CN116574216A - Nine-carbon petroleum resin and preparation method thereof - Google Patents
Nine-carbon petroleum resin and preparation method thereof Download PDFInfo
- Publication number
- CN116574216A CN116574216A CN202310675684.4A CN202310675684A CN116574216A CN 116574216 A CN116574216 A CN 116574216A CN 202310675684 A CN202310675684 A CN 202310675684A CN 116574216 A CN116574216 A CN 116574216A
- Authority
- CN
- China
- Prior art keywords
- carbon
- reaction
- styrene
- petroleum resin
- methyl styrene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 75
- 229920005989 resin Polymers 0.000 title claims abstract description 66
- 239000011347 resin Substances 0.000 title claims abstract description 66
- 239000003208 petroleum Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 92
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims abstract description 79
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 32
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- -1 hydroxyl compound Chemical class 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 16
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 12
- 239000000920 calcium hydroxide Substances 0.000 claims description 12
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 9
- 239000011968 lewis acid catalyst Substances 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 150000002440 hydroxy compounds Chemical class 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000008096 xylene Substances 0.000 claims description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 7
- 229920000180 alkyd Polymers 0.000 abstract description 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 52
- 239000000463 material Substances 0.000 description 33
- 238000003756 stirring Methods 0.000 description 28
- 229910015900 BF3 Inorganic materials 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 18
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 15
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 13
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 13
- 229910052794 bromium Inorganic materials 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000006386 neutralization reaction Methods 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 11
- 230000001276 controlling effect Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 235000019445 benzyl alcohol Nutrition 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 239000011344 liquid material Substances 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 239000011343 solid material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- LRTOHSLOFCWHRF-UHFFFAOYSA-N 1-methyl-1h-indene Chemical compound C1=CC=C2C(C)C=CC2=C1 LRTOHSLOFCWHRF-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- IYQYZZHQSZMZIG-UHFFFAOYSA-N tricyclo[5.2.1.0(2.6)]deca-3,8-diene, 4.9-dimethyl Chemical compound C1C2C3C=C(C)CC3C1C=C2C IYQYZZHQSZMZIG-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 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
- C08F240/00—Copolymers of hydrocarbons and mineral oils, e.g. petroleum resins
-
- 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
- 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
- C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
-
- 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
- C08F212/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
Landscapes
- 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 provides a carbon nine petroleum resin and a preparation method thereof, in particular to a preparation method of the carbon nine petroleum resin, hydroxyl compound and methyl styrene are subjected to alkylation reaction, and then methyl styrene, carbon nine fraction and styrene are added for copolymerization reaction after the reaction to obtain the carbon nine petroleum resin. The invention utilizes the carbon nine fraction and simultaneously adds hydroxyl compound, methyl styrene and styrene, and the methyl styrene and the styrene adjust the content of relevant components in the carbon nine fraction; the hydroxyl compound and the introduced methyl styrene and styrene are subjected to alkylation reaction, and the prepared carbon nine petroleum resin has high hydroxyl value, good compatibility with EVA, alkyd and the like, and wide product adaptability.
Description
Technical Field
The invention relates to the technical field of petroleum resin, in particular to a carbon nine petroleum resin and a preparation method thereof.
Background
Petroleum resin is solid or viscous liquid polymer with relatively low molecular weight and is prepared with C5/C9 fraction as side product of ethylene unit as main material. Monomers and molecular structures composed of resins are roughly classified into aromatic hydrocarbon petroleum resins, aliphatic petroleum resins, alicyclic petroleum resins, and the like.
The aromatic hydrocarbon petroleum resin, also called C9 petroleum resin, is obtained by polymerizing the ethylene byproduct C9 fraction as a raw material, wherein the raw material is mainly cracking C9 fraction oil of an ethylene device byproduct, which accounts for about 10% -20% of the yield of ethylene, and the fraction oil has complex components and is rich in unsaturated hydrocarbons such as styrene, methyl styrene, dicyclopentadiene, indene, methyl cyclopentadiene dimer and the like.
At present, there are two main methods for producing petroleum resins using C9 fractions: one is a cationic catalytic low-temperature polymerization method (abbreviated as a cold polymerization method), and the other is a heating-initiated radical polymerization method (abbreviated as a hot polymerization method). The thermal polymerization process of the carbon nine petroleum resin has the advantages of simple process, high conversion rate and yield, stable product performance and the like, and has the main defects that a resin product with high quality performance cannot be obtained, the hue and compatibility of the resin are generally poor, the high-end market demand cannot be met, the thermal polymerization process is generally only applied to the fields of alkyd paint, rubber mixing and the like, and the added value of the product is low.
The cold polymerization carbon nine petroleum resin is resin with certain softening point obtained through copolymerization of polyolefin component in C9 fraction under the condition of catalyst or peroxide initiator. The main polymerizable components in the C9 fraction all contain large conjugated electron cloud structures, and the main polymerizable components are easy to copolymerize with certain monomers with electrophilic groups; in addition, the aromatic ring is also an ideal electrophilic substitution reaction substrate, and polar groups are easily introduced into the aromatic ring for chemical modification. In patent CN1091751a, water-soluble C9 petroleum resin is prepared by solution radical copolymerization or radical emulsion polymerization of polar molecules such as acrylic acid, maleic anhydride, etc. and C9 distillate oil under the initiation of peroxide or azo compound. Therefore, there is an urgent need to find a new method for preparing the carbon nine petroleum resin. Accordingly, the prior art is subject to further development.
Disclosure of Invention
The invention aims to overcome the technical defects and provide a carbon nine petroleum resin and a preparation method thereof.
In order to achieve the technical purpose, the invention adopts the following technical scheme: the preparation process includes alkylation of hydroxyl compound with methyl styrene, copolymerization with methyl styrene, carbon nine fraction and styrene, and filtering to eliminate impurity to obtain carbon nine petroleum resin.
Further, when the hydroxyl compound and the methyl styrene are subjected to alkylation reaction, the molar ratio of the hydroxyl compound to the methyl styrene is (1-3): 1.
further, the mass ratio of the total amount of methyl styrene and styrene added in the alkylation reaction and copolymerization reaction is (1-5): 1.
further, the reaction temperature of the alkylation reaction is 40-80 ℃, and the reaction temperature of the copolymerization reaction is 10-25 ℃.
Further, the alkylation reaction is specifically performed as follows: mixing hydroxyl compound and methyl styrene in xylene and/or toluene solvent, and adding Lewis acid catalyst; the specific process of the copolymerization reaction is as follows: adding methyl styrene, carbon nine fraction and Lewis acid catalyst, then dripping styrene for reaction for 1-2h, adding calcium hydroxide and sodium hydroxide for reaction again for 30-60min, and stopping the reaction.
Further, the ratio of the mass of the solvent to the total mass of the first olefin is more than 1:1, wherein the first olefin comprises methyl styrene and styrene which are respectively added in the alkylation reaction and the copolymerization reaction; the mass of the calcium hydroxide is as follows: the mass of the hydroxyl compound added in the alkylation reaction, the mass of the methyl styrene added in the copolymerization reaction, the mass of the carbon nine fraction and the total mass of the styrene are 2%; the mass of the sodium hydroxide is 10% of the mass of the calcium hydroxide.
Further, the mass of the hydroxyl compound is m1, and m1 is 15% of the total mass of the product carbon nine petroleum resin; the total mass of the second olefin is m2, m2=m1/0.15-m 1; the second olefin comprises methyl styrene added in alkylation reaction, methyl styrene added in copolymerization reaction, components participating in copolymerization reaction in carbon nine fraction and styrene; the mass of the component participating in the copolymerization reaction in the carbon nine fraction is m3, m3=m2× (40% to 60%); the mass of the Lewis acid catalyst added in the alkylation reaction is 0.1 to 0.2 percent of the total mass of the hydroxyl compound and the methyl styrene added in the alkylation reaction; the mass of the Lewis acid catalyst added in the copolymerization reaction is 0.1 to 0.2 percent of the total mass of the components participating in the copolymerization reaction, the methyl styrene and the styrene in the carbon nine fraction added in the copolymerization reaction.
Further, the hydroxyl compound is benzyl alcohol or p-tert-butylphenol.
Further, the post-treatment also comprises distillation at 220 ℃ to remove the solvent and unreacted low molecular weight substances.
In addition, the invention also provides the carbon nine petroleum resin prepared by the method.
The beneficial effects are that:
1. the invention utilizes the carbon nine fraction and simultaneously adds hydroxyl compound, methyl styrene and styrene, and the methyl styrene and the styrene adjust the content of relevant components in the carbon nine fraction; the hydroxyl compound and the introduced methyl styrene and styrene are subjected to alkylation reaction, and the prepared carbon nine petroleum resin has high hydroxyl value, good compatibility with EVA, alkyd and the like, and wide product adaptability.
2. The carbon nine petroleum resin prepared by the invention has light color number and stable product quality.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
According to the embodiment of the invention, the preparation method of the carbon nine petroleum resin is provided, the hydroxyl compound and the methyl styrene are subjected to alkylation reaction, then the methyl styrene, the carbon nine fraction and the styrene are added for copolymerization reaction after the reaction, and the carbon nine petroleum resin is obtained through post-treatment of filtering and impurity removing. Hydroxyl compound, methyl styrene and styrene are added to the carbon nine fraction, and the content of relevant components in the carbon nine fraction is regulated by the added methyl styrene and styrene, so that the methyl styrene and the styrene are increased in the whole reaction process; the hydroxyl compound and the introduced methyl styrene and styrene are subjected to alkylation reaction, and the prepared carbon nine petroleum resin has high hydroxyl value, good compatibility with EVA, alkyd and the like, and wide product adaptability. The methylstyrene is not added at one time, but is added separately in the alkylation reaction and the copolymerization reaction, and if the amount of the methylstyrene added at one time is excessive, the self-polymerization of the methylstyrene is likely to occur.
The carbon nine fraction was prepared by the following procedure: the method is characterized by taking the carbon nonaromatic hydrocarbon as a raw material, and firstly treating the carbon nonaromatic hydrocarbon as follows: the distillation range of the distillation cut by atmospheric distillation is 180-200 ℃. The contents of the components in the fractions are as follows: styrene 0, methyl styrene 9%, indene 33%, methyl indene 12%, naphthalene 0.3%, and the balance 45.7% of components participating in the copolymerization reaction in the carbon nine fraction.
In some embodiments, the amount of hydroxyl compound added may be calculated based on the predicted final yield of the carbon nine petroleum resin, with the amount of hydroxyl compound added being 15% of the total mass of the carbon nine petroleum resin, which is the predicted final yield of the carbon nine petroleum resin.
In some embodiments, the amount of catalyst used in the alkylation reaction is from 0.1% to 0.2% of the hydroxy compound and methyl styrene in the alkylation reaction.
In some embodiments, the mass fraction of the carbon nine fraction that participates in the copolymerization is 54.3%.
In some embodiments, the lewis acid catalyst may be boron trifluoride, but may also be aluminum trichloride or ferric chloride, not limited to boron trifluoride alone.
The following is a description of specific embodiments.
Example 1:
step 101: 450g of solvent xylene, 108.1g of hydroxyl compound benzyl alcohol and 118.2g of methyl styrene are sequentially added into the reactor, and the materials are continuously stirred in the adding process, wherein the molar ratio of the benzyl alcohol to the methyl styrene is 1:1, a step of;
step 102: filling nitrogen into the reactor, and controlling the temperature to be raised to 40 ℃ by using a constant-temperature water bath to keep the temperature of initial materials in the reactor constant;
step 103: after the initial temperature is constant, boron trifluoride 0.34g is sequentially introduced, and the reaction temperature is controlled to be 60 ℃ by adjusting the water bath temperature;
step 104: stopping introducing boron trifluoride after the temperature is not increased any more, continuing stirring for 0.5h, and reducing the temperature in the reactor to 5 ℃;
step 105: then 137.8g of methyl styrene and 500g of treated carbon nine fraction are added in sequence, and the materials are continuously stirred in the adding process;
step 106: boron trifluoride 0.74g was again introduced successively;
step 107: 85.31g of styrene is slowly added dropwise, stirred and the temperature of the materials in the reactor is controlled to be 15 ℃;
step 108: after the materials are obviously thickened, stirring is continued for 1h;
step 109: 19g of calcium hydroxide with the granularity of 400 meshes is added and stirred for 30min; then adding 1.9g of 10% sodium hydroxide, and continuously stirring for 30min;
step 110: sampling and detecting the pH value to be 7.2, stopping stirring after the neutralization reaction is finished, and stopping the polymerization reaction;
step 111: filtering to remove solid materials;
step 112: the filtered liquid material is distilled to 220 ℃ under normal pressure, and the solvent and unreacted low molecular substances, namely the carbon nine petroleum resin, are removed.
Wherein, the mass ratio of the total methyl styrene to the styrene in the whole process is 3:1.
in addition, nitrogen or boron trifluoride environment was maintained in the flask throughout the process until neutralization.
Example 2
Step 101: 550g of solvent xylene, 150.2g of hydroxy compound p-tert-butylphenol (PTBP) and 118.2g of methyl styrene are sequentially added into the reactor, and the materials are continuously stirred in the adding process, wherein the molar ratio of benzyl alcohol to methyl styrene is 1:1, a step of;
step 102: filling nitrogen into the reactor, and controlling the temperature to be raised to 40 ℃ by using a constant-temperature water bath to keep the temperature of initial materials in the reactor constant;
step 103: after the initial temperature is constant, boron trifluoride 0.40g is sequentially introduced, and the reaction temperature is controlled to be 60 ℃ by adjusting the water bath temperature;
step 104: stopping introducing boron trifluoride after the temperature is not increased any more, continuing stirring for 0.5h, and reducing the temperature in the reactor to 0 ℃;
step 105: then adding 173.9g of methyl styrene and 850g of treated carbon nine fraction in sequence, and continuously stirring the materials in the adding process;
step 106: boron trifluoride 1.1g is introduced again successively;
step 107: slowly dropwise adding 97.4g of styrene, stirring, and controlling the temperature of the materials in the reactor to be 20 ℃;
step 108: after the materials are obviously thickened, stirring is continued for 1h;
step 109: 27.8g of calcium hydroxide with the granularity of 400 meshes is added and stirred for 30min; 2.78g of 10% sodium hydroxide is added and stirring is continued for 30min;
step 110: sampling and detecting the pH value to be 7.2, stopping stirring after the neutralization reaction is finished, and stopping the polymerization reaction;
step 111: filtering to remove solid materials;
step 112: and (3) distilling the filtered liquid material to 220 ℃ under normal pressure, and removing the solvent and unreacted low molecular substances to obtain the carbon nine petroleum resin.
Wherein, the mass ratio of the total methyl styrene to the styrene in the whole process is 3:1.
in addition, nitrogen or boron trifluoride environment was maintained in the flask throughout the process until neutralization.
Example 3
Step 101: 400g of solvent toluene, 108.1g of hydroxyl compound benzyl alcohol and 118.2g of methyl styrene are sequentially added into the reactor, and the materials are continuously stirred in the adding process, wherein the molar ratio of the benzyl alcohol to the methyl styrene is 1:1, a step of; the method comprises the steps of carrying out a first treatment on the surface of the
Step 102: filling nitrogen into the reactor, and controlling the temperature to be raised to 60 ℃ by using a constant-temperature water bath to keep the temperature of initial materials in the reactor constant;
step 103: after the initial temperature is constant, boron trifluoride 0.34g is sequentially introduced, and the reaction temperature is controlled to be 80 ℃ by adjusting the water bath temperature;
step 104: stopping introducing boron trifluoride after the temperature is not increased any more, continuing stirring for 0.5h, and reducing the temperature in the reactor to 3 ℃;
step 105: then 137.8g of methyl styrene and 500g of treated carbon nine fraction are added in sequence, and the materials are continuously stirred in the adding process;
step 106: boron trifluoride 0.74g was again introduced successively;
step 107: 85.31g of styrene is slowly added dropwise, stirred and the temperature of the materials in the reactor is controlled to be 25 ℃;
step 108: after the materials are obviously thickened, stirring is continued for 1h;
step 109: 19g of calcium hydroxide with the granularity of 400 meshes is added and stirred for 30min; then adding 1.9g of 10% sodium hydroxide, and continuously stirring for 30min;
step 110: sampling and detecting the pH value to be 7.3, stopping stirring after the neutralization reaction is finished, and stopping the polymerization reaction;
step 111: filtering to remove solid materials;
step 112: and (3) distilling the filtered liquid material to 220 ℃ under normal pressure, and removing the solvent and unreacted low molecular substances to obtain the carbon nine petroleum resin.
Wherein, the mass ratio of the total methyl styrene to the styrene in the whole process is 3:1.
in addition, nitrogen or boron trifluoride environment was maintained in the flask throughout the process until neutralization.
Example 4:
step 101: 500g of solvent xylene, 150.2g of hydroxy compound p-tert-butylphenol (PTBP) and 118.2g of methylstyrene are sequentially added into the reactor, and the materials are continuously stirred in the adding process, wherein the mol ratio of the p-tert-butylphenol to the methylstyrene is 1:1, a step of;
step 102: filling nitrogen into the reactor, and controlling the temperature to be raised to 40 ℃ by using a constant-temperature water bath to keep the temperature of initial materials in the reactor constant;
step 103: after the initial temperature is constant, boron trifluoride 0.4g is sequentially introduced, and the reaction temperature is controlled to be 60 ℃ by adjusting the water bath temperature;
step 104: stopping introducing boron trifluoride after the temperature is not increased any more, continuing stirring for 0.5h, and reducing the temperature in the reactor to 5 ℃;
step 105: then 94.6g of methyl styrene and 783.7g of treated carbon nine fraction are added in sequence, and the materials are continuously stirred in the adding process;
step 106: boron trifluoride 1.1g is introduced again successively;
step 107: slowly dripping 212.8g of styrene, stirring, and controlling the temperature of the materials in the reactor to be 20 ℃;
step 108: after the materials are obviously thickened, stirring is continued for 1h;
step 109: 27.2g of calcium hydroxide with the granularity of 400 meshes is added and stirred for 30min; 2.72g of 10% sodium hydroxide is added and stirring is continued for 30min;
step 110: sampling and detecting the PH value to be 7.1, stopping stirring after the neutralization reaction is finished, and stopping the polymerization reaction;
step 111: filtering to remove solid materials;
step 112: and (3) distilling the filtered liquid material to 220 ℃ under normal pressure, and removing the solvent and unreacted low molecular substances to obtain the carbon nine petroleum resin.
Wherein, the mass ratio of the total methyl styrene consumption to the styrene in the whole process is 1:1.
in addition, nitrogen or boron trifluoride environment was maintained in the flask throughout the process until neutralization.
Example 5:
step 101: 500g of solvent xylene, 150.2g of hydroxy compound p-tert-butylphenol (PTBP) and 236.4g of methylstyrene are sequentially added into the reactor, and the materials are continuously stirred in the adding process, wherein the molar ratio of the p-tert-butylphenol to the methylstyrene is 2:1, a step of;
step 102: filling nitrogen into the reactor, and controlling the temperature to be raised to 40 ℃ by using a constant-temperature water bath to keep the temperature of initial materials in the reactor constant;
step 103: after the temperature is constant, boron trifluoride 0.58g is sequentially introduced, and the reaction temperature is controlled to be 60 ℃ by adjusting the water bath temperature;
step 104: stopping introducing boron trifluoride after the temperature is not increased any more, continuing stirring for 0.5h, and reducing the temperature in the reactor to 5 ℃;
step 105: then 82.8g of methyl styrene and 783.7g of treated carbon nine fraction are added in sequence, and the materials are continuously stirred in the adding process;
step 106: boron trifluoride 0.92g was again introduced successively;
step 107: 106.4g of styrene is slowly added dropwise, stirred, and the temperature of the materials in the reactor is controlled to be 15 ℃;
step 108: after the materials are obviously thickened, stirring is continued for 1h;
step 109: 27.2g of calcium hydroxide with the granularity of 400 meshes is added and stirred for 30min; 2.72g of 10% sodium hydroxide is added and stirring is continued for 30min;
step 110: sampling and detecting the PH value to be 7.1, stopping stirring after the neutralization reaction is finished, and stopping the polymerization reaction;
step 111: filtering to remove solid materials;
step 112: and (3) distilling the filtered liquid material to 220 ℃ under normal pressure, and removing the solvent and unreacted low molecular matters to obtain the carbon nine petroleum resin with high hydroxyl value, light color number and high softening point.
Wherein, the mass ratio of the total methyl styrene to the styrene in the whole process is 3:1.
in addition, nitrogen or boron trifluoride environment was maintained in the flask throughout the process until neutralization.
Example 6:
step 101: 550g of solvent xylene, 150.2g of hydroxy compound p-tert-butylphenol (PTBP) and 354.6g of methylstyrene are sequentially added into the reactor, and the materials are continuously stirred in the adding process, wherein the molar ratio of the p-tert-butylphenol to the methylstyrene is 3:1, a step of;
step 102: filling nitrogen into the reactor, and controlling the temperature to be raised to 40 ℃ by using a constant-temperature water bath to keep the temperature of materials in the reactor constant;
step 103: after the temperature is constant, boron trifluoride 0.76g is sequentially introduced, and the reaction temperature is controlled to be 60 ℃ by adjusting the water bath temperature;
step 104: stopping introducing boron trifluoride after the temperature is not increased any more, continuing stirring for 0.5h, and reducing the temperature in the reactor to 0 ℃;
step 105: then 70.95g of methyl styrene and 627g of treated carbon nine fraction are added in sequence, and the materials are continuously stirred in the adding process;
step 106: boron trifluoride 0.74g was again introduced successively;
step 107: 85.11g of styrene is slowly added dropwise, stirred and the temperature of the materials in the reactor is controlled to be 15 ℃;
step 108: after the materials are obviously thickened, stirring is continued for 1h;
step 109: adding 25.8g of calcium hydroxide with the granularity of 400 meshes, and stirring for 30min; 2.58g of 10 percent sodium hydroxide is added and stirring is continued for 30 minutes;
step 110: sampling and detecting the PH value to be 7.1, stopping stirring after the neutralization reaction is finished, and stopping the polymerization reaction;
step 111: filtering to remove solid materials;
step 112: and (3) distilling the filtered liquid material to 220 ℃ under normal pressure, and removing the solvent and unreacted low molecular substances to obtain the carbon nine petroleum resin.
Wherein the mass ratio of the total methyl styrene to the styrene in the whole process is 5:1.
in addition, nitrogen or boron trifluoride environment was maintained in the flask throughout the process until neutralization.
Comparative example 1:
in comparison with example 4, no p-tert-butylphenol, methylstyrene and styrene were added, and only the carbon nine fraction was used as a starting material for the reaction, and the other steps were identical.
Analytical tests were performed on examples-6 and comparative examples 1-2, and the test analytical methods were as follows:
wax spray point: EVA, wax and resin in the mass ratio of 6:6:8 are poured into a 25ml colorimetric tube after melting, a thermometer is inserted into the colorimetric tube, the thermometer is arranged in the middle of the liquid and is continuously and gently stirred until mist shielding of the thermometer water silver balls occurs, and the temperature indication of the thermometer is read, so that the wax mist point is obtained.
Alkyd mutual dissolution: firstly, mixing a solvent with petroleum resin in a mass ratio of 1:1, after dissolving, mixing long-oil alkyd resin with the petroleum resin solution after mixing and dissolving in a mass ratio of 1:1, coating the mixture on a transparent glass slide, and observing whether the mixture is clear or not after standing for 24 hours. If clear, it is noted as good.
Volatile components: weighing about 5g of petroleum resin by using a dried beaker, placing the petroleum resin in an oven at 185 ℃, taking out the petroleum resin after 4 hours, placing the petroleum resin in a dryer for cooling to room temperature, weighing the petroleum resin, and taking the lost weight as a volatile component.
The test results are shown in Table 1.
TABLE 1 results of Performance test of nine carbon Petroleum resins
As shown in the performance test results of the nine-carbon petroleum resin in Table 1, for examples 1-6, comparative examples 1 and 2 show that the PTBP effect of the hydroxyl compound in example 2 is slightly better, and the hydroxyl value is ensured to be high at the same time; comparing example 1 with example 3, under the condition of the same materials, the methyl styrene of example 3 is firstly charged and reacts at an increased temperature (step 102), the softening point is reduced when the temperature is increased, the reaction is more sufficient, and the bromine number is reduced; comparative example 2 and example 4, which are PTBP, have properly increased styrene content, increased softening point, more complete reaction, and reduced bromine number; comparative example 2 and example 5, the same material, increased first methyl styrene content, decreased softening point, insufficient reaction, and relatively high bromine number; in comparative example 2 and example 6, the amount of styrene was reduced, the amount of first shot of methylstyrene was increased, and the softening point was reduced to a greater extent than in example 5, and the bromine number was reduced to a greater extent. The above shows that the bromine number and softening point of the carbon nine petroleum resin can be influenced by the feeding proportion of the first methyl styrene, the softening point is reduced when the first methyl styrene feeding amount is increased, and the bromine number is increased; the amount of methyl styrene added for the first time is reduced, the softening point is increased, and the bromine number is reduced. The feeding ratio of the styrene to the methyl styrene can influence the softening point and the bromine number of the carbon nine petroleum resin, the styrene amount is increased and reacted relatively severely, the softening point is relatively increased, the bromine number is reduced, the styrene amount is reduced, and the softening point and the bromine number are reduced. The reaction temperature of the methyl styrene during the first feeding can influence the softening point and the bromine number of the carbon nine petroleum resin, the softening point is reduced when the temperature is increased, the bromine number is reduced, and the softening point and the bromine number are increased when the temperature is reduced.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (10)
1. A preparation method of carbon nine petroleum resin is characterized in that hydroxy compound and methyl styrene are subjected to alkylation reaction, and then methyl styrene, carbon nine fraction and styrene are added for copolymerization reaction after the alkylation reaction to obtain the carbon nine petroleum resin.
2. The method for producing a carbon nine petroleum resin according to claim 1, wherein when the hydroxy compound is alkylated with methyl styrene, the molar ratio of the hydroxy compound to methyl styrene is (1-3): 1.
3. the method for producing a carbon nine petroleum resin according to claim 1, wherein the mass ratio of total amount of methyl styrene and styrene added in the alkylation reaction and copolymerization reaction is (1-5): 1.
4. the method for producing a carbon nine petroleum resin according to claim 1, wherein the reaction temperature of the alkylation reaction is 40 to 80 ℃.
5. The method for producing a carbon nine petroleum resin according to claim 1, wherein the reaction temperature of the copolymerization reaction is 10 to 25 ℃.
6. The method for preparing a carbon nine petroleum resin according to claim 1, wherein the specific process of the alkylation reaction is as follows: mixing hydroxyl compound and methyl styrene in xylene and/or toluene solvent, and adding Lewis acid catalyst; the specific process of the copolymerization reaction is as follows: adding methyl styrene, carbon nine fraction and Lewis acid catalyst, then dripping styrene for reaction for 1-2h, adding calcium hydroxide and sodium hydroxide for reaction again for 30-60min, and stopping the reaction.
7. The method for producing a carbon nine petroleum resin according to claim 6, wherein the ratio of the mass of the solvent to the total mass of the first olefins is > 1:1, the first olefins being methyl styrene and styrene added in the alkylation reaction and the copolymerization reaction, respectively;
the mass of the calcium hydroxide is as follows: the mass of the hydroxyl compound added in the alkylation reaction, the mass of the methyl styrene added in the copolymerization reaction, the mass of the carbon nine fraction and the total mass of the styrene are 2%;
the mass of the sodium hydroxide is 10% of the mass of the calcium hydroxide.
8. The method for producing a carbon-nine petroleum resin according to claim 6, wherein,
the mass of the hydroxyl compound is m1, and m1 is 15% of the total mass of the product carbon nine petroleum resin;
the total mass of the second olefin is m2, m2=m1/0.15-m 1; the second olefin comprises methyl styrene added in alkylation reaction, methyl styrene added in copolymerization reaction, components participating in copolymerization reaction in carbon nine fraction and styrene;
the mass of the component involved in the copolymerization reaction contained in the carbon nine fraction is m3, m3=m2× (40% to 60%);
the mass of the Lewis acid catalyst added in the alkylation reaction is 0.1 to 0.2 percent of the total mass of the hydroxyl compound and the methyl styrene added in the alkylation reaction;
the mass of the Lewis acid catalyst added in the copolymerization reaction is 0.1 to 0.2 percent of the total mass of the components participating in the copolymerization reaction, the methyl styrene and the styrene in the carbon nine fraction added in the copolymerization reaction.
9. The method for producing a carbon nine petroleum resin according to claim 1, wherein the copolymerization is further followed by filtration to remove impurities and distillation at 220 ℃.
10. A carbon-nine petroleum resin prepared by the method of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310675684.4A CN116574216A (en) | 2023-06-08 | 2023-06-08 | Nine-carbon petroleum resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310675684.4A CN116574216A (en) | 2023-06-08 | 2023-06-08 | Nine-carbon petroleum resin and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116574216A true CN116574216A (en) | 2023-08-11 |
Family
ID=87543968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310675684.4A Pending CN116574216A (en) | 2023-06-08 | 2023-06-08 | Nine-carbon petroleum resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116574216A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000248150A (en) * | 1999-03-04 | 2000-09-12 | Arakawa Chem Ind Co Ltd | Modifier for polyolefin resin, and polyolefin resin composition |
| CN102746459A (en) * | 2012-06-27 | 2012-10-24 | 宁波职业技术学院 | Preparation method of cold polymerized styrene-indene resin |
| CN109337012A (en) * | 2018-08-31 | 2019-02-15 | 恒河材料科技股份有限公司 | A kind of preparation method of phenol modified copolymer Petropols |
| CN112646076A (en) * | 2020-12-22 | 2021-04-13 | 广东新华粤石化集团股份公司 | Carbon-nine liquid petroleum resin and preparation method thereof |
-
2023
- 2023-06-08 CN CN202310675684.4A patent/CN116574216A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000248150A (en) * | 1999-03-04 | 2000-09-12 | Arakawa Chem Ind Co Ltd | Modifier for polyolefin resin, and polyolefin resin composition |
| CN102746459A (en) * | 2012-06-27 | 2012-10-24 | 宁波职业技术学院 | Preparation method of cold polymerized styrene-indene resin |
| CN109337012A (en) * | 2018-08-31 | 2019-02-15 | 恒河材料科技股份有限公司 | A kind of preparation method of phenol modified copolymer Petropols |
| CN112646076A (en) * | 2020-12-22 | 2021-04-13 | 广东新华粤石化集团股份公司 | Carbon-nine liquid petroleum resin and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3607761B2 (en) | Thermally polymerized dicyclopentadiene / vinyl aromatic resin | |
| KR0170755B1 (en) | Resin use for tackification | |
| CN103073831A (en) | Block copolymer, and preparation method and application thereof | |
| CN105254808A (en) | Method for preparing modified petroleum resin | |
| CN103382238A (en) | Polymerization method for m-pentadiene petroleum resin | |
| CN102140150B (en) | Preparation method for acrylic ester rubber | |
| CN116574216A (en) | Nine-carbon petroleum resin and preparation method thereof | |
| US3905948A (en) | Process for the preparation of petroleum resins | |
| TW583205B (en) | A method for producing copolymer | |
| EP0233074A2 (en) | Low color aromatic resins | |
| EP3404049A1 (en) | (meth)acrylate polymer | |
| US4048132A (en) | Printing ink composition | |
| CN102746459A (en) | Preparation method of cold polymerized styrene-indene resin | |
| US3023200A (en) | Dicyclopentadiene alkylation polymers | |
| CN113880989A (en) | Method for thermally polymerizing carbon five carbon nine copolymerized petroleum resin and application thereof | |
| JPH0229411A (en) | Novel production of petroleum resin suitable for production of printing ink, varnish and paint | |
| GB2173808A (en) | Free radical initiated polymerization of polymerizable ethylenically unsaturated monomer component in the presence of hydrogen peroxide | |
| CN105754024A (en) | Synthesis method of butyl rubber with high isoprene content | |
| CN1039036A (en) | The manufacture method of atactic butadiene styrene copolymer | |
| JPS5835528B2 (en) | Improved continuous production method for hydrocarbon resins | |
| CN114195939B (en) | Tubular reactor and thermal polymerization to C 5 /C 9 Method for copolymerizing petroleum resin | |
| JPS6264811A (en) | Production of light-color petroleum resin for paint | |
| CN1150213C (en) | Atomic group-transfer free radical polymerization initiation system of fullerene halide derivative | |
| CN105968243B (en) | A kind of preparation method of polyisoprene catalyst | |
| JPS5825316A (en) | Hydrocarbon resin having hydroxyl value of more than 6 with small phenolic smell and manufacture |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |