JP3296926B2 - Hydrogenated diene copolymer and composition thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrogenated diene copolymer having excellent vibration damping performance and excellent flexibility at low temperatures, and to provide the hydrogenated diene copolymer with impact resistance and vibration damping performance. It relates to the applied composition.

[0002]

2. Description of the Related Art A styrene-isoprene block copolymer is known as a thermoplastic elastomer having a vibration damping property (Japanese Patent Application Laid-Open No. 2-102212). It is also known that a composite material having excellent vibration damping properties can be obtained by combining this thermoplastic elastomer and plastics (JP-A-2-300250, JP-A-3-300250).
No. 43244). However, since this thermoplastic elastomer has a glass transition temperature near room temperature, there is a problem that, when blended with plastics, the impact resistance is low at low temperatures.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a material having an excellent balance between vibration damping performance and low-temperature impact resistance.

[0004]

Means for Solving the Problems The present inventors have made intensive studies on the above points, and as a result, have reached the present invention.
That is, the present invention has a number average molecular weight of 2,500 to 1,000.
And a block (A) composed of polybutadiene having a 1,2 bond content of 30 mol% or less and a number average molecular weight of 1
000 to 200,000, and the vinyl bond amount is 3
A block (B) comprising polyisoprene or isoprene-butadiene copolymer of 0 mol% or less and polyisoprene, polybutadiene or isoprene-butadiene having a number average molecular weight of 10,000 to 200,000 and a vinyl bond amount of 40 mol% or more. The present invention relates to a hydrogenated diene-based copolymer obtained by hydrogenating a diene-based copolymer having at least one block (C) made of a polymer and having a number average molecular weight of 22,500 to 500,000, and a composition thereof.

Hereinafter, the present invention will be described in more detail.

The block (A) constituting the hydrogenated diene copolymer of the present invention has a number average molecular weight of 2,500 to 1,000.
It is necessary that the polybutadiene has a molecular weight of 00 and a 1,2 bond content of 30 mol% or less.

[0007] The number average molecular weight of the mechanical strength of the hydrogenated diene-based copolymer per se is lowered in the case 2500 is less than the reverse
On the other hand, if it exceeds 100,000, the hydrogenated solution after the hydrogenation reaction becomes waxy, which makes the handling difficult, which is not preferable.

If the amount of 1,2 bonds exceeds 30 mol%, the crystallinity of the block (A) decreases, and the mechanical strength of the hydrogenated diene copolymer itself decreases, which is not preferable.

Block (A) in hydrogenated diene copolymer
Is preferably 5 to 90% by weight. If it is less than 5% by weight, the mechanical strength of the hydrogenated diene-based copolymer itself decreases, and if it exceeds 90% by weight, sufficient vibration damping performance cannot be obtained, which is not preferable.

The block (B) constituting the hydrogenated diene copolymer of the present invention has a number average molecular weight of 10,000 to 200.
It is necessary to be made of polyisoprene or isoprene-butadiene copolymer having a molecular weight of 000 and a vinyl bond content of 30 mol% or less.

The number average molecular weight of the block (B) is 1000
If it is less than 0, the mechanical strength of the hydrogenated diene-based copolymer itself decreases, and if it exceeds 200,000, the melt viscosity increases and the processability deteriorates.

When the vinyl bond content is more than 30 mol%, the hydrogenated diene copolymer cannot obtain flexibility at low temperature, and when the composition is used, the impact resistance at low temperature cannot be obtained. Not preferred.

The block (B) is made of polyisoprene or isoprene-butadiene copolymer. When importance is placed on flexibility at low temperatures, it is preferable to use polyisoprene. On the other hand, when importance is placed on mechanical strength. It is preferable to use an isoprene-butadiene copolymer.

When the isoprene-butadiene copolymer is used, the butadiene ratio is preferably in the range of 80% by weight or less. If the butadiene content exceeds 80% by weight, the crystallinity becomes high and rubber elasticity is lost. In this case, the polymerization form of isoprene and butadiene is preferably a random or tapered form.

Block (B) in hydrogenated diene copolymer
Is preferably 5 to 90% by weight. If it is less than 5% by weight, the flexibility at low temperature of the hydrogenated diene copolymer or the impact resistance at low temperature when the composition is obtained cannot be obtained. It is not preferable because sufficient vibration damping performance and low-temperature flexibility cannot be obtained.

[0016] that make up the hydrogenated diene-based copolymer of the present invention <br/> block (C) has a number average molecular weight of from 10,000 to 200
It is necessary to be made of polyisoprene, polybutadiene or isoprene-butadiene copolymer having a molecular weight of 000 and a vinyl bond content of 40 mol% or more.

The number average molecular weight of the block (C) is 1000
If it is less than 0, the mechanical strength of the hydrogenated diene-based copolymer itself decreases, and if it exceeds 200,000, the melt viscosity increases and the processability deteriorates. On the other hand, if the vinyl bond content is less than 40 mol%, vibration damping performance near room temperature cannot be obtained, which is not preferable.

The block (C) is a polyisoprene, polybutadiene or isoprene-butadiene copolymer. When importance is placed on vibration damping performance at room temperature, it is preferable to use a polyisoprene or isoprene-butadiene copolymer. More preferred is polyisoprene.

When an isoprene-butadiene copolymer is used, the ratio between isoprene and butadiene is not particularly limited. In this case, the polymerization form of isoprene and butadiene may be any of block, random, and tapered.

Block (C) in hydrogenated diene copolymer
Is preferably 5 to 90% by weight. If the content is less than 5% by weight, sufficient vibration damping performance cannot be obtained, and if it exceeds 90% by weight, the flexibility of the hydrogenated diene-based copolymer at a low temperature is impaired, resulting in a composition. Is not preferable because impact resistance at low temperatures cannot be obtained.

The form of the hydrogenated diene copolymer may be linear or branched. There is no particular limitation on the order in which the blocks are combined.
It is enough if you can get it.

The hydrogenation ratio of the hydrogenated diene copolymer of the present invention is preferably at least 70%. If it is lower than 70%, the block (A) does not exhibit crystallinity, so that sufficient mechanical strength of the hydrogenated diene copolymer itself cannot be obtained, which is not preferable. Also, from the viewpoint of heat resistance and weather resistance, the hydrogenation rate is preferably 70% or more, more preferably 80% or more.

The hydrogenated diene copolymer of the present invention can be obtained by the following method.

First, the diene copolymer before hydrogenation is:
It is produced by a method in which monomers are sequentially added and polymerized using an alkyllithium compound as an initiator, or a method in which monomers are sequentially added and polymerized using an alkyllithium compound as an initiator and then coupled with a coupling agent.

Examples of the alkyl lithium compound include an alkyl compound having an alkyl residue having 1 to 10 carbon atoms, and particularly preferred are methyl lithium, ethyl lithium, pentyl lithium and butyl lithium. As the coupling agent, dichloromethane, dibromomethane, dichloroethane, dibromoethane, dibromobenzene and the like are used. Examples of the dilithium compound naphthalene dilithium, di lithio hexyl benzene. The amount used is determined depending on the molecular weight to be determined, and generally about 0.1 part by weight of initiator based on 100 parts by weight of all monomers used for polymerization.
It is used in the range of 01 to 0.2 parts by weight.

The amount of vinyl bonds in isoprene, butadiene or isoprene-butadiene of the block (C) is 4
In order to have 0 mol% or more, a Lewis base is used in the polymerization as a cocatalyst. Examples of Lewis bases are dimethyl ether, diethyl ether, ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, glycol ethers such as diethylene glycol dimethyl ether, triethylamine, N, N, N ',
N'-tetramethylethylenediamine (TMEDA), N
Amine compounds such as -methylmorpholine. These Lewis bases are used in an amount of about 0.1 to 1000 times the mole number of lithium of the polymerization initiator.

At the time of polymerization, it is preferable to use a solvent in order to facilitate control. As the solvent, an organic solvent inert to the polymerization initiator is used. Particularly, the carbon number is 6-1.
2, aliphatic, alicyclic and aromatic hydrocarbons are preferably used. Examples include hexane, heptane, cyclohexane, methylcyclohexane, benzene and the like.

The polymerization is carried out by any of the polymerization methods from 0 to 0.
The reaction is performed at a temperature of 80 ° C. for a period of 0.5 to 50 hours.

Next, hydrogenation of the diene copolymer is performed by a known method. For the hydrogenation reaction, a method in which hydrogen in a molecular state is reacted with a known hydrogenation catalyst in a state of being dissolved in a hydrogenation catalyst and a solvent inert to the reaction is preferably used. As a catalyst to be used, Raney nickel or a metal such as Pt, Pd, Ru, Rh, Ni
Heterogeneous catalysts such as those supported on carriers such as alumina and diatomaceous earth, or transition metals and alkylaluminum compounds,
A Ziegler-based catalyst composed of a combination of an alkyllithium compound and the like is used. The reaction is carried out at a hydrogen pressure of normal pressure to 200 kg / cm ² , a reaction temperature of normal temperature to 250 ° C., and a reaction time of 0.1 to 100 hours. The hydrogenated diene copolymer obtained after the reaction is obtained by coagulating the reaction solution with methanol or the like and then heating or drying under reduced pressure, or pouring the reaction solution into boiling water, removing the solvent by azeotropic distillation, and heating or It is obtained by drying under reduced pressure.

The hydrogenated diene-based copolymer of the present invention is used alone as a molding material, but it can be used as a composition by blending with other polymers, thereby exhibiting excellent functions and effects. There is. Examples of the polymer include NR, IR, BR, SBR, EPR, EPD
M, butyl rubber, boribene, low molecular weight polyisoprene, low molecular weight polybutadiene, low molecular weight isoprene-butadiene copolymer and hydrogenated products thereof, styrene-butadiene block copolymer and styrene-isoprene block copolymer and hydrogenated these Products, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene copolymer such as ethylene-methyl methacrylate copolymer, thermoplastic polyurethane, thermoplastic polyester, thermoplastic polyamide, polyethylene, polypropylene, etc. Polyolefin, polystyrene, AB
Examples include styrene resins such as S resin and AES resin, polyamide resins, polyester resins, and the like. Further, the above-mentioned polymer may have a functional group added to the molecular chain or the molecular terminal.

The blending ratio of these polymers varies depending on the purpose, but is preferably 95% by weight or less based on the hydrogenated diene copolymer of the present invention.

The composition of the present invention may contain various additives as long as the properties are not impaired. Examples thereof include 5-250 parts by weight of a plasticizer / softening agent such as oil with respect to 100 parts by weight of the polymer component.
Up to 300 parts by weight of carbon black, silica, calcium carbonate, talc, mica, glass fiber and other reinforcing agents or fillers, and 0.01 to 5 parts by weight of antioxidants, ultraviolet absorbers, coloring agents and the like. Can be In particular, mica is preferably used because it improves vibration damping performance.

The hydrogenated diene copolymer and the composition of the present invention are mixed by a kneader, a roll, and an extruder, and can be easily formed into a molded product by a general molding method such as press molding, injection molding or extrusion molding. it can.

The composition of the present invention is optionally used after crosslinking. As the crosslinking agent, sulfur, peroxide, or the like is used. Crosslinking can be easily carried out using a general method and apparatus used for ordinary crosslinking of rubber.

The hydrogenated diene copolymer and composition of the present invention can be used as molding materials for automobile interior materials, exterior materials, sheets,
Used for films, hoses, tubes, medical materials, sporting goods, toys, household goods, textiles, etc. Further, it can be applied to a cloth or used as a laminate with a thermoplastic resin, a thermosetting resin, a steel plate, a plywood, an elastomer, or the like.

[0036]

The present invention will be described more specifically with reference to the following examples. In addition, each measured value in an Example and a comparative example was calculated | required by the following method.分子 The molecular weight is a number average molecular weight determined by GPC.ミ ク ロ The microstructure was calculated from the NMR spectrum. The hydrogenation ratio was calculated from the ratio of the iodine value of the diene copolymer before and after the hydrogenation reaction measured. ◎ Vibration control performance is 0, 2 determined by dynamic viscoelasticity measurement
The tan δ value at 0 and 40 ° C. was evaluated.衝 撃 Impact strength was measured with an Izod tester (JIS K7110).

Example 1 In a 5-liter pressure-resistant reactor replaced with dry nitrogen, isoprene, butadiene, and isoprene were polymerized in that order using cyclohexane as a solvent, n-butyllithium as a polymerization catalyst, and THF as a vinylating agent. to obtain a a-B-C type diene copolymer. The resulting copolymer in cyclohexane, using Pd-C as a hydrogenation catalyst, the hydrogen pressure 20kg
/ Cm ² to obtain a hydrogenated diene copolymer (I). Table 1 shows the molecular characteristics. The resulting hydrogenated diene copolymer (I) to prepare a composition by kneading at 200 ° C. by Brabender Plasticorder according to the formulation are shown in Table 3, the press-molded samples at 210 ° C. -20, The measurement of the Izod impact strength at 25 ° C. and the measurement of tan δ at 0, 20, and 40 ° C. were performed. Table 3 shows the measurement results.

Example 2 Polymerization and hydrogenation were carried out in the same manner as in Example 1 except that a mixture of isoprene and butadiene (isoprene / butadiene = 50/50), butadiene, and isoprene were polymerized in this order, and a hydrogenated diene-based copolymer was obtained. Polymer (II) was obtained. Table 1 shows the molecular characteristics. The obtained hydrogenated diene copolymer (II) was kneaded, molded and measured in the same manner as in Example 1. Table 3 shows the measurement results.

Example 3 Isoprene, butadiene, and a mixture of isoprene and butadiene
Polymerization and hydrogenation were carried out in the same manner as in Example 1 except that the polymerization was carried out in the order of the compound (isoprene / butadiene = 50/50) to obtain a hydrogenated diene copolymer (III). Table 1 shows the molecular characteristics. Obtained hydrogenated diene copolymer (III)
Was kneaded, molded and measured in the same manner as in Example 1. Table 3 shows the measurement results.

Comparative Example 1 Polymerization was carried out in the order of isoprene and butadiene, and polymerization and hydrogenation were carried out in the same manner as in Example 1 except that THF was not used to obtain a hydrogenated diene copolymer (IV). Table 1 shows the molecular characteristics. The obtained hydrogenated diene copolymer (IV) was kneaded, molded and measured in the same manner as in Example 1. Table 3 shows the measurement results.

[0041]

[Table 1]

Comparative Example 2 Example 1 except that butadiene and isoprene were polymerized in this order.
Polymerization and hydrogenation were carried out in the same manner as described above to obtain a hydrogenated diene copolymer (V). The obtained hydrogenated diene copolymer (V) was kneaded, molded and measured in the same manner as in Example 1. Table 3 shows the measurement results.

Comparative Example 3 Styrene, isoprene, and styrene were polymerized in this order, and THF was added.
Was used as a vinylating agent, and polymerization and hydrogenation were carried out in the same manner as in Example 1 to obtain a styrene-based block copolymer (I). Table 2 shows the molecular characteristics. The obtained styrenic block copolymer (I) was kneaded, molded and measured in the same manner as in Example 1. Table 3 shows the measurement results.

[0044]

[Table 2]

[0045]

[Table 3]

From the results shown in Table 3, it can be seen that the composition containing the hydrogenated diene copolymer of the present invention is a material having excellent vibration damping performance and low-temperature impact strength.

[0047]

The composition comprising the hydrogenated diene copolymer of the present invention is a material having an excellent balance between vibration damping performance and low temperature impact resistance, and is required to have vibration damping performance and impact resistance. Can be used for applications.

Continuation of the front page (56) References JP-A-5-271324 (JP, A) JP-A-4-255734 (JP, A) JP-A-3-74409 (JP, A) JP-A-56-304043 (JP) JP-A-3-188114 (JP, A) JP-A-7-238111 (JP, A) JP-A-7-173269 (JP, A) JP-A-5-112726 (JP, A) 47-40473 (JP, B1) JP-B 46-20814 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 8/00-8/50

Claims (5)

(57) [Claims] (1) a number average molecular weight of 2,500 to 100,000
And a block (A) composed of polybutadiene having a 1,2 bond content of 30 mol% or less, and a number average molecular weight of 100
A block (B) made of polyisoprene or an isoprene-butadiene copolymer having a vinyl bond content of 30 to 200 mol% and a number average molecular weight of 10,000 to 200,000 and a vinyl bond amount of 40 mol% A hydrogenated diene system obtained by hydrogenating a diene copolymer having a number average molecular weight of 22,500 to 500,000 containing at least one block (C) made of the above polyisoprene, polybutadiene or isoprene-butadiene copolymer. Copolymer. 2. The water according to claim 1, wherein the block (B) is made of polyisoprene having a vinyl bond amount of 30 mol% or less, and the block (C) is made of an isoprene-butadiene copolymer having a vinyl bond amount of 40 mol% or more. Addition diene copolymer. 3. The hydrogenated diene-based copolymer according to claim 1, wherein the proportion of the block (A), block (B) or block (C) in the hydrogenated diene-based copolymer is 5 to 90% by weight, respectively. Copolymer. 4. The hydrogenated diene copolymer has a hydrogenation ratio of 70%.
The hydrogenated diene copolymer according to any one of claims 1 to 3, which is described above. 5. A composition comprising the hydrogenated diene copolymer according to claim 1 and another polymer.