CN112250794A - Preparation method of modified m-pentadiene petroleum resin - Google Patents
Preparation method of modified m-pentadiene petroleum resin Download PDFInfo
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- 229920005989 resin Polymers 0.000 title claims abstract description 49
- 239000011347 resin Substances 0.000 title claims abstract description 49
- 239000003208 petroleum Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 66
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000203 mixture Substances 0.000 claims abstract description 65
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical class Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 57
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000003756 stirring Methods 0.000 claims abstract description 43
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical class C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims abstract description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002994 raw material Substances 0.000 claims abstract description 34
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229940087305 limonene Drugs 0.000 claims abstract description 33
- 235000001510 limonene Nutrition 0.000 claims abstract description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 19
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 18
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000000706 filtrate Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000001256 steam distillation Methods 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229920006112 polar polymer Polymers 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F240/00—Copolymers of hydrocarbons and mineral oils, e.g. petroleum resins
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method of modified pentadiene petroleum resin, which comprises the following steps: adding n-hexane into the device, introducing nitrogen, adding a catalyst, stirring and heating to 40-45 ℃, dropwise adding a mixture of a piperylene raw material, styrene, isoamylene and limonene, stirring for 30-50min at 40-50 ℃, filtering, washing and distilling the filtrate, and cooling to obtain the modified piperylene petroleum resin; the catalyst is a mixture of modified aluminum chloride and phosphoric acid, and the modified aluminum chloride is prepared by the following process: adding anhydrous aluminum trichloride into anhydrous ethanol, stirring at 8-15 ℃, dropwise adding a mixture of dimethylformamide and 1, 4-naphthalenedicarboxylic acid, stirring, adding silicon dioxide and activated carbon, standing for 5-10h, drying, and roasting at 200-300 ℃ for 3-5 h. The preparation method of the modified pentadiene petroleum resin provided by the invention has the advantages of simple process, high yield, low chroma of the obtained resin, high softening point, good compatibility and good tackifying property.
Description
Technical Field
The invention relates to the technical field of petroleum resin, in particular to a preparation method of modified pentadiene petroleum resin.
Background
The m-pentadiene petroleum resin is aliphatic C5 petroleum resin obtained by polymerization of m-pentadiene as a raw material, has the characteristics of light color, low density, high saturation and the like, has better tackifying property, thermal stability and lighter color compared with alicyclic C5 petroleum resin, copolymer resin of C5 and C9 fractions and the like, and is widely used in the industries of adhesives, hot-melt road marking paints, coatings, printing ink, rubber auxiliaries and the like at present. In recent years, along with the expansion of the application field of petroleum resin and the increase of market demand, higher requirements are put on the performance of piperylene petroleum resin, and the application of the conventional piperylene petroleum resin is limited due to the defects of low softening point, poor compatibility with other polar polymers due to lack of polar groups and slightly insufficient tackifying effect.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a preparation method of modified pentadiene petroleum resin, which has the advantages of simple process, high yield, low chroma of the obtained resin, high softening point, good compatibility and good tackifying property.
The invention provides a preparation method of modified pentadiene petroleum resin, which comprises the following steps: adding n-hexane into a reaction device, introducing nitrogen, adding a catalyst, stirring and heating to 40-45 ℃, dropwise adding a mixture of a piperylene raw material, styrene, isoamylene and limonene, stirring and reacting at 40-50 ℃ for 30-50min after dropwise adding is finished, filtering after the reaction is finished, washing and distilling filtrate, and cooling to obtain the modified piperylene petroleum resin;
wherein the catalyst is a mixture of modified aluminum chloride and phosphoric acid, and the weight ratio of the modified aluminum chloride to the phosphoric acid is 80-95: 2-4; the modified aluminum chloride is prepared according to the following process: adding anhydrous aluminum trichloride into anhydrous ethanol, stirring uniformly at the temperature of 8-15 ℃, dropwise adding a mixture of dimethylformamide and 1, 4-naphthalenedicarboxylic acid, stirring, adding silicon dioxide and activated carbon, standing for 5-10h, drying, and roasting at the temperature of 200-300 ℃ for 3-5h to obtain the modified aluminum chloride.
Preferably, the rotation speed of the stirring is 300-450 r/min.
Preferably, in the mixture of the piperylene raw material, the styrene, the isoamylene and the limonene, the weight ratio of the piperylene raw material, the styrene, the isoamylene and the limonene is 10-20: 1-2: 1-4: 3-7.
Preferably, the weight ratio of the piperylene raw material, the mixture of styrene, isoamylene and limonene, the catalyst and the normal hexane is 100: 4.5-7: 100-150.
Preferably, during the process of dripping the mixture of the m-pentadiene raw material, the styrene, the isoamylene and the limonene, the dripping time is 65-75min, 8-10% of the weight of the mixture is dripped in the first 10-20min, 15-22% of the weight of the mixture is dripped in the middle 10-20min, and the rest of the mixture is dripped in the rest time.
Preferably, the distillation comprises steam distillation with nitrogen and superheated steam; the temperature of the steam distillation is 250-265 ℃, and the time is 50-120 min.
Preferably, in the preparation process of the modified aluminum chloride, the weight ratio of anhydrous aluminum trichloride, anhydrous ethanol, dimethylformamide, 1, 4-naphthalene dicarboxylic acid, silicon dioxide and activated carbon is 3-5: 50-75: 1-2: 0.5-1.3: 10-20: 5-15.
Preferably, in the preparation process of the modified aluminum chloride, a mixture of dimethylformamide and 1, 4-naphthalenedicarboxylic acid is added dropwise and then stirred for 3 to 5 hours.
Preferably, in the preparation process of the modified aluminum chloride, the drying is vacuum drying, and the temperature of the vacuum drying is 50-70 ℃.
Preferably, the mass content of piperylene in the piperylene raw material is 65-70 wt%.
Preferably, the temperature is maintained at 40-45 ℃ during the dropwise addition of the mixture of piperylene raw material, styrene, isoamylene and limonene.
In the preparation method of the modified m-pentadiene petroleum resin, a mixture of styrene, isoamylene and limonene is specifically selected to react with m-pentadiene, the double bond content in a system is adjusted, meanwhile, the rigidity and the rotational steric hindrance of a molecular chain are improved, the softening point of the prepared resin is high, the chroma of the resin is reduced, the obtained resin is light in color, the wax haze point is less than 85 ℃, the tackifying property is high, the compatibility with a polar polymer is good, and the application range of the resin is widened; in the preparation process of modified aluminum chloride, dimethylformamide and 1, 4-naphthalene dicarboxylic acid are specifically selected as raw materials and react with anhydrous aluminum trichloride to obtain a complex, a naphthalene structure and an amide structure are introduced into molecules, so that the complex is good in heat resistance, silicon dioxide and activated carbon are added, the silicon dioxide and the activated carbon are uniformly dispersed on the surfaces of the silicon dioxide and the activated carbon, and are not easily decomposed in the using process, and the proportion of the silicon dioxide and the activated carbon to phosphoric acid is 80-95: 2-4, the two components play a synergistic effect, the catalytic effect is good, and the resin yield is high.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A preparation method of modified m-pentadiene petroleum resin comprises the following steps: adding n-hexane into a reaction device, introducing nitrogen, adding a catalyst, stirring and heating to 45 ℃, dropwise adding a mixture of a piperylene raw material, styrene, isoamylene and limonene, stirring and reacting for 50min at 40 ℃ after dropwise adding is finished, filtering after the reaction is finished, washing and distilling filtrate, and cooling to obtain the modified piperylene petroleum resin;
wherein the catalyst is a mixture of modified aluminum chloride and phosphoric acid, and the weight ratio of the modified aluminum chloride to the phosphoric acid is 80: 2; the modified aluminum chloride is prepared according to the following process: adding anhydrous aluminum trichloride into anhydrous ethanol, stirring uniformly at 15 ℃, dropwise adding a mixture of dimethylformamide and 1, 4-naphthalenedicarboxylic acid, stirring, adding silicon dioxide and activated carbon, standing for 5h, drying, and roasting for 3h at 270 ℃ to obtain the modified aluminum chloride.
Example 2
A preparation method of modified m-pentadiene petroleum resin comprises the following steps: adding n-hexane into a reaction device, introducing nitrogen, adding a catalyst, stirring and heating to 40 ℃, dropwise adding a mixture of a piperylene raw material, styrene, isoamylene and limonene, stirring and reacting at 50 ℃ for 40min after dropwise adding is finished, filtering after the reaction is finished, washing and distilling the filtrate, and cooling to obtain the modified piperylene petroleum resin;
wherein the catalyst is a mixture of modified aluminum chloride and phosphoric acid, and the weight ratio of the modified aluminum chloride to the phosphoric acid is 95: 4; the modified aluminum chloride is prepared according to the following process: adding anhydrous aluminum trichloride into anhydrous ethanol, stirring uniformly at 8 ℃, dropwise adding a mixture of dimethylformamide and 1, 4-naphthalenedicarboxylic acid, stirring, adding silicon dioxide and activated carbon, standing for 10 hours, drying, and roasting for 4 hours at 220 ℃ to obtain the modified aluminum chloride.
Example 3
A preparation method of modified m-pentadiene petroleum resin comprises the following steps: adding n-hexane into a reaction device, introducing nitrogen, adding a catalyst, stirring and heating to 44 ℃, wherein the stirring speed is 450r/min, and dropwise adding a mixture of a m-pentadiene raw material, styrene, isoamylene and limonene, wherein the weight ratio of the m-pentadiene raw material to the mixture of the styrene, the isoamylene and the limonene to the catalyst to the n-hexane is 100: 4.5: 150, the weight ratio of piperylene raw material, styrene, isoamylene and limonene is 10: 2: 1: 7, in the process of dropwise adding a mixture of a piperylene raw material, styrene, isoamylene and limonene, the dropwise adding time is 65min, 8% of the weight of the mixture is dropwise added in the first 20min, 15% of the weight of the mixture is dropwise added in the middle 20min, the rest of the mixture is dropwise added in the rest time, stirring and reacting are carried out at 44 ℃ for 50min after the dropwise adding is finished, the stirring rotating speed is 450r/min, filtering is carried out after the reaction is finished, and the filtrate is washed, distilled and cooled to obtain the modified piperylene petroleum resin; the distillation comprises steam distillation by introducing nitrogen and superheated steam; the temperature of the steam distillation is 255 ℃, and the time is 120 min;
wherein the catalyst is a mixture of modified aluminum chloride and phosphoric acid, and the weight ratio of the modified aluminum chloride to the phosphoric acid is 85: 3; the modified aluminum chloride is prepared according to the following process: adding anhydrous aluminum trichloride into anhydrous ethanol, uniformly stirring at 9 ℃, dropwise adding a mixture of dimethylformamide and 1, 4-naphthalenedicarboxylic acid, stirring for 3 hours, adding silicon dioxide and activated carbon, and standing for 8 hours, wherein the weight ratio of the anhydrous aluminum trichloride, the anhydrous ethanol, the dimethylformamide, the 1, 4-naphthalenedicarboxylic acid, the silicon dioxide and the activated carbon is 3: 75: 1: 1: 13: 5, roasting at 230 ℃ for 5 hours after vacuum drying to obtain the modified aluminum chloride; the temperature of the vacuum drying was 70 ℃.
Example 4
A preparation method of modified m-pentadiene petroleum resin comprises the following steps: adding n-hexane into a reaction device, introducing nitrogen, adding a catalyst, stirring and heating to 42 ℃, dropwise adding a mixture of a piperylene raw material, styrene, isoamylene and limonene, stirring and reacting at 42 ℃ for 35min after dropwise adding is finished, filtering after the reaction is finished, washing and distilling the filtrate, and cooling to obtain the modified piperylene petroleum resin; wherein the rotating speed of the stirring is 300 r/min; in the mixture of the m-pentadiene raw material, the styrene, the isoamylene and the limonene, the weight ratio of the m-pentadiene raw material to the styrene to the isoamylene to the limonene is 20: 1: 4: 3; the weight ratio of the piperylene raw material, the mixture of styrene, isoamylene and limonene, the catalyst and n-hexane is 100: 7: 100, respectively; in the process of dropwise adding the mixture of the m-pentadiene raw material, the styrene, the isoamylene and the limonene, the dropwise adding time is 75min, 10% of the weight of the mixture is dropwise added in the first 10min, 22% of the weight of the mixture is dropwise added in the middle 10min, and the rest of the mixture is dropwise added in the rest time; the distillation comprises steam distillation by introducing nitrogen and superheated steam; the temperature of the steam distillation is 265 ℃, and the time is 50 min;
the catalyst is a mixture of modified aluminum chloride and phosphoric acid, and the weight ratio of the modified aluminum chloride to the phosphoric acid is 93: 2; the modified aluminum chloride is prepared according to the following process: adding anhydrous aluminum trichloride into anhydrous ethanol, stirring uniformly at 12 ℃, dropwise adding a mixture of dimethylformamide and 1, 4-naphthalenedicarboxylic acid, stirring for 5 hours, adding silicon dioxide and activated carbon, standing for 7 hours, drying in vacuum, and roasting for 3.5 hours at 200 ℃ to obtain the modified aluminum chloride; wherein the weight ratio of anhydrous aluminum trichloride, anhydrous ethanol, dimethylformamide, 1, 4-naphthalene dicarboxylic acid, silicon dioxide and active carbon is 5: 50: 2: 0.5: 20: 15; the temperature of the vacuum drying was 50 ℃.
Example 5
A preparation method of modified m-pentadiene petroleum resin comprises the following steps: adding n-hexane into a reaction device, introducing nitrogen, adding a catalyst, stirring and heating to 43 ℃, dropwise adding a mixture of a piperylene raw material, styrene, isoamylene and limonene, stirring and reacting for 45min at 43 ℃ after dropwise adding is finished, filtering after the reaction is finished, washing and distilling filtrate, and cooling to obtain the modified piperylene petroleum resin; wherein the rotating speed of the stirring is 350 r/min; in the mixture of the m-pentadiene raw material, the styrene, the isoamylene and the limonene, the weight ratio of the m-pentadiene raw material to the styrene to the isoamylene to the limonene is 15: 1: 2.8: 6; the weight ratio of the piperylene raw material, the mixture of styrene, isoamylene and limonene, the catalyst and n-hexane is 100: 6: 143; in the process of dropwise adding the mixture of the m-pentadiene raw material, the styrene, the isoamylene and the limonene, the dropwise adding time is 68min, 8% of the weight of the mixture is dropwise added in the first 18min, 17% of the weight of the mixture is dropwise added in the middle 18min, and the rest of the mixture is dropwise added in the rest time; the distillation comprises steam distillation by introducing nitrogen and superheated steam; the temperature of the steam distillation is 250 ℃, and the time is 60 min;
the catalyst is a mixture of modified aluminum chloride and phosphoric acid, and the weight ratio of the modified aluminum chloride to the phosphoric acid is 87: 2.8 of; the modified aluminum chloride is prepared according to the following process: adding anhydrous aluminum trichloride into anhydrous ethanol, stirring uniformly at 12 ℃, dropwise adding a mixture of dimethylformamide and 1, 4-naphthalenedicarboxylic acid, stirring for 3.8 hours, adding silicon dioxide and activated carbon, standing for 8.5 hours, drying in vacuum, and roasting for 3 hours at 300 ℃ to obtain the modified aluminum chloride; wherein the weight ratio of anhydrous aluminum trichloride, anhydrous ethanol, dimethylformamide, 1, 4-naphthalene dicarboxylic acid, silicon dioxide and active carbon is 3: 72: 1: 1.3: 10: 8; the temperature of the vacuum drying was 50 ℃.
Example 6
A preparation method of modified m-pentadiene petroleum resin comprises the following steps: adding n-hexane into a reaction device, introducing nitrogen, adding a catalyst, stirring and heating to 40 ℃, dropwise adding a mixture of a piperylene raw material, styrene, isoamylene and limonene, stirring and reacting at 40 ℃ for 39min after dropwise adding is finished, filtering after the reaction is finished, washing and distilling the filtrate, and cooling to obtain the modified piperylene petroleum resin;
wherein the stirring speed is 420 r/min;
in the mixture of the m-pentadiene raw material, the styrene, the isoamylene and the limonene, the weight ratio of the m-pentadiene raw material to the styrene to the isoamylene to the limonene is 17: 1.3: 1: 4;
the weight ratio of the piperylene raw material, the mixture of styrene, isoamylene and limonene, the catalyst and n-hexane is 100: 5: 110;
in the process of dropwise adding the mixture of the m-pentadiene raw material, the styrene, the isoamylene and the limonene, the dropwise adding time is 70min, 9% of the weight of the mixture is dropwise added in the first 13min, 20% of the weight of the mixture is dropwise added in the middle 13min, and the rest of the mixture is dropwise added in the rest time;
the distillation comprises steam distillation by introducing nitrogen and superheated steam; the temperature of the steam distillation is 259 ℃, and the time is 105 min;
the catalyst is a mixture of modified aluminum chloride and phosphoric acid, and the weight ratio of the modified aluminum chloride to the phosphoric acid is 91: 2; the modified aluminum chloride is prepared according to the following process: adding anhydrous aluminum trichloride into anhydrous ethanol, stirring uniformly at 10 ℃, dropwise adding a mixture of dimethylformamide and 1, 4-naphthalenedicarboxylic acid, stirring for 4 hours, adding silicon dioxide and activated carbon, standing for 6 hours, drying, and roasting for 4.5 hours at 255 ℃ to obtain the modified aluminum chloride; wherein the weight ratio of anhydrous aluminum trichloride, anhydrous ethanol, dimethylformamide, 1, 4-naphthalene dicarboxylic acid, silicon dioxide and active carbon is 4: 58: 1.8: 0.7: 15: 11; the drying is vacuum drying, and the temperature of the vacuum drying is 70 ℃.
The resins prepared by the methods of examples 1-6 were tested for their properties, wherein the softening point was as defined in GB/T2294-; weighing 50g of sample, dissolving the sample in 50g of toluene (which conforms to GB/T3406-2010), and measuring the chromaticity according to the regulation of GB/T22295-2008; taking a certain amount of resin, putting the resin into a baking oven at 200 ℃, taking out the resin after three hours, and analyzing the change of the chromaticity of the resin to determine the thermal stability; tests show that the resin prepared by the invention has a softening point of more than or equal to 115.3 ℃, a chroma of 1.5-2, a chroma change of 3-4 after being put into an oven, and a resin yield of more than or equal to 84.7%.
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 (9)
1. The preparation method of the modified m-pentadiene petroleum resin is characterized by comprising the following steps: adding n-hexane into a reaction device, introducing nitrogen, adding a catalyst, stirring and heating to 40-45 ℃, dropwise adding a mixture of a piperylene raw material, styrene, isoamylene and limonene, stirring and reacting at 40-50 ℃ for 30-50min after dropwise adding is finished, filtering after the reaction is finished, washing and distilling filtrate, and cooling to obtain the modified piperylene petroleum resin;
wherein the catalyst is a mixture of modified aluminum chloride and phosphoric acid, and the weight ratio of the modified aluminum chloride to the phosphoric acid is 80-95: 2-4; the modified aluminum chloride is prepared according to the following process: adding anhydrous aluminum trichloride into anhydrous ethanol, stirring uniformly at the temperature of 8-15 ℃, dropwise adding a mixture of dimethylformamide and 1, 4-naphthalenedicarboxylic acid, stirring, adding silicon dioxide and activated carbon, standing for 5-10h, drying, and roasting at the temperature of 200-300 ℃ for 3-5h to obtain the modified aluminum chloride.
2. The method for preparing modified piperylene petroleum resin as claimed in claim 1, wherein the rotation speed of the stirring is 300-450 r/min.
3. The method of claim 1, wherein the weight ratio of piperylene raw material, styrene, isoamylene, limonene is 10-20: 1-2: 1-4: 3-7.
4. The method for preparing modified piperylene petroleum resin of claim 1, wherein the weight ratio of the piperylene raw material, styrene, a mixture of isoamylene and limonene, a catalyst and n-hexane is 100: 4.5-7: 100-150.
5. The method of claim 1, wherein the dropping time of the mixture of piperylene, styrene, isoamylene and limonene is 65-75min, 8-10% of the weight of the mixture is dropped for the first 10-20min, 15-22% of the weight of the mixture is dropped for the middle 10-20min, and the rest of the mixture is dropped for the remaining time.
6. The method of claim 1, wherein said distillation comprises steam distillation with nitrogen and superheated steam; the temperature of the steam distillation is 250-265 ℃, and the time is 50-120 min.
7. The method for preparing modified piperylene petroleum resin of claim 1, wherein in the preparation process of modified aluminum chloride, the weight ratio of anhydrous aluminum trichloride, anhydrous ethanol, dimethylformamide, 1, 4-naphthalene dicarboxylic acid, silica and activated carbon is 3-5: 50-75: 1-2: 0.5-1.3: 10-20: 5-15.
8. The method of claim 1, wherein the mixture of dimethylformamide and 1, 4-naphthalenedicarboxylic acid is added dropwise and stirred for 3-5 hours during the preparation of the modified aluminum chloride.
9. A method of preparing a modified piperylene petroleum resin as claimed in any one of claims 1 to 8 wherein during the preparation of the modified aluminium chloride, the drying is vacuum drying at a temperature of 50 to 70 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN102351990A (en) * | 2011-07-29 | 2012-02-15 | 长春工业大学 | Method for preparing m-pentadiene petroleum resin |
| CN108219068A (en) * | 2018-01-10 | 2018-06-29 | 安徽同心化工有限公司 | Controllable high-performance polymer resin of a kind of melt viscosity and preparation method thereof |
| CN110003388A (en) * | 2019-03-26 | 2019-07-12 | 恒河材料科技股份有限公司 | A kind of preparation method of hydrogenation modification C5 Petropols |
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| 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 |
| CN101891863A (en) * | 2010-06-13 | 2010-11-24 | 宁波职业技术学院 | Method for preparing styrene modified C5 petroleum resin |
| CN102351990A (en) * | 2011-07-29 | 2012-02-15 | 长春工业大学 | Method for preparing m-pentadiene petroleum resin |
| CN108219068A (en) * | 2018-01-10 | 2018-06-29 | 安徽同心化工有限公司 | Controllable high-performance polymer resin of a kind of melt viscosity and preparation method thereof |
| CN110003388A (en) * | 2019-03-26 | 2019-07-12 | 恒河材料科技股份有限公司 | A kind of preparation method of hydrogenation modification C5 Petropols |
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