CN108017758A - A kind of modified dicyclopentadiene hydrogenated petroleum resin and preparation method thereof - Google Patents
A kind of modified dicyclopentadiene hydrogenated petroleum resin and preparation method thereof Download PDFInfo
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- CN108017758A CN108017758A CN201610961416.9A CN201610961416A CN108017758A CN 108017758 A CN108017758 A CN 108017758A CN 201610961416 A CN201610961416 A CN 201610961416A CN 108017758 A CN108017758 A CN 108017758A
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- dicyclopentadiene
- petroleum resin
- petropols
- hydrogenated petroleum
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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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- Polymers & Plastics (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of modified dicyclopentadiene hydrogenated petroleum resin and preparation method thereof.The present invention's comprises the following steps that：(1) dicyclopentadiene and modifying agent are subjected to heat polymerization in organic solvent, generate Petropols；Wherein：The modifying agent is allyl imidazole or N vinyl imidazoles；(2) Petropols for obtaining step (1) carry out hydrogenation reaction under the action of catalyst and obtain modified dicyclopentadiene hydrogenated petroleum resin.Preparation method of the present invention is simple, and obtained modification dicyclopentadiene hydrogenated petroleum resin heat endurance 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 dicyclopentadiene hydrogenated petroleum resin and preparation method thereof, belong to petrochemical technology
Field.
Background technology
Contain activated double bonds in dicyclopentadiene monomer, addition reaction easily occurs, a series of polymer can be produced, it should
It is very wide with field.Since dicyclopentadiene polymer resin is deep there are form and aspect, cohesive force is poor, compatible with elastomeric material
The shortcomings of property is poor, so as to limit its use scope.With the continuous development in each field, to the quality requirement of Petropols
It is higher and higher, wherein, it is the development of adhesive and sealant application, particularly transparent pressure sensitive adhesive tape, outdoor fluid sealant, disposable
The application of modifying agent of amenities, medical adhesive tape, traffic paint and polyolefin is required for lighter color, odorless and stability good
Petropols.Therefore, processing need to be modified to dicyclopentadiene petroleum resin, wherein function monomer is total to dicyclopentadiene
It has been polymerized to the focus of common concern in the industry.
The prior art improves the performance of dicyclopentadiene copolymer, such as Chinese patent application by adding modifying agent copolymerization
(CN1479755A) toward about 5wt%~25wt% styrene is added in 95wt%~75wt%DCPD monomers, it is small to produce a kind of Mz
In 2000 aromatic modified resin, the heat endurance of product is improved；Chinese patent application (CN105085815A) uses non-cyclopentadienyl
Metallic catalyst is catalyzed dicyclopentadiene and longer chain- alkene (1- butylene, 1- hexenes or 1- octenes etc.) is copolymerized, and is improved altogether
Polymers chain flexibility and processability.WO2015153058A1 is copolymerized using styrene, C5 or terpenes and DCPD, produces silane-functional
Change resin combination；United States Patent (USP) US5,502,140 and US5,739,239 disclose the thermal polymerization of DCPD and α-methylstyrene
Copolymer, makes the dicyclopentadiene petroleum resin after being modified have enough aromatic hydrocarbon contents.
As described above, comonomer of the prior art using styrene, alpha-olefin and maleic anhydride as dicyclopentadiene,
Only for being improved in a certain respect, therefore its use scope is restricted, for the work(of the special active imidazole group of structure
Energy monomer has no report.
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 dicyclopentadiene non-hydrogenated petroleum
Resin and preparation method thereof.The present invention is modified polymerisation first with unsaturated alkyl imidazoles, then by less harsh
Hydroconversion condition hydrogenation, obtain that heat endurance is high, good with the compatibility of elastomer (such as SIS and SBS) in hot melt adhesive, color
Relatively shallower multi-functional hydrogenated petroleum resin.
Technical scheme is specifically described as follows.
The present invention provides a kind of preparation method of modified dicyclopentadiene hydrogenated petroleum resin, comprises the following steps that：
(1) dicyclopentadiene and modifying agent are subjected to heat polymerization in organic solvent, generate Petropols；Wherein：
The modifying agent is allyl imidazole or N- vinyl imidazoles；
(2) Petropols for obtaining step (1) carry out hydrogenation reaction under the action of catalyst and obtain modified bicyclic penta
Diene hydrogenation Petropols.
In above-mentioned steps (1), organic solvent is any one of pentamethylene, hexamethylene, benzene, toluene or dimethylbenzene or more
Kind.
In above-mentioned steps (1), the mass ratio of dicyclopentadiene and organic solvent is 1：1~1：5, modifying agent and bicyclic penta 2
The mass ratio of alkene is 1：1~1：14, reaction temperature is 230~270 DEG C, and reaction pressure is 1.0~3.0MPa, and the reaction time is
180~360min.Preferably, the mass ratio of dicyclopentadiene and organic solvent is 1：1~1：2, modifying agent and dicyclopentadiene
Mass ratio be 1：2~1：3, reaction temperature is 240~260 DEG C, and reaction pressure be 1.5~2.0MPa, the reaction time is 240~
300min。
In above-mentioned steps (2), catalyst is skeletal nickel catalyst.The average pore size of skeletal nickel catalyst is 2.0~20.0
Nanometer, nickel content is 40~80wt%.
In above-mentioned steps (2), the molar ratio of Petropols and hydrogen is 1:2~1:5, catalyst amount is Petropols
0.5~3.0wt%, reaction time are 120~300min, and reaction pressure is 4.0~10.0MPa, and reaction temperature is 170~250
℃.Preferably, catalyst amount is 1.0~2.0wt% of Petropols, and the reaction time is 180~240min, and reaction pressure is
6.0~8.0MPa, reaction temperature are 200~220 DEG C.
The present invention also provides the modification dicyclopentadiene hydrogenated petroleum resin that a kind of above-mentioned preparation method obtains.
Compared to the prior art, the beneficial effects of the present invention are：It is modified using the function monomer of active imidazole group, its
Structure is special, and nitrogen-atoms of the molecular structure medium vinyl group directly with imidazole ring is connected, unlike acrylamide class formation,
Vinyl group is not conjugated structure with carbonyl, its these molecular characterizations make it in ionic liquid, separation, medicine and catalysis neck
There is good application in domain etc., contains tertiary amine functional group on its polymer molecular chain, has ion exchange, complexing behavior, catalysis
Activity, bio-physiological activity and the series of characteristics such as heat-resisting.In addition, modified dicyclopentadiene hydrogenated petroleum resin is a kind of molecule
The linear polymer of relatively low (500~2000) is measured, by introducing functional groups in dcpd resin, is avoided as far as possible
There are crosslinking caused by avtive spot heterogeneity in propagation process, its heat endurance can be greatly improved, promote and other resins
Mixing disperse, also have compatibility well with elastomer (such as SIS and SBS) in hot melt adhesive, simultaneously because modified resin
Color is relatively shallower, only needs less harsh hydroconversion condition 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 the material rich in DCPD,
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 3 (step 2) of table after reaction,
Weigh and analyze the indices (softening point, molecular weight distribution and bromine number etc.) of resin sample, the results are shown in Table 5.Using gel color
Spectrometry measure naval stores molecular weight distributing index (Mw/Mn), softening point is analyzed using ring and ball method GB/2294, using iodimetric titration
(SWB2301-62) Bromine Number analysis is carried out.
1) enter after DCPD raw materials are mixed with organic solvent in reaction kettle, and carried out under the modification of unsaturated alkyl imidazoles
Heat polymerization.
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.%) |
| CPD | 0.3 |
| DCPD | 84.0 |
| NB | 9.5 |
| It is other | 6.2 |
Table 2
| Modifying agent | The mass ratio of modifying agent and raw material DCPD | |
| Embodiment 1 | Allyl imidazole | 1∶2 |
| Embodiment 2 | Allyl imidazole | 1∶4 |
| Embodiment 3 | N- vinyl imidazoles | 1∶1 |
| Embodiment 4 | N- vinyl imidazoles | 1∶2 |
| Embodiment 5 | N- vinyl imidazoles | 1∶3 |
| Embodiment 6 | N- vinyl imidazoles | 1∶2.8 |
| Embodiment 7 | N- vinyl imidazoles | 1∶2.5 |
| Embodiment 8 | N- vinyl imidazoles | 1∶2.2. |
| Embodiment 9 | N- vinyl imidazoles | 1∶4 |
| Embodiment 10 | Allyl imidazole | 1∶3 |
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
Claims (9)
1. a kind of preparation method of modified dicyclopentadiene hydrogenated petroleum resin, it is characterised in that comprise the following steps that：
(1) dicyclopentadiene and modifying agent are subjected to heat polymerization in organic solvent, generate Petropols；Wherein：It is described
Modifying agent is allyl imidazole or N- vinyl imidazoles；
(2) Petropols for obtaining step (1) carry out hydrogenation reaction under the action of catalyst and obtain modified dicyclopentadiene
Hydrogenated petroleum resin.
2. preparation method according to claim 1, it is characterised in that in step (1), organic solvent is pentamethylene, hexamethylene
Any one or more of alkane, benzene, toluene or dimethylbenzene.
3. preparation method according to claim 1, it is characterised in that in step (1), dicyclopentadiene and organic solvent
Mass ratio is 1：1~1：5, the mass ratio of modifying agent and dicyclopentadiene is 1：1~1：14, reaction temperature is 230~270 DEG C,
Reaction pressure is 1.0~3.0MPa, and the reaction time is 180~360min.
4. preparation method according to claim 1, it is characterised in that in step (1), dicyclopentadiene and organic solvent
Mass ratio is 1：1~1：2, the mass ratio of modifying agent and dicyclopentadiene is 1：2~1：3, reaction temperature is 240~260 DEG C, instead
It is 1.5~2.0MPa to answer pressure, and the reaction time is 240~300min.
5. preparation method according to claim 1, it is characterised in that in step (2), catalyst is skeletal nickel catalyst.
6. preparation method according to claim 5, it is characterised in that the average pore size of skeletal nickel catalyst for 2.0~
20.0 nanometers, nickel content is 40~80wt%.
7. preparation method according to claim 1, it is characterised in that in step (2), the molar ratio of Petropols and hydrogen
For 1:2~1:5, catalyst amount is 0.5~3.0wt% of Petropols, and the reaction time is 120~300min, reaction pressure
For 4.0~10.0MPa, reaction temperature is 170~250 DEG C.
8. preparation method according to claim 7, it is characterised in that in step (2), catalyst amount is Petropols
1.0~2.0wt%, reaction time are 180~240min, and reaction pressure is 6.0~8.0MPa, and reaction temperature is 200~220
℃。
A kind of 9. modification dicyclopentadiene hydrogenated petroleum resin that preparation method according to one of claim 1-8 obtains.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114656319A (en) * | 2022-04-02 | 2022-06-24 | 淄博鲁华泓锦新材料集团股份有限公司 | Preparation method of high-purity dicyclopentadiene |
| CN115819675A (en) * | 2022-11-29 | 2023-03-21 | 新疆力铭鑫通石油化工有限公司 | Process for preparing hydrogenated petroleum resin by modification |
| CN115926031A (en) * | 2022-12-04 | 2023-04-07 | 新疆力铭鑫通石油化工有限公司 | Method for preparing hydrogenated petroleum resin |
| CN117264361A (en) * | 2023-09-25 | 2023-12-22 | 上海方田粘合剂技术有限公司 | High-elasticity styrene copolymer-based resin capable of being pressed and bonded at normal temperature and preparation method thereof |
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| CN1479755A (en) * | 2000-12-11 | 2004-03-03 | ��˹����ѧ��֬��˾ | Thermally polymerized copolymers made from styrene and dicyclopentadiene monomers |
| CN104945560A (en) * | 2015-06-29 | 2015-09-30 | 安徽同心化工有限公司 | Hydrogenated styrene-modified dicyclopentadiene petroleum resin and preparation method thereof |
| WO2015147027A1 (en) * | 2014-03-26 | 2015-10-01 | 丸善石油化学株式会社 | Method for producing hydrogenated petroleum resin |
| CN105646786A (en) * | 2016-02-29 | 2016-06-08 | 山东玉皇化工有限公司 | Method for preparing dicyclopentadiene hydrogenated petroleum resin from dicyclopentadiene directly |
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| CN1479755A (en) * | 2000-12-11 | 2004-03-03 | ��˹����ѧ��֬��˾ | Thermally polymerized copolymers made from styrene and dicyclopentadiene monomers |
| WO2015147027A1 (en) * | 2014-03-26 | 2015-10-01 | 丸善石油化学株式会社 | Method for producing hydrogenated petroleum resin |
| CN104945560A (en) * | 2015-06-29 | 2015-09-30 | 安徽同心化工有限公司 | Hydrogenated styrene-modified dicyclopentadiene petroleum resin and preparation method thereof |
| CN105646786A (en) * | 2016-02-29 | 2016-06-08 | 山东玉皇化工有限公司 | Method for preparing dicyclopentadiene hydrogenated petroleum resin from dicyclopentadiene directly |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114656319A (en) * | 2022-04-02 | 2022-06-24 | 淄博鲁华泓锦新材料集团股份有限公司 | Preparation method of high-purity dicyclopentadiene |
| CN115819675A (en) * | 2022-11-29 | 2023-03-21 | 新疆力铭鑫通石油化工有限公司 | Process for preparing hydrogenated petroleum resin by modification |
| CN115926031A (en) * | 2022-12-04 | 2023-04-07 | 新疆力铭鑫通石油化工有限公司 | Method for preparing hydrogenated petroleum resin |
| CN115926031B (en) * | 2022-12-04 | 2024-04-16 | 新疆力铭鑫通石油化工有限公司 | Method for preparing hydrogenated petroleum resin |
| CN117264361A (en) * | 2023-09-25 | 2023-12-22 | 上海方田粘合剂技术有限公司 | High-elasticity styrene copolymer-based resin capable of being pressed and bonded at normal temperature and preparation method thereof |
| CN117264361B (en) * | 2023-09-25 | 2024-03-08 | 上海方田粘合剂技术有限公司 | High-elasticity styrene copolymer-based resin capable of being pressed and bonded at normal temperature and preparation method thereof |
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Application publication date: 20180511 |