CN108690177B - Star-shaped SEPS elastomer and preparation method thereof - Google Patents
Star-shaped SEPS elastomer and preparation method thereof Download PDFInfo
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- CN108690177B CN108690177B CN201810556816.0A CN201810556816A CN108690177B CN 108690177 B CN108690177 B CN 108690177B CN 201810556816 A CN201810556816 A CN 201810556816A CN 108690177 B CN108690177 B CN 108690177B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229920001971 elastomer Polymers 0.000 title claims abstract description 17
- 239000000806 elastomer Substances 0.000 title claims abstract description 17
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 title claims abstract description 17
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 72
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 61
- 239000003292 glue Substances 0.000 claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 239000007822 coupling agent Substances 0.000 claims abstract description 19
- 238000001704 evaporation Methods 0.000 claims abstract description 11
- 230000008020 evaporation Effects 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 35
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 28
- 229920000642 polymer Polymers 0.000 claims description 27
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 26
- 238000006116 polymerization reaction Methods 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000003999 initiator Substances 0.000 claims description 23
- UIEKYBOPAVTZKW-UHFFFAOYSA-L naphthalene-2-carboxylate;nickel(2+) Chemical compound [Ni+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UIEKYBOPAVTZKW-UHFFFAOYSA-L 0.000 claims description 23
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 239000004593 Epoxy Substances 0.000 claims description 16
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 16
- 229930195729 fatty acid Natural products 0.000 claims description 16
- 239000000194 fatty acid Substances 0.000 claims description 16
- 229920001195 polyisoprene Polymers 0.000 claims description 13
- -1 fatty acid ester Chemical class 0.000 claims description 12
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 10
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 8
- 235000012424 soybean oil Nutrition 0.000 claims description 7
- 239000003549 soybean oil Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003495 polar organic solvent Substances 0.000 claims description 6
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 claims description 5
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 5
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 238000005859 coupling reaction Methods 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 9
- 239000004793 Polystyrene Substances 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 229920002223 polystyrene Polymers 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 230000003712 anti-aging effect Effects 0.000 description 8
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000011056 performance test Methods 0.000 description 8
- 238000009738 saturating Methods 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 6
- 239000010687 lubricating oil Substances 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 150000004982 aromatic amines Chemical class 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 238000001035 drying Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000003981 vehicle 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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
- C08F297/044—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes using a coupling agent
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
Abstract
The invention provides a preparation method of a star-shaped SEPS elastomer, which comprises the following steps: (1) isoprene, styrene and a coupling agent are used as raw materials to react to obtain a base glue solution before hydrogenation reaction: (2) carrying out hydrogenation reaction on the base glue solution before hydrogenation reaction in the step (1) under the action of a catalyst; (3) carrying out flash evaporation concentration on the glue solution obtained after the hydrogenation reaction in the step (2); (4) and (4) performing direct dry devolatilization on the flash-evaporated glue solution obtained in the step (3) to obtain the SEPS elastomer. The SEPS elastomer prepared by the preparation method has excellent performance which is mainly reflected in the aspects of high molecular weight, high viscosity, high shear resistance and the like, and the product performance and the production process fill the blank in the field in China.
Description
Technical Field
The invention belongs to the technical upgrading of high polymer materials, and relates to a star-shaped SEPS elastomer and a preparation method thereof.
Background
When the lubricating oil needs a certain viscosity to work in the using process, a sufficiently thick oil film is formed on the friction surface to prevent the friction surface from contacting, and a better lubricating property is achieved. The additive (modifier) makes up and improves the deficiency of the base oil in performance, and endows certain new characteristics to the lubricating oil with special service performance. For example, in order to ensure that the lubricating oil can meet the requirements at both cold and high temperatures, it is necessary to add a viscosity index improver to a low viscosity lubricating oil used in cold regions to maintain a high viscosity of the lubricating oil at high temperatures during vehicle operation. The addition of viscosity index improvers having dispersancy properties is widely used because of the greatly reduced production costs of lubricating oils. The dispersive viscosity index improver mainly comprises two types: the viscosity index improver of the dispersed ethylene propylene copolymer and the viscosity index improver of the dispersed hydrogenated styrene diene copolymer.
US 4089794 discloses a dispersed ethylene-propylene copolymer viscosity index improver, which is obtained by copolymerizing ethylene-propylene with grafted maleic anhydride and then aminating or esterifying. The amine or ester includes polyamine, polyalcohol, alcohol amine or their mixture. The viscosity index improver has a certain dispersing effect, but the control effect on soot and oil sludge is not ideal due to low grafting rate of maleic anhydride.
US 6107257 discloses a viscosity index improver of a dispersive ethylene-propylene copolymer, the structure of which contains aromatic amine compounds as polar groups, and the dispersion effect on soot is greatly enhanced. However, the used arylamine is very easy to be oxidized in the reaction to darken the color, if the reaction is insufficient, the residual arylamine can seriously affect the appearance of the product, and the residual arylamine is difficult to remove due to the high boiling point of the arylamine, usually about 20 hours is needed, so that more energy is consumed, and the production cost is greatly increased.
US 4141847 discloses a dispersed hydrogenated styrene diene copolymer viscosity index improver obtained by reacting a hydrogenated styrene diene copolymer with an unsaturated acid or anhydride followed by an amine reaction.
US 4077893 discloses a similar viscosity index improver, except that a polyol is used instead of an amine.
The two processes for synthesizing the hydrogenated styrene diene viscosity index improver have the same defects: namely, the method comprises a free radical reaction process and a condensation reaction process, and the two processes require high temperature, so that the energy consumption is increased, side reactions such as coupling and degradation are easy to occur, and the performance of the product is seriously influenced. In addition, the grafting rate and the degree of functionalization are difficult to control, and the reaction reproducibility is poor.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a block copolymer (SEPS) elastomer consisting of star-shaped hydrogenated styrene and conjugated diene and a preparation method thereof, the SEPS elastomer prepared by the preparation method has excellent performance, mainly reflects the aspects of high molecular weight, high viscosity, high shear resistance and the like, and the product performance and the production process fill the blank in the field in China.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the purposes of the invention is to provide a preparation method of a star-shaped SEPS elastomer, which is characterized by comprising the following steps:
(1) isoprene, styrene and a coupling agent are used as raw materials to react to obtain a base glue solution before hydrogenation reaction:
(2) carrying out hydrogenation reaction on the base glue solution before hydrogenation reaction in the step (1) under the action of a catalyst;
(3) carrying out flash evaporation concentration on the glue solution obtained after the hydrogenation reaction in the step (2);
(4) and (4) performing direct dry devolatilization on the flash-evaporated glue solution obtained in the step (3) to obtain the SEPS elastomer.
As the preferred technical scheme of the invention, the method for obtaining the base glue solution before hydrogenation reaction by the reaction in the step (1) comprises the following steps:
(a) adding isoprene into a solvent, uniformly stirring, and then adding an initiator to initiate a polymerization reaction to obtain polyisoprene;
(b) reacting the polyisoprene obtained in the step (a) with a coupling agent and a styrene mixture to obtain linear or multi-branched polymer mixed glue solution;
(c) and (c) adding a terminating agent to carry out termination reaction after the reaction in the step (b) is finished, so as to obtain the base glue solution before hydrogenation reaction.
As a preferred technical scheme of the invention, the solvent in the step (a) is a non-polar organic solvent.
Preferably, the non-polar organic solvent is cyclohexane.
Preferably, the amount of isoprene used in step (a) is 80-100% of the sum of the mass of isoprene and styrene, excluding 100%, such as 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99%, but not limited to the recited values, and other unrecited values within the range of values are also applicable.
Preferably, the initiator of step (a) is an alkyl lithium, preferably n-butyl lithium.
Preferably, the polymerization temperature in step (a) is 40 to 55 ℃, such as 40 ℃, 42 ℃, 44 ℃, 46 ℃, 48 ℃, 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃ or 55 ℃, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the polymerization pressure in step (a) is 0.1 to 0.5MPa, such as 0.1MPa, 0.15MPa, 0.2MPa, 0.25MPa, 0.3MPa, 0.35MPa, 0.4MPa, 0.45MPa or 0.5MPa, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the polymerization time in step (a) is 10-30 min, such as 10min, 12min, 15min, 18min, 20min, 22min, 25min, 28min or 30min, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
Preferably, the amount of styrene used in step (b) is 0 to 20% of the sum of the mass of isoprene and styrene, excluding 0%, such as 0.1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, or 20%, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the temperature of the reaction in step (b) is 70 to 85 ℃, such as 70 ℃, 72 ℃, 74 ℃, 76 ℃, 78 ℃, 80 ℃, 82 ℃, 84 ℃ or 85 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the pressure of the reaction in step (b) is 0.2 to 0.5MPa, such as 0.2MPa, 0.25MPa, 0.3MPa, 0.35MPa, 0.4MPa, 0.45MPa or 0.5MPa, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the reaction time in step (b) is 20-180 min, such as 20min, 30min, 60min, 90min, 120min, 150min or 180min, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
As the preferred technical scheme of the invention, the method for obtaining the base glue solution before hydrogenation reaction by the reaction in the step (1) comprises the following steps:
(A) adding a coupling agent and a styrene mixture into a solvent, uniformly stirring, and then adding an initiator to initiate polymerization reaction to obtain a hyperbranched active center;
(B) reacting the hyperbranched active center obtained in the step (A) with isoprene to obtain linear or multi-branched polymer mixed glue solution;
(C) and (B) adding a terminating agent after the reaction in the step (B) is finished to carry out termination reaction, thus obtaining the base glue solution before hydrogenation reaction.
As a preferred technical scheme of the invention, the solvent in the step (A) is a non-polar organic solvent.
Preferably, the non-polar organic solvent is cyclohexane.
Preferably, the amount of styrene used in step (a) is 0 to 20% of the sum of the mass of isoprene and styrene, excluding 0%, such as 0.1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, or 20%, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the initiator of step (A) is an alkyl lithium, preferably n-butyl lithium.
Preferably, the polymerization temperature in step (A) is 40-55 deg.C, such as 40 deg.C, 42 deg.C, 44 deg.C, 46 deg.C, 48 deg.C, 50 deg.C, 51 deg.C, 52 deg.C, 53 deg.C, 54 deg.C or 55 deg.C, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
Preferably, the pressure of the polymerization reaction in step (A) is 0.1 to 0.5MPa, such as 0.1MPa, 0.15MPa, 0.2MPa, 0.25MPa, 0.3MPa, 0.35MPa, 0.4MPa, 0.45MPa or 0.5MPa, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the polymerization time in step (A) is 10-30 min, such as 10min, 12min, 15min, 18min, 20min, 22min, 25min, 28min or 30min, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
Preferably, the amount of isoprene used in step (B) is 80 to 100% of the sum of the mass of isoprene and styrene, excluding 100%, such as 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99%, but not limited to the recited values, and other values not recited in this range are also applicable.
Preferably, the reaction temperature in step (B) is 50-90 deg.C, such as 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, 85 deg.C or 90 deg.C, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the pressure of the reaction in step (B) is 0.2 to 0.5MPa, such as 0.2MPa, 0.25MPa, 0.3MPa, 0.35MPa, 0.4MPa, 0.45MPa or 0.5MPa, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the reaction time in step (B) is 20-60 min, such as 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferred technical scheme of the invention, the coupling agent in the step (b) and the coupling agent in the step (A) are respectively and independently divinylbenzene and/or epoxy fatty acid ester.
Preferably, the epoxy fatty acid ester comprises any one of or a combination of at least two of epoxidized soybean oil, epoxidized fatty acid methyl ester, epoxidized fatty acid ethyl ester, epoxy diluent (epoxy value ≧ 0.6) or epoxidized fatty acid butyl ester, and the combination is exemplified by the following typical but non-limiting examples: a combination of epoxidized soybean oil and epoxidized fatty acid methyl ester, a combination of epoxidized fatty acid methyl ester and epoxidized fatty acid ethyl ester, a combination of epoxidized fatty acid ethyl ester and an epoxy diluent (the epoxy value is not less than 0.6), a combination of an epoxy diluent (the epoxy value is not less than 0.6) and epoxy fatty acid butyl ester, a combination of epoxy fatty acid butyl ester and epoxidized soybean oil, a combination of epoxidized soybean oil, epoxidized fatty acid methyl ester and epoxy fatty acid ethyl ester, and the like.
Preferably, the epoxy fatty acid ester has an epoxy value of 4.0 to 7.0, such as 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, or 7.0, but not limited to the recited values, and other values not recited within the range are equally applicable.
Preferably, the molar ratio of the coupling agent of step (b) to the initiator of step (a) and the molar ratio of the coupling agent of step (a) to the initiator of step (a) are each independently (0.5 to 10: 1), such as 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1 or 10:1, but not limited to the recited values, and other values not recited within this range of values are equally applicable.
Preferably, the terminating agent in step (C) and step (C) is an alcohol terminating agent.
Preferably, the alcohol terminating agent comprises any one of methanol, ethanol, isopropanol, tert-butanol or octadecanol or a combination of at least two of these, typical but non-limiting examples being: a combination of methanol and ethanol, a combination of ethanol and isopropanol, a combination of isopropanol and tert-butanol, a combination of tert-butanol and octadecanol, or a combination of methanol, ethanol and isopropanol, etc., preferably methanol or isopropanol.
Preferably, the amount of the terminating agent added in step (C) and step (C) is independently 1.0 to 1.2 times, such as 1.0 times, 1.05 times, 1.1 times, 1.15 times or 1.20 times, etc. of the molar amount of the initiator, but is not limited to the recited values, and other values not recited in the above range are also applicable.
Preferably, the termination reaction temperature in step (C) and step (C) is 70 to 85 ℃, such as 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃, 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃ or 85 ℃ respectively, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the time for terminating the reaction in step (C) and step (C) is 10-15 min, such as 10min, 11min, 12min, 13min, 14min or 15min, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
In the invention, the coupling agent and the styrene are added simultaneously, compared with the traditional method of adding the coupling agent and the styrene step by step, the method has the advantages of short reaction time, low reaction temperature, polymerization reaction and coupling reaction temperature not higher than 100 ℃, less side reaction, easy control of product structure and no generation of other impurity polymers and cross-linked polymers; the product has excellent performance, takes styrene and a coupling agent as cores, and has excellent thickening capability, shear stability and dispersibility.
As a preferred technical scheme of the invention, the catalyst in the step (2) comprises a main catalyst and a cocatalyst.
Preferably, the procatalyst comprises any one of nickel naphthenate, nickel acetylacetonate or nickel isooctanoate, or a combination of at least two of these, typical but non-limiting examples being: nickel naphthenate and nickel acetylacetonate, nickel acetylacetonate and nickel isooctanoate, nickel isooctanoate and nickel naphthenate or nickel naphthenate, nickel acetylacetonate and nickel isooctanoate, and the like.
Preferably, the amount of the main catalyst is 2-10 mg, such as 2mg, 3mg, 4mg, 5mg, 6mg, 7mg, 8mg, 9mg, or 10mg, per gram of the base cement solution before hydrogenation reaction, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the cocatalyst comprises triisobutylaluminum and/or triethylaluminum.
Preferably, the molar ratio of the cocatalyst to the main catalyst is (2-10): 1, such as 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, but not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the hydrogenation reaction in step (2) is carried out at a temperature of 60 to 100 ℃, such as 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the hydrogenation reaction in step (2) is carried out at a pressure of 1.0 to 6.0MPa, such as 1.0MPa, 2.0MPa, 3.0MPa, 3.5MPa, 4.0MPa, 4.5MPa, 5.0MPa, 5.5MPa or 6.0MPa, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the hydrogenation reaction time in step (2) is 1-5 h, such as 1h, 2h, 3h, 3.5h, 4h, 4.5h or 5h, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
In a preferred embodiment of the present invention, the pressure of the flash concentrated dope in step (3) is 0.3 to 2.0MPa, such as 0.3MPa, 0.5MPa, 0.8MPa, 1.0MPa, 1.2MPa, 1.5MPa, 1.8MPa, 2.0MPa, etc., but is not limited to the above-mentioned values, and other values within the above-mentioned range are also applicable, and preferably 0.5 to 1.5 MPa.
Preferably, the flow rate of the flash evaporation concentrated glue solution in the step (3) is 3.0-6.5 m3H, e.g. 3.0m3/h、3.5m3/h、4.0m3/h、4.5m3/h、5.0m3/h、5.5m3/h、6.0m3H or 6.5m3And/h, but not limited to, the recited values, and other values not recited within the range of values are also applicable, and are preferably 3.0 to 4.5m3/h。
Preferably, the pressure of the flash evaporation in the step (3) is 0 to 0.1MPa, 0.01MPa, 0.02MPa, 0.03MPa, 0.04MPa, 0.05MPa, 0.06MPa, 0.07MPa, 0.08MPa, 0.09MPa or 0.1MPa, but is not limited to the recited values, and other values in the range are also applicable, preferably 0.01 to 0.05 MPa.
Preferably, the temperature of the flash evaporation in step (3) is 0 to 250 ℃, such as 10 ℃, 20 ℃, 50 ℃, 80 ℃, 100 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ or 200 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 130 to 200 ℃.
As a preferable technical scheme of the invention, the direct dry devolatilization in the step (4) adopts a twin-screw extrusion devolatilization machine.
Preferably, the twin-screw extrusion devolatilization machine comprises any one of a co-rotating intermeshing type twin-screw extruder, a counter-rotating non-intermeshing twin-screw extruder, or a co-rotating non-intermeshing twin-screw extruder.
Preferably, the pressure of the flash-evaporated glue solution entering the devolatilizer is 0 to 4.0MPa, such as 0.5MPa, 1.0MPa, 1.5MPa, 2.0MPa, 2.5MPa, 3.0MPa, 3.5MPa or 4.0MPa, but the pressure is not limited to the recited values, and other values not recited in the above range are also applicable, preferably 1.0 to 3.5 MPa.
Preferably, the barrel temperature of each section of the twin-screw extruder is 130 to 240 ℃, such as 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃ or 240 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the devolatilizer feed concentration is from 30% to 70%, such as 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, or 70%, and the like, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the devolatilizer speed is 100 to 500rpm, such as 100rpm, 150rpm, 200rpm, 250rpm, 300rpm, 350rpm, 400rpm, 450rpm, or 500rpm, but not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the devolatilizer vacuum is in the range of-0.01 to-0.10 MPa, such as-0.01 MPa, -0.02MPa, -0.03MPa, -0.04MPa, -0.05MPa, -0.06MPa, -0.07MPa, -0.08MPa, -0.09MPa, or-0.1 MPa, but not limited to the recited values, and other values not recited in this range of values are equally applicable, preferably-0.07 to-0.09 MPa.
Preferably, the post-devolatilization tank pressure is 0.05 to 0.5MPa, such as 0.05MPa, 0.1MPa, 0.15MPa, 0.2MPa, 0.25MPa, 0.3MPa, 0.35MPa, 0.4MPa, 0.45MPa, or 0.5MPa, but is not limited to the recited values, and other values within this range are equally applicable, preferably 0.05 to 0.3 MPa.
Preferably, the flow rate of the solvent steam in the post-devolatilization tank is 300-600 m3E.g. 100m3/h、200m3/h、300m3/h、400m3/h、450m3/h、500m3/h、550m3H or 600m3And/h, etc., but are not limited to the recited values, and other values not recited within the numerical range are equally applicable.
In the invention, a melt pump is additionally arranged at the front section of the devolatilization machine.
Wherein, the temperature of the pump body of the melt pump is required to be controlled at 80-300 ℃, preferably 100-250 ℃, such as 100 ℃, 120 ℃, 150 ℃, 170 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃ or 250 ℃, but not limited to the enumerated values, and other non-enumerated values in the numerical value range are also applicable;
the melt pump speed is controlled to be 0 to 70r/min, preferably 10 to 60r/min, such as 10r/min, 20r/min, 30r/min, 40r/min, 50r/min or 60r/min, but not limited to the values listed, and other values not listed in the range of the values are also applicable.
In the invention, the direct dry devolatilization process adopts an underwater granulation mode.
Wherein the pressure of the die plate in the cutting chamber is controlled to be 0.0 to 20.0MPa, preferably 10 to 15.0MPa, such as 10.0MPa, 11.0MPa, 12.0MPa, 13.0MPa, 14.0MPa or 15.0MPa, but not limited to the values listed, and other values not listed in the numerical range are also applicable;
the temperature of the cutting template is controlled to be 0-280 ℃, preferably 0-250 ℃, such as 0 ℃, 50 ℃, 100 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃ or 250 ℃, but not limited to the recited values, and other non-recited values in the value range are also applicable;
the temperature of the template heat conducting oil is required to be controlled to be 100-300 ℃, preferably 200-280 ℃, such as 200 ℃, 220 ℃, 240 ℃, 260 ℃ or 280 ℃, but is not limited to the recited values, and other values not recited in the numerical range are also applicable;
the rotation speed of the cutter of the granulator is required to be controlled to be 100-3000 r/min, preferably 500-2500 r/min, such as 500r/min, 1000r/min, 1500r/min, 1600r/min, 1700r/min, 1800r/min, 1900r/min, 2000r/min or 2500r/min, but the rotation speed is not limited to the values listed, and other values not listed in the numerical range are also applicable;
the pre-cutter thrust opening is desirably controlled to be 0% to 50%, preferably 30% to 40%, for example 30%, 32%, 34%, 36%, 38% or 40%.
In order to prevent the material from sticking to the cutting blade, wax is added to the water for granulation, and the wax concentration is controlled to be 0 to 5%, preferably 1.0 to 3.0%, for example, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2.0%, 2.2%, 2.6%, or 3.0%, but not limited to the values listed, and other values not listed in the range of the values are also applicable.
The invention adopts direct dry devolatilization, and has the advantages of low energy consumption and high efficiency. In the traditional process, the solvent in the polymer solution is removed by adopting traditional steam stripping, while the stripping desolventizing with higher energy consumption and the subsequent drying dehydration process are cancelled in the direct devolatilization process, the energy consumption of the direct devolatilization technology is only 50 percent of that of the common condensation drying method, and the pollution is small.
In the invention, the VOC reduction treatment is carried out on the product after the direct dry devolatilization process, the treatment process is to inject deionized water into the devolatilization machine, the injection amount is 10-50% of the glue solution amount, preferably 30-40%, such as 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39% or 40% and the like; the temperature of the injected water is 0 to 100 ℃, for example, 0 ℃, 20 ℃, 40 ℃, 60 ℃, 80 ℃ or 100 ℃, but is not limited to the recited values, and other values not recited in the above numerical ranges are also applicable.
The second object of the present invention is to provide a star-shaped SEPS elastomer prepared by any of the above-mentioned methods.
Compared with the prior art, the invention has at least the following beneficial effects:
the invention provides a preparation method of a star-shaped SEPS elastomer, wherein the SEPS elastomer prepared by the preparation method has excellent performance, mainly reflects high molecular weight, high viscosity and high shear resistance, the number average molecular weight of the product is 40-90 ten thousand, and the viscosity of toluene (25%) can reach more than 50000mPa & s.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The specific embodiment of the invention provides a preparation method of a star-shaped SEPS elastomer, which comprises the following steps:
(1) isoprene, styrene and a coupling agent are used as raw materials to react to obtain a base glue solution before hydrogenation reaction:
(2) carrying out hydrogenation reaction on the base glue solution before hydrogenation reaction in the step (1) under the action of a catalyst;
(3) carrying out flash evaporation concentration on the glue solution obtained after the hydrogenation reaction in the step (2);
(4) and (4) performing direct dry devolatilization on the flash-evaporated glue solution obtained in the step (3) to obtain the SEPS elastomer.
Example 1
In a 5L stainless steel hydrogenation reactor equipped with a magnetic rotary stirrer, 2500g of cyclohexane was charged, 440 g of isoprene was added after the temperature reached about 45 ℃ and 3.2g of n-butyllithium initiator was added after the temperature reached about 50 ℃, 32g of styrene and 2g of divinylbenzene were added after the isoprene polymerization reached the peak temperature, the temperature was raised to 80 ℃ for 30 minutes for coupling reaction, and then 0.5g of isopropanol was added to terminate the coupling reaction. Adding a nickel naphthenate/triisobutylaluminum hydrogenation catalyst into a polymer glue solution, wherein the nickel naphthenate is 4mgNi/g polymer, Al/Ni is 5, uniformly mixing, introducing hydrogen to perform hydrogenation reaction, reacting at the temperature of 80 ℃, under the pressure of 5MPa for 4 hours, and saturating more than 96% of unsaturated bonds in hydrogenated polyisoprene and saturating less than 2% of aromatic unsaturated bonds in a polystyrene block.
The glue solution is boiled in water and dried, and the molecular weight, the physical property and the hydrogenation degree are respectively analyzed. And (3) testing results: the molecular weight is 85 ten thousand at most by GPC, and the viscosity of the product toluene (25%) reaches more than 50000 mPa.s.
Example 2
In a 5L stainless steel hydrogenation reactor equipped with a magnetic rotary stirrer, 2500g of cyclohexane was charged, 440 g of isoprene was added after the temperature reached about 45 ℃ and 3.2g of n-butyllithium initiator was added after the temperature reached about 50 ℃, 32g of styrene and 2g of divinylbenzene were added after the isoprene polymerization reached the peak temperature, the temperature was raised to 80 ℃ for 30 minutes for coupling reaction, and then 0.5g of isopropanol was added to terminate the coupling reaction. Adding a nickel naphthenate/triisobutylaluminum hydrogenation catalyst into a polymer glue solution, wherein the nickel naphthenate is 4mgNi/g polymer, Al/Ni is 5, uniformly mixing, introducing hydrogen to perform hydrogenation reaction, reacting at the temperature of 80 ℃, under the pressure of 5MPa for 4 hours, and saturating more than 97% of unsaturated bonds in hydrogenated polyisoprene and saturating less than 2% of aromatic unsaturated bonds in a polystyrene block. Adding 7.5 g of anti-aging agent (Irganox 1076 and W95 mixed according to the weight ratio of 2: 1), stirring for 15min, and sending to a double-screw devolatilization machine for solvent removal. The feeding pressure of the devolatilization machine is 0.5MPa, the feeding concentration is 30 percent, the temperature of each cylinder body is controlled at 130-180 ℃, the rotating speed of the devolatilization machine is 100rpm, and the vacuum degree of the devolatilization machine is controlled at-0.01 MPa to-0.05 MPa, so that the compact particles are obtained.
And (3) carrying out performance test on the product: the molecular weight is 81 ten thousand at most, and the viscosity of toluene (25%) of the product reaches more than 50000 mPa.s.
Example 3
In a 5L stainless steel hydrogenation reactor equipped with a magnetic rotary stirrer, 2500g of cyclohexane was charged, 440 g of isoprene was added after the temperature reached about 45 ℃ and 3.2g of n-butyllithium initiator was added after the temperature reached about 50 ℃, 32g of styrene and 1.7g of divinylbenzene were added after the isoprene polymerization reached the peak temperature, the temperature was raised to 80 ℃ for 60 minutes for coupling reaction, and then 0.5g of isopropanol was added to terminate the coupling reaction. Adding a nickel naphthenate/triisobutylaluminum hydrogenation catalyst into a polymer glue solution, wherein the nickel naphthenate is 3.5mgNi/g polymer, Al/Ni is 5, uniformly mixing, introducing hydrogen to carry out hydrogenation reaction, the reaction temperature is 80 ℃, the hydrogen pressure is 5MPa, the reaction time is 3 hours, more than 97 percent of unsaturated bonds in the hydrogenated polyisoprene are saturated, and less than 2 percent of aromatic unsaturated bonds in a polystyrene block are saturated. Adding 7.5 g of anti-aging agent (Irganox 1076 and W95 mixed according to the weight ratio of 2: 1), stirring for 15min, and sending to a double-screw devolatilization machine for solvent removal. The feeding pressure of the devolatilization machine is 1.0MPa, the feeding concentration is 40 percent, the temperature of each cylinder body is controlled at 130-180 ℃, the rotating speed of the devolatilization machine is 150rpm, and the vacuum degree of the devolatilization machine is controlled at-0.01 MPa to-0.05 MPa, so that the compact particles are obtained.
And (3) carrying out performance test on the product: the molecular weight is 70 ten thousand at most, and the viscosity (25%) of toluene reaches above 45000 mPa.s.
Example 4
In a 5L stainless steel hydrogenation reactor with magnetic rotary stirring, 3000g of cyclohexane was charged, 500g of isoprene was added when the temperature reached about 45 ℃ and 4.5g of n-butyllithium initiator was added when the temperature reached about 50 ℃, 40g of styrene and 2.7g of divinylbenzene were added when the isoprene polymerization reached the peak temperature, the temperature was raised to 80 ℃ for 90 minutes for coupling reaction, and then 0.8g of isopropanol was added to terminate. Adding a nickel naphthenate/triisobutylaluminum hydrogenation catalyst into a polymer glue solution, wherein the nickel naphthenate is 3.5mgNi/g polymer, Al/Ni is 5, uniformly mixing, introducing hydrogen to carry out hydrogenation reaction, the reaction temperature is 80 ℃, the hydrogen pressure is 5MPa, the reaction time is 4.5 hours, more than 95% of unsaturated bonds in polyisoprene after hydrogenation are saturated, and less than 2% of aromatic unsaturated bonds in a polystyrene block are saturated. Adding 7.5 g of anti-aging agent (Irganox 1076 and W95 mixed according to the weight ratio of 2: 1), stirring for 15min, and sending to a double-screw devolatilization machine for solvent removal. The feeding pressure of the devolatilization machine is 1.5MPa, the feeding concentration is 50 percent, the temperature of each cylinder body is controlled to be 150-200 ℃, the rotating speed of the devolatilization machine is 200rpm, and the vacuum degree of the devolatilization machine is controlled to be-0.03 MPa to-0.08 MPa, so that the compact particles are obtained.
And (3) carrying out performance test on the product: the molecular weight is 60 ten thousand at most, and the viscosity (25%) of toluene reaches above 40000 mPa.s.
Example 5
In a 5L stainless steel hydrogenation reactor with magnetic rotary stirring, 3000g of cyclohexane was charged, 500g of isoprene was added when the temperature reached about 45 ℃ and 4.5g of n-butyllithium initiator was added when the temperature reached about 50 ℃, 40g of styrene and 4.0g of divinylbenzene were added when the isoprene polymerization reached the peak temperature, the temperature was raised to 80 ℃ for 90 minutes for coupling reaction, and then 0.8g of isopropanol was added to terminate. Adding a nickel naphthenate/triisobutylaluminum hydrogenation catalyst into a polymer glue solution, wherein the nickel naphthenate is 5.5mgNi/g of polymer, the Al/Ni is 5, uniformly mixing, introducing hydrogen to carry out hydrogenation reaction, the reaction temperature is 80 ℃, the hydrogen pressure is 5MPa, the reaction time is 6 hours, more than 95 percent of unsaturated bonds in the hydrogenated polyisoprene are saturated, and less than 2 percent of aromatic unsaturated bonds in a polystyrene block are saturated. Adding 8.5 g of anti-aging agent (Irganox 1076 and W95 mixed according to the weight ratio of 2: 1), stirring for 15min, and sending to a double-screw devolatilization machine for solvent removal. The feeding pressure of the devolatilization machine is 2.5MPa, the feeding concentration is 50 percent, the temperature of each cylinder body is controlled to be 180-240 ℃, the rotating speed of the devolatilization machine is 300rpm, and the vacuum degree of the devolatilization machine is controlled to be-0.05 MPa-0.10 MPa, so that the compact particles are obtained.
And (3) carrying out performance test on the product: the molecular weight is 80 ten thousand at most, and the viscosity (25%) of toluene reaches more than 50000 mPa.s.
Example 6
In a 5L stainless steel hydrogenation reactor with magnetic rotary stirring, 2500g of cyclohexane was charged, 440 g of isoprene was added after the temperature reached about 45 ℃ and 2.2g of n-butyllithium initiator was added after the temperature reached about 50 ℃, 32g of styrene and 3.6g of epoxidized soybean oil were added after the isoprene polymerization reached the peak temperature, the temperature was raised to 80 ℃ for 20 minutes for coupling reaction, and then 0.5g of isopropanol was added to terminate. Adding a nickel naphthenate/triisobutylaluminum hydrogenation catalyst into a polymer glue solution, wherein the nickel naphthenate accounts for 2mgNi/g of polymer, the Al/Ni accounts for 4, uniformly mixing, introducing hydrogen into the mixture to perform hydrogenation reaction, reacting at the temperature of 80 ℃, under the pressure of 5MPa for 3 hours, and saturating more than 97% of unsaturated bonds in hydrogenated polyisoprene and less than 2% of aromatic unsaturated bonds in a polystyrene block. Adding 7.5 g of anti-aging agent (Irganox 1076 and W95 mixed according to the weight ratio of 2: 1), stirring for 15min, and sending to a double-screw devolatilization machine for solvent removal. The feeding pressure of the devolatilization machine is 0.5MPa, the feeding concentration is 30 percent, the temperature of each cylinder body is controlled at 130-180 ℃, the rotating speed of the devolatilization machine is 150rpm, and the vacuum degree of the devolatilization machine is controlled at-0.01 MPa to-0.05 MPa, so that the compact particles are obtained.
And (3) carrying out performance test on the product: the molecular weight is 45 ten thousand at most, and the viscosity (25%) of the product toluene reaches above 40000 mPa.s.
Example 7
In a 5L stainless steel hydrogenation reactor with magnetic rotary stirring, 2500g of cyclohexane was charged, 750 g of isoprene was added when the temperature reached about 45 ℃ and 2.8g of n-butyllithium initiator was added when the temperature reached about 50 ℃, 55g of styrene and 6.3g of epoxidized soybean oil were added when the isoprene polymerization reached the peak temperature, the temperature was raised to 80 ℃ for 30 minutes for coupling reaction, and then 0.5g of isopropanol was added to terminate the coupling reaction. Adding a nickel naphthenate/triisobutylaluminum hydrogenation catalyst into a polymer glue solution, wherein the nickel naphthenate accounts for 3mgNi/g of polymer, the Al/Ni accounts for 4, uniformly mixing, introducing hydrogen into the polymer glue solution to perform hydrogenation reaction, reacting at the temperature of 80 ℃, under the pressure of 4MPa for 4 hours, and saturating more than 97% of unsaturated bonds in hydrogenated polyisoprene and less than 2% of aromatic unsaturated bonds in a polystyrene block. Adding 7.5 g of anti-aging agent (Irganox 1076 and W95 mixed according to the weight ratio of 2: 1), stirring for 15min, and sending to a double-screw devolatilization machine for solvent removal. The feeding pressure of the devolatilization machine is 0.5MPa, the feeding concentration is 30 percent, the temperature of each cylinder body is controlled at 130-180 ℃, the rotating speed of the devolatilization machine is 150rpm, and the vacuum degree of the devolatilization machine is controlled at-0.01 MPa to-0.05 MPa, so that the compact particles are obtained.
And (3) carrying out performance test on the product: the molecular weight is 55 ten thousand at most, and the viscosity (25%) of toluene reaches above 45000 mPa.s.
Example 8
In a 5L stainless steel hydrogenation reactor with magnetic rotary stirring, 2500g of cyclohexane is added, 4.3 g of divinylbenzene solution and 50g of styrene are added when the temperature reaches about 45 ℃, 2.0g of n-butyllithium initiator is added when the temperature rises to about 50 ℃, the reaction is carried out for 20 minutes, then 200g of isoprene is added, and when the polymerization reaction reaches the peak temperature, 0.5g of methanol is added for termination. Adding a nickel naphthenate/triisobutylaluminum hydrogenation catalyst into a polymer glue solution, wherein the nickel naphthenate accounts for 3mgNi/g of polymer, the Al/Ni accounts for 4, uniformly mixing, introducing hydrogen into the polymer glue solution to perform hydrogenation reaction, reacting at the temperature of 80 ℃, under the pressure of 4MPa for 4 hours, and saturating more than 97% of unsaturated bonds in hydrogenated polyisoprene and less than 2% of aromatic unsaturated bonds in a polystyrene block. Adding 7.5 g of anti-aging agent (Irganox 1076 and W95 are mixed according to the weight ratio of 2: 1), stirring for 15min, sending to a double-screw devolatilization machine for solvent removal, and sending to the double-screw devolatilization machine for solvent removal. The feeding pressure of the devolatilization machine is 0.5MPa, the feeding concentration is 30 percent, the temperature of each cylinder body is controlled at 130-180 ℃, the rotating speed of the devolatilization machine is 150rpm, and the vacuum degree of the devolatilization machine is controlled at-0.01 MPa to-0.05 MPa, so that the compact particles are obtained.
And (3) carrying out performance test on the product: the molecular weight is 40 ten thousand at most, and the viscosity (25%) of the product toluene reaches above 40000 mPa.s.
Example 9
In a 5L stainless steel hydrogenation reactor with magnetic rotary stirring, 2000g cyclohexane was added, 4.3 g divinylbenzene solution and 10g styrene were added when the temperature reached about 45 ℃, 2.6g n-butyllithium initiator was added when the temperature reached about 50 ℃, reaction was carried out for 15 minutes, then 200g isoprene was added, and when the polymerization reached the peak temperature, 0.5g methanol was added to terminate. Adding a nickel naphthenate/triisobutylaluminum hydrogenation catalyst into a polymer glue solution, wherein the nickel naphthenate accounts for 3mgNi/g of polymer, the Al/Ni accounts for 4, uniformly mixing, introducing hydrogen into the polymer glue solution to perform hydrogenation reaction, reacting at the temperature of 80 ℃, under the pressure of 4MPa for 4 hours, and saturating more than 97% of unsaturated bonds in hydrogenated polyisoprene and less than 2% of aromatic unsaturated bonds in a polystyrene block. Adding 7.5 g of anti-aging agent (Irganox 1076 and W95 mixed according to the weight ratio of 2: 1), stirring for 15min, and sending to a double-screw devolatilization machine for solvent removal. The feeding pressure of the devolatilization machine is 0.5MPa, the feeding concentration is 30 percent, the temperature of each cylinder body is controlled to be 120-180 ℃, the rotating speed of the devolatilization machine is 150rpm, and the vacuum degree of the devolatilization machine is controlled to be-0.01 MPa-0.05 MPa, so that the compact particles are obtained.
And (3) carrying out performance test on the product: the molecular weight is 55 ten thousand at most, and the viscosity (25%) of the toluene of the product reaches 44000 mPa.s.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (48)
1. A preparation method of a star-shaped SEPS elastomer is characterized by comprising the following steps:
(1) isoprene, styrene and a coupling agent are used as raw materials to react to obtain a base glue solution before hydrogenation reaction:
(2) carrying out hydrogenation reaction on the base glue solution before hydrogenation reaction in the step (1) under the action of a catalyst;
(3) carrying out flash evaporation concentration on the glue solution obtained after the hydrogenation reaction in the step (2);
(4) performing direct dry devolatilization on the flash-evaporated glue solution obtained in the step (3) to obtain an SEPS elastomer;
the catalyst in the step (2) comprises a main catalyst and a cocatalyst, wherein the main catalyst comprises any one or the combination of at least two of nickel naphthenate, nickel acetylacetonate or nickel isooctanoate;
wherein, the method for obtaining the base glue solution before hydrogenation reaction by the reaction in the step (1) comprises the following steps:
(a) adding isoprene into a solvent, uniformly stirring, and then adding an initiator lithium alkyl to initiate a polymerization reaction to obtain polyisoprene;
(b) reacting the polyisoprene obtained in the step (a) with a coupling agent and a styrene mixture to obtain linear or multi-branched polymer mixed glue solution, wherein the coupling agent is divinylbenzene and/or epoxy fatty acid ester;
(c) adding a terminating agent to carry out termination reaction after the reaction in the step (b) is finished, so as to obtain a basic glue solution before hydrogenation reaction;
wherein the molar ratio of the coupling agent in the step (b) to the initiator in the step (a) is (0.5-10) to 1;
or the method for obtaining the base glue solution before hydrogenation reaction by the reaction in the step (1) comprises the following steps:
(A) adding a coupling agent and a styrene mixture into a solvent, uniformly stirring, and then adding an initiator alkyllithium to initiate polymerization reaction to obtain a hyperbranched active center, wherein the coupling agent is divinylbenzene and/or epoxy fatty acid ester;
(B) reacting the hyperbranched active center obtained in the step (A) with isoprene to obtain linear or multi-branched polymer mixed glue solution;
(C) adding a terminating agent after the reaction in the step (B) is finished to carry out termination reaction to obtain a base glue solution before hydrogenation reaction;
wherein the molar ratio of the coupling agent in the step (A) to the initiator in the step (A) is (0.5-10): 1.
2. The method according to claim 1, wherein the solvent in the step (a) is a nonpolar organic solvent.
3. The method of claim 2, wherein the non-polar organic solvent is cyclohexane.
4. The preparation method according to claim 1, wherein the isoprene in the step (a) is used in an amount of 80 to 100% of the sum of the mass of isoprene and styrene, excluding 100%;
the dosage of the styrene in the step (b) is 0-20% of the mass sum of the isoprene and the styrene, and 0% is not included.
5. The method according to claim 1, wherein the initiator in the step (a) is n-butyllithium.
6. The method according to claim 1, wherein the polymerization temperature in the step (a) is 40 to 55 ℃.
7. The method according to claim 1, wherein the polymerization in step (a) is carried out at a pressure of 0.1 to 0.5 MPa.
8. The method according to claim 1, wherein the polymerization time in step (a) is 10 to 30 min.
9. The method according to claim 1, wherein the temperature of the reaction in the step (b) is 70 to 85 ℃.
10. The method according to claim 1, wherein the pressure of the reaction in the step (b) is 0.2 to 0.5 MPa.
11. The method according to claim 1, wherein the reaction time in the step (b) is 20 to 180 min.
12. The method according to claim 1, wherein the solvent in the step (A) is a nonpolar organic solvent.
13. The method of claim 12, wherein the non-polar organic solvent is cyclohexane.
14. The preparation method according to claim 1, wherein the amount of the styrene used in the step (A) is 0 to 20% of the sum of the mass of the isoprene and the mass of the styrene, excluding 0%;
the amount of the isoprene in the step (B) is 80-100% of the mass sum of the isoprene and the styrene, and 100% is excluded.
15. The method according to claim 1, wherein the initiator in the step (A) is n-butyllithium.
16. The method according to claim 1, wherein the polymerization temperature in the step (A) is 40 to 55 ℃.
17. The method according to claim 1, wherein the polymerization pressure in step (A) is 0.1 to 0.5 MPa.
18. The method according to claim 1, wherein the polymerization time in step (A) is 10 to 30 min.
19. The method according to claim 1, wherein the temperature of the reaction in the step (B) is 50 to 90 ℃.
20. The method according to claim 1, wherein the pressure of the reaction in the step (B) is 0.2 to 0.5 MPa.
21. The method according to claim 1, wherein the reaction time in the step (B) is 20 to 60 min.
22. The method according to claim 1, wherein the epoxidized fatty acid ester comprises any one or a combination of at least two of epoxidized soybean oil, epoxidized fatty acid methyl ester, epoxidized fatty acid ethyl ester and epoxidized fatty acid butyl ester.
23. The method according to claim 22, wherein the epoxidized fatty acid ester has an epoxy value of 4.0 to 7.0.
24. The method according to claim 1, wherein the terminating agent in step (C) and the terminating agent in step (C) are each independently an alcohol terminating agent.
25. The method of claim 24, wherein the alcohol terminator comprises any one of methanol, ethanol, isopropanol, tert-butanol, or octadecanol, or a combination of at least two thereof.
26. The method of claim 25, wherein the alcohol terminator is methanol or isopropanol.
27. The method according to claim 1, wherein the amount of the terminating agent added in step (C) and step (C) is 1.0 to 1.2 times the molar amount of the initiator, respectively.
28. The method according to claim 1, wherein the temperature for terminating the reaction in the step (C) and the reaction in the step (C) are each independently 70 to 85 ℃.
29. The method according to claim 1, wherein the time for terminating the reaction in step (C) and step (C) is 10 to 15min, respectively.
30. The preparation method according to claim 1, wherein the amount of the main catalyst is 2-10 mg per gram of the base glue solution before the hydrogenation reaction.
31. The process according to claim 1, wherein the cocatalyst comprises triisobutylaluminum and/or triethylaluminum.
32. The preparation method according to claim 31, wherein the molar ratio of the cocatalyst to the main catalyst is (2-10): 1.
33. The preparation method according to claim 1, wherein the temperature of the hydrogenation reaction in the step (2) is 60 to 100 ℃.
34. The preparation method according to claim 1, wherein the pressure of the hydrogenation reaction in the step (2) is 1.0 to 6.0 MPa.
35. The preparation method according to claim 1, wherein the hydrogenation reaction time in the step (2) is 1-5 h.
36. The preparation method according to claim 1, wherein the pressure of the flash evaporation concentrated glue solution in the step (3) is 0.3-2.0 MPa.
37. The preparation method according to claim 1, wherein the flow rate of the flash evaporation concentrated glue solution in the step (3) is 3.0-6.5 m3/h。
38. The preparation method according to claim 1, wherein the pressure of the flash evaporation in the step (3) is 0.01 to 0.05 MPa.
39. The method according to claim 1, wherein the flash evaporation in step (3) is carried out at a temperature of 130 to 200 ℃.
40. The method of claim 1, wherein said direct dry devolatilization of step (4) is performed using a twin screw extrusion devolatilizer.
41. The method of claim 40, wherein said twin screw extrusion devolatilization machine comprises any one of a co-rotating intermeshing twin screw extruder, a counter-rotating non-intermeshing twin screw extruder, or a co-rotating non-intermeshing twin screw extruder.
42. The preparation method of claim 40, wherein the flash evaporated glue solution enters a devolatilization machine at a pressure of 1.0-3.5 MPa.
43. The preparation method of claim 40, wherein the barrel temperature of each section of the twin-screw extruder is 130-240 ℃.
44. The method of claim 40, wherein the devolatilizer feed concentration is between 30% and 70%.
45. The method of claim 40, wherein the devolatilizer speed is 100 to 500 rpm.
46. The method of claim 40, wherein the devolatilizer vacuum is between-0.01 and-0.10 MPa.
47. The method of claim 40, wherein the post-devolatilization tank pressure is from 0.05 to 0.5 MPa.
48. The method of claim 44, wherein the post-devolatilization tank solvent vapor flow rate is 300-600 m3。
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Citations (4)
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|---|---|---|---|---|
| WO2002048221A1 (en) * | 2000-12-11 | 2002-06-20 | Eastman Chemical Resins, Inc. | Thermally polymerized copolymers made from styrene and dicyclopentadiene monomers |
| CN101817911A (en) * | 2009-02-26 | 2010-09-01 | 中国石油化工股份有限公司 | Star block copolymer prepared from isoprene, butadiene and styrene, and preparation method and application thereof |
| CN103382241A (en) * | 2012-05-04 | 2013-11-06 | 中国石油天然气股份有限公司 | Star-shaped isoprene-b-butadiene-styrene terpolymer and preparation method thereof |
| CN104628901A (en) * | 2013-11-12 | 2015-05-20 | 中国石油化工股份有限公司 | Partially hydrogenated ternary copolymerized rubber with star block structure, preparation method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002048221A1 (en) * | 2000-12-11 | 2002-06-20 | Eastman Chemical Resins, Inc. | Thermally polymerized copolymers made from styrene and dicyclopentadiene monomers |
| CN101817911A (en) * | 2009-02-26 | 2010-09-01 | 中国石油化工股份有限公司 | Star block copolymer prepared from isoprene, butadiene and styrene, and preparation method and application thereof |
| CN103382241A (en) * | 2012-05-04 | 2013-11-06 | 中国石油天然气股份有限公司 | Star-shaped isoprene-b-butadiene-styrene terpolymer and preparation method thereof |
| CN104628901A (en) * | 2013-11-12 | 2015-05-20 | 中国石油化工股份有限公司 | Partially hydrogenated ternary copolymerized rubber with star block structure, preparation method and application thereof |
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