CN112279964A - Method for preparing modified m-pentadiene petroleum resin by using composite catalyst - Google Patents
Method for preparing modified m-pentadiene petroleum resin by using composite catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 229920005989 resin Polymers 0.000 title claims abstract description 42
- 239000011347 resin Substances 0.000 title claims abstract description 42
- 239000003208 petroleum Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 60
- 239000000203 mixture Substances 0.000 claims abstract description 52
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 46
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000003756 stirring Methods 0.000 claims abstract description 43
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 42
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 33
- 239000010439 graphite Substances 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 31
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 30
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 claims abstract description 30
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 30
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 24
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 claims abstract description 23
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 22
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 18
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- GAODDBNJCKQQDY-UHFFFAOYSA-N 2-methyl-4,6-bis(octylsulfanylmethyl)phenol Chemical compound CCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCC)=C1 GAODDBNJCKQQDY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 15
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 15
- 229910052786 argon Inorganic materials 0.000 claims abstract description 15
- 239000004611 light stabiliser Substances 0.000 claims abstract description 15
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 14
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 12
- 239000008096 xylene Substances 0.000 claims abstract description 12
- 230000003213 activating effect Effects 0.000 claims abstract description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000010992 reflux Methods 0.000 claims abstract description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 11
- 238000007598 dipping method Methods 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000178 monomer Substances 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 abstract 2
- 238000002791 soaking Methods 0.000 description 6
- 238000002604 ultrasonography Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- -1 coatings Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
Classifications
-
- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers
-
- 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
- C08K2003/2255—Oxides; Hydroxides of metals of molybdenum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention discloses a method for preparing modified m-pentadiene petroleum resin by using a composite catalyst, which comprises the following steps: uniformly mixing aluminum nitrate and anhydrous methanol, adding water and expanded graphite for impregnation, dropwise adding ammonia water, stirring, carrying out ultrasonic treatment, standing, washing, filtering, activating, then adding a sodium carbonate aqueous solution for impregnation, drying and roasting to obtain a material A; under the protection of argon, anhydrous aluminum trichloride and xylene are mixed, added into the material A, heated to reflux, stirred, filtered, washed and dried, and then mixed with phosphoric acid and SbCl3Mixing to obtain a composite catalyst; cyclohexane is used as a solvent, a composite catalyst is used as a catalyst, a pentadiene raw material, styrene, 2-methyl-1-butene and myrcene are used as monomers to carry out polymerization reaction, and the mixture is mixed with an antioxidant 1520, a light stabilizer Tinuvin 622LD, an antioxidant DTDTP, expandable graphite, molybdenum trioxide and N-phenyl-alpha naphthylamine after post-treatment, stirred at the temperature of 160-180 ℃ and cooled.
Description
Technical Field
The invention relates to the technical field of petroleum resin, in particular to a method for preparing modified m-pentadiene petroleum resin by using a composite catalyst.
Background
Pentadiene petroleum resin is one of C5 aliphatic petroleum resins, and because it has good compatibility to oil products, grease and synthetic resins, it can be dissolved in many solvents, and after being mixed with other substances, it has good water resistance, acid resistance, low melting point and good adhesion, and it has been widely used in the industries of adhesives, coatings, rubber tires, paper making, etc. Piperylene petroleum resin has many advantages, but also has the defects of low softening point, poor thermo-oxidative stability of unsaturated double bonds contained in a molecular structure and the like, and the application of piperylene petroleum resin in many fields is limited.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a method for preparing modified m-pentadiene petroleum resin by using a composite catalyst, the process is simple, the resin yield is high, the obtained resin has high softening point, good compatibility with other polymers and excellent thermal-oxidative-aging resistance.
The invention provides a method for preparing modified pentadiene petroleum resin by using a composite catalyst, which comprises the following steps:
s1, uniformly mixing aluminum nitrate and anhydrous methanol, adding water and expanded graphite, stirring and dipping for 40-60min, dropwise adding ammonia water, stirring for 10-20min, carrying out ultrasonic treatment for 30-60min, standing, washing, filtering, activating at 165 ℃ for 120-180min, then adding sodium carbonate aqueous solution, dipping for 2-5h, vacuum drying, and roasting for 2-4h under the conditions of 600 ℃ and argon protection to obtain a material A;
s2, under the protection of argon, mixing anhydrous aluminum trichloride with xylene, adding the mixture into the material A, heating the mixture to reflux, stirring the mixture for reaction for 8 to 10 hours, and filtering, washing and drying the mixture after the reaction is finished to obtain a material B;
s3, mixing the material B, phosphoric acid and SbCl3According to the weight ratio of 70-95: 2-4: 9-15 to obtain the composite catalyst;
s4, adding cyclohexane into a reaction device, introducing nitrogen, adding a composite catalyst, stirring and heating to 45-50 ℃, dropwise adding a mixture of a m-pentadiene raw material, styrene, 2-methyl-1-butene and myrcene, continuously stirring and reacting at 45-50 ℃ for 30-60min after the dropwise adding is finished, filtering after the reaction is finished, and washing, distilling and cooling the filtrate to obtain a material C;
s5, mixing the material C with an antioxidant 1520, a light stabilizer Tinuvin 622LD, an antioxidant DTDTP, expandable graphite, molybdenum trioxide and N-phenyl-alpha naphthylamine, stirring for 30-50min at the temperature of 160-180 ℃, and cooling to obtain the modified pentadiene petroleum resin.
Preferably, in S1, the expanded graphite has an expanded volume of 300-400 mL/g.
Preferably, in S1, the standing time is 3-5 h; the power of the ultrasonic wave is 500-550W.
Preferably, in S1, the concentration of the sodium carbonate aqueous solution is 1.5-2.5 mol/L.
Preferably, in S1, the weight ratio of aluminum nitrate, anhydrous methanol, water, expanded graphite and ammonia water is 1-2: 100-200: 800-1300: 4-8: 300-500.
Preferably, in S1, the dropping speed of the ammonia water is 3.5-5 g/min.
Preferably, in S2, the weight ratio of anhydrous aluminum trichloride to xylene to the material A is 3-5: 80-120: 5-10.
Preferably, in S4, the weight ratio of cyclohexane, composite catalyst, piperylene raw material, styrene, 2-methyl-1-butene, myrcene is 80-100: 2-5: 70-85: 2-9: 1-3: 1-5.
Preferably, in S4, the time for dropping the mixture of piperylene raw material, styrene, 2-methyl-1-butene and myrcene is 60-90min, 30-40% of the mass of the mixture is dropped for the first 20-30min, 15-25% of the mass of the mixture is dropped for the middle 10-20min, and the rest of the mixture is dropped for the rest.
Preferably, in S5, the weight ratio of the material C, the antioxidant 1520, the light stabilizer Tinuvin 622LD, the antioxidant DTDTDTDTP, the expandable graphite, the molybdenum trioxide and the N-phenyl-alpha naphthylamine is 100: 0.05-0.12: 0.01-0.1: 0.01-0.3: 0.5-3: 0.1-1: 0.01-0.12.
Preferably, the piperylene feedstock is a by-product of ethylene having a piperylene content of 65-74% by weight.
Preferably, the temperature is maintained at 45-50 ℃ during the dropping of the mixture of piperylene raw material, styrene, 2-methyl-1-butene and myrcene.
The method for preparing modified pentadiene petroleum resin by using the composite catalyst comprises the steps of firstly using aluminum nitrate and expanded graphite as raw materials, controlling reaction conditions, loading alumina on the surface of the expanded graphite, then activating at the temperature of 150-165 ℃ for 120-180min, dipping in a sodium carbonate aqueous solution, obtaining a material A after roasting, wherein the material A has large specific surface area and more active sites, and after being mixed with aluminum trichloride, the material A has high loading amount, can reduce the contact between the aluminum trichloride and water, improves the thermal stability of the material A, and can be mixed with phosphoric acid and SbCl3According to the weight ratio of 70-95: 2-4: the composite catalyst obtained by mixing the 9-15 weight ratio is used as a catalyst for preparing m-pentadiene petroleum resin, the catalytic activity is high, and the resin yield is high; styrene, 2-methyl-1-butene, myrcene and piperylene are specifically selected to be matched as polymerization monomers, the obtained resin has high softening point and good compatibility with other polymers, and then an antioxidant 1520, a light stabilizer Tinuvin 622LD, an antioxidant DTDTDTP, expandable graphite, molybdenum trioxide and N-phenyl-alpha naphthylamine are added, so that the performances of all the substances are cooperated, the optimal matching effect is exerted, and the styrene, the 2-methyl-1-butene, the myrcene and the piperylene are endowed with the best matching effectThe resin has excellent thermo-oxidative aging resistance, weather resistance and storage stability; the softening point of the finished resin product prepared by the method is more than or equal to 126 ℃ (the softening point is measured by adopting the method specified in GB/T4507-84), and the resin yield is more than or equal to 88.3%; heating at 190 deg.C for 4h with Gardner color number change of 1.2 or less, and storing at 40 deg.C for 15d with Gardner color number change of 1 or less; and (3) weather resistance test: the Gardner color number change is less than or equal to 1.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A method for preparing modified m-pentadiene petroleum resin by utilizing a composite catalyst comprises the following steps:
s1, uniformly mixing aluminum nitrate and anhydrous methanol, adding water and expanded graphite, stirring and dipping for 60min, dropwise adding ammonia water, stirring for 10min, carrying out ultrasonic treatment for 60min, standing, washing, filtering, activating at 156 ℃ for 120min, then adding a sodium carbonate aqueous solution, dipping for 5h, vacuum drying, and roasting for 4h under the conditions of 500 ℃ and argon protection to obtain a material A;
s2, under the protection of argon, mixing anhydrous aluminum trichloride with xylene, adding the mixture into the material A, heating the mixture to reflux, stirring the mixture for reaction for 8 hours, and filtering, washing and drying the mixture after the reaction is finished to obtain a material B;
s3, mixing the material B, phosphoric acid and SbCl3According to the following steps of 80: 4: 9 to obtain a composite catalyst;
s4, adding cyclohexane into a reaction device, introducing nitrogen, adding a composite catalyst, stirring and heating to 45 ℃, dropwise adding a mixture of a m-pentadiene raw material, styrene, 2-methyl-1-butene and myrcene, continuously stirring and reacting at 45 ℃ for 30min after dropwise adding, filtering after the reaction is finished, and washing, distilling and cooling the filtrate to obtain a material C;
and S5, mixing the material C with an antioxidant 1520, a light stabilizer Tinuvin 622LD, an antioxidant DTDTDTP, expandable graphite, molybdenum trioxide and N-phenyl-alpha naphthylamine, stirring for 50min at 160 ℃, and cooling to obtain the modified pentadiene petroleum resin.
Example 2
A method for preparing modified m-pentadiene petroleum resin by utilizing a composite catalyst comprises the following steps:
s1, uniformly mixing aluminum nitrate and anhydrous methanol, adding water and expanded graphite with an expansion volume of 400mL/g, stirring and soaking for 40min, dropwise adding ammonia water, and stirring for 20min, wherein the weight ratio of the aluminum nitrate to the anhydrous methanol to the water to the expanded graphite to the ammonia water is 2: 200: 1000: 8: 300, dropwise adding ammonia water at a speed of 3.5g/min, performing ultrasound for 30min, wherein the power of the ultrasound is 550W, standing for 3h, washing, filtering, activating at 165 ℃ for 130min, then adding a sodium carbonate aqueous solution with the concentration of 1.5mol/L, soaking for 2h, performing vacuum drying, and roasting for 2h at 600 ℃ under the protection of argon to obtain a material A;
s2, under the protection of argon, mixing anhydrous aluminum trichloride and xylene, and adding the mixture into a material A, wherein the weight ratio of the anhydrous aluminum trichloride to the xylene to the material A is 3: 120: 5, heating to reflux, stirring for reaction for 9 hours, and filtering, washing and drying after the reaction is finished to obtain a material B;
s3, mixing the material B, phosphoric acid and SbCl3According to the following steps of 95: 2: 15 to obtain a composite catalyst;
s4, adding cyclohexane into a reaction device, introducing nitrogen, adding a composite catalyst, stirring and heating to 50 ℃, dropwise adding a mixture of a m-pentadiene raw material, styrene, 2-methyl-1-butene and myrcene, wherein the weight ratio of the cyclohexane to the composite catalyst to the m-pentadiene raw material to the styrene to the 2-methyl-1-butene to the myrcene is 80: 5: 70: 7: 1: 1, continuously stirring and reacting at 50 ℃ for 60min after the dropwise addition is finished, filtering after the reaction is finished, and washing, distilling and cooling the filtrate to obtain a material C; wherein, the time for dripping the mixture of the m-pentadiene raw material, the styrene, the 2-methyl-1-butene and the myrcene is 60min, 40 percent of the mass of the mixture is dripped in the first 30min, 15 percent of the mass of the mixture is dripped in the middle 20min, and the rest of the mixture is dripped in the rest time;
s5, mixing the material C with an antioxidant 1520, a light stabilizer Tinuvin 622LD, an antioxidant DTDTP, expandable graphite, molybdenum trioxide and N-phenyl-alpha naphthylamine, wherein the weight ratio of the material C to the antioxidant 1520 to the light stabilizer Tinuvin 622LD, the antioxidant DTDTP to the expandable graphite to the molybdenum trioxide to the N-phenyl-alpha naphthylamine is 100: 0.12: 0.01: 0.3: 0.5: 1: 0.01, stirring for 30min at 180 ℃, and cooling to obtain the modified piperylene petroleum resin.
Example 3
A method for preparing modified m-pentadiene petroleum resin by utilizing a composite catalyst comprises the following steps:
s1, uniformly mixing aluminum nitrate and anhydrous methanol, adding water and expanded graphite with an expansion volume of 300mL/g, stirring and soaking for 46min, dropwise adding ammonia water, and stirring for 18min, wherein the weight ratio of the aluminum nitrate to the anhydrous methanol to the water to the expanded graphite to the ammonia water is 1.2: 100: 800: 4: 500, dropwise adding ammonia water at a speed of 5g/min, performing ultrasound for 38min at a power of 500W, standing for 5h, washing, filtering, activating at 150 ℃ for 180min, adding a 2mol/L sodium carbonate aqueous solution, soaking for 4h, performing vacuum drying, and roasting at 520 ℃ for 3.3h under the protection of argon to obtain a material A;
s2, under the protection of argon, mixing anhydrous aluminum trichloride and xylene, and adding the mixture into a material A, wherein the weight ratio of the anhydrous aluminum trichloride to the xylene to the material A is 5: 80: 7, heating to reflux, stirring for reaction for 10 hours, and filtering, washing and drying after the reaction is finished to obtain a material B;
s3, mixing the material B, phosphoric acid and SbCl3According to the proportion of 70: 2.7: 11 to obtain a composite catalyst;
s4, adding cyclohexane into a reaction device, introducing nitrogen, adding a composite catalyst, stirring and heating to 46 ℃, dropwise adding a mixture of a m-pentadiene raw material, styrene, 2-methyl-1-butene and myrcene, wherein the weight ratio of the cyclohexane to the composite catalyst to the m-pentadiene raw material to the styrene to the 2-methyl-1-butene to the myrcene is 100: 2: 85: 4: 2: 5, continuously stirring and reacting at 46 ℃ for 40min after the dropwise addition is finished, filtering after the reaction is finished, and washing, distilling and cooling the filtrate to obtain a material C; wherein, the time for dripping the mixture of the m-pentadiene raw material, the styrene, the 2-methyl-1-butene and the myrcene is 90min, 40 percent of the mass of the mixture is dripped in the first 20min, 15 percent of the mass of the mixture is dripped in the middle 10min, and the rest of the mixture is dripped in the rest time;
s5, mixing the material C with an antioxidant 1520, a light stabilizer Tinuvin 622LD, an antioxidant DTDTP, expandable graphite, molybdenum trioxide and N-phenyl-alpha naphthylamine, wherein the weight ratio of the material C to the antioxidant 1520 to the light stabilizer Tinuvin 622LD, the antioxidant DTDTP to the expandable graphite to the molybdenum trioxide to the N-phenyl-alpha naphthylamine is 100: 0.05: 0.1: 0.01: 3: 0.1: 0.12, stirring for 42min at 168 ℃, and cooling to obtain the modified piperylene petroleum resin.
Example 4
A method for preparing modified m-pentadiene petroleum resin by utilizing a composite catalyst comprises the following steps:
s1, uniformly mixing aluminum nitrate and anhydrous methanol, adding water and expanded graphite, stirring and dipping for 55min, dropwise adding ammonia water, and stirring for 13min, wherein the weight ratio of the aluminum nitrate to the anhydrous methanol to the water to the expanded graphite to the ammonia water is 1: 130: 1300: 6: 410, dropwise adding ammonia water at a speed of 4.1g/min, performing ultrasound for 55min, wherein the power of the ultrasound is 550W, standing for 3.5h, washing, filtering, activating at 150 ℃ for 140min, then adding a sodium carbonate aqueous solution with the concentration of 2.5mol/L, soaking for 3h, performing vacuum drying, and roasting for 2.5h at 600 ℃ under the protection of argon gas to obtain a material A;
s2, under the protection of argon, mixing anhydrous aluminum trichloride with xylene, adding the mixture into the material A, heating to reflux, stirring to react for 8.5 hours, and filtering, washing and drying after the reaction is finished to obtain a material B; wherein, the weight ratio of the anhydrous aluminum trichloride, the dimethylbenzene to the material A is 3.8: 110: 10;
s3, mixing the material B, phosphoric acid and SbCl3According to a formula of 77: 3: 12 to obtain a composite catalyst;
s4, adding cyclohexane into a reaction device, introducing nitrogen, adding a composite catalyst, stirring and heating to 49 ℃, dropwise adding a mixture of a m-pentadiene raw material, styrene, 2-methyl-1-butene and myrcene, continuously stirring and reacting at 49 ℃ for 55min after dropwise adding, filtering after the reaction is finished, and washing, distilling and cooling the filtrate to obtain a material C; wherein the weight ratio of cyclohexane, composite catalyst, pentadiene raw material, styrene, 2-methyl-1-butene and myrcene is 92: 3: 80: 2: 1.7: 2; dripping the mixture of m-pentadiene raw material, styrene, 2-methyl-1-butene and myrcene for 70min, dripping 40% of the mixture in the first 20min, dripping 25% of the mixture in the middle 10min, and dripping the rest of the mixture in the rest time;
s5, mixing the material C with an antioxidant 1520, a light stabilizer Tinuvin 622LD, an antioxidant DTDTP, expandable graphite, molybdenum trioxide and N-phenyl-alpha naphthylamine, stirring for 38min at 172 ℃, and cooling to obtain the modified pentadiene petroleum resin; wherein the weight ratio of the material C, the antioxidant 1520, the light stabilizer Tinuvin 622LD, the antioxidant DTDTP, the expandable graphite, the molybdenum trioxide and the N-phenyl-alpha naphthylamine is 100: 0.1: 0.03: 0.21: 0.7: 0.9: 0.05.
example 5
A method for preparing modified m-pentadiene petroleum resin by utilizing a composite catalyst comprises the following steps:
s1, uniformly mixing aluminum nitrate and anhydrous methanol, adding water and expanded graphite, stirring and dipping for 40min, dropwise adding ammonia water, and stirring for 15min, wherein the weight ratio of the aluminum nitrate to the anhydrous methanol to the water to the expanded graphite to the ammonia water is 1.2: 170: 900: 7: performing ultrasonic treatment for 50min at 350, standing, washing, filtering, activating at 160 ℃ for 150min, adding a sodium carbonate aqueous solution, soaking for 2h, performing vacuum drying, and roasting for 3.5h at 550 ℃ under the protection of argon gas to obtain a material A; wherein the standing time is 4 hours; the power of the ultrasonic wave is 520W; the concentration of the sodium carbonate aqueous solution is 1.8 mol/L; the dropping speed of the ammonia water is 4.7 g/min;
s2, under the protection of argon, mixing anhydrous aluminum trichloride with xylene, adding the mixture into the material A, heating the mixture to reflux, stirring the mixture for reaction for 8 hours, and filtering, washing and drying the mixture after the reaction is finished to obtain a material B; wherein, the weight ratio of anhydrous aluminum trichloride, dimethylbenzene to the material A is 4.3: 90: 8;
s3, mixing the material B, phosphoric acid and SbCl3According to the following steps of 90: 3: 11 to obtain a composite catalyst;
s4, adding cyclohexane into a reaction device, introducing nitrogen, adding a composite catalyst, stirring and heating to 45 ℃, dropwise adding a mixture of a m-pentadiene raw material, styrene, 2-methyl-1-butene and myrcene, continuously stirring and reacting for 45min at 45 ℃ after dropwise adding, filtering after the reaction is finished, and washing, distilling and cooling the filtrate to obtain a material C; wherein the weight ratio of cyclohexane, composite catalyst, pentadiene raw material, styrene, 2-methyl-1-butene and myrcene is 85: 4: 78: 9: 3: 3; the time for dripping the mixture of the m-pentadiene raw material, the styrene, the 2-methyl-1-butene and the myrcene is 80min, 30% of the mass of the mixture is dripped in the first 30min, 15% of the mass of the mixture is dripped in the middle 20min, and the rest of the mixture is dripped in the rest time;
s5, mixing the material C with an antioxidant 1520, a light stabilizer Tinuvin 622LD, an antioxidant DTDTP, expandable graphite, molybdenum trioxide and N-phenyl-alpha naphthylamine, stirring for 45min at 170 ℃, and cooling to obtain the modified pentadiene petroleum resin; wherein the weight ratio of the material C, the antioxidant 1520, the light stabilizer Tinuvin 622LD, the antioxidant DTDTP, the expandable graphite, the molybdenum trioxide and the N-phenyl-alpha naphthylamine is 100: 0.08: 0.08: 0.1: 2.3: 0.4: 0.1.
the above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A method for preparing modified m-pentadiene petroleum resin by utilizing a composite catalyst is characterized by comprising the following steps:
s1, uniformly mixing aluminum nitrate and anhydrous methanol, adding water and expanded graphite, stirring and dipping for 40-60min, dropwise adding ammonia water, stirring for 10-20min, carrying out ultrasonic treatment for 30-60min, standing, washing, filtering, activating at 165 ℃ for 120-180min, then adding sodium carbonate aqueous solution, dipping for 2-5h, vacuum drying, and roasting for 2-4h under the conditions of 600 ℃ and argon protection to obtain a material A;
s2, under the protection of argon, mixing anhydrous aluminum trichloride with xylene, adding the mixture into the material A, heating the mixture to reflux, stirring the mixture for reaction for 8 to 10 hours, and filtering, washing and drying the mixture after the reaction is finished to obtain a material B;
s3, mixing the material B, phosphoric acid and SbCl3According to the weight ratio of 70-95: 2-4: 9-15 to obtain the composite catalyst;
s4, adding cyclohexane into a reaction device, introducing nitrogen, adding a composite catalyst, stirring and heating to 45-50 ℃, dropwise adding a mixture of a m-pentadiene raw material, styrene, 2-methyl-1-butene and myrcene, continuously stirring and reacting at 45-50 ℃ for 30-60min after the dropwise adding is finished, filtering after the reaction is finished, and washing, distilling and cooling the filtrate to obtain a material C;
s5, mixing the material C with an antioxidant 1520, a light stabilizer Tinuvin 622LD, an antioxidant DTDTP, expandable graphite, molybdenum trioxide and N-phenyl-alpha naphthylamine, stirring for 30-50min at the temperature of 160-180 ℃, and cooling to obtain the modified pentadiene petroleum resin.
2. The method for preparing modified piperylene petroleum resin using composite catalyst as claimed in claim 1, wherein the expanded volume of the expanded graphite is 300-400mL/g in S1.
3. The method for preparing a modified piperylene petroleum resin using the composite catalyst as claimed in claim 1, wherein the standing time is 3-5h in S1; the power of the ultrasonic wave is 500-550W.
4. The method for preparing a modified piperylene petroleum resin using the composite catalyst as claimed in claim 1, wherein the concentration of the sodium carbonate aqueous solution is 1.5-2.5mol/L in S1.
5. The method for preparing modified piperylene petroleum resin using composite catalyst as claimed in claim 1, wherein in S1, the weight ratio of aluminum nitrate, anhydrous methanol, water, expanded graphite, ammonia water is 1-2: 100-200: 800-1300: 4-8: 300-500.
6. The method for preparing a modified piperylene petroleum resin using the composite catalyst as claimed in claim 1, wherein the dropping speed of the ammonia water in S1 is 3.5-5 g/min.
7. The method for preparing modified piperylene petroleum resin using composite catalyst as claimed in claim 1, wherein in S2, the weight ratio of anhydrous aluminum trichloride, xylene, material a is 3-5: 80-120: 5-10.
8. The method for preparing modified piperylene petroleum resin using composite catalyst as claimed in claim 1, wherein in S4, the weight ratio of cyclohexane, composite catalyst, piperylene raw material, styrene, 2-methyl-1-butene, myrcene is 80-100: 2-5: 70-85: 2-9: 1-3: 1-5.
9. The method for preparing a modified piperylene petroleum resin using the composite catalyst as claimed in claim 1, wherein in S4, the time for dropping the mixture of the piperylene raw material, styrene, 2-methyl-1-butene and myrcene is 60-90min, and 30-40% of the mass of the mixture is dropped for the first 20-30min, 15-25% of the mass of the mixture is dropped for the middle 10-20min, and the remaining mixture is dropped for the remaining time.
10. The method for preparing modified piperylene petroleum resin using composite catalyst according to any one of claims 1 to 9, wherein in S5, the weight ratio of material C, antioxidant 1520, light stabilizer Tinuvin 622LD, antioxidant DTDTP, expandable graphite, molybdenum trioxide, N-phenyl-alpha naphthylamine is 100: 0.05-0.12: 0.01-0.1: 0.01-0.3: 0.5-3: 0.1-1: 0.01-0.12.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1304038A (en) * | 1970-04-24 | 1973-01-24 | ||
| US4098982A (en) * | 1977-03-08 | 1978-07-04 | Arizona Chemical Company | Cationic polymerization of piperylene using as the catalyst system an aluminum halide and an inorganic phosphoric acid |
| JPH01158012A (en) * | 1987-08-19 | 1989-06-21 | Asahi Chem Ind Co Ltd | Production of conjugated diene based polymers |
| CN1249732A (en) * | 1997-01-08 | 2000-04-05 | 赫尔克里士公司 | Solid acids as catalyst for preparation of hydrocarbon resins |
| JP2001354727A (en) * | 2000-06-15 | 2001-12-25 | Idemitsu Petrochem Co Ltd | Styrene copolymer and manufacturing method therefor |
| CN1518561A (en) * | 2001-05-04 | 2004-08-04 | Random or block co-or terpolymers produced by using of metal complex catalysts | |
| CN102351990A (en) * | 2011-07-29 | 2012-02-15 | 长春工业大学 | Method for preparing m-pentadiene petroleum resin |
| CN102399346A (en) * | 2011-07-29 | 2012-04-04 | 长春工业大学 | Catalysis system and method for preparing m-pentadiene petroleum resin |
| CN104277179A (en) * | 2014-09-24 | 2015-01-14 | 中国石油化工股份有限公司 | Method for producing pentadiene petroleum resin by employing free radical thermal polymerization |
| CN106459328A (en) * | 2014-04-02 | 2017-02-22 | 科腾聚合物美国有限责任公司 | Block copolymers containing a copolymer myrcene block |
-
2020
- 2020-10-29 CN CN202011176635.9A patent/CN112279964A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1304038A (en) * | 1970-04-24 | 1973-01-24 | ||
| US4098982A (en) * | 1977-03-08 | 1978-07-04 | Arizona Chemical Company | Cationic polymerization of piperylene using as the catalyst system an aluminum halide and an inorganic phosphoric acid |
| JPH01158012A (en) * | 1987-08-19 | 1989-06-21 | Asahi Chem Ind Co Ltd | Production of conjugated diene based polymers |
| CN1249732A (en) * | 1997-01-08 | 2000-04-05 | 赫尔克里士公司 | Solid acids as catalyst for preparation of hydrocarbon resins |
| JP2001354727A (en) * | 2000-06-15 | 2001-12-25 | Idemitsu Petrochem Co Ltd | Styrene copolymer and manufacturing method therefor |
| CN1518561A (en) * | 2001-05-04 | 2004-08-04 | Random or block co-or terpolymers produced by using of metal complex catalysts | |
| CN102351990A (en) * | 2011-07-29 | 2012-02-15 | 长春工业大学 | Method for preparing m-pentadiene petroleum resin |
| CN102399346A (en) * | 2011-07-29 | 2012-04-04 | 长春工业大学 | Catalysis system and method for preparing m-pentadiene petroleum resin |
| CN106459328A (en) * | 2014-04-02 | 2017-02-22 | 科腾聚合物美国有限责任公司 | Block copolymers containing a copolymer myrcene block |
| CN104277179A (en) * | 2014-09-24 | 2015-01-14 | 中国石油化工股份有限公司 | Method for producing pentadiene petroleum resin by employing free radical thermal polymerization |
Non-Patent Citations (4)
| Title |
|---|
| 何杰等主编: "《工业催化》", 31 July 2014, 中国矿业大学出版社 * |
| 汪多仁编著: "《新型粘合剂与涂料化学品》", 31 May 2000, 中国建材工业出版社 * |
| 郑春满等编著: "《高等合成化学——方法与实践》", 30 September 2018, 国防工业出版社 * |
| 陈连璋编著: "《沸石分子筛催化》", 31 December 1990, 大连理工大学出版社 * |
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