CN1485353A - Method for production of dicyclopentadiene hydrogenated petroleum resin - Google Patents
Method for production of dicyclopentadiene hydrogenated petroleum resin Download PDFInfo
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- CN1485353A CN1485353A CNA021371156A CN02137115A CN1485353A CN 1485353 A CN1485353 A CN 1485353A CN A021371156 A CNA021371156 A CN A021371156A CN 02137115 A CN02137115 A CN 02137115A CN 1485353 A CN1485353 A CN 1485353A
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- petroleum resin
- dicyclopentadiene
- hydrogenated petroleum
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- reaction
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Abstract
A method of preparing dicyclopentadiene hydrogenant petroleum resin, comprises hydrogenating dicyclopentadiene petroleum resin in an organic solvent at the presence of a catalyst, the reaction temperature is 220- 320degree C, the reaction hydrogen pressure is 6.0-12.0Mpa, the reaction time is 2-6 hours. Active components of the resin are Pd and Pt. The contents of Pd and Pt are 0.1- 1.0wt% and 0.05-0.5wt%, respectively. The carrier of the catalyst is gamma-Al2O3, the specific surface are is 150-250m2/g, the volume is 0.5-0.9ml/g. Hydrogenant resin prepared from dicyclopentadiene petroleum resin through the catalyst has a lowered content of unsaturated hydrocarbon bonds, and the color of the resin is improved to water-white.
Description
Technical field
The present invention relates to dicyclopentadiene petroleum resin prepares dicyclopentadiene hydrogenated petroleum resin by shortening preparation method.
Background technology
Dicyclopentadiene petroleum resin is made by hot polymerization by dicyclopentadiene usually, it is the relatively low thermoplastic hydrocarbon resin of a kind of number-average molecular weight, utilize it and other resin to have this characteristic of consistency preferably, be often used as tackifier and binding agent, obtained at aspects such as hot melt adhesive, Pressuresensitive Tape, ink printing and rubber using widely.Dicyclopentadiene derives from the C5 fraction separated product of petroleum cracking system ethylene by-product greatly at present, the dicyclopentadiene petroleum resin ubiquity form and aspect that this dicyclopentadiene makes are dark, flavor is smelly, unsaturated hydrocarbons linkage content height, thermostability and defective such as oxidative stability is low, cohesive force is relatively poor, with a lot of resinous substrates can not be compatible well, relatively poor as the tackifier result of use.Usually people adopt the method for hydrogenation to improve the performance of dicyclopentadiene petroleum resin, can reduce the content of unsaturated hydrocarbons key effectively by hydrogenation, thereby can improve the thermostability of dicyclopentadiene petroleum resin and consistency etc.
Patent US4,384,080 and US4,952,639 have described the hydrogenation of petroleum resin method of making hydrogenation catalyst with precious metals such as nickel, palladium, platinum, rhenium, rutheniums, and generally adopting the single component metal is the catalyst activity component.Patent US4,540,480 have introduced a kind of hydrogenation of petroleum resin method, and the active ingredient of catalyst system therefor is used in combination above-mentioned precious metal, and the carrier of catalyzer generally adopts Al
2O
3, it is said that the catalyzer that adopts has higher active and long work-ing life, the hydrogenated petroleum resin iodine number≤60g/100g that obtains, gardner form and aspect≤1.Existing these hydrogenation of petroleum resin methods are remarkable for the unsaturated hydrocarbons linkage content effect that reduces dcpd resin, but improve aspect the form and aspect of resin not very good.Particularly separate in the dicyclopentadiene that obtains and contain more impurity by the C5 fraction of petroleum cracking system ethylene by-product, usually purity only is 75～85wt%, other impurity that contains comprises unknown dipolymer, trimer, indenes class, isoprene dimer, benzene and toluene etc., the dicyclopentadiene petroleum resin that makes is unsaturated hydrocarbons linkage content height not only, and form and aspect are darker.This dicyclopentadiene petroleum resin can not obtain form and aspect ideal hydrogenation resin with existing general hydrogenation of petroleum resin method.
Summary of the invention
The invention provides a kind of preparation method of dicyclopentadiene hydrogenated petroleum resin, its technical problem to be solved is that the hydrogenated petroleum resin that makes not only requires the unsaturated hydrocarbons linkage content low, thermostability and oxidative stability are good, and form and aspect also should be improved completely.It is that the dicyclopentadiene petroleum resin that raw material makes carries out hydrotreatment that this method is used for the C5 fraction with petroleum cracking system ethylene by-product is separated the dicyclopentadiene that obtains, and can obtain the ideal effect equally.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
A kind of preparation method of dicyclopentadiene hydrogenated petroleum resin, this method is carried out hydrogenation reaction with dicyclopentadiene petroleum resin in the presence of catalyzer in organic solvent, temperature of reaction is 220～320 ℃, and the reaction hydrogen pressure is 6.0～12.0MPa, and the reaction times is 2～6 hours.Catalyzer is that active ingredient is the loaded catalyst of Pd and Pt, and the content of Pd is 0.1～1.0wt%, and the content of Pt is 0.05～0.5wt%, and support of the catalyst is γ-Al
2O
3, its specific surface is 150～250m
2/ g, pore volume are 0.5～0.9ml/g.
The content of above-mentioned catalyst activity component Pd is preferably 0.3～0.5wt%; The content of Pt is preferably 0.1～0.2wt%; Catalyst consumption is generally dicyclopentadiene petroleum resin: catalyzer=100: 1.0～4.0 (weight ratio); Temperature of reaction is preferably 280～300 ℃; The reaction hydrogen pressure is preferably 8.0～10.0MPa.Above-mentioned organic solvent can be selected from any in normal hexane, normal heptane, hexanaphthene, methylcyclohexane, ethylcyclohexane, 60～90 ℃ of sherwood oils or 90～120 ℃ of sherwood oils usually.
The pickling process that catalyzer can adopt those skilled in the art to know prepares, and the starting material of Pd can adopt PdCl
2, the starting material of Pt can adopt H
2PtCl
6Elder generation is with PdCl during preparation
2And H
2PtCl
6Be dissolved in the HCl solution, then with γ-Al
2O
3Pour in the solution and flood.Oven dry while stirring just can make finished catalyst behind the mixture ageing after high-temperature roasting.
Key of the present invention is that the catalyzer that is adopted selected suitable active ingredient and selected the suitable γ-Al of physical structure
2O
3As carrier, the contriver found through experiments, this catalyzer has demonstrated beyond thought effect aspect the form and aspect of dicyclopentadiene petroleum resin improving, even the dicyclopentadiene petroleum resin that obtains with the relatively poor dicyclopentadiene hot polymerization that is obtained by the C5 fraction separation of form and aspect is a raw material, the hydrogenation resin that makes by hydrogenation reaction not only unsaturated hydrocarbons linkage content obviously reduces, and the resin form and aspect are improved to and are water white.
Embodiment
In an embodiment, the testing method of each index is as follows:
Softening temperature: ring and ball method (GB4507-84)
Form and aspect: iron-cobalt colorimetry, i.e. gardner method (GB1722-79)
Bromine number: volumetry (SH/T0236-92)
Hydrogenation ratio:
Dicyclopentadiene petroleum resin raw material index:
Softening temperature (℃) 118
Bromine number (g bromine/100g) 83.7
Form and aspect 7
[embodiment 1～8]
One, Preparation of catalysts:
Take by weighing a certain amount of PdCl
2And H
2PtC
16, it is dissolved among the HCl of 0.1N, getting specific surface is 150～250m
2/ g, pore volume are γ-Al of 0.5～0.9ml/g
2O
3As carrier.With this Al
2O
3Pour in the above-mentioned solution aging 2 hours into.With infrared lamp it is dried while stirring, this catalyst precursor is placed chamber type electric resistance furnace in 300 ℃ of following roastings 1 hour again, in 500 ℃ of following roastings 3 hours, it was standby to obtain finished catalyst again.Catalyzer index and the catalyst consumption of each embodiment see Table 1.
Two, hydrogenation reaction:
At a capacity is that 2L is with adding 200ml hexanaphthene in the autoclave that stirs, and the dicyclopentadiene petroleum resin raw material of the broken shape of 200g, the catalyzer of aequum is added in the still again.With nitrogen and hydrogen the air in the still fully being replaced successively, is 280～300 ℃ in temperature then, and hydrogen pressure is to react 2～6 hours under the condition of 8.0～10.0MPa.Hydrogenation products reclaims after filtration that catalyzer, precipitation reclaim solvent, stripping takes off light and processes such as decompression dehydration and cooling forming, obtains the hydrogenated petroleum resin product.Product carries out index analysis, and the product index of each embodiment sees Table 2.The filtering recovering catalyst of product, precipitation reclaim solvent, stripping takes off processes such as light and decompression dehydration and cooling forming and adopts usual way well known in the art, are no longer described in detail among the embodiment.
Table 1.
| Pd content (%) | Pt content (%) | Catalyst levels (resin/catalyst, weight ratio) | |
| Embodiment 1 | ????0.1 | ????0.48 | ????4.0 |
| Embodiment 2 | ????0.1 | ????0.40 | ????3.0 |
| Embodiment 3 | ????0.2 | ????0.35 | ????3.0 |
| Embodiment 4 | ????0.3 | ????0.20 | ????2.5 |
| Embodiment 5 | ????0.5 | ????0.10 | ????2.5 |
| Embodiment 6 | ????0.7 | ????0.10 | ????2.0 |
| Embodiment 7 | ????0.9 | ????0.08 | ????1.5 |
| Embodiment 8 | ????1.0 | ????0.05 | ????1.0 |
Table 2.
| Softening temperature (℃) | Bromine number (the g bromine/100g) | Form and aspect | Hydrogenation ratio (%) | |
| Embodiment 1 | ????108 | ????3.2 | Water white | ????96 |
| Embodiment 2 | ????113 | ????4.2 | Water white | ????95 |
| Embodiment 3 | ????105 | ????3.3 | Water white | ????96 |
| Embodiment 4 | ????105 | ????2.5 | Water white | ????97 |
| Embodiment 5 | ????111 | ????3.0 | Water white | ????96 |
| Embodiment 6 | ????108 | ????3.8 | Water white | ????95 |
| Embodiment 7 | ????104 | ????5.0 | Water white | ????94 |
| Embodiment 8 | ????101 | ????5.0 | Water white | ????94 |
Claims (7)
1, a kind of preparation method of dicyclopentadiene hydrogenated petroleum resin, this method is carried out hydrogenation reaction with dicyclopentadiene petroleum resin in the presence of catalyzer in organic solvent, temperature of reaction is 220～320 ℃, the reaction hydrogen pressure is 6.0～12.0MPa, reaction times is 2～6 hours, and the catalyst activity component is Pd and Pt, and the content of Pd is 0.1～1.0wt%, the content of Pt is 0.05～0.5wt%, and support of the catalyst is γ-Al
2O
3, its specific surface is 150～250m
2/ g, pore volume are 0.5～0.9ml/g.
2, the preparation method of dicyclopentadiene hydrogenated petroleum resin according to claim 1, the content that it is characterized in that described catalyst activity component Pd is 0.3～0.5wt%.
3, the preparation method of dicyclopentadiene hydrogenated petroleum resin according to claim 1, the content that it is characterized in that described catalyst activity component Pt is 0.1～0.2wt%.
4, the preparation method of dicyclopentadiene hydrogenated petroleum resin according to claim 1 is characterized in that described catalyst consumption is a dicyclopentadiene petroleum resin: catalyzer=100: 1.0～4.0 weight ratios.
5, the preparation method of dicyclopentadiene hydrogenated petroleum resin according to claim 1 is characterized in that described temperature of reaction is 280～300 ℃.
6, the preparation method of dicyclopentadiene hydrogenated petroleum resin according to claim 1 is characterized in that described reaction hydrogen pressure is 8.0～10.0MPa.
7, the preparation method of dicyclopentadiene hydrogenated petroleum resin according to claim 1 is characterized in that described organic solvent is selected from any in normal hexane, normal heptane, hexanaphthene, methylcyclohexane, ethylcyclohexane, 60～90 ℃ of sherwood oils or 90～120 ℃ of sherwood oils.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021371156A CN1189494C (en) | 2002-09-24 | 2002-09-24 | Method for production of dicyclopentadiene hydrogenated petroleum resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021371156A CN1189494C (en) | 2002-09-24 | 2002-09-24 | Method for production of dicyclopentadiene hydrogenated petroleum resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1485353A true CN1485353A (en) | 2004-03-31 |
| CN1189494C CN1189494C (en) | 2005-02-16 |
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100404568C (en) * | 2005-06-28 | 2008-07-23 | 中国石油天然气集团公司 | Prepn of C5 hydrogenated petroleum resin |
| CN112191245A (en) * | 2020-09-28 | 2021-01-08 | 浙江工业大学 | Ultrathin eggshell type noble metal alloy catalyst for catalytic hydrogenation reaction of C5 petroleum resin and preparation method and application thereof |
-
2002
- 2002-09-24 CN CNB021371156A patent/CN1189494C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100404568C (en) * | 2005-06-28 | 2008-07-23 | 中国石油天然气集团公司 | Prepn of C5 hydrogenated petroleum resin |
| CN112191245A (en) * | 2020-09-28 | 2021-01-08 | 浙江工业大学 | Ultrathin eggshell type noble metal alloy catalyst for catalytic hydrogenation reaction of C5 petroleum resin and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1189494C (en) | 2005-02-16 |
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