KR20210023677A - Modified polyisobutylene elastomers for rubber compounding, and rubber composition comprising the same - Google Patents

Abstract

The present invention relates to a modified polyisobutylene polymer for rubber compounding including polyisobutylene having isobutylene as a main chain, unsaturated dicarboxylic anhydride, and a silane compound, and more particularly, 20 to 80 wt% of polyisobutylene having isobutylene as a main chain, 1 to 20 wt% of unsaturated dicarboxylic anhydride, and 1 to 60 wt% of a silane compound. In particular, when the polyisobutylene polymer of the present invention is used as an additive for rubber, the dispersibility of a filler can be significantly increased and both grip performance and rolling resistance can be improved.

Description

Modified polyisobutylene elastomers for rubber compounding, and rubber composition comprising the same}

The present invention relates to a modified polyisobutylene polymer for rubber blending and a rubber composition comprising the same.

Polyisobutylene (polybutene) is a polymerization of an olefin component having 4 (C4) carbon atoms, which is generally derived from the decomposition process of naphtha, using a Friedel-Craft type catalyst, and has a number average molecular weight ( Mn) is about 300 to 10,000.

Among the C4 raw materials, 1,3-butadiene is extracted and the remainder is called C4 raffinate-1, which includes iso-butane and normal-butane paraffins and 1- Olefins such as 1-butene, 2-butene, and isobutene are included, and the content of isobutene is approximately 30 to 50% by weight. The C4 residue-1 is mainly used in the production of methyl-t-butylether (MTBE) or polyisobutylene (polybutene), which is an octane number improving agent, and iso part of the olefin component of C4 residue-1 Since tens have the highest reactivity, the resulting polyisobutylene (polybutene) is mainly composed of isobutene units. Polyisobutylene (polybutene) increases in viscosity with an increase in molecular weight, and has a viscosity of about 4 to 40000 cSt (centi-stokes) at 100°C.

In Korean Laid-Open Patent Publication No. 10-2011-0072253, a method of improving the gripping performance of a tire tread using highly reactive polyisobutylene (polybutene) is known. In addition, Korean Laid-Open Patent Publication No. 10-2007-0096748 discloses a method of improving abrasion performance, fuel economy performance, and braking performance by using a carboxylated liquid isoprene rubber. As such, efforts are underway to improve braking performance and fuel economy performance in rubber, especially tire treads.

Regarding the improvement of grip, Korean Patent Laid-Open Publication No. 10-2016-0002044 uses a master batch in which pellet-type plant resins such as sesame resin, sunflower resin, and coconut resin are added to styrene-butadiene rubber under high-speed conditions. A composition that exhibits excellent grip performance and abrasion resistance is proposed. As already mentioned, the grip force is a technology that allows the tire surface to adhere well to the road surface, and it is advantageous that the tire is excellent in elasticity as long as it is possible. However, when considered together with the rolling resistance, the rolling resistance is advantageous as the adhesion to the road surface is lower, so that the rolling resistance and the gripping force of the tire are opposite to each other. That is, a tire having low rolling resistance is advantageous in fuel efficiency, but adhesion with the road may be weak when the road is wet. Accordingly, the recent development of tires is proceeding in a way that tries to control both at the same time, rather than a one-dimensional method of increasing rolling resistance or increasing grip.

For example, Korean Laid-Open Patent Publication No. 10-2015-0024701 and US Patent No. 8,637,606 apply a modified terpene phenol resin having a high softening point together with silica, so that phenol (PHENOL) is compatible with synthetic rubber. It is disclosed that it is possible to improve the grip performance on wet road surfaces without deteriorating the rolling resistance performance by increasing the fluidity of the resin by increasing it. In addition, Korean Patent Registration No. 10-1591276 includes 20 to 50 parts by weight of epoxidized natural rubber having a Tg of -50 to -40°C, a pattern viscosity of 60 to 80°C, and an epoxidation degree of 5 to 50%, A rubber composition capable of improving the braking power of wet road surfaces and improving the durability performance with low rotational resistance performance or fuel economy performance in a balanced manner without deteriorating the wear resistance performance was proposed. Despite these various attempts, there is a need for a technology that simultaneously satisfies the tire's rolling resistance and grip.

Korean Patent Application Publication No. 10-2011-0072253 Republic of Korea Patent Publication No. 10-2007-0096748 Republic of Korea Patent Publication No. 10-2016-0002044 Republic of Korea Patent Publication No. 10-2015-0024701 U.S. Patent No. 8,637,606

It is an object of the present invention to provide a modified polyisobutylene polymer for rubber blending capable of producing a rubber composition having excellent dispersibility when mixed with a filler and excellent in gripping performance and rolling resistance.

The modified polyisobutylene polymer for rubber formulation according to the present invention includes polyisobutylene whose main chain is isobutylene; Unsaturated dicarboxylic anhydride; And a silane compound; may be prepared by mixing.

More specifically, the modified polyisobutylene polymer for rubber blending includes 20 to 80% by weight of polyisobutylene whose main chain is isobutylene; 1 to 20% by weight of unsaturated dicarboxylic anhydride; And 1 to 60% by weight of a silane compound; may be prepared by mixing.

In the modified polyisobutylene polymer for rubber compounding according to an embodiment of the present invention, the polyisobutylene whose main chain is isobutylene has a number average molecular weight of 350 g/mol to 6,000 g/mol. have.

In the modified polyisobutylene polymer for rubber blending according to an embodiment of the present invention, the molecular weight distribution of polyisobutylene whose main chain is isobutylene may be 1 to 5.

In the modified polyisobutylene polymer for rubber formulation according to an embodiment of the present invention, the unsaturated dicarboxylic anhydride is maleic anhydride, itaconic anhydride, citraconic anhydride. ), propenyl succinic anhydride, and 2-pentendioic anhydride.

In the modified polyisobutylene polymer for rubber formulation according to an embodiment of the present invention, the silane compound may contain an amino group.

In the modified polyisobutylene polymer for rubber blending according to an embodiment of the present invention, the silane compound may satisfy Formula 1 below.

[Formula 1]

In formula 1,

R ₁ and R ₂ are each independently selected from (C1-C5)alkylene, (C1-C5)aminoalkylene, carbonylene and (C1-C5)alkylcarbonylene, and are the same as or different from each other;

R ₃ , R ₄ and R ₅ are independently of each other hydrogen, hydroxy, (C1-C20)alkyl, (C1-C12)cycloalkyl, (C2-C14)acyloxy, (C4-C20)aryloxy, (C5 -C30) is selected from aroxy, (C1-C20)amine and (C1-C12)alkoxy, each the same or different;

A is methylene, S _n or ((R ₆ )NR ₇ ) _n , wherein R ₆ is hydrogen or (C1-C5)alkyl, R ₇ is (C1-C5)alkylene, and n is 1-10 Is the integer of

In the modified polyisobutylene polymer for rubber formulation according to an embodiment of the present invention, the silane compound is 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, N-(2-aminoethyl)-3 -Aminopropyl triethoxysilane, 3-aminopropyl methyldiethoxysilane, 3-aminopropyl silanetriol, 3-aminopropyl methyldimethoxysilane, 3-(2-aminoethylamino)propyl dimethoxymethylsilane, 3 -(2-aminoethylamino)propyl trimethoxysilane, 2-ethanediamine N-(2-aminoethyl)-N'-[3-(trimethoxysilyl)propyl]-1, 1-[3-( Trimethoxysilyl)propyl]urea and 1-[3-(triethoxysilyl)propyl)]urea.

The modified polyisobutylene polymer for rubber formulation according to an embodiment of the present invention may be characterized in that it contains nitrogen.

The modified polyisobutylene polymer for rubber formulation according to an embodiment of the present invention may be characterized in that it contains a carbonyl group.

The modified polyisobutylene polymer for rubber formulation according to an embodiment of the present invention may be characterized in that it contains an amide group.

The modified polyisobutylene polymer for rubber formulation according to an embodiment of the present invention may have a Si content of 0.05 to 10% by mass as a result of X-ray fluorescence analysis.

The modified polyisobutylene polymer for rubber formulation according to an embodiment of the present invention may be characterized in that the glass transition temperature is -50°C or less.

In the modified polyisobutylene polymer for rubber blending according to an embodiment of the present invention, the modified polyisobutylene polymer for rubber blending may have a Brookfield viscosity of 5 to 10,000 cP at 150°C.

The modified polyisobutylene polymer for rubber formulation according to an embodiment of the present invention may have a number average molecular weight of 580 to 10,000 g/mol, and a molecular weight distribution of 1 to 5.

The present invention also provides a rubber composition. The rubber composition according to the present invention includes a modified polyisobutylene polymer for rubber blending according to an embodiment of the present invention; Rubber base; And a filler.

In the rubber composition according to an embodiment of the present invention, the filler may include at least one selected from silica and carbon black.

In the rubber composition according to an embodiment of the present invention, the rubber base is butadiene rubber, butyl rubber, emulsion polymerization styrene butadiene rubber (E-SBR), solution polymerization styrene butadiene rubber (S-SBR), epichlorohydrin rubber, nitrile. Rubber, hydrogenated nitrile rubber, brominated polyisobutyl isoprene-co-paramethyl styrene (BIMS) rubber, urethane rubber, fluorine rubber, silicone rubber, styrene ethylene butadiene styrene copolymer rubber, ethylene It may include one or two or more selected from propylene rubber, ethylene propylene diene monomer rubber, hypalon rubber, chloroprene rubber, ethylene vinyl acetate rubber, and acrylic rubber.

The rubber composition according to an embodiment of the present invention includes 50 to 150 parts by weight of silica, 5 to 20 parts by weight of carbon black, 2 to 40 parts by weight of a modified polyisobutylene polymer for rubber blending, and 2 to 15 parts by weight based on 100 parts by weight of the rubber base. It may contain parts by weight of a silane coupling agent.

The present invention also provides a tire tread, and the tire tread according to the present invention may include a rubber composition according to an embodiment of the present invention.

The modified polyisobutylene polymer for rubber formulation according to the present invention includes polyisobutylene whose main chain is isobutylene; Unsaturated dicarboxylic anhydride; And a silane compound; characterized in that it is produced by mixing, and when applied to the rubber composition, the dispersibility of the filler is improved, and the braking performance and rolling resistance performance are simultaneously improved, thereby exhibiting high grip performance and low rolling resistance. .

Advantages and features of the embodiments of the present invention, and a method of achieving them will be apparent with reference to the embodiments described below in detail. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in a variety of different forms, and only these embodiments make the disclosure of the present invention complete, and are common knowledge in the technical field to which the present invention pertains. It is provided to completely inform the scope of the invention to those who have, and the invention is only defined by the scope of the claims. The same reference numerals refer to the same elements throughout the specification.

In describing the embodiments of the present invention, if it is determined that a detailed description of a known function or configuration may unnecessarily obscure the subject matter of the present invention, a detailed description thereof will be omitted. In addition, terms to be described later are terms defined in consideration of functions in an embodiment of the present invention, which may vary according to the intention or custom of users or operators. Therefore, the definition should be made based on the contents throughout the present specification. For example, polyisobutylene may be referred to as polybutene.

The modified polyisobutylene polymer for rubber formulation according to the present invention includes polyisobutylene whose main chain is isobutylene; Unsaturated dicarboxylic anhydride; And a silane compound; may be prepared by mixing.

More specifically, the modified polyisobutylene polymer for rubber formulation according to the present invention includes 20 to 80% by weight of polyisobutylene whose main chain is isobutylene; 1 to 20% by weight of unsaturated dicarboxylic anhydride; And 1 to 60% by weight of a silane compound; may be prepared by mixing. The prepared modified polyisobutylene polymer may have a Si content of 0.05 to 10% by mass as a result of analysis through X-ray fluorescence analysis (XRF), and more preferably 0.5 to 5% by mass. When each component is mixed to satisfy the above content range to prepare a modified polyisobutylene polymer, and mixed with a rubber base and a filler to prepare a rubber composition, the dispersibility of the filler in the rubber composition can be improved.

The modified polyisobutylene polymer according to an embodiment of the present invention may have a glass transition temperature of -50°C or less, preferably -60 to -100°C, and more preferably -65 to -90°C. In addition, the modified polyisobutylene polymer may have a viscosity of 5 to 10,000 cP as measured by a Brookfield viscometer at 150° C., and more preferably 50 to 5,000 cP. By satisfying the above-described glass transition temperature and viscosity range, the difference (ΔG') of the storage modulus due to the Payne effect when mixing with the rubber base and the filler later is 2.4 or less, preferably 2.1 or less. It can be confirmed, and based on this, it can be confirmed that the filler is evenly distributed. In this case, ΔG' means the difference between the storage modulus _G'20% -G' _0.02% measured when the elongation is 0.02% and 20%.

The modified polyisobutylene polymer according to an embodiment of the present invention may have a number average molecular weight of 580 to 10,000 g/mol, and a molecular weight distribution of 1 to 5. When preparing a rubber composition by mixing a modified polyisobutylene polymer satisfying the molecular weight and molecular weight distribution with a rubber base and a filler, the grip performance and rolling resistance performance are simultaneously improved. 0.25 or more, and the dynamic loss factor based on 60° C. may be less than 0.094. More preferably, the number average molecular weight may be 900 to 3,000 g/mol, and the molecular weight distribution may be 1 to 3, and the dynamic loss factor based on 0°C of the manufactured rubber may be 0.27 or more, and the dynamic loss factor based on 60°C may be 0.090 or less. . At this time, the dynamic loss coefficient based on 0℃ may be an index indicating wet grip, and the higher the dynamic loss coefficient based on 0℃ means that the grip performance is excellent, and the dynamic loss coefficient based on 60℃ is rolling resistance. Resistance), and the lower the value, the better the rolling resistance. That is, according to the present invention, when a modified polyisobutylene polymer having a number average molecular weight of 580 to 10,000 g/mol and a molecular weight distribution of 1 to 5 is added to the rubber composition, braking performance and rolling property are simultaneously improved. It can improve performance.

Meanwhile, for preparing a modified polyisobutylene polymer according to an embodiment of the present invention, polyisobutylene whose main chain is isobutylene has a number average molecular weight of 350 g/mol to 6,000 g/mol, preferably 700 g/mol to 3,000 g/mol, molecular weight distribution may be 1 to 5, preferably 1 to 3. The viscosity of the polyisobutylene may be 2 cSt to 10,000 cSt, preferably 100 cSt to 2,000 cSt at 100°C.

In addition, the polyisobutylene according to an embodiment of the present invention may have a terminal vinylidene (α-vinylidene) content of 80 mol% or more, more preferably 85 mol% or more, based on ^{13 C-NMR.} When the terminal vinylidene content is less than 80 mol%, even if the prepared modified polyisobutylene polymer is mixed with the rubber composition, both the grip performance and the rolling performance improvement effect of the prepared rubber may be insignificant. At this time, the upper limit of the terminal vinylidene content is not particularly limited, and may be, for example, 99 mol% or less, more specifically 95 mol% or less.

The silane compound according to an embodiment of the present invention may be characterized by containing an amino group, and more preferably, in the modified polyisobutylene polymer according to an embodiment of the present invention, the silane compound satisfies the following Formula 1 It can be a compound.

[Formula 1]

In formula 1,

R ₁ and R ₂ are each independently selected from (C1-C5)alkylene, (C1-C5)aminoalkylene, carbonylene and (C1-C5)alkylcarbonylene, and are the same as or different from each other;

R ₃ , R ₄ and R ₅ are independently of each other hydrogen, hydroxy, (C1-C20)alkyl, (C1-C12)cycloalkyl, (C2-C14)acyloxy, (C4-C20)aryloxy, (C5 -C30) is selected from aroxy, (C1-C20)amine and (C1-C12)alkoxy, each the same or different;

A is methylene, S _n or ((R ₆ )NR ₇ ) _n , wherein R ₆ is hydrogen or (C1-C5)alkyl, R ₇ is (C1-C5)alkylene, and n is 1-10 Is the integer of

Even more preferably, R ₁ and R ₂ are independently of each other (C1-C3)alkylene;

R ₃ , R ₄ and R ₅ are each independently hydrogen, hydroxy, (C1-C5)alkyl or (C1-C5)alkoxy;

A is methylene, S _n or ((R ₆ )NR ₇ ) _n , wherein R ₆ is hydrogen or (C1-C5)alkyl, R ₇ is (C2-C4)alkylene, and n is 2-5 Is the integer of

When a modified polyisobutylene polymer is prepared by mixing a silane compound satisfying the above range, there is an advantage of further improving the dispersibility of the filler.

As a specific example, the silane compound is specifically the compound is 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, N-(2-aminoethyl)-3-aminopropyl triethoxysilane, 3-amino Propyl methyldiethoxysilane, 3-aminopropyl silanetriol, 3-aminopropyl methyldimethoxysilane, 3-(2-aminoethylamino)propyl dimethoxymethylsilane, 3-(2-aminoethylamino)propyl trime Toxoxysilane, 2-ethanediamine N-(2-aminoethyl)-N'-[3-(trimethoxysilyl)propyl]-1, 1-[3-(trimethoxysilyl)propyl]urea and 1- [3-(triethoxysilyl)propyl)] may be one or two or more selected from urea and the like.

In the modified polyisobutylene polymer according to an embodiment of the present invention, the unsaturated dicarboxylic anhydride is maleic anhydride, itaconic anhydride, citraconic anhydride, pro It may be one or two or more selected from phenyl succinic anhydride and 2-pentendioic anhydride.

Further, the modified polyisobutylene polymer prepared by mixing the polyisobutylene, unsaturated dicarboxylic anhydride, and a silane compound may contain nitrogen, preferably a nitrogen atom bonded by a covalent bond. . In addition, the modified polyisobutylene polymer may include a carbonyl group, more preferably an imide group or an amide group. For example, the amide group may include a pyrrolidine-2,5-dione group.

The present invention also provides a rubber composition.

The rubber composition according to the present invention includes a modified polyisobutylene polymer for rubber blending according to an embodiment of the present invention; Rubber base; And a filler.

As described above, by mixing the modified polyisobutylene polymer, the rubber composition according to an embodiment of the present invention has the advantage that the filler is uniformly dispersed and exhibits excellent grip performance and rolling resistance.

In the rubber composition according to an embodiment of the present invention, the rubber base is butadiene rubber, butyl rubber, emulsion polymerization styrene butadiene rubber (E-SBR), solution polymerization styrene butadiene rubber (S-SBR), epichlorohydrin rubber, nitrile. Rubber, hydrogenated nitrile rubber, brominated polyisobutyl isoprene-co-paramethyl styrene (BIMS) rubber, urethane rubber, fluorine rubber, silicone rubber, styrene ethylene butadiene styrene copolymer rubber, ethylene Propylene rubber, ethylene propylene diene monomer rubber, hypalon rubber, chloroprene rubber, ethylene vinyl acetate rubber, acrylic rubber, etc. may include one or more selected from, and more preferably, the rubber base is butadiene rubber, styrene butadiene rubber And one or two or more selected from butyl rubber and the like.

More preferably, the rubber base may include styrene butadiene rubber, wherein the styrene butadiene rubber has a styrene content of 9 to 19%, a vinyl group content of 10 to 54% of butadiene, and a styrene content of 20 to 28% , It may be used that the vinyl content is 40-72% in butadiene, or the styrene content is 30-42% in butadiene, and the vinyl content is 20-70% in butadiene.

In the rubber composition according to an embodiment of the present invention, the filler may be used without limitation if it is a filler generally used in a rubber composition, more preferably a rubber composition for a tire tread, and the present invention is not limited thereto. As a specific and non-limiting example, the filler may include one or more selected from silica and carbon black.

In this case, the silica may be used without limitation in the case of silica particles used for rubber, preferably rubber for tire tread. Specifically, the silica has a specific surface area (CTAB) of 80 m2/g to 300 m2/g, preferably 110 m2/g to 220 m2/g, more preferably 150 m2/g to 180 m2/g, and the most Preferably it may be 165 m 2 /g. When the specific surface area is lower than the above-described range, the reinforcement property is lowered, resulting in a problem of lowering strength, and when the specific surface area is higher than the above-described range, the viscosity increases and the dispersion is inhibited when the rubber is mixed.

In addition, if the carbon black is also a carbon black commonly used for tire tread rubber, etc., it can be used without limitation, and preferably those having a grade of 500 to 600 may be used. As a specific and non-limiting example, N110, N121, N134, N220, N231, N234, N242, N293, N299, S315, N326, N330, N332, N339, N343, N347, N351, N358, N375, N539, N550, Commercial carbon blacks such as N582, N630, N642, N650, N660, N683, N754, N762, N765, N774, N787, N907, N908, N990 or N991 may be used, and the present invention is not limited thereto.

Furthermore, the rubber composition according to an embodiment of the present invention may further include a silane coupling agent, in which case a commercial product such as Si-69 is used, or bis-(3-triethoxysilylpropyl) -Tetrasulfane (Bis-(3-triethoxysilylpropyl)-tetrasulfane; TESPT), (Bis-(3-ethoxysilylpropyl) disulfane; ESPD), N-[2 (vinylbenzyl) A known material such as amino)-3-aminopropyltrimethoxysilane (N-[2(vinylbenzylamino)-aminopropyltrimethoxysilane) may be used, but the present invention is not limited thereto.

The rubber composition according to an embodiment of the present invention comprises 50 to 150 parts by weight of silica, 5 to 20 parts by weight of carbon black, 2 to 40 parts by weight of modified polyisobutylene polymer and 2 to 15 parts by weight of the rubber base based on 100 parts by weight. It may contain a silane coupling agent, preferably 60 to 120 parts by weight of silica, 7 to 15 parts by weight of carbon black, 5 to 20 parts by weight of modified polyisobutylene polymer, and 3 to 10 parts by weight of silane based on 100 parts by weight of the rubber base. It may contain a coupling agent.

The rubber composition according to an embodiment of the present invention may further include additives commonly used in the rubber composition. As a specific and non-limiting example, the rubber composition may further include additives such as antioxidants, activators, vulcanizing agents, and vulcanization accelerators, and the amount of each additive added may vary depending on the type of additive and the use of the rubber to be produced. However, as a specific and non-limiting example, 0.5 to 5 parts by weight of an additive may be added, respectively, based on 100 parts by weight of the rubber base, but the present invention is not limited thereto.

As a specific and non-limiting example, the vulcanizing agent may use sulfur, morpholine disulfide, and the like, and the vulcanization accelerator may be sulfenamide-based, thiazole-based, thiuram-based, thiourea-based, guanidine-based, dithiocarbamic acid-based , Aldehyde-amine-based or aldehyde-ammonia-based, imidazoline-based and xanthate-based vulcanization accelerators and the like can be used.

As a specific example of the sulfenamide system, for example, CBS (N-cyclohexyl-2-benzothiazylsulfenamide), TBBS (N-tert-butyl-2-benzothiazylsulfenamide), N,N-dicyclohexyl One or more sulfenamide compounds selected from -2-benzothiazylsulfenamide, N-oxydiethylene-2-benzothiazylsulfenamide, and N,N-diisopropyl-2-benzothiazolesulfenamide, etc. And the like, and examples of the thiazole type include MBT (2-mercaptobenzothiazole), MBTS (dibenzothiazyl disulfide), sodium salt of 2-mercaptobenzothiazole, zinc salt, copper salt, and cyclo Hexylamine salt, 2-(2,4-dinitrophenyl)mercaptobenzothiazole and 2-(2,6-diethyl-4-morpholinothio)benzothiazole, etc. Sol-based compounds and the like may be used, and as the thiuram-based TMTD (tetramethylthiuram disulfide), tetraethylthiuram disulfide, tetramethylthiuram monosulfide, dipentamethylenethiuram disulfide, dipentamethylenethiuram monosulfide, One or two or more thiuram-based compounds selected from dipentamethylenethiuram tetrasulfide, dipentamethylenethiuram hexasulfide, tetrabutylthiuram disulfide, pentamethylenethiuram tetrasulfide, and the like can be used. , For example, one or two or more selected from thiourea compounds such as thiacarbamide, diethylthiourea, dibutylthiourea, trimethylthiourea and diorthotolylthiourea, etc. can be used. One or two or more guanidine compounds selected from diphenylguanidine, diorthotolylguanidine, triphenylguanidine, orthotolylbiguanide, and diphenylguanidinephthalate may be used, but the present invention is not limited thereto.

The present invention also provides a tire tread comprising the rubber composition according to an embodiment of the present invention. As described above, the tire tread according to the present invention has excellent grip performance and rolling resistance, and thus has an advantage of exhibiting excellent fuel economy compared to other tire treads under the same conditions. At this time, the tire tread may specifically be a tire tread used for a passenger car, an SUV, a bus, a truck, or an electric vehicle, but the present invention is not limited thereto.

Hereinafter, the present invention will be described in detail by examples and comparative examples. The following examples are only intended to aid understanding of the present invention, and the scope of the present invention is not limited by the following examples.

[Production Example 1] Preparation of HRPB 350 modified polyisobutylene polymer

Polyisobutylene (POLYISOBUTYLENE, Mn 351 g/mol, PD=1.1, ¹³ C-NMR based α-vinylidene 80.6 mol%, viscosity 3 cSt@100°C, 500 g, 1.42 mol), maleic anhydride (172 g) in a 1 L autoclave , 1.75 mol) and reacted at 200° C. for 12 hours with a mechanical steer (MECHANICAL STIRRER). In order to remove unreacted maleic anhydride, nitrogen bubbling was performed for 2 hours to obtain polyisobutylene succinic anhydride (POLYISOBUTYLENESUCCINIC ANHYDRIDE [PIBSA-1]). Through column chromatography, a conversion rate of 79.1% was confirmed.

Put PIBSA-1 (500 g, 1.11 mol) and 3-aminopropyltriethoxysilane (491 g, 2.22 mol) prepared above in a 1 L autoclave in 500 mL of toluene and a Dean-Stark device ( dean-stark apparatus) at 120°C for 4 hours. After removing the unreacted compound, 650 g of modified polyisobutylene (yield: 88.3%) was obtained.

The polymerized modified polyisobutylene was confirmed to have a number average molecular weight of 633 g/mol, a weight average molecular weight of 837 g/mol, and a molecular weight distribution of 1.3. The Tg using DSC was -75°C, the Brookfield viscosity was 7 cP@150°C, and the result of checking the Si content using XRF was 2.2% by mass of Si.

[Production Example 2] Preparation of HRPB550 modified polyisobutylene polymer

Polyisobutylene (Mn 595 g/mol, PD=1.4, ¹³ C-NMR based α-vinylidene 81.0 mol%, viscosity 30.1 cSt@100° C., 300 g, 0.5 mol), maleic anhydride (60.0 g, 0.6mol) and reacted for 12 hours at 230°C with a mechanical steer. In order to remove unreacted maleic anhydride, nitrogen bubbling was performed for 2 hours to obtain polyisobutylenesuccinic anhydride (PIBSA-2). The conversion rate was confirmed to be 84.4% through column chromatography.

In a 1L autoclave, PIBSA-2 (300g, 0.46mol) and 3-aminopropyltriethoxysilane (214g, 0.97mol) were added to 200mL of toluene and reacted at 120°C for 4 hours under a Dean-Stark apparatus. Let it. After removing the unreacted compound, 340 g of modified polyisobutylene (yield: 93%) was obtained.

The polymerized modified polyisobutylene was confirmed to have a number average molecular weight of 819 g/mol, a weight average molecular weight of 1,448 g/mol, and a molecular weight distribution of 1.8. The Tg using DSC was -72°C, the Brookfield viscosity was 85 cP@150°C, and the result of checking the Si content using XRF was 1.8 mass% of Si.

[Preparation Example 3] Preparation of HRPB 750 modified polyisobutylene polymer

Polyisobutylene (Mn 742 g/mol, PD=1.3, ¹³ C-NMR based α-vinylidene 87.0 mol%, viscosity 86 cSt@100°C, 500 g, 0.67 mol), maleic anhydride (72 g, 0.74) in a 1 L autoclave mol) and reacted at 200° C. for 12 hours with a mechanical steer. In order to remove unreacted maleic anhydride, nitrogen bubbling was performed for 2 hours to obtain polyisobutylenesuccinic anhydride (PIBSA-3). The conversion rate was confirmed to be 84.4% through column chromatography.

PIBSA-3 (500 g, 0.60 mol) prepared above and 3-aminopropyltriethoxysilane (268 g, 1.21 mol) were added to 500 mL of toluene in a 1 L autoclave and reacted at 120° C. for 4 hours under a Dean-Stark apparatus. . After removing the unreacted compound, 560 g of modified polyisobutylene (yield: 96%) was obtained.

The polymerized modified polyisobutylene was confirmed to have a number average molecular weight of 1,088 g/mol, a weight average molecular weight of 2,103 g/mol, and a molecular weight distribution of 1.9. The Tg using DSC was -70°C, the Brookfield viscosity was 106 cP@150°C, and the result of checking the Si content using XRF was measured as 1.5% by mass of Si.

[Production Example 4] Preparation of HRPB1000 modified polyisobutylene polymer

Polyisobutylene (Mn 992 g/mol, PD=1.4, ¹³ C-NMR based α-vinylidene 88.3 mol%, viscosity 193 cSt@100°C, 500 g, 0.5 mol), maleic anhydride (52 g, 0.5 mol) in a 1 L autoclave mol) and reacted at 230° C. for 12 hours with a mechanical steer. In order to remove unreacted maleic anhydride, nitrogen bubbling was performed for 2 hours to obtain polyisobutylenesuccinic anhydride (PIBSA-4). Conversion rate of 78.4% was confirmed through column chromatography.

PIBSA-4 (500 g, 0.45 mol) prepared above and 3-aminopropyltriethoxysilane (211 g, 0.95 mol) were added to 500 mL of toluene in a 1 L autoclave and reacted at 120° C. for 4 hours under a Dean-Stark apparatus. Let it. After removing the unreacted compound, 550 g (yield: 96%) of modified polyisobutylene was obtained.

The polymerized modified polyisobutylene was confirmed to have a number average molecular weight of 1,266 g/mol, a weight average molecular weight of 2,174 g/mol, and a molecular weight distribution of 1.7. The Tg using DSC was -69°C, the Brookfield viscosity was 250 cP@150°C, and the result of checking the Si content using XRF was 1.3% by mass of Si.

[Production Example 5] Preparation of HRPB 1300 modified polyisobutylene polymer

Polyisobutylene (Mn 1,312 g/mol, PD=1.6, ¹³ C-NMR based α-vinylidene 89.6 mol%, viscosity 431 cSt@100°C, 500 g, 0.38 mol), maleic anhydride (45 g, 0.46 mol) in a 1 L autoclave mol) and reacted at 200° C. for 12 hours with a mechanical steer. In order to remove unreacted maleic anhydride, nitrogen bubbling was performed for 2 hours to obtain polyisobutylenesuccinic anhydride (PIBSA-5). Through column chromatography, the conversion rate was confirmed to be 86.7%.

PIBSA-5 (500 g, 0.35 mol) prepared above and 3-aminopropyltriethoxysilane (156 g, 0.71 mol) were added to 500 mL of toluene in a 1 L autoclave and reacted at 120° C. for 4 hours under a Dean-Stark apparatus. Let it. After removing the unreacted compound, 550 g of modified polyisobutylene (yield: 95.4%) was obtained.

The polymerized modified polyisobutylene was confirmed to have a number average molecular weight of 1,929 g/mol, a weight average molecular weight of 3,452 g/mol, and a molecular weight distribution of 1.8. The Tg using DSC was -69°C, the Brookfield viscosity was 375 cP@150°C, and the result of checking the Si content using XRF was 1.1 mass% of Si.

[Production Example 6] Preparation of HRPB1800 modified polyisobutylene polymer

Polyisobutylene (Mn 1,792 g/mol, PD=1.5, ¹³ C-NMR based α-vinylidene 87.5 mol%, viscosity 1,279 cSt@100°C, 500 g, 0.28 mol), maleic anhydride (29 g, 0.3) in a 1 L autoclave mol) and reacted at 230° C. for 12 hours with a mechanical steer. In order to remove unreacted maleic anhydride, nitrogen bubbling was performed for 2 hours to obtain polyisobutylenesuccinic anhydride (PIBSA-6). Through column chromatography, a conversion rate of 76.4% was confirmed.

PIBSA-6 (500 g, 0.26 mol) prepared above and 3-aminopropyltriethoxysilane (123 g, 0.56 mol) were added to 500 mL of toluene in a 1 L autoclave and reacted at 120° C. for 4 hours under a Dean-Stark apparatus. Let it. After removing the unreacted compound, 510 g of modified polyisobutylene (yield: 92.4%) was obtained.

The polymerized modified polyisobutylene was confirmed to have a number average molecular weight of 1,950 g/mol, a weight average molecular weight of 4,700 g/mol, and a molecular weight distribution of 2.4. The Tg using DSC was -70°C, the Brookfield viscosity was 776cP@150°C, and the result of checking the Si content using XRF was 0.9% by mass of Si.

[Production Example 7] Preparation of HRPB 2000 modified polybutene polymer

Polyisobutylene (Mn 1,980 g/mol, PD=1.6, ¹³ C-NMR based α-vinylidene 81.4 mol%, viscosity 1400 cSt@100°C, 500 g, 0.25 mol), maleic anhydride (28 g, 0.29) in a 1 L autoclave mol) and reacted at 200° C. for 12 hours with a mechanical steer. In order to remove unreacted maleic anhydride, nitrogen bubbling was performed for 2 hours to obtain polyisobutylenesuccinic anhydride (PIBSA-7). Through column chromatography, a conversion rate of 76.8% was confirmed.

PIBSA-7 (500 g, 0.25 mol) prepared above and 3-aminopropyl triethoxysilane (110 g, 0.50 mol) were added to 500 mL of toluene in a 1 L autoclave and reacted at 120° C. for 4 hours under a Dean-Stark apparatus. Let it. After removing the unreacted compound, 540 g of modified polybutene (yield: 93%) was obtained.

The polymerized modified polybutene was confirmed to have a number average molecular weight of 2,209 g/mol, a weight average molecular weight of 5,219 g/mol, and a molecular weight distribution of 2.4. The Tg using DSC was -68°C, the Brookfield viscosity was 882 cP@150°C, and the result of checking the Si content using XRF was 0.8% by mass of Si.

[Production Example 8] Preparation of HRPB2300 modified polyisobutylene polymer

Polyisobutylene Mn 2,264 g/mol, PD=1.7, ¹³ C-NMR based α-vinylidene 85.7 mol%, viscosity 1,477 cSt@100°C, 500 g, 0.22 mol), maleic anhydride (23.0 g, 0.23) in a 1L autoclave mol) and reacted at 230° C. for 12 hours with a mechanical steer. In order to remove unreacted maleic anhydride, nitrogen bubbling was performed for 2 hours to obtain polyisobutylenesuccinic anhydride (PIBSA-8). Through column chromatography, a conversion rate of 77.4% was confirmed.

PIBSA-8 (300 g, 0.13 mol) 3-aminopropyltriethoxysilane (61 g, 0.27 mol) prepared above was added to 200 mL of toluene in a 1 L autoclave and reacted at 120° C. for 4 hours under a Dean-Stark apparatus. . After removing the unreacted compound, 280 g of modified polyisobutylene (yield: 91.3%) was obtained.

The polymerized modified polyisobutylene was confirmed to have a number average molecular weight of 2,350 g/mol, a weight average molecular weight of 5,632 g/mol, and a molecular weight distribution of 2.4. The Brookfield viscosity was 900 cP@150°C, the Tg using DSC was -68°C, and the result of checking the Si content using XRF was 0.7% by mass of Si.

[Preparation Example 9] Preparation of HRPB3000 modified polyisobutylene polymer

Polyisobutylene (Mn 3,213 g/mol, PD=1.7, ¹³ C-NMR based α-vinylidene 85.2 mol%, viscosity 3,200 cSt@100° C., 500 g, 0.16 mol), maleic anhydride (20.0 g, 0.20mol) and reacted for 12 hours at 230°C with a mechanical steer. In order to remove unreacted maleic anhydride, nitrogen bubbling was performed for 2 hours to obtain polyisobutylenesuccinic anhydride (PIBSA-9). Through column chromatography, a conversion rate of 77.4% was confirmed.

In a 1L autoclave, the prepared PIBSA-9 (300g, 0.09 mol) 3-aminopropyltriethoxysilane (40g, 0.18 mol) was added to 200 mL of toluene and reacted at 120° C. for 4 hours under a Dean-Stark apparatus. Let it. After removing the unreacted compound, 290 g of modified polyisobutylene (yield: 88.1%) was obtained.

The polymerized modified polyisobutylene was confirmed to have a number average molecular weight of 3,862 g/mol, a weight average molecular weight of 9,948 g/mol, and a molecular weight distribution of 2.6. The Brookfield viscosity was 4,600 cP@150°C, the Tg using DSC was -65°C, and the result of checking the Si content using XRF was 0.1% by mass of Si.

[Production Example 10] Preparation of HRPB5000 modified polyisobutylene polymer

Polyisobutylene (=Mn 5,897 g/mol, PD=1.8, ¹³ C-NMR based α-vinylidene 87.0 mol%, viscosity 11,322 cSt@100°C, 500 g, 0.1 mol), maleic anhydride (10.0 g) in a 1 L autoclave , 0.1mol) and reacted for 12 hours at 230°C with a mechanical steer. In order to remove unreacted maleic anhydride, nitrogen bubbling was performed for 2 hours to obtain polyisobutylenesuccinic anhydride (PIBSA-10). Conversion rate of 70.4% was confirmed through column chromatography.

PIBSA-10 (300 g, 0.5 mol) 3-aminopropyltriethoxysilane (25 g, 0.1 mol) prepared above was added to 200 mL of toluene in a 1 L autoclave and reacted at 120° C. for 4 hours under a Dean-Stark apparatus. . After removing the unreacted compound, 250 g of modified polyisobutylene (yield: 80.7%) was obtained.

The polymerized modified polyisobutylene was confirmed to have a number average molecular weight of 6,187 g/mol, a weight average molecular weight of 19,750 g/mol, and a molecular weight distribution of 3.2. The Brookfield viscosity was 9,100 cP@150°C, the Tg using DSC was -60°C, and the result of checking the Si content using XRF was 0.05% by mass of Si.

[Production Example 11] Preparation of HRPB 260 modified polyisobutylene polymer

Polyisobutylene (Mn 260 g/mol, PD=1.2, ¹³ C-NMR based α-vinylidene 78.4 mol%, viscosity 5 cSt@40°C, 500 g, 1.92 mol), maleic anhydride (192 g, 1.96 mol) in a 1 L autoclave mol) and reacted at 200° C. for 12 hours with a mechanical steer. In order to remove unreacted maleic anhydride, nitrogen bubbling was performed for 2 hours to obtain polyisobutylenesuccinic anhydride (PIBSA-11). Conversion rate was confirmed by 76.1% through column chromatography.

PIBSA-11 (500 g, 1.39 mol) prepared above and 3-aminopropyltriethoxysilane (690 g, 3.12 mol) were added to 500 mL of toluene in a 1 L autoclave and reacted at 120° C. for 4 hours under a Dean-Stark apparatus. . After removing the unreacted compound, 700 g of modified polyisobutylene (yield: 92%) was obtained.

The polymerized modified polyisobutylene was confirmed to have a number average molecular weight of 543 g/mol, a weight average molecular weight of 751 g/mol, and a molecular weight distribution of 1.4. The Tg using DSC was -75°C, the Brookfield viscosity was 4 cP@150°C, and the result of checking the Si content using XRF was 2.3 mass% of Si.

[Production Example 12] Preparation of HRPB7000 modified polyisobutylene polymer

Polyisobutylene (Mn 7,096 g/mol, PD=2.5, ¹³ C-NMR α-vinylidene 80.4 mol%, viscosity 24,734 cSt@100°C, 500 g, 0.07 mol), maleic anhydride (10.0 g, 0.1) in a 1L autoclave mol) and reacted at 230° C. for 12 hours with a mechanical steer. In order to remove unreacted maleic anhydride, nitrogen bubbling was performed for 2 hours to obtain polyisobutylenesuccinic anhydride (PIBSA-12). Conversion rate was confirmed by 75.1% through column chromatography.

PIBSA-12 (300 g, 0.4 mol) 3-aminopropyltriethoxysilane (18 g, 0.08 mol) prepared above was added to 200 mL of toluene in a 1 L autoclave and reacted at 120° C. for 4 hours under a Dean-Stark apparatus. . After removing the unreacted compound, 250 g of modified polyisobutylene (yield: 80.7%) was obtained.

The polymerized modified polyisobutylene was confirmed to have a number average molecular weight of 7,641 g/mol, a weight average molecular weight of 22,812 g/mol, and a molecular weight distribution of 3.0. The Brookfield viscosity was 12,000 cP@150°C, the Tg using DSC was -60°C, and the result of checking the Si content using XRF was 0.05% by mass of Si.

[Production Example 13] Preparation of HRPB1000 modified polyisobutylene polymer

Polyisobutylene (Mn 997 g/mol, PD=1.4, ¹³ C-NMR based α-vinylidene 68.3 mol%, viscosity 197 cSt@100°C, 500 g, 0.5 mol), maleic anhydride (52 g) in a 1 L autoclave , 0.5 mol) and reacted at 230° C. for 12 hours with a mechanical steer. In order to remove unreacted maleic anhydride, nitrogen bubbling was performed for 2 hours to obtain polyisobutylenesuccinic anhydride (PIBSA-13). The conversion rate was confirmed to be 73.4% through column chromatography.

PIBSA-13 (500 g, 0.45 mol) prepared above and 3-aminopropyltriethoxysilane (211 g, 0.95 mol) were added to 500 mL of toluene in a 1 L autoclave, and at 120° C. for 4 hours under a Dean-Stark apparatus. It reacts during. After removing the unreacted compound, 481 g of modified polyisobutylene (yield: 84%) was obtained.

The polymerized modified polyisobutylene was confirmed to have a number average molecular weight of 1,175 g/mol, a weight average molecular weight of 1,986 g/mol, and a molecular weight distribution of 1.7. The Tg using DSC is -70°C, the Brookfield viscosity is 220 cP@150°C, and the result of checking the Si content using XRF is 1.2% by mass of Si.

The physical properties of the modified isobutylene polymers prepared in Preparation Examples 1 to 6 are shown in Table 1 below.

Polyisobutylene Modified polyisobutylene polymer Mn α-vinylidene (mol%) Mn Molecular weight distribution Viscosity
(cP) Si content
(mass%) Tg
(℃) Manufacturing Example 1 351 80.6 633 1.3 7 2.2 -75 Manufacturing Example 2 595 81.0 819 1.8 85 1.8 -72 Manufacturing Example 3 742 87.0 1,088 1.9 106 1.5 -70 Manufacturing Example 4 992 88.3 1,266 1.7 250 1.3 -69 Manufacturing Example 5 1,312 89.6 1,929 1.8 375 1.1 -69 Manufacturing Example 6 1,792 87.5 1,950 2.4 776 0.9 -70 Manufacturing Example 7 1,980 81.4 2,209 2.4 882 0.8 -68 Manufacturing Example 8 2,264 85.7 2,350 2.4 900 0.7 -68 Manufacturing Example 9 3,213 85.2 3,862 2.6 4,600 0.1 -65 Manufacturing Example 10 5,897 87.0 6,187 3.2 9,100 0.05 -60 Manufacturing Example 11 260 78.4 543 1.4 4 2.3 -75 Manufacturing Example 12 7,096 80.4 7,641 3.0 12,000 0.05 -60 Manufacturing Example 13 997 68.3 1,175 1.7 220 1.2 -70

Preparation of rubber composition (Examples 1 to 10 and Comparative Examples 1 to 5)

[Example 1]

Styrene butadiene rubber 1 (Styrene 25%, vinyl 63%, TDAE 37.5 phr, SBR1) 48.1 parts by weight, styrene butadiene rubber 2 (Styrene 10%, vinyl 39%, SBR2) 45 parts by weight, and butadiene rubber (KBR-01, Prepare a rubber base containing 20 parts by weight of Kumho Petrochemical, BR), and 5 parts by weight of carbon black, 70 parts by weight of silica (US7000GR, Evonik, CTAB 165m ² /g), based on 100 parts by weight of the rubber base, Si-69 5.6 parts by weight, zinc oxide 3.0 parts by weight, stearic acid 2.0 parts by weight, sulfur (Miwon Chemical) 1.6 parts by weight as a vulcanizing agent, CBS (N-cyclohexyl-2-benzothiazylsulfenamide) 1.6 parts by weight as a vulcanization accelerator Parts, DPG (1,3 di-phenylguanidine) 2 parts by weight and 6.875 parts by weight of the modified polyisobutylene prepared in Preparation Example 1 were mixed in a sealed banbari mixer to prepare a master batch, and then an open twin-screw roll mill A mixed rubber was prepared and vulcanized at 165° C. for 10 minutes to prepare a rubber, and the composition of the rubber composition is shown in Table 2.

[Example 2]

In the same manner as in Example 1, except that the modified polyisobutylene polymer prepared in Preparation Example 2 was used instead of the modified polyisobutylene polymer prepared in Preparation Example 1 above.

[Example 3]

In the same manner as in Example 1, except that the modified polyisobutylene polymer prepared in Preparation Example 3 was used instead of the modified polyisobutylene polymer prepared in Preparation Example 1 above.

[Example 4]

The same procedure as in Example 1 was performed, except that the modified polyisobutylene polymer prepared in Preparation Example 4 was used instead of the modified polyisobutylene polymer prepared in Preparation Example 1.

[Example 5]

In the same manner as in Example 1, except that the modified polyisobutylene polymer prepared in Preparation Example 5 was used instead of the modified polyisobutylene polymer prepared in Preparation Example 1 above.

[Example 6]

The same procedure as in Example 1 was performed, except that the modified polyisobutylene polymer prepared in Preparation Example 6 was used instead of the modified polyisobutylene polymer prepared in Preparation Example 1.

[Example 7]

The same procedure as in Example 1 was performed, except that the modified polyisobutylene polymer prepared in Preparation Example 7 was used instead of the modified polyisobutylene polymer prepared in Preparation Example 1.

[Example 8]

In the same manner as in Example 1, except that the modified polyisobutylene polymer prepared in Preparation Example 8 was used instead of the modified polyisobutylene polymer prepared in Preparation Example 1 above.

[Example 9]

In the same manner as in Example 1, except that the modified polyisobutylene polymer prepared in Preparation Example 9 was used instead of the modified polyisobutylene polymer prepared in Preparation Example 1 above.

[Example 10]

In the same manner as in Example 1, except that the modified polyisobutylene polymer prepared in Preparation Example 10 was used instead of the modified polyisobutylene polymer prepared in Preparation Example 1 above.

[Comparative Example 1]

It was prepared in the same manner as the rubber of Example 1, but when preparing the rubber composition, 6.875 parts by weight of rubber compounded (TDAE) oil was mixed without adding the polymer of Preparation Example 1 to prepare a rubber.

[Comparative Example 2]

It was prepared in the same way as the rubber of Example 1, but when preparing the rubber composition, 6.875 parts by weight of a commercial terpene resin (Terpene Phenol resin, yasuhara Chemical T160) was mixed instead of the polymer in Preparation Example 1 to prepare a rubber.

[Comparative Example 3]

It was prepared in the same manner as in the preparation of the rubber of Example 1, except that the modified polyisobutylene polymer prepared in Preparation Example 11 was used instead of the Preparation Example 1 polymer when preparing the rubber composition. .

[Comparative Example 4]

It was prepared in the same manner as in the preparation of the rubber of Example 1, except that the modified polyisobutylene polymer prepared in Preparation Example 12 was used instead of the Preparation Example 1 polymer when preparing the rubber composition. .

[Comparative Example 5]

It was prepared in the same manner as in the preparation of the rubber of Example 1, except that the modified polyisobutylene polymer prepared in Preparation Example 13 was used instead of the Preparation Example 1 polymer when preparing the rubber composition. .

The specific composition of the rubber composition is shown in Tables 2 and 3 below.

Division (phr) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Polymer SBR1 48.1 Left east Left east Left east Left east Left east Left east Left east Left east Left east SBR2 45 Left east Left east Left east Left east Left east Left east Left east Left east Left east BR 20 Left east Left east Left east Left east Left east Left east Left east Left east Left east Filler Silica 70 Left east Left east Left east Left east Left east Left east Left east Left east Left east Carbon black 5 Left east Left east Left east Left east Left east Left east Left east Left east Left east Silane (Si-69) 5.6 Left east Left east Left east Left east Left east Left east Left east Left east Left east Manufacturing Example 1 6.875 - - - - - - - - - Manufacturing Example 2 - 6.875 - - - - - - - - Manufacturing Example 3 - - 6.875 - - - - - - - Manufacturing Example 4 - - - 6.875 - - - - - - Manufacturing Example 5 - - - - 6.875 - - - - - Manufacturing Example 6 - - - - - 6.875 - - - - Manufacturing Example 7 - - - - - - 6.875 - - - Manufacturing Example 8 - - - - - - - 6.875 - - Manufacturing Example 9 - - - - - - - - 6.875 - Manufacturing Example 10 - - - - - - - - - 6.875 Zinc oxide 3 Left east Left east Left east Left east Left east Left east Left east Left east Left east Stearic acid 2 Left east Left east Left east Left east Left east Left east Left east Left east Left east Final
MB sulfur 1.6 Left east Left east Left east Left east Left east Left east Left east Left east Left east CBS 1.6 Left east Left east Left east Left east Left east Left east Left east Left east Left east DPG 2 Left east Left east Left east Left east Left east Left east Left east Left east Left east

Division (phr) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Polymer SBR1 48.1 Left east Left east Left east Left east SBR2 45 Left east Left east Left east Left east BR 20 Left east Left east Left east Left east Filler Silica 70 Left east Left east Left east Left east Carbon black 5 Left east Left east Left east Left east Silane (Si-69) 5.6 Left east Left east Left east Left east Oil & Chemical Oil (TDAE) 6.875 - - - - Terpene resin - 6.875 - - - Manufacturing Example 11 - - 6.875 - - Manufacturing Example 12 - - - 6.875 - Manufacturing Example 13 - - - - 6.875 Zinc oxide 3 Left east Left east Left east Left east Stearic acid 2 Left east Left east Left east Left east Final
MB sulfur 1.6 Left east Left east Left east Left east CBS 1.6 Left east Left east Left east Left east DPG 2 Left east Left east Left east Left east

The physical properties of each manufactured rubber composition are measured by the following method, but in consideration of the fact that the physical properties of the rubber composition may partially change depending on the surrounding environmental conditions, the results of measurement under the same conditions on the same date are shown in Tables 4 and 5. Indicated.

Check Payne Effect

The pane effect is a storage modulus measured when the elongation is 0.02% and 20%, and the smaller the change width, the better the dispersion of silica is, resulting in excellent rolling resistance, and overall rubber properties can be improved. For the rubbers prepared in Examples and Comparative Examples, using ALPHA Technologies' RPA 2000, using a specimen weight of 7 g or more, measuring the pane effect value with a 0.02 to 20% strain sweep at a rate of 1 Hz at 60°C. , Tables 4 and 5 show the difference in storage modulus measured when the elongation is 0.02% and 20% (ΔG'=G' _20% -G' _0.02%).

Measurement of grip performance and rolling resistance through dynamic loss factor

At 0℃, the Tanδ value corresponds to the gripping force, and the higher this value, the better the gripping force, whereas at 60℃, the Tanδ value corresponds to the rotational resistance, and the smaller this value, the better the rolling resistance [M . J. Wang, Rubber. Chem. Technol., 71, 520 (1998)]. Using DMTS (Dynamic Mechanical Thermal Spectrometry; GABO, EPLEXOR 500N) for the rubbers prepared in Examples and Comparative Examples, the dynamic loss coefficient and glass transition temperature (Tg) were measured based on 0°C and 60°C, and the results were measured. It is shown in Tables 4 and 5. During the measurement, the test conditions were Frequency: 10Hz, Strain (Static strain: 3%, Dynamic strain: 0.25%), and Temperature: -60 ~ 70℃.

Division (phr) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Payne Effect ΔG'
Uncured 3.3 2.9 2.5 2.8 3.8 DMA Tg -30.1 -26.0 -30.5 -27.4 -29.2 Tanδ@0℃ 0.2465 0.2989 0.2507 0.2728 0.2656 Tanδ@60℃ 0.0940 0.1030 0.0955 0.0990 0.0971

Division (phr) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Payne Effect ΔG'
Uncured 2.3 2.0 2.1 2.1 2.0 2.1 1.9 1.8 2.1 2.4 DMA Tg -29.8 -29.6 -29.1 -28.9 -29.1 -28.7 -29.3 -29.7 -28.7 -28 Tanδ@0℃ 0.2557 0.2607 0.2707 0.2748 0.2779 0.2848 0.2879 0.2938 0.3018 0.2908 Tanδ@60℃ 0.0932 0.0896 0.0855 0.0839 0.0827 0.0848 0.0867 0.0870 0.0890 0.0933

Comparative Examples 1 to 5 of Table 4 are those exceeding the range of the molecular weight suggested by the present inventors, respectively, a rubber compounding oil, a terpene resin, and Examples 1 to 10 of Table 5 are modified polyisobutylene polymers having different molecular weights from each other. This is the measurement result of the physical properties of the added rubber composition.

Referring to Tables 4 and 5, in the case of the ΔG' value indicating the degree of dispersion of fillers such as carbon black and silica, the number average molecular weight satisfies the range of 350 g/mol to 6,000 g/mol, and α-vinylidene is Examples 1 to 10 in which a modified polyisobutylene polymer synthesized with 80 mol% or more of polyisobutylene was added showed a ΔG' value of 2.4 or less, and a molecular weight range of 600 g/mol to 3,200 g/mol. In the case of Examples 2 to 9 using polyisobutylene, the ΔG' value was even better as 2.1 or less.

On the other hand, comparison using a modified polyisobutylene polymer synthesized from a rubber blended oil, a terpene resin, or a polyisobutylene having a number average molecular weight of 350 g/mol to 6,000 g/mol out of or α-vinylidene less than 80 mol% In the case of Examples 1 to 5, a high ΔG' value of 2.5 or more was shown, indicating that the filler was not well dispersed. From this, it was confirmed that the dispersibility of silica and carbon black was remarkably improved when the modified polyisobutylene polymer according to the example of the present invention was applied.

On the other hand, Examples 1 to 10 showed a value of 0.255 or more in the case of Tanδ@0°C, which shows excellent braking performance as the value is higher, and a value of 0.094 or less in the case of Tanδ@60°C, which shows excellent rolling resistance performance as the value is lower. As shown, both the braking performance and the rolling resistance performance were improved compared to the comparative example.

In particular, in the case of Examples 3 to 8, a modified polyisobutylene polymer having a number average molecular weight of 900 to 3,000 g/mol was prepared from polyisobutylene having a number average molecular weight of 700 to 3,000 g/mol, and the rubber composition Tanδ@0℃ showed a value of 0.2707 or more and Tanδ@60℃ less than 0.0870, which further improved the braking performance and rolling resistance performance.

In addition, in the case of Comparative Example 2, as a terpene resin was added instead of the modified polyisobutylene polymer, the braking performance was improved compared to Comparative Example 1, but the Tanδ@60°C value was rather increased to 0.1030, which lowered the rolling resistance performance. .

Modified polyisobutylene polymers prepared from polyisobutylene having a number average molecular weight not satisfying the range of 350 g/mol to 6,000 g/mol, or α-vinylidene less than 80 mol% (Preparation Examples 11 to 13) In the case of Comparative Examples 3 to 5 to which was added, the braking performance was excellent, but the lower the value of Tanδ@60°C, indicating the effect of improving fuel economy, was measured to be 0.094 or higher, and the rolling resistance performance was poor compared to the Example, and Comparative Example 1 and In comparison, it was confirmed that the rolling resistance performance was hardly improved.

From the above results, it can be clearly confirmed that when the modified polyisobutylene polymer according to the present invention is added to the coarse composition, the dispersibility of silica is increased, so that braking performance and fuel efficiency performance can be improved at the same time.

Claims (20)

Polyisobutylene whose main chain is isobutylene;
Unsaturated dicarboxylic anhydride; And
Silane compounds;
Modified polyisobutylene polymer for rubber formulation, characterized in that produced by mixing. The method of claim 1,
The modified polyisobutylene polymer for rubber blending includes 20 to 80% by weight of polyisobutylene whose main chain is isobutylene; 1 to 20% by weight of unsaturated dicarboxylic anhydride; And 1 to 60% by weight of a silane compound; a modified polyisobutylene polymer for rubber blending, characterized in that prepared by mixing. The method of claim 1,
The polyisobutylene whose main chain is isobutylene has a number average molecular weight of 350 g/mol to 6,000 g/mol. The method of claim 1,
Modified polyisobutylene polymer for rubber formulation, characterized in that the molecular weight distribution of the polyisobutylene whose main chain is isobutylene is 1 to 5. The method of claim 1,
The unsaturated dicarboxylic anhydride is maleic anhydride, itaconic anhydride, citraconic anhydride, propenyl succinic anhydride, and 2-pentenedianic anhydride. Modified polyisobutylene polymer for rubber blending, characterized in that it is one or more than one selected from (2-pentendioic anhydride) The method of claim 1,
The silane compound is a modified polyisobutylene polymer for rubber formulation, characterized in that it contains an amino group The method of claim 6,
The silane compound is a modified polyisobutylene polymer for rubber formulation that satisfies the following formula (1).
[Formula 1]

(In formula 1,
R ₁ and R ₂ are each independently selected from (C1-C5)alkylene, (C1-C5)aminoalkylene, carbonylene and (C1-C5)alkylcarbonylene, and are the same as or different from each other;
R ₃ , R ₄ and R ₅ are independently of each other hydrogen, hydroxy, (C1-C20)alkyl, (C1-C12)cycloalkyl, (C2-C14)acyloxy, (C4-C20)aryloxy, (C5 -C30) is selected from aroxy, (C1-C20)amine and (C1-C12)alkoxy, each the same or different;
A is methylene, S _n or ((R ₆ )NR ₇ ) _n , wherein R ₆ is hydrogen or (C1-C5)alkyl, R ₇ is (C1-C5)alkylene, and n is 1-10 Is the integer of ) The method of claim 6,
The silane compound is 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, N-(2-aminoethyl)-3-aminopropyl triethoxysilane, 3-aminopropyl methyldiethoxysilane, 3 -Aminopropyl silanetriol, 3-aminopropyl methyldimethoxysilane, 3-(2-aminoethylamino)propyl dimethoxymethylsilane, 3-(2-aminoethylamino)propyl trimethoxysilane, 2-ethandiamine N-(2-aminoethyl)-N'-[3-(trimethoxysilyl)propyl]-1, 1-[3-(trimethoxysilyl)propyl]urea and 1-[3-(triethoxy Silyl) propyl)] a modified polyisobutylene polymer for rubber formulation, characterized in that one or two or more selected from urea. The method of claim 1,
The modified polyisobutylene polymer for rubber blending is a modified polyisobutylene polymer for rubber blending, characterized in that it contains nitrogen. The method of claim 1,
The modified polyisobutylene polymer for rubber blending is a modified polyisobutylene polymer for rubber blending, characterized in that it contains a carbonyl group. The method of claim 1,
The modified polyisobutylene polymer for rubber blending is a modified polyisobutylene polymer for rubber blending, characterized in that it contains an amide group. The method of claim 1,
The modified polyisobutylene polymer for rubber blending is a modified polyisobutylene polymer for rubber blending, wherein the Si content is 0.05 to 10% by mass as a result of X-ray fluorescence analysis. The method of claim 1,
The modified polyisobutylene polymer for rubber blending is a modified polyisobutylene polymer for rubber blending, characterized in that the glass transition temperature is -50°C or less. The method of claim 1,
The modified polyisobutylene polymer for rubber blending has a Brookfield viscosity of 5 to 10,000 cP at 150°C. The method of claim 1,
The modified polyisobutylene polymer for rubber blending is a modified polyisobutylene polymer for rubber blending, characterized in that the number average molecular weight is 580 to 10,000 g/mol. The method of claim 1,
The modified polyisobutylene polymer for rubber blending has a molecular weight distribution of 1 to 5. The modified polyisobutylene polymer for rubber blending according to any one of claims 1 to 16;
Rubber base; And
Rubber composition comprising a; filler. The method of claim 17,
The filler is a rubber composition comprising at least one selected from silica and carbon black. The method of claim 17,
The rubber base is butadiene rubber, butyl rubber, emulsion polymerization styrene butadiene rubber (E-SBR), solution polymerization styrene butadiene rubber (S-SBR), epichlorohydrin rubber, nitrile rubber, hydrogenated nitrile rubber, brominated polyisobutyl Isoprene-co-paramethyl styrene (BIMS) rubber, urethane rubber, fluorine rubber, silicone rubber, styrene ethylene butadiene styrene copolymer rubber, ethylene propylene rubber, ethylene propylene diene monomer rubber, hypalon A rubber composition comprising one or two or more selected from rubber, chloroprene rubber, ethylene vinyl acetate rubber, and acrylic rubber. The method of claim 17,
The rubber composition comprises 50 to 150 parts by weight of silica, 5 to 20 parts by weight of carbon black, 2 to 40 parts by weight of a modified polyisobutylene polymer for rubber blending, and 2 to 15 parts by weight of a silane coupling agent based on 100 parts by weight of the rubber base. Rubber composition.