CN108017759A - A kind of modified pentadiene hydrogenated petroleum resin and preparation method thereof - Google Patents
A kind of modified pentadiene hydrogenated petroleum resin and preparation method thereof Download PDFInfo
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- CN108017759A CN108017759A CN201610966259.0A CN201610966259A CN108017759A CN 108017759 A CN108017759 A CN 108017759A CN 201610966259 A CN201610966259 A CN 201610966259A CN 108017759 A CN108017759 A CN 108017759A
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- pentadiene
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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
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
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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
- C08F240/00—Copolymers of hydrocarbons and mineral oils, e.g. petroleum resins
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- Chemical Kinetics & Catalysis (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention discloses a kind of modified pentadiene hydrogenated petroleum resin and preparation method thereof.The present invention is first using glyoxaline compound as modifying agent, and m-pentadiene modified Petropols are made in addition modifying agent in pentadiene polymerization process；Modified pentadiene hydrogenated petroleum resin is prepared in m-pentadiene modified Petropols catalytic hydrogenation again.The modification pentadiene hydrogenated petroleum resin heat endurance that the present invention obtains is high, good with the compatibility of elastomer (such as SIS and SBS) in hot melt adhesive, and color is relatively shallower.
Description
Technical field
The present invention relates to a kind of modified pentadiene hydrogenated petroleum resin and preparation method thereof, belongs to petrochemical technology neck
Domain.
Background technology
It is also higher and higher to the quality requirement of Petropols with the continuous development in each field, wherein, adhesive and sealing
Agent application development, particularly transparent pressure sensitive adhesive tape, outdoor fluid sealant, disposable sanitary articles, medical adhesive tape, traffic paint with
And the application of the modifying agent of polyolefin is required for the good Petropols of lighter color, odorless and stability.
Since light dydrocarbon resin is big there are brittleness, polar group is lacked on molecule, the shortcomings of color and luster is deep, in order to widen resin
Application field, the prior art improve the performance of Petropols, such as Chinese patent application by adding modifying agent copolymerization
CN201410494202.6 is rich in pentadiene cut as raw material using what cracking of ethylene was isolated, adds cyclopentadiene/bicyclic penta
Diene is styrene copolymerized, improves naval stores volume color and luster and molecular weight distribution；Chinese patent application CN201310237557.2
Using acrylic acid as grafted monomers, modified C5 Petropols are obtained, product is mainly used for the additives such as adhesive, ink, coating；It is beautiful
State patent US82757986A and EP1987030111 propose to add a stream boiling in the course of the polymerization process between 80 to 260 DEG C
Aromatic compound be modified, make it is modified after copolymerized petroleum resin there is enough aromatic hydrocarbon contents.Japan Patent
JP59236846 is copolymerized by maleic anhydride and cyclopentadiene or pentadiene, is improved the flow behavior of copolymer and can be processed
Property, it is used as electric insulation resin casting especially suitable for using.
As described above, comonomer of the prior art using aromatic compound, alkene and acid anhydrides as pentadiene, only
For being improved in a certain respect, therefore its use scope is restricted.For the function of the special active imidazole group of structure
Monomer has no report, and a hot spot of polymeric material field is the preparation and application of polymer microballoon, nanoscale to micron
The polymer microballoon of level is because having the specificity such as specific surface area is big, strong adsorption, cohesion are big and surface respond is strong
Matter, is widely used for many new and high technology necks such as analytical chemistry, biomedicine, standard metering, solid phase carrier, high performance liquid chromatography
Domain.
The content of the invention
For overcome the deficiencies in the prior art, it is an object of the invention to provide a kind of modified pentadiene non-hydrogenated petroleum tree
Fat and preparation method thereof.The present invention is modified by adding glyoxaline compound in pentadiene polymerization process, and is passed through
Less harsh hydroconversion condition production heat endurance is high, good with the compatibility of elastomer (such as SIS and SBS) in hot melt adhesive,
The relatively shallower multi-functional hydrogenated petroleum resin of color.
Technical scheme is specifically described as follows.
The present invention provides a kind of preparation method of modified pentadiene hydrogenated petroleum resin, comprises the following steps that：
(1) pentadiene, catalyst, modifying agent and organic solvent are added in reaction kettle, it is poly- that catalysis is carried out under normal pressure
Reaction is closed, obtains m-pentadiene modified Petropols；Wherein：The catalyst is lewis acid, and the modifying agent is imidazoles
Compound；
(2) the m-pentadiene modified Petropols that step (1) obtains carry out catalytic hydrogenation reaction and obtain hydrogenated petroleum resin.
In above-mentioned steps (1), the organic solvent is any one in pentamethylene, hexamethylene, benzene, toluene or dimethylbenzene
Kind is a variety of.
In above-mentioned steps (1), the catalyst is Eorontrifluoride etherate or alchlor.
In above-mentioned steps (1), the modifying agent is allyl imidazole or N- vinyl imidazoles.
In above-mentioned steps (1), the mass ratio of pentadiene and organic solvent is 1: 1~1：5, modifying agent and pentadiene
Mass ratio is 1：2~1：8, the mass ratio of catalyst and pentadiene is 1: 40~1：100, reaction temperature is 40~100 DEG C, instead
It is 180~360min between seasonable.Preferably, the mass ratio of pentadiene and organic solvent is 1：1~1：2, modifying agent and penta
The mass ratio of diene is 1: 4~1：6, the mass ratio of catalyst and pentadiene is 1: 60~1：80, reaction temperature is 60~80
DEG C, the reaction time is 240~300min.
In above-mentioned steps (2), catalyst is skeletal nickel catalyst.Preferably, in skeletal nickel catalyst, nickel content for 40~
80wt%, average pore size are 2.0~20.0 nanometers.
In above-mentioned steps (2), the molar ratio of m-pentadiene modified Petropols and hydrogen is 1: 2~1：5, catalyst amount
For 0.5~3.0wt% of m-pentadiene modified Petropols, the reaction time is 120~300min, reaction pressure for 4.0~
10.0MPa, reaction temperature are 170~250 DEG C.Preferably, catalyst amount for m-pentadiene modified Petropols 1.0~
2.0wt%, reaction time are 180~240min, and reaction pressure is 6.0~8.0MPa, and reaction temperature is 200~220 DEG C.
The present invention also provides the modification pentadiene hydrogenated petroleum resin that a kind of above-mentioned preparation method obtains.
In the present invention, modifying agent is a kind of function monomer for containing active imidazole group, its structure is special, in molecular structure
Vinyl group is directly connected with the nitrogen-atoms of imidazole ring, and unlike acrylamide class formation, vinyl group is with carbonyl for not
Conjugated structure, its these molecular characterizations make it have good answer in ionic liquid, separation, medicine and catalytic field etc.
With, contain tertiary amine functional group on its polymer molecular chain, have ion exchange, complexing behavior, catalytic activity, bio-physiological activity
With the series of characteristics such as heat-resisting.The modification pentadiene non-hydrogenated petroleum of the present invention is a kind of relatively low linear polymer of molecular weight,
By introducing functional groups in pentadiene resin, its heat endurance can be greatly improved, promote the mixing with other resins
It is scattered, also there is compatibility well with elastomer (such as SIS and SBS) in hot melt adhesive, simultaneously because modified resin color phase
To shallower, less harsh hydroconversion condition is only needed to obtain the tackifier resins of shallower colourity.
Embodiment
Below by specific embodiment, the invention will be further described.
Embodiment 1~10 carries out the preparation of hydrogenated petroleum resin according to the following steps：Reaction raw materials are rich in pentadiene
Material, it, which is mainly formed, is shown in Table 1, and each process condition is shown in Table 2 (steps 1), 3 (step 1) of table and 4 (step 2) of table, reaction knot
Shu Hou, weighs and analyzes the indices (softening point, molecular weight distribution and bromine number etc.) of resin sample, the results are shown in Table 5, and other
Polymer performance of dissolving each other is shown in Table 6.Using gel chromatography naval stores molecular weight distributing index (Mw/Mn), using ring and ball method
GB/2294 analyzes softening point, and Bromine Number analysis is carried out using iodimetric titration (SWB2301-62).
1) pentadiene raw material, organic solvent, catalyst and modifying agent are added in reaction kettle, and it is poly- to carry out catalysis under normal pressure
Reaction is closed, then by generating m-pentadiene modified Petropols after neutralizing and washing removing catalyst.
2) Petropols obtained by step 1) carry out hydrogenation reaction under the action of skeletal nickel catalyst and obtain high-quality
Hydrogenated petroleum resin.
3) hydrogenated petroleum resin of high-quality is obtained after the material recycle solvent obtained by step 2).
Table 1.
| Component | Content (wt.%) |
| Pentadiene | 67 |
| Cyclopentene | 19 |
| Pentamethylene | 6.0 |
| DCPD | 2.0 |
| It is other | 6.0 |
Table 2
Table 3
Table 4
| Catalyst amount/wt% | Reaction temperature/DEG C | Reaction pressure/Mpa | Reaction time/min | |
| Embodiment 1 | 0.5 | 250 | 10.0 | 120 |
| Embodiment 2 | 1.0 | 220 | 8.0 | 180 |
| Embodiment 3 | 1.3 | 205 | 6.0 | 220 |
| Embodiment 4 | 1.1 | 210 | 7.0 | 210 |
| Embodiment 5 | 1.5 | 206 | 6.2 | 225 |
| Embodiment 6 | 1.8 | 210 | 7.2 | 200 |
| Embodiment 7 | 1.6 | 205 | 6.5 | 230 |
| Embodiment 8 | 2.0 | 220 | 7.5 | 190 |
| Embodiment 9 | 2.5 | 200 | 6.8 | 240 |
| Embodiment 10 | 3.0 | 170 | 4.0 | 300 |
Table 5
Table 6
Claims (10)
1. a kind of preparation method of modified pentadiene hydrogenated petroleum resin, it is characterised in that comprise the following steps that：
(1) pentadiene, catalyst, modifying agent and organic solvent are added in reaction kettle, it is anti-that catalytic polymerization is carried out under normal pressure
Should, obtain m-pentadiene modified Petropols；Wherein：The catalyst is lewis acid, and the modifying agent is imidazoles chemical combination
Thing；
(2) the m-pentadiene modified Petropols that step (1) obtains carry out catalytic hydrogenation reaction and obtain hydrogenated petroleum resin.
2. preparation method as claimed in claim 1, it is characterised in that in step (1), the organic solvent be selected from pentamethylene,
Any one or more in hexamethylene, benzene, toluene or dimethylbenzene.
3. preparation method as claimed in claim 1, it is characterised in that in step (1), the catalyst is boron trifluoride-second
Ether or alchlor.
4. preparation method as claimed in claim 1, it is characterised in that in step (1), the modifying agent for allyl imidazole or
N- vinyl imidazoles.
5. preparation method as claimed in claim 1, it is characterised in that in step (1), the quality of pentadiene and organic solvent
Than for 1：1~1：5, the mass ratio of modifying agent and pentadiene is 1：2~1：8, the mass ratio of catalyst and pentadiene is 1：
40~1：100, reaction temperature is 40~100 DEG C, and the reaction time is 180~360min.
6. preparation method as claimed in claim 5, it is characterised in that the mass ratio of pentadiene and organic solvent is 1：1~
1：2, the mass ratio of modifying agent and pentadiene is 1：4~1：6, the mass ratio of catalyst and pentadiene is 1: 60~1：80,
Reaction temperature is 60~80 DEG C, and the reaction time is 240~300min.
7. preparation method as claimed in claim 1, it is characterised in that in step (2), catalyst is skeletal nickel catalyst.
8. preparation method as claimed in claim 7, it is characterised in that in skeletal nickel catalyst, nickel content is 40~80wt%,
Average pore size is 2.0~20.0 nanometers.
9. preparation method as claimed in claim 1, it is characterised in that in step (2), m-pentadiene modified Petropols and hydrogen
The molar ratio of gas is 1: 2~1：5, catalyst amount be m-pentadiene modified Petropols 0.5~3.0wt%, the reaction time
For 120~300min, reaction pressure is 4.0~10.0MPa, and reaction temperature is 170~250 DEG C.
A kind of 10. modification pentadiene hydrogenated petroleum resin that preparation method according to one of claim 1-9 obtains.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111100244A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Modified pentadiene hydrogenated petroleum resin and preparation method thereof |
| CN111100243A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Modified carbon-acanthopanax hydrogen petroleum resin and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111100244A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Modified pentadiene hydrogenated petroleum resin and preparation method thereof |
| CN111100243A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Modified carbon-acanthopanax hydrogen petroleum resin and preparation method thereof |
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