CN1944483A - Aluminum trichloride/nucleophilic reagent composite catalystic system and its use in synthesizing petroleum resin - Google Patents
Aluminum trichloride/nucleophilic reagent composite catalystic system and its use in synthesizing petroleum resin Download PDFInfo
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- CN1944483A CN1944483A CN 200610104734 CN200610104734A CN1944483A CN 1944483 A CN1944483 A CN 1944483A CN 200610104734 CN200610104734 CN 200610104734 CN 200610104734 A CN200610104734 A CN 200610104734A CN 1944483 A CN1944483 A CN 1944483A
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- aluminum trichloride
- petroleum resin
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Abstract
The present invention discloses one kind of petroleum resin synthesizing catalyst system comprising aluminum trichloride and nucleohilic reagent at the weight ratio of 1/10-1/2 and forming homogeneous transparent solution through mixing at room temperature. The composite catalyst system has homogeneously dispersed aluminum trichloride and capacity of stabilizing the synthesizing process, and the polymerized system has relatively low viscosity and easy post-treatment. The petroleum resin synthesized with the catalyst system has high softening point of 85-120 deg.c, high compatibility, active component converting rate of 60-85 %, average molecular weight of 300-600 and expanded use range.
Description
Technical field
The present invention relates to a kind of composite catalyst system that is used for the petroleum resin polyreaction, relate in particular to a kind of aluminum chloride and nucleophilic reagent compound catalyst system.
Background technology
Petroleum resin are the cracking cut C with the ethylene unit by product
5Solid-state or the thick liquid state, the relative molecular mass that make for polymerizable raw material are lower than 2000 polymkeric substance, have that acid number is low, compatibility good, fusing point is low, binding property is good, water-fast and characteristics such as chemicals-resistant.Petroleum resin can be used as the fields such as additive of tackiness agent, printing ink, rubber tackifier, paper sizing agent and various coating.
Because C
5Raw material monomer composition more complicated (comprise cyclic diolefine: as cyclopentadiene, dicyclopentadiene; Diene: as isoprene, cis or trans m-pentadiene; Monoene: as iso-butylene, 1-butylene, suitable or anti-2-butylene, 2-methyl-2-butene, 3-methyl-1-butene, 2-methyl-1-butene alkene, 1-amylene, suitable or anti-2-amylene; Ring monoene such as cyclopentenes etc.), most petroleum resin all adopt the cationoid polymerisation under the Lewis acid catalysis.The catalyzer that is adopted is the Friedel-Craffs system, comprising: BF
3, BF
3Complex compound, AlCl
3, chlorination aluminum alkyls, alchlor, titanium tetrafluoride, tin tetrachloride, SiO
2Load BF
3Complex compound, the perhaps binary complex of these halogenide and aromatic compound and change thing and the ternary complex of aromatic compound and hydrogen halide etc.
Catalyzer aluminum chloride pressed powder be the most frequently used catalyzer of petroleum resin polymerization it.But directly use aluminum trichloride catalyst that a lot of shortcomings are arranged, in air, be easy to suction, cause reinforced difficulty as the aluminum chloride pressed powder, measure inaccurate, in addition, the complex shape of aluminum chloride own, particle size is inhomogeneous, easy conglomerate in raw material monomer.The conventional stirring is difficult to guarantee that each dispersion state is identical, causes identical prescription different polymerism and result, production technique instability to occur.
Chinese patent 97107458.5 discloses a kind of C 5 petroleum resin synthetic composite catalyst system that is applicable to, this composite catalyst system adopts two kinds of component: A, aromatic ether compounds, is mainly phenyl ether; B, AlCl
3, two kinds of components are at certain solvent such as pentane, hexane, toluene, dimethylbenzene, formulated in the chloroform etc., compare with the one-component catalyzer, have higher softening temperature and better consistency with this composite catalyst system synthetic C5 resin, but have the unsettled phenomenon of production technique equally.
Summary of the invention
The object of the present invention is to provide a kind of by aluminum trichloride (anhydrous) (AlCl
3) and nucleophilic reagent be composited and be used for the homogeneous catalyst system of synthesizing petroleum resin.
Aluminum trichloride/nucleophilic reagent composite catalystic system of the present invention is that the aluminum trichloride (anhydrous) powder is mixed with weight ratio part of 1: 2～1: 10 with nucleophilic reagent, and stirs the homogeneous phase transparent solution that forms at normal temperatures.
Described nucleophilic reagent is ether, sherwood oil, methyl-phenoxide, and ethyl acetate, phenyl ethyl ether, 4-methylbenzene methyl ether, 4-ethylbenzene ether, 4-ethylbenzene methyl ether or 4-tolyl ethyl ether, at least a in the ethyl benzoate.
Aluminum trichloride/nucleophilic reagent composite catalystic system of the present invention, application in the synthesizing petroleum resin polyreaction: be with raw material monomer, composite catalyst system and reagent and additive in polymerization by following weight ratio part proportioning after, at polymerization temperature: under 60～180 ℃, polyreaction 1～16 hour; Then polyreaction is got product and obtain unhydrided petroleum resin through alkali cleaning, washing, underpressure distillation.
Raw material monomer: 200 parts
Aluminum trichloride/nucleophilic reagent composite catalystic system: 3～8 parts
Wherein raw material monomer is C5 or C9 or the C10 that produces in the petrochemical complex cracking process.
The present invention has the following advantages compared with the prior art:
1, adopts aluminum trichloride/nucleophilic reagent composite catalystic agent of the present invention, solved solid catalyst AlCl in the petroleum resin polymerization
3Homodisperse problem has realized the stability of synthesis technique; Easily reinforced simultaneously, be easy to metering, can realize continuous operation.
2, because AlCl
3Scattered, size is little, and the viscosity of system is low relatively after the polymerization, and aftertreatment is easy.
3, utilize aluminum trichloride/nucleophilic reagent composite catalystic agent of the present invention, the synthetic petroleum resin have higher softening temperature and better consistency: softening temperature is between 85～120 ℃, the active ingredient transformation efficiency reaches 60～85%, molecular-weight average reaches 300～600, has expanded the use range of petroleum resin.
4, owing to the boiling point height of nucleophilic reagent in the composite catalyst system, be not easy volatilization, help safety in production.
Embodiment
Below by specific embodiment composite catalyst system of the present invention and the application in the synthesizing petroleum resin polyreaction thereof are further described.
The preparation of embodiment 1, composite catalyst system: at normal temperatures the aluminum trichloride (anhydrous) powder is mixed with weight ratio part of 1: 2 with methyl-phenoxide, and stir homogeneous phase transparent solution that 30s forms at normal temperatures promptly.
The polymerization of petroleum resin: with the composite catalyst of above-mentioned preparation with 3: 200 weight ratio part joins 90 ℃ C
10In the raw material monomer, stir (rotating speed 200rpm), slowly be warming up to 130 ℃, reacted 6 hours, and temperature of reaction was risen to 150 ℃ then, reacted 6 hours, question response obtains unhydrided petroleum resin with reaction product after finishing after alkali cleaning, washing, underpressure distillation aftertreatment.After measured, the transformation efficiency of resin is 77%, and softening temperature is 116 ℃, and colourity is 16, and number-average molecular weight is～410, and molecular weight distributing index (Mw/Mn) is 1.57.
The preparation of embodiment 2, composite catalyst system: at normal temperatures the aluminum trichloride (anhydrous) powder is mixed with weight ratio part of 1: 5 with phenyl ethyl ether, stir 1min and form homogeneous transparent solution promptly.
The polymerization of petroleum resin: with the composite catalyst of above-mentioned preparation with 5: 200 weight ratio part joins 90 ℃ C
5In the raw material monomer, stir (rotating speed 200rpm), slowly be warming up to 125 ℃, reacted 6 hours, temperature of reaction is risen to 145 ℃ then, reacted 6 hours, reaction is finished in the back.Reactant is obtained unhydrided petroleum resin after alkali cleaning, washing, underpressure distillation aftertreatment.The transformation efficiency of resin is 65%, and softening temperature is 113 ℃, and colourity is 16, and number-average molecular weight is～400, and molecular weight distributing index (Mw/Mn) is 1.6.
The preparation of embodiment 3, composite catalyst system: at normal temperatures the aluminum trichloride (anhydrous) powder is mixed with weight ratio part of 1: 5 with ethyl benzoate, stir 2min and form homogeneous transparent solution promptly.
The polymerization of petroleum resin: with the composite catalyst of above-mentioned preparation with 8: 200 weight ratio part joins 90 ℃ C
9Stir in the raw material monomer (rotating speed 200rpm), slowly be warming up to 130 ℃, reacted 6 hours, temperature of reaction is risen to 145 ℃ then, reacted 6 hours, reaction is finished in the back.Reactant is obtained unhydrided petroleum resin after alkali cleaning, washing, underpressure distillation aftertreatment.The softening temperature of resin is 84 ℃, and number-average molecular weight is～289, and molecular weight distributing index (Mw/Mn) is 1.49.
Adopt the embodiment of aluminum chloride and other nucleophilic reagent preparation composite catalyst system the same, repeat no more here.
In the foregoing description, the softening temperature of petroleum resin adopts ring and ball method to press the GB2294-80 standard test.The Gardner of resin (Gardner) colourity is according to the GB1722-79 standard test; The molecular weight of resin is measured by gel permeation chromatography (GPC).
Claims (3)
1, a kind of aluminum trichloride/nucleophilic reagent composite catalystic system that is used for synthesizing petroleum resin is characterized in that: with aluminum trichloride (anhydrous) powder and the nucleophilic reagent abundant mixing of weight ratio part with 1: 2～1: 10, form homogeneous phase transparent solution promptly at normal temperatures.
2, aluminum trichloride/nucleophilic reagent composite catalystic system as claimed in claim 1, it is characterized in that: described nucleophilic reagent is ether, sherwood oil, methyl-phenoxide, ethyl acetate, phenyl ethyl ether, 4-methylbenzene methyl ether, 4-ethylbenzene ether, 4-ethylbenzene methyl ether or 4-tolyl ethyl ether, at least a in the ethyl benzoate.
3, the application of aluminum trichloride/nucleophilic reagent composite catalystic system as claimed in claim 1 in the synthesizing petroleum resin polyreaction, be with raw material monomer, composite catalyst system and reagent and additive in polymerization by following weight ratio part proportioning after, at polymerization temperature: under 60～180 ℃, polyreaction 1～16 hour; Then polyreaction is got product and obtain unhydrided petroleum resin through alkali cleaning, washing, underpressure distillation.
Raw material monomer: 200 parts
Aluminum trichloride/nucleophilic reagent composite catalystic system: 3～8 parts
Wherein raw material monomer is C5 or C9 or the C1 that produces in the petrochemical complex cracking process.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610104734XA CN100494235C (en) | 2006-10-09 | 2006-10-09 | Aluminum trichloride/nucleophilic reagent composite catalystic system and its use in synthesizing petroleum resin |
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|---|---|---|---|
| CNB200610104734XA CN100494235C (en) | 2006-10-09 | 2006-10-09 | Aluminum trichloride/nucleophilic reagent composite catalystic system and its use in synthesizing petroleum resin |
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| CN1944483A true CN1944483A (en) | 2007-04-11 |
| CN100494235C CN100494235C (en) | 2009-06-03 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101412789B (en) * | 2007-10-18 | 2012-04-18 | 中国石化上海石油化工股份有限公司 | Method for utilizing waste liquid from cyclopentadiene production using C9 distillate |
| CN103127882A (en) * | 2013-01-31 | 2013-06-05 | 宁波职业技术学院 | Method to continuously add anhydrous aluminum trichloride catalysts |
| CN106543362A (en) * | 2016-11-17 | 2017-03-29 | 恒河材料科技股份有限公司 | A kind of preparation method of C5/C10 copolymer resinses |
| CN108822257A (en) * | 2018-07-04 | 2018-11-16 | 濮阳市瑞森石油树脂有限公司 | A kind of preparation method of light color low softening point modified petroleum resin |
-
2006
- 2006-10-09 CN CNB200610104734XA patent/CN100494235C/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101412789B (en) * | 2007-10-18 | 2012-04-18 | 中国石化上海石油化工股份有限公司 | Method for utilizing waste liquid from cyclopentadiene production using C9 distillate |
| CN103127882A (en) * | 2013-01-31 | 2013-06-05 | 宁波职业技术学院 | Method to continuously add anhydrous aluminum trichloride catalysts |
| CN103127882B (en) * | 2013-01-31 | 2016-05-04 | 宁波职业技术学院 | A kind of method that Catalyzed by Anhydrous Aluminium Chloride agent adds continuously |
| CN106543362A (en) * | 2016-11-17 | 2017-03-29 | 恒河材料科技股份有限公司 | A kind of preparation method of C5/C10 copolymer resinses |
| CN106543362B (en) * | 2016-11-17 | 2018-10-19 | 恒河材料科技股份有限公司 | A kind of preparation method of C5/C10 copolymer resins |
| CN108822257A (en) * | 2018-07-04 | 2018-11-16 | 濮阳市瑞森石油树脂有限公司 | A kind of preparation method of light color low softening point modified petroleum resin |
| CN108822257B (en) * | 2018-07-04 | 2021-04-30 | 濮阳市瑞森石油树脂有限公司 | Preparation method of light-color low-softening-point modified petroleum resin |
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|---|---|
| CN100494235C (en) | 2009-06-03 |
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