JPH05287084A - Production of multicomponent multiphase polymer material having three-dimensional bicontinuous microphase separation structure - Google Patents

Production of multicomponent multiphase polymer material having three-dimensional bicontinuous microphase separation structure

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JPH05287084A
JPH05287084A JP9314092A JP9314092A JPH05287084A JP H05287084 A JPH05287084 A JP H05287084A JP 9314092 A JP9314092 A JP 9314092A JP 9314092 A JP9314092 A JP 9314092A JP H05287084 A JPH05287084 A JP H05287084A
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molecular weight
polymer
copolymer
polymer chain
structure
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JP3245683B2 (en
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Hiroichi Hasegawa
Takeji Hashimoto
竹治 橋本
博一 長谷川
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Res Dev Corp Of Japan
新技術事業団
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Abstract

(57) [Summary] [Objective] To provide a method for easily producing a multi-component multi-phase polymer material having a three-dimensional co-continuous micro phase separation structure (bicontinuous structure) in a wide copolymerization composition range. .. [Structure] An ABA type triblock copolymer consisting of two types of mutually incompatible polymer chains A and B, in which the block chains at both ends have different molecular weights of two times or more. Form the coalescence. Further, an AB type diblock copolymer or an ABA type triblock copolymer composed of two types of mutually incompatible polymer chains A and B has different molecular weights or copolymerization compositions. A-B type diblock copolymer or A-B-A type triblock copolymer, or a homopolymer of a polymer chain A having a small molecular weight and a homopolymer of a polymer chain A having almost the same molecular weight, or a molecular weight A homopolymer of the polymer chain A having a large distribution or a polymer having compatibility with the polymer chain A is melt-kneaded or solution-mixed and molded.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a multi-component polymer,
The present invention relates to a method for producing a multi-component multi-phase polymer material which three-dimensionally penetrates each other throughout the material to form a continuous network structure, that is, has a three-dimensional bicontinuous microphase-separated structure (bicontinuous structure). The multi-component multi-phase polymer material having this structure can be used in a wide range of industrial fields, and examples thereof include application to ultrafiltration membranes, carriers such as catalysts, and functional polymer supports.

[0002]

2. Description of the Related Art A block or graft copolymer in which mutually incompatible polymer chains are linked by a covalent bond has a phase-separated structure which can be enlarged more than the spread of constituent molecular chains because of its connectivity. However, it is known to exhibit a unique multiphase structure called a submicron size microphase-separated structure. Generally, in the case of a microphase-separated structure composed of A component and B component, a structure in which spheres of B component are packed in a cubic lattice in a medium of A component, and a cylinder of B component is hexagonal in a medium of A component Three types of structures have been known for a long time, including a structure packed in a lattice and an alternating layered structure of A component and B component, but in these structures, both components do not have three-dimensional continuity.

The present inventors have found that in such a microphase-separated structure, there is a structure in which both A and B components penetrate three-dimensionally, that is, a bicontinuous structure, and a diblock It has already been announced that the structure of a polymer can be controlled only by the copolymer composition. That is, if the copolymerization composition is controlled so that the volume fraction of one component is 62 to 66%, a large number of components called a tetrapod network structure or an OBDD structure become a medium, and a small number of components are doubled. A bicontinuous structure that forms the diamond network is formed ["
Macromolecules "20, 1651 (19
87)]. Further, it is known that an OBDD structure can be produced by subjecting a diblock copolymer having a cylinder-like and alternating layered microphase-separated structure to a solution-mixing film formation of a homopolymer of one of the components. [Winey, "M
acromolecules "25, 422 (199
2)], even in that case, the total volume fraction of the components is limited to a narrow range of 64-67%.

The multi-component multi-phase polymer material having this three-dimensional bicontinuous micro-phase separation structure (bicontinuous structure) has excellent mechanical strength because stress is dispersed by the three-dimensional network structure. Also, since both components form a continuous phase together, they have excellent substance permeability and conductivity and are extremely useful polymer materials. However, in the method for realizing a bicontinuous structure with a block copolymer alone as described above, it is necessary to control the copolymerization composition within a narrow range so that the volume fraction of each component falls within the narrow range. With the above difficulties. This is also the case when the homopolymer of the A component is simply mixed with the AB type diblock copolymer,
There is a problem that the composition of the material is limited to a narrow range.

[0005]

According to the present invention, the volume fraction of one component is adjusted to, for example, 60 number% by simply controlling the polymerization or mixing the block copolymer with the block copolymer or the homopolymer. It is an object of the present invention to provide a method for easily producing a multi-component multi-phase polymer material having a bicontinuous structure in a wide volume fraction range, and thus in a wide copolymerization composition range, without being restricted by such restrictions. And

[0006]

DISCLOSURE OF THE INVENTION The present inventors have proposed a multi-component multi-phase polymer material containing a block copolymer, which has a bicontinuous structure in which both component phases penetrate three-dimensionally. Various studies were conducted on the manufacturing method. as a result,
The following factors are responsible for the formation of bicontinuous structure: (a) Control of the curvature of the microphase-separated interface. (B) Control of packing of molecular chains in the microphase-separated phase. It was found that the volume fraction of each component is not necessarily an important factor for forming a bicontinuous structure if these can be controlled, and the present invention has been completed.

(A) Control of curvature of microphase-separated interface. First, (a) the control of the curvature of the microphase-separated interface will be described. Now, when considering an AB type diblock copolymer consisting of two types of mutually incompatible polymer chains A and B, if the molecular volumes of the two are equal, the curvature of the microphase-separated interface is 0. That is, it becomes a plane and an alternating layered micro phase separation structure is formed. However, when the molecular volume of the polymer chain A becomes larger than the molecular volume of the polymer chain B, the polymer chain A phase becomes dense and the polymer chain B phase becomes sparse when the interface remains flat. In order to avoid such a situation and keep the density of both phases constant, the interface becomes a curved surface, and a micro phase separation structure having a cylindrical or spherical curved surface as an interface is formed.

Generally, a curved surface is classified into an ellipsoidal surface, a paraboloidal surface and a hyperboloidal surface according to its curvature. The interface of a micro phase separation structure having a spherical curved surface as an interface is an ellipsoidal surface, a cylinder shape or a planar shape. The interface of the micro phase separation structure having a curved surface as an interface belongs to a parabolic surface, and its curvature always takes 0 or a positive value. However, the interface of the microphase-separated structure of the bicontinuous structure is a hyperboloid and has a saddle shape in which convex portions and concave portions are combined, so that its curvature has both positive and negative values.

Therefore, in a block copolymer consisting of two types of mutually incompatible polymer chains A and B, a block copolymer in which the molecular volume of the polymer chain A is always larger than that of the polymer chain B is used. A bicontinuous structure is more likely to occur when the molecular volume of the polymer chain A is larger or smaller than that of the polymer chain B than that of the polymer. From this point of view, in order to form a bicontinuous structure, it is sufficient to have a distribution in the molecular volume of each polymer chain of the block copolymer (of course, the average curvature of the interface of the bicontinuous structure is 0). Since it takes a finite value that is close but not 0, the average molecular volume of polymer chain A and polymer chain B
It goes without saying that the ratio of the average molecular volumes of must give such an average curvature). That is, in order to form the bicontinuous structure by controlling the curvature of the microphase-separated interface in (a), the molecular volume of each polymer chain of the block copolymer may have a distribution.

The inventors of the present invention have made up each polymer chain of this block copolymer (hereinafter, this polymer chain is also referred to as a block chain).
It was found that the following two methods can be adopted as a method of giving distribution to the molecular volume of That is, (a) a method of giving a molecular weight distribution between each block chain. (B) A method of swelling the polymer chain A of the block copolymer with a homopolymer or a heteropolymer. Is. First (a)
The method of imparting a molecular weight distribution between the block chains is performed by synthesizing a block copolymer having a molecular weight distribution or a composition distribution between the block chains. This method
Specifically, it is a method of synthesizing an ABA type triblock copolymer in which the molecular weights of the polymer chains A at both ends are 2 to 5 times different. Further, an AB type diblock copolymer or an ABA type diblock copolymer or an ABA type triblock copolymer having a different molecular weight or copolymerization composition is added to the AB type diblock copolymer or ABA type triblock copolymer. The same effect as that of the block copolymer having a molecular weight distribution or a composition distribution between the respective block chains can be obtained also by the method of melt-mixing or solution-mixing the coalescence.

The second method (b) is to use a block copolymer consisting of a polymer chain A and a polymer chain B, which has a smaller molecular weight than the polymer chain A of the block copolymer. A homopolymer of the same type or a heteropolymer having compatibility with the polymer chain A (which may be a homopolymer or a copolymer) are mixed to form a block copolymer. In this method, the apparent molecular volume of the polymer chain A of the block copolymer is changed by swelling the polymer chain A with the homopolymer or the heteropolymer.

In the method (b), when a homopolymer of the same type as the polymer chain A is used, the ratio of the molecular weight M H of the homopolymer to the molecular weight M B of the polymer chain A of the block copolymer. r (= M H / M B ) is an important factor. This ratio r is 1
The smaller the molecular weight M H of the homopolymer, the smaller the molecular weight M B of the polymer chain A of the block copolymer, the better the polymer chain A is swollen by the homopolymer and the apparent molecular volume. However, when r is close to 1, the polymer chain A is hardly swollen, and the homopolymer becomes localized in the center of the microphase. When r is extremely larger than 1, the block copolymer is And the homopolymer phase-separates macroscopically. The same applies to the case where a heteropolymer having compatibility with the polymer chain A is used, but in this case, the interaction (attracting or attracting each other between the block copolymer and the heteropolymer, Since a repulsive force) works, it is necessary to select r in consideration of this point as well.

It should be noted here that the bicontinuous interface has a hyperboloid parallel to a hyperboloid having a mean curvature of 0 (referred to as a minimal surface), or a hyperboloid having a constant mean curvature close to the hyperboloid. Although it is considered to be a curved surface, the average curvature is close to 0 in any case, so when mixing block copolymers, homopolymers or heterogeneous polymers, the average curvature of the microphase-separated interface deviates much from 0. You have to hold it down so that it doesn't exist.

(B) Control of packing of molecular chains in the microphase-separated phase. Next, the control of packing of molecular chains in the (b) microphase-separated phase will be described. Another method for forming a bicontinuous structure in a method for producing a multicomponent multiphase polymer material containing a block copolymer as a component, which has a bicontinuous structure in which both component phases penetrate three-dimensionally One factor is the control of packing of block and homopolymer chains of the block copolymer into the microphase separated phase space. The difficulty of the filling affects the formation of the bicontinuous structure. That is, since one end of the block chain of the block copolymer is constrained within the microphase-separated interface, the packing mode within the microphase-separated phase space is also constrained.
This effect is particularly remarkable in the bicontinuous structure.

The figure shows schematic views of cross sections of various microphase-separated phases. FIG. 1 shows an alternating layered structure, and FIG. 2 shows a sphere or cylinder.
Structure, Figure 3 is a kind of bicontinuous structure OB
It is a schematic diagram about a DD structure. In the case of FIGS. 1 and 2, no matter where one end of the block chain of the block copolymer 2 is placed on the interface 1 shown by the thick line, the space given to the block chain is the same. However, in the case of FIG. 3, the width of the space given to the block chain differs between the block chain indicated by the arrow a and the block chain indicated by the arrow b. This is because the block chain indicated by the arrow b must fill the extra space surrounded by the dotted line. However, if the block chain shown by the arrow of b is larger than the block chain shown by the arrow of a, or if the space surrounded by the dotted line can be filled with a polymer that is not bound by the interface, there is a problem in filling the molecular chain. The points disappear. In the former case, the molecular weight of the block chain indicated by the arrow b may be increased, that is, the block chain of the block copolymer may have a molecular weight distribution. In the latter case, a homopolymer having substantially the same molecular weight as the block chain of the block copolymer (r = 1) is mixed so that the homopolymer is localized in the center of the microphase.

Therefore, from the viewpoint of controlling the packing of the molecular chains in the (b) microphase-separated phase, there are the following two methods for satisfying the requirement for forming a bicontinuous structure. That is, (c) a method in which each block chain has a molecular weight distribution. (D) A method of mixing a homopolymer having a molecular weight almost equal to that of the block chain. Is.

As described above, in order to form the bicontinuous structure by simultaneously performing (a) control of the curvature of the microphase-separated interface and (b) control of packing of the molecular chains in the microphase-separated phase, (A) A method of providing a molecular weight distribution between each block chain. (B) A method of swelling the polymer chains of the block copolymer with a homopolymer or a heteropolymer. (C) A method of giving each block chain a molecular weight distribution. (D) A method of mixing a homopolymer having a molecular weight almost equal to that of the block chain. Is to combine with any one of.

Therefore, in order to form a bicontinuous structure, (i) a method of providing a molecular weight distribution between each block chain. (Ii) A method in which a method of swelling the polymer chain A of the block copolymer with a homopolymer or a heteropolymer and a method of mixing a homopolymer having a molecular weight almost equal to that of the block chain are combined. Can be done by

The present invention has been completed based on the above examination. That is, the present invention is an ABA type triblock copolymer comprising 1.2 kinds of mutually incompatible polymer chains A and B, wherein the block chains at both ends have a molecular weight of 2 to 2 A method for producing a multi-component multi-phase polymer material having a three-dimensional bi-continuous micro phase separation structure, which comprises melt-molding or solution-casting triblock copolymers different in 5 times (claim 1),

2. An AB type diblock copolymer or an ABA type triblock copolymer consisting of two types of mutually incompatible polymer chains A and B is added to the molecular weight or copolymer. AB type diblock copolymers or AB having different polymerization compositions
A method for producing a multi-component multi-phase polymer material having a three-dimensional co-continuous micro phase separation structure, characterized by melt-mixing or solution-mixing an A-type triblock copolymer and molding (claim 2);

3. An AB type diblock copolymer or an ABA type triblock copolymer consisting of two types of mutually incompatible polymer chains A and B is added to the block copolymer. Polymerization of a homopolymer of a polymer chain A having a smaller molecular weight than that of the polymer and a polymer having a molecular weight approximately equal to that of the polymer chain A of the block copolymer by melt mixing or solution mixing A method for producing a multi-component multi-phase polymer material having a three-dimensional bicontinuous micro-phase separation structure characterized by (claim 3),

4. An AB type diblock copolymer or an ABA type triblock copolymer consisting of two types of mutually incompatible polymer chains A and B is added to the block copolymer. A homopolymer or high polymer of the polymer chain A having a molecular weight of the polymer chain A and a number average molecular weight which are substantially equal to or smaller than each other and a ratio of the weight average molecular weight to the number average molecular weight of 1.5 or more. A method for producing a multi-component multi-phase polymer material having a three-dimensional bicontinuous micro-phase separation structure, characterized by melt-mixing or solution-mixing a polymer having compatibility with the molecular chain A and molding. ,.

The present invention will be described in more detail. AB type diblock copolymer or AB comprising two types of mutually incompatible polymer chains A and B used in the method of the present invention
The polymer chain A and the polymer chain B of the -A type triblock copolymer and the homopolymer may be of any type as long as they are polymers other than the crystalline polymer and the rigid polymer. Polymer chain A
Is, for example, polystyrene, poly-α-methylstyrene, polymethylmethacrylate, poly-2-vinylpyridine, etc., and the polymer chain B is, for example, polyisobutylene,
Examples include polybutadiene, polyethylene propylene, polyethylene butene, polydimethyl siloxane and polyethylene oxide.

When one of these polymer chains A and B is selected to synthesize a di- or triblock copolymer, if the block chain has a molecular weight of 10,000 or more, the block The polymer chains of the copolymer are surely incompatible with each other and also cause microphase separation.

Examples of the AB type diblock copolymer include polystyrene-polyisobutylene diblock copolymer, polystyrene-polybutadiene diblock copolymer, polystyrene-polyethylene propylene diblock copolymer, polystyrene-polyethylene butene diene. Block copolymers and the like. The ABA type triblock copolymer is a polystyrene-polyisobutylene-polystyrene triblock copolymer, polystyrene-polybutadiene-polystyrene triblock copolymer, polystyrene-polyethylenepropylene-polystyrene triblock copolymer, polystyrene- Examples thereof include polyethylene butene-polystyrene triblock copolymer.

In the invention of claim 1, the molecular weights of the polymer chains A at both ends of the ABA type triblock copolymer are made different. This ABA type triblock copolymer can be produced by varying the molecular weights of the block chains A at both ends by adjusting the supply amount of each monomer during the synthesis by the sequential polymerization method. Also, this A-B-A
The type triblock copolymer can also be synthesized by a coupling reaction between homopolymers having a wide molecular weight distribution and having a reactive group at the terminal. The difference in the molecular weights of the polymer chains A at both ends is preferably 2 to 5 times. If it is 2 times or less, a bicontinuous structure is unlikely to be formed, and if it is 5 times or more, block chains at both ends may separately form a microphase, which is not preferable. It is composed of these two types of incompatible polymer chains A and B, and the polymer chains A at both ends have a molecular weight of 2 to
When an ABA type triblock copolymer having a difference of 5 times is melt-molded or solution-cast by a usual method, a molded product having a bicontinuous structure is obtained.

In the invention of claim 2, the above-mentioned A-
A B-type diblock copolymer or an ABA type triblock copolymer, which has a different molecular weight or copolymerization composition from A
-B type diblock copolymer or ABA type triblock copolymer is melt mixed or solution mixed. When the triblock copolymer is polymerized by a usual polymerization method, generally, the block chains at both ends have the same molecular weight.
Regarding the structure formation, the -BA type triblock copolymer is an A-1 / 2B type diblock copolymer obtained by cutting in the middle of the B block (the molecular weight of the polymer chain B is 1/2). Works the same as. That is, the A 1 -B-A 2 type triblock copolymer is a diblock copolymer called A 1 -1 / 2B and A 2
It is considered to be equivalent to a 1: 1 mixture of diblock copolymers called -1 / 2B. Therefore, when the block copolymers having different molecular weights or different copolymerization compositions are mixed in forming the structure, the molecular weights of the polymer chains at both ends are different from each other.
It behaves similarly to the BA type triblock copolymer. By molding the melt-mixed or solution-mixed product, a molded product having a bicontinuous structure is obtained.

Further, in the invention of claim 3, the above A
-B-type diblock copolymer or ABA-type triblock copolymer, a homopolymer of a polymer chain A having a smaller molecular weight than the block chain of the block copolymer and the block copolymer A polymer having a molecular weight approximately equal to the molecular weight of the block chain is melt mixed or solution mixed. Generally, a triblock copolymer is produced in which the block chains on both ends have the same molecular weight. The molecular weight of the above-mentioned homopolymer having a small molecular weight of the polymer chain A mixed with the block copolymer is the ratio of the molecular weight M H of the homopolymer to the molecular weight M B of the polymer chain A of the block copolymer (M H It is preferred that / M B = r) is significantly lower than 1, for example 0.5 or less. By mixing these homopolymers of the low molecular weight polymer chain A,
The polymer chain A of the block copolymer swells and its molecular volume increases. Further, the molecular chain packing is performed by mixing a polymer having a molecular weight almost equal to the molecular weight of the block chain of the block copolymer. Therefore, a molded product having a bicontinuous structure is obtained by molding a melt-mixed or solution-mixed product of the above-mentioned two kinds of homopolymers of the polymer chain A.

Further, in the invention of claim 4, the above A
-B type diblock copolymer or ABA type triblock copolymer, the molecular weight of the polymer chain A of the block copolymer is almost equal to or smaller than, and the ratio of the weight average molecular weight to the number average molecular weight. Is melt-mixed or solution-mixed with a homopolymer of the polymer chain A having a molecular weight distribution of 1.5 or more or a polymer having compatibility with the polymer chain A. When this homopolymer having a wide molecular weight distribution is mixed, the polymer chain A of the block copolymer swells due to the action of the polymer component having a smaller molecular weight than the polymer chain A of the block copolymer therein, and The microphase-separated phase space is filled by the action of the polymer component having a molecular weight almost equal to that of the polymer chain A of the block copolymer therein. Also, when a polymer having compatibility with the polymer chain A is used, swelling and filling are similarly performed. Therefore, when the above mixture is molded, a molded article having a bicontinuous structure can be obtained.

At this time, when a homopolymer having a narrow molecular weight distribution with a ratio of the weight average molecular weight to the number average molecular weight of about 1 and a low molecular weight is used, the above-mentioned volume fraction is from 64 to 67%.
The bicontinuous structure is formed only in a limited range, and the structure is also limited to the OBDD structure. When the homopolymer satisfying the above conditions of the present invention is used, the range of the volume fraction can be extremely widened, and in addition to the OBDD structure, a lamella catenoid structure, a T-surface structure and a disoade order. It is possible to obtain molded articles having various bicontinuous structures such as structures.

The above-described technique for producing a multi-component multi-phase polymer material having a bicontinuous structure according to the present invention has, for example, excellent mechanical function as a separation membrane (selective permeation membrane). It can be applied to the modification of polymer materials that have not been put into practical use due to problems with moldability and moldability. That is, first, for a functional polymer capable of forming a separation membrane,
The second component such as polystyrene, poly α-methyl styrene, polymethylmethacrylate excellent in mechanical strength,
It is introduced by a block copolymerization reaction or a coupling reaction to synthesize a block copolymer. When the bicontinuous structure of this block copolymer is produced by the method of the present invention, it becomes possible to impart mechanical strength, water resistance and moldability without impairing the function of this material.

Further, one component of the polymeric material having a bicontinuous structure produced by the present invention is decomposed by ozone, ultraviolet rays, or the like, or the mixed homopolymer is extracted with a selective solvent to obtain 100 It is possible to obtain a porous membrane having a very uniform pore size of up to several hundreds of liters, and this porous membrane can be used as an ultrafiltration membrane and further as a carrier for catalysts and the like.

Further, the polymeric material having a bicontinuous structure in the present invention is extremely useful for the use as a film as described above, but the bicontinuous structure is a thermodynamically stable equilibrium structure. Various molded articles can be obtained by injection molding or other molding methods.

The bicontinuous structure can be prepared by using a graft copolymer according to the same principle as described above. Therefore, instead of the above reaction, a relatively simple graft reaction of the second component is carried out. And a bicontinuous structure is produced by a graft copolymer. In these cases, the three-dimensional network structure formed by the second component serves as an excellent support for the functional polymer and at the same time retains the substance permeability and conductivity of the functional polymer.

[0035]

【Example】

Example 1 An ABA type triblock copolymer consisting of two types of mutually incompatible polymer chains A and B, in which the block chains at both ends have different molecular weights, Manufacturing example. An asymmetric triblock copolymer composed of polystyrene-polyisoprene-polystyrene was synthesized by a sequential living anionic polymerization method using n-hexane as a solvent and n-butyllithium as an initiator. The molecular weights of the polystyrene chain, polyisoprene chain and polystyrene chain of each block of this asymmetric triblock copolymer are 10,000, 70,000 and 2, respectively.
It was 10,000 (total molecular weight 100,000). This asymmetric triblock copolymer was dissolved in toluene, which is a common good solvent, to obtain 10
% Solution, and a film was formed from this solution. The resulting membrane is
It had a bicontinuous structure in which the polystyrene phase formed a three-dimensional network and the polyisoprene phase served as a medium. The volume fraction of polyisoprene in this asymmetric triblock copolymer was 73%. This means that in the present invention, it is possible to form a bicontinuous structure far beyond the volume fraction range of 62 to 66% for forming a bicontinuous structure of a conventional diblock copolymer.

Example 2 An AB type diblock copolymer consisting of two types of mutually incompatible polymer chains A and B was added to the A type B block copolymer having different molecular weights.
-Production example in which a B-type diblock copolymer is melt-kneaded or solution-mixed to form a film. Two types of polystyrene-polyisobrene diblock copolymers were synthesized by a sequential living anion polymerization method using tetrahydrofuran as a solvent and S-butyllithium as an initiator. The polystyrene chains and polyisobrene chains of one of these polystyrene-polyisobrene diblock copolymers have molecular weights of 11,000 and 21,000 (total molecular weight of 32,000), respectively, and the polystyrene chain of the other one. The molecular weights of the and polyisoprene chains were 49,000 and 32,000 (total molecular weight 81,000), respectively. Both had narrow molecular weight distributions. Each of these diblock copolymers was individually dissolved in toluene to prepare a 10% solution.
The microphase-separated structure of the sample formed from each solution was an alternating layered structure.

However, the above-mentioned two kinds of diblock copolymers were mixed in a weight ratio of 50:50, dissolved in toluene to obtain a 10% solution, and the microphase-separated structure of the sample formed from this solution was A bicontinuous structure was shown. The volume fraction of polyisoprene component in this mixture was 55%. As described above, according to the present invention, it is possible to form a bicontinuous structure even if it is largely outside the volume fraction range of 62 to 66% for forming a bicontinuous structure by a conventional diblock copolymer. Further, when the above film-formed product was subjected to ozone decomposition treatment and the polyisoprene component therein was selectively removed, a porous film having a three-dimensional network structure was obtained. The pore diameter of this porous membrane was 100 Å and was uniform. The pore diameter of the porous membrane could be controlled and changed by changing the total molecular weight.

Example 3 An AB type diblock copolymer consisting of two types of mutually incompatible polymer chains A and B was added to a polymer chain A having a smaller molecular weight than the polymer chain A. Homopolymer and polymer chain A
An example of a production method of melt-kneading or solution-mixing a film of a homopolymer of a polymer chain A whose molecular weight is almost the same as A polystyrene-polyisoprene diene block copolymer was synthesized by a sequential living anionic polymerization method using cyclohexane as a solvent and s-butyllithium as an initiator. The polystyrene chains and polyisoprene chains had molecular weights of 50,000 and 50,000 (total molecular weight of 100,000), respectively, and the molecular weight distribution was narrow. The microphase-separated structure of the sample in which this polystyrene-polyisoprene diblock copolymer was formed alone from a 10% solution of toluene had an alternating layered structure. However, a polystyrene-polyisoprene diene block copolymer was added to a commercially available monodisperse polystyrene homopolymer having a molecular weight of 10,000 and a commercially available monodisperse polystyrene homopolymer having a molecular weight of 60,000. Monodisperse polystyrene homopolymer having a molecular weight of 10,000: Monodisperse polystyrene homopolymer having a molecular weight of 60,000 = 50: 25:
The microphase-separated structure of the sample prepared by mixing in a weight ratio of 25 and forming a film from a 10% toluene solution showed a bicontinuous structure. In this case, the volume fraction of the polystyrene phase is 72%, and the bicontinuous structure is formed even though the volume ratio of the diblock copolymer is out of the range 62-66%. There is.

Example 4 An AB type diblock copolymer consisting of two kinds of mutually incompatible polymer chains A and B was added to a polymer having compatibility with the polymer chain A and having a large molecular weight distribution. A production example in which a polymer C is mixed in a solution to form a film. A polystyrene-polyisoprene diene block copolymer was synthesized by a sequential living anionic polymerization method using tetrahydrofuran as a solvent and s-butyllithium as an initiator. The polystyrene chains and polyisoprene chains have molecular weights of 270,000 and 250,000 (total molecular weight of 520,000),
The molecular weight distribution was narrow. This diblock copolymer was dissolved alone in toluene to prepare a 10% solution. When the structure of a sample formed from this solution was examined, the microphase-separated structure was an alternating layered structure.

On the other hand, a polyvinyl methyl ether homopolymer synthesized by a cationic polymerization method using toluene as a solvent and boron trifluoride diethyl ether as an initiator is added to the above diblock copolymer (the molecular weight distribution is rather broad). , And the average molecular weight of 27,000) were mixed in a weight ratio of 80:20 and dissolved in toluene to prepare a 10% solution. When the structure of the sample formed from this solution was examined, the microphase-separated structure was a kind of bicontinuous lamella catenoid structure. Polyvinyl methyl ether has compatibility with polystyrene and is considered to be solubilized in the polystyrene layer. In that case, polystyrene +
The volume fraction of the polyvinyl methyl ether phase is 59%, and the bicontinuous structure can be formed even if the volume fraction of the conventional diblock copolymer is out of the range of 62 to 66%. there were.

Further, the average molecular weight of the polyvinyl methyl ether homopolymer is 27,000, which is very small compared to the molecular weight of polystyrene chain of 270,000 (r << 1), but has a bicontinuous structure. Appearance is considered to be an effect of the interaction between the polystyrene chain and the polyvinyl methyl ether homopolymer. Therefore, when mixing a homopolymer or copolymer of a polymer different from the block chain, the optimum r
Must be adjusted to the individual case.

[0042]

In the conventional method of forming a bicontinuous structure with a block copolymer, it was necessary to control the copolymerization composition within a narrow range. However, according to the present invention, the copolymerization composition can be controlled within a narrow range. It is not necessary to adjust the molecular weight of both ends of a triblock copolymer composed of polymer chains that are incompatible with each other, or to mix a homopolymer, a copolymer or a block copolymer with the block copolymer. It can be formed by a simple method. Then, the obtained multi-component multi-phase polymer material having a bicontinuous structure has excellent mechanical strength, and since each component is a continuous phase with each other,
It is possible to maintain substance permeability, conductivity, etc., and it is also possible to obtain a uniform porous body having a pore size of 100 to several hundred Å by selectively removing one phase. Therefore, the present invention can be applied in various fields and is extremely useful.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of a microphase-separated phase having an alternating layered structure.

FIG. 2 is a schematic sectional view of a microphase-separated phase having a cylinder-like structure.

FIG. 3 is a schematic sectional view of a microphase-separated phase having a bicontinuous structure.

[Explanation of symbols]

 1. Interface 2. Block copolymer

Claims (4)

[Claims]
1. An ABA type triblock copolymer comprising two types of mutually incompatible polymer chains A and B, wherein the molecular weight of the block chains at both ends is 2 to 5 times. A method for producing a multi-component multi-phase polymer material having a three-dimensional co-continuous micro phase separation structure, which comprises melt-molding or solution-casting different triblock copolymers.
2. An AB type diblock copolymer or A comprising two types of incompatible polymer chains A and B.
-AB type triblock copolymers, AB type diblock copolymers having different molecular weights or copolymerization compositions or AB-
A method for producing a multi-component multi-phase polymer material having a three-dimensional co-continuous micro phase separation structure, which comprises melt-mixing or solution-mixing an A-type triblock copolymer and molding.
3. An AB type diblock copolymer or A comprising two kinds of mutually incompatible polymer chains A and B.
In the BA type triblock copolymer, the molecular weight of the homopolymer of the polymer chain A having a smaller molecular weight than that of the polymer chain A of the block copolymer and the molecular weight of the polymer chain A of the block copolymer are almost the same. A method for producing a multi-component multi-phase polymer material having a three-dimensional co-continuous micro phase-separated structure, which comprises melt-mixing or solution-mixing polymers of equal molecular weight and molding.
4. An AB type diblock copolymer or A comprising two kinds of mutually incompatible polymer chains A and B.
-The B-A type triblock copolymer, the molecular weight of the polymer chain A of the block copolymer and the number average molecular weight are substantially equal or small, and the ratio of the weight average molecular weight to the number average molecular weight is 1.5 or more. A polymer having a three-dimensional bicontinuous micro-phase separation structure characterized by melt-mixing or solution-mixing a homopolymer of a polymer chain A having a molecular weight distribution of 1 or a polymer having compatibility with the polymer chain A and molding. Method for producing multi-phase polymer material with multiple components.
JP09314092A 1992-04-13 1992-04-13 Method for producing multi-component multi-phase polymer material having three-dimensional co-continuous micro phase separation structure Expired - Fee Related JP3245683B2 (en)

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