CN103641938A - Initiator for alkene monomer polymerization reaction - Google Patents
Initiator for alkene monomer polymerization reaction Download PDFInfo
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- CN103641938A CN103641938A CN201310726322.XA CN201310726322A CN103641938A CN 103641938 A CN103641938 A CN 103641938A CN 201310726322 A CN201310726322 A CN 201310726322A CN 103641938 A CN103641938 A CN 103641938A
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- Prior art keywords
- polymerization
- initiator
- compound
- vinyl monomer
- butyronitrile
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 27
- 239000000178 monomer Substances 0.000 title claims abstract description 15
- 239000003999 initiator Substances 0.000 title abstract description 39
- 150000001336 alkenes Chemical class 0.000 title abstract 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims abstract description 6
- 238000012662 bulk polymerization Methods 0.000 claims abstract description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 11
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 7
- IHHBESJMKGMIPU-UHFFFAOYSA-N C(CCC)#N.C1(=CC=CC=C1)C1=CC=CC=C1 Chemical compound C(CCC)#N.C1(=CC=CC=C1)C1=CC=CC=C1 IHHBESJMKGMIPU-UHFFFAOYSA-N 0.000 claims description 5
- 229940125782 compound 2 Drugs 0.000 claims description 5
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 abstract description 7
- 239000003505 polymerization initiator Substances 0.000 abstract description 4
- -1 acrylic ester Chemical class 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 2
- DRIXCPODDGFEDD-UHFFFAOYSA-N 2,3-diphenylbutanenitrile Chemical compound C=1C=CC=CC=1C(C)C(C#N)C1=CC=CC=C1 DRIXCPODDGFEDD-UHFFFAOYSA-N 0.000 abstract 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000000379 polymerizing effect Effects 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 125000000129 anionic group Chemical group 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 238000007710 freezing Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- BTMRYSYEOPOPBR-UHFFFAOYSA-N benzene;ethane Chemical class CC.C1=CC=CC=C1 BTMRYSYEOPOPBR-UHFFFAOYSA-N 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an initiator for alkene monomer polymerization reaction, and belongs to the technical field of imitators. A compound 2,3-diphenyl butyronitrile is applied to initiating polymerization of alkene monomers such as acrylic ester, metacrylic acid ester and styrene, the polymerization method mainly refers to bulk polymerization or solution polymerization, and the initiated polymerization temperature is 70-130 DEG C. The compound 2,3-diphenyl butyronitrile can be dissolved by the solvent adopted in solution polymerization. By adopting the initiator, a polymerization initiator system is expanded, and polymers with high molecular weight are easily obtained.
Description
Technical field
The present invention relates to a kind of new purposes of compound, especially 2, the new purposes of 3-phenylbenzene butyronitrile, can be used as initiator for causing the polymerization of vinyl monomer, belongs to initiator technical field.
Background technology
Macromolecular compound is generally made by initiator system trigger monomer generation polymerization.Initiator system plays indispensable effect in macromolecular compound preparation process, makes a general survey of polymer science developing history, and initiator system evolution history is exactly the development history of polymer science.Existing high molecular polymerization initiator system divides five large classes, is respectively free radical initiator system, cationic initiator system, anionic initiator system, polycoordination initiator system and group transfer polymerization initiator system.
Polycoordination initiator system is very successful initiator system, and what several influential plastics, rubber clone adopted is polycoordination initiator system.But polycoordination initiator system is had relatively high expectations to polymerization environment, and initiator system preparation is complicated, higher to transportation, storage request.
Anionic initiation system is prepared complexity equally, to transportation, storage request is higher, very high to polymerization environmental requirement.And anionic initiation system use range is very narrow, successfully Industrial products only have several.
Positively charged ion initiator system range of application is narrower, and group transfer polymerization does not also have practical application.
In macromolecular compound preparation, free radical initiator system is most widely used general.Mainly be divided into two classes: thermal initiation system, redox system.On the molecular structure of radical initiator, there is weak bond, easily resolve into free radical.Thermal initiation system is single compound, by heating, the weak bond in compound is ruptured, and produces free radical and initiated polymerization mainly divides azo-compound and superoxide two classes.Thermal initiation system, easy to use, be main initiator system prepared by macromolecular compound.Redox system is two components, and a kind of is superoxide, and a kind of is reductive agent.Use range is narrower compared with thermal initiation system.
The relative cationic initiator system of free radical initiator system, anionic initiator system, polycoordination initiator system is many easily, and major advantage is as follows: 1, component is single, and preparation is simple; 2, easy to use; 3, storage, movement requirement are lower.But, because it mostly is azo, peroxide compound, there is the risk of blast.Also a lot of inconvenience of having given use, storage and travelling belt.
Summary of the invention
The present invention relates to the compound in a kind of organic synthesis field, the polymerization of the vinyl monomer such as this compound can Methyl Methacrylate, ethyl propenoate, vinylbenzene.Because being solid-state under its normal temperature, thus be convenient to storage, transportation, and preparation method is simple, cost is lower, when possessing the general advantage of free radical initiator system, has also overcome the part defect of conventional free radical initiator, has expanded initiator system.
The initiator the present invention relates to, is compound 2,3-phenylbenzene butyronitrile, and its structural formula is
The preparation method of the compound that the present invention mentions (I), by the preparation of improving one's methods, concrete synthetic method comprises the steps:
By phase-transfer catalyst TEBAC and highly basic NaOH(or KOH) be dissolved in distilled water, under agitation condition, slowly drip the mixed solution of chlorinated benzene ethane and two kinds of raw materials of benzyl cyanide, after 50～60 ℃ of reaction 8～10h, add the static termination reaction of ice-water bath or normal temperature, with dichloromethane solvent, extract afterwards, extract organic layer, then use anhydrous MgSO
4dry, solvent evaporated, column chromatography for separation is purified, and gets final product to obtain compound (I).Reaction equation is as follows:
The compound the present invention relates to can be used for causing the polymerization of vinyl monomer, especially (methyl) esters of acrylic acid or cinnamic polymerization, as acrylate, methacrylic ester, vinylbenzene etc., the polymerization process relating to is mainly mass polymerization or solution polymerization, and initiated polymerization temperature is 70-130 ℃.The solvent adopting during solution polymerization can dissolved compound (I).
Compound of the present invention is as initiator; substantially the same with conventional initiator usage; as nitrogen protection etc.; and the present invention has use and storage security; simple to operate, synthetic method is simple, and cost is lower; and the advantage of the polymkeric substance that the molecular weight that is easy to get is higher, has expanded polymerization initiator system.
Accompanying drawing explanation
Fig. 1 is the compound 2 of preparation, 3-phenylbenzene butyronitrile
1h NMR spectrogram.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition, after having read the content of the present invention's instruction, those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally.
Initiator A: the preparation of 2,3-phenylbenzene butyronitrile (structural formula 1):
By consisting of phase-transferring agent benzyl triethyl ammonium bromide (TEBAC) (4.587g, 0.02mol), NaOH solid (4g left and right, 0.1mol) join in 10ml distilled water, under magnetic agitation, chlorinated benzene ethane (2.81g, 0.02mol) and benzyl cyanide (2.34g, 0.02mol) are slowly added drop-wise in reaction system, after 50～60 ℃ of reaction 8～10h, add the static termination reaction of ice-water bath or normal temperature.With dichloromethane solvent extraction, extract organic layer, then use anhydrous MgSO afterwards
4dry, solvent evaporated, column chromatography for separation is purified, and gets final product to obtain compd A.
Embodiment 1
1g methyl methacrylate monomer, 0.0222g initiator A and 2ml toluene solvant are joined in polymerizing pipe, mix rear good seal, under liquid nitrogen freezing or cold condition, vacuumize-inflated with nitrogen 5 times repeatedly.Polymerizing pipe is put into after reacting 10h under 80 ℃ of oil baths and takes out polymerizing pipe, termination reaction under low temperature.Then with sherwood oil or methanol/water=1:1 solvent deposition polymkeric substance, 50 ℃ of vacuum drying ovens its transformation efficiency that dries to constant weight is 32.01%, records polymkeric substance number-average molecular weight (M
n)=90714, molecular weight distribution width (PDI)=1.74.The blank group that does not add initiator A under the same terms does not have polymerization completely.
1g methyl methacrylate monomer, 0.0222g initiator A and 2ml toluene solvant are joined in polymerizing pipe, mix rear good seal, under liquid nitrogen freezing or cold condition, vacuumize-inflated with nitrogen 5 times repeatedly.Polymerizing pipe is put into after reacting 10h under 85 ℃ of oil baths and takes out polymerizing pipe, termination reaction under low temperature.Then with sherwood oil or methanol/water=1:1 solvent deposition polymkeric substance, 50 ℃ of vacuum drying ovens its transformation efficiency that dries to constant weight is 52.44%, records polymkeric substance number-average molecular weight (M
n)=91531, molecular weight distribution width (PDI)=1.77.Although and under the same terms, do not add blank group of slightly polymerization of initiator A, polymerization amount is considerably less.
About 1.04g styrene monomer and 0.0222g initiator A are joined in polymerizing pipe, mix rear good seal, under liquid nitrogen freezing or cold condition, vacuumize-inflated with nitrogen 5 times repeatedly.Polymerizing pipe is put into after reacting 3h under 120 ℃ of oil baths and takes out polymerizing pipe, termination reaction under low temperature.Then with sherwood oil or methanol/water=1:1 solvent deposition polymkeric substance, 50 ℃ of vacuum drying ovens its transformation efficiency that dries to constant weight is 52.20%, records polymkeric substance M
n=153042, PDI=1.78.
Embodiment 4
About 1.04g styrene monomer and 0.0222g initiator A are joined in polymerizing pipe, mix rear good seal, under liquid nitrogen freezing or cold condition, vacuumize-inflated with nitrogen 5 times repeatedly.Polymerizing pipe is put into after reacting 3h under 130 ℃ of oil baths and takes out polymerizing pipe, termination reaction under low temperature.Then with sherwood oil or methanol/water=1:1 solvent deposition polymkeric substance, 50 ℃ of vacuum drying ovens its transformation efficiency that dries to constant weight is 62.73%, records polymkeric substance M
n=122334, PDI=1.85.
Claims (5)
1. compound 2, and 3-phenylbenzene butyronitrile is for causing the polymerization of vinyl monomer.
2. according to the compound of claim 12,3-phenylbenzene butyronitrile is used for causing the polymerization of vinyl monomer, it is characterized in that, polymerization process is mainly mass polymerization or solution polymerization.
3. according to the compound of claim 12,3-phenylbenzene butyronitrile, for causing the polymerization of vinyl monomer, is characterized in that, compound 2, and 3-phenylbenzene butyronitrile is for causing the polymerization of vinyl monomer, and initiated polymerization temperature is 70-130 ℃.
4. according to the compound of claim 22,3-phenylbenzene butyronitrile, for causing the polymerization of vinyl monomer, is characterized in that, the solvent adopting during solution polymerization can dissolved compound 2,3-phenylbenzene butyronitrile.
5. according to arbitrary compound 2 of claim 1-4,3-phenylbenzene butyronitrile is used for causing the polymerization of vinyl monomer, it is characterized in that, described vinyl monomer is acrylate, methacrylic ester or vinylbenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310726322.XA CN103641938B (en) | 2013-12-25 | 2013-12-25 | A kind of initiator that can be used for vinyl monomer polyreaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310726322.XA CN103641938B (en) | 2013-12-25 | 2013-12-25 | A kind of initiator that can be used for vinyl monomer polyreaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103641938A true CN103641938A (en) | 2014-03-19 |
| CN103641938B CN103641938B (en) | 2015-10-28 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310726322.XA Expired - Fee Related CN103641938B (en) | 2013-12-25 | 2013-12-25 | A kind of initiator that can be used for vinyl monomer polyreaction |
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| Country | Link |
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| CN (1) | CN103641938B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348564A (en) * | 2015-10-30 | 2016-02-24 | 成都新柯力化工科技有限公司 | Preparation method of inorganic powder specially used for low-density composite ivory boards |
| CN108059690A (en) * | 2017-12-20 | 2018-05-22 | 西安理工大学 | Initiation system containing alkyl trifluoroborate and its method for triggering monomer polymerization |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675491A (en) * | 2012-01-10 | 2012-09-19 | 北京化工大学 | Novel initiating system, and preparation method and application thereof |
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2013
- 2013-12-25 CN CN201310726322.XA patent/CN103641938B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675491A (en) * | 2012-01-10 | 2012-09-19 | 北京化工大学 | Novel initiating system, and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| TAKAYUKI OTSU ET AL: "Role of Initiator-Transfer Agent-Terminator (Iniferter) in Radical Polymerizations: Polymer Design by Organic Disulfides as Iniferters", 《MAKROMOL. CHEM., RPPID COMRNUN》 * |
| TAKAYUKI OTSU: "Iniferter Concept and Living Radical Polymerization", 《JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY》 * |
| 刘洪波: "位阻效应对引发- 转移- 终止剂 引发和控制活性自由基聚合的影响", 《顺德职业技术学院学报》 * |
| 姚献东等: "碳-碳键型活性自由基聚合引发体系的研究现状", 《高分子材料科学与工程》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348564A (en) * | 2015-10-30 | 2016-02-24 | 成都新柯力化工科技有限公司 | Preparation method of inorganic powder specially used for low-density composite ivory boards |
| CN105348564B (en) * | 2015-10-30 | 2018-06-26 | 太原理工大学 | A kind of compound art post paperboard special inorganic raw powder's production technology of low-density |
| CN108059690A (en) * | 2017-12-20 | 2018-05-22 | 西安理工大学 | Initiation system containing alkyl trifluoroborate and its method for triggering monomer polymerization |
| CN108059690B (en) * | 2017-12-20 | 2020-08-18 | 西安理工大学 | Initiation system containing alkyl trifluoroborate and method for initiating monomer polymerization by using initiation system |
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