JP2795718B2 - Polymer composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stereoregular methacrylate polymer composition, and more particularly, to a composition comprising isotactic polymethyl methacrylate and syndiotactic polymethacrylate.

The polymer composition provided by the present invention forms a stereocomplex, and is characterized by its higher-order structure, and is useful as a membrane material for separation or filtration, a gel base material, and the like.

2. Description of the Related Art Among polymethacrylates, polymethyl methacrylate, in particular, has a high degree of transparency and has already been used as a molded article having excellent transparency in a wide range of fields. In addition, polymethyl methacrylate having excellent stereoregularity includes isotactic polymethyl methacrylate (hereinafter abbreviated as iso-PMMA) and syndiotactic polymethyl methacrylate (hereinafter synd-PMMA). ) Are blended under appropriate conditions to form a crystalline stereocomplex [J. Phrys.
m., 65 896 (1961)]. This stereocomplex has unique physical properties different from iso-PMMA or synd-PMMA, such as good water permeability, flexibility and toughness, and excellent solvent resistance. It is known to have physical properties. The stereo complex is one of polymer
Very sensitive to secondary structural changes, for example, iso-P
MMA and synd-polyethyl methacrylate, synd-PMMA and iso
Polyethyl methacrylate, iso-PMMA and synd-n-butyl polymethacrylate, iso-PMMA and synd-polyisopropyl methacrylate, iso-PMMA and synd-polyphenyl methacrylate, iso-PMMA and synd-polymethacrylic acid It is also known that compositions of methylbenzyl, iso-PMMA and synd-polydimethylbenzyl methacrylate do not form a stereocomplex. So far the above iso
-As a syndiotactic polymer that forms a stereo complex with PMMA, besides synd-PMMA, syndiotactic polyisobutyl methacrylate [Polymer, 2
2 124 (1981) Reference and syndiotactic polymethacrylic acid [Polymer, 19 1171 (1978) Reference is only reported.

Conventionally, the crystal structure of the stereo complex comprising the iso-PMMA and the synd-PMMA has been studied, and the stereo complex forms an iso-PMMA chain syn.
d-PMMA consists of a double helix surrounded by a chain, synd-P
All methyl ester groups in the MMA chain have been reported to be oriented outwards of the helix [Macromolecules, 22
3337 (1989)].

It is also known that a stereocomplex comprising iso-PMMA and synd-PMMA provides a selectively permeable membrane or hollow fiber having excellent dimensional stability (Japanese Patent Application Laid-Open No. Sho 50-12).
However, as described above, under the current situation where the combination of polymers forming a stereocomplex is extremely limited, it is difficult to improve the physical and chemical properties by changing the primary structure of the polymer. Since it is practically impossible, at present, the unique physical properties derived from the stereocomplex are utilized only in limited applications depending on limited polymer properties.

Under such circumstances, if a stereo complex having various physical and chemical properties depending on the primary structure can be obtained in such a situation, unique physical properties derived from the stereo complex in an application field utilizing the properties Can be fully utilized, and the use thereof can be changed.

Accordingly, an object of the present invention is to provide a novel stereoregulated methacrylate polymer composition capable of forming a stereocomplex.

Means for Solving the Problems The present inventors have conducted intensive studies for solving the above problems, and as a result, surprisingly, iso-PMMA and synd-PMMA
The formation of stereocomplexes between stereo-regulated polymethacrylates, which were considered to be unique phenomena that occur only with a few exceptions, and between iso-PMMA and synd-polymethacrylates having a specific structure The present invention has been found.

According to the present invention, the above object is achieved by isotactic polymers having a main chain substantially consisting of the following repeating unit [1] and syndiotactic polymers having a main chain substantially consisting of the following repeating unit [2] This is achieved by providing a polymer composition wherein the ratio of the former polymer to the latter polymer is in the range of 99: 1 to 1:99 by weight.

Wherein R represents a hydrogen atom or forms a bond together with either X ¹ or X ² ; when R represents a hydrogen atom, X ¹ , X ² , Y ¹ and Y ² represents a hydrogen atom; Z ¹ and Z ² represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms; Z ¹ and Z ² do not simultaneously represent a hydrogen atom; or X ¹ , X ² , Y ¹ , Y ² , Z ¹ and Z ² are the carbon atoms to which they are attached C ² and C ³ and the carbon atoms
X together with C ¹ forms an optionally substituted cycloalkane ring or cycloalkene ring; X ¹ or X ²
When one of the two forms a bond with R, the other represents a hydrogen atom, Y ¹ and Y ² represent a hydrogen atom, and Z ¹ and Z ² represent a hydrogen atom or a carbon atom having 1 to 18 carbon atoms. Represents a monovalent hydrocarbon radical or Y ¹ , Y ² , Z ¹ and Z ²
Together with carbon atoms C ² and C ³ to which they are attached and carbon atom C ¹ form a cycloalkene ring, benzene ring or naphthalene ring which may have a substituent. Examples of the monovalent hydrocarbon group having 1 to 18 carbon atoms represented by Z ¹ and Z ² in the repeating unit [2] include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and an isobutyl group. , T-butyl group, ventil group, hexyl group, heptyl group, octyl group, nonyl group, decyl group,
Dodecyl group, cetyl group, stearyl group, propenyl group,
Butenyl and octenyl groups. X ¹ ,
X ² , Y ¹ , Y ² , Z ¹ and Z ² are, as a cycloalkane ring or a cycloalkene ring formed together with carbon atoms C ² and C ³ to which they are bonded and carbon atom C ¹ ,
For example, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cyclohexene ring, and the like, and these rings are a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, Alkyl groups such as a ventil group, a hexyl group, a heptyl group, and an octyl group; alkoxyl groups such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, and a t-butoxy group;
It may have a substituent such as a halogen atom such as a chlorine atom and a bromine atom. Further, Y ¹ , Y ² , Z ¹ and Z ² each have a carbon atom C ² and C ³ to which they are bonded and a cycloalkene ring which may have a substituent formed together with the carbon atom C ¹ As a cyclobutene ring, a cyclopentene ring,
And a cyclohexene ring. Further, Y ¹ , Y ² , Z ¹ and Z ² are carbon atoms C ² and C ³ to which they are bonded and a substituent of a benzene ring or a naphthalene ring formed together with the carbon atom C ¹ as a substituent. Alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl; methoxy, ethoxy, propoxy, Alkoxyl groups such as propoxy group, butoxy group, isobutoxy group and t-butoxy group; halogen atoms such as fluorine atom, chlorine atom and bromine atom;

Here, the isotacticity and the syndiotacticity referred to in the present invention mean a tacticity represented by a triplet, and are values obtained from proton NMR or carbon-13 NMR measurement.

The isotactic polymer in which the main chain, which is one of the components constituting the polymer composition of the present invention, substantially consists of the above repeating unit [1] is specifically an isotactic polymethyl methacrylate or an isotactic polymer. A block polymer or a graft polymer containing polymethyl methacrylate as a component, and a polymer having a repeating unit [1] having a chain portion having an isotacticity of 60% or more and a number average degree of polymerization of 20 or more is preferable. A polymer having a tacticity of 70% or more and a number average degree of polymerization of 20 or more is more preferable. The isotacticity and degree of polymerization of the repeating unit [1] are important factors that govern stereocomplex formation. If the isotacticity and the degree of polymerization do not reach the above-mentioned values, it becomes difficult to form a stereocomplex with the syndiotactic polymer.

The syndiotactic polymer having a main chain substantially consisting of the above-mentioned repeating unit [2], which is another constituent of the polymer composition of the present invention, is specifically a homopolymer consisting of the repeating unit [2], A random copolymer consisting of the unit [2] and a unit provided by methyl methacrylate, isobutyl methacrylate or methacrylic acid, or a block polymer or a graft polymer containing these syndiotactic polymers as one component. The syndiotacticity of the chain part consisting of the repeating unit [2] or the chain part consisting of the repeating unit [2] and the unit provided by methyl methacrylate, isobutyl methacrylate or methacrylic acid is 50% or more and the average degree of polymerization is A polymer having 15 or more is preferable, and a polymer having a syndiotacticity of 60% or more and an average degree of polymerization of 20 or more is more preferable.

The repeating unit [2] is a unit derived from methacrylic acid ester, and can be divided into the following four repeating units depending on the ester moiety.

(In the formula, Z ¹¹ and Z ²¹ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, and they do not simultaneously represent a hydrogen atom.) The repeating unit is a methacrylic acid of a substituted isobutyl alcohol. Esters derived from esters and substituted isobutyl alcohols include, for example, 2-methylbutyl alcohol, 2
-Ethylbutyl alcohol, 2-methylhexyl alcohol, 2-methyldodecyl alcohol, 2-methylstearyl alcohol, 2-butyldodecyl alcohol and the like.

Wherein X ¹² , X ²² , Y ¹² , Y ²² , Z ¹² and Z ²² have a substituent together with the carbon atoms C ² and C ³ to which they are attached and the carbon atom C ¹ This repeating unit forms a cycloalkane ring or a cycloalkene ring which may be substituted.) The repeating unit is derived from a methacrylic acid ester of an optionally substituted cycloalkylmethyl alcohol or cycloalkenylmethyl alcohol, and has a substituent. As cycloalkyl methyl alcohol and cycloalkenyl methyl alcohol which may be, for example, cyclopropyl methyl alcohol, cyclobutyl methyl alcohol, cyclopentyl methyl alcohol,
Cyclohexylmethyl alcohol, (2-cyclohexen-1-yl) methyl alcohol and the like can be mentioned.

(Wherein, ^one of X ^{13 and} X ²³ forms a bond together with R ¹ , the other represents a hydrogen atom, and Y ¹³ and Y ²³
Represents a hydrogen atom, and Z ¹³ and Z ²³ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, or Y
¹³ , Y ²³ , Z ¹³ and Z ²³ together with the carbon atoms C ² and C ³ to which they are attached and the carbon atom C ¹ form a cycloalkene ring which may have a substituent. This repeating unit is derived from methacrylic acid, substituted methallyl alcohol or methacrylic acid ester of cycloalkenylmethyl alcohol which may have a substituent having a double bond at the β-position, and forms a reactive double bond. Have. Examples of such alcohols include methallyl alcohol, 2-ethylallyl alcohol, 2-hexylallyl alcohol, 2,3-dimethylallyl alcohol, (1-cyclobuten-1-yl) methyl alcohol, and (1-cyclopentene- 1-yl) methyl alcohol, (1-cyclohexen-1-yl) methyl alcohol, and the like.

(Wherein, one of X ^{14 and} X ²⁴ together with R ² forms a bond, the other represents a hydrogen atom, and Y ¹⁴ , Y ²⁴ , Z
¹⁴ and Z ²⁴ are the carbon atoms C ² and C to which they are attached
³ and to form a benzene ring or a naphthalene ring which may have a substituent together with the carbon atom C ^1. This repeating unit is derived from methacrylic acid ester of benzyl alcohol or naphthylmethyl alcohol which may have a substituent, and the benzyl alcohol and naphthylmethyl alcohol which may have a substituent include, for example, benzyl alcohol, m-methylbenzyl alcohol, p-methylbenzyl alcohol, m-methoxybenzyl alcohol, p-methoxybenzyl alcohol, m-chlorobenzyl alcohol, p-chlorobenzyl alcohol, m-bromobenzyl alcohol, p
-Bromobenzyl alcohol, m-fluorobenzyl alcohol, p-fluorobenzyl alcohol, α-naphthylmethyl alcohol, β-naphthylmethyl alcohol and the like.

It constitutes the polymer composition of the present invention. The composition ratio of the isotactic polymer whose main chain consists essentially of the above-mentioned repeating unit [1] and the syndiotactic polymer whose main chain consists essentially of the above-mentioned repeating unit [2] is 99: 1 to 1 by weight.
It is in the range of 1:99, preferably in the range of 98: 2 to 2:98. When the isotactic polymer or syndiotactic polymer is a block polymer or a graft polymer, a syndio containing a recurring unit [2] and an isotactic chain portion composed of the recurring unit [1] in the block polymer or the graft polymer. It is sufficient that the composition ratio of the tactical chain portion is within the above range.
When the composition ratio is out of the above range, although a stereo complex is formed, characteristics based on the stereo complex are not sufficiently exhibited.

The polymer composition of the present invention can form a stereocomplex with an isotactic polymer whose main chain substantially consists of the above-mentioned repeating unit [1], and whose main chain consists essentially of the above-mentioned repeating unit [2]. May contain a syndiotactic polymer other than the syndiotactic polymer, i.e., methyl methacrylate, isobutyl methacrylate or methacrylic acid, and the content of the syndiotactic polymer is the same as that of the polymer composition of the present invention. It is necessary to be within a range that does not impair the function and effect.

The polymer composition of the present invention comprises an isotactic polymer having a main chain substantially consisting of the above repeating unit [1] and a syndiotactic polymer having a main chain substantially consisting of the above repeating unit [2]. It is prepared by solution-blending or melt-blending a predetermined amount under appropriate conditions. From the viewpoint that the formation of a stereocomplex can be effectively promoted, a method of performing a heat treatment after solution-blending an isotactic polymer and a syndiotactic polymer is preferable. The solvent used in the solution blending may be any solvent that dissolves the zindiotactic polymer and the isotactic polymer, and examples thereof include dimethylformamide, acetonitrile, benzene, toluene, chlorobenzene, chloroform, and carbon tetrachloride. These solvents are used alone or as a mixture.

The isotactic polymer in which the main chain constituting the polymer composition of the present invention substantially consists of the above repeating unit [1] and the syndiotactic polymer in which the main chain consists essentially of the above repeating unit [2] are Each can be manufactured according to a known method.

Action The polymer composition of the present invention forms a stereocomplex, in which a syndiotactic polymer having a main chain substantially consisting of the above-mentioned repeating unit [2] is used, and a main chain substantially consisting of the above-mentioned repeating unit [2]. It is presumed that the syndiotactic polymer has a double helical structure surrounding the isotactic polymer of [1], and all the ester portions of the syndiotactic polymer face the outside of the helix. The unique physical and chemical properties of the polymer composition of the present invention are based on the unique higher-order structure of the stereocomplex, and are considered to be strongly influenced by the primary structure of the ester portion of the polymer. .

Examples Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to the Examples. In the examples, "parts" represents "parts by weight".

Example 1 A three-way cock was attached to a glass amble heated and dried under vacuum, and the atmosphere was replaced with dry nitrogen. Then, 10 ml of toluene and 0.6 mmol of (Et) ₃ Al were added, and the mixture was cooled to −78 ° C. This is t
After adding 0.2 mmol of BuLi, 1.83 g of benzyl methacrylate
Was added to initiate polymerization. After 144 hours, the polymerization was terminated by adding methanol containing a small amount of hydrochloric acid, and the reaction mixture was poured into a large amount of hexane to precipitate the polymer. The produced polymer was separated by filtration, washed with hexane, dilute hydrochloric acid and water in that order, and dried under reduced pressure. A synd-polybenzyl methacrylate having a degree of polymerization of 61.3%, a number average degree of polymerization of 35, and syndiotacticity of 91.3% was obtained.

Subsequently, t-BuMgBr was used as an initiator in toluene at -60.
100 parts of the obtained iso-PMMA (number average degree of polymerization 330, isotacticity 97.3%) polymerized at ℃ and 176 parts of the synd-polybenzyl methacrylate were mixed in a chloroform solution, and n
-Precipitated in hexane and dried at 40 ° C under reduced pressure. continue
The composition was heat-treated at 80 ° C. for 48 hours to obtain a composition comprising a stereocomplex having a melting temperature of 109 ° C. by DSC measurement.

Examples 2 to 6 The iso-PMMA used in Example 1 and various synd-polymethacrylates synthesized by the same method as described in Example 1 were mixed in a chloroform solution, and mixed in n-hexane. The precipitate was dried at 40 ° C. under reduced pressure. Subsequently, heat treatment was performed at each heat treatment temperature for 48 hours to obtain a composition comprising a stereocomplex. Table 1 shows the properties of the synd-polymethacrylate and the melting of the composition. The solution temperature is shown.

Example 7 100 parts of iso-PMMA used in Example 1 and synd-polymethacrylic acid 2-polymerized in the same manner as described in Example 1
A 1% N, N-dimethylformamide solution consisting of 150 parts of methylbutyl (number average polymerization degree 128, syndiotacticity 89%) was prepared and left at 0 ° C. to obtain a gel by stereocomplex formation. .

Example 8 100 parts of iso-PMMA used in Example 1 and 9.3 parts of synd-polybenzyl methacrylate were mixed in a chloroform solution, precipitated in n-hexane, and dried at 40 ° C. under reduced pressure. Subsequently, the composition was heat-treated at 80 ° C. for 24 hours to obtain a composition comprising a stereocomplex having a melting temperature of 107 ° C. by DSC measurement.

Example 9 3 parts of iso-PMMA used in Example 1 and 100 parts of synd-polybenzyl methacrylate were mixed in a chloroform solution, precipitated in n-hexane, and dried at 40 ° C. under reduced pressure.
Subsequently, the composition was heat-treated at 80 ° C. for 24 hours to obtain a composition comprising a stereocomplex having a melting temperature of 110 ° C. by DSC measurement.

Example 10 Synd-poly (benzyl methacrylate-methyl methacrylate) (benzyl methacrylate content: 45 wt%) obtained by polymerizing 100 parts of iso-PMMA used in Example 1 and polymerization in the same manner as in Example 1. ) Were mixed in a chloroform solution, precipitated in n-hexane and dried at 40 ° C under reduced pressure. Subsequently, a heat treatment was performed at 80 ° C. for 48 hours to obtain a composition comprising a stereocomplex having a melting temperature of 120 ° C. by DSC measurement.

Example 11 100 parts of iso-PMMA used in Example 1, 97 parts of synd-polybenzyl methacrylate, and t-BuLi- (Et) ₃ Al were used as initiators to synthesize synd- obtained by polymerization at -78 ° C in toluene. PMMA
(Number average degree of polymerization 226, syndiotacticity 88.7%) 40
The parts were mixed in a chloroform solution, precipitated in n-hexane and dried at 40 ° C. under reduced pressure. Subsequently, heat treatment was performed at 80 ° C. for 48 hours to obtain a composition comprising a stereocomplex having a melting temperature of 116 ° C. by DSC measurement.

According to the present invention, various novel stereoregular methacrylate polymer compositions capable of forming a stereocomplex are provided.

The polymer composition provided by the present invention has excellent properties based on a unique higher-order structure derived from a stereocomplex, such as good water permeability, flexibility and toughness, and physical properties such as excellent solvent resistance. It has excellent physical and chemical properties depending on the syndiotactic polymer constituting the stereocomplex and is useful as a membrane material such as a separation membrane or a filtration membrane, a base material for a gel, or the like.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C08L 33/04-33/12 B01D 71/40

Claims (5)

(57) [Claims] (1) an isotactic polymer whose main chain consists essentially of the following repeating unit [1]; and a syndiotactic polymer whose main chain consists essentially of the following repeating unit [2]. A composition wherein the ratio of the polymer to the polymer is in the range of 99: 1 to 1:99 by weight. Wherein R represents a hydrogen atom or forms a bond together with either X ¹ or X ² ; when R represents a hydrogen atom, X ¹ , X ² , Y ¹ and Y ² represents a hydrogen atom; Z ¹ and Z ² represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms; Z ¹ and Z ² do not simultaneously represent a hydrogen atom; or X ¹ , X ² , Y ¹ , Y ² , Z ¹ and Z ² are the carbon atoms to which they are attached C ² and C ³ and the carbon atoms
X together with C ¹ forms an optionally substituted cycloalkane ring or cycloalkene ring; X ¹ or X ²
When one of the two forms a bond with R, the other represents a hydrogen atom, Y ¹ and Y ² represent a hydrogen atom, and Z ¹ and Z ² represent a hydrogen atom or a carbon atom having 1 to 18 carbon atoms. Represents a monovalent hydrocarbon radical or Y ¹ , Y ² , Z ¹ and Z ²
Together with carbon atoms C ² and C ³ to which they are attached and carbon atom C ¹ form a cycloalkene ring, benzene ring or naphthalene ring which may have a substituent. ) 2. The composition according to claim 1, wherein the syndiotactic polymer has a main chain substantially consisting of the following repeating unit [2-1]. (In the formula, Z ¹¹ and Z ²¹ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, and they do not simultaneously represent a hydrogen atom.) 3. The composition according to claim 1, wherein the syndiotactic polymer has a main chain substantially consisting of the following repeating unit [2-2]. Wherein X ¹² , X ²² , Y ¹² , Y ²² , Z ¹² and Z ²² have a substituent together with the carbon atoms C ² and C ³ to which they are attached and the carbon atom C ¹ Form a cycloalkane ring or a cycloalkene ring which may be optionally substituted.) 4. The composition according to claim 1, wherein the syndiotactic polymer has a main chain substantially consisting of the following repeating unit [2-3]. (Wherein, ^one of X ^{13 and} X ²³ forms a bond together with R ¹ , the other represents a hydrogen atom, and Y ¹³ and Y ²³
Represents a hydrogen atom, and Z ¹³ and Z ²³ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, or Y
¹³ , Y ²³ , Z ¹³ and Z ²³ together with the carbon atoms C ² and C ³ to which they are attached and the carbon atom C ¹ form a cycloalkene ring which may have a substituent. ) 5. The composition according to claim 1, wherein the syndiotactic polymer has a main chain substantially consisting of the following repeating unit [2-4]. (Wherein, one of X ^{14 and} X ²⁴ together with R ² forms a bond, the other represents a hydrogen atom, and Y ¹⁴ , Y ²⁴ , Z
¹⁴ and Z ²⁴ are the carbon atoms C ² and C to which they are attached
³ and to form a benzene ring or a naphthalene ring which may have a substituent together with the carbon atom C ^1. )