JPH0625424A - Novel polymer and its production - Google Patents

Abstract

PURPOSE:To obtain a novel polymer which combines the properties of a nonpolar polymer and those of a polar polymer and is useful as, e.g. a modifier for other plastics by causing a specific polymer to add a given block copolymer. CONSTITUTION:A block copolymer (C) which comprises at least 1 block consisting of a polymer of an aromatic vinyl having a given number-average mol.wt. and at least 1 block consisting of a conjugated diene polymer in which at least 70% of the C-C double bonds have been hydrogenated and having a given number-average mol.wt., is represented by the formula {A.B}m or A{B.A}n (where (m) and (n) each is 1 or larger) and has a given number-average mol.wt., is reacted with maleic anhydride to cause the anhydride to add the diene units of the copolymer (C) in a given amount. A given amount of an acrylic polymer having a given number-average mol.wt. is caused to add the anhydride moieties which have been added, thereby forming pendant polymeric groups having a given number-average mol.wt. and represented by formula I and/or II (wherein R<1> is a 1-4C alkyl and R<2> is an acrylic polymer residue).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel polymer having both properties of a non-polar polymer and a polar polymer and having a use as a modifier and a compatibilizer for other plastics and a process for producing the same. .

[0002]

2. Description of the Related Art A block copolymer composed of a block of a polymer of a vinyl aromatic compound and a block of a polymer of a conjugated diene compound having a carbon-carbon double bond hydrogenated has a heat resistance and It is well known as a thermoplastic elastomer having excellent weather resistance and is mixed with other plastics as a modifier for improving various properties. Properties obtained by mixing with other plastics are, for example, elasticity improvement such as imparting flexibility and improving fluidity, and the polarity of a block composed of a polymer of a vinyl aromatic compound in a block copolymer. And a non-polarity of a block composed of a polymer of a conjugated diene compound and having its carbon-carbon double bond hydrogenated, can be synergistically exerted.

[0003]

However, the compatibility between the thermoplastic elastomer composed of the block copolymer and other plastics has its own limit. For example, the effect obtained is not sufficient for the purpose of improving adhesion by mixing the block copolymer with a nonpolar plastic.

Further, for the purpose of improving the compatibility with polar plastics or providing a function as a modifier for non-polar plastics, the copolymerization of the above block copolymer is carried out. A maleic anhydride-modified block copolymer (C-1) in which maleic anhydride is added to the hydrogenated conjugated diene compound portion in the coalescence is known. The maleic anhydride-modified block copolymer (C-1) to which maleic anhydride is added has improved compatibility depending on the type of plastic to be mixed, but there is a limit to the improvement of the mixed state, and polar plastics in particular are used. When added to a mixture of two or more types of plastics, i.e., and non-polar plastics, little improvement in compatibility can be expected. Further, there is almost no improvement in the action of the nonpolar plastic as a modifier.

On the other hand, the present invention has good compatibility with both polar plastics and non-polar plastics and has a property of excellent modification effect. In particular, two types of polar plastics and non-polar plastics are used. The present invention provides a novel polymer having a highly improved compatibilizing effect, which is remarkably improved in the mixed state when it is added to a mixed plastic, and a production method for accurately obtaining the novel polymer.

[0006]

The invention according to claim 1 has a number average molecular weight of 1000 comprising a polymer of a vinyl aromatic compound.
.About.50000 block (A) and a polymer of a conjugated diene compound, the carbon-carbon double bond of which is 7
Number average molecular weight of 20,000 with 0% or more hydrogenated
And one or more of 200,000 blocks (B),
The rational expression is {(A) ・ (B)} _m or (A)
A number average molecular weight of 30,000 to 4,000 displayed by {(B) · (A)} _n (where m and n represent integers of 1 or more)
00 block copolymer (C), maleic anhydride was added to the conjugated diene compound portion in the block copolymer (C) per monomer unit of the conjugated diene compound in the block copolymer (C). 0.1 to 5.0 mol% is added, and
A number average molecular weight of 500 is added to the added maleic anhydride.
0 to 70,000 acrylic polymer is 0. 0 per monomer unit of the conjugated diene compound in the block copolymer (C).
01-1.0 mol% is added, and the portion is represented by [Chemical formula 5] and / or [Chemical formula 6]. Number average molecular weight 31000-45
It consists of 0000 polymers.

[0007]

[Chemical 5]

[0008]

[Chemical 6]

Further, the invention of claim 2 is such that the number average molecular weight of a polymer of a vinyl aromatic compound is 1,000 to 5,000.
One or more of block (A) of 0 and a polymer of a conjugated diene compound and 70% or more of the carbon-carbon double bonds thereof are hydrogenated.
And one or more of block (B) of 00, and the rational expression is {(A) · (B)} _m or (A) {(B) ·
(A)} _n (wherein m and n represent integers of 1 or more), the block copolymer (C) having a number average molecular weight of 30,000 to 400,000 is reacted with maleic anhydride to form a block. After obtaining a maleic anhydride modified block copolymer (C-1) in which maleic anhydride is added to the conjugated diene compound part in the copolymer (C), the maleic anhydride modified block copolymer ( C-1) is reacted with an acrylic polymer having a number average molecular weight of 5,000 to 70,000 having a primary amino group or a secondary amino group at the molecular end, whereby maleic anhydride is converted into the block copolymer ( 0.1 to 5.0 mol% is added per monomer unit of the conjugated diene compound in C), and the acrylic polymer is a block copolymer (C) to the added maleic anhydride. ) Adding 0.01 to 1.0 mole% per monomer unit of the conjugated diene compound, the moiety is [Formula 7]
And / or number average molecular weight 3100 represented by [Chemical Formula 8]
0 to 450,000 polymers are obtained.

[0010]

[Chemical 7]

[0011]

[Chemical 8]

In the novel polymer of the present invention having the above structure and the method for producing the same, the monomer forming the block (A) having a number average molecular weight of 1,000 to 50,000 and comprising a polymer of a vinyl aromatic compound is, for example, styrene, One or more kinds of α-methylstyrene, 3-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, and the like, which is made of a polymer of a conjugated diene compound and has a carbon-carbon double bond The monomer of the conjugated diene compound forming the block (B) having a number average molecular weight of 20,000 to 200,000 in which 70% or more is hydrogenated is
For example, 1 of isoprene, butadiene, pentadiene, etc.
It consists of more than one seed. From the viewpoint of various mechanical strength and properties as an elastic body in the novel polymer of the present invention, it is most preferable to use isoprene or a mixture of isoprene and butadiene as the monomer of the conjugated diene compound. .

A block whose rational expression is represented by {(A). (B)} _m or (A) {(B). (A)} _n (where m and n represent integers of 1 or more). In the copolymer (C), when the number average molecular weight of the block made of a polymer of a vinyl aromatic compound is less than 1000, the elasticity of the target polymer becomes insufficient, and it is suitable as a modifier for other plastics. Disappears. When the number average molecular weight of the block made of the vinyl aromatic compound polymer exceeds 50,000, the polymer becomes hard and loses elasticity.

Further, the rational expression is displayed as {(A). (B)} _m or (A) {(B). (A)} _n (where m and n represent integers of 1 or more). In the block copolymer (C) having a number of molecular weights of less than 20,000, the block is composed of a polymer of a conjugated diene compound and 70% or more of the carbon-carbon double bonds thereof are hydrogenated. The elasticity becomes insufficient and the mechanical strength becomes insufficient. Further, when the number average molecular weight of the block composed of a polymer of a conjugated diene compound and having 70% or more of its carbon-carbon double bonds hydrogenated exceeds 200,000, the melt viscosity of the polymer becomes extremely high, and the fluidity is increased. Is significantly deteriorated, resulting in poor suitability for mixing with other plastics.

In the block copolymer (C) having a number average molecular weight of 30,000 to 400,000, represented by the rational formula {(A) · (B)} _m or (A) {(B) · (A)} _n . m and n may be integers of 1 or more, but 5 or less are preferable. The block copolymer (C)
Is a block copolymer represented by {(A) · (B)} _m (where m represents an integer of 1 or more) and (A) {(B)
It may be a mixture with a block copolymer represented by (A)} _n (n represents an integer of 1 or more).

{(A) ・ (B)} _m or (A)
In the block copolymer represented by {(B) · (A)} _n , when the hydrogenation rate of the carbon-carbon double bond of the block composed of the polymer of the conjugated diene compound is less than 70%, the purpose is When the polymer is subjected to operations such as kneading and mixing, there is thermal deterioration at high temperatures, and the durability of the resulting molded article becomes insufficient. From these, it is more preferable that the hydrogenation rate of the carbon-carbon double bond of the block made of the polymer of the conjugated diene compound is 80% or more.

One or more blocks (A) composed of a polymer of a vinyl aromatic compound and a block (B-1) composed of a polymer of a conjugated diene compound before its carbon-carbon double bond is hydrogenated. And one or more of which have a rational expression of {(A) · (B-1)} _m or (A) {(B-1)
The block copolymer (C-2) represented by (A)} _n (wherein m and n represent an integer of 1 or more) is obtained by known anionic polymerization. For example, (1) using alkyl lithium such as butyl lithium as a polymerization initiator, a method of sequentially polymerizing a vinyl aromatic compound and a conjugated diene compound to form a block polymerization, (2) alkyl lithium such as butyl lithium It is possible to use, for example, a method in which the polymerization of a vinyl aromatic compound and the polymerization of a conjugated diene compound are sequentially performed using a polymerization initiator, and then block polymerization is formed by a coupling method using a coupling agent. As the alkyl lithium, an alkyl compound having an alkyl residue having 1 to 10 carbon atoms can be used, and methyl lithium, ethyl lithium, butyl lithium and the like are particularly preferable. Further, as the coupling agent used in the coupling method, dichloromethane, dibromobutane, dibromobenzene, tin tetrachloride, etc. can be used. The amounts of the polymerization initiator and the coupling agent used in the coupling method are determined according to the molecular weight of the target block copolymer (C-2). In addition, during the polymerization of the block copolymer (C-2), in order to facilitate the control of the reaction, a hydrocarbon-based solvent inert to the polymerization initiator and the coupling agent, for example, a simple solvent. Prime number 5
~ 12 aliphatic, alicyclic and aromatic hydrocarbons, specifically solvents such as hexane, cyclohexane, toluene, etc. may be used.

The hydrogenated block copolymer (C) can be obtained by a known method of reacting the block copolymer (C-2) with hydrogen in the presence of a catalyst. This hydrogenation reaction is
For example, a homogeneous catalyst such as a Ziegler catalyst obtained by combining an organic compound of a transition metal with an alkyl compound such as aluminum, an alkaline earth metal, or an alkali, or Raney nickel, or a metal such as palladium, platinum, or ruthenium is used as carbon or silica Using a heterogeneous catalyst supported on diatomaceous earth, alumina, etc., atmospheric pressure to 100 kg /
It can be carried out by a method of contacting cm ² of hydrogen at room temperature to 200 ° C. for 0.1 to 100 hours. It should be noted that this hydrogenation reaction is preferably carried out in the presence of a solvent in order to facilitate its control, and for example, it is suitable to use a hydrocarbon solvent such as hexane or cyclohexane.

The reaction for obtaining the block copolymer (C-1) to which maleic anhydride is added is an addition reaction of maleic anhydride to the block copolymer (C) obtained by the hydrogenation reaction, and the conjugated diene Maleic anhydride is added to the polymer portion of the compound, and such addition reaction can be carried out in either a solution state or a solid phase reaction, and a known method can be used. The reaction of the block copolymer (C) with maleic anhydride in a solution state is performed by, for example, adding the block copolymer (C to a solvent containing an aromatic hydrocarbon such as toluene or xylene or an alicyclic hydrocarbon such as cyclohexane). ) Is dissolved, maleic anhydride is added thereto, and then heated at 90 to 250 ° C. for about 0.5 to 50 hours. In addition, the solid phase reaction
The block copolymer (C) and maleic anhydride are heated to 100 to 300 ° C. for 0.1 to 20 by a closed mixer such as a kneader or a Banbury mixer or an extruder such as a single screw or twin screw extruder. It is performed by mixing and stirring for about a minute. The modified portion of the maleic anhydride modified block copolymer (C-1) by the addition of maleic anhydride is, for example, [Formula 9] or [Formula 10] when the conjugated diene compound monomer is isoprene. ]] Is displayed.

[0020]

[Formula 9]

[0021]

[Formula 10]

When the block copolymer (C) is reacted with maleic anhydride, organic peroxides such as diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, and dicumyl are used to accelerate the reaction. Peroxide, 2,5-dimethyl, 2,5-di, (t-
Dialkyl peroxide such as butylperoxy) hexane, peroxyketal, ketone peroxide and the like can be used.

The addition amount of maleic anhydride is 0.10 per monomer unit of the conjugated diene compound in the block copolymer (C).
When it is less than 1 mol%, the modifying effect of the obtained new polymer is not sufficient, and the reaction exceeding 5.0 mol% is difficult, and the elasticity of the obtained polymer is lowered. Will be a factor. Therefore, the amount of maleic anhydride added is 0.1 to 5% per monomer unit of the conjugated diene compound.
It is 0 mol%, preferably 0.3 to 3.0 mol%.

The acrylic polymer to be reacted with the maleic anhydride added to the hydrogenated conjugated diene compound part in the block copolymer (C) has a primary amino group or secondary amino group at the molecular end. Which is an acrylic polymer having a thiol group and a compound having a primary amino group or a secondary amino group, and is present in the presence of an acrylic monomer such as acrylic acid, methyl acrylate or ethyl acrylate. , One or a mixture of two or more monomers of acrylic acid ester such as butyl acrylate and methacrylic acid ester such as methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, etc. as a radical polymerization initiator It is obtained by polymerizing. As the compound having a thiol group and a primary amino group or a secondary amino group, aminomethanethiol, 2-aminoethanethiol, 3-aminopropanethiol, 4-aminobutanethiol and the like can be used. As the radical polymerization initiator, known compounds such as azo compounds such as azobisisobutyronitrile and organic peroxides such as benzoyl peroxide can be used. The polymerization reaction in which an acrylic monomer is polymerized in the presence of a compound having a thiol group and a primary amino group or a secondary amino group is carried out by adding a thiol group and a primary amino group or a secondary amino group to the acrylic monomer. It can be carried out by adding a radical polymerization initiator after adding a compound having a secondary amino group. In order to facilitate the control of the reaction at this time, for example, an aromatic hydrocarbon such as benzene or toluene, or a solvent such as acetic acid ester such as methyl acetate or ethyl acetate can be used.

If the number average molecular weight of the acrylic polymer added to the maleic anhydride-modified block copolymer (C-1) is less than 5000, the modifying action of the obtained polymer is not sufficient, and , 70,000, the reaction with the maleic anhydride-modified block copolymer (C-1) becomes difficult. Therefore, the acrylic polymer to be subjected to the addition reaction with the maleic anhydride-modified block copolymer (C-1) has a number average molecular weight of 5,000 to 70,000, preferably 7
000 to 50,000.

Maleic anhydride-modified block copolymer (C
The reaction between -1) and the acrylic polymer having a primary amino group or a secondary amino group at the molecular end can be carried out by either reaction in a solution state or solid phase reaction. The reaction in a solution state is carried out, for example, by using aromatic hydrocarbons such as benzene and toluene, acetic acid esters such as methyl acetate and ethyl acetate, maleic anhydride modified block copolymer (C-1) and a primary chain at the molecular end. 50 to 2 by dissolving with an acrylic polymer having an amino group or a secondary amino group,
Depending on the method of heating reaction at 00 ° C., and the solid phase reaction, a closed mixer such as a kneader or a Banbury mixer,
Alternatively, a maleic anhydride-modified block copolymer (C-1) and a first terminal are attached to the molecular ends by a single-screw or twin-screw extruder.
It can be carried out by mixing and stirring an acrylic polymer having a primary amino group or a secondary amino group under heating at 80 to 250 ° C. for 0.1 to 20 minutes. When the addition amount of the acrylic polymer per monomer unit of the conjugated diene compound in the block copolymer (C) is less than 0.01 mol%, the modifying action resulting from the addition of the acrylic polymer Is not sufficient, and if 1.0 mol% or more is added, the elasticity of the polymer becomes insufficient.

Maleic anhydride-modified block copolymer (C
If the number average molecular weight of the polymer obtained by reacting -1) with an acrylic polymer having a primary amino group or a secondary amino group at the molecular end becomes less than 31,000, a The physical properties are remarkably deteriorated, and 4
When it exceeds 50,000, the melt viscosity is largely increased and the miscibility with other plastics becomes insufficient.

[0028]

EXAMPLES The concrete constitutions of the novel polymer of the present invention and the method for producing the same are described below. "Example 1" 600 ml of cyclohexane and 0.5 of butyl lithium were placed in a pressure-resistant reaction vessel which was dried and then replaced with nitrogen.
Add ml and raise the temperature to 50 ° C, and add styrene 1
By sequentially adding 0 ml, 120 ml of isoprene and 10 ml of styrene and polymerizing, "a block composed of a styrene polymer-a block composed of an isoprene polymer-"
Thus, a block copolymer consisting of a styrene polymer was obtained. The number average molecular weight of this copolymer is 152,000.
The number average molecular weight of the block made of the styrene polymer in the copolymer is 9,800, and the number average molecular weight of the block made of the isoprene polymer is 132,000.
The obtained copolymer was dissolved in 500 ml of cyclohexane, Pd-C (Pd: 5% by weight) was added, and hydrogenation reaction was carried out at a hydrogen pressure of 35 kg / cm ² and 120 ° C. After completion of the reaction, the catalyst was removed and the polymer was recovered to obtain a hydrogenated block copolymer (C). The hydrogenation rate of the obtained hydrogenated block copolymer (C) was 95.1% from the measurement result of iodine value.

Then, 5 of the hydrogenated block copolymer (C)
To 0 g, 2.0 g of maleic anhydride and 2,5-dimethyl,
2,5-di (t-butylperoxy) hexane 0.1 g
Add and, and add 22 with Brabender Plasticorder
The mixture was kneaded at 0 ° C for 5 minutes to obtain a maleic anhydride modified block copolymer (C-1) to which maleic anhydride was added.
The obtained maleic anhydride-modified block copolymer (C-
The addition amount of maleic anhydride in 1) was 1.5 mol% per monomer unit of isoprene in the block copolymer (C-1) from the measurement result of acid value.

On the other hand, in another pressure-resistant reaction vessel, 350 ml of ethyl acetate, 6 g of 2-aminoethylthiol and 2
Introducing 00 g of methyl methacrylate monomer and 10 g of azobisisobutyronitrile as a reaction initiator,
A polymerization reaction was carried out by heating to 70 ° C. to obtain a methyl methacrylate polymer having a number average molecular weight of 37600 having an average of 1.01 primary amino groups at the terminals.

Thereafter, 30 g of the maleic anhydride-modified block copolymer (C-1) described above and 20 g of methyl methacrylate polymer were kneaded with a Brabender Plasticorder at 200 ° C. for 7 minutes to give maleic anhydride. The maleic anhydride portion of the modified block copolymer (C-1) is reacted with a methyl methacrylate polymer having a primary amino group at the terminal, and the methyl methacrylate polymer is an isoprene monomer unit of an isoprene block. 0.03 mol% per
A new polymer (a) having been added was obtained.

The number average molecular weight of the novel polymer (a) measured by a membrane osmometer is 163,000. In addition, the novel polymer (a), by the measurement of the infrared absorption spectrum,
Acid anhydride group C near 1800 cm ^-1 and 1880 cm ^-1
= O based absorption, 1720 cm ^-1 based on C = O of a carboxyl group, 1640 cm ^-1 based on C = O of an amide bond represented by [Formula 5], 1
It has an absorption based on C═O of the cyclic imide bond represented by [Formula 6] near 710 cm ^−1, and has a maleic acid and / or maleic anhydride content with respect to the hydrogenated block copolymer (C). It was confirmed that a polymer in which an acrylic polymer was added by an amide bond through was obtained.

[Example 2] In the step of obtaining the hydrogenated block copolymer (C) in Example 1, only the amount of each monomer in the step of sequentially adding styrene, isoprene and styrene is changed, All other steps were the same as the steps of obtaining the hydrogenated block copolymer (C) of Example 1 to obtain another hydrogenated block copolymer (C) having a number average molecular weight of 106000. The number average molecular weight of the block composed of the styrene polymer in the hydrogenated block copolymer (C) is 12
500, the number average molecular weight of the block composed of the isoprene polymer was 70200, and the hydrogenation rate was 96.9% from the measurement result of iodine value.

Next, 5 of the hydrogenated block copolymer (C)
0 g, maleic anhydride 3.5 g and 2,5-dimethyl,
0.2 g of 2,5-di (t-butylperoxy) hexane
Add and, and add 22 with Brabender Plasticorder
The mixture was kneaded at 0 ° C for 5 minutes to obtain a maleic anhydride modified block copolymer (C-1) to which maleic anhydride was added.
The obtained maleic anhydride-modified block copolymer (C-
The addition amount of maleic anhydride in 1) was 2.3 mol% per monomer unit of isoprene in the maleic anhydride-modified block copolymer (C-1) from the measurement result of acid value.

On the other hand, in another pressure-resistant reaction vessel, the amounts of azobisisobutyronitrile and 2-aminoethylthiol as reaction initiators were changed under the polymerization conditions of the methyl methacrylate polymer in Example 1. All other conditions were the same as the corresponding conditions of Example 1 to obtain a methyl methacrylate polymer having a number average molecular weight of 21,500 having an average of 0.98 primary amino groups at the terminals.

Thereafter, 25 g of the above maleic anhydride-modified block copolymer (C-1) and 25 g of methyl methacrylate polymer were kneaded with a Brabender Plasticorder at 200 ° C. for 7 minutes to give maleic anhydride. The maleic anhydride portion of the modified block copolymer (C-1) is reacted with a methyl methacrylate polymer having a primary amino group at the terminal, and the methyl methacrylate polymer is an isoprene monomer unit of an isoprene block. 0.04 mol% per
A new polymer (b) having been added was obtained.

The number average molecular weight of the novel polymer (b) measured by a membrane osmometer is 107,000. In addition, the novel polymer (b) is measured by infrared absorption spectrum,
Acid anhydride group C near 1800 cm ^-1 and 1880 cm ^-1
= O based absorption, 1720 cm ^-1 based on C = O of a carboxyl group, 1640 cm ^-1 based on C = O of an amide bond represented by [Formula 5], 1
It has an absorption based on C═O of the cyclic imide bond represented by [Formula 6] near 710 cm ^−1, and has a maleic acid and / or maleic anhydride content with respect to the hydrogenated block copolymer (C). It was confirmed that a polymer in which an acrylic polymer was added by an amide bond through was obtained.

Example 3 600 ml of cyclohexane and 0.7 ml of butyllithium were placed in a pressure resistant reaction vessel which had been dried and then replaced with nitrogen, heated to 50 ° C., and 52 ml of styrene and 110 ml of isoprene were successively added. By adding and polymerizing, a block copolymer composed of a styrene polymer and a block composed of an isoprene polymer was obtained. The number average molecular weight of this copolymer is 1
The number average molecular weight of the block made of the styrene polymer in the copolymer was 43500, and the number average molecular weight of the block made of the isoprene polymer was 6940.
It is 0. The obtained copolymer was dissolved in 500 ml of cyclohexane, Pd-C (Pd: 5% by weight) was added, and hydrogenation reaction was carried out at a hydrogen pressure of 35 kg / cm ² and 120 ° C. After completion of the reaction, the catalyst was removed and the polymer was recovered to obtain a hydrogenated block copolymer (C). The hydrogenation rate of the obtained hydrogenated block copolymer (C) was 97.4% from the measurement result of iodine value.

Then, 5 of the hydrogenated block copolymer (C)
0 g, maleic anhydride 5.0 g and 2,5-dimethyl,
Add 2,5- (t-butylperoxy) hexane (0.3 g) and use a Brabender Plasticorder to add 220
The mixture was kneaded at 5 ° C for 5 minutes to obtain a maleic anhydride-modified block copolymer (C-1) to which maleic anhydride was added. Obtained maleic anhydride-modified block copolymer (C-1)
From the measurement result of the acid value, the amount of maleic anhydride added was 2.6 mol% per monomer unit of isoprene in the block copolymer (C-1).

Thereafter, 20 g of the maleic anhydride-modified block copolymer (C-1) described above and a number average molecular weight of 37600 having an average of 1.01 primary amino groups at the terminals obtained in Example 1 were 37600. 30 g of methyl methacrylate polymer
And were kneaded for 7 minutes at 200 ° C. with a Brabender Plasticorder, and the maleic anhydride portion of the maleic anhydride-modified block copolymer (C-1) and a methyl methacrylate copolymer having a primary amino group at the end were mixed. React with the union,
A new polymer (c) was obtained in which the methyl methacrylate polymer was added at 0.05 mol% per isoprene monomer unit of the isoprene block.

The number average molecular weight of the novel polymer (c) measured by a membrane osmometer is 114,000. In addition, the novel polymer (c) is
Acid anhydride group C near 1800 cm ^-1 and 1880 cm ^-1
= O based absorption, 1720 cm ^-1 based on C = O of a carboxyl group, 1640 cm ^-1 based on C = O of an amide bond represented by [Formula 5], 1
It has an absorption based on C═O of the cyclic imide bond represented by [Formula 6] near 710 cm ^−1, and has a maleic acid and / or maleic anhydride content with respect to the hydrogenated block copolymer (C). It was confirmed that a polymer in which an acrylic polymer was added by an amide bond through was obtained.

[Experiment] Each of the novel polymers (a) to (c) obtained in Examples 1 to 3 and polypropylene (PP) and methyl methacrylate polymer (PMMA) are shown in a predetermined column of [Table 1]. After kneading with a Brabender plastic coater at a composition ratio by weight shown in (3), press molding was performed to a thickness of 2.0 mm to obtain three types of sheets. In addition, polypropylene and methyl methacrylate polymer are listed in [Table 1].
After kneading with a Brabender plastic coater in the mixing ratio shown in the predetermined column, a sheet for comparison was obtained by press molding to a thickness of 2.0 mm. By measuring the mechanical properties of each of the obtained sheets, the novel polymer (a) to
The action of (c) as a compatibilizer was evaluated. The dispersed particle size of the polymer in each sheet was observed by an electron microscope. The results are shown in [Table 2].

[0043]

[Table 1]

[0044]

[Table 2]

[0045]

ACTIONS AND EFFECTS The novel polymer of the present invention has properties of both a non-polar polymer and a polar polymer. Therefore, when it is mixed with a plastic such as polyolefin, the adhesion and coating properties of the mixture are improved. Further, when mixed with a polar polymer such as polyamide, the flexibility of the mixture is improved. Further, the novel polymer of the present invention exhibits excellent action and effect as a compatibilizing agent when mixing a nonpolar polymer and a polar polymer. Furthermore, according to the method for producing a novel polymer of the present invention, a useful polymer having both properties of the above-mentioned non-polar polymer and polar polymer can be easily and accurately obtained.

[Chemical 9]

[Chemical 10]

Claims (2)

[Claims] 1. One or more blocks (A) having a number average molecular weight of 1,000 to 50,000 made of a polymer of a vinyl aromatic compound and 70% or more of the carbon-carbon double bond made of a polymer of a conjugated diene compound. With hydrogenated number average molecular weight of 20,000 to 200,000 (B)
, And the rational expression is {(A) · (B)} _m or (A) {(B) · (A)} _n (where m and n represent integers of 1 or more). ) Number average molecular weight 3000
0-400000 block copolymer (C), maleic anhydride in the portion of the conjugated diene compound in the block copolymer (C), a monomer of the conjugated diene compound in the block copolymer (C) 0.1 to 5.0 mol% per unit is added, and the acrylic polymer having a number average molecular weight of 5,000 to 70,000 is added to the maleic anhydride added to the conjugated diene in the block copolymer (C). Addition of 0.01 to 1.0 mol% per monomer unit of the compound, the portion being represented by [Chemical formula 1] and / or [Chemical formula 2]
A novel polymer comprising 000 to 450,000 polymers. [Chemical 1] [Chemical 2] 2. One or more blocks (A) having a number average molecular weight of 1,000 to 50,000 comprising a polymer of a vinyl aromatic compound and 70% or more of the carbon-carbon double bond comprising a polymer of a conjugated diene compound. With hydrogenated number average molecular weight of 20,000 to 200,000 (B)
And one or more of, and the rational expression is {(A) · (B)}
number average molecular weight 30 represented by _m or (A) {(B) · (A)} _n (where m and n are integers of 1 or more)
Maleic anhydride modification in which maleic anhydride is added to the conjugated diene compound part in the block copolymer (C) by reacting 000 to 400000 block copolymer (C) with maleic anhydride After obtaining the block copolymer (C-1), the maleic anhydride-modified block copolymer (C-1) and a number average molecular weight of 5,000 having a primary amino group or a secondary amino group at the molecular end. ~ 700
By reacting with an acrylic polymer of 00, maleic anhydride is added in an amount of 0.1 to 5.0 mol% per monomer unit of the conjugated diene compound in the block copolymer (C), and The acrylic polymer is added to the added maleic anhydride in an amount of 0.01 to 1.0 mol% per monomer unit of the conjugated diene compound in the block copolymer (C), and the portion is A method for producing a novel polymer, characterized in that a polymer having a number average molecular weight of 31,000 to 450,000 represented by [Chemical Formula 3] and / or [Chemical Formula 4] is obtained. [Chemical 3] [Chemical 4]