CN113563514A - Hydrogenated polystyrene-conjugated diene random copolymer and preparation method and application thereof - Google Patents
Hydrogenated polystyrene-conjugated diene random copolymer and preparation method and application thereof Download PDFInfo
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- 239000004793 Polystyrene Substances 0.000 title claims abstract description 83
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 83
- 150000001993 dienes Chemical class 0.000 title claims abstract description 75
- 229920005604 random copolymer Polymers 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000011049 filling Methods 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000012545 processing Methods 0.000 claims abstract description 15
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- 230000000712 assembly Effects 0.000 claims abstract description 11
- 238000000429 assembly Methods 0.000 claims abstract description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims description 49
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 31
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- 238000006116 polymerization reaction Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- 229920001577 copolymer Polymers 0.000 claims description 25
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- 239000003292 glue Substances 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 18
- 238000009826 distribution Methods 0.000 claims description 16
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
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- 239000003999 initiator Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
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- 230000003213 activating effect Effects 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
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- 230000003197 catalytic effect Effects 0.000 claims description 2
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- 229920000642 polymer Polymers 0.000 description 63
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 32
- 229920001971 elastomer Polymers 0.000 description 17
- 239000005060 rubber Substances 0.000 description 17
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- 229910052740 iodine Inorganic materials 0.000 description 9
- 239000011630 iodine Substances 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000155 melt Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 6
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 5
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- 150000004678 hydrides Chemical class 0.000 description 5
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- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 5
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- 150000003440 styrenes Chemical class 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
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- 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 description 3
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- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- RTACIUYXLGWTAE-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene;styrene Chemical compound C=CC=C.CC(=C)C=C.C=CC1=CC=CC=C1 RTACIUYXLGWTAE-UHFFFAOYSA-N 0.000 description 2
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- 238000011925 1,2-addition Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 235000007173 Abies balsamea Nutrition 0.000 description 1
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 244000018716 Impatiens biflora Species 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
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- 239000003963 antioxidant agent Substances 0.000 description 1
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- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
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- 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
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 238000009905 homogeneous catalytic hydrogenation reaction Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
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- 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 1
- 230000003287 optical effect Effects 0.000 description 1
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Images
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
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
-
- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers 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
- C08F236/04—Copolymers 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
- C08F236/10—Copolymers 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 with vinyl-aromatic monomers
Abstract
The invention discloses a hydrogenated polystyrene-conjugated diene random copolymer, a preparation method and application thereof. The hydrogenated polystyrene-conjugated diene random copolymer is obtained by hydrogenating a polystyrene-conjugated diene random copolymer, shows thermoplastic behavior, has the characteristics of high stiffness, low cold flow, good static stability, low-temperature cohesion, easy peeling, low melting point, good melt fluidity, large operation elasticity, no crosslinking and the like at the temperature of below 150 ℃, and is particularly suitable for being used as a protective material for filling and positioning in the cutting processing of metal appliances or matched assemblies.
Description
Technical Field
The invention relates to a hydrogenated polystyrene-conjugated diene random copolymer, a preparation method and application thereof, in particular to a hydrogenated polystyrene-conjugated diene random copolymer with thermoplastic behavior, a method for preparing the hydrogenated polystyrene-conjugated diene random copolymer by anionic polymerization and application thereof as a filling positioning protection material in cutting processing of metal appliances or matching assemblies, belonging to the technical field of special high-molecular materials for filling protection.
Background
The metal, especially titanium alloy, of high-end precision apparatus or mating parts needs to be fixed during the machining, cutting and forming process of machine tool, otherwise the rotating parts are easy to deform during cutting and forming, which results in the precision reduction of the apparatus mating parts, excessive error or poor effect during use, such as the manufacture of the air exhaust parts for stabilizing the aircraft.
The filler used in the manufacture of the appliance or the fitting piece has the characteristics of low modulus, easy cutting, low melting point, high stiffness, no cold flow, low high-temperature sagging flow, no crosslinking at the melting temperature, good thermal stability, easy stripping and removal (like the stripping of a balsam peel) after the product is formed and the like. The existing polymers such as styrene butadiene rubber for shoe materials and tires, SBS, SEBS, SEPS or polyolefin and the like do not have the characteristics. The original appliance or the filler of the matching part is mainly solid paraffin, namely the paraffin is melted and then poured into the combination part, and the combination part is cut after cooling and solidification. The melting point of the paraffin is not higher than 80 ℃, and the paraffin removed in the processing or cleaning of the assembly belongs to Newtonian fluid and is easy to flow vertically to other parts to influence other links or processing procedures, so the method is not adopted at present.
The existing fillers are polystyrene thermoplastic polymers, such as K25S, the melting point of which is not higher than 150 ℃, the polymers are formed by mixing two polymers, and the polymer molecules contain a small amount of butadiene 1, 2-addition units and polystyrene block units, however, no relevant documents describe the preparation method and the polymer behavior. However, Chinese patent (CN107793542A) describes a method for synthesizing hydrogenated styrene/isoprene block copolymer by using nonpolar alkane and toluene as polymerization solventIn the anionic polymerization system of the agent, a diblock copolymer or a multiblock copolymer containing a styrene block and an isoprene block is synthesized, then the copolymer is hydrogenated to obtain a hydrogenated styrene/isoprene block copolymer, and the diblock or multiblock hydrogenated styrene/isoprene block copolymer is applied to optical fibers and optical cable filling factice. In Chinese patent (CN102731739A), a star polymer used as a viscosity index improver of lubricating oil and a preparation method and application thereof are disclosed, and particularly, the star polymer is provided with asymmetric arms and consists of two different types of polymer arms, wherein the first type of arm is hydrogenated polyisoprene homopolymer, the second type of arm is a copolymer with a hydrogenated polyisoprene-hydrogenated polybutadiene-polystyrene block structure, a polystyrene block is close to the core of the star polymer in the copolymer arm, a hydrogenated polybutadiene block is in the middle of the arm, and a hydrogenated isoprene block is outside the arm, the polymer shows excellent tackifying effect and shear stability of oil products, and has lower pumping viscosity and low-temperature start viscosity in formulated engine oil. The star polymer has too high molecular weight and low melt index, and is not suitable for being used as a material for filling and protecting metal appliances or fittings. In addition, Chinese patent (CN104945559A) describes a hydrogenated polystyrene-b-styrene/butadiene/isoprene random copolymer and a preparation method and application thereof. The hydrogenated polystyrene-b-styrene/butadiene/isoprene random copolymer consists of Sn-b-BSmIR、(Sn-b-BSmI)2Si(CH3)2、(Sn-b-BSmI)3SiCH3And (S)n-b-BSmI)4The mixed polymer of Si composition is obtained by hydrogenation. The prepared hydrogenated polystyrene-b-styrene/butadiene/isoprene random copolymerization has good comprehensive mechanical property and aging resistance, and has double bonds for vulcanization; the polymer is suitable for outdoor sealing materials, but is not suitable for filling and protecting metal appliances or fittings. In the text (chemical industry and engineering, preparation and characterization of star-type hydrogenated random copolymer HSSIBR at 2012: 04), Divinylbenzene (DVB) as coupling agent and cyclohexane as solvent are introducedPreparing star-shaped styrene-isoprene-butadiene ternary random copolymer (SSIBR) by anionic polymerization; nickel naphthenate and triisobutyl aluminum are used as catalysts to react for 4 hours at 60 ℃ and 4.0MPa hydrogen pressure, and hydrogenated star-shaped styrene-isoprene-butadiene ternary random copolymer (HSSIBR) with the hydrogenation degree of 100% is prepared. The additive is used as a viscosity index improver of lubricating oil, the shear stability of the additive is improved, and the low-temperature performance of the additive is obviously improved. Similarly, in the text (science and engineering of polymer materials, molecular structure of viscosity index improver HSD at stage 11 of 2012), a hydrogenated styrene/conjugated diene (butadiene, isoprene) copolymer (HSD) is introduced as a viscosity index improver, where HSD is a highly hydrogenated styrene-butadiene block copolymer with high butadiene content, styrene has a mass fraction of 18.5%, butadiene has a mass fraction of 81.5%, butadiene has a degree of hydrogenation of 98.0%, the one-arm number-average molecular weight is 6.47 × 104g/mol, the number of coupling arms is 7.10, and the coupling efficiency is 86.44%. The polymer is also used as a thickener for lubricating oil, but the polymer has the defects of large molecular weight, high modulus, high strength, high melting point and the like, so that the polymer is not suitable for being used as a filling protective material for metal appliances or processing matching parts. However, hydrogenated polymers such as SEPS-4010, SEPS-4030 and SEBS-501 available on the market have too high molecular weight, a melting point of 200 ℃ or higher, poor melt fluidity and low handling elasticity, and are not suitable for filling and protecting materials in metal appliances or processing matching parts.
In view of the above, the conventional literature and commercially available polymers such as styrene-conjugated dienes, hydrides and polyolefins mainly exhibit the defects of high strength, high viscosity, difficult peeling, high melting point, difficult flowing, poor thermal stability, easy crosslinking, and loss of fluidity, and thus cannot satisfy the filling protection of the processing and molding of metal appliances or mating members.
Disclosure of Invention
Aiming at the defects of low stiffness, large cold flow property, poor static stability, high melting point, poor melt fluidity, low operation elasticity, easy crosslinking at high temperature, large cohesion of the polymer, high modulus, difficult peeling and the like of a high molecular material used as the filler of the appliances or the matching pieces in the prior art, the high molecular material is not suitable for being used as a filling protection material in the processing of metal appliances or matching pieces. The first object of the present invention is to provide a hydrogenated polystyrene-conjugated diene random copolymer which exhibits thermoplastic behavior, has high stiffness at room temperature, low cold flow, good static stability, low cohesion at low temperature, and is easily peelable, and exhibits low melting point at 150 ℃ or lower, good melt fluidity, high handling elasticity, and no crosslinking, and which is mainly used as a protective material for filling and positioning in the cutting process of metal appliances or mating assemblies, such as a filler for cutting protection in the processing of aircraft engines, missile empennage exhaust assemblies, and the like, and in which a hydrogenated thermoplastic polymer filled in the cutting process of metal appliances or mating assemblies is cut along with the cutting of the metal or alloy assemblies, and after the assembly is molded, the filled thermoplastic polymer is easily peeled off like a vellum, easy to clear; in addition, the filled thermoplastic polymer also has the characteristics of easy melting and convenient casting and forming.
Another object of the present invention is to provide a process for producing a hydrogenated polystyrene-conjugated diene random copolymer with simple operation at low cost.
The third purpose of the invention is to provide the application of the hydrogenated polystyrene-conjugated diene random copolymer as a filling and positioning protection material in the cutting processing of metal appliances or matching assemblies, the copolymer is used for filling in the cutting protection in the processing process of aircraft engines, missile empennage exhaust assemblies and the like, is easy to strip out and remove, and has the characteristics of easy melting and convenient casting and forming.
In order to achieve the above technical object, the present invention provides a hydrogenated polystyrene-conjugated diene random copolymer obtained by hydrogenating a polystyrene-conjugated diene random copolymer;
the polystyrene-conjugated diene random copolymer has the following expression: S-B/D;
wherein the content of the first and second substances,
S-B is a random copolymerization block of styrene and conjugated diene;
d is a divinylbenzene branched node randomly distributed in S-B.
The hydrogenated polystyrene-conjugated diene random copolymer of the present invention may also be referred to as a thermoplastic polymer for filling. The hydrogenated polystyrene-conjugated diene random copolymer is obtained by hydrogenating a polystyrene-conjugated diene random copolymer, the polystyrene-conjugated diene random copolymer is a polystyrene-conjugated diene random copolymer with wider molecular mass distribution due to the introduction of a small amount of branching unit divinylbenzene, and the polystyrene-conjugated diene random copolymer is subjected to branching chain extension, and the obtained hydrogenated polymer is used as a virgin rubber before hydrogenation, so that the obtained hydrogenated polymer can better show that the polymer has lower cohesive force and modulus so as to be convenient for removal after the filling of metal appliances or matching assemblies is finished.
The molecular structural formula of the hydrogenated polystyrene-conjugated diene random copolymer or the thermoplastic polymer for filling of the present invention can be simply expressed by, for example:
SEB/D or SEP/D or SEBP/D
These 3 expressions are mainly due to the fact that the hydrogenated polystyrene-conjugated diene random copolymer produced by using different conjugated dienes has a certain difference in structure, and different structural units are formed by hydrogenation. Wherein S is a styrene unit; e is an ethylene unit; b is an isobutyl unit; p is an isopropyl unit; d is a divinylbenzene branching node.
In a preferred embodiment, the degree of hydrogenation of the conjugated diene unit in the polystyrene-conjugated diene random copolymer is > 95%, and more preferably > 98%. If the degree of hydrogenation is low, the iodine value is too high, which results in that the hydrogenated polystyrene-conjugated diene random copolymer gels when melted by heating due to crosslinking of the double bonds, thereby losing fluidity and being unfavorable for the cast molding of the assembly.
As a preferred embodiment, the conjugated diene includes at least one of butadiene, isoprene, and piperylene.
In a preferred embodiment, the polystyrene-conjugated diene random copolymer has a block mass ratio S/B of (20 to 30)/(80 to 70). An appropriate amount of styrene is important for maintaining high stiffness and stability of the hydrogenated polystyrene-conjugated diene random copolymer at room temperature.
In a preferred embodiment, the polystyrene-conjugated diene random copolymer has a number average molecular weight Mn of 10000 to 70000 and a molecular mass distribution index of greater than 1.75. The polystyrene-conjugated diene random copolymer preferably has a number average molecular weight Mn of 23000 to 28000. The preferred molecular weight distribution ensures that the hydrogenated filled thermoplastic polymer has a lower melting temperature and higher melt flow; and the wider molecular weight distribution can ensure that the polymer has higher stiffness and stability at room temperature, namely, the polymer after casting does not flow cold.
In a preferred embodiment, the polystyrene-conjugated diene random copolymer contains 0.08 to 0.16% by mass of a divinylbenzene unit based on the mass of the conjugated diene, and the divinylbenzene unit has a branching degree of 3 to 6. The molecular chain of the hydrogenated polystyrene-conjugated diene random copolymer is of a long-chain branched structure, and the long-chain branched polymer has the characteristics of wide molecular mass distribution, high entanglement degree among molecular chains and cold flow resistance.
The hydrogenated polystyrene-conjugated diene random copolymer has a melting temperature of not higher than 150 ℃ and a melt index of 1500-2000 g/10 min. Generally, the polymer is melted at a high temperature of 200-350 ℃ to cause decomposition or carbonization of the polymer.
The invention also provides a preparation method of the hydrogenated polystyrene-conjugated diene random copolymer, which comprises the steps of adding a solvent and an activating agent into a polymerization reaction kettle, heating to the initial polymerization temperature, simultaneously dropwise adding an initiator and a mixed monomer consisting of divinyl benzene, styrene and conjugated diene into the polymerization reaction kettle, carrying out polymerization reaction to obtain a polystyrene-conjugated diene copolymer glue solution, transferring the polystyrene-conjugated diene copolymer glue solution into a hydrogenation reaction kettle, carrying out hydrogenation reaction, condensing water vapor, and drying to obtain the hydrogenated polystyrene-conjugated diene random copolymer glue solution.
As a preferable scheme, the dropping time of the initiator and the mixed monomer is not less than 60 min.
In a preferred embodiment, the initial polymerization temperature is 50 to 60 ℃.
As a preferable scheme, the temperature is controlled not to exceed 85 ℃ in the polymerization reaction process, and after the initiator and the mixed monomer are added, the polymerization reaction is carried out for 20-25 min.
As a preferable scheme, the hydrogenation reaction adopts a titanium-based or nickel-based catalytic system to carry out selective catalytic hydrogenation.
As a preferable scheme, in the hydrogenation reaction process, the temperature is controlled to be 65-85 ℃, the time is 2.5-3.0 h, and the hydrogen pressure is 1.2-1.6 MPa.
The method for producing a hydrogenated polystyrene-conjugated diene random copolymer of the present invention is mainly produced in the following two-step process.
The first step is as follows: preparation of polystyrene-conjugated diene random copolymer:
the preparation process of the polymer is completed by adopting a method known in the industry, namely cyclohexane is used as a polymerization solvent, n-butyl lithium is used as an initiator, tetrahydrofuran is used as an activating agent, the agents are commonly used in the industry, and alternative agents are also conventional, and the specific operation method is as follows: adding a certain amount of cyclohexane and a small amount of THF (activating agent) into a sealed steel container with a stirrer, heating the polymerization solution to 50-60 ℃ by using a hot water bath, then respectively and simultaneously dropwise adding a set amount of n-butyllithium and a pre-mixed uniformly mixed monomer containing 0.05-0.12% of divinylbenzene, namely styrene and conjugated diene into a polymerization kettle, wherein the dropwise adding time of the n-butyllithium and the mixed monomer is not less than 60min, the polymerization temperature is not higher than 85 ℃, and after the dropwise adding of the materials is finished, carrying out polymerization reaction for 20-25 min to obtain the polystyrene-conjugated diene copolymerized glue solution.
The second step is that: hydrogenation of polystyrene-conjugated diene random copolymer:
pressing the prepared polystyrene-conjugated diene copolymer glue solution into a hydrogenation kettle, adding a catalyst for hydrogenation, introducing hydrogen, performing hydrogenation reaction, stopping hydrogenation when the hydrogenation degree of the polymer is higher than 95%, adding an antioxidant 1076 with the mass part of 0.3-0.4% of the total dry glue into the glue solution, uniformly mixing, and finally condensing, drying and briquetting the polymer glue solution containing the antioxidant by using water vapor to obtain the hydrogenated polystyrene-conjugated diene random copolymer.
In the preparation process of the hydrogenated polystyrene-conjugated diene copolymer, n-butyllithium is preferably selected as an initiator, and the mixed monomers are respectively added dropwise in a manner and under the condition that the continuous dropwise adding time is not less than 60min, which is well known by technical personnel in the industry, so that the basis and guarantee for preparing the polymer with wide molecular mass distribution are provided.
The hydrogenation process of the polystyrene-conjugated diene copolymer is realized according to SEBS or SEPS hydrogenation process well known in the industry. The hydrogenation catalyst can be preferably selected from dicyclopentadiene titanium dichloride (titanium series) or a coordination complex (nickel series) formed by mixing triisobutylaluminum and nickel naphthenate for selective catalytic hydrogenation. The preferable hydrogenation temperature is 65-85 ℃, the hydrogenation time is 2.5-3.0 h, and the hydrogenation hydrogen pressure is 1.2-1.6 MPa, so that the hydrogenation degree of the conjugated diene unit of the polystyrene-conjugated diene copolymer can be ensured to be not less than 95%. Generally speaking, the amount of dicyclopentadiene titanium dichloride used for titanium hydrogenation is 0.025-0.035 g/100g polymer; the amount of the nickel-aluminum complex used for hydrogenation of nickel is 0.4 to 0.6m.mol/100g polymer in terms of Ni.
The invention also provides an application of the hydrogenated polystyrene-conjugated diene random copolymer as a filling positioning protection material in the cutting processing of metal appliances or matching assemblies.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
the existing high polymer materials such as SEPS, SEBS, polyolefin and the like have the defects of high molecular weight, large melting point, poor melt fluidity, low operation elasticity, difficult peeling, poor thermal stability, easy crosslinking, loss of fluidity and the like, and are difficult to meet the application requirements of processing, molding, filling and protecting materials of metal appliances or matching pieces. The hydrogenated polystyrene-conjugated diene copolymer provided by the technical scheme of the invention has proper molecular mass and wider molecular mass distribution index, and is beneficial to lower melting temperature when being heated; and the branched chain links contained in the hydrogenated polystyrene-conjugated diene copolymer endow the molecular chains of the hydrogenated polystyrene-conjugated diene copolymer with higher entanglement or high entanglement, and the polymer (or melt) has difficulty in relative movement of the molecules under the dragging of the branched chains of long-chain molecules, does not flow at room temperature and keeps higher stiffness. On the other hand, the hydrogenated polystyrene-conjugated diene copolymer provided by the invention has high entanglement degree, and molecules can be oriented and unwound under the actions of melting, stirring and shearing, so that the copolymer has good thixotropy, thinned melt viscosity, good melt fluidity and easy casting; the adoption of a homogeneous catalytic hydrogenation method gives a lower iodine value to the hydrogenated polystyrene-conjugated diene copolymer, which is beneficial to the fact that the hydrogenated polystyrene-conjugated diene copolymer is not decomposed or crosslinked at a high melting temperature; the cast hydrogenated polystyrene-conjugated diene copolymer has the characteristics of low modulus, easy stripping and removal and the like. Namely, the hydrogenated polystyrene-conjugated diene copolymer prepared by the present invention is very suitable for use as a material for filling and protecting a metal appliance or a fitting piece by processing molding.
The hydrogenated polystyrene-conjugated diene copolymer can be prepared by using traditional equipment and processes, has simple preparation method and low cost, and can be used as a technical index and characteristic behavior of a thermoplastic filled polymer which are comparable with those of the prior commercially available K25S polymer.
Drawings
FIG. 1 is a schematic diagram of a hydrogenated polystyrene-conjugated diene copolymer of the present invention and a schematic diagram of a metal-filled protective device.
Detailed Description
The present invention is illustrated by the following examples, which are not intended to limit the scope or practice of the invention.
The number average molecular weight and molecular weight distribution index of the polymer were measured by Gel Permeation Chromatography (GPC) in the following examples; determining the microstructure content of the polymer by H-NMR spectroscopy by using Aacend (TM) 400; the melt index of the finished green polymer was determined using a Zwick Roell Mflow tester at 150 ℃.
Example 1
Adding 3500mL of cyclohexane solution of 10 mass percent n-hexane into a 5-liter polymerization kettle under the protection of nitrogen, then adding 0.5mL of tetrahydrofuran, heating to 55-60 ℃ by using steam, adding 108mL of n-butyllithium solution of 0.2mol/L into a test mirror of the polymerization kettle and a mixed monomer mixed with 100g of styrene, 400g of butadiene and 0.35mL of divinylbenzene in a monomer metering tank into the polymerization kettle continuously within 60min, and continuing to polymerize for 25min at the temperature of not higher than 85 ℃ after the addition of the butyl lithium and the monomer is finished to obtain the raw polymer. As a result, it was found that the polymer crude rubber had Mn of 23500, a molecular mass distribution index of 1.82 and a vinyl unit content of 16.8% in the number average molecular weight.
And then, pressing the polymer-containing virgin rubber into a hydrogenation kettle, adding 0.13g of dicyclopentadiene titanium dichloride with the mass part of 99%, controlling the hydrogen pressure to be 1.3-1.5 MPa, stirring and reacting at 70-80 ℃ for 120min, measuring the iodine value of the polymer to be 3.6g/100g of the polymer, stopping the hydrogenation reaction at the moment, and coagulating, extruding, granulating and drying the rubber solution to obtain the raw rubber. The melt index of the hydride is determined to be 1830g/10 min; after the briquetting glue is kept still for 24 hours at 65 ℃, no glue block has a vertical flow phenomenon.
Example 2
The relevant process conditions for the polymerization part in example 1 were kept unchanged except that the amount of butadiene charged was 300g, the amount of divinylbenzene was 0.32mL, 0.2mol/L of n-butyllithium was 85mL, and the continuous dropping time of butyllithium and the mixed monomers was 70 min. As a result, it was found that the polymer crude rubber had a number average molecular weight of Mn 25500, a molecular mass distribution index of D2.18, and a vinyl unit content of 15.7%.
And then, pressing the polymer-containing virgin rubber into a hydrogenation kettle, adding 0.15g of dicyclopentadiene titanium dichloride with the mass part of 99%, controlling the hydrogen pressure to be 1.3-1.5 MPa, stirring and reacting at 70-80 ℃ for 130min, measuring the iodine value of the polymer to be 3.3g/100g of the polymer, stopping the hydrogenation reaction at the moment, and coagulating, extruding, granulating and drying the rubber solution to obtain the raw rubber. Measuring the melt index of the hydride to be 1640g/10 min; after the briquetting glue is kept still for 24 hours at 65 ℃, no glue block has a vertical flow phenomenon.
Example 3
The relevant process conditions for the polymerization section in example 1 were kept unchanged except that 130g of styrene, 310g of butadiene, 0.50mL of divinylbenzene, 80mL of 0.2mol/L n-butyllithium and 65min of continuous dropwise addition of butyllithium and the mixed monomers were added. As a result, the number average molecular weight of the polymer crude rubber was determined to be Mn 27300, molecular mass distribution index D2.04, and vinyl unit content 16.3%.
And then, pressing the polymer-containing virgin rubber into a hydrogenation kettle, adding 0.14g of dicyclopentadiene titanium dichloride with the mass part of 99%, controlling the hydrogen pressure to be 1.3-1.5 MPa, stirring and reacting at 70-80 ℃ for 150min, measuring the iodine value of the polymer to be 2.2g/100g of the polymer, stopping the hydrogenation reaction at the moment, and coagulating, extruding, granulating and drying the rubber solution to obtain the raw rubber. The melt index of the hydride is measured to be 1530g/10min, and no gel block has a sagging phenomenon after the briquetting gel is stood for 24 hours at 65 ℃.
Example 4
Adding 3500mL of cyclohexane solution of 10 mass percent n-hexane into a 5L polymerization kettle under the protection of nitrogen, then adding 0.5mL of tetrahydrofuran, heating to 55-60 ℃ by using water vapor, adding 95mL of n-butyllithium solution of 0.2mol/L into a test mirror of the polymerization kettle and a mixed monomer mixed with 100g of styrene, 400g of isoprene and 0.40mL of divinylbenzene in a monomer metering tank into the polymerization kettle continuously within 65min, and continuing to polymerize for 25min at the temperature of not higher than 85 ℃ after the butyl lithium and the monomer are completely added to obtain the raw polymer. As a result, it was found that the polymer crude rubber had Mn of 26400 for the number average molecular weight, a molecular mass distribution index of 2.08 and an isopropenyl unit content of 17.2%.
And then, pressing the raw rubber containing the polymer into a hydrogenation kettle, adding 12.5mL (wherein nNi/nAl is 3.5/1, the Ni content is 0.20mol/L, and the solvent is cyclohexane) of coordination complex formation liquid consisting of triisobutyl aluminum and nickel naphthenate, controlling the hydrogen pressure to be 1.3-1.5 MPa, stirring and reacting at 70-85 ℃ for 120min, measuring the iodine value of the polymer to be 3.2g/100g, and the hydrogenation degree to be 95.7%, stopping the hydrogenation reaction, and coagulating, extruding, granulating and drying the rubber liquid to obtain the raw rubber. Measuring the melting index of the hydride to be 1590g/10 min; the briquetting glue does not have the phenomenon of vertical flow after standing for 24 hours at 65 ℃.
Example 5
The relevant process conditions in example 4 were kept unchanged except that 85mL of butyllithium, 350g of isoprene and 60min of butyllithium and mixed monomer were added; the catalyst Ni/Al complex formation liquid for the hydrogenation unit is 14.0mL, and the hydrogenation time is 150 min.
As a result, a bulk polymer having a number average molecular weight Mn of 26600, a molecular mass distribution index of 1.86, an iodine value of 1.2g/100g polymer, a degree of hydrogenation of 98.3% and a melt index of 1580g/10min was obtained; the briquetting glue does not have the phenomenon of vertical flow after standing for 24 hours at 65 ℃.
Example 6
The relevant process conditions in example 4 were kept unchanged except that 80mL of butyllithium and 300g of divinylbenzene, 0.45mL of isoprene, were added; 13.0mL of Ni/Al complex formation solution serving as a catalyst for the hydrogenation unit, and the hydrogenation time is 180 min.
As a result, a bulk polymer having a number average molecular weight Mn of 25200, a molecular mass distribution index of 2.06, an iodine value of 1.3g/100g of the polymer, a degree of hydrogenation of 98.4% and a melt index of 1670g/10min was obtained; the briquetting glue does not have the phenomenon of vertical flow after standing for 24 hours at 65 ℃.
Example 7
The relevant process conditions in example 4 were kept unchanged except that 105mL of butyllithium, 0.53mL of divinylbenzene, 200g of isoprene and 180g of butadiene were added; 16.0mL of Ni/Al complex formation solution serving as a catalyst for the hydrogenation unit, and the hydrogenation time is 120 min.
The resulting bulk polymer had a number average molecular weight Mn of 24200, a molecular mass distribution index of 2.03, an iodine value of 3.7g/100g polymer, a degree of hydrogenation of 95.7% and a melt index of 1720g/10 min; the briquetting glue does not have the phenomenon of vertical flow after standing for 24 hours at 65 ℃.
Example 8
The results of weighing 150g of each of the hydrogenated polymers prepared in examples 1 to 7 and commercially available SBS-788 and SEBS-501 in 9 500mL beakers, placing the beakers in an oil bath, and heating the beakers are shown in Table 1.
TABLE 1
Claims (14)
1. A hydrogenated polystyrene-conjugated diene random copolymer characterized in that: obtained by hydrogenating a polystyrene-conjugated diene random copolymer;
the polystyrene-conjugated diene random copolymer has the following expression: S-B/D;
wherein the content of the first and second substances,
S-B is a random copolymerization block of styrene and conjugated diene;
d is a divinylbenzene branched node randomly distributed in S-B.
2. A hydrogenated polystyrene-conjugated diene random copolymer according to claim 1, wherein: the degree of hydrogenation of the conjugated diene unit in the polystyrene-conjugated diene random copolymer is > 95%.
3. A hydrogenated polystyrene-conjugated diene random copolymer according to claim 1, wherein: the conjugated diene comprises at least one of butadiene, isoprene and piperylene.
4. A hydrogenated polystyrene-conjugated diene random copolymer according to claim 1, wherein: the polystyrene-conjugated diene random copolymer has a block mass ratio S/B of (20-30)/(80-70).
5. A hydrogenated polystyrene-conjugated diene random copolymer according to claim 1, wherein: the polystyrene-conjugated diene random copolymer has the number average molecular weight Mn of 10000-70000 and the molecular mass distribution index of more than 1.75.
6. A hydrogenated polystyrene-conjugated diene random copolymer according to claim 5, wherein: the polystyrene-conjugated diene random copolymer has a number average molecular weight Mn of 23000-28000.
7. A hydrogenated polystyrene-conjugated diene random copolymer according to claim 1, wherein: the polystyrene-conjugated diene random copolymer comprises 0.08-0.16% by mass of a divinylbenzene unit based on the mass of a conjugated diene, and the divinylbenzene unit has a branching degree of 3-6.
8. The process for producing a hydrogenated polystyrene-conjugated diene random copolymer according to any one of claims 1 to 7, wherein: adding a solvent and an activating agent into a polymerization reaction kettle, heating to the initial polymerization temperature, simultaneously dropwise adding an initiator and a mixed monomer consisting of divinyl benzene, styrene and conjugated diene into the polymerization reaction kettle, carrying out polymerization reaction to obtain a polystyrene-conjugated diene copolymer glue solution, transferring the polystyrene-conjugated diene copolymer glue solution into a hydrogenation reaction kettle, carrying out hydrogenation reaction, condensing water vapor, and drying to obtain the polystyrene-conjugated diene copolymer glue solution.
9. The process for producing a hydrogenated polystyrene-conjugated diene random copolymer according to claim 8, wherein: the dropping time of the initiator and the mixed monomer is not less than 60 min.
10. The process for producing a hydrogenated polystyrene-conjugated diene random copolymer according to claim 8, wherein: the initial polymerization temperature is 50-60 ℃.
11. The process for producing a hydrogenated polystyrene-conjugated diene random copolymer according to claim 8, wherein: and controlling the temperature not to exceed 85 ℃ in the polymerization reaction process, and carrying out polymerization reaction for 20-25 min after the initiator and the mixed monomer are added.
12. The process for producing a hydrogenated polystyrene-conjugated diene random copolymer according to claim 8, wherein: the hydrogenation reaction adopts a titanium system or nickel system catalytic system to carry out selective catalytic hydrogenation.
13. The process for producing a hydrogenated polystyrene-conjugated diene random copolymer according to claim 8, wherein: in the hydrogenation reaction process, the temperature is controlled to be 65-85 ℃, the time is 2.5-3.0 h, and the hydrogen pressure is 1.2-1.6 MPa.
14. Use of a hydrogenated polystyrene-conjugated diene random copolymer according to any one of claims 1 to 7, wherein: the material is used as a filling positioning protection material in the cutting processing of metal tools or matching assemblies.
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| CN1276390A (en) * | 1999-06-07 | 2000-12-13 | 北京燕山石油化工公司研究院 | Process for preparing randomly solution polymerized butadiene-styrene rubber with low 1,2-structure and wide molecular weight distribution |
| CN1489607A (en) * | 2001-01-25 | 2004-04-14 | ������������ʽ���� | Improved hydrogenated styrene/conjugated diene/styrene block copolymer and process for producing thereof |
| CN105175659A (en) * | 2015-07-23 | 2015-12-23 | 湖南博瑞康新材料有限公司 | Transparent hydrogenated polystyrene-b-random copolymerized conjugated diene/styrene resin and preparation method therefor |
| CN111718454A (en) * | 2019-03-20 | 2020-09-29 | 中国石油化工股份有限公司 | Partially hydrogenated styrene-b-conjugated diene/divinylbenzene random copolymer and preparation and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1276390A (en) * | 1999-06-07 | 2000-12-13 | 北京燕山石油化工公司研究院 | Process for preparing randomly solution polymerized butadiene-styrene rubber with low 1,2-structure and wide molecular weight distribution |
| CN1489607A (en) * | 2001-01-25 | 2004-04-14 | ������������ʽ���� | Improved hydrogenated styrene/conjugated diene/styrene block copolymer and process for producing thereof |
| CN105175659A (en) * | 2015-07-23 | 2015-12-23 | 湖南博瑞康新材料有限公司 | Transparent hydrogenated polystyrene-b-random copolymerized conjugated diene/styrene resin and preparation method therefor |
| CN111718454A (en) * | 2019-03-20 | 2020-09-29 | 中国石油化工股份有限公司 | Partially hydrogenated styrene-b-conjugated diene/divinylbenzene random copolymer and preparation and application thereof |
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