CN114846031A - Branched polydienes, rubber compositions based thereon - Google Patents

Branched polydienes, rubber compositions based thereon Download PDF

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CN114846031A
CN114846031A CN201980103047.1A CN201980103047A CN114846031A CN 114846031 A CN114846031 A CN 114846031A CN 201980103047 A CN201980103047 A CN 201980103047A CN 114846031 A CN114846031 A CN 114846031A
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neodymium
hydride
polymer
butadiene
compound
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塔蒂亚娜·亚历山德罗娃·亚特谢瓦
斯韦特兰娜·阿莱斯纳·拉格诺娃
莉莉亚·安德烈夫娜·博伊科
奥莉加·伊娃诺娃·阿特梅瓦
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Sibur Holding PJSC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F136/06—Butadiene
    • 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
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and 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
    • C08F36/04—Homopolymers and 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
    • C08F36/06—Butadiene
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/54—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof
    • C08F4/545—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof rare earths being present, e.g. triethylaluminium + neodymium octanoate
    • 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
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/24—Haloalkylation
    • 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
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • 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
    • C08F8/40—Introducing phosphorus atoms or phosphorus-containing groups
    • 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
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • 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
    • C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C08L15/02—Rubber derivatives containing halogen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract

The present invention relates to the production of synthetic polymers used in the manufacture of tires and rubber technology products in the electrical industry and other fields. In particular, the present invention relates to a process for the production of a branched polydiene by polymerization of a conjugated diene, the process comprising the steps of: preparing a catalyst composite comprised of a lanthanide compound, an organoaluminum compound, a conjugated diene, and a halogen-containing component; polymerizing a conjugated diene in the presence of the catalyst composite; post-polymerization modification with at least one branching agent selected from halogen-containing compounds, phosphorus-nitrogen compounds, or mixtures thereof; terminating, a plasticizer is introduced into the polymer, wherein the plasticizer is a low molecular weight polymer having a molecular weight of 1500g/mol to 50,000g/mol, and the polymer is degassed and dried. In yet another aspect, the present invention relates to a process for producing a rubber composition based on the above branched polydienes. The technical result of the present invention is the production of a branched polydiene characterized by a mooney viscosity of about 40 Mooney Units (MU) to about 49 mooney units, and a branching coefficient as characterized by a mechanical loss tangent tg δ (1200%) of about 4.7 to about 5.3. The polydienes produced according to the present invention have improved processability, improved distribution of filler in the polymer matrix, and rubber compositions based on said polydienes are characterized by improved elastic-hysteresis properties (i.e., mooney viscosity ML (1+4), MU, payne effect Δ (G '1% -G' 50%), kPa, Tan δ at 60 ℃ 10% deformation.

Description

Branched polydienes, rubber compositions based thereon
Technical Field
The present invention relates to the production of synthetic polymers used in the manufacture of tires and rubber technology products in the electrical industry and other fields.
In particular, the present invention relates to a process for the production of a branched polydiene by polymerization of a conjugated diene, the process comprising the steps of: preparing a catalyst composite comprising a lanthanide compound, an organoaluminum compound, a conjugated diene, and a halogen-containing component; polymerizing a conjugated diene in the presence of the catalyst composite; post-polymerization modification using at least one branching agent selected from halogen-containing compounds, phosphorus-nitrogen compounds, or mixtures thereof; terminating, a plasticizer is introduced into the polymer, wherein the plasticizer is a low molecular weight polymer having a molecular weight of 1500g/mol to 50,000g/mol, and the polymer is degassed and dried. In yet another aspect, the present invention relates to a process for producing a rubber composition based on the above branched polydienes.
The branched polydienes prepared according to the present invention have a Mooney viscosity index of 40 Mooney Units (MU) to 49 Mooney units, a polydispersity index in the range of 2.16 to 2.60, a branching coefficient as characterized by the mechanical loss tangent tg δ (1200%) of about 4.7 to about 5.3, and a content of 1,4-cis units of 96, 0% to 98.0%. The rubber compositions based on the polydienes produced are characterized by low mooney viscosity and exhibit good elastic-hysteresis characteristics.
Background
Today, in order to improve competitiveness, it is of utmost importance for rubber manufacturers to have advantages in terms of properties considered in the environmental signs of the tire. In furtherance of this goal, rolling resistance indices of 20% to 30% of fuel consumption for automotive transportation must be optimized. A reduction in rolling resistance will not only reduce fuel consumption but also cause a reduction in carbon dioxide emissions.
The wide range of low molecular weight polymers (so-called liquid rubbers) appearing on the market makes it possible to obtain winter studless tires with improved grip under winter conditions. Some companies have used liquid rubbers as reinforcing additives in tread compounds (tread compounds). In the tests, the treads thus obtained exhibit high plasticity and remain flexible even at low temperatures, and also exhibit improved grip on ice.
Patent RU2394692(SUMITOMO rubber INDASTRIES, LTD (JP),07.20.2010) describes the production of a rubber composition for the sidewalls of pneumatic tires, said rubber composition comprising: 100 parts by mass of a first rubber component composed of 30 to 70% by mass of a natural rubber and 70 to 30% by mass of an epoxidized natural rubber; 20 to 60 parts by mass of silica; and 3 to 60 parts by mass of a second rubber component composed of a liquid rubber and a vulcanizing agent. This provides an "eco-type" pneumatic tire having improved durability (improved heat resistance, crack resistance, ozone resistance).
However, the introduction of liquid rubber at the step of compounding the rubber does not ensure its uniform distribution in the polymer matrix and, in addition, requires additional energy consumption. Further, according to the patent, only liquid polyisoprene rubber (natural rubber) is used.
The use of liquid polydienes as part of a rubber composition is well known. Patent EP2082899(CONTINENTAL AG (DE),18.05.2011) describes a process for producing rubber compositions consisting of 5 to 50 parts by mass of a liquid low-viscosity polymer. The resulting blend exhibits improved elasticity at low temperatures and improved tensile modulus at 300% elongation.
Liquid rubber is also introduced at the step of rubber mixing, and no improvement in the physical and mechanical properties of the rubber mixture and in the elastic hysteresis properties is mentioned in the patent.
From US8975324(RANDALL AMY M (US), AGARWAL SHEEL P (US), hargerother WILLIAM L (US), BRIDGESTONE CORP (JP),10.03.2015) a process is known for improving the abrasion resistance of rubber compositions for the manufacture of tire treads using functionalized liquid polybutadienes. The rubber composition according to the invention comprises a conjugated diene polymer or copolymer; at least one filler; an amount of 2phr to 10phr of a liquid unsaturated carboxylic anhydride functionalized polybutadiene; 0.2 to 5phr of zinc oxide; and 1phr to 100phr of process oil. In this patent, a liquid rubber is introduced at the step of kneading the rubber, and a comparison of a rubber composition having a liquid rubber with a rubber composition based on an oil-extended polymer shows that the former has a Mooney viscosity 10% to 28% higher than that of the latter, which indicates poor processability; further, the vulcanization rate of the rubber composition with the liquid rubber is 1.5 times to 2 times lower.
A rubber composition prepared as disclosed in US6472461(BRIDGESTONE CORP (JP),29.10.2002) consists of: 1) a rubber component comprising a) at least one natural or synthetic diene rubber, b) a low molecular weight polybutadiene in an amount of 6% or more based on the rubber component, such as an average molecular weight of 5,000 to 30,000 as measured by gel permeation chromatography based on polystyrene molecular weight, and having a 1,4-cis structure content of 60% to 98%; 2) polyethylene staple fibers having an average length of 10mm or less; and 3) a blowing agent. The invention relates to a method for producing a pneumatic tire exhibiting improved braking performance on ice.
The inventors do not provide data on the indices of importance to the tire manufacturer-the wear of the rubber, the elasticity-hysteresis characteristics at 60 ℃ and the strength characteristics.
RU2429252 (britestone CORP (JP),20.09.2011) also describes a process for introducing low molecular weight polymers at the step of compounding rubber. A rubber mixture is prepared by mixing 1 to 60 parts by weight of a low-molecular weight conjugated diene-based polymer (B) having a weight average molecular weight as measured by gel permeation chromatography and converted to polystyrene of more than 30,000 to not more than 200,000 per 100 parts by weight of the rubber component (a) mixed with (B). The rubber component (a) comprises a natural rubber and/or a polyisoprene rubber, and optionally at least one rubber selected from a styrene-butadiene copolymer rubber, a polybutadiene rubber and an isobutylene isoprene rubber. The composition according to the present invention has excellent processability and heat resistance during production, a high storage elastic modulus and a small loss tangent (tg δ).
However, the introduction of liquid rubber at the step of compounding the rubber does not ensure its uniform distribution in the polymer matrix.
It is known that during the post-polymerization modification with maleic acid (maleic) fragments and the polymerization modification, the active centers (growing macromolecules) interact with the carbonyl groups and then the molecular parameters and the plastic-elastic properties of the polybutadiene are changed. In addition, new phenomena have been discovered. In particular, when a modifier is introduced directly into the final catalyst composite (polymerization modification), the modifier not only interrupts the polymerization process, but also provides results close to the post-polymerization modification (v.l. zolotarev, On the mechanism of the process of post-polymerization modification of the novel 1,4-cis-polybutadiene, j. "vysolomol kuryan soybean source" [ High Molecular Compounds ], phase 3, pages 3 to 5, 2015).
However, the use of maleated polybutadiene alone for modification does not impart optimum performance characteristics to the rubber regardless of the time of its incorporation.
A promising direction is the post-polymerization modification of low molecular weight polymers, which has an effect on the properties of 1,4-cis polybutadiene and rubber compositions based thereon.
The process for preparing polybutadiene as disclosed in US7112632(POLIMERI EUROPA SPA (IT),26.09.2006) is closest to the essence of the present invention. According to the method, the process for preparing polybutadiene comprises: (a) polymerizing butadiene; (b) treating the polymer solution obtained on completion of step (a) with a coupling agent selected from: (i) unsaturated natural oils; (ii) butadiene and/or isoprene oligomers; (iii) copolymers of butadiene and/or isoprene with vinyl aromatic monomers; the unsaturated groups (unsaturation) present in compounds (i) to (iii) are at least partially substituted with a group selected from epoxides, anhydrides and esters; (c) recovering the polybutadiene with a low branching content obtained when step (b) is completed. According to this patent, the polymers obtained have a low branching content.
However, it is known that good processability of rubber compounds is ensured by using branched polymers. The patent does not contain any information about the homogeneity of the filler distribution in the polymer matrix, and about the improvement in the abrasion resistance and processability of the obtained polymer.
Disclosure of Invention
The object of the present invention is to improve the processability of the polymer in the step of rubber compounding.
This object is solved by developing a process for preparing a branched polydiene by polymerization of a conjugated diene, the process comprising: preparing a catalyst composite comprising a lanthanide compound, an organoaluminum compound, a conjugated diene, and a halogen-containing component; polymerizing a conjugated diene in the presence of the catalyst composite; post-polymerization modification with at least one branching agent selected from halogen-containing compounds, phosphorus-nitrogen compounds or mixtures thereof; terminating, a plasticizer is introduced into the polymer, wherein the plasticizer is a low molecular weight polymer having a molecular weight of 1500g/mol to 50,000g/mol, and the polymer is degassed, isolated, and dried.
The technical result of the present invention is the production of a branched polydiene characterized by a mooney viscosity of about 40 Mooney Units (MU) to about 49 mooney units, and a branching coefficient as characterized by a mechanical loss tangent tg δ (1200%) of about 4.7 to about 5.3. The polydienes prepared according to the present invention have improved processability, improved distribution of filler in the polymer matrix, and rubber compositions based on the polydienes are characterized by improved elastic-hysteresis properties (i.e., mooney viscosity ML (1+4), MU, Payne effect Δ (G '1% -G' 50%), kPa, tg δ at 10% deformation at 60 ℃).
According to the invention, the modification is carried out by using at least one branching agent selected from halogen-containing compounds, phosphorus-nitrogen compounds or mixtures thereof.
Compounds useful as branched halogen-containing compounds include thionyl chloride, diphenyltin dichloride, phenyltin trichloride, triphenyltin chloride, dibutyltin dichloride, butyltin trichloride, tin tetrachloride, and silicon tetrachloride.
The phosphorus-nitrogen compounds are those having a structure based on repeating units (-P ═ N-) n Wherein n is an integer from 3 to 24.
The branching agent interacts with the polymer at the living end of its polymer chain. Branching agents affect the mooney viscosity and branching coefficient of the polymer, affecting changes in the molecular weight characteristics of the polymer, such as number average molecular weight Mn, weight average molecular weight Mw, polydispersity Mw/Mn, and the like.
Plasticizers (softeners) are substances that facilitate processing of the polymer when incorporated into the polymer. In this case, the plasticizer does not chemically interact with the polymer; only physical mixing occurs. The plasticizer is generally added at the step of mixing the rubber. The presence of a classical liquid plasticizer in the formulation of the rubber mixture allows, to a certain extent, homogenization of the rubber mixture during the step of mixing the rubber; however, in most cases, significant dosages (15 parts by weight on average) adversely affect the complex physicochemical properties of the resulting vulcanizates.
The distinguishing feature of the present invention is the introduction of the plasticizer in the form of a solution in an inert organic solvent at the step of preparing the polymer. This technique allows the use of low doses of plasticizer (in an amount 6 or more times lower than the amount introduced at the step of mixing the rubber) and increases the processability by at least 6% to 10% compared to polymers which undergo only post-polymerization modification without the addition of plasticizer.
According to the present invention, a plasticizer is used in the step of preparing the polymer, wherein the plasticizer is a low molecular weight polymer having a molecular weight of 1,500g/mol to 50,000 g/mol. Non-functionalized low molecular weight polybutadiene, polybutadiene functionalized with maleic anhydride or triethoxysilane, and non-functionalized low molecular weight polyisoprene and polyisoprene functionalized with maleic anhydride are preferably used as such plasticizers.
Non-functionalized low molecular weight polybutadiene and polybutadiene functionalized with maleic anhydride or triethoxysilane are most preferred as plasticizers because they have the same microstructure as neodymium polybutadiene.
Exemplary commercially available plasticizers are: isoprene homopolymers (e.g., LIR-30, LIR-50 produced by Kuraray co., Ltd.), maleic anhydride modified polyisoprene (e.g., MIP-004Kuraray co., Ltd.), non-functionalized low molecular weight ("liquid") polybutadiene (e.g., Polyvest 130 from Evonik), maleic anhydride functionalized polybutadiene (e.g., Polyvest 75MA from Evonik or Ricon 130 m a 8, Ricon 130 m a 10, Ricon 130 m a 13, Ricon 1031, Ricon 1731, Ricon 2031, Ricon 1756 from Cray Valley), or triethoxysilane functionalized polybutadiene (e.g., Polyvest EP-E60, Polyvest EP-E80, Polyvest E-100 from Evonik). The properties of the plasticizer (liquid rubber) used according to the present invention are shown in table 2.
The dose of the plasticizer according to the present invention is 0.5 to 5.0 mass%, preferably 0.7 to 2.0 mass%, and the most preferred dose of the plasticizer according to the present invention is 0.8 to 1.5 mass%, based on the polymer. The dosage of the plasticizer above the defined range results in a significant decrease in the mooney viscosity of the polymer and in a decrease in the conditional tensile strength in the rubber composition. A dose of less than 0.5 mass% does not cause improvement in the characteristics of the polymer and the rubber composition based thereon.
The catalyst compound used according to the present invention comprises a lanthanide compound, an organoaluminum compound, and a halogen-containing component. Compounds useful as lanthanide compounds include compounds containing at least one lanthanide atom from the following: neodymium, lanthanum, cerium, praseodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. Neodymium is preferred.
Compounds comprising lanthanides include, but are not limited to, them, such as carboxylates, organophosphates (in particular alkyl and aryl phosphates), organophosphonates (in particular alkyl and aryl phosphonates), organophosphinates (in particular alkyl and aryl phosphinates), carbamates, lanthanides xanthates, beta-diketonates (beta-diketonates), halides, oxyhalides, alcoholates.
Neodymium carboxylates include neodymium formate, neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium valerate, neodymium gluconate, neodymium citrate, neodymium fumarate, neodymium lactate, neodymium maleate, neodymium oxalate, neodymium 2-ethylhexanoate, neodymium neodecanoate, neodymium naphthenate, neodymium stearate, neodymium oleate, neodymium benzoate, and neodymium picolinate.
Neodymium organophosphates include neodymium dibutyl phosphate, neodymium diphenyl phosphate, neodymium dihexyl phosphate, neodymium diheptyl phosphate, neodymium dioctyl phosphate, neodymium bis (1-methylheptyl) phosphate, neodymium bis (2-ethylhexyl) phosphate, neodymium didecyl phosphate, neodymium didodecyl phosphate, neodymium dioctadecyl phosphate, neodymium bis (n-nonylphenyl) phosphate, neodymium butyl (2-ethylhexyl) phosphate, neodymium (1-methylphenyl) (2-ethylhexyl) phosphate, and neodymium (2-ethylhexyl) (n-nonylphenyl) phosphate.
Neodymium organophosphates include neodymium butylphosphonate, neodymium pentylphosphonate, neodymium hexylphosphonate, neodymium heptylphosphonate, neodymium octylphosphonate, neodymium (1-methylheptyl) phosphonate, neodymium (2-ethylhexyl) phosphonate, neodymium decylphosphonate, neodymium dodecylphosphonate, neodymium octadecylphosphonate, neodymium oleylphosphonate, neodymium phenylphosphonate, neodymium (n-nonylphenyl) phosphonate, neodymium butyl (butylphosphonate), neodymium pentyl (pentylphosphate), neodymium hexyl (hexylphosphonate), neodymium heptyl (heptylphosphonate), neodymium octyl (octylphosphonate), neodymium (1-methylheptyl) phosphonate, neodymium (2-ethylhexyl) phosphonate, neodymium decyl (decylphosphonate), neodymium dodecyl (dodecylphosphonate), neodymium octadecyl (octadecylphosphonate), neodymium oleyl (oleylphosphonate) phosphonate, Neodymium phenyl (phenylphosphonate), neodymium (n-nonylphenyl) ((n-nonylphenyl) phosphonate), neodymium butyl ((2-ethylhexyl) phosphonate), neodymium (2-ethylhexyl) (butylphosphonate), neodymium (1-methylheptyl) ((2-ethylhexyl) phosphonate), neodymium (2-ethylhexyl) ((1-methylheptyl) phosphonate), neodymium (2-ethylhexyl) ((n-nonylphenyl) phosphonate) and neodymium (p-nonylphenyl) ((2-ethylhexyl) phosphonate).
Neodymium organophosphinates include neodymium butylphosphinate, neodymium pentylphosphinate, neodymium hexylphosphinate, neodymium heptylphosphinate, neodymium octylphosphinate, (neodymium 1-methylheptyl) phosphinate, (neodymium 2-ethylhexyl) phosphinate, neodymium decyphosphinate, neodymium dodecylphosphinate, neodymium octadecylphosphinate, neodymium oleylphosphinate, neodymium phenylphosphinate, (neodymium n-nonylphenyl) phosphinate, neodymium dibutylphosphinate, neodymium dipentyphosphinate, neodymium dihexylphosphinate, neodymium diheptylphosphinate, neodymium dioctylphosphinate, neodymium bis (1-methylheptyl) phosphinate, neodymium bis (2-ethylhexyl) phosphinate, neodymium tris- [ bis (2-ethylhexyl) phosphinate ] neodymium, neodymium didecylphosphinate, neodymium didodecylphosphinate, neodymium dioctadeylphosphinate, neodymium dioleylphosphinate, neodymium diphenylphosphinate, neodymium, Neodymium bis (n-nonylphenyl) phosphinate, neodymium butyl (2-ethylhexyl) phosphinate, neodymium (1-methylheptyl) (2-ethylhexyl) phosphinate, and neodymium (2-ethylhexyl) (n-nonylphenyl) phosphinate.
Carboxylic acid salts of neo-acids are most preferred due to their faster and more complete alkylation, which results in more active catalyst compounds.
Neodymium carboxylates and neodymium organophosphites are preferably used, with neodymium neodecanoate and neodymium tris- [ bis (2-ethylhexyl) phosphate ] or mixtures thereof being most preferred.
Compounds suitable for use as organoaluminum compounds according to this invention include: trialkylaluminum compounds, triphenylaluminum or dialkylaluminum hydrides, alkylaluminum dihydrides, in particular trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-tert-butylaluminum, triphenylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, dihexylaluminum hydride, diisohexylaluminum hydride, dioctylaluminum hydride, diisooctylaluminum hydride, phenylethylaluminum hydride, phenyl-n-propylaluminum hydride, phenylisopropylaluminum hydride, phenyl-n-butylaluminum hydride, phenylisobutylaluminum hydride, benzylethylaluminum hydride, benzyl-n-butylaluminum hydride, benzylisobutylaluminum hydride, benzylisopropylaluminum hydride and the like.
Preference is given to using alkylaluminums or alkylaluminum hydrides, or mixtures thereof. Most preferred is triethylaluminum, triisobutylaluminum, diisobutylaluminum hydride or mixtures thereof.
Compounds useful as conjugated dienes according to the present invention include 1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene, piperylene, 2-methyl-3-ethyl-1, 3-butadiene, 3-methyl-1, 3-pentadiene, 2-methyl-3-ethyl-1, 3-pentadiene, 3-methyl-1, 3-pentadiene, 1, 3-hexadiene, 2-methyl-1, 3-hexadiene, 1, 3-heptadiene, 3-methyl-1, 3-heptadiene, 1, 3-octadiene, 3-butyl-1, 3-octadiene, 3, 4-dimethyl-1, 3-hexadiene, 2, 3-pentadiene, 3-butadiene, isoprene, butadiene, isoprene, butadiene, isoprene, butadiene, isoprene, butadiene, isoprene, butadiene, isoprene, butadiene, isoprene, butadiene, isoprene, butadiene, isoprene, butadiene, isoprene, butadiene, isoprene, butadiene, isoprene, butadiene, isoprene, butadiene, isoprene, butadiene, isoprene, butadiene, isoprene, butadiene, isoprene, butadiene, isoprene, butadiene, isoprene, butadiene, isoprene, butadiene, isoprene, butadiene, isoprene, butadiene, 4, 5-diethyl-1, 3-octadiene, phenyl-1, 3-butadiene, 2, 3-diethyl-1, 3-butadiene, 2, 3-di-n-propyl-1, 3-butadiene and 2-methyl-3-isopropyl-1, 3-butadiene.
The most preferred conjugated dienes are 1, 3-butadiene and isoprene.
The compound used as the halogen-containing component in the catalyst composite may include halogenated organic compounds of aluminum and tin, specifically, for example, dimethylaluminum chloride, diethylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide, diethylaluminum bromide, diisobutylaluminum bromide, dimethylaluminum fluoride, diethylaluminum fluoride, diisobutylaluminum fluoride, dimethylaluminum iodide, diethylaluminum iodide, diisobutylaluminum iodide, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dibromide, ethylaluminum dibromide, methylaluminum difluoride, ethylaluminum difluoride, methylaluminum sesquichloride, ethylaluminum sesquichloride, isobutylaluminum sesquichloride or a mixture thereof, and trimethyltin chloride, trimethyltin bromide, triethyltin chloride, triethyltin bromide, di-tert-butyltin dichloride, di-tert-butyltin dibromide, dibutyltin dichloride, dibutyltin, Dibutyl tin dibromide, tributyl tin chloride, tributyl bromide, and the like, or mixtures thereof.
Preferred halogen-containing components are ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum chloride or mixtures thereof.
The polymerization solvent is an inert organic solvent, such as an aliphatic hydrocarbon, in particular, such as butane, pentane, hexane, heptane; alicyclic hydrocarbons, in particular cyclopentane, cyclohexane; mono-olefins, such as 1-butene, 2-butene, or mixtures thereof; aromatic hydrocarbons, such as, in particular, benzene, toluene, xylene, which may be used alone or in a mixture with one another.
According to the proposed process, the most preferred hydrocarbon solvents are the solvents: it is a mixture of cyclohexane and hexane or cyclohexane and nefras (a commercial grade hexane-heptane fraction of paraffins of dearomatized gasoline obtained by a catalytic reforming process, boiling point 65 ℃ to 75 ℃) in a ratio of (30 to 55) ÷ (70 to 45).
The catalyst composite for polymerization process according to the present invention comprises a lanthanide compound (A), a conjugated diene (B), an organoaluminum compound (C) and a halogen-containing component (D) in a molar ratio of (A) to (B) to (C) of 1 (5 to 30) to (8 to 30) to (1.5 to 3.0).
The preferred molar ratio of (A) component (B) component (C) component (D) is 1 (5 to 20) to (8 to 20) to (1.8 to 2.8).
The most preferred molar ratio of (A) component, (B) component, (C) component, (D) component is 1 (10 to 15) to (2.1 to 2.5).
The process for preparing the diene polymer is a batch or continuous process carried out in a hydrocarbon solvent by feeding a hydrocarbon mixture into a polymerization vessel (reactor/autoclave), wherein the hydrocarbon mixture consists of the monomer and the solvent and a catalyst composite premixed with the solvent, wherein the catalyst composite comprises a lanthanide compound, a conjugated diene, an organoaluminum compound, and a halogen-containing component. The concentration of the monomer in the solvent is usually 7 to 12% by mass, preferably 9 to 10%. Concentrations below 7% lead to a reduction in the energy efficiency of the process, while concentrations above 12% lead to an increase in the viscosity of the polymerization product and, consequently, to an increase in the energy consumption during the isolation and drying of the rubber.
A Catalyst Complex (CC) was prepared by: introducing an organoaluminium compound (most preferably triisobutylaluminium, triethylaluminium, diisobutylaluminium hydride or a mixture thereof), a lanthanide compound (most preferably a carboxylate salt, in particular neodecane or neodymium tris- [ bis (2-ethylhexyl) phosphate) into a solution of a conjugated diene (most preferably 1, 3-butadiene) in an aliphatic solvent; the resulting mixture is aged at a temperature of 23 ± 2 ℃ for 2 hours to 20 hours, and then a halogen-containing component (most preferably, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum chloride or a mixture thereof) is added, and the (A) component (B) component (C) component (D) component is present in a molar ratio of 1 (5 to 30) to (8 to 30) to (1,5 to 3,0), wherein (A) is a lanthanide compound, (B) is a conjugated diene, (C) is an organoaluminum compound, and (D) is a halogen-containing component. The dosage of the catalyst composite is calculated on the basis of the monomer (hydrocarbon mixture) and on the basis of the lanthanide (metal) for component (a), i.e. from 1.0 to 3.0mol of lanthanide per 1 ton of monomer.
The polymerization time is from 1.5 hours to 3 hours. The monomer conversion rate reaches 95 to 99 percent.
At a monomer conversion of at least 95% was reached, 2kg of the polymerization product were discharged, an antioxidant solution was added in an amount of 0.2 to 0.4% by mass, based on the polymer, to stabilize the polymer, degassed and dried on a roller at a temperature of 75 to 85 ℃. The resulting product was used as an unmodified reference sample. The reference polymer has a mooney viscosity of 30MU to 39MU and is characterized by a linear structure: its branching coefficient, as characterized by the mechanical loss tangent tg δ (1200%), is from 9 units to 7 units.
Then, a branching agent selected from phosphorus-nitrogen compounds and/or halogen-containing compounds is fed to the remaining polymerization product. The branching process is carried out at a temperature of 60 ℃ to 90 ℃ for 5 minutes to 3 hours, preferably 20 minutes to 1 hour, with constant stirring. At the end of the branching process, 2kg of the polymerization product were discharged, an antioxidant solution was added to the polymer in an amount of 0.2 to 0.4 mass% based on the polymer, degassed and dried on a roll at a temperature of 75 to 85 ℃.
Modification temperatures below 60 ℃ lead to an increase in the viscosity of the polymer, which is undesirable because it adds unavoidable difficulties in the isolation and processing of the polymer. At the same time, the end groups of the polymer chain tend to lose their activity at temperatures above 90 ℃ and, therefore, a high degree of branching of the polymer is not possible.
Compounds which can be used as Branching Agents (BA) according to the invention are phosphorus-nitrogen compounds and/or halogen-containing compounds.
Suitable halogen-containing compounds may include tin compounds, i.e., tin tetrachloride, methyltin trichloride, dimethyltin dichloride, ethyltin trichloride, diethyltin dichloride, n-butyltin trichloride, di-n-butyltin dichloride, phenyltin trichloride, diphenyltin dichloride, and silicon compounds such as silicon tetrafluoride, silicon tetrachloride, silicon tetrabromide, and silicon tetraiodide.
Tin tetrachloride, methyl tin trichloride, ethyl tin trichloride, butyl tin trichloride and silicon tetrachloride are preferred. In the most preferred embodiment, tin tetrachloride and silicon tetrachloride are used.
The dosage of branching agent introduced depends on the desired characteristics of the final product, such as the mooney viscosity of the polymer, while the increase in mooney viscosity of the polymer after branching thereof (Δ ML,%) compared to the unbranched polymer is 30% to 40% and the branching coefficient (characteristic of the branching degree of the polymer) characterized by the mechanical loss tangent tg δ (1200%) as measured on an RPA (rubber processing analyzer) device at a frequency of 0.1Hz and a temperature of 100 ℃ is changed by 35% to 50% by mass.
According to the invention, the molar ratio of the halogen-containing compound chosen as branching agent BA to the lanthanide is from 1.0 to 20, preferably from 2 to 15, most preferably from 5.0 to 10.0. An increase in the dose beyond 20.0 moles did not result in an improvement in the polymer properties, but led to excessive consumption of BA. A reduction in molar dosages of less than 1.0 per lanthanide does not alter the properties of the polymer and rubber respectively.
According to the invention, the phosphorus-nitrogen compounds are those having a structure based on repeating units (-P ═ N-) n Wherein n is an integer from 3 to 24. Exemplary compounds for use as phosphorus-nitrogen compounds are, but are not limited to, the following:
2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4, 6-triphosphazene (2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4, 6-triphosphorine);
2,4, 6-trichloro-2, 4, 6-triphenoxy cyclotriphosphazene;
1,1-diphenyl-3,3,5, 5-tetramethlylaminotriphosphazene (1,1-diphenyl-3,3,5, 5-tetramethylnitrilotriphosphonitrile);
2,2,4,4-tetrachloro-6, 6-dimethylmercaptocyclotriphosphazene (2,2,4,4-tetrachloro-6, 6-dimethyllmercaptochlorotrifluorazatrien);
ethoxypentafluorocyclotriphosphazene;
(trifluoroethoxy) pentachlorotriphosphazene;
(ii) a hexafluorocyclotriphosphazene;
4,4,6,6-tetrachloro-1,3,5-triaza-2,4, 6-triphosphaexane-1, 3,5-triene-2,2-diamine (4,4,6,6-tetrachloro-1,3,5-triaza-2,4, 6-triphosphaohexa-1, 3,5-triene-2, 2-diamine);
2,4, 6-trichloro-2, 4, 6-trifluoro-1, 3,5-triaza-2 λ 5,4 λ 5,6 λ 5-triphosphacyclohexa-1, 3, 5-triene;
2,4, 6-trichloro-2, 4, 6-tris (phenoxy) -1,3, 5-triphosphor;
trichloride trinitride diamide tetrachloride;
octachlorocyclotetraphosphazene;
1, 1-dimethyl-3, 3,5, 5-tetrachlorocyclotriphosphazene;
2,2,4, 4-tetrachloro-6-isopropyl-2 λ 5,4 λ 5,6 λ 5- [1,3,5,2,4,6] triaza triphenylphosphine (triphosphine);
1-methyl-1, 3,3,5, 5-pentachlorocyclotriphosphazene;
1,3,5,2,4, 6-triazatriphosphabenzene, 2,4, 6-tribromo-2, 4, 6-trifluoro-polymeric dialdehyde;
4, 6-difluoro-2-N, N-2,2-N', 4-N, N-6, 6-N-octamethyl-1, 3,5-triaza-2 λ 5,4 λ 5,6 λ 5-triphosphax-cyclohexa-1, 3,5-triene-2,2, 4, 6-tetramine;
2,2,4,4,6, 6-hexahydro-2, 2,4,4,6, 6-hexapropoxy-propoxy-1, 2,3,4,5, 6-triazatriphosphabenzene;
1,1-diphenyl-3,3,5, 5-tetramethyamino-triphosphazene, and the like.
In a preferred embodiment, chlorine-containing phosphorus-nitrogen compounds containing from 2 to 6 chlorine atoms are used.
In a most preferred embodiment, the compounds used are: 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4, 6-triphosphazene; 2,4, 6-trichloro-2, 4, 6-triphenoxy cyclotriphosphazene; 2,2,4,4-tetrachloro-6, 6-dimethylmercaptocyclotriphosphazene; 4,4,6,6-tetrachloro-1,3,5-triaza-2,4, 6-triphosphacyclohexa-1, 3,5-triene-2,2-diamine or mixtures thereof.
According to the invention, the dosage of the phosphorus-nitrogen compound chosen as BA is between 0.5 and 15.0mol per mol of lanthanide. An increase of the molar dose based on lanthanides above 15.0 does not lead to an improvement of the properties of the polymer and of the rubber, but leads to an excessive consumption of the modifier. A molar reduction of less than 0.5 based on the lanthanide does not improve the respective properties of the polymer and the rubber.
The most preferred dosage of the chlorine-containing phosphorus-nitrogen compound is 1.0 to 5.0mol per 1mol of lanthanide, since this modifier amount allows to achieve the best properties of the polymer and of the polymer-based rubber with relatively little consumption of modifier.
The resulting branched polymer is characterized by a mooney viscosity of 44MU to 53MU, and a branching coefficient as characterized by a mechanical loss tangent tg δ (1200%) of 4.0 to 5.0. Furthermore, the increase in mooney viscosity of the branched polymer relative to the unmodified reference sample was in the range of 30% to 50%.
The increase (%) in viscosity was calculated by the following formula:
ΔML 2/1 ＝(ML 2 -ML 1 )/ML 1 *100，
wherein Δ ML 2/1 Is an increase in the mooney viscosity of the branched polymer relative to the linear polymer;
ML 2 is the mooney viscosity of the branched polymer;
ML 1 is the mooney viscosity of the linear polymer;
the change (%) in polymer branching is calculated from the following formula:
Δtgδ1200％2/1＝(tgδ1200％2-tgδ1200％ 1 )/tgδ1200％ 1 *100，
wherein Δ tg δ 1200% 2/1 Is the change in branching of the polymer relative to the linear polymer;
tgδ1200％ 2 the branching coefficient of the branched polymer expressed as the mechanical loss tangent determined with a variable amplitude of 0% to 1200%, a frequency of 0.1Hz and a temperature of 100 ℃;
tgδ1200％ 1 the branching coefficient of the linear polymer is expressed as the mechanical loss tangent determined at a variable amplitude of 0% to 1200%, a frequency of 0.1Hz and a temperature of 100 ℃.
Further, a solution of 0.2 to 0.4 mass% of an antioxidant based on the amount of the polymer and 0.5 to 5.0 mass% of a plasticizer of a low molecular weight polymer having a molecular weight of 1500 to 5000g/mol based on the amount of the polymer is introduced into the remaining polymerization product, stirred for 5 to 10 minutes, degassed and dried on a roll at a temperature of 75 to 85 ℃.
The plasticizer dosage is calculated such that the polymer viscosity does not decrease by more than 10% after introduction of the plasticizer, and the branching coefficient does not change by more than 10%. Otherwise, the conditional tensile strength is deteriorated.
Reduction of viscosity ML 3/2 Calculated from the following formula:
ΔML 3/2 ＝(ML 2 -ML 3 )/ML 2 *100，
wherein Δ ML 3/2 Is a decrease in the mooney viscosity of the polymer;
ML 2 is the mooney viscosity of the branched polymer;
ML 3 is the Mooney viscosity of the polymer which is branched and modified with a plasticizer.
The change (%) in polymer branching is calculated from the following formula:
Δtgδ1200％ 3/2 ＝(tgδ1200％ 3 -tgδ1200％2)/tgδ1200％ 2 *100，
wherein Δ tg δ 1200% 3/2 Is a change in polymer branching;
tgδ1200％ 2 the branching coefficient of the branched polymer expressed as the mechanical loss tangent determined at a variable amplitude of 0% to 1200%, a frequency of 0.1Hz and a temperature of 100 ℃;
tgδ1200％ 3 the branching coefficient of the branched and modified polymers is expressed as the mechanical loss tangent determined with a variable amplitude of 0% to 1200%, a frequency of 0.1Hz and a temperature of 100 ℃.
The rubber compositions were processed on rolls after mixing, wherein the preparation of the rubber compositions for vulcanization, the vulcanization of the test samples and the preparation were carried out according to ASTM D3182 and ASTM D3189. The ASTM D3189 formulations are presented in table 1.
The branched polydienes prepared according to the present invention have a mooney viscosity index of 40MU to 49MU, a polydispersity index in the range of 2.16 to 2.60, a branching coefficient as characterized by the mechanical loss tangent tg δ (1200%) of 4.7 to 5.3, wherein the content of 1,4-cis units is 96, 0% to 98.0%. The rubber mixtures obtained on the basis of the polydienes prepared are characterized by a low Mooney viscosity, a good distribution of the filler in the polymer matrix and good elastic-hysteresis properties (i.e. ML (1+4), MU, the payne effect Δ (G '1% -G' 50%), kPa, tg δ at 60 ℃ 10% deformation).
The use of BA and plasticizer according to the present invention provides branched polydienes that exhibit better processability results and better elastic-hysteresis properties in rubber composition testing than unmodified polymers, polymers modified with only one BA or mixtures thereof but no plasticizer, and than polymers prepared using plasticizer alone.
TABLE 1 formulation of rubber mixtures (ASTM 3189)
Composition (I) Parts by weight of
Butadiene rubber 100.0
Carbon black N330(IRB 8) 60.0
Zinc oxide paint 3.0
Commercial grade stearic acid 2.0
Naphthenic oil 15.0
Gaseous sulfur 1.5
Sulfenamide T 0.9
In total: 182.40
EMBODIMENTS FOR CARRYING OUT THE INVENTION
Embodiments of the invention are disclosed below. It will be understood by those skilled in the art that the present invention is not limited to the examples presented only, and that the same effects can be achieved in other embodiments without exceeding the object of the claimed invention.
Test methods for evaluating the properties of the polymers prepared by the claimed methods are disclosed below.
1. Percent conversion is determined gravimetrically by precipitating the polymer from the polymerization product with ethanol, drying the isolated polymer and calculating the weight fraction of polymer in the polymerization product.
2. The molecular weight properties of the rubber were measured using gel permeation chromatography using a gel chromatograph with a refraction detector (Waters Breeze System) according to the method provided by the inventors of the present invention. Dissolving a rubber sample in freshly distilled tetrahydrofuran, the weight concentration of the polymer in the solution being 2 mg/ml; general calibration was performed with polystyrene standards. Polydienes were calculated using Kuhn-Mark-Houwink constants (K ═ 0.00041, α ═ 0.693). And (3) testing conditions are as follows:
groups of 4 high-resolution columns (300 mm in length, 7.8mm in diameter) equipped with Styragel (HR3, HR4, HR5, HR6), which allow an analytical molecular weight of 500amu to 1X 10 7 Polymers of amu;
flow 1cm 3 Tetrahydrofuran solvent per minute;
the temperature of the thermostatted column and refractometer was 3000 ℃.
3. Mooney viscosity was determined according to ASTM D1646.
4. The complex dynamic shear modulus G' (kPa) for evaluating the distribution of filler in a rubber composition and the silanized elastic component of the filler was determined on an RPA-2000 rubber processing Analyzer (Alpha Technologies) at 0.1Hz and 100 ℃ in the deformation range of 1% to 450%. The difference between the storage moduli measured at strain amplitudes of 1% and 50% is CG '═ G' (G '1% -G' 43%), i.e. the payne effect.
5. The branching coefficient, characterized by the mechanical loss tangent tg δ (1200%), was determined on an RPA-2000 rubber processability analyzer (Alpha Technologies) using the following test patterns: the variation of tg δ was evaluated at a frequency of 0.1Hz and a temperature of 100 ℃ over a variable shear amplitude ranging from 10% to 1200% amplitude.
Example 1 (according to the prototype)
Butadiene (BD) was polymerized in a hydrocarbon solvent in the presence of a catalyst complex prepared based on neodymium versatate (Nd), and then diisobutylaluminum hydride (DIBAG) as an alkylating agent, diethylaluminum chloride (DEAC) as a halogen donor, neodymium versatate (NdV3), diisobutylaluminum hydride (DIBAH) were added. DIBAH was used in 8-fold molar excess relative to the neodymium dose, while DEAC was used in 3-fold molar excess. The dosage of the catalyst composite was 2.8mol neodymium per 1 ton Butadiene (BD). The polymerization was carried out in a 20 liter reactor equipped with a mixing device and a jacket for heat removal. The polymerization process lasted for 90 minutes. At the end of the polymerization, 2 liters of polymerization product were discharged from the reactor; the monomer conversion was 98%. A phenolic antioxidant (Irganox 1520) was added to the selected aliquot in an amount of 0.06 mass%. The solvent was removed and rolling was carried out at a temperature of 80 ℃. The branching coefficient of the polymer and the molecular weight properties (MMC) measured by GPC are determined in selected aliquots; the Mooney viscosity of the linear polymer produced was 35 MU. A solution of maleinized polybutadiene, Ricon 130 MA 8, in a mixture of hexanes (concentration of solution 0.15mol/L) was fed to the remaining polymerization product in the reactor at a dose of 1.2mol per Nd at a temperature of 90 ℃. After 10 minutes, the primary antioxidant (Irganox 565) and the secondary antioxidant (TNPP) were added and the resulting modified polymer was discharged. The mooney viscosity of the modified polymer was 43MU and tg δ 1200% ═ 5.567, i.e. the polymer obtained was branched.
Example 2 (comparative)
Polymerizing Butadiene (BD) in a hydrocarbon solvent in the presence of a preformed catalyst complex of: neodymium neodecanoate-Butadiene (BD) -diisobutylaluminum hydride (DIBAH) -ethylaluminum sesquichloride (EASC) in a molar ratio of components 1:10:12: 2.5. The time for aging the composite at a temperature of 23 ℃ was 22 hours. The polymerization was carried out in a 20 liter reactor. The dried residue equals 11%. The dosage of the catalyst composite was 1.8mol of neodymium per 1 ton of Butadiene (BD). After achieving a conversion of more than 95% based on the monomers, 2kg of the polymerization product were discharged, a solution of a phenolic antioxidant was introduced in an amount of 0.3% by mass based on the polymer to stabilize the polymer, degassed and dried on a roll at a temperature of 75 ℃ to 85 ℃. Thereafter, physical and mechanical properties as well as molecular weight properties were determined (table 3). To the remaining polymer were added a solution of an antioxidant in an amount of 0.3 mass% based on the polymer and a low molecular weight polybutadiene Polyvest 130 in an amount of 0.8 mass% (8 g per kg of polybutadiene), stirred for 10 minutes, degassed and dried on a roll at a temperature of 80 ℃. Physical and mechanical properties, molecular weight properties, increase in polymer viscosity and change in branching coefficient (mechanical loss tangent tg δ (1200%)) are shown in table 3.
Example 3 (comparative)
Butadiene (BD) is polymerized in a hydrocarbon solvent in the presence of the following catalyst complex: neodymium neodecanoate-Butadiene (BD) -diisobutylaluminum hydride (DIBAH) -ethylaluminum sesquichloride (EASC) in a molar ratio of components 1:10:11: 2.5. The compound was aged at a temperature of 24 ℃ for a period of 20 hours. The dosage of the catalyst composite was 1.7mol of neodymium per 1 ton of Butadiene (BD).
After achieving a conversion of more than 95% based on monomer, the branching agent 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4, 6-triphosphates (HCF) was fed in a dose of 1.0mol based on neodymium. The modification process was continued for 60 minutes at a temperature of 80 ℃ with constant stirring, and then 2kg of the polymerization product were discharged, an antioxidant solution was introduced in an amount of 0.4% by mass based on the polymer, degassed and dried on a roll at a temperature of 80 ℃. The characteristics of the obtained polymer are shown in table 3.
Example 4 (according to the invention)
Polymerizing Butadiene (BD) in a hydrocarbon solvent in the presence of the following catalyst complex: neodymium neodecanoate-Butadiene (BD) -diisobutylaluminum hydride (DIBAH) -ethylaluminum sesquichloride (EASC) in a component molar ratio of 1:10:13:2.5, wherein the amount of neodymium neodecanoate is given based on the amount of neodymium. The dosage of the catalyst composite was 1.7mol of neodymium per 1 ton of Butadiene (BD). After achieving a conversion of more than 95% based on monomer, 2kg of the polymerization product were discharged, a phenolic antioxidant solution was introduced in an amount of 0.3% by mass based on the polymer to stabilize the polymer, degassed and dried on a roll at a temperature of 75 ℃ (step 1), the branching agent 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4, 6-triphosphazene (HCF) was fed to the remaining polymer at a dose of 1.3mol per 1mol of neodymium, 2kg of the polymerization product was discharged, an antioxidant solution was introduced therein in an amount of 0.4% by mass based on the polymer, degassed and dried on a roll at a temperature of 80 ℃ (step 2). To the remaining polymer were added an antioxidant solution in an amount of 0.4 mass% based on the polymer and a low molecular weight polybutadiene Polyvest 130 in an amount of 1.5 mass% (15 g per kg of polybutadiene), stirred for 10 minutes, degassed and dried on a roll at a temperature of 80 ℃ (step 3). The physical and mechanical properties, molecular weight properties of the polymers obtained in the different steps are shown in table 3.
Example 5
The procedure is analogous to example 4, except that 2,4, 6-trichloro-2, 4, 6-Triphenoxycyclotriphosphazene (THF) is used as branching agent at a dose of 1.5mol per 1mol of neodymium. The modification process was continued for 60 minutes at a temperature of 80 ℃ with constant stirring.
The physical and mechanical properties, molecular weight properties of the polymers obtained in the different steps are shown in table 3.
Example 6
The procedure is analogous to example 4, except that 2,4, 6-trichloro-2, 4, 6-Triphenoxycyclotriphosphazene (THF) is used as branching agent at a dose of 1.8mol based on neodymium (step 2). Polyvest EP-ST-E60 was used as a plasticizer at a dose of 0.8 mass% (8 g per kg of polybutadiene) and stirred for 5 minutes.
The physical and mechanical properties, molecular weight properties of the polymers obtained in the different steps are shown in table 3.
Example 7
The procedure is similar to example 4, except that a catalyst composite is prepared based on gadolinium versatate (GdV 3). The dosage of branching agent (HCF) was 1.5mol per 1mol of gadolinium. Liquid polyisoprene LIR 50 was used as a plasticizer in step 3 at a dosage of 0.8 mass% based on polymer (8 g per 1kg polybutadiene).
The physical and mechanical properties, molecular weight properties of the polymers obtained in the different steps are shown in table 3.
Example 8
The procedure was similar to example 5 except that the catalyst composite prepared comprised neodymium tris- [ bis (2-ethylhexyl) phosphate ] (NdP3), Butadiene (BD) and diisobutylaluminum hydride (DIBAH); and ethylaluminum sesquichloride (EASC) was used as chlorinating agent. The molar ratio of BD: Nd: DIBAH: EASC components of the catalyst composite was 10:1:15: 2.7. The time for aging the composite at a temperature of 25 ℃ was 22 hours.
1,1-diphenyl-3,3,5, 5-tetramethyaminotriphosphazene (DPP) is used as branching agent in an amount of 0.5mmol per 1mol of neodymium in step 2.
The physical and mechanical properties, molecular weight properties of the polymers obtained in the different steps are shown in table 3.
Example 9
The procedure was similar to example 7 except that the catalyst composite prepared comprised neodymium tris- [ bis (2-ethylhexyl) phosphate ] (NdP3), Butadiene (BD) and diisobutylaluminum hydride (DIBAH); and ethylaluminum sesquichloride (EASC) was used as chlorinating agent. The molar ratio of BD: Nd: DIBAH: EASC components of the catalyst composite was 10:1:15: 2.7. The time for aging the composite at a temperature of 25 ℃ was 22 hours.
1,1-diphenyl-3,3,5, 5-tetramethyaminotriphosphazene (DPP) is used as branching agent in step 2 in an amount of 1.5mmol per 1mol of neodymium. In step 3, liquid polyisoprene LIR 30 was used as plasticizer at a dosage of 1.0 mass% based on polymer (10 g per 1kg polybutadiene).
The physical and mechanical properties, molecular weight properties of the polymers obtained in the different steps are shown in table 3.
Example 10
The procedure is similar to example 8 except that the catalyst composite prepared comprises praseodymium versatate (PrV 3), Butadiene (BD) and diisobutylaluminum hydride (DIBAH) and ethylaluminum sesquichloride (EASC). The molar ratio of BD: Nd: DIBAH: EASC components of the catalyst composite was 10:1:11: 2.2. The time for aging the composite at a temperature of 22 ℃ was 19 hours.
HCF was used as branching agent at a dosage of 0.2mol per 1mol of praseodymium. In step 30, liquid polyisoprene LIR 30 is used as plasticizer at a dosage of 1.5 mass% based on polymer (15 g per 1kg polybutadiene).
The physical and mechanical properties, molecular weight properties of the polymers obtained at the different steps are shown in table 3.
Example 11
The procedure is analogous to example 8, except that HCF is used as branching agent at a dosage of 1.8mol per 1mol of neodymium (step 2). Polyvest EP-ST-E80, a liquid polybutadiene functionalized with triethoxysilane having a degree of silylation of 80%, was used as plasticizer in an amount of 1.0 mass%, based on polymer (10 g per 1kg of polybutadiene).
The physical and mechanical properties, molecular weight properties of the polymers obtained in the different steps are shown in table 3.
Example 12
The procedure is analogous to example 10, except that a liquid triethoxysilane-functionalized polybutadiene having a degree of silylation of 100% was used as plasticizer in an amount of 1.5% by mass, based on polymer (15 g per 1kg of polybutadiene), Polyvet EP-ST-E80.
The physical and mechanical properties, molecular weight properties of the polymers obtained in the different steps are shown in table 3.
Example 13
The procedure is analogous to example 10, except that the dosage of branching agent is 1.2mol per 1mol of neodymium and that the maleinised liquid rubber Ricon 131MA 10 is used as plasticizer in an amount of 0.8 mass%, based on the polymer (8 g per 1kg of polybutadiene).
The physical and mechanical properties, molecular weight properties of the polymers obtained in the different steps are shown in table 3.
Example 14
The procedure is analogous to example 8, except that the dosage of the branching agent DFF is 5.0mol per 1mol of neodymium. As plasticizer, a non-functionalized liquid polybutadiene Polyvest EP-ST-E130 was used in an amount of 2% by mass, based on the polymer (20 g per 1kg of polybutadiene).
The physical and mechanical properties, molecular weight properties of the polymers obtained in the different steps are shown in table 3.
Example 15
The procedure is analogous to example 13, except that thionyl chloride (SOCl) is used in an amount of 5mol per 1mol of neodymium 2 ) As a branching agent.
The physical and mechanical properties, molecular weight properties of the polymers obtained in the different steps are shown in table 3.
Example 16
The procedure is analogous to example 11, except that thionyl chloride is used as branching agent in an amount of 7.0mol per 1mol of neodymium and maleinised liquid rubber Ricon 130 MA 8% is used as plasticizer in an amount of 1.5 mass% based on the polymer (15 g per 1kg of polybutadiene).
The physical and mechanical properties, molecular weight properties of the polymers obtained in the different steps are shown in table 3.
Example 17
The procedure is analogous to example 14, except that tin tetrachloride (SnCl) is used in a dose of 2.5mol per 1mol of neodymium 4 ) As a branching agent.
The physical and mechanical properties, molecular weight properties of the polymers obtained in the different steps are shown in table 3.
Example 18
The procedure is analogous to example 14, except that tin tetrachloride (SnCl) is used in a dose of 5.0mol per 1mol of neodymium 4 ) As branching agent, and as plasticizer, a liquid triethoxysilane-functionalized polybutadiene Polyvest EP-ST-E80 with a degree of silylation of 100% was used in an amount of 5% by mass based on polymer (50 g per 1kg of polybutadiene).
The physical and mechanical properties, molecular weight properties of the polymers obtained in the different steps are shown in table 3.
Example 19
The procedure is analogous to example 9, except that a catalyst composite is prepared based on neodymium tris- [ (2-ethyl) hexanoate ] (NdEh3), the dose of DFF is 15mol per 1mol of neodymium (step 2), and the dose of plasticizer LIR 30 in step 3 is 0.5 mass% based on the polymer (5 g per 1kg of polybutadiene).
The physical and mechanical properties, molecular weight properties of the polymers obtained in the different steps are shown in table 3.
Example 20
The procedure is analogous to example 18, except that a catalyst composite is prepared on the basis of neodymium tris- [ bis (2-ethylhexyl) phosphate ], the dosage of tin tetrachloride used as branching agent is 20mol per 1mol of neodymium, and Ricon 131MA 10 is used as plasticizer at a dosage of 0.5 mass% per polymer (5 g per 1kg of polybutadiene).
The physical and mechanical properties, molecular weight properties of the polymers obtained in the different steps are shown in table 3.
Example 21
The procedure is analogous to example 19, except that a catalyst composite is prepared based on neodymium neodecanoate. The molar ratio of BD: Nd: DIBAH: EASC components of the catalyst composite was 10:1:13: 2.0. The time for aging the composite at a temperature of 22 ℃ was 19 hours. Branching agent SiCl 4 The dosage of (A) is 1.0mol per 1mol of neodymium; polyvest EP-ST-E MA75 was used as plasticizer at a dosage of 0.5 mass%, based on polymer (5 g per 1kg of polybutadiene).
The physical and mechanical properties, molecular weight properties of the polymers obtained in the different steps are shown in table 3.
Samples of the polymers obtained in examples 1 to 22 were tested in the formulation of rubber compositions (ASTM 3189) and the test results are shown in table 4.
Figure BDA0003698035790000211
Note that:
polyvet EP-ST-E60-liquid polybutadiene functionalized with triethoxysilane, degree of silylation 60%
Polyvest EP-ST-E80-liquid polybutadiene functionalized with triethoxysilane, degree of silylation 80%
Polyvest EP-ST-E100-liquid polybutadiene functionalized with triethoxysilane, degree of silylation 100%
Polyvest 130(S) -non-functionalized liquid polybutadiene (S) containing an antioxidant
Polyvest EP-ST-E MA 75-liquid polybutadiene functionalized with maleic anhydride
LIR 30-liquid polyisoprene, degree of silanization 30%
LIR 50-liquid polyisoprene, degree of silanization 50%
Ricon 130 MA 8-liquid maleic anhydride functionalized polybutadiene with 8 maleic acid groups
Ricon 131MA 10-maleic anhydride functionalized liquid polybutadiene with 10 maleic acid groups
Figure BDA0003698035790000231
Figure BDA0003698035790000241
Figure BDA0003698035790000251
Figure BDA0003698035790000261
Figure BDA0003698035790000271
Note that:
-for branching agents, the dosages are given in moles per 1mol of lanthanide; for plasticizers, the dosages are given in mass% based on 100% polymer
Abbreviations used in table 3:
NdP 3-Neodymium tris- [ bis (2-ethylhexyl) phosphate ]
NdV 3-Neodymium Neodecanoate
GdV3 gadolinium versatate
NdEh 3-Tri- [ (2-Ethyl) hexanoic acid ] Neodymium
DEAC-diethylaluminum chloride
EASC-ethylaluminum sesquichloride
HCP-2,2,4,4,6, 6-hexachloro-1,3,5-triaza-2,4, 6-triphosphatene;
TCP-2,4, 6-trichloro-2, 4, 6-triphenoxy cyclotriphosphazene;
DPP-1, 1-diphenyl-3,3,5, 5-tetrametamidotriphosphazene;
SiCl 4-silicon tetrachloride
SOCl 2-thionyl chloride
Δ ML 2/1 (%) -increase in viscosity of the polymer obtained in step 2 compared to the polymer obtained in step 1 calculated by the formula provided in the summary of the invention section
Δ tg δ 1200% 2/1 (%) -change in branching coefficient of the polymer obtained in step 2 compared to the polymer obtained in step 1 calculated by the formula provided in the summary of the invention section,
Δ ML 3/2 (%) -the decrease in mooney viscosity of the branched polymer obtained in step 2 after introduction of the plasticizer (step 3) calculated by the formula provided in the summary of the invention section,
Δ tg δ 1200% 3/2 (%) -change in branching coefficient of the polymer obtained in step 3 compared to the polymer obtained in step 2 calculated by the formula provided in the summary of the invention section
Figure BDA0003698035790000291
Figure BDA0003698035790000301
As can be seen from table 4, the proposed process for preparing branched polydienes can increase the processability of rubber compositions by 6 to 10% (based on the mooney viscosity index) and can improve the distribution of the filler in the polymer matrix (evaluated by the payne effect parameter).
When only the modifier is used without the plasticizer, the desired range of the branching coefficient tg δ (1200%) of about 4.7 to about 5.3 cannot be achieved, and therefore, processability of the rubber composition and distribution of the filler in such a polymer are poor.
The technical solution according to the present invention therefore allows to produce branched polydienes characterized by a mooney viscosity of from about 40MU to about 49MU and a branching coefficient as characterized by a mechanical loss tangent tg δ (1200%) of from about 4.7 to about 5.3. The polydienes prepared according to the present invention have improved processability, improved distribution of filler in the polymer matrix, and rubber compositions based on the polydienes are characterized by improved elastic-hysteresis properties (i.e., mooney viscosity ML (1+4), MU, payne effect Δ (G '1% -G' 50%), kPa, tg δ at 10% deformation at 60 ℃).

Claims (17)

1. A process for producing a branched polydiene by polymerization of a conjugated diene, comprising:
preparing a catalyst composite comprising a lanthanide compound, an organoaluminum compound, a conjugated diene, and a halogen-containing component;
polymerizing the conjugated diene in the presence of the catalyst composite;
post-polymerization modification with at least one branching agent selected from halogen-containing compounds, phosphorus-nitrogen compounds, or mixtures thereof;
terminating;
introducing at least one plasticizer to the polymer, wherein the plasticizer is a low molecular weight polymer having a molecular weight of from 1500g/mol to 5000 g/mol;
the polymer is degassed and dried.
2. The method of claim 1, wherein the branching agent is a halogen-containing compound selected from the group consisting of: thionyl chloride, diphenyltin dichloride, phenyltin trichloride, triphenyltin chloride, dibutyltin dichloride, butyltin trichloride, tin tetrachloride or silicon tetrachloride, preferably tin tetrachloride, methyltin trichloride, ethyltin trichloride, butyltin trichloride or silicon tetrachloride, most preferably tin tetrachloride or silicon tetrachloride.
3. The method according to claim 1, characterized in that the molar ratio of the halogen-containing compound to the lanthanide selected as the branching agent is from 1.0 to 20, preferably from 2.0 to 15; the molar ratio is most preferably 5.0 to 10.0.
4. The method of claim 1, wherein said branching agent is a compound having a repeating unit (-P ═ N-) n The phosphorus-nitrogen compound of chemical structure (la), wherein n is an integer from 3 to 24; preferably, the branching agent is a chlorine-containing phosphorus-nitrogen compound containing 2 to 6 chlorine atoms.
5. Method according to claim 4, characterized in that the branching agent is a chlorine-containing phosphorus-nitrogen compound selected from the group comprising: 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4, 6-triphosphazene; 2,4, 6-trichloro-2, 4, 6-triphenoxy cyclotriphosphazene; 2,2,4,4-tetrachloro-6, 6-dimethylmercaptocyclotriphosphazene or 4,4,6,6-tetrachloro-1,3,5-triaza-2,4, 6-triphosphacylohexane-1, 3,5-triene-2, 2-diamine.
6. Method according to claim 1, characterized in that the dosage of the phosphorus-nitrogen compound selected as the branching agent is 0.5 to 15.0mol per 1mol of lanthanide, preferably 1.0 to 5.0mol per 1mol of lanthanide.
7. Process according to any one of claims 1 to 6, characterized in that the plasticizer is a non-functionalized low molecular weight polybutadiene, a polybutadiene functionalized with maleic anhydride or triethoxysilane, a non-functionalized low molecular weight polyisoprene, or a polyisoprene functionalized with maleic anhydride, preferably a non-functionalized low molecular weight polybutadiene or a polybutadiene functionalized with maleic anhydride or triethoxysilane.
8. The method according to any one of claims 1 to 7, characterized in that the dose of the plasticizer is from 0.5 to 5.0 mass%, preferably from 0.7 to 2.0 mass%, most preferably from 0.8 to 1.5 mass%, based on the polymer.
9. The method according to any one of claims 1 to 8, characterized in that the lanthanide compound in the catalyst composite is neodymium carboxylate or neodymium organophosphate.
10. The method of claim 9, characterized in that the lanthanide compound in the catalyst composite is neodymium neodecanoate, neodymium tris- [ bis (2-ethylhexyl) phosphate ], or a mixture thereof.
11. The process according to any one of claims 1 to 10, characterized in that the organoaluminum compound is a compound selected from the group comprising: trialkylaluminum, triphenylaluminum or dialkylaluminum hydride, alkylaluminum dihydrides, in particular trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-tert-butylaluminum, triphenylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, dihexylaluminum hydride, diisohexylaluminum hydride, dioctylaluminum hydride, diisooctylaluminum hydride, phenylethylaluminum hydride, phenyl-n-propylaluminum hydride, phenylisopropylaluminum hydride, phenyl-n-butylaluminum hydride, phenylisobutylaluminum hydride, benzylethylaluminum hydride, benzyl-n-butylaluminum hydride, benzylisobutylaluminum hydride, and benzylisopropylaluminum hydride, preferably triethylaluminum, triisobutylaluminum hydride, Diisobutylaluminum hydride or mixtures thereof.
12. Process according to any one of claims 1 to 11, characterized in that the conjugated diene is a compound selected from the group comprising: 1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene, piperylene, 2-methyl-3-ethyl-1, 3-butadiene, 3-methyl-1, 3-pentadiene, 2-methyl-3-ethyl-1, 3-pentadiene, 3-methyl-1, 3-pentadiene, 1, 3-hexadiene, 2-methyl-1, 3-hexadiene, 1, 3-heptadiene, 3-methyl-1, 3-heptadiene, 1, 3-octadiene, 3-butyl-1, 3-octadiene, 3, 4-dimethyl-1, 3-hexadiene, 4, 5-diethyl-1, 3-octadiene, phenyl-1, 3-butadiene, 2, 3-diethyl-1, 3-butadiene, 2, 3-di-n-propyl-1, 3-butadiene, and 2-methyl-3-isopropyl-1, 3-butadiene, with 1, 3-butadiene and isoprene being preferred.
13. The process according to any one of claims 1 to 12, characterized in that the catalyst composite for polymerization comprises a lanthanide compound (a), a conjugated diene (B), an organoaluminum compound (C) and a halogen-containing component (D) in a molar ratio of (a) to (B) to (C) to (D) of 1 (5 to 30) to (8 to 30) to (1.5 to 3.0), wherein the molar amount of the lanthanide compound (a) is calculated on the molar amount of the lanthanide.
14. A branched polydiene prepared by the method of any one of claims 1 to 13.
15. A branched polydiene, characterized by a mooney viscosity of 40 to 49 mooney units, and a branching coefficient expressed as a mechanical loss tangent tg δ (1200%) of 4.7 to 5.3, measured using a variable shear amplitude in the amplitude range of 10% to 1200%, a frequency of 0.1Hz, and a temperature of 100 ℃.
16. A branched polydiene according to claim 14 or claim 15, characterized by a payne effect Δ (G '1% -G' 50%), Tan δ at 60 ℃ 10% deformation.
17. A rubber mixture based on the polydiene according to any one of claims 14 to 16.
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