CN116836318A - Rare earth butadiene rubber and preparation method thereof - Google Patents
Rare earth butadiene rubber and preparation method thereof Download PDFInfo
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- CN116836318A CN116836318A CN202310890382.9A CN202310890382A CN116836318A CN 116836318 A CN116836318 A CN 116836318A CN 202310890382 A CN202310890382 A CN 202310890382A CN 116836318 A CN116836318 A CN 116836318A
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- catalyst
- rare earth
- butadiene rubber
- mixed solution
- earth butadiene
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- 229920002857 polybutadiene Polymers 0.000 title claims abstract description 70
- 239000005062 Polybutadiene Substances 0.000 title claims abstract description 69
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 69
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 166
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 68
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000011259 mixed solution Substances 0.000 claims abstract description 53
- 238000002156 mixing Methods 0.000 claims abstract description 37
- -1 aluminum alkyl hydride Chemical class 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 150000004820 halides Chemical class 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 34
- 125000004432 carbon atom Chemical group C* 0.000 claims description 27
- 229910052779 Neodymium Inorganic materials 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000003607 modifier Substances 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 11
- 238000012546 transfer Methods 0.000 description 11
- 230000032683 aging Effects 0.000 description 10
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- GBBWHMQDUNQEEU-UHFFFAOYSA-N 4-chlorobutylalumane Chemical group ClCCCC[AlH2] GBBWHMQDUNQEEU-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- LAIUFBWHERIJIH-UHFFFAOYSA-N 3-Methylheptane Chemical compound CCCCC(C)CC LAIUFBWHERIJIH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241001441571 Hiodontidae Species 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 238000010074 rubber mixing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VLJXXKKOSFGPHI-UHFFFAOYSA-N 3-methylhexane Chemical compound CCCC(C)CC VLJXXKKOSFGPHI-UHFFFAOYSA-N 0.000 description 1
- SEEOMASXHIJCDV-UHFFFAOYSA-N 3-methyloctane Chemical compound CCCCCC(C)CC SEEOMASXHIJCDV-UHFFFAOYSA-N 0.000 description 1
- TYSIILFJZXHVPU-UHFFFAOYSA-N 5-methylnonane Chemical compound CCCCC(C)CCCC TYSIILFJZXHVPU-UHFFFAOYSA-N 0.000 description 1
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- UZGARMTXYXKNQR-UHFFFAOYSA-K 7,7-dimethyloctanoate;neodymium(3+) Chemical compound [Nd+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O UZGARMTXYXKNQR-UHFFFAOYSA-K 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- CPDVHGLWIFENDJ-UHFFFAOYSA-N dihexylalumane Chemical compound C(CCCCC)[AlH]CCCCCC CPDVHGLWIFENDJ-UHFFFAOYSA-N 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- KFGIWFDCFBPRNI-UHFFFAOYSA-N dipentylaluminum Chemical compound CCCCC[Al]CCCCC KFGIWFDCFBPRNI-UHFFFAOYSA-N 0.000 description 1
- XOCWTYIVWYOSGQ-UHFFFAOYSA-N dipropylalumane Chemical compound C(CC)[AlH]CCC XOCWTYIVWYOSGQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- MWSOLOKEHHPOBC-UHFFFAOYSA-N pentylaluminum Chemical compound CCCCC[Al] MWSOLOKEHHPOBC-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 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
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/06—Butadiene
Landscapes
- 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 application relates to rare earth butadiene rubber and a preparation method thereof. The preparation method of the rare earth butadiene rubber comprises the following steps: mixing a solvent with butadiene monomer to prepare a first mixed solution; adding a first catalyst into the first mixed solution to prepare a second mixed solution; adding a second catalyst and a third catalyst into the second mixed solution to perform polymerization reaction to prepare rare earth butadiene rubber; wherein, in the course of polymerization reaction, adding quality regulator; the first catalyst comprises an aluminum alkyl hydride, the second catalyst comprises a rare earth catalyst, and the third catalyst comprises a halide.
Description
Technical Field
The application relates to the technical field of polymers, in particular to rare earth butadiene rubber and a preparation method thereof.
Background
The rare earth butadiene rubber is polybutadiene rubber with high cis-1, 4-structure prepared by butadiene polymerization, has the advantages of regular molecular chain structure, high strength, low heat generation, high wet skid resistance, low rolling resistance and the like, and can greatly improve the quality and performance of the tire when being used as a raw material for manufacturing the tire.
In the traditional rare earth butadiene rubber preparation process, a rare earth catalyst, diisobutyl aluminum hydride and a halogen-containing catalyst are adopted to carry out synergistic catalytic polymerization so as to prepare the rare earth butadiene rubber. Along with the wide application of the rare earth butadiene rubber, the preparation process requirements on the rare earth butadiene rubber are higher and higher, on one hand, certain conversion rate needs to be ensured, so that the cost is reduced, and on the other hand, the quality of the prepared rare earth butadiene rubber needs to be quickly adjusted, so that the Mooney viscosity of the prepared rare earth butadiene rubber, particularly the Mooney after mixing, is reduced, and the processing of subsequent products is facilitated. However, in the conventional preparation method, the catalyst is generally aged in advance to improve the catalytic activity and further improve the monomer conversion rate, however, the viscosity of the catalyst is difficult to adjust in the preparation process, so that the Mooney viscosity of the prepared rare earth butadiene rubber is improved during mixing, which is not beneficial to the processing of subsequent products and the industrialized production of the rare earth butadiene rubber product.
Accordingly, the conventional technology has yet to be improved.
Disclosure of Invention
Based on the above, it is necessary to provide a rare earth butadiene rubber and a preparation method thereof, wherein the conversion rate of the preparation method of the rare earth butadiene rubber is high, and the prepared rare earth butadiene rubber has low viscosity and is easy to process.
In a first aspect of the application, a method for preparing rare earth butadiene rubber is provided, comprising the following steps:
mixing a solvent with butadiene monomer to prepare a first mixed solution;
adding a first catalyst into the first mixed solution to prepare a second mixed solution;
adding a second catalyst and a third catalyst into the second mixed solution to perform polymerization reaction to prepare rare earth butadiene rubber;
wherein, in the course of the said polymerization reaction, add the quality regulator;
the first catalyst comprises an aluminum alkyl hydride, the second catalyst comprises a rare earth catalyst, and the third catalyst comprises a halide.
In the preparation method of the rare earth butadiene rubber, before the polymerization reaction, a specific kind of catalyst is added into butadiene monomers according to a specific sequence, and then a mass regulator is added in the polymerization reaction process, so that the catalyst maintains a certain catalytic activity, the butadiene monomers have higher conversion rate, and simultaneously, the polymerization process is easy to regulate, thereby achieving the purpose of quickly regulating the quality of the polymer, further, the conversion rate of the prepared rare earth butadiene rubber is improved, and meanwhile, the Mooney viscosity of the prepared rare earth butadiene rubber, particularly the Mooney viscosity after mixing is reduced, the processing difficulty of subsequent products is reduced, and the preparation is easy.
Furthermore, in the preparation method, each catalyst can have higher conversion rate of butadiene monomer without aging treatment, and the Mooney viscosity of the butadiene monomer after mixing is reduced, so that the preparation time can be further shortened, the preparation flow is simplified, and the preparation cost is further reduced.
In some of these embodiments, the step of preparing the second mixed solution comprises the steps of:
and mixing the second catalyst and the third catalyst, and then adding the mixed solution into the second mixed solution.
In some of these embodiments, the ratio of the number of moles of the first catalyst, the second catalyst, and the third catalyst is (10 to 50): 1: (1-4).
In some of these embodiments, the molar ratio of the second catalyst to the butadiene monomer is 1 (1X 10) 2 ～1×10 5 )。
In some of these embodiments, none of the first catalyst, the second catalyst, and the third catalyst is aged.
In some embodiments, the method for preparing rare earth butadiene rubber satisfies at least one of the following conditions (a) - (c):
(a) The structure of the aluminum alkyl hydride is shown as a formula (1):
L n AlT 1(3-n)
(1)，
wherein each occurrence of L is independently selected from substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms; t (T) 1 H, n is any integer from 1 to 2;
(b) The rare earth catalyst comprises neodymium alkyl carboxylate;
(c) The structure of the halide is shown as a formula (2):
X m AlT 2(3-m)
(2)
wherein each occurrence of X is independently selected from substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms; t (T) 2 Halogen, m is any integer from 1 to 2.
In some of these embodiments, the quality modifier satisfies at least one of the following conditions (d) - (e):
(d) The quality regulator is an alkyl aluminum compound;
(e) The mass of the mass regulator is 0.01-0.5% of the mass of the butadiene monomer.
In some of these embodiments, the polymerization reaction is carried out at a temperature of 30℃to 80℃for a period of 0.5h to 3h.
In some of these embodiments, the mass modifier is added when the polymerization reaction has proceeded for 10min to 90 min.
The Mooney viscosity of the prepared rare earth butadiene rubber is further reduced by selecting the time for adding the quality regulator.
The start time of the polymerization reaction was counted as the addition of the second catalyst and the third catalyst to the second mixed solution.
In a second aspect of the application, there is provided a rare earth butadiene rubber prepared by the method of preparing the rare earth butadiene rubber of the first aspect.
The rare earth butadiene rubber prepared by the preparation method has low viscosity, particularly the Mooney viscosity after raw rubber mixing, is easy to process, and is beneficial to the industrialized production of rare earth butadiene rubber products.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the application. Also, like reference numerals are used to designate like parts throughout the accompanying drawings.
FIG. 1 is a flow chart of a process for preparing rare earth butadiene rubber in one embodiment;
reference numerals illustrate:
10. a polymerization reaction kettle; 11. a stirrer; 20. a first delivery conduit; 30. a second delivery conduit; 40. a third delivery conduit; 50. a fourth conveying pipeline; 60. a fifth conveying pipe; 70. a sixth conveying pipeline; 80. a first mixing kettle; 90. and a second mixing kettle.
Detailed Description
The present application will be described in further detail with reference to specific examples. The present application may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
In the present application, the term "alkyl" refers to a group formed by the loss of one hydrogen from an alkane, for example, methyl group formed by the loss of one hydrogen from methane. Alkyl groups include alkanyl and cycloalkyl groups.
The term "alkanyl" refers to an alkane in which the carbon atoms are all joined by a single carbon-carbon bond and are not cyclic, and the remaining valences are all hydrogen-bonded to form a group upon loss of one hydrogen, including straight chain alkanyl and branched alkanyl. Similarly, "cycloalkyl" aryl is a radical formed by losing one hydrogen from a cycloalkane, and cycloalkane refers to an alkane in which carbon atoms are all connected by carbon-carbon single bonds and part of the carbon atoms are connected end to form a ring, and the remaining valence bonds are all combined with hydrogen.
In the present application, the "alkyl group having 1 to 30 carbon atoms" may have 1 to 30 carbon atoms, and include 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, and refers to a group formed by losing one hydrogen from an alkane containing 1 to 30 carbon atoms, and non-limiting examples include ethane, n-propane, isopropyl, n-butane, isobutane, 2-ethylbutane, 3-dimethylbutane, n-pentane, isopentane, neopentane, 1-methylpentane, 3-methylpentane, 2-ethylpentane, 4-methyl-2-pentane, n-hexane, 1-methylhexane, 2-ethylhexane, 2-butylhexane, n-heptane, 1-methylheptane, 2-dimethylheptane, 2-ethylheptane, n-octane, n-nonane, n-decane.
In the present application, halogen groups include chlorine, fluorine, bromine, iodine.
In summary, in the conventional rare earth butadiene rubber preparation process, it is difficult to prepare rare earth butadiene rubber with both high conversion rate and low viscosity. To address this problem, those skilled in the art have focused on developing new catalytic systems, but with little success.
The technicians have accidentally found during long-term synthetic studies and production processes: when preparing rare earth butadiene rubber, the time of adding the catalyst into butadiene monomer has influence on conversion rate and viscosity control, and the time of adding different types of catalysts into butadiene monomer has different influence on conversion rate and viscosity control.
Based on the method, the technical staff of the application obtain the preparation method of the rare earth butadiene rubber with high conversion rate and low viscosity after a great amount of creative exploration.
The application provides a preparation method of rare earth butadiene rubber, which comprises the following steps S10-S30.
Step S10, mixing a solvent with butadiene monomer to prepare a first mixed solution.
Step S20, adding the first catalyst into the first mixed solution to prepare a second mixed solution.
And step S30, adding a second catalyst and a third catalyst into the second mixed solution to perform polymerization reaction, so as to prepare the rare earth butadiene rubber.
Wherein, during the polymerization reaction, a quality regulator is added.
The first catalyst comprises an aluminum alkyl hydride, the second catalyst comprises a rare earth catalyst, and the third catalyst comprises a halide.
In the preparation method of the rare earth butadiene rubber, before the polymerization reaction, a specific kind of catalyst is added into butadiene monomers according to a specific sequence, and then a mass regulator is added in the polymerization reaction process, so that the catalyst maintains a certain catalytic activity, the butadiene monomers have higher conversion rate, and simultaneously, the polymerization process is easy to regulate, thereby achieving the purpose of quickly regulating the quality of the polymer, further, the conversion rate of the prepared rare earth butadiene rubber is improved, and meanwhile, the Mooney viscosity of the prepared rare earth butadiene rubber, particularly the Mooney viscosity after mixing is reduced, the processing difficulty of subsequent products is reduced, and the preparation is easy.
Furthermore, in the preparation method, each catalyst can have higher conversion rate of butadiene monomer without aging treatment, and the Mooney viscosity of the butadiene monomer after mixing is reduced, so that the preparation time can be further shortened, the preparation flow is simplified, and the preparation cost is further reduced.
In some of these embodiments, the step of preparing the second mixed solution in step S20 includes the steps of:
the second catalyst and the third catalyst are mixed and then added into the second mixed solution.
Referring to fig. 1 specifically, fig. 1 is a process flow chart of preparing rare earth butadiene rubber in an embodiment, which includes a polymerization reactor 10, a first conveying pipeline 20, a second conveying pipeline 30, a third conveying pipeline 40, a fourth conveying pipeline 50, a fifth conveying pipeline 60, a sixth conveying pipeline 70, a first mixing reactor 80 and a second mixing reactor 90, wherein the reaction reactor 10 is provided with a stirrer 11, the first conveying pipeline 20 and the second conveying pipeline 30 are connected with one end of the first mixing reactor 80, the other end of the first mixing reactor 80 is connected with the polymerization reactor 10, the third conveying pipeline 40 and the fourth conveying pipeline 50 are connected with one end of the second mixing reactor 90, the other end of the second mixing reactor 90 is connected with the polymerization reactor 10, and the fifth conveying pipeline 60 and the sixth conveying pipeline 70 are respectively and directly connected with the polymerization reactor 10.
It will be appreciated that the number of connection ports of the polymerization reactor 10 may be one or more, and that when there is only one connection port, it may be connected to a plurality of transfer pipes by switching connection valves.
In preparing the rare earth butadiene rubber, the first and second transfer pipes 20 and 30 are used to transfer butadiene monomer and solvent, respectively, the first mixing tank 80 is used to mix butadiene monomer and solvent to prepare a first mixed solution, and transfer the first mixed solution to the polymerization tank 10, then the fifth transfer pipe 60 transfers the first catalyst to the polymerization tank 10 to mix with the first mixed solution in the polymerization tank 10, prepare a second mixed solution, and then the third transfer pipe 40 and the fourth transfer pipe 50 are used to transfer the second catalyst and the third catalyst to the second mixing tank 90, respectively, to mix with the second mixed solution, and start the agitator 11 in the polymerization tank 10 to perform polymerization reaction, and during the polymerization reaction, transfer the mass regulator to the polymerization tank 10 through the sixth transfer pipe 70 to prepare the rare earth butadiene rubber.
In some of these embodiments, the ratio of the moles of the first catalyst, the second catalyst, and the third catalyst is (10 to 50): 1: (1-4).
The proportion of each catalyst is further regulated to further improve the catalytic effect and reduce the viscosity of the product.
In some of these embodiments, the ratio of the moles of the first catalyst, the second catalyst, and the third catalyst is (20 to 50): 1: (1-4).
In some of these embodiments, the ratio of the moles of the first catalyst, the second catalyst, and the third catalyst is (20 to 50): 1: (2-4).
The above "(10 to 50): 1: (1-4) ", values include the minimum and maximum values of the range, and each value between such minimum and maximum values, specific examples include, but are not limited to, the point values in the embodiments and: 10:1: (1-4), 20:1: (1-4), 30:1: (1-4), 40:1: (1-4), 50:1: (1-4), 10:1: 1. 20:1: 1. 30:1: 1. 40:1: 1. 50:1: 1. 10:1: 2. 20:1: 2. 30:1: 2. 40:1: 2. 50:1: 2. 10:1: 3. 20:1: 3. 30:1: 3. 40:1: 3. 50:1: 3. 10:1: 4. 20:1: 4. 30:1: 4. 40:1: 4. 50:1:4, a step of; and a range of arbitrary two point values.
In some of these embodiments, the molar ratio of the second catalyst to butadiene monomer is 1 (1X 10) 2 ～1×10 5 )。
The above-mentioned "1 (1X 10) 2 ～1×10 5 ) "wherein values include the minimum and maximum values of the range, and each value between such minimum and maximum values, specific examples include, but are not limited to, point values in the embodiments and: 1:1×10 2 、1:5×10 2 、1:1×10 3 、1:5×10 3 、1:1×10 4 、1:5×10 4 、1:1×10 5 The method comprises the steps of carrying out a first treatment on the surface of the And a range of arbitrary two point values.
In some embodiments, none of the first catalyst, the second catalyst, and the third catalyst is aged.
In some embodiments, the structure of the aluminum alkyl hydride is shown in formula (1):
L n AlT 1(3-n)
(1)，
wherein each occurrence of L is independently selected from substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms; t (T) 1 And H and n are any integer from 1 to 2.
n is 1 or 2.
In some of these embodiments, n is 2.
Wherein, when n is 2, each L may be the same or different.
In some of these embodiments, each occurrence of L is independently selected from alkyl groups having 1 to 20 carbon atoms.
In some of these embodiments, each occurrence of L is independently selected from the group consisting of an alkanyl radical having from 1 to 20 carbon atoms.
In some of these embodiments, each occurrence of L is independently selected from the group consisting of an alkanyl radical having from 1 to 10 carbon atoms.
In some of these embodiments, each occurrence of L is independently selected from the group consisting of C1-6 alkanyl.
In some embodiments, each occurrence of L is independently selected from any one of methyl, ethyl, propyl, n-butyl, isobutyl, pentyl, hexyl.
In some of these embodiments, each L is the same.
In some of these embodiments, the alkylaluminum hydride comprises at least one of diethylaluminum hydride, dipropylaluminum hydride, dibutylaluminum hydride, dipentylaluminum hydride and dihexylaluminum hydride.
In some of these embodiments, the rare earth catalyst comprises neodymium alkyl carboxylate.
In some of these embodiments, neodymium alkyl carboxylates contain cycloalkyl groups having 3 to 20 carbon atoms or alkanyl groups having 3 to 6 carbon atoms.
In some of these embodiments, the rare earth catalyst comprises neodymium naphthenate, neodymium isooctanoate, and neodymium neodecanoate.
In some of these embodiments, the neodymium cycloalkyl carboxylate contains a cycloalkyl group having 3 to 10 carbon atoms.
In some embodiments, neodymium alkyl carboxylate contains any of the cyclopropyl and cyclohexyl structures.
In some of these embodiments, the halide has the structure shown in formula (2):
X m AlT 2(3-m)
(2)
wherein each occurrence of X is independently selected from substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms; t (T) 2 Halogen, m is any integer from 1 to 2.
m is 1 or 2.
In some of these embodiments, T 2 Including at least one of chlorine, bromine and iodine.
In some of these embodiments, T 2 Including at least one of chlorine, bromine and iodine.
In some embodiments, each occurrence of X is independently selected from alkyl groups having 1 to 20 carbon atoms.
In some of these embodiments, each occurrence of X is independently selected from the group consisting of an alkanyl radical having from 1 to 20 carbon atoms.
In some of these embodiments, each occurrence of X is independently selected from the group consisting of an alkanyl radical having from 1 to 10 carbon atoms.
In some of these embodiments, each occurrence of X is independently selected from the group consisting of alkanyl groups having 1 to 6 carbon atoms.
In some embodiments, each occurrence of X is independently selected from any one of methyl, ethyl, propyl, n-butyl, isobutyl, pentyl, hexyl.
In some embodiments, each X is the same.
In some of these embodiments, the halide comprises at least one of diethyl aluminum chloride, sesquiethyl aluminum chloride, diisobutyl aluminum chloride.
In some of these embodiments, the mass modifier is an alkyl aluminum compound.
In some of these embodiments, the aluminum alkyl compound includes an alkyl group having 1 to 20 carbon atoms.
In some of these embodiments, the aluminum alkyl compound includes an alkyl group having 1 to 10 carbon atoms.
In some of these embodiments, the aluminum alkyl compound includes an alkyl group having 1 to 6 carbon atoms.
In some of these embodiments, the alkyl aluminum compound includes at least one structure of methyl, ethyl, propyl, n-butyl, isobutyl, pentyl, hexyl.
In some of these embodiments, the alkyl aluminum compound comprises at least one of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, pentylaluminum, trihexylaluminum, trioctylaluminum.
In some of these embodiments, the mass modifier is 0.01% to 0.5% of the mass of the butadiene monomer.
In the foregoing "0.01% -0.5%", values include the minimum value and the maximum value of the range, and each value between such minimum value and maximum value, and specific examples include, but are not limited to, the point values and the following in the embodiments: 0.01%, 0.015%, 0.02%, 0.025%, 0.03%, 0.035%, 0.04%, 0.045%, 0.05%, 0.055%, 0.06%, 0.065%, 0.07%, 0.075%, 0.08%, 0.09%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%; and a range of arbitrary two point values.
In some of these embodiments, the polymerization reaction is carried out at a temperature of 30℃to 80℃for a period of 0.5h to 3h.
In some of these embodiments, the mass modifier is added when the polymerization reaction has proceeded for 10min to 90 min.
Further, a mass regulator is added when the polymerization reaction proceeds to 1/18 to 1/3 of the total polymerization reaction time.
In the research process, technicians further regulate and control the adding time of the quality regulator by repeatedly researching and testing the change condition of the Mooney viscosity of the glue solution in the reaction kettle in the polymerization reaction process so as to further improve the effect efficiency of quality regulation and control, achieve the aim of quickly regulating and controlling the quality, and further reduce the Mooney viscosity of the prepared butadiene rubber after mixing by selecting the time of adding the quality regulator.
In some embodiments, the solvent includes an alkane compound having 5 to 10 carbon atoms.
In some embodiments, the solvent comprises a paraffinic compound having 5 to 10 carbon atoms.
In some embodiments, the solvent is n-hexane.
In some of these embodiments, the mass ratio of solvent to butadiene monomer is (2-5): 1.
An embodiment of the present application also provides a butadiene rubber, which is prepared by the method for preparing the butadiene rubber of the first aspect.
The butadiene rubber prepared by the preparation method has low viscosity, particularly the Mooney viscosity after rubber mixing, and is favorable for the industrialized production of butadiene rubber products
The application will be described in connection with specific embodiments, but the application is not limited thereto, and it will be appreciated that the appended claims outline the scope of the application, and those skilled in the art, guided by the inventive concept, will appreciate that certain changes made to the embodiments of the application will be covered by the spirit and scope of the appended claims.
The following are specific examples
Example 1
1. Preparation of rare earth butadiene rubber
Referring to fig. 1, a specific preparation process flow chart is shown, a first conveying pipeline 20 and a second conveying pipeline 30 are respectively used for conveying butadiene monomer and solvent, a first mixing kettle 80 is used for mixing butadiene monomer and solvent n-hexane to prepare a first mixed solution, the first mixed solution is conveyed to a polymerization kettle 10, then a fifth conveying pipeline 60 conveys a first catalyst to the polymerization kettle 10 to be mixed with the first mixed solution in the polymerization kettle 10 to prepare a second mixed solution, a third conveying pipeline 40 and a fourth conveying pipeline 50 are respectively used for conveying a second catalyst and a third catalyst to a second mixing kettle 90 to be mixed, the mixed solution is conveyed to the polymerization kettle 10 to be mixed with the second mixed solution, a stirrer 11 in the polymerization kettle 10 is started to perform polymerization at 50 ℃, a mass regulator is conveyed to the polymerization kettle 10 to continue the reaction after the polymerization reaction starts for 15min, and butadiene rubber is prepared for 3h.
Wherein the mass ratio of butadiene monomer to solvent n-hexane is 1:3, the first catalyst is diethyl aluminum hydride, the second catalyst is neodymium naphthenate, and the third catalyst is sesquiethyl aluminum chloride; the molar ratio of the first catalyst, the second catalyst and the third catalyst is 15:1:1.2, and the molar ratio of the second catalyst to the butadiene monomer is 1:1×10 3 The method comprises the steps of carrying out a first treatment on the surface of the The mass regulator is triethylaluminum, and the addition amount is 0.15% of the mass of butadiene monomer.
2. Testing
(1) The conversion of butadiene monomer was measured by weighing: after the reaction is finished, absolute ethyl alcohol is added into the reaction kettle, then the kettle cover is opened, white solid polybutadiene in the kettle is taken out in a manual mode, dried and weighed, and the conversion rate of the white solid polybutadiene is calculated.
Conversion = M1/(M2) ×100%
M1 represents the mass of the harvested rare earth butadiene rubber; m2 represents the mass of butadiene monomer charged.
(2) The raw rubber Mooney viscosity ML (1+4) at 100℃was measured in accordance with the standard GB/T1232.1-2016.
(3) Mixing raw rubber of rare earth butadiene rubber according to a C2 method in GB/T8660-2018, mixing, and testing the Mooney viscosity ML (1+4) of the mixed rubber according to the standard GB/T1232.1-2016 by a Mooney machine to obtain a mixed rubber sample.
The specific test results are shown in Table 1.
Examples 2 to 5
Examples 2 to 5 are identical to example 1, except that: the ratio of the number of moles of each catalyst was different from that of example 1, in which the ratio of the number of moles of the first catalyst, the second catalyst, and the third catalyst in example 2 was 30:1:4, the ratio of the number of moles of the first catalyst, the second catalyst, and the third catalyst in example 3 was 50:1:2, the ratio of the number of moles of the first catalyst, the second catalyst, and the third catalyst in example 4 was 10:1:1, and the ratio of the number of moles of the first catalyst, the second catalyst, and the third catalyst in example 5 was 15:1:3.
Other process conditions and parameters were the same as in example 1, and specific test results are shown in Table 1.
Comparative example 1
1. Under the protection of nitrogen, adding a first catalyst, a second catalyst and a fourth catalyst into n-hexane serving as an inert organic solvent, and aging for 40min at the temperature of minus 30-60 ℃ to obtain a ternary aging liquid; mixing the ternary ageing liquid with a third catalyst, ageing for 1h at the temperature of minus 30-60 ℃ to obtain quaternary ageing liquid, and conveying the quaternary ageing liquid into a polymerization kettle.
2. Mixing butadiene monomer with solvent oil n-hexane to obtain mixed solution, conveying the mixed solution into a polymerization kettle, mixing the mixed solution with quaternary ageing solution for polymerization reaction, carrying out polymerization reaction at 50 ℃, adding a quality regulator into the polymerization kettle 15min after the polymerization reaction is started, and preparing butadiene rubber raw rubber.
Wherein in the step 2, the mass ratio of the butadiene monomer to the solvent n-hexane is 1:3, the first catalyst is diethyl aluminum hydride, the second catalyst is neodymium naphthenate, the third catalyst is chlorobutyl aluminum, and the fourth catalyst is butadiene; the ratio of the number of moles of the first catalyst, the second catalyst, the third catalyst and the fourth catalyst is 1:15:1:1.2:50, the molar ratio of the second catalyst to the butadiene monomer in step 2 is 1:1×10 3 The method comprises the steps of carrying out a first treatment on the surface of the The mass regulator is triethylaluminum, and the addition amount is 0.15% of the mass of the butadiene monomer in the step 2.
Other process parameters and conditions were the same as in example 1. The specific results are shown in Table 1.
Comparative example 2
Comparative example 2 is substantially the same as example 1 except that: the adding time of each catalyst is different, and specifically: mixing butadiene monomer and n-hexane solvent to prepare a first mixed solution, conveying the first mixed solution into a polymerization reaction kettle, conveying a third catalyst into the polymerization kettle to be mixed with the first mixed solution, adding the mixed solution of the first catalyst and the second catalyst for polymerization reaction, and adding a quality regulator at 15min of the polymerization reaction.
Wherein the mass ratio of the butadiene monomer to the solvent n-hexane is 1:3, the first catalyst is diethyl aluminum hydride, the second catalyst is neodymium naphthenate, and the third catalyst is chlorobutyl aluminum; the molar ratio of the first catalyst, the second catalyst and the third catalyst is 15:1:1.2, and the molar ratio of the second catalyst to the butadiene monomer is 1:1×10 3 The method comprises the steps of carrying out a first treatment on the surface of the The mass regulator is triethylaluminum, and the addition amount is 0.15% of the mass of butadiene monomer.
Other process parameters and conditions were the same as in example 1. The specific results are shown in Table 1.
Comparative example 3
Comparative example 3 is substantially the same as example 1 except that: the adding time of each catalyst is different, and specifically: mixing butadiene monomer and n-hexane solvent to prepare a first mixed solution, conveying the first mixed solution into a polymerization reaction kettle, conveying a second catalyst into the polymerization kettle to be mixed with the first mixed solution, adding the mixed solution of the first catalyst and a third catalyst for polymerization reaction, and adding a quality regulator at 15min of the polymerization reaction.
Wherein the mass ratio of the butadiene monomer to the solvent n-hexane is 1:3, the first catalyst is diethyl aluminum hydride, the second catalyst is neodymium naphthenate, and the third catalyst is chlorobutyl aluminum; the molar ratio of the first catalyst, the second catalyst and the third catalyst is 15:1:1.2, and the molar ratio of the second catalyst to the butadiene monomer is 1:1×10 3 The method comprises the steps of carrying out a first treatment on the surface of the The mass regulator is triethylaluminum, and the addition amount is 0.15% of the mass of butadiene monomer.
Other process parameters and conditions were the same as in example 1. The specific results are shown in Table 1.
Comparative example 4
Comparative example 4 is substantially the same as example 1 except that: the adding time of each catalyst is different, and specifically: the method comprises the steps of mixing butadiene monomers and n-hexane serving as a solvent to prepare a first mixed solution, conveying the first mixed solution to a polymerization reaction kettle, and then conveying a first catalyst, a second catalyst and a third catalyst to the polymerization kettle to be mixed with the first mixed solution for polymerization reaction.
Wherein the mass ratio of the butadiene monomer to the solvent n-hexane is 1:3, the first catalyst is diethyl aluminum hydride, the second catalyst is neodymium naphthenate, and the third catalyst is chlorobutyl aluminum; the molar ratio of the first catalyst, the second catalyst and the third catalyst is 15:1:1.2, and the molar ratio of the second catalyst to the butadiene monomer is 1:1×10 3 The method comprises the steps of carrying out a first treatment on the surface of the The mass regulator is triethylaluminum, and the addition amount is 0.15% of the mass of butadiene monomer.
Other process parameters and conditions were the same as in example 1. The specific results are shown in Table 1.
Comparative example 5
Comparative example 5 is substantially the same as example 1 except that: the adding time of each catalyst is different, and specifically: mixing butadiene monomer and n-hexane solvent to prepare a first mixed solution, conveying the first mixed solution into a polymerization reaction kettle, and then sequentially conveying the first catalyst, the second catalyst and the third catalyst into the polymerization kettle to be mixed with the first mixed solution for polymerization reaction.
Wherein the mass ratio of the butadiene monomer to the solvent n-hexane is 1:3, the first catalyst is diethyl aluminum hydride, the second catalyst is neodymium naphthenate, and the third catalyst is chlorobutyl aluminum; the molar ratio of the first catalyst, the second catalyst and the third catalyst is 15:1:1.2, and the molar ratio of the second catalyst to the butadiene monomer is 1:1×10 3 The method comprises the steps of carrying out a first treatment on the surface of the The mass regulator is triethylaluminum, and the addition amount is 0.15% of the mass of butadiene monomer.
Other process parameters and conditions were the same as in example 1. The specific results are shown in Table 1.
The conversion and the Mooney viscosity of each of the examples and comparative examples are shown in Table 1.
TABLE 1
Analysis of the conversion and mooney viscosity comparison data for examples and comparative examples 1-5 in table 1 shows that: on the basis of the same types and proportions of the catalysts, the preparation process is adopted, the specific types of catalysts are added into butadiene monomers according to a specific sequence, and then a quality regulator is added in the polymerization reaction process, so that the conversion rate of the prepared rare earth butadiene rubber is improved, the Mooney viscosity of the rare earth butadiene rubber is reduced, particularly the Mooney viscosity after mixing is reduced, and the processing difficulty of subsequent products is reduced.
Furthermore, in the preparation method provided by the application, each catalyst can be used for enabling the butadiene monomer to have higher conversion rate without aging treatment, and reducing the Mooney viscosity after mixing, so that the preparation time can be further shortened, the preparation flow is simplified, and the preparation cost is further reduced.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples merely represent a few embodiments of the present application, which are described in more detail and are not to be construed as limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. The scope of the application should therefore be determined from the appended claims, and the description and drawings may be used to interpret the contents of the claims.
Claims (10)
1. The preparation method of the rare earth butadiene rubber is characterized by comprising the following steps of:
mixing a solvent with butadiene monomer to prepare a first mixed solution;
adding a first catalyst into the first mixed solution to prepare a second mixed solution;
adding a second catalyst and a third catalyst into the second mixed solution to perform polymerization reaction to prepare rare earth butadiene rubber;
wherein, in the course of the said polymerization reaction, add the quality regulator;
the first catalyst comprises an aluminum alkyl hydride, the second catalyst comprises a rare earth catalyst, and the third catalyst comprises a halide.
2. The method for preparing rare earth butadiene rubber according to claim 1, wherein the step of preparing the second mixed solution comprises the steps of:
and mixing the second catalyst and the third catalyst, and then adding the mixed solution into the second mixed solution.
3. The method for producing a rare earth butadiene rubber according to claim 1, wherein the ratio of the number of moles of the first catalyst, the second catalyst and the third catalyst is (10 to 50): 1: (1-4).
4. A process for producing a rare earth butadiene rubber as claimed in any one of claims 1-3, wherein the molar ratio of said second catalyst to said butadiene monomer is 1 (1X 10) 2 ～1×10 5 )。
5. The method for producing a rare earth butadiene rubber according to any one of claims 1 to 3, wherein none of the first catalyst, the second catalyst, and the third catalyst is aged.
6. The method for preparing rare earth butadiene rubber according to any one of claims 1-3, wherein the method for preparing rare earth butadiene rubber satisfies at least one of the following conditions (a) - (c):
(a) The structure of the aluminum alkyl hydride is shown as a formula (1):
L n AlT 1(3-n) (1)，
wherein each occurrence of L is independently selected from substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms; t (T) 1 H, n is any integer from 1 to 2;
(b) The rare earth catalyst comprises neodymium alkyl carboxylate;
(c) The structure of the halide is shown as a formula (2):
X m AlT 2(3-m) (2)
wherein each occurrence of X is independently selected from substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms; t (T) 2 Halogen, m is any integer from 1 to 2.
7. A method for producing a rare earth butadiene rubber as defined in any one of claims 1 to 3, wherein said quality modifier satisfies at least one of the following conditions (d) to (e):
(d) The quality regulator is an alkyl aluminum compound;
(e) The mass of the mass regulator is 0.01-0.5% of the mass of the butadiene monomer.
8. The method for preparing rare earth butadiene rubber according to any one of claims 1-3, wherein the polymerization reaction temperature is 30-80 ℃ and the time is 0.5-3 h.
9. The method for producing a rare earth butadiene rubber according to claim 8, wherein the mass modifier is added when the polymerization reaction is performed for 10 to 90 minutes.
10. A rare earth butadiene rubber prepared by the method for preparing a rare earth butadiene rubber according to any one of claims 1 to 9.
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Address after: 318 Waihuan West Road, Jiaxing Port District, Jiaxing City, Zhejiang Province, China Applicant after: Zhejiang Chuanhua Synthetic Materials Co.,Ltd. Address before: 618 Waihuan West Road, Jiaxing Port Area, Jiaxing City, Zhejiang Province, 314000 Applicant before: ZHEJIANG TRANSFAR SYNTHETIC MATERIALS Co.,Ltd. |
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