtain aminated Polystyrene was added to 500kg of N,N-dimethylformamide, and then slowly added to the reactor after stirring and mixing; 12kg of ammonium thiocyanate, 14.6kg of 1-carboxyethyl-3 -Methylimidazole hydrogen sulfate and 100kg N,N-dimethylformamide were mixed uniformly, and the temperature was controlled at -5°C and stirred for 30min; the addition was completed in 20min, then the temperature was raised to room temperature, and the reaction was stirred for 10h. After the reaction was completed, the material was Precipitate in water, wash the filtrate with ethanol after filtration, and obtain the polymer-type PVC heat stabilizer after drying.
所述的硝化反应助剂为一种金属负载固体酸助剂，其制备方法为：Described nitration reaction assistant is a kind of metal-loaded solid acid assistant, and its preparation method is:
将10kg硅胶粉在300℃下活化处理30min后冷却到室温，分散到60kg纯水中，将0.5kg四氯化锆与5kg乙醇混合均匀后缓慢的加入到反应釜中，控制在30min加完，然后搅拌反应1h后过滤，纯水洗涤后在100℃真空干燥后即可得到所述的一种金属负载固体酸助剂。10kg of silica gel powder was activated at 300°C for 30min, cooled to room temperature, dispersed into 60kg of pure water, 0.5kg of zirconium tetrachloride and 5kg of ethanol were mixed uniformly and then slowly added to the reaction kettle, and the addition was controlled within 30min. Then, after stirring and reacting for 1 hour, filtering, washing with pure water, and vacuum drying at 100° C., the metal-supported solid acid auxiliary agent can be obtained.
所述的硅胶粉的粒径为500目。The particle size of the silica gel powder is 500 meshes.
所述的乙醇为无水乙醇。The ethanol is absolute ethanol.
所述的浓硫酸和浓硝酸的混合酸中浓硫酸和浓硝酸的体积比为1.5:1。In the mixed acid of described concentrated sulfuric acid and concentrated nitric acid, the volume ratio of concentrated sulfuric acid and concentrated nitric acid is 1.5:1.
所述的还原剂为硫代硫酸钠。The reducing agent is sodium thiosulfate.
所述的超声分散功率为1kW。The ultrasonic dispersion power is 1kW.
稳定效果测试采用刚果红方法：将5gPVC干粉与0.1g稳定剂混合均匀后倒入试管，然后将试管浸入180℃的油浴中加热，样品上表面跟油浴上表面齐平。同时放置一张刚果红试 纸于样品上方，刚果红试纸最下端距样品上表面2.5cm。样品浸入油浴到上方刚果红试纸变蓝色的时间即是样品热稳定时间；每个样品测量两次，取平均值为稳定时间，精确至半分。当单个值与平均值的相对偏差大于10％时，其结果应放弃并重新测定。聚苯乙烯材料的接枝率按照增重率计算。The stability effect test adopts the Congo red method: mix 5g of PVC dry powder and 0.1g of stabilizer evenly, pour it into a test tube, and then immerse the test tube in an oil bath at 180°C for heating. The upper surface of the sample is flush with the upper surface of the oil bath. At the same time, place a Congo red test paper above the sample, and the bottom end of the Congo red test paper is 2.5 cm from the upper surface of the sample. The time when the sample is immersed in the oil bath until the Congo red test paper above turns blue is the thermal stabilization time of the sample; each sample is measured twice, and the average value is the stabilization time, accurate to half a minute. When the relative deviation of a single value from the mean value is greater than 10%, the result should be discarded and re-determined. The grafting rate of polystyrene material is calculated according to the weight gain rate.
用以上实施例制备热稳定的性能测试结果如下表所示：The performance test results of preparing thermal stability with the above examples are shown in the following table:
| 热稳定时间(min)Thermal stabilization time (min) | 聚苯乙烯接枝率(％)Grafting rate of polystyrene (%) | |
| 实施例1Example 1 | 16.516.5 | 21.621.6 |
| 实施例2Example 2 | 1717 | 22.022.0 |
| 实施例3Example 3 | 1818 | 23.223.2 |
| 对比例1Comparative Example 1 | 11.511.5 | 10.410.4 |
| 对比例2Comparative Example 2 | 1313 | 14.814.8 |
| 对比例3Comparative Example 3 | 13.513.5 | 16.616.6 |
Claims (7)
- 一种聚合物型PVC热稳定剂的制备方法，其具体方案如下：A kind of preparation method of polymer type PVC heat stabilizer, its concrete scheme is as follows:按照质量份数，将100-150份的聚苯乙烯粉末和0.2-2份的硝化反应助剂超声分散到300-500份的浓硫酸和浓硝酸混合酸中，在控温35-55℃，搅拌反应60-120min，完成后洗涤、干燥后将得到1-胺丙基-3-甲基咪唑硝酸盐加入到200-500份的质量份数为5％-10％的还原剂溶液中，控温在60-80℃，搅拌反应4-8h，过滤后洗涤，在60-80℃下真空干燥5-10h，将得到的得到氨基化聚苯乙烯加入到500-800份的N,N-二甲基甲酰胺中，搅拌混合均匀后缓慢的加入到反应釜中；所述的反应釜中预先将12-16份的硫氰酸铵，14.6-20.3份的1-羧乙基-3-甲基咪唑硫酸氢盐和100-200份的N,N-二甲基甲酰胺混合均匀，并控温在-5-5℃搅拌30-60min；控制在20-60min加入完毕，然后升温到室温，搅拌反应10-18h，完成反应后将物料在水中沉析，过滤后用乙醇洗涤滤出物，干燥后即可得到所述的一种聚合物型PVC热稳定剂。According to the parts by mass, ultrasonically disperse 100-150 parts of polystyrene powder and 0.2-2 parts of nitration reaction assistant into 300-500 parts of concentrated sulfuric acid and concentrated nitric acid mixed acid, at a temperature of 35-55 ℃, The reaction is stirred for 60-120min, and after washing and drying, the obtained 1-aminopropyl-3-methylimidazole nitrate is added to 200-500 parts of a reducing agent solution with a mass fraction of 5%-10%, and controlled temperature at 60-80°C, stirring and reacting for 4-8h, washing after filtration, vacuum drying at 60-80°C for 5-10h, and adding the obtained aminated polystyrene to 500-800 parts of N,N-diphenylene In methylformamide, slowly add to the reaction kettle after stirring and mixing evenly; in the reaction kettle, 12-16 parts of ammonium thiocyanate, 14.6-20.3 parts of 1-carboxyethyl-3-methylformamide are preliminarily added. The imidazole hydrogen sulfate and 100-200 parts of N,N-dimethylformamide are mixed evenly, and the temperature is controlled at -5-5°C and stirred for 30-60min; the addition is completed at 20-60min, and then the temperature is raised to room temperature, The reaction is stirred for 10-18 hours. After the reaction is completed, the material is precipitated in water. After filtration, the filtrate is washed with ethanol. After drying, the polymer-type PVC heat stabilizer can be obtained.
- 根据权利要求1所述的一种聚合物型PVC热稳定剂的制备方法，其特征在于：所述的硝化反应助剂为一种金属负载固体酸助剂，其制备方法为：The preparation method of a polymer-type PVC heat stabilizer according to claim 1, wherein the nitration reaction assistant is a metal-loaded solid acid assistant, and the preparation method is:按照质量份数，将10-15份的硅胶粉在300-400℃下活化处理30-120min后冷却到室温，然后加入到14-20份的质量份数为5.4％-7.5％的五氯化钼水溶液中，室温搅拌5-20h后过滤，在80-120℃下干燥后放入到450-600℃的马弗炉中煅烧3-6h，完成后降温到室温，分散到60-80份的纯水中，将0.5-3份的四氯化锆与5-10份的乙醇混合均匀后缓慢的加入到反应釜中，控制在30-50min加完，然后搅拌反应1-5h后过滤，纯水洗涤后在100-120℃真空干燥后即可得到所述的一种金属负载固体酸助剂。According to the parts by mass, 10-15 parts of silica gel powder is activated at 300-400 ° C for 30-120 min, cooled to room temperature, and then added to 14-20 parts by mass of 5.4%-7.5% pentachloride Molybdenum aqueous solution, stirred at room temperature for 5-20h, filtered, dried at 80-120°C, put into a muffle furnace at 450-600°C for 3-6h calcination, cooled to room temperature after completion, and dispersed to 60-80 parts of In pure water, 0.5-3 parts of zirconium tetrachloride and 5-10 parts of ethanol are mixed uniformly and then slowly added to the reaction kettle, controlled to be added within 30-50 minutes, and then stirred and reacted for 1-5 hours, filtered, and purified. After washing with water and drying under vacuum at 100-120 DEG C, the metal-loaded solid acid auxiliary can be obtained.
- 根据权利要求2所述的一种聚合物型PVC热稳定剂的制备方法，其特征在于：所述的硅胶粉的粒径为500-800目。The method for preparing a polymer-type PVC heat stabilizer according to claim 2, wherein the particle size of the silica gel powder is 500-800 mesh.
- 根据权利要求2所述的一种聚合物型PVC热稳定剂的制备方法，其特征在于：所述的乙醇为无水乙醇。The preparation method of a polymer-type PVC heat stabilizer according to claim 2, wherein the ethanol is anhydrous ethanol.
- 根据权利要求1所述的一种聚合物型PVC热稳定剂的制备方法，其特征在于：所述的浓硫酸和浓硝酸的混合酸中浓硫酸和浓硝酸的体积比为1.5-2:1。The preparation method of a kind of polymer-type PVC heat stabilizer according to claim 1, is characterized in that: the volume ratio of concentrated sulfuric acid and concentrated nitric acid in the mixed acid of described concentrated sulfuric acid and concentrated nitric acid is 1.5-2:1 .
- 根据权利要求1所述的一种聚合物型PVC热稳定剂的制备方法，其特征在于：所述的还原剂为硫代硫酸钠或亚硫酸钠或亚硫酸氢钠。The preparation method of a polymer-type PVC heat stabilizer according to claim 1, wherein the reducing agent is sodium thiosulfate or sodium sulfite or sodium bisulfite.
- 根据权利要求1所述的一种聚合物型PVC热稳定剂的制备方法，其特征在于：所述的超声分散功率为1-5kW。The method for preparing a polymer-type PVC heat stabilizer according to claim 1, wherein the ultrasonic dispersion power is 1-5kW.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2020/139766 WO2022134122A1 (en) | 2020-12-26 | 2020-12-26 | Preparation method for polymeric pvc heat stabilizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2020/139766 WO2022134122A1 (en) | 2020-12-26 | 2020-12-26 | Preparation method for polymeric pvc heat stabilizer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2022134122A1 true WO2022134122A1 (en) | 2022-06-30 |
Family
ID=82157244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2020/139766 WO2022134122A1 (en) | 2020-12-26 | 2020-12-26 | Preparation method for polymeric pvc heat stabilizer |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2022134122A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116789505A (en) * | 2023-03-29 | 2023-09-22 | 万载县建坤化工有限公司 | Color reagent for fireworks and crackers and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1463792A (en) * | 2002-06-03 | 2003-12-31 | 北京石油化工学院材料与化工学院 | Novel molybdenum phosphorized hydrogenation desulfurization denitrification de-olefin catalyst and method for making same |
| CN101857579A (en) * | 2010-06-10 | 2010-10-13 | 浙江工业大学 | Synthesis method of 2-amino-5,6-dichlorobenzothiazole |
| KR20160080555A (en) * | 2014-12-30 | 2016-07-08 | 주식회사 케이씨텍 | Polishing slurry composition |
| CN105885043A (en) * | 2016-05-04 | 2016-08-24 | 江汉大学 | Preparation method of polyaniline nano-microsphere with core-shell structure |
| CN106589201A (en) * | 2015-10-15 | 2017-04-26 | 中国科学院过程工程研究所 | Hydrophilic modification method of polystyrene material and product thereof |
-
2020
- 2020-12-26 WO PCT/CN2020/139766 patent/WO2022134122A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1463792A (en) * | 2002-06-03 | 2003-12-31 | 北京石油化工学院材料与化工学院 | Novel molybdenum phosphorized hydrogenation desulfurization denitrification de-olefin catalyst and method for making same |
| CN101857579A (en) * | 2010-06-10 | 2010-10-13 | 浙江工业大学 | Synthesis method of 2-amino-5,6-dichlorobenzothiazole |
| KR20160080555A (en) * | 2014-12-30 | 2016-07-08 | 주식회사 케이씨텍 | Polishing slurry composition |
| CN106589201A (en) * | 2015-10-15 | 2017-04-26 | 中国科学院过程工程研究所 | Hydrophilic modification method of polystyrene material and product thereof |
| CN105885043A (en) * | 2016-05-04 | 2016-08-24 | 江汉大学 | Preparation method of polyaniline nano-microsphere with core-shell structure |
Non-Patent Citations (3)
| Title |
|---|
| LV CHAN-TING, ZHENG YU-BIN, LIU JIAN-PING: "Synthesis of a Novel Polymeric Organic Thermal Stabilizer for PVC", CHINESE JOURNAL OF SYNTHETIC CHEMISTRY, vol. 15, no. 6, 20 December 2007 (2007-12-20), CN , pages 768 - 770, XP055946633, ISSN: 1005-1511 * |
| LV DONG-WEI,XIAO LIN-FEI,SU DAN,LIU DAN,WU WEI(: "Immobilized BrФnsted ionic liquids:Heterogeneous catalyst for synthesis of cyclic carbonates from carbon dioxide and epoxides", MODERN CHEMICAL INDUSTRY, vol. 31, no. S1, 30 June 2011 (2011-06-30), pages 271 - 274+276, XP009537750, ISSN: 0253-4320, DOI: 10.16606/j.cnki.issn0253-4320.2011.s1.080 * |
| WU JINMING,TANG YANFENG,SHEN AIBAO: "Synthesis of 5-Nitrosalicylaldehyde Catalyzed by H6PMo9V3O40 Supported on Silica Gel", CHINESE JOURNAL OF APPLIED CHEMISTRY, vol. 29, no. 5, 10 May 2012 (2012-05-10), pages 545 - 550, XP055946634, ISSN: 1000-0518, DOI: 10.3724/SP.J.1095.2012.00263 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116789505A (en) * | 2023-03-29 | 2023-09-22 | 万载县建坤化工有限公司 | Color reagent for fireworks and crackers and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2021208596A1 (en) | Catalyst for ozone decomposition, preparation method therefor and use thereof | |
| CN103551201B (en) | A kind of preparation method of copper hydroxyphosphate catalyst | |
| WO2023035886A1 (en) | Method for producing cuprous chloride through high-value utilization of chlorine ion-containing wastewater | |
| WO2022134122A1 (en) | Preparation method for polymeric pvc heat stabilizer | |
| CN103145189B (en) | Preparation method of potassium ferrate | |
| CN106311163B (en) | A kind of preparation method of the chitosan of arsenic-adsorbing/iron hydroxide compound adsorbent | |
| CN112547099A (en) | Low-temperature cerium-based sulfur-resistant water-resistant denitration catalyst and preparation method thereof | |
| CN106311280A (en) | Copper sulfide containing mercury removal agent and preparation method thereof | |
| WO2019144475A1 (en) | Method for preparing high-valence iron salt | |
| CN111333741A (en) | High molecular compound dechlorinating agent and preparation method thereof | |
| CN109603861B (en) | Ag-AgICl/Bi3O4Br0.5Cl0.5Composite photocatalyst and preparation method and application thereof | |
| CN111804300A (en) | Ozone oxidation catalyst for advanced treatment of organic wastewater and preparation method thereof | |
| CN113797942B (en) | Phosphorus-modified copper-based catalyst for hydrochlorination of acetylene as well as preparation method and application thereof | |
| CN111921516B (en) | Preparation method of photocatalyst with super-strong degradation effect | |
| CN105396598B (en) | Preparation method and application of low-temperature denitration Ni-based composite oxide honeycomb monolithic catalyst | |
| CN108786866A (en) | A kind of catalyst without mercury and preparation method thereof for acetylene method synthesis vinyl chloride thereof | |
| US3514270A (en) | Manufacture of bismuth magnesium aluminosilicate | |
| CN103537308B (en) | Preparation method of tetrahydroxy copper phosphate catalyst | |
| CN108435136B (en) | Preparation method of printing and dyeing wastewater quick decolorizing agent | |
| CN113318768A (en) | Composite photocatalyst and preparation method thereof | |
| CN113214120A (en) | Preparation method of perfluorohexyl ethyl sulfonate | |
| CN106928466B (en) | Preparation method of Cr-MOFs | |
| CN112889837A (en) | Transition metal solid acid air bactericide and preparation method and application thereof | |
| CN110776477A (en) | Method for preparing DM by oxidizing M with hydrogen peroxide | |
| CN112090427A (en) | Low steam-gas ratio carbon monoxide high-temperature shift catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 20966685 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 20966685 Country of ref document: EP Kind code of ref document: A1 |
|
| 32PN | Ep: public notification in the ep bulletin as address of the adressee cannot be established |
Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 27/11/2023) |