CN114057939A - Modified liquid resin and preparation method thereof - Google Patents
Modified liquid resin and preparation method thereof Download PDFInfo
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- CN114057939A CN114057939A CN202010775322.9A CN202010775322A CN114057939A CN 114057939 A CN114057939 A CN 114057939A CN 202010775322 A CN202010775322 A CN 202010775322A CN 114057939 A CN114057939 A CN 114057939A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
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- 238000005406 washing Methods 0.000 claims abstract description 35
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- 238000000034 method Methods 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 24
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- 239000002904 solvent Substances 0.000 claims abstract description 19
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 16
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- 239000000203 mixture Substances 0.000 claims abstract description 13
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- 230000003472 neutralizing effect Effects 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 6
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- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 22
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 16
- 229910015900 BF3 Inorganic materials 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 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 claims description 8
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 6
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011282 acid tar Substances 0.000 claims description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 150000003739 xylenols Chemical class 0.000 claims description 3
- 239000012855 volatile organic compound Substances 0.000 abstract description 15
- 230000007613 environmental effect Effects 0.000 abstract description 10
- 239000007787 solid Substances 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 238000001704 evaporation Methods 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 63
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
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- 230000001070 adhesive effect Effects 0.000 description 7
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011280 coal tar Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
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- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 150000001907 coumarones Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
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- 239000012776 electronic material Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
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- 238000005984 hydrogenation reaction Methods 0.000 description 1
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- 150000007529 inorganic bases Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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Images
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
- C08F244/00—Coumarone-indene copolymers
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a modified liquid resin and a preparation method thereof, wherein the preparation method of the modified liquid resin comprises the following steps: preparing raw oil with indene content of 5-55% by using crude indene and a solvent, then removing pyridine and phenol by using conventional acid washing and alkali washing methods, further neutralizing to obtain C2SN, separating heavy fraction from the bottom of a tower by using a decoloring tower, and evaporating decolored oil CSN from the top of the tower; adding a catalyst into a mixture of the destaining oil CSN, the phenolic compound and the styrene, and polymerizing at the temperature of 5-50 ℃ to obtain polymerized oil; washing the polymerized oil with water, distilling to remove impurities without polymerization to obtain modified liquid resin; the modified liquid resin has functional groups, is in a liquid state at normal temperature, can be well compatible with other polar resins in the using process, does not need to be dissolved by adding a solvent, and solves the environmental problems in the aspects of VOCs and the like caused by using solid resin.
Description
Technical Field
The invention relates to the field of resin preparation, relates to a preparation method of liquid resin, and particularly relates to modified liquid resin and a preparation method thereof.
Background
Coumarone-indene resin (abbreviated as coumarone resin) has excellent performances of acid resistance, alkali resistance, adhesiveness, plasticization, reinforcement and the like, is dissolved in solvents such as chlorohydrocarbon, esters, ketones, ethers and the like, has good compatibility with various resins such as natural rubber, epoxy resin and the like, is widely used by people as a modifier of various resins for a long time, and is mainly applied to the fields of coatings, electronic materials, adhesives, sealants, rubber, printing ink and the like;
the typical production process flow of the coumarone resin comprises the working procedures of distillation and cutting fraction, acid washing for removing pyridine, polymerization, washing, curing and the like, and finally a solid coumarone resin product is prepared; some researches related to coumarone resin are also available in the prior art, for example, (1) application No. 201110076405.X discloses a coumarone resin production method, heavy benzene is fractionated by coal tar, indene and indene are fractionated by the heavy benzene, indene and indene are polymerized in the same solution to obtain coumarone resin, and the concrete procedures are coal tar heaving removal, heavy benzene hydrogenation reaction impurity removal, primary separation, indene and indene dephenolization, indene and indene depyridine removal, indene and indene polymerization and the like to prepare coumarone resin; (2) rujinshou et al, "continuous process for producing coumarone-indene resin with high softening point" teaches that coumarone resin with a softening point of 100-; (3) application No. 201410482242.9 discloses a method for producing a high softening point coumarone resin, comprising the steps of: washing raw material crude indene with an aqueous solution of inorganic base; adding light flash oil into the washed crude indene to dilute the crude indene, uniformly mixing, adding a catalyst, and carrying out polymerization reaction on the crude indene at 50-100 ℃ for 0.8-1 h to obtain polymer oil; aging the polymerized oil at 50-120 ℃ for 0.5-4 h, then carrying out flash evaporation to remove light components, and finally carrying out granulation to obtain the coumarone resin with the softening point not lower than 110 ℃. (4) Application number 201610470598.X discloses a production method of modified tackified coumarone resin, wherein HW type organic waste is subjected to pretreatment device and polymerization distillation to obtain modified coumarone petroleum resin with softening point of 80-150 ℃; (5) application No. 201210223313.4 discloses a method for preparing a high softening point light-colored cold polyindene resin, comprising: the ethylene cracking byproduct C9 fraction is subjected to rectification, high-temperature depolymerization, polymerization, catalysis removal and reduced pressure rectification to obtain indene resin, wherein the softening point is 120-150 ℃. Because the product prepared by the disclosed technology is solid coumarone resin, organic solvents are required to be added for dissolving in the subsequent use, and the organic solvents can cause the problem of environmental VOCs; also disclosed is an aromatic hydrocarbon liquid petroleum resin and a process for producing the same, as in application No. 96119529.0, comprising: the warm yellow transparent thick liquid resin is obtained by distilling, polymerizing, terminating, filtering and distilling petroleum pyrolysis oil serving as a raw material at normal temperature; although the product is a liquid resin, the product has poor compatibility with polar resins in use and does not react with other components due to the absence of functional groups, and has relatively poor viscosity, resulting in a limited range of use of the liquid resin.
In recent years, in order to promote energy conservation and environmental protection, as the situation of atmospheric prevention and control in China needs to further control volatile organic compounds, the national environmental protection department issues a notice of property tax [ 2015 ] 16, and 4% of consumption tax is imposed on solvent-based coatings with VOC content higher than 420 g/L; in addition, the ministry of industry and informatization and the ministry of finance and industry 2016, 7, 8 jointly issue a text of notification of the ministry of finance and industry of industry and informatization about the action plan of volatile organic compound reduction in the important industry (Ministry of industry and communications [ 2016 ] 217), and also specify the low (no) VOC products, solvent reduction and other aspects of the industries such as coatings, adhesives and the like. In 5/2020 < 2020 volatile organic compound control attack & solidation scheme (survey draft) > requires strict implementation of national and local product VOCs content limit standards, and 12 behaviors violating the legal and regulatory standards are mainly investigated: producing, selling and using products such as paint, printing ink, adhesive, cleaning agent and the like which do not meet the national or local VOCs (volatile organic compounds) content limit standard.
In view of the above, it is desirable to develop a liquid resin with functional groups, which not only has good compatibility with other polar resins, but also does not need to be dissolved by adding an organic solvent during the use process, and thus does not cause environmental problems such as VOCs.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a modified liquid resin and a preparation method thereof, wherein the raw material composition is adjusted by adding a modifier, so that the modified liquid resin with functional groups is obtained, has a lower softening point, is in a liquid state at normal temperature, has good compatibility with other polar resins in the using process, does not need to be dissolved by adding an organic solvent, and solves the environmental problems of VOCs and the like caused by using solid resin.
In order to achieve the purpose, the invention adopts the following technical scheme:
the first aspect of the present invention provides a method for preparing a modified liquid resin, comprising the steps of:
s1, preparing raw oil, namely preparing raw oil with the indene content of 5-55% by using crude indene and a solvent;
s2, removing pyridine and phenol from the raw oil by a conventional acid washing and alkali washing method, and further neutralizing to obtain C2 SN;
s3, decoloring and distilling, wherein the C2SN subjected to depyridinization and dephenolization passes through a decoloring tower, heavy fractions are separated from the bottom of the tower, and a decolored oil CSN for polymerization is evaporated from the top of the tower;
s4, polymerizing, namely adding a catalyst into the mixture of the destaining oil CSN, the phenolic compound and the styrene, and polymerizing at the temperature of 5-50 ℃ to obtain polymerized oil;
and S5, distilling, washing the polymerized oil, distilling, and removing impurities without polymerization to obtain the modified liquid resin.
Preferably, in the step S1, the crude indene includes the following components in percentage by mass: indene: 60% -75%, dicyclopentadiene: 3.2% -7.5%, methyl styrene: 2.5% -6%, styrene: 0.01 to 0.5 percent.
Preferably, in step S1, the solvent is selected from one or more of toluene, xylene, p-toluene and flash oil.
Preferably, in the step S3, the heavy fraction includes naphthalene, acid tar and asphalt.
Preferably, in step S4, the phenolic compound is selected from one or more of phenol, o-cresol, m-cresol, p-cresol, and xylenol.
Preferably, in step S4, the mass ratio of the phenolic compound to the styrene to the CSN is 1: (1-5): (1-6).
Preferably, in the step S4, the catalyst is selected from one or more of aluminum trichloride, boron trifluoride and titanium tetrachloride.
Preferably, in the step S4, the catalyst accounts for 0.3% to 7% of the mass of the mixture.
Preferably, the catalyst accounts for 1-5% of the mass of the mixed material.
Preferably, in the step S4, the temperature is 10-30 ℃.
Preferably, in the step S4, the polymerization time is 1 to 5 hours.
Preferably, the polymerization time is 2 to 3 hours.
The second aspect of the present invention is a modified liquid resin prepared according to the preparation method as provided in the first aspect.
Preferably, the viscosity of the modified liquid resin is more than or equal to 1150 mPas, and the hydroxyl value is more than 180 mgKOH/g.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the modified liquid resin and the preparation method thereof, the styrene and the phenolic compound are added as the modifier to adjust the raw material composition and control the process parameters, so that the modified liquid resin with the hydroxyl functional group is obtained, and the modified liquid resin has good compatibility with other polar resins in the using process and meets the requirements of the market on the polar resins, so that the modified liquid resin has wider applicability in the application fields of coatings, adhesives and the like;
2. the method adds working procedures on the prior art, is simple and convenient to operate, is suitable for industrial production, and the prepared modified liquid resin with the hydroxyl functional group is in a liquid state at normal temperature, does not need to be dissolved by adding a solvent during use, solves the environmental problems in the aspects of VOCs and the like caused by using solid resin, meets the requirement of environmental protection, and has wider applicability in the application fields of coatings, adhesives and the like.
Drawings
FIG. 1 is a process flow diagram of the present invention for modifying liquid resins.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way.
As shown in fig. 1, the preparation method of the modified liquid resin of the present invention comprises the steps of:
s1, preparing raw oil, namely preparing raw oil with the indene content of 5-55% by using crude indene and a solvent; wherein the crude indene comprises the following components in percentage by mass: indene: 60% -75%, dicyclopentadiene: 3.2% -7.5%, methyl styrene: 2.5% -6% and styrene: 0.01 to 0.5 percent; the solvent is selected from one or more of toluene, xylene, p-toluene and flash oil; the flash oil refers to light fractions from the initial boiling point to 200 ℃ such as crude oil or coal tar, and is a colorless to brown transparent liquid.
S2, removing pyridine and phenol, namely, carrying out acid washing on the raw oil by sulfuric acid with the concentration of 30-60% and alkali washing by sodium hydroxide with the concentration of 1-10% to remove pyridine and phenol, and further neutralizing to obtain C2 SN;
s3, decoloring and distilling, wherein the C2SN subjected to depyrogenation and dephenolization passes through a decoloring tower, heavy fractions such as naphthalene, acid tar and asphalt are separated from the bottom of the tower, and decolored oil CSN for polymerization is evaporated from the top of the tower;
s4, polymerizing, namely adding a catalyst into a mixture of the destaining oil CSN, the phenolic compound and the styrene, and polymerizing for 1-5 hours at the temperature of 5-50 ℃ to obtain polymerized oil; wherein the phenolic compound and the styrene are used as modifiers; the mass ratio of the phenolic compound to the styrene to the destaining oil CSN is 1: (1-5): (1-6); the catalyst accounts for 0.3-7% of the mass of the mixed material, and the preferable catalyst accounts for 1-5% of the mass of the mixed material; the phenolic compound is selected from one or more of phenol, o-cresol, m-cresol, p-cresol and xylenol; the catalyst is selected from one or more of aluminum trichloride, boron trifluoride and titanium tetrachloride;
during polymerization, the temperature is preferably 10-30 ℃, and the reaction time is preferably 2-3 h.
S5, distilling, namely washing the polymerized oil, distilling to remove impurities without polymerization to obtain modified liquid resin; wherein impurities which are not polymerized refer mainly to solvent and unreacted monomers.
The viscosity of the modified liquid resin obtained by the preparation method is more than or equal to 1150 mPas, and the hydroxyl value is more than 180 mgKOH/g.
Example 1
S1, preparing raw oil, and preparing the raw oil with the indene content of 5% by compounding crude indene and toluene; wherein the crude indene comprises the following components in percentage by mass: 70.16% indene, 5.16% dicyclopentadiene, 4.13% methylstyrene and 0.01% styrene;
s2, removing pyridine and phenol, feeding the raw oil into an acid washing tank for removing pyridine and phenol, neutralizing with alkali after acid washing, and washing with water to obtain neutral C2 SN;
s3, decoloring and distilling, feeding the washed C2SN into a decoloring tower, and distilling decolored oil CSN for polymerization from the top of the tower.
S4, polymerizing, namely adding a catalyst BF3 into a mixture of the decolored oil CSN, the o-cresol and the styrene, and polymerizing for 2 hours at the temperature of 20 ℃ to obtain polymerized oil; wherein the ratio of o-cresol: styrene: the mass ratio of the destaining oil CSN is 1:1:1, and the catalyst BF3 accounts for 3% of the mass of the mixed material.
S5, distilling, washing the polymerized oil, entering a distillation system, removing solvent and micromolecules to obtain modified liquid resin with the molecular weight of 322Mw, wherein the modified liquid resin is obtained; the modified liquid resin had a viscosity of 1150 mPas and a hydroxyl value of 227.3 mgKOH/g.
Example 2
S1, preparing raw oil, and preparing the raw oil with the indene content of 10% by compounding crude indene and toluene; wherein the crude indene comprises the following components in percentage by mass: 70.16% indene, 5.16% dicyclopentadiene, 4.13% methylstyrene and 0.01% styrene;
s2, removing pyridine and phenol, feeding the raw oil into an acid washing tank for removing pyridine and phenol, neutralizing with alkali after acid washing, and washing with water to obtain neutral C2 SN;
s3, decoloring and distilling, feeding the washed C2SN into a decoloring tower, and distilling decolored oil CSN for polymerization from the top of the tower.
S4, polymerizing, namely adding a catalyst BF3 into a mixture of the decolored oil CSN, the o-cresol and the styrene, and polymerizing for 2 hours at the temperature of 20 ℃ to obtain polymerized oil; wherein the ratio of o-cresol: styrene: the mass ratio of the destaining oil CSN is 1:1.4:2, and the catalyst BF3 accounts for 3% of the mass of the mixed material.
S5, distilling, washing the polymerized oil, entering a distillation system, removing solvent and micromolecules to obtain modified liquid resin with the molecular weight of 344 Mw; the modified liquid resin had a viscosity of 1530 mPas and a hydroxyl value of 214.8 mgKOH/g.
Example 3
S1, preparing raw oil, and preparing the raw oil with the indene content of 10% by compounding crude indene and toluene; wherein the crude indene comprises the following components in percentage by mass: 70.16% indene, 5.16% dicyclopentadiene, 4.13% methylstyrene and 0.01% styrene;
s2, removing pyridine and phenol, feeding the raw oil into an acid washing tank for removing pyridine and phenol, neutralizing with alkali after acid washing, and washing with water to obtain neutral C2 SN;
s3, decoloring and distilling, feeding the washed C2SN into a decoloring tower, and distilling decolored oil CSN for polymerization from the top of the tower.
S4, polymerizing, namely adding a catalyst BF3 into a mixture of the decolored oil CSN, the o-cresol and the styrene, and polymerizing for 2 hours at the temperature of 20 ℃ to obtain polymerized oil; wherein the ratio of o-cresol: styrene: the mass ratio of the destaining oil CSN is 1:2:3, and the catalyst BF3 accounts for 3% of the mass of the mixed material.
And S5, distilling, washing the polymerized oil, feeding the polymerized oil into a distillation system, and removing the solvent and small molecules to obtain the modified liquid resin with the molecular weight of 366Mw, wherein the viscosity of the modified liquid resin is 1670mPa & S, and the hydroxyl value is 183.9 mgKOH/g.
Example 4
S1, preparing raw oil, and preparing the raw oil with the indene content of 5% by compounding crude indene and toluene; wherein the crude indene comprises the following components in percentage by mass: 70.16% indene, 5.16% dicyclopentadiene, 4.13% methylstyrene and 0.01% styrene;
s2, removing pyridine and phenol, feeding the raw oil into an acid washing tank for removing pyridine and phenol, neutralizing with alkali after acid washing, and washing with water to obtain neutral C2 SN;
s3, decoloring and distilling, feeding the washed C2SN into a decoloring tower, and distilling decolored oil CSN for polymerization from the top of the tower.
S4, polymerizing, namely adding a catalyst BF3 into a mixture of the decolored oil CSN, the o-cresol and the styrene, and polymerizing for 2 hours at the temperature of 20 ℃ to obtain polymerized oil; wherein the ratio of o-cresol: styrene: the mass ratio of the destaining oil CSN is 1:3:5, and the catalyst BF3 accounts for 3% of the mass of the mixed material.
S5, distilling, washing the polymerized oil, entering a distillation system, removing solvent and micromolecules to obtain modified liquid resin with molecular weight of 381Mw, wherein the modified liquid resin is obtained; the modified liquid resin had a viscosity of 1748 mPas and a hydroxyl value of 181.9 mgKOH/g.
Comparative example 1
S1, preparing raw oil, and preparing the raw oil with the indene content of 45% by compounding crude indene and toluene; wherein the crude indene comprises the following components in percentage by mass: 70.16% indene, 5.16% dicyclopentadiene, 4.13% methylstyrene and 0.01% styrene;
s2, removing pyridine and phenol, feeding the raw oil into an acid washing tank for removing pyridine and phenol, neutralizing with alkali after acid washing, and washing with water to obtain neutral C2 SN;
s3, decoloring and distilling, feeding the washed C2SN into a decoloring tower, and distilling decolored oil CSN for polymerization from the top of the tower.
S4, polymerizing, namely adding a catalyst BF3 into the destaining oil CSN, and polymerizing for 2 hours at the temperature of 60 ℃ to obtain polymerized oil; the catalyst BF3 accounted for 0.5% of the mass of the destaining oil CSN.
And S5, distilling, washing the polymerized oil, and entering a distillation system to remove the solvent and micromolecules to obtain the solid resin with the molecular weight of 1180Mw and the softening point of 100 ℃.
The modified liquid resin and the preparation method thereof have the advantages that styrene and phenolic compounds are added as modifiers in the polymerization step, so that the prepared modified liquid resin has hydroxyl functional groups, the modified liquid resin is convenient to be well compatible with other polar resins, and can react with other components, and the like, so that the application range of the modified liquid resin is wider.
Therefore, according to the modified liquid resin and the preparation method thereof, the raw material composition is adjusted by adding the modifier, and the process parameters are controlled, so that the modified liquid resin with the hydroxyl functional group is obtained, and the modified liquid resin has good compatibility with other polar resins in the using process and meets the requirements of the market on the polar resins, so that the modified liquid resin has wider applicability in the application fields of coatings, adhesives and the like; the preparation method provided by the invention adds working procedures on the basis of the original process technology, is simple and convenient to operate and suitable for industrial production, the prepared modified liquid resin with the hydroxyl functional group is in a liquid state at normal temperature, and is not required to be dissolved by adding a solvent during use, so that the environmental problems in the aspects of VOCs (volatile organic compounds) and the like caused by using solid resin are solved, and the preparation method meets the environmental protection requirement, and therefore, the preparation method has wider applicability in the application fields of coatings, adhesives and the like.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (14)
1. A preparation method of modified liquid resin is characterized by comprising the following steps:
s1, preparing raw oil, namely preparing raw oil with the indene content of 5-55% by using crude indene and a solvent;
s2, removing pyridine and phenol from the raw oil by a conventional acid washing and alkali washing method, and further neutralizing to obtain C2 SN;
s3, decoloring and distilling, wherein the C2SN subjected to depyridinization and dephenolization passes through a decoloring tower, heavy fractions are separated from the bottom of the tower, and a decolored oil CSN for polymerization is evaporated from the top of the tower;
s4, polymerizing, namely adding a catalyst into the mixture of the destaining oil CSN, the phenolic compound and the styrene, and polymerizing at the temperature of 5-50 ℃ to obtain polymerized oil;
and S5, distilling, washing the polymerized oil, distilling, and removing impurities without polymerization to obtain the modified liquid resin.
2. The preparation method according to claim 1, wherein in the step S1, the crude indene comprises the following components in percentage by mass: indene: 60% -75%, dicyclopentadiene: 3.2% -7.5%, methyl styrene: 2.5% -6%, styrene: 0.01 to 0.5 percent.
3. The method of claim 1, wherein in step S1, the solvent is selected from one or more of toluene, xylene, p-toluene, and flash oil.
4. The method according to claim 1, wherein in step S3, the heavy fraction includes naphthalene, acid tar, and pitch.
5. The method of claim 1, wherein in step S4, the phenolic compound is selected from one or more of phenol, o-cresol, m-cresol, p-cresol, and xylenol.
6. The method according to claim 1, wherein in step S4, the mass ratio of the phenolic compound to the styrene to the CSN is 1: (1-5): (1-6).
7. The method according to claim 1, wherein in step S4, the catalyst is one or more selected from the group consisting of aluminum trichloride, boron trifluoride, and titanium tetrachloride.
8. The method according to claim 1, wherein in step S4, the catalyst accounts for 0.3-7% of the mass of the mixture.
9. The method of claim 8, wherein the catalyst comprises 1% to 5% by weight of the mixed material.
10. The method according to claim 1, wherein the temperature in step S4 is 10 to 30 ℃.
11. The method according to claim 1, wherein in step S4, the polymerization time is 1 to 5 hours.
12. The method of claim 11, wherein the polymerization time is 2 to 3 hours.
13. A modified liquid resin prepared by the method according to any one of claims 1 to 12.
14. The modified liquid resin of claim 12, having a viscosity of greater than or equal to 1150 mPa-s and a hydroxyl number of greater than 180 mgKOH/g.
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Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE654625A (en) * | 1963-10-21 | 1965-02-15 | ||
US3799913A (en) * | 1971-12-30 | 1974-03-26 | Neville Chemical Co | Production of hydrocarbon resin compositions from alpha-methyl styrene,indene and vinyl toluene |
US4113931A (en) * | 1973-07-14 | 1978-09-12 | Rutgerswerke Aktiengesellschaft | Process for the continuous production of indene resins |
JPH02124913A (en) * | 1988-11-04 | 1990-05-14 | Nippon Steel Chem Co Ltd | Preparation of coumarone resin |
JPH06136096A (en) * | 1992-10-28 | 1994-05-17 | Sumitomo Bakelite Co Ltd | Sealing resin composition |
CN105566569A (en) * | 2014-10-11 | 2016-05-11 | 上海宝钢化工有限公司 | Hydroxyl coumarone resin and preparation method thereof |
CN107325228A (en) * | 2017-08-03 | 2017-11-07 | 恒河材料科技股份有限公司 | A kind of tetrahydroindene is modified the preparation method of C 9 petroleum resin |
CN108102029A (en) * | 2016-11-24 | 2018-06-01 | 上海宝钢化工有限公司 | Production method of low-odor coumarone resin |
CN108192024A (en) * | 2016-12-08 | 2018-06-22 | 上海宝钢化工有限公司 | Liquid coumarone resin and preparation method thereof |
-
2020
- 2020-08-05 CN CN202010775322.9A patent/CN114057939A/en active Pending
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE654625A (en) * | 1963-10-21 | 1965-02-15 | ||
US3799913A (en) * | 1971-12-30 | 1974-03-26 | Neville Chemical Co | Production of hydrocarbon resin compositions from alpha-methyl styrene,indene and vinyl toluene |
US4113931A (en) * | 1973-07-14 | 1978-09-12 | Rutgerswerke Aktiengesellschaft | Process for the continuous production of indene resins |
JPH02124913A (en) * | 1988-11-04 | 1990-05-14 | Nippon Steel Chem Co Ltd | Preparation of coumarone resin |
JPH06136096A (en) * | 1992-10-28 | 1994-05-17 | Sumitomo Bakelite Co Ltd | Sealing resin composition |
CN105566569A (en) * | 2014-10-11 | 2016-05-11 | 上海宝钢化工有限公司 | Hydroxyl coumarone resin and preparation method thereof |
CN108102029A (en) * | 2016-11-24 | 2018-06-01 | 上海宝钢化工有限公司 | Production method of low-odor coumarone resin |
CN108192024A (en) * | 2016-12-08 | 2018-06-22 | 上海宝钢化工有限公司 | Liquid coumarone resin and preparation method thereof |
CN107325228A (en) * | 2017-08-03 | 2017-11-07 | 恒河材料科技股份有限公司 | A kind of tetrahydroindene is modified the preparation method of C 9 petroleum resin |
Non-Patent Citations (2)
Title |
---|
POH, BT 等: "Dependence of Adhesion Property of SMR L-based Adhesives on Antioxidants", 《JOURNAL OF ELASTOMERS AND PLASTICS》 * |
孙培勤: "生物油精炼提质工艺研究", 《中外能源》 * |
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Address after: Weisan Road Chemical Office Building, Baoshan District, Shanghai, 2004 Applicant after: Baowu Carbon Technology Co.,Ltd. Address before: Weisan Road Chemical Office Building, Baoshan District, Shanghai, 2004 Applicant before: BAOWU CARBON MATERIAL TECHNOLOGY Co.,Ltd. |
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