WO2014088092A1 - 末端ボリン酸基変性ポリマー、その製造法およびそれを含有するゴム組成物 - Google Patents
末端ボリン酸基変性ポリマー、その製造法およびそれを含有するゴム組成物 Download PDFInfo
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- WO2014088092A1 WO2014088092A1 PCT/JP2013/082811 JP2013082811W WO2014088092A1 WO 2014088092 A1 WO2014088092 A1 WO 2014088092A1 JP 2013082811 W JP2013082811 W JP 2013082811W WO 2014088092 A1 WO2014088092 A1 WO 2014088092A1
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- WIPO (PCT)
- Prior art keywords
- terminal
- acid group
- borinic acid
- modified polymer
- rubber composition
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Classifications
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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
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0025—Compositions of the sidewalls
-
- 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
Definitions
- the present invention relates to a terminal borinic acid group-modified polymer, a production method thereof, and a rubber composition containing the same. More particularly, the present invention relates to a terminal borinic acid group-modified polymer that improves the dispersibility of silica used as a compounding agent for a composition for automobile pneumatic tires, a method for producing the same, and a rubber composition containing the same.
- silica is compounded as a reinforcing filler in a tire rubber composition.
- the dispersibility of silica in the composition is low, and even if a large amount of silica can be added, there is a problem that the effect cannot be sufficiently exhibited. It is done.
- Patent Document 1 discloses an elastomer / filling that is useful as a tire component and the like, in which a reinforcing filler is uniformly dispersed by forming the reinforcing filler in the elastomer host material in situ from its precursor.
- a method for producing a composite material is described, and in order to composite silica as a filler, a reaction from a filler precursor is required.
- Patent Document 2 also discloses p-boronic acid ester of aniline as a functionalizing agent useful for functionalizing rubbery and living polymers with fillers such as carbon black and silica. Reaction products with carbonyl compounds such as aldehydes and ketones are used. In this case, the terminal structure to be introduced is limited.
- Patent Documents 3 to 4 an olefinic double bond of a styrene-hydrogenated diene block copolymer is added with a boron-containing group that can be converted into a boronic acid group or a boronic acid group in the presence of water. Describes a modified polymer that is introduced into the side chain of the block copolymer and used as a compatibility modifier and an adhesion-imparting agent.
- Patent Documents 3 to 4 modification of the polymer is carried out.
- an anionic polymerization initiator such as n-butyllithium or sec-butyllithium is used to form a boronic acid ester.
- a vinyl polymer or a diene polymer having a functional group comprising a polyhydric alcohol ester of boronic acid is obtained by performing a polymerization reaction of styrene in the presence.
- As the monohydric alcohol ester 3-mercaptopropylboronic acid ethylene glycol ester is added and used from the beginning of the polymerization reaction. It is stated that the obtained polymer does not increase in viscosity when melt-kneaded with a thermoplastic resin having a hydroxyl group, particularly EVA, exhibits stable melting behavior and is also useful as a compatibility improver. .
- a terminal boric acid group-modified polymer comprising at least one polymer of a styrene monomer and a diene monomer having a borinic acid group at least at the molecular end.
- a terminal boronic acid group-modified polymer is obtained by polymerizing at least one of a styrene monomer and a diene monomer in the presence of an anionic polymerization initiator, and then adding a cyclic boronic acid anhydride to stop the polymerization reaction.
- the modified polymer produced and obtained is used by blending with a diene rubber.
- a borinic acid group, which is a functional group on the benzene ring, can be easily introduced at the molecular end.
- the dispersibility of the silica compounded in the rubber composition is improved.
- This rubber composition for tires is suitably used for molding cap tread portions, side tread portions and the like of pneumatic tires.
- the terminal borinic acid group-modified polymer is prepared by allowing at least one of styrene monomer, diene and diene monomer to undergo a polymerization reaction in the presence of an anionic polymerization initiator, and then adding a cyclic boronic acid anhydride to stop the polymerization reaction. Manufactured by.
- styrene monomer styrene, ⁇ -methylstyrene, p-methylstyrene and the like are used, and as the diene monomer, 1,3-butadiene, isoprene, chloroprene and the like are used, preferably 1,3-butadiene and isoprene. More preferably, 1,3-butadiene is used.
- 1,3-butadiene preferably 1,3-butadiene and isoprene. More preferably, 1,3-butadiene is used.
- the copolymer is generally a random copolymer, but it may be a block copolymer.
- the polymerization reaction is performed in the presence of an anionic polymerization initiator such as n-butyllithium or sec-butyllithium.
- the amount of the anionic polymerization initiator is used in a proportion of about 0.0001 to 5 mol%, preferably about 0.0005 to 0.5 mol%, relative to the molar amount of the monomer (mixture) used.
- 2,2-ditetrahydrofurylpropane, N, N, N ′ used in a proportion of about 10 to 300 mol%, preferably about 50 to 200 mol%, relative to the molar amount of initiator used.
- N'-tetramethylethylenediamine and the like are added. These compounds act as a randomizer in an anion initiator and a growth species activator or copolymerization when a nonpolar solvent such as cyclohexane or methylcyclohexane is used in the polymerization reaction.
- the polymerization reaction is carried out using a hydrocarbon solvent such as cyclohexane, methylcyclohexane, toluene, tetrahydrofuran and the like at about -100 to 100 ° C., generally at room temperature to 70 ° C. for about 1 minute to 5 hours.
- a cyclic boronic acid anhydride such as phenyl boronic acid anhydride or its p-methyl or p-fluoro substituted product is added to the polymerization reaction system to stop the polymerization reaction.
- the amount of cyclic boronic anhydride is sufficient to introduce the end groups of the resulting polymer, for example, about 100-1000 mol%, preferably about 100-400 mol, based on the molar amount of anionic initiator used. % Is used.
- the cyclic boronic acid anhydride forms a borinic acid group (RR′BOH group) at least at the polymer molecule end.
- RR′BOH group borinic acid group
- the reaction is carried out as follows: To form a modified polymer having terminal borinic acid groups with-[B (R 1 ) O] n-linkages (n: 0-50).
- the obtained terminal borinic acid-modified polymer has a number average molecular weight Mn of 1,000 to 10,000,000, generally 3,000 to 1,000,000.
- the obtained terminal boric acid-modified polymer is blended with a diene rubber, particularly a silica-containing diene rubber.
- the terminal borinic acid-modified polymer is used in a proportion of 0.1 to 30 parts by mass, preferably 1 to 10 parts by mass in 100 parts by mass of the total amount with the diene rubber. If the proportion of the terminal borinic acid-modified polymer is used less than this, the desired modification effect cannot be obtained, whereas if it is used in a proportion higher than this, the processability of the unvulcanized rubber is lowered.
- Diene rubbers include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), chloroprene rubber (CR), butyl rubber (IIR), nitrile rubber (NBR), styrene butadiene rubber (SBR), etc. Or as a blend rubber, preferably NR, BR or a blend rubber thereof.
- SBR either emulsion polymerization SBR (E-SBR) or solution polymerization SBR (S-SBR) can be used.
- the diene rubber composition 10 to 150 parts by mass, preferably 30 to 130 parts by mass of silica or both silica and carbon black are added per 100 parts by mass of the terminal borinic acid-modified polymer-containing diene rubber. . Addition of these fillers, particularly silica, reduces rolling resistance and the like, but when used in a proportion higher than this, conversely deteriorates rolling resistance and the like.
- Silica having a BET specific surface area (according to ASTM D1993-03) of 70 to 200 m 2 / g, preferably 70 to 190 m 2 / g is used.
- These include dry process silica manufactured by pyrolysis of silicon halides or organosilicon compounds, and wet process silica manufactured by decomposition of sodium silicate with acid. Therefore, wet method silica is preferably used.
- a commercial product marketed for the rubber industry can be used as it is.
- Silane coupling agent is added in an amount of 1 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the diene rubber containing the terminal borinic acid-modified polymer.
- furnace black such as SAF, ISAF, HAF, FEF, GPF, SRF is generally used.
- compounding agents generally used as rubber compounding agents for example, reinforcing agents or fillers such as talc, clay, graphite, calcium silicate, processing aids such as stearic acid, zinc oxide, softening agents, A plasticizer, an antiaging agent, and the like are appropriately blended and used as necessary.
- reinforcing agents or fillers such as talc, clay, graphite, calcium silicate, processing aids such as stearic acid, zinc oxide, softening agents, A plasticizer, an antiaging agent, and the like are appropriately blended and used as necessary.
- Preparation of the composition is carried out by kneading by a general method using a kneader such as a kneader, a Banbury mixer or a mixer and an open roll, and the obtained composition is molded into a predetermined shape,
- the rubber is vulcanized at a vulcanization temperature corresponding to the type of diene rubber, vulcanizing agent and vulcanization accelerator used and the blending ratio thereof to form a tread portion of a pneumatic tire.
- Example 1 In a two-necked flask with a volume of 100 ml, Cyclohexane (Kanto Chemicals) 7ml 2,2-ditetrahydrofurylpropane 0.243 g (1.32 mmol) (Tokyo Chemical Products) n-BuLi hexane solution 2ml (3.14mmol) (Kanto Chemicals; concentration 1.57 mol / L) was charged at room temperature, and 5.59 g (53.7 mmol) of styrene (Kanto Chemical) was added to the solution. Was added dropwise at 0 ° C. and stirred at room temperature for 3 hours. afterwards, Phenylboronic acid anhydride (Hokuko Chemical) 1.55 g (4.97 mmol) Of 10 ml of tetrahydrofuran (Kanto Chemicals) was added to stop the polymerization reaction.
- Phenylboronic acid anhydride Hokuko Chemical
- Mn 4510 Mn (number average molecular weight) is measured by SEC (size exclusion chromatography), and the value is estimated as the molecular weight in terms of polystyrene.
- PDI 1.2 PDI (polydispersity) is calculated as Mw / Mn using Mw (weight average molecular weight) measured by SEC and Mn. The closer the PDI value is to 1, the more the polymer whose molecular weight distribution is controlled. It shows that it was obtained Rf: 0.58 The Rf value was measured by TLC (thin layer chromatography) on a silica plate, and the smaller the value, the higher the affinity with silica.
- Example 2 In Example 1, the amount of 2,2-ditetrahydrofurylpropane was changed to 0.245 g (1.33 mmol), the amount of styrene was changed to 5.66 g (54.3 mmol), and p-methylphenyl instead of phenylboronic anhydride. Boronic acid anhydride (Hokuko Chemical Co., Ltd.) 1.89 g (5.34 mmol), white solid, product having terminal-B (p-CH 3 C 6 H 4 ) OH group (terminal modified polystyrene) 5.21 g (Yield 92%) was obtained.
- Boronic acid anhydride Hokuko Chemical Co., Ltd.
- Example 3 In Example 1, the amount of 2,2-ditetrahydrofurylpropane was changed to 0.245 g (1.33 mmol), the amount of styrene was changed to 5.70 g (54.7 mmol), and p-fluorophenyl was substituted for phenylboronic anhydride. 1.64 g (4.48 mmol) of boronic acid anhydride (Hokuko Chemical Co., Ltd.) was used, white solid, 5.19 g of product (terminal-modified polystyrene) having terminal-B (p-FC 6 H 4 ) OH groups (end-modified polystyrene) 91%).
- boronic acid anhydride Hokuko Chemical Co., Ltd.
- Example 4 In Example 1, the amount of 2,2-ditetrahydrofurylpropane was 0.218 g (1.18 mmol) and the amount of n-BuLi in n-hexane (concentration 1.50 mol / L) was 1 ml (1.50 mmol). The amount of anhydride was changed to 0.949 g (3.04 mmol), respectively, and 16.8 g (46.6 mmol) of a 15 wt% n-hexane solution of 1,3-butadiene was used instead of styrene. 2.11 g (84% yield) of a product having C 6 H 5 ) OH groups (end-modified polybutadiene) was obtained.
- Example 5 In Example 4, the amount of 2,2-ditetrahydrofurylpropane was 0.208 g (1.13 mmol), the amount of n-BuLi was 2 ml (3.00 mmol), and the amount of 1,3-butadiene in n-hexane was 16.4 g ( 45.5 mmol), and 1.93 g (5.45 mmol) of p-methylphenylboronic anhydride was used in place of phenylboronic anhydride, and was a colorless viscous liquid, terminal -B (p-CH 3 C 6 2.24 g (yield 91%) of a product having H 4 ) OH groups (end-modified polybutadiene) was obtained.
- Example 6 In Example 4, the amount of 2,2-ditetrahydrofurylpropane was changed to 0.283 g (1.53 mmol), the amount of 1,3-butadiene in n-hexane was changed to 16.6 g (46.0 mmol), and phenylboronic acid Using 0.880 g (2.41 mmol) of p-fluorophenylboronic acid anhydride instead of anhydride, a colorless viscous liquid product having terminal-B (p-FC 6 H 4 ) OH groups (terminal-modified polybutadiene) 2.19 g (88% yield) was obtained.
- Example 7 In Example 1, the amount of 2,2-ditetrahydrofurylpropane was 0.218 g (1.18 mmol) and the amount of n-BuLi in n-hexane (concentration 1.50 mol / L) was 1 ml (1.50 mmol).
- the amount of anhydride was changed to 0.743 g (2.48 mmol), respectively, and instead of styrene alone, a mixture of 13.3 g (36.9 mmol) of a 15 wt% n-hexane solution of 1,3-butadiene and 3.23 g (31.0 mmol) of styrene was used to obtain 4.45 g (yield 85%) of a product (terminal-modified polystyrene-butadiene) having a terminal-B (C 6 H 5 ) OH group in the form of a colorless viscous liquid.
- Example 8 In Example 7, the amount of 2,2-ditetrahydrofurylpropane was 0.223 g (1.21 mmol), the amount of 1,3-butadiene in a 15 wt% n-hexane solution and the amount of styrene were 13.6 g (37.7 mmol) and 3.43 g.
- Example 9 In Example 7, the amount of 2,2-ditetrahydrofurylpropane was 0.283 g (1.53 mmol), the amount of 1,3-butadiene in 15 wt% n-hexane and the amount of styrene were 14.6 g (40.4 mmol) and 3.52 g.
- Comparative Example 7 (standard example) Among the above components, the components other than the vulcanization accelerator and sulfur are kneaded for 5 minutes in a 1.7 L closed Banbury mixer, the kneaded product is discharged out of the mixer and cooled to room temperature, and then the same Banbury mixer. Was used to mix the vulcanization accelerator and sulfur. The obtained unvulcanized rubber composition was press vulcanized at 150 ° C. for 30 minutes to obtain a vulcanized rubber. The following items were measured for the unvulcanized rubber composition and the vulcanized rubber.
- RPA GCSWEEPSTD
- Unvulcanized rubber was vulcanized at 160 ° C for 20 minutes, and the resulting vulcanized rubber was used with RPA2000 (strain shear stress measuring machine manufactured by ⁇ -Technology Co.) according to ASTM D6204.
- the numerical value of the Payne effect is an index based on Comparative Example 7, and the index is preferably less than 100, and the smaller the index, the better the reduction or suppression of the Payne effect (the better the dispersibility of the silane)
- Hardness (20 ° C) Conforms to JIS K 6253: 2006 corresponding to ISO 48. This hardness (20 ° C) is expressed as an index with Comparative Example 7 as 100. The larger this index, the higher the hardness and the steering stability.
- Fully automatic tension test JIS K 6251/6301: 2006 compatible with ISO 48
- Comparative Example 8 Reference Example In Comparative Example 7, instead of 110.00 parts by mass of SBR (Asahi Kasei E581), unmodified synthetic SBR (stopped with methanol; Comparative Example 8) or B-terminal SBR (stopped with phenylboronic acid anhydride; Reference Example) 80.00 parts by mass were used, and 30.00 parts by mass of process oil was further added.
- Comparative Examples 7 to 8 and the Reference Example are shown in Table 3 below.
- 80.00 parts by mass was used for confirming the effect of phenylboronic anhydride-terminated SBR, and a rubber composition having high hardness, high elongation, and high vulcanization pain effect was obtained. confirmed.
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Abstract
Description
(RO)3Si(CH2)3-(S)n-(CH2)3Si(OR)3
R:炭素数1~2のアルキル基
n:1~4の整数
例えばビス(3-トリエトキシシリルプロピル)テトラスルフィド、ビス(2-トリエトキシシリルエチル)テトラスルフィド、ビス(3-トリメトキシシリルプロピル)テトラスルフィド、ビス(3-トリエトキシシリルプロピル)ジスルフィド等が好んで用いられる。
容量100mlの二口フラスコ中に、
シクロヘキサン(関東化学製品) 7ml
2,2-ジテトラヒドロフリルプロパン 0.243g(1.32ミリモル)
(東京化成製品)
n-BuLiヘキサン溶液 2ml(3.14ミリモル)
(関東化学製品;濃度1.57モル/L)
を室温条件下で仕込み、その溶液に
スチレン(関東化学製品) 5.59g(53.7ミリモル)
を0℃で滴下し、室温条件下で3時間攪拌した。その後、
フェニルボロン酸無水物(北興化学工業製品) 1.55g(4.97ミリモル)
のテトラヒドロフラン(関東化学製品)10mlの溶液を加え、重合反応を停止させた。
Mn:4510
Mn(数平均分子量)は、SEC(サイズ排除型クロマトグラフィー)で測定し、その値はポリスチレン換算の分子量として見積もられている
PDI:1.2
PDI(多分散度)は、SECで測定したMw(重量平均分子量)とMnの値を用いてMw/Mnとして計算しており、そのPDIの値が1に近いほど分子量分布を制御したポリマーが得られたことを示している
Rf:0.58
Rf値は、シリカプレートのTLC(薄層クロマトグラフィー)で測定し、その値が小さいほどシリカとの親和性が高いことを示している
1H-NMR(CDCl3、20℃):δ=7.8(br)
7.5~7.4(br)
7.4~6.9(br)
6.9~6.7(br)
6.7~6.2(br)
2.3~2.0(br)
2.0~1.2(br)
1.2~0.9(br)
0.8~0.7(br)
実施例1において、2,2-ジテトラヒドロフリルプロパン量を0.245g(1.33ミリモル)に、スチレン量を5.66g(54.3ミリモル)にそれぞれ変更し、またフェニルボロン酸無水物の代わりにp-メチルフェニルボロン酸無水物(北興化学工業製品)1.89g(5.34ミリモル)を用い、白色固体状で、末端-B(p-CH3C6H4)OH基を有する生成物(末端変性ポリスチレン)5.21g(収率92%)を得た。
Mn:3590
PDI:1.2
Rf:0.65
1H-NMR(CDCl3、20℃):δ=7.6(br)
7.4~6.9(br)
6.9~6.7(br)
6.7~6.2(br)
2.3~2.0(br)
2.0~1.2(br)
1.2~0.9(br)
0.8~0.7(br)
実施例1において、2,2-ジテトラヒドロフリルプロパン量を0.245g(1.33ミリモル)に、スチレン量を5.70g(54.7ミリモル)にそれぞれ変更し、またフェニルボロン酸無水物の代わりにp-フルオロフェニルボロン酸無水物(北興化学工業製品)1.64g(4.48ミリモル)を用い、白色固体状で、末端-B(p-FC6H4)OH基を有する生成物(末端変性ポリスチレン)5.19g(収率91%)を得た。
Mn:3370
PDI:1.2
Rf:0.76
1H-NMR(CDCl3、20℃):δ=7.9(br)
7.5(br)
7.4~6.9(br)
6.9~6.7(br)
6.7~6.2(br)
2.3~2.0(br)
2.0~1.2(br)
1.2~0.9(br)
0.8~0.7(br)
実施例1において、2,2-ジテトラヒドロフリルプロパン量を0.218g(1.18ミリモル)に、n-BuLiのn-ヘキサン溶液(濃度1.50モル/L)量を1ml(1.50ミリモル)に、フェニルボロン酸無水物量を0.949g(3.04ミリモル)にそれぞれ変更し、またスチレンの代わりに1,3-ブタジエンの15重量%n-ヘキサン溶液16.8g(46.6ミリモル)を用い、無色粘性液体で、末端-B(C6H5)OH基を有する生成物(末端変性ポリブタジエン)を2.11g(収率84%)を得た。
Mn:9890
PDI:1.0
Rf:0.71
1H-NMR(CDCl3、20℃):δ=7.8(br)
7.5~7.4(br)
5.9~5.3(br)
5.1~4.8(br)
2.7~1.8(br)
1.8~0.9(br)
0.8~0.7(br)
実施例4において、2,2-ジテトラヒドロフリルプロパン量を0.208g(1.13ミリモル)に、n-BuLi量を2ml(3.00ミリモル)に、1,3-ブタジエンのn-ヘキサン溶液量を16.4g(45.5ミリモル)にそれぞれ変更し、またフェニルボロン酸無水物の代わりにp-メチルフェニルボロン酸無水物1.93g(5.45ミリモル)を用い、無色粘性液体状で、末端-B(p-CH3C6H4)OH基を有する生成物(末端変性ポリブタジエン)を2.24g(収率91%)得た。
Mn:5620
PDI:1.1
Rf:0.76
1H-NMR(CDCl3、20℃):δ=7.6(br)
7.4(br)
5.9~5.3(br)
5.1~4.7(br)
2.8~1.8(br)
1.7~0.9(br)
0.9~0.7(br)
実施例4において、2,2-ジテトラヒドロフリルプロパン量を0.283g(1.53ミリモル)に、1,3-ブタジエンのn-ヘキサン溶液量を16.6g(46.0ミリモル)にそれぞれ変更し、またフェニルボロン酸無水物の代わりにp-フルオロフェニルボロン酸無水物0.880g(2.41ミリモル)を用い、無色粘性液体状で、末端-B(p-FC6H4)OH基を有する生成物(末端変性ポリブタジエン)を2.19g(収率88%)得た。
Mn:3380
PDI:1.1
Rf:0.70
1H-NMR(CDCl3、20℃):δ=7.9(br)
7.5(br)
5.8~5.2(br)
5.1~4.8(br)
2.9~1.7(br)
1.7~0.8(br)
0.8~0.7(br)
実施例1において、2,2-ジテトラヒドロフリルプロパン量を0.218g(1.18ミリモル)に、n-BuLiのn-ヘキサン溶液(濃度1.50モル/L)量を1ml(1.50ミリモル)に、フェニルボロン酸無水物量を0.743g(2.48ミリモル)にそれぞれ変更し、またスチレン単体の代わりに1,3-ブタジエンの15重量%n-ヘキサン溶液13.3g(36.9ミリモル)とスチレン3.23g(31.0ミリモル)との混合物を用い、無色粘性液体状で、末端-B(C6H5)OH基を有する生成物(末端変性ポリスチレン-ブタジエン)4.45g(収率85%)を得た。
Mn:11800
PDI:1.0
Rf:0.75
1H-NMR(CDCl3、20℃):δ=7.7(br)
7.5~7.4(br)
7.2~6.2(br)
5.7~4.4(br)
2.8~0.7(br)
実施例7において、2,2-ジテトラヒドロフリルプロパン量を0.223g(1.21ミリモル)に、1,3-ブタジエンの15重量%n-ヘキサン溶液量とスチレン量を13.6g(37.7ミリモル)と3.43g(32.9ミリモル)にそれぞれ変更し、またフェニルボロン酸無水物の代わりにp-メチルフェニルボロン酸無水物0.754g(2.13ミリモル)を用い、無色粘性液体状で、末端-B(p-CH3C6H4)OH基を有する生成物(末端変性ポリスチレン-ブタジエン)4.81g(収率88%)を得た。
Mn:13800
PDI:1.0
Rf:0.68
1H-NMR(CDCl3、20℃):δ=7.6(br)
7.3(br)
7.2~6.2(br)
5.7~4.4(br)
2.8~0.7(br)
実施例7において、2,2-ジテトラヒドロフリルプロパン量を0.283g(1.53ミリモル)に、1,3-ブタジエンの15重量%n-ヘキサン溶液量とスチレン量を14.6g(40.4ミリモル)と3.52g(33.8ミリモル)にそれぞれ変更し、またフェニルボロン酸無水物の代わりにp-フルオロフェニルボロン酸無水物0.878g(2.40ミリモル)を用い、無色粘性液体状で、末端-B(p-FC6H4)OH基を有する生成物(末端変性ポリスチレン-ブタジエン)5.14g(収率90%)を得た。
Mn:6260
PDI:1.1
Rf:0.77
1H-NMR(CDCl3、20℃):δ=7.9(br)
7.5(br)
7.2~6.2(br)
5.7~4.4(br)
2.8~0.7(br)
実施例1~3、実施例4~6および実施例7~9において、各種ボロン酸無水物を用いず、末端基を-H基とした場合(比較例1~3)および各種ボロン酸無水物の代わりにγ-クロロプロピルトリメトキシシラン(6.41ミリモル)を用い、末端基を-(CH2)3Si(OCH3)3(比較例4~6)とした場合の収率、Mn、PDIおよびRfの値は、次の表2に示される。
表2
比較例 収率(%) Mn PDI Rf
1 97 2820 1.1 0.89
2 85 9820 1.0 0.77
3 86 7820 1.1 0.79
4 91 3560 1.1 0.83
5 80 6270 1.1 0.83
6 88 7200 1.2 0.77
以上の各成分の内、加硫促進剤および硫黄を除く各成分を1.7L密閉式バンバリーミキサ中で5分間混練し、混練物を混合機外に放出して室温迄冷却した後、同じバンバリーミキサを用いて、加硫促進剤および硫黄を混合した。得られた未加硫ゴム組成物を150℃で30分間プレス加硫し、加硫ゴムを得た。
未加硫ゴム組成物および加硫ゴムについて、次の各項目の測定を行った。
RPA(GCSWEEPSTD:加硫ペイン効果):
未加硫ゴムを160℃で20分間加硫し、得られた加硫ゴムを用いて、ASTM D6204に準拠してRPA2000(α-テクノロジー社製歪せん断応力測定機)を用いて、歪0.56%の歪せん断応力G′(0.56%)と、歪100%の歪せん断応力G′(100%)を測定し、G′(0.56%)とG′(100%)の差(絶対値)を算出した
ペイン効果の数字は比較例7を基準とする指数であり、指数が100未満であるのが好ましく、指数が小さいほどペイン効果の低減または抑制が良好なこと(シランの分散性が良好であること)を示す
硬度(20℃):ISO 48に対応するJIS K 6253:2006準拠
この硬度(20℃)を比較例7を100とする指数で表す
この指数が大きい程硬度が高く、操縦安定性が良好である
ことを示している
全自動引張り試験:ISO 48に対応するJIS K 6251/6301:2006準拠
全自動引張り(EB)および高温引張り(EB)を比較例7を100
とする指数で表す
この指数が大きい程ゴムの伸びが良いことを示している
比較例7において、SBR(旭化成製品E581)110.00質量部の代りに、未変性合成SBR(メタノールで停止;比較例8)またはB末端SBR(フェニルボロン酸無水物で停止;参考例)80.00質量部を使用し、さらに30.00質量部のプロセスオイルを添加して用いた。
Claims (12)
- 少なくとも分子末端にボリン酸基を有する、スチレンモノマーおよびジエンモノマーの少なくとも一種の重合体よりなる末端ボリン酸基変性ポリマー。
- スチレンモノマーがスチレンまたはその誘導体である請求項1記載の末端ボリン酸基変性ポリマー。
- ジエンモノマーが1,3-ブタジエンまたはイソプレンである請求項1記載の末端ボリン酸基変性ポリマー。
- 数平均分子量Mnが1,000~10,000,000である請求項1記載の末端ボリン酸基変性ポリマー。
- アニオン性重合開始剤の存在下で、スチレンモノマーおよびジエンモノマーの少なくとも一種を重合反応させた後、環状ボロン酸無水物を添加して重合反応を停止させることを特徴とする末端ボリン酸基変性ポリマーの製造法。
- アニオン性重合開始剤がn-ブチルリチウムまたは第2ブチルリチウムである請求項5記載の末端ボリン酸基変性ポリマーの製造法。
- 環状ボロン酸無水物がフェニルボロン酸無水物、そのp-メチルまたはp-フルオロ置換体である請求項5記載の末端ボリン酸基変性ポリマーの製造法。
- 請求項1記載の末端ボリン酸変性ポリマーをジエン系ゴムに配合してなるジエン系ゴム組成物。
- ジエン系ゴムおよび末端ボリン酸変性ポリマーの合計量100質量部中、末端ボリン酸変性ポリマーを0.1~30質量部配合した請求項10記載のジエン系ゴム組成物。
- さらに、シリカ10~150質量部およびシラン系カップリング剤1~20質量部を配合した請求項9記載のジエン系ゴム組成物。
- 空気入りタイヤのキャップトレッド部および/またはサイドトレッド部成形用として用いられる請求項8、9または10記載のジエン系ゴム組成物。
- 請求項11記載のジエン系ゴム組成物から成形されたキャップトレッド部および/またはサイドトレッド部を有する空気入りタイヤ。
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US14/650,069 US20150315324A1 (en) | 2012-12-06 | 2013-12-06 | Terminal borinic acid group-modified polymer, method of manufacturing the same and rubber composition containing the same |
CN201380063784.6A CN105051081A (zh) | 2012-12-06 | 2013-12-06 | 末端硼酸基改性聚合物、其制备方法以及含有该末端硼酸基改性聚合物的橡胶组合物 |
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JP2017160412A (ja) * | 2014-12-19 | 2017-09-14 | ザ・グッドイヤー・タイヤ・アンド・ラバー・カンパニー | ホウ素基を含有する官能化エラストマー |
WO2022044633A1 (ja) | 2020-08-31 | 2022-03-03 | 株式会社クラレ | ホウ素含有官能基を有する変性重合体を含む重合体組成物及びその製造方法 |
WO2022172925A1 (ja) * | 2021-02-12 | 2022-08-18 | 株式会社クラレ | ホウ素含有官能基を有する水添共役ジエン変性重合体を含む水添重合体組成物及びその製造方法 |
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US11492426B2 (en) | 2020-08-07 | 2022-11-08 | The Goodyear Tire & Rubber Company | Functionalized polymer, rubber composition and pneumatic tire |
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- 2013-12-06 WO PCT/JP2013/082811 patent/WO2014088092A1/ja active Application Filing
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- 2013-12-06 DE DE112013005848.0T patent/DE112013005848T5/de not_active Withdrawn
- 2013-12-06 CN CN201380063784.6A patent/CN105051081A/zh active Pending
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JP2000095817A (ja) * | 1999-11-01 | 2000-04-04 | Kuraray Co Ltd | 反応性オレフィン系重合体 |
JP2006176788A (ja) * | 2001-02-01 | 2006-07-06 | Kuraray Co Ltd | ブロック共重合体および熱可塑性樹脂組成物 |
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JP2017160412A (ja) * | 2014-12-19 | 2017-09-14 | ザ・グッドイヤー・タイヤ・アンド・ラバー・カンパニー | ホウ素基を含有する官能化エラストマー |
WO2022044633A1 (ja) | 2020-08-31 | 2022-03-03 | 株式会社クラレ | ホウ素含有官能基を有する変性重合体を含む重合体組成物及びその製造方法 |
WO2022172925A1 (ja) * | 2021-02-12 | 2022-08-18 | 株式会社クラレ | ホウ素含有官能基を有する水添共役ジエン変性重合体を含む水添重合体組成物及びその製造方法 |
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