CN117362495B - Food-grade medium molecular weight polyisobutene and preparation and application thereof - Google Patents
Food-grade medium molecular weight polyisobutene and preparation and application thereof Download PDFInfo
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- CN117362495B CN117362495B CN202311489164.0A CN202311489164A CN117362495B CN 117362495 B CN117362495 B CN 117362495B CN 202311489164 A CN202311489164 A CN 202311489164A CN 117362495 B CN117362495 B CN 117362495B
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- 229920002367 Polyisobutene Polymers 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 71
- 239000003999 initiator Substances 0.000 claims abstract description 60
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 54
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 49
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 35
- -1 ketone compounds Chemical class 0.000 claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 29
- 230000032683 aging Effects 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 238000009826 distribution Methods 0.000 claims abstract description 15
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- 150000002170 ethers Chemical class 0.000 claims abstract description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 36
- 239000013078 crystal Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 239000012454 non-polar solvent Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002798 polar solvent Substances 0.000 claims description 11
- RMSGBIDKBWPHMJ-UHFFFAOYSA-N 1-tert-butyl-4-ethoxybenzene Chemical compound CCOC1=CC=C(C(C)(C)C)C=C1 RMSGBIDKBWPHMJ-UHFFFAOYSA-N 0.000 claims description 5
- UAEPNZWRGJTJPN-UHFFFAOYSA-N Methylcyclohexane Natural products CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 59
- 235000013305 food Nutrition 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 17
- 229940044631 ferric chloride hexahydrate Drugs 0.000 abstract description 15
- 238000012546 transfer Methods 0.000 abstract description 10
- 230000000536 complexating effect Effects 0.000 abstract description 8
- 229940032296 ferric chloride Drugs 0.000 abstract description 7
- 230000009471 action Effects 0.000 abstract description 3
- 238000010538 cationic polymerization reaction Methods 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 66
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 229910052757 nitrogen Inorganic materials 0.000 description 33
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 26
- 238000000034 method Methods 0.000 description 22
- 230000000977 initiatory effect Effects 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 13
- 238000009835 boiling Methods 0.000 description 11
- 238000004140 cleaning Methods 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- 238000007599 discharging Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- 238000003825 pressing Methods 0.000 description 11
- 238000005086 pumping Methods 0.000 description 11
- 239000013557 residual solvent Substances 0.000 description 11
- 229940057046 ethyl menthane carboxamide Drugs 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 229940112822 chewing gum Drugs 0.000 description 4
- 235000015218 chewing gum Nutrition 0.000 description 4
- 239000004831 Hot glue Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002270 exclusion chromatography Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/08—Butenes
- C08F110/10—Isobutene
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The embodiment of the invention discloses food-grade medium molecular weight polyisobutene and a preparation method and application thereof. The polyisobutene has the chemical formula of- [ CH 2-C(CH3)2]n -. The preparation method comprises the following steps: preparing an initiator system; adding a third component into the initiator system to initiate polymerization of the monomer, so as to prepare the food-grade medium-molecular-weight polyisobutene; the initiator system comprises ferric trichloride hexahydrate, anhydrous ferric trichloride and a solvent; the third component comprises at least one of ketone compounds, ether compounds and amide compounds; the monomer is selected from isobutene compounds; the polymerization reaction of the monomer occurs at a temperature ranging from-30 ℃ to-80 ℃. According to the invention, ferric chloride hexahydrate and anhydrous ferric chloride are compounded to serve as an initiator, and high reaction activity can be formed through low-temperature aging and complexing. Under the action of the third component, the phenomenon that chain transfer easily occurs in the cationic polymerization is inhibited, and the narrow molecular weight distribution preparation of the molecular weight polyisobutene in the food grade is realized.
Description
Technical Field
The invention relates to the technical field of high molecular polymer preparation, in particular to food-grade medium molecular weight polyisobutene and preparation and application thereof.
Background
Polyisobutene is a product obtained by cationic polymerization of the monomer isobutene, and is a linear saturated polymer. The polyisobutene has three molecular weight products of high, medium and low, the high molecular weight polyisobutene is white solid, the medium molecular weight polyisobutene is semisolid, the glass transition temperature is 198K-243K, the elasticity can be kept at the temperature of minus 50 ℃, and the polyisobutene has excellent weather resistance, insulating property, cold flow property, ultraviolet resistance and chemical inertness. The polyisobutene with medium molecular weight is widely applied to the fields of shockproof damping adhesive, pressure-sensitive adhesive, chewing gum and the like. The food-grade polyisobutene with medium molecular weight is an important branch of downstream application of polyisobutene products, and has huge market demand, but the products are required to be tasteless and have no biotoxicity, do not contain any heavy metals, and cannot generate potential danger to human bodies.
In the synthesis process of the polyisobutene with medium molecular weight, alCl 3、BF3 and the like are generally used as positive ion polymerization initiators, and the catalysts have high toxicity, and the key point is that the initiators are difficult to remove, so that the residual metal content in the material is high, and the quality of the product, especially the quality of the material applied to the food field, is greatly influenced.
In the prior art, feCl 3 and an oxygen-containing compound react in a second organic solvent to form a FeCl 3 complex, and titanium tetrachloride is added to be mixed to obtain a compound initiator solution, so that the polyisobutene with medium molecular weight can be prepared under the condition of relatively high temperature, but the method does not completely get rid of the use of heavy metal catalysts. A further initiator system comprising FeCl 3 and complexing agent is used for preparing polyisobutene with high reactivity and its copolymer with number average molecular weight of 500-6000 g/mol, but the core idea of this process is to promote chain transfer to obtain low molecular weight products, which does not provide a new process for preparing polyisobutene with medium molecular weight.
Disclosure of Invention
The invention aims to provide food-grade medium molecular weight polyisobutene and preparation and application thereof, which are used for solving at least one technical problem, and realizing green preparation of the medium molecular weight polyisobutene and avoiding metal residues on the basis of inhibiting chain transfer phenomenon which is easy to occur in positive ion polymerization.
Embodiments of the present invention are implemented as follows:
a food grade medium molecular weight polyisobutylene having the formula- [ CH 2-C(CH3)2]n -, wherein n has a value in the range of 180< n <1800;
the polyisobutene contains Mn, and the content range of Mn is 10000-100000 g/mol;
preferably, the Mn content is 20000g/mol, 30000g/mol, 40000g/mol.
The molecular weight distribution of the polyisobutene is 1.0-1.5.
A process for preparing a food-grade medium molecular weight polyisobutylene comprising:
Preparing an initiator system;
adding a third component into the initiator system to initiate polymerization of the monomer, so as to prepare the food-grade medium-molecular-weight polyisobutene;
the initiator system comprises ferric trichloride hexahydrate, anhydrous ferric trichloride and a solvent;
the third component comprises at least one of ketone compounds, ether compounds and amide compounds;
the monomer is selected from isobutene compounds;
The temperature range of the monomer polymerization reaction is between minus 30 ℃ and minus 80 ℃;
The polyisobutylene is a polyisobutylene as previously described.
Wherein the monomer polymerization reaction is a positive ion polymerization reaction of the monomer.
Wherein the carbocation active center is stabilized and chain transfer is suppressed by adding a third component, and narrow molecular weight distribution control can be achieved
The conversion rate of the intermediate molecular weight polyisobutene prepared by the method is more than 85%.
In the polyisobutene with medium molecular weight prepared by the method, the content of the measured residual metal ions is only 10% of the residual amount of other traditional catalysts. The residual metal ions in the polymer can be rapidly removed in a simple post-treatment process, and the final ion removal rate can reach 100%.
In the preferred embodiment of the invention, in the preparation method of the food-grade medium molecular weight polyisobutene, the ferric trichloride hexahydrate in the initiator system is crystal water saturated ferric trichloride and is prepared by separating ferric chloride from an aqueous solution, wherein the chemical formula of the ferric trichloride is FeCl 3·6H2 O;
The anhydrous ferric trichloride in the initiator system is an ionic crystal, and the anhydrous ferric trichloride is prepared by heating ferric trichloride hexahydrate and removing water in the saturated ferric trichloride of crystal water, wherein the chemical formula is FeCl 3.
Ferric chloride is a novel green initiator suitable for positive ion polymerization, when ferric chloride is separated out from an aqueous solution, feCl 3·6H2 O is taken as six crystal waters, and ferric chloride hexahydrate is orange-yellow crystal. And heating to remove water in the crystal to obtain the black brown ion crystal anhydrous ferric trichloride.
However, in ferric chloride hexahydrate, the molar ratio of crystal water is excessive and can not be directly used for a polymerization initiator, so that the reaction system is innovatively compounded by ferric chloride hexahydrate and anhydrous ferric trichloride, and no additional initiator is needed to be added, thereby simplifying experimental steps.
The compound primer system is a green catalytic system and does not contain heavy metals. Meanwhile, the low-temperature aging and complexing can generate higher reaction activity with a small addition amount, and the activity is far higher than that of the traditional Lewis acids such as TiCl 4、BF3 and the like.
The high-efficiency new catalytic system formed by compounding the crystal water saturated ferric trichloride and the anhydrous ferric trichloride not only can solve the defects that the traditional catalytic system is large in dosage and difficult to remove because of containing metal ions, but also can stabilize an active center under the action of a third component, and can realize rapid initiation and rapid growth in the polymerization process, and the product realizes narrow molecular weight distribution control.
The technical effects are as follows: by selecting different forms of ferric trichloride and using ferric trichloride hexahydrate and anhydrous ferric trichloride in the preparation process, an initiator system is optimized, so that the preparation process of the food-grade medium-molecular-weight polyisobutene is controlled and improved.
In a preferred embodiment of the present invention, in the above-described process for preparing a food-grade medium molecular weight polyisobutylene, the molar ratio of the iron trichloride hexahydrate to the iron trichloride anhydrous in the initiator system is 1 (5 to 29).
Preferably, the molar ratio of the ferric trichloride hexahydrate to the ferric trichloride anhydrous is 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:20, 1:25.
In a preferred embodiment of the present invention, in the above-mentioned method for preparing a food-grade medium molecular weight polyisobutylene, after the initiator system is prepared, the initiator system is aged at a low temperature to activate the initiator system;
The temperature range of the low-temperature aging of the initiator system is between minus 30 ℃ and minus 80 ℃;
the low-temperature aging time of the initiator system ranges from 2min to 20min.
The initiator compound is a green catalytic system and does not contain any heavy metal;
the initiator complex system can generate higher reaction activity through low-temperature aging and complexing without adding other auxiliary initiators.
After compounding, the high-activity initiating system subjected to low-temperature aging and complexing can realize rapid initiation and rapid growth in a solvent, but the excessively rapid reaction speed can lead to large heat release amount in unit time, chain transfer is easy to occur and the reaction is stopped, so that the conversion rate is low and the molecular weight distribution is wide.
In a preferred embodiment of the present invention, in the above-described process for preparing a food-grade medium molecular weight polyisobutylene, the ketone compound is benzophenone;
the ether compound adopts p-tert-butyl phenetole;
the amide compound adopts food-grade N-ethyl menthane amide.
In a preferred embodiment of the present invention, in the above process for preparing a food grade medium molecular weight polyisobutylene, the molar ratio of the ferric trichloride hexahydrate to the third component is 1 (0.1 to 10).
In a preferred embodiment of the present invention, in the above process for the preparation of food grade medium molecular weight polyisobutene, the solvent is a polar solvent and/or a non-polar solvent.
In a preferred embodiment of the present invention, in the above-mentioned method for preparing a food-grade medium molecular weight polyisobutylene, the polar solvent is a chlorinated alkane;
Preferably, the chlorinated alkane compound is at least one selected from chloromethane and dichloromethane.
The nonpolar solvent adopts at least one of a hexane compound, a methylcyclohexane compound and a cyclohexane compound;
The volume ratio of the polar solvent to the nonpolar solvent is (0-5) (5-10).
Preferably, the volume ratio of the polar solvent to the nonpolar solvent is (0-2): 2-10.
Use of a food grade medium molecular weight polyisobutylene in chewing gum bases, food adhesives, food packaging, food grade hot melt adhesives and medical plasters, said polyisobutylene being as described above.
The embodiment of the invention has the beneficial effects that:
according to the invention, ferric chloride hexahydrate and anhydrous ferric chloride are compounded to serve as an initiator, and high reaction activity can be formed through low-temperature aging and complexing. Under the action of the third component, the phenomenon that chain transfer easily occurs in the cationic polymerization is inhibited, and the narrow molecular weight distribution preparation of the molecular weight polyisobutene in the food grade is realized.
The primer system is a green catalytic system without heavy metal, can generate higher reaction activity in a nonpolar solvent with little compound addition, and avoids serious damage to the environment due to the fact that a high-polarity chlorinated solvent is toxic, volatile and strong in corrosiveness.
The food-grade medium molecular weight polyisobutene prepared by the invention does not need to add other auxiliary initiator, simplifies experimental steps, and has much higher reaction activity than the traditional Lewis acid such as TiCl 4、BF3 and the like after low-temperature aging and complexing.
The food-grade medium molecular weight polyisobutene prepared by the invention can reduce the residual amount of the initiator in the polymer and simplify the purification step. Even complete removal can be achieved by a simple dissolution-alcohol washing process, reducing the post-treatment cost. The prepared polymer has extremely low ion content, can reach higher food grade, and reduces industrialization cost.
The invention uses the third component to complex with the active center, reduces the probability of chain transfer, and ensures that the prepared polymer has narrow molecular weight distribution and high conversion rate.
The unique compound ferric trichloride high-activity initiating system can be used for preparing the polymer without ultralow temperature, so that the production energy consumption of deep refrigeration is reduced.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic representation of the molecular structure of a food-grade medium molecular weight polyisobutylene according to the present invention;
FIG. 2 is a schematic representation of the structure of the preparation of the food-grade medium molecular weight polyisobutene according to the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein can be arranged and designed in a wide variety of different configurations.
Referring to FIG. 1, an embodiment of the present invention provides a food grade medium molecular weight polyisobutylene having the formula- [ CH 2-C(CH3)2]n -, wherein n has a value in the range of 180< n <1800;
the polyisobutene contains Mn, and the content range of Mn is 10000-100000 g/mol;
preferably, the Mn content is 20000g/mol, 30000g/mol, 40000g/mol.
The molecular weight distribution of the polyisobutene is 1.0-1.5.
Referring to fig. 2, the embodiment of the invention further provides a method for preparing food-grade medium molecular weight polyisobutylene, which comprises:
Preparing an initiator system;
adding a third component into the initiator system to initiate polymerization of the monomer, so as to prepare the food-grade medium-molecular-weight polyisobutene;
the initiator system comprises ferric trichloride hexahydrate, anhydrous ferric trichloride and a solvent;
the third component comprises at least one of ketone compounds, ether compounds and amide compounds;
the monomer is selected from isobutene compounds;
The temperature range of the monomer polymerization reaction is between minus 30 ℃ and minus 80 ℃;
The polyisobutylene is a polyisobutylene as previously described.
Wherein the monomer polymerization reaction is a positive ion polymerization reaction of the monomer.
Wherein the carbocation active center is stabilized and chain transfer is suppressed by adding a third component, and narrow molecular weight distribution control can be achieved
The conversion rate of the intermediate molecular weight polyisobutene prepared by the method is more than 85%.
In the polyisobutene with medium molecular weight prepared by the method, the content of the measured residual metal ions is only 10% of the residual amount of other traditional catalysts. The residual metal ions in the polymer can be rapidly removed in a simple post-treatment process, and the final ion removal rate can reach 100%.
In the preferred embodiment of the invention, in the preparation method of the food-grade medium molecular weight polyisobutene, the ferric trichloride hexahydrate in the initiator system is crystal water saturated ferric trichloride and is prepared by separating ferric chloride from an aqueous solution, wherein the chemical formula of the ferric trichloride is FeCl 3·6H2 O;
The anhydrous ferric trichloride in the initiator system is an ionic crystal, and the anhydrous ferric trichloride is prepared by heating ferric trichloride hexahydrate and removing water in the saturated ferric trichloride of crystal water, wherein the chemical formula is FeCl 3.
The technical effects are as follows: by selecting different forms of ferric trichloride and using ferric trichloride hexahydrate and anhydrous ferric trichloride in the preparation process, an initiator system is optimized, so that the preparation process of the food-grade medium-molecular-weight polyisobutene is controlled and improved.
In a preferred embodiment of the present invention, in the above-described process for preparing a food-grade medium molecular weight polyisobutylene, the molar ratio of the iron trichloride hexahydrate to the iron trichloride anhydrous in the initiator system is 1 (5 to 29).
Preferably, the molar ratio of the ferric trichloride hexahydrate to the ferric trichloride anhydrous is 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:20, 1:25.
In a preferred embodiment of the present invention, in the above-mentioned method for preparing a food-grade medium molecular weight polyisobutylene, after the initiator system is prepared, the initiator system is aged at a low temperature to activate the initiator system;
The temperature range of the low-temperature aging of the initiator system is between minus 30 ℃ and minus 80 ℃;
the low-temperature aging time of the initiator system ranges from 2min to 20min.
The initiator compound is a green catalytic system and does not contain any heavy metal;
the initiator complex system can generate higher reaction activity through low-temperature aging and complexing without adding other auxiliary initiators.
In a preferred embodiment of the present invention, in the above-described process for preparing a food-grade medium molecular weight polyisobutylene, the ketone compound is benzophenone;
the ether compound adopts p-tert-butyl phenetole;
the amide compound adopts food-grade N-ethyl menthane amide.
In a preferred embodiment of the present invention, in the above process for preparing a food grade medium molecular weight polyisobutylene, the molar ratio of the ferric trichloride hexahydrate to the third component is 1 (0.1 to 10).
In a preferred embodiment of the present invention, in the above process for the preparation of food grade medium molecular weight polyisobutene, the solvent is a polar solvent and/or a non-polar solvent.
In a preferred embodiment of the present invention, in the above-mentioned method for preparing a food-grade medium molecular weight polyisobutylene, the polar solvent is a chlorinated alkane;
Preferably, the chlorinated alkane compound is at least one selected from chloromethane and dichloromethane.
The nonpolar solvent adopts at least one of a hexane compound, a methylcyclohexane compound and a cyclohexane compound;
The volume ratio of the polar solvent to the nonpolar solvent is (0-5) (5-10).
Preferably, the volume ratio of the polar solvent to the nonpolar solvent is (0-2): 2-10.
Embodiments of the present invention also provide for the use of a food grade medium molecular weight polyisobutylene in chewing gum bases, food adhesives, food packaging, food grade hot melt adhesives and medical plasters, the polyisobutylene being as described above.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
(One) example 1:
Before the reaction, the 4-liter low-temperature polymerization kettle is heated and baked, a fully-closed temperature controller is used for ensuring that the internal temperature of the polymerization kettle reaches more than 75 ℃, residual solvent and moisture are removed under reduced pressure, and meanwhile, nitrogen is continuously pumped and discharged for about 20 times to ensure that the inside of the polymerization kettle is in a nitrogen atmosphere, and a charging tank is used for cleaning, baking and nitrogen pumping and discharging in the same standard. And then cooling, and preparing to start feeding when the temperature in the polymerization kettle reaches below the boiling point of the chloromethane and isobutene monomers. 1000g of hexane, 540g of isobutene and 0.1M of food-grade N-ethyl menthane carboxamide were added. Adding 0.5M ferric trichloride and 0.1M ferric chloride hexahydrate, adding 10g of hexane, mixing to prepare an initiating system, aging for 5min, pressing nitrogen into a reaction kettle to initiate polymerization, adding a large amount of methanol to terminate the reaction, removing the solvent from the product, and drying.
(II) example 2:
Before the reaction, the 4-liter low-temperature polymerization kettle is heated and baked, a fully-closed temperature controller is used for ensuring that the internal temperature of the polymerization kettle reaches more than 75 ℃, residual solvent and moisture are removed under reduced pressure, and meanwhile, nitrogen is continuously pumped and discharged for about 20 times to ensure that the inside of the polymerization kettle is in a nitrogen atmosphere, and a charging tank is used for cleaning, baking and nitrogen pumping and discharging in the same standard. And then cooling, and preparing to start feeding when the temperature in the polymerization kettle reaches below the boiling point of the chloromethane and isobutene monomers. 100g of methyl chloride, 1000g of hexane, 540g of isobutene and 0.1M of p-tert-butylphenetole are added. Adding 2.9M ferric trichloride as a coinitiator and 0.1M ferric chloride hexahydrate, adding 20g of dichloromethane, mixing to prepare an initiation system, aging for 5min, pressing nitrogen into a reaction kettle to initiate polymerization, adding a large amount of methanol to terminate the reaction, removing the solvent from the product, and drying.
(III) example 3:
Before the reaction, the 4-liter low-temperature polymerization kettle is heated and baked, a fully-closed temperature controller is used for ensuring that the internal temperature of the polymerization kettle reaches more than 75 ℃, residual solvent and moisture are removed under reduced pressure, and meanwhile, nitrogen is continuously pumped and discharged for about 20 times to ensure that the inside of the polymerization kettle is in a nitrogen atmosphere, and a charging tank is used for cleaning, baking and nitrogen pumping and discharging in the same standard. And then cooling, and preparing to start feeding when the temperature in the polymerization kettle reaches below the boiling point of the chloromethane and isobutene monomers. 200g of methylene chloride, 1000g of hexane, 540g of isobutene and 0.15M of food-grade N-ethyl menthane carboxamide are added. Adding 1.7M ferric trichloride and 0.1M ferric chloride hexahydrate, adding 15g of dichloromethane, mixing to prepare an initiating system, aging for 5min, pressing nitrogen into a reaction kettle to initiate polymerization, adding a large amount of methanol to terminate the reaction, removing the solvent from the product, and drying.
(IV) example 4:
Before the reaction, the 4-liter low-temperature polymerization kettle is heated and baked, a fully-closed temperature controller is used for ensuring that the internal temperature of the polymerization kettle reaches more than 75 ℃, residual solvent and moisture are removed under reduced pressure, and meanwhile, nitrogen is continuously pumped and discharged for about 20 times to ensure that the inside of the polymerization kettle is in a nitrogen atmosphere, and a charging tank is used for cleaning, baking and nitrogen pumping and discharging in the same standard. And then cooling, and preparing to start feeding when the temperature in the polymerization kettle reaches below the boiling point of the chloromethane and isobutene monomers. 200g of methylene chloride, 1000g of cyclohexane, 540g of isobutene and 0.2M of p-tert-butylphenetole are added. Adding 2.3M ferric trichloride and 0.1M ferric chloride hexahydrate, adding 15g of dichloromethane, mixing to prepare an initiating system, aging for 5min, pressing nitrogen into a reaction kettle to initiate polymerization, adding a large amount of methanol to terminate the reaction, removing the solvent from the product, and drying.
(Fifth) example 5:
before the reaction, the 4-liter low-temperature polymerization kettle is heated and baked, a fully-closed temperature controller is used for ensuring that the internal temperature of the polymerization kettle reaches more than 75 ℃, residual solvent and moisture are removed under reduced pressure, and meanwhile, nitrogen is continuously pumped and discharged for about 20 times to ensure that the inside of the polymerization kettle is in a nitrogen atmosphere, and a charging tank is used for cleaning, baking and nitrogen pumping and discharging in the same standard. And then cooling, and preparing to start feeding when the temperature in the polymerization kettle reaches below the boiling point of the chloromethane and isobutene monomers. 100g of methyl chloride, 1000g of hexane, 540g of isobutene and 0.1M of food-grade N-ethyl menthane carboxamide are added. Adding 2.9M ferric trichloride and 0.1M ferric chloride hexahydrate, adding 15g of dichloromethane, mixing to prepare an initiating system, aging for 5min, pressing nitrogen into a reaction kettle to initiate polymerization, adding a large amount of methanol to terminate the reaction, removing the solvent from the product, and drying.
Sixth example 6:
before the reaction, the 4-liter low-temperature polymerization kettle is heated and baked, a fully-closed temperature controller is used for ensuring that the internal temperature of the polymerization kettle reaches more than 75 ℃, residual solvent and moisture are removed under reduced pressure, and meanwhile, nitrogen is continuously pumped and discharged for about 20 times to ensure that the inside of the polymerization kettle is in a nitrogen atmosphere, and a charging tank is used for cleaning, baking and nitrogen pumping and discharging in the same standard. And then cooling, and preparing to start feeding when the temperature in the polymerization kettle reaches below the boiling point of the chloromethane and isobutene monomers. 1000g methylcyclohexane, 540g isobutylene, and 0.1M food grade N-ethyl menthane carboxamide were added. Adding 1.7M ferric trichloride and 0.1M ferric chloride hexahydrate, adding 10g of dichloromethane, mixing to prepare an initiating system, aging for 10min, pressing nitrogen into a reaction kettle to initiate polymerization, adding a large amount of methanol to terminate the reaction, removing the solvent from the product, and drying.
(Seventh) example 7:
Before the reaction, the 4-liter low-temperature polymerization kettle is heated and baked, a fully-closed temperature controller is used for ensuring that the internal temperature of the polymerization kettle reaches more than 75 ℃, residual solvent and moisture are removed under reduced pressure, and meanwhile, nitrogen is continuously pumped and discharged for about 20 times to ensure that the inside of the polymerization kettle is in a nitrogen atmosphere, and a charging tank is used for cleaning, baking and nitrogen pumping and discharging in the same standard. And then cooling, and preparing to start feeding when the temperature in the polymerization kettle reaches below the boiling point of the chloromethane and isobutene monomers. 1000g of hexane, 540g of isobutene and 0.1M of food-grade N-ethyl menthane carboxamide were added. Adding 1.1M ferric trichloride and 0.1M ferric chloride hexahydrate, adding 10g of dichloromethane, mixing to prepare an initiating system, aging for 15min, pressing nitrogen into a reaction kettle to initiate polymerization, adding a large amount of methanol to terminate the reaction, removing the solvent from the product, and drying.
(Eighth) example 8:
Before the reaction, the 4-liter low-temperature polymerization kettle is heated and baked, a fully-closed temperature controller is used for ensuring that the internal temperature of the polymerization kettle reaches more than 75 ℃, residual solvent and moisture are removed under reduced pressure, and meanwhile, nitrogen is continuously pumped and discharged for about 20 times to ensure that the inside of the polymerization kettle is in a nitrogen atmosphere, and a charging tank is used for cleaning, baking and nitrogen pumping and discharging in the same standard. And then cooling, and preparing to start feeding when the temperature in the polymerization kettle reaches below the boiling point of the chloromethane and isobutene monomers. 200g of methylene chloride, 1000g of cyclohexane, 540g of isobutene and 0.2M of food-grade N-ethyl menthane carboxamide are added. Adding 1.7M ferric trichloride and 0.1M ferric chloride hexahydrate, adding 15g of dichloromethane, mixing to prepare an initiating system, aging for 20min, pressing nitrogen into a reaction kettle to initiate polymerization, adding a large amount of methanol to terminate the reaction, removing the solvent from the product, and drying.
(Ninth) comparative example 1:
Before the reaction, the 4-liter low-temperature polymerization kettle is heated and baked, a fully-closed temperature controller is used for ensuring that the internal temperature of the polymerization kettle reaches more than 75 ℃, residual solvent and moisture are removed under reduced pressure, and meanwhile, nitrogen is continuously pumped and discharged for about 20 times to ensure that the inside of the polymerization kettle is in a nitrogen atmosphere, and a charging tank is used for cleaning, baking and nitrogen pumping and discharging in the same standard. And then cooling, and preparing to start feeding when the temperature in the polymerization kettle reaches below the boiling point of the chloromethane and isobutene monomers. 1000g of hexane and 540g of isobutene were added. Adding 1.1M ferric trichloride and 0.1M ferric chloride hexahydrate, adding 10g of hexane, mixing to prepare an initiating system, aging for 5min, pressing nitrogen into a reaction kettle to initiate polymerization, adding a large amount of methanol to terminate the reaction, removing the solvent from the product, and drying.
(Ten) comparative example 2:
Before the reaction, the 4-liter low-temperature polymerization kettle is heated and baked, a fully-closed temperature controller is used for ensuring that the internal temperature of the polymerization kettle reaches more than 75 ℃, residual solvent and moisture are removed under reduced pressure, and meanwhile, nitrogen is continuously pumped and discharged for about 20 times to ensure that the inside of the polymerization kettle is in a nitrogen atmosphere, and a charging tank is used for cleaning, baking and nitrogen pumping and discharging in the same standard. And then cooling, and preparing to start feeding when the temperature in the polymerization kettle reaches below the boiling point of the chloromethane and isobutene monomers. 1000g of hexane, 540g of isobutene and 0.1M of food-grade N-ethyl menthane carboxamide were added. Adding 0.6M titanium tetrachloride as a co-initiator and 0.6M water as a main initiator, mixing to prepare an initiation system, aging for 5min, pressing nitrogen into a reaction kettle to initiate polymerization, adding a large amount of methanol to terminate the reaction, removing the solvent from the product, and drying.
(Eleven) comparative example 3:
before the reaction, the 4-liter low-temperature polymerization kettle is heated and baked, a fully-closed temperature controller is used for ensuring that the internal temperature of the polymerization kettle reaches more than 75 ℃, residual solvent and moisture are removed under reduced pressure, and meanwhile, nitrogen is continuously pumped and discharged for about 20 times to ensure that the inside of the polymerization kettle is in a nitrogen atmosphere, and a charging tank is used for cleaning, baking and nitrogen pumping and discharging in the same standard. And then cooling, and preparing to start feeding when the temperature in the polymerization kettle reaches below the boiling point of the chloromethane and isobutene monomers. 1000g of hexane, 540g of isobutene and 0.1M of food-grade N-ethyl menthane carboxamide were added. Adding 9.0M titanium tetrachloride as a co-initiator and 0.6M water as a main initiator, mixing to prepare an initiation system, aging for 5min, pressing nitrogen into a reaction kettle to initiate polymerization, adding a large amount of methanol to terminate the reaction, removing the solvent from the product, and drying.
(Twelve) Performance test
In the examples of the present invention, the average molecular weight and molecular weight distribution of the polymer were determined by GB/T36214.5-2018 volume exclusion chromatography, and absolute determination was performed by using a light scattering method. The results of the examples are shown in Table 1 and the results of the comparative examples are shown in Table 2.
Table 1 shows the reaction temperature, the molecular weight of the product and the total conversion
As shown in Table 1, ferric chloride hexahydrate and anhydrous ferric chloride are compounded to serve as an initiator, and the initiator can form higher reaction activity through low-temperature aging and complexing, so that the method is applicable to nonpolar solvents, can reduce or even eliminate chlorinated solvents, and can avoid the problems of toxicity, easy volatilization, strong corrosiveness and serious environmental damage. Meanwhile, no additional auxiliary catalyst is needed, the preparation of the polyisobutene with high conversion rate and medium molecular weight can be realized with little use amount, and the conversion rate can reach more than 85% even at-30 ℃. The molecular weight distribution of the product is less than 1.5 when the third component is matched.
TABLE 2 data sheet for reaction temperature, product molecular weight and total conversion for comparative examples
As shown in tables 1 and 2, it can be seen that the effect of the third component is remarkable by comparing comparative example 1 with example 1. The high-activity initiation system can realize rapid initiation and rapid growth, but the excessively rapid reaction speed can lead to large heat release amount in unit time, and chain transfer is easy to occur to terminate, so that the conversion rate is low, and the molecular weight distribution is wide. Therefore, by adding the food-grade N-ethyl menthane carboxamide third component, the active center is stabilized, chain transfer is inhibited, and the conversion rate can be greatly improved, and meanwhile, the preparation of a product with narrow molecular weight distribution can be realized.
As shown in tables 1 and 2, by comparing comparative example 2 with example 1, it can be seen that the compounding reactivity of the invention is far greater than that of titanium tetrachloride, but the titanium tetrachloride cannot successfully initiate polymerization reaction under nonpolar solvent with the same addition amount, and the monomer conversion rate is only 15%.
As shown in tables 1 and 2, by comparing comparative example 3 with example 1, it can be seen that the conversion rate can reach 50% when titanium tetrachloride is used 15 times as much as the main initiator, and the reaction can be initiated in a nonpolar solvent. But this also leads to a drastic increase in the amount of metal residue, which has not been removed effectively by simple purification processes.
The embodiment of the invention aims to protect food-grade medium molecular weight polyisobutene and preparation and application thereof, and has the following effects:
1. the food-grade medium molecular weight polyisobutene prepared by the invention has narrow molecular weight distribution, can well prevent the change of the molecular weight, and ensures that the processing of fragments is relatively easy, thereby improving the mouthfeel of the food.
2. Because ferric trichloride has high Lewis acidity, the food-grade medium molecular weight polyisobutene prepared by the invention can realize high reaction activity with a small addition amount, and the polymer preparation is not required to be carried out at an extremely low temperature.
3. In the food-grade medium-molecular-weight polyisobutenes prepared according to the invention, the content of residual metal ions measured in the unpurified polymer is only 10% of the residual amount of the other catalysts.
4. The method can rapidly remove the residual metal ions in the polymer by a simple dissolution-alcohol washing method in the post-treatment process of the polymer, and the removal rate of the metal ions can reach 100% after three times of washing.
5. The food-grade medium molecular weight polyisobutene prepared by the invention can be widely applied to the fields of chewing gum bases, food adhesives, food packages, food-grade hot melt adhesives and medical plasters.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explanation of the principles of the present invention and are in no way limiting of the invention. Accordingly, any modification, equivalent replacement, improvement, etc. made without departing from the spirit and scope of the present invention should be included in the scope of the present invention. Furthermore, the appended claims are intended to cover all such changes and modifications that fall within the scope and boundary of the appended claims, or equivalents of such scope and boundary.
Claims (6)
1. A process for preparing a food-grade medium molecular weight polyisobutylene comprising:
Preparing an initiator system;
adding a third component into the initiator system to initiate polymerization of the monomer, so as to prepare the food-grade medium-molecular-weight polyisobutene;
the initiator system comprises ferric trichloride hexahydrate, anhydrous ferric trichloride and a solvent;
the third component comprises at least one of ketone compounds, ether compounds and amide compounds;
the monomer is selected from isobutene compounds;
The temperature range of the monomer polymerization reaction is between minus 30 ℃ and minus 80 ℃;
The chemical formula of the polyisobutene is- [ CH 2-C(CH3)2]n -, wherein the value range of n is 180< n <1800;
the polyisobutene contains Mn, and the content range of Mn is 10000-100000 g/mol;
The molecular weight distribution of the polyisobutene is 1.0-1.5;
the ketone compound adopts benzophenone;
the ether compound adopts p-tert-butyl phenetole;
the amide compound adopts food-grade N-ethyl menthane amide;
In the initiator system, the mole ratio of the ferric trichloride hexahydrate to the anhydrous ferric trichloride is 1 (5-29).
2. A process for preparing a food-grade medium molecular weight polyisobutene according to claim 1 characterized in that,
The ferric trichloride hexahydrate in the initiator system is crystal water saturated ferric trichloride and is prepared by separating out ferric chloride from an aqueous solution, wherein the chemical formula of the ferric chloride is FeCl 3·6H2 O;
The anhydrous ferric trichloride in the initiator system is an ionic crystal, and the anhydrous ferric trichloride is prepared by heating ferric trichloride hexahydrate and removing water in the saturated ferric trichloride of crystal water, wherein the chemical formula is FeCl 3.
3. A process for preparing a food-grade medium molecular weight polyisobutene according to claim 1 characterized in that,
After the initiator system is prepared, ageing the initiator system at a low temperature to activate the initiator system;
The temperature range of the low-temperature aging of the initiator system is between minus 30 ℃ and minus 80 ℃;
the low-temperature aging time of the initiator system ranges from 2min to 20min.
4. A process for preparing a food-grade medium molecular weight polyisobutene according to claim 1 characterized in that,
The mole ratio of the ferric trichloride hexahydrate to the third component is 1 (0.1-10).
5. A process for preparing a food-grade medium molecular weight polyisobutene according to claim 1 characterized in that,
The solvent is a polar solvent and/or a nonpolar solvent.
6. A process for preparing a food-grade medium molecular weight polyisobutene according to claim 5 characterized in that,
The polar solvent adopts chlorinated alkane compounds;
The nonpolar solvent adopts at least one of a hexane compound, a methylcyclohexane compound and a cyclohexane compound;
The volume ratio of the polar solvent to the nonpolar solvent is (0-5) (5-10).
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0853514A (en) * | 1994-01-12 | 1996-02-27 | Kanegafuchi Chem Ind Co Ltd | Production of isobutene-based polymer |
| CN1201800A (en) * | 1998-06-19 | 1998-12-16 | 北京石油化工学院 | Inductive system for activated cation |
| JP2009126889A (en) * | 2007-11-20 | 2009-06-11 | Kaneka Corp | Method for producing isobutylene polymer |
| CN110183560A (en) * | 2019-06-14 | 2019-08-30 | 华东理工大学 | A method of middle-molecular-weihydroxyethyl polyisobutene is prepared using ferrotitanium composite catalyst |
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| DE10162567A1 (en) * | 2001-12-19 | 2003-07-03 | Basf Ag | Polyisobutenes and polyisobutene derivatives for lubricant compositions |
| JP3992525B2 (en) * | 2002-04-04 | 2007-10-17 | 株式会社カネカ | Method for producing isobutylene polymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0853514A (en) * | 1994-01-12 | 1996-02-27 | Kanegafuchi Chem Ind Co Ltd | Production of isobutene-based polymer |
| CN1201800A (en) * | 1998-06-19 | 1998-12-16 | 北京石油化工学院 | Inductive system for activated cation |
| JP2009126889A (en) * | 2007-11-20 | 2009-06-11 | Kaneka Corp | Method for producing isobutylene polymer |
| CN110183560A (en) * | 2019-06-14 | 2019-08-30 | 华东理工大学 | A method of middle-molecular-weihydroxyethyl polyisobutene is prepared using ferrotitanium composite catalyst |
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