CN1293212A - Process for synthesizing pentadiene resin by cationic polymerization - Google Patents
Process for synthesizing pentadiene resin by cationic polymerization Download PDFInfo
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- CN1293212A CN1293212A CN 99116972 CN99116972A CN1293212A CN 1293212 A CN1293212 A CN 1293212A CN 99116972 CN99116972 CN 99116972 CN 99116972 A CN99116972 A CN 99116972A CN 1293212 A CN1293212 A CN 1293212A
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- pentadiene
- component
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- synthesizing
- ether
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- 229920005989 resin Polymers 0.000 title claims abstract description 27
- 239000011347 resin Substances 0.000 title claims abstract description 27
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 18
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 10
- 230000008569 process Effects 0.000 title abstract description 4
- 238000010538 cationic polymerization reaction Methods 0.000 title abstract description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- -1 aromatic ether compound Chemical class 0.000 claims abstract description 7
- 150000005826 halohydrocarbons Chemical class 0.000 claims abstract description 6
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- WSWPHHNIHLTAHB-UHFFFAOYSA-N 1-ethoxy-4-methylbenzene Chemical compound CCOC1=CC=C(C)C=C1 WSWPHHNIHLTAHB-UHFFFAOYSA-N 0.000 claims description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 2
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 abstract 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 150000002430 hydrocarbons Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000000047 product Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 239000002841 Lewis acid Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 238000005120 petroleum cracking Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- 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 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical group ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 229910018287 SbF 5 Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001941 cyclopentenes Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polyethers (AREA)
Abstract
A process for synthesizing pentadiene resin by cationic polymerization uses fatty hydrocarbon, arylhydrocarbon or halohydrocarbon as reaction solvent, and features that the polymerization reaction takes place under existance of the catalyst containing components A and B. Said component A is substituted aromatic ether compound, such as phenyl methylether, phenylether, etc. Component B is AlCl3. The mol ratio of A to B shall be controlled in the range of 0.1-10.0, preferably 0.5-3.5. The resultant product features better compatibility, higher softening point and higher level of reactive yield.
Description
The present invention relates to be used for the method for synthesizing pentadiene resin.
The a considerable amount of C 5 fractions of by-product are rich in diolefins such as isoprene, cyclopentadiene and m-pentadiene in the process of petroleum cracking system ethene in the C 5 fraction.These diolefin chemical property are active, are the valuable sources of chemical industry.Wherein the content of m-pentadiene in C 5 fraction is usually about 15～25%, by C 5 fraction being separated and making with extra care that can to make purity be m-pentadiene more than 60%, is that raw material can make pentadiene resin by cationoid polymerisation with it.Comparing to the C 5 fraction without separating treatment is mixing carbon five resins that raw material directly makes, and pentadiene resin has advantages such as lighter color, thickening property be good.Therefore pentadiene resin has important use to be worth in the manufacturing field of products such as thermosol, pressure sensitive adhesive, thermosol coating and pavement marker lacquer.
M-pentadiene is produced pentadiene resin by cationoid polymerisation and is adopted Lewis acid such as metal or non-metallic halide to be catalyzer usually, and these Lewis acid comprise AlCl
3, (CH
3CH
2) AlCl
2, (CH
3CH
2)
2AlCl, BF
3, AlBr
3, FeCl
3, SbF
5, SnCl
4Or TiCl
4Deng, in these Lewis acid, the most widely used is AlCl
3Because there is certain limitation in this to the control of reaction the Lewis acid catalyst of single component in polymerization process, therefore researching and developing the compound catalyst system has been subjected to common attention.Propose at AlCl as patent US 4,419,503
3Catalystic converter system in introduce HCl improving catalytic activity, and patent US4,008,360 and 4,068,062 proposition of US active halohydrocarbon (RX) is introduced catalystic converter system.By RX/AlCl
3The consistency of the pentadiene resin product that the composite catalyst system of forming makes by cationoid polymerisation obtains improvement to a certain degree, decreases but the defective of these catalyst systems is the pentadiene resin product softening temperatures that make.Generally know that the low pentadiene resin product of softening temperature is easier to make, and the application under some weather condition needs the pentadiene resin product that higher softening temperature is arranged.
The purpose of this invention is to provide a kind of method by the cationoid polymerisation synthesizing pentadiene resin, it has overcome the defective of prior art, adopt the pentadiene resin product of this method preparation to have consistency and higher softening temperature preferably, and reaction yield also have higher level.
The method of synthesizing pentadiene resin provided by the invention is a reaction solvent with aliphatic hydrocarbon, aromatic hydrocarbons or halohydrocarbon, and polyreaction is carried out in the presence of following catalyzer:
Catalyzer contains two kinds of components of A, B, wherein:
A is an a kind of substituted aromatic ether compound with following structural:
Wherein R is C
1～C
6Alkyl,
R ＇ is C
0～C
6Alkyl, wherein R ＇ is C
0Alkyl the time represent that R ＇ does not exist, B is AlCl
3, the mol ratio of A and B is A/B=0.1～10.0.
When A was taken from a kind of in methyl-phenoxide, phenyl ethyl ether, 4-methylbenzene methyl ether, 4-ethylbenzene ether, 4-ethylbenzene methyl ether or the 4-tolyl ethyl ether, the contriver thought that effect is better.The mol ratio of A and B should be controlled in 0.1～10.0 the scope, A/B=0.5～3.5th wherein, preferable selection.
Catalyzer can adopt conventional blending method to be prepared
Temperature of reaction and reaction pressure are same as the prior art, and general temperature of reaction all can be carried out in 0～80 ℃ scope, and reaction pressure can adopt normal pressure usually.
The contriver found through experiments, and the aromatic ether compounds of introducing said structure in catalyst system can make that reaction soln becomes aryl ethers-AlCl
3-solvent homogeneous system (it is solvent that the pentadiene resin building-up reactions generally adopts aliphatic hydrocarbon, aromatic hydrocarbons or halohydrocarbon), being aggregated in of m-pentadiene makes reaction tend to be steady and is easy to control in the homogeneous phase solution, because homogeneous reaction has better repeatability, help the stable of quality product.In addition, polyreaction makes also that in homogeneous system the molecular weight distribution of product narrows down, thereby has improved the consistency of product greatly, and generally knows that consistency is important performance index of petroleum resin.
On the other hand, the contriver finds after deliberation, and compared with prior art, the introducing of above-mentioned aromatic ether compounds in catalyst system also makes the colourity of pentadiene resin product reduce and softening temperature obtains raising, wherein to the most worthy that influences of softening temperature.The explanation that the contriver in theory still can not be satisfied with at present that influences to softening temperature, in fact the effect of electron pair donor in the cationic polymerization system is very complicated, it is generally acknowledged lone-pair electron and positively charged ion formation complexing action to a certain degree in ethers-O-functional group, make the state in chainpropagation active centre that change take place, for example make the stability of carbocation obtain increasing, but it is pointed out that above complexing action is one and is difficult to the directly chemical process of confirmation.
Below will further describe the present invention, can find out positively effect of the present invention significantly by the reaction yield of comparative example and embodiment, the data such as colourity, softening temperature and sign product consistency of product by comparative example and embodiment.
Comparative example or embodiment:
One, m-pentadiene raw material:
The m-pentadiene raw material adopts the C 5 fraction through the petroleum cracking system ethylene by-product of separating treatment, and it consists of (weight %):
Pentamethylene 3.5
Cyclopentenes 19.5
Instead-m-pentadiene 46.3
Suitable-m-pentadiene 25.9
Cyclopentadiene 1.0
Dicyclopentadiene 1.3
C
6Hydrocarbon summation 2.0
Other impurity 0.5
Two, yield:
Three, the performance index of pentadiene resin product
1, colourity: adopt Jia Shi (Gardner) method to press GBl722-79 and measure.
2, softening temperature: adopt ring and ball method to press GB2294-80 and measure.
3, consistency: adopt the cloud point of rosin products and EVA (ethylene-vinyl acetate copolymer) and paraffin blend to characterize, its measuring method is: be the mixture heating up fusion of paraffin/EVA/ rosin products=50/25/25 with weight ratio and be warming up to 200 ℃, slowly cooling after stirring a little is when transparent clarifying temperature when melting body and beginning to occur white vaporific turbid phenomenon is considered as the cloud point of resin.Obviously, lower cloud point has been reacted resin and has been had consistency preferably.
Four, Preparation of catalysts and reaction process:
In the reaction flask that temperature control unit, whipping appts, condenser (the upper end outlet connects the CaO drying tube) and nitrogen conduit are housed, add 2 grams (1.5 * 10
-2Mole) AlCl
3With 100 milliliters of toluene, stir and heat above-mentioned suspension and add a certain amount of chlorallylene or the aromatic ether compounds, AlCl to be suspended
3Is all beginning to drip total amount after the dissolving? the m-pentadiene raw material of gram.
Control whole m-pentadiene raw materials and dripped off in 1 hour, dropwise the back and continue reaction 30 minutes, temperature of reaction maintains 25 ± 5 ℃ scope, and whole process must be implemented nitrogen protection, and reaction pressure is a normal pressure.
Reaction finishes the back, and to add 50 ml concns be the NaOH aqueous solution neutralization reaction liquid of 5% (w.t.), leaves standstill after abundant stirring and divide lixiviating solution, with 100 ml waters rinsing reaction solution and branch vibration layer at twice.Unreacted m-pentadiene and toluene are removed in distillation then, isolate liquid-state oligomers with steam distillation in 200～250 ℃ again under nitrogen protection, by the pentadiene resin product that gets molten state at the bottom of the matrass.
What following table was listed is catalyst system composition and the result data of comparative example and embodiment, and catalyzer is made up of A and B, and A is by listed in the table, and B is AlCl
3 
Claims (4)
1, a kind of method by the cationoid polymerisation synthesizing pentadiene resin is a reaction solvent with aliphatic hydrocarbon, aromatic hydrocarbons or halohydrocarbon, it is characterized in that polyreaction carries out in the presence of following catalyzer:
Catalyzer mainly contains two kinds of components of A, B, wherein:
A is a kind of aromatic ether compounds with following structural:
Wherein R is C
1-C
6Alkyl,
R ' is C
0～C
6Alkyl, wherein R ' is C
0Alkyl the time represent that R ' does not exist, B is AlCl
3, the mol ratio of A and B is A/B=0.1～10.0.
2, the method for synthesizing pentadiene resin according to claim 1 is characterized in that component A in the catalyzer is any in methyl-phenoxide, phenyl ethyl ether, 4-methylbenzene methyl ether, 4-ethylbenzene ether, 4-ethylbenzene methyl ether or the 4-tolyl ethyl ether.
3, the method for synthesizing pentadiene resin according to claim 1, the mol ratio that it is characterized in that catalyst A component and B component is A/B=0.5～3.5.
4,, it is characterized in that catalyzer adopts the blending method preparation according to the method for claim 1,2 or 3 described synthesizing pentadiene resins.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99116972 CN1293212A (en) | 1999-10-14 | 1999-10-14 | Process for synthesizing pentadiene resin by cationic polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99116972 CN1293212A (en) | 1999-10-14 | 1999-10-14 | Process for synthesizing pentadiene resin by cationic polymerization |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1293212A true CN1293212A (en) | 2001-05-02 |
Family
ID=5279626
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99116972 Pending CN1293212A (en) | 1999-10-14 | 1999-10-14 | Process for synthesizing pentadiene resin by cationic polymerization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1293212A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103382238A (en) * | 2012-05-04 | 2013-11-06 | 青岛伊科思新材料股份有限公司 | Polymerization method for m-pentadiene petroleum resin |
| CN105937567A (en) * | 2015-03-05 | 2016-09-14 | 威伯科欧洲公司 | Axis of a land vehicle, land vehicle with such a suspension and disc brake and brake support of such land vehicle |
-
1999
- 1999-10-14 CN CN 99116972 patent/CN1293212A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103382238A (en) * | 2012-05-04 | 2013-11-06 | 青岛伊科思新材料股份有限公司 | Polymerization method for m-pentadiene petroleum resin |
| CN105937567A (en) * | 2015-03-05 | 2016-09-14 | 威伯科欧洲公司 | Axis of a land vehicle, land vehicle with such a suspension and disc brake and brake support of such land vehicle |
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