JP4417154B2 - NOVEL POLYMER AND PROCESS FOR PRODUCING THE SAME - Google Patents

Description

The present invention relates to a method for producing a stretched film made of a novel polymer.

A polymer having a functional group such as a hydroxyl group in the molecule exhibits various physical properties such as hydrophilicity and adhesiveness, derived from the functional group, and various functional packaging materials and various functional moldings depending on the physical properties. It can be used for materials, various sheets, films, fibers, various coating agents, various functional alloys, components of blends, and the like.
As such polymers, for example, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, poly (hydroxyethyl methacrylate), one-end or both-end hydroxypolybutadiene, one-end or both-end hydroxypolyisoprene have been known for a long time. Yes. In recent years, for example, unsaturated polymers obtained by ring-opening metathesis polymerization of a cycloalkene having 7 to 12 carbon atoms having a functional group such as 5-cyclooctene-1,2-diol have been converted to hydrogen such as palladium carbon. Polymers obtained by hydrogenation in the presence of an oxidization catalyst are known, and some of such polymers are known to be useful as components of packaging materials having high oxygen barrier properties ( (See Patent Documents 1 and 2).
On the other hand, polymers containing reactive functional groups such as vinylidene groups are useful as synthetic intermediates that can be derived into various functional materials by reactions such as addition reactions. As polymers having such reactive functional groups, polymers of allenes such as allene and methylallene are known (see, for example, Patent Documents 3 and 4). Also known are polymers of allene derivatives such as alkoxyallenes; allenyl sulfides; arenic acid esters; substituted allenes having functional groups such as amide, urethane and imide, and polymers of hydroxymethylallene (non-patented). References 1 and 2 and Patent Reference 5).

Furthermore, when the polymer having a functional group described above has a carbon-carbon double bond, the heat resistance and weather resistance may be inferior, but the carbon-carbon double existing in the molecule may occur. Such problems can be avoided by hydrogenating some or all of the bonds. Hydrogenation of the polymer can be carried out using various metal catalysts such as nickel, palladium, platinum, titanium, rhodium, etc., especially when the polymer to be subjected to hydrogenation has a functional group such as a hydroxyl group. When a functional group such as a hydroxyl group is present at the allylic position, there is a problem that these functional groups are eliminated during the hydrogenation reaction.
As an example that can solve such a problem, a hydrogenated polymer characterized by hydrogenating an unsaturated polymer having a specific functional group in the presence of palladium or platinum supported on basic activated carbon Has been proposed (see Patent Document 6).

WO99 / 50331 pamphlet International Publication No. 00/18579 Pamphlet Japanese Patent Publication No. 44-858 Japanese Examined Patent Publication No. 45-41395 JP 2003-73425 A JP 2002-338621 A Journal of Synthetic Organic Chemistry, Vol.56, 260-267 (1998) Angew. Chem. Int. Ed., 39 (2000), 3667

By developing polymer compounds with new chemical structures and their analogs that have hydroxyl groups, we can provide polymer compounds with different characteristics from existing polymers, as well as intermediates to other useful polymer compounds A wide range of applications can be expected. In particular, by developing polymer compounds having hydroxyl groups rich in flexibility and analogs thereof, when performing processing that requires flexibility, such as bag making processing by deep drawing and biaxial stretching processing It is also possible to provide a polymer compound that is less likely to cause unevenness and cracks.
Therefore, an object of the present invention is to provide a method for producing a stretched film comprising such a novel polymer compound.

（式中、Ｘは水酸基、保護基によって保護された水酸基、または水酸基もしくは保護基によって保護された水酸基を有する炭化水素基を表す。なお、式（１）〜（４）におけるＸは互いに同一であっても異なっていてもよい。）で示される構造単位〔以下、式（１）〜（４）で示される構造単位をそれぞれ構造単位（１）〜（４）と略称することがある〕から主としてなり、それらの割合（モル比）が以下の関係式（Ａ）を満足する重合体を提供することによって解決される。
〔構造単位（１）と構造単位（２）の合計量〕／〔構造単位（３）と構造単位（４）の合計量〕＝７０／３０〜０／１００ （Ａ） According to the present invention, the above problem is
The following formulas (1) to (4)

(In the formula, X represents a hydroxyl group, a hydroxyl group protected by a protecting group, or a hydrocarbon group having a hydroxyl group or a hydroxyl group protected by a protecting group. X in formulas (1) to (4) are the same as each other. The structural units represented by formulas (1) to (4) may be abbreviated as structural units (1) to (4), respectively. The problem is solved by providing a polymer in which the ratio (molar ratio) of the polymer satisfies the following relational expression (A).
[Total amount of structural unit (1) and structural unit (2)] / [Total amount of structural unit (3) and structural unit (4)] = 70/30 to 0/100 (A)

In addition, the present invention provides a method for producing such a novel polymer as a polymer mainly composed of a structural unit represented by the above formula (1) and / or formula (2) (the weight of allenes having a functional group). There is provided a method for producing a polymer comprising hydrogenating a carbon-carbon double bond (which is a kind of polymer).
In addition, in the above-mentioned Patent Document 6, there is no example in which a polymer derived from allenes is hydrogenated, and it has a functional group such as a hydroxyl group provided by the present invention and is hydrogenated. Polyalene and its physical properties have not been known so far.

  ADVANTAGE OF THE INVENTION According to this invention, the novel polymer which has a hydroxyl group which can be induced | guided | derived from the polymers of allenes, such as hydroxymethyl allene, its analog, and those manufacturing methods are provided. Furthermore, it is possible to provide a molded article such as a film having excellent flexibility made of them.

  In formulas (1) to (4) representing the structural units constituting the polymer of the present invention, when X represents a hydroxyl group protected by a protecting group, the hydroxyl protecting group has been conventionally used as a hydroxyl protecting group. For example, an alkyl group such as a methyl group, an ethyl group or a t-butyl group; an aralkyl group such as a benzyl group; an aryl group such as a phenyl group; a methoxymethyl group or an ethoxyethyl group; Alkoxy groups such as acetyl, propionyl, benzoyl and trifluoroacetyl; alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl and benzyloxycarbonyl; phenoxycarbonyl Group, aryloxycarbonyl group such as naphthoxycarbonyl group; trimethyl Lil group, t- butyl dimethyl silyl group, substituted silyl group such as triphenylsilyl group; a methanesulfonyl group, p- toluenesulfonyl group, a sulfonyl group such as a trifluoromethanesulfonyl group. Specific examples of the hydroxyl group protected by the protecting group represented by X include alkoxy groups such as methoxy group, ethoxy group, t-butoxy group and benzyloxy group; methoxymethyleneoxy group, methoxyethyleneoxy group, ethoxyethylene Alkoxyalkyloxy groups such as oxy groups; acyloxy groups such as acetyloxy groups, trifluoroacetyloxy groups, and benzoyloxy groups; methoxycarbonyloxy groups, ethoxycarbonyloxy groups, t-butoxycarbonyloxy groups, phenyloxycarbonyloxy groups, Alkoxycarbonyloxy group or aryloxycarbonyloxy group such as benzyloxycarbonyloxy group; siloxy group such as trimethylsiloxy group and t-butyldimethylsiloxy group; methanesulfonyloxy group, p-toluene Ruhoniruokishi group, a sulfonyloxy group such as trifluoromethanesulfonyloxy group.

In addition, when X represents a hydrocarbon group having a hydroxyl group or a hydroxyl group protected by a protecting group, the carbon number thereof (in the case of a hydrocarbon group having a hydroxyl group protected by a protecting group, the carbon number of the protecting group is excluded) Is usually 1-20, preferably 1-8, more preferably 1-4.
The hydrocarbon group having a hydroxyl group or a hydroxyl group protected by a protecting group may contain two or more hydroxyl groups or hydroxyl groups protected by a protecting group, or a plurality of hydroxyl groups or hydroxyl groups protected by protecting groups are condensed. Thus, a cyclic structure containing an oxygen atom such as cyclic ether, cyclic acetal, or lactone may be used.

  Specific examples of the hydroxyl group or the hydrocarbon group having a hydroxyl group protected by a protecting group include alkyl groups such as a methyl group, an ethyl group, a propyl group, an n-hexyl group, an n-octyl group, a cyclohexyl group, and a cyclooctyl group. A hydrogen atom substituted with a hydroxyl group or a hydroxyl group protected by a protecting group (hydroxymethyl group, methoxymethyl group, acetoxymethyl group, trimethylsiloxymethyl group, etc.); a hydrogen atom of an aralkyl group such as a benzyl group is hydroxyl group or protected A group substituted by a hydroxyl group protected by a group; a cyclic group containing an oxygen atom (glycidyl group, methylglycidyl group, phenylglycidyl group, tetrahydrofuranyl group, tetrahydropyranyl group, 1,2-methylenedioxyethyl group) 1,2-methylenedioxypropyl group, 1,3-methylene Oxypropyl group, 1,2-isopropylidenedioxyethyl group, 1,2-isopropylidenedioxypropyl group, 1,3-isopropylidenedioxypropyl group, γ-butyrolactyl group, δ-valerolactyl group, etc.) It is done.

  X in the formulas (1) to (4) is preferably a hydroxyl group or a hydroxyl group protected by a protecting group, and more preferably a hydroxyl group.

  The number average molecular weight (Mn) of the polymer of the present invention is not particularly limited, but is preferably in the range of 1,000 to 1,000,000 from the viewpoint of moldability and mechanical properties. More preferably in the range of 2,000 to 500,000, and still more preferably in the range of 5,000 to 100,000.

  The molecular weight distribution (Mw / Mn) defined by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer of the present invention is not particularly limited, but the balance between moldability and mechanical properties is good. Therefore, it is preferably in the range of 1.0 ≦ Mw / Mn ≦ 2.5, more preferably in the range of 1.0 ≦ Mw / Mn ≦ 2.0, 1.0 ≦ Mw / Mn More preferably, it is within the range of ≦ 1.5.

In the polymer of the present invention, the arrangement of the structural units (1) to (4) is not particularly limited, and any of random, block, and taper is possible.
Moreover, the polymer of this invention may contain the structural unit from which X in Formula (1)-(4) differs, such as a hydroxyl group and an acetoxy group, for example.

  Moreover, the polymer of this invention may contain structural units other than structural unit (1)-(4). The content (molar ratio) of other structural units is 80 mol% or less, preferably 40 mol% or less, more preferably 30 mol% or less, based on the total of the structural units (1) to (4).

  Examples of other structural units include structural units derived from alkyl allenes such as n-butyl allene, t-butyl allene, and n-hexyl allene; methoxy allene, n-propoxy allene, i-propoxy allene, n-butoxy allene, Structural units derived from alkoxyallenes such as t-butoxyallene; structural units derived from allene derivatives such as phenylallene, N-allenylpyrrolidone, N-allenyloxazolidone; derived from isonitriles such as 1-phenylethylisonitrile A structural unit derived from a conjugated diene such as 1,3-butadiene.

  In the polymer of the present invention, [total amount of structural unit (1) and structural unit (2)] / [total amount of structural unit (3) and structural unit (4)] is the heat resistance and weather resistance of the polymer. From the viewpoint, it is 70/30 to 0/100 (molar ratio), preferably 50/50 to 0/100 (molar ratio), and more preferably 10/90 to 0/100 (molar ratio). Preferably, it is 0/100 (molar ratio).

  The structural unit (1) and the structural unit (2) are structural units corresponding to a structure containing a double bond in the polymer side chain, and the structural unit (3) and the structural unit (4) have a double bond in the polymer side chain. A structural unit corresponding to a hydrogenated structure. When the polymer side chain contains both a double bond and a structure in which the double bond is hydrogenated, the polymer of the present invention is widely used by utilizing two kinds of structures having such reactivity differences. This makes it highly useful, for example. Considering such a case, [total amount of structural unit (1) and structural unit (2)] / [total amount of structural unit (3) and structural unit (4)] = 70/30 to 0.5 / 99.5 (molar ratio) is also very preferable as the polymer of the present invention. [Total amount of structural unit (1) and structural unit (2)] / [structural unit (3) and structural unit (4 ))] = 70/30 to 1/99 (molar ratio) is particularly preferred as the polymer of the present invention.

  In the polymer of the present invention, the ratio (molar ratio) between the structural unit (1) and the structural unit (2) is not particularly limited, and can be arbitrarily changed within the range of 0/100 to 100/0. , And can be set as appropriate in consideration of desired physical properties. Moreover, there is no restriction | limiting in particular also about the ratio (molar ratio) of a structural unit (3) and a structural unit (4), It can change arbitrarily in the range of 0 / 100-100 / 0, and the desired physical property is shown. It can be set as appropriate in consideration.

  The polymer of the present invention uses a polymer mainly composed of the structural unit represented by the above formula (1) and / or formula (2) (hereinafter sometimes abbreviated as a precursor) for hydrogenation reaction, -It can be produced by adding hydrogen to a carbon double bond.

The precursor has the formula CH ₂ ═C═CH—CH ₂ —X (I)
(Wherein X is as defined above), and can be produced by polymerizing a monomer mainly composed of an allene derivative.

Specific examples of the allene derivative represented by the formula (I) include, for example, hydroxymethyl allene, hydroxyethyl allene, trimethylsiloxymethyl allene and the like.
As the allene derivative represented by the formula (I), one type may be used, or two or more types may be used in combination.

  The allene derivative represented by the formula (I) is produced using a known method described in literatures such as L. Brandsma, HD Verkruijsse, “Synthesis of Acetylenes, Allenes and Cumulenes” Elsevier, New York Can do.

The precursor may contain a structural unit composed of another monomer other than the allene derivative represented by the formula (I). The content (molar ratio) of structural units composed of other monomers is 80 mol% or less, preferably 40 mol% or less, more preferably based on the total of structural units composed of allene derivatives represented by formula (I). Is 30 mol% or less.
Examples of other monomers include alkyl allenes such as n-butyl allene, t-butyl allene and n-hexyl allene; methoxy allene, n-propoxy allene, i-propoxy allene, n-butoxy allene, t-butoxy allene and the like. Alkoxy allenes; arylene derivatives such as phenyl allene, N-allenyl pyrrolidone and N-allenyl oxazolidone; isonitriles such as 1-phenylethyl isonitrile; conjugated dienes such as 1,3-butadiene and the like.

The structural unit represented by the formula (1) in the precursor is a structural unit produced when the allene derivative represented by the formula (I) undergoes so-called 1,2-polymerization, and is represented by the formula (2). The structural unit is a structural unit produced when the allene derivative represented by the formula (I) undergoes so-called 2,3-polymerization.
The proportion (molar ratio) of the structural units represented by the formula (1) and the formula (2) in the precursor is not particularly limited, and the reaction conditions in the polymerization of the allene derivative represented by the formula (I) are adjusted. Thus, it is possible to appropriately adjust the proportion (molar ratio) of the above-described structural units in the precursor.

The polymerization of the allene derivative represented by the formula (I) is usually carried out using a π-allyl nickel catalyst.
Examples of the π-allyl nickel catalyst include bis (1,5-cyclooctadiene) nickel, allyl acetate, allyl chloroacetate, allyl bromoacetate, allyl iodoacetate, allyl benzoate, allyl in a nitrogen atmosphere and in toluene. What can be prepared from allyl compounds, such as trifluoroacetate, allyl chloride, allyl bromide, and allyl iodide, is mentioned. The allyl compound is preferably allyl trifluoroacetate or allyl chloride from the viewpoint of catalyst stability.
The amount of the π-allyl nickel catalyst used is usually in the range of 0.01 to 10%, preferably 0.05 to 3% in terms of molar ratio with respect to the allene derivative represented by the formula (I).

  In order to obtain a precursor mainly composed of the structural unit represented by the formula (1), trialkylphosphine such as tributylphosphine and trioctylphosphine; triphenylphosphine, tri-o-tolylphosphine, tri-m -Triarylphosphine such as tolylphosphine and tri-p-tolylphosphine; phosphite such as triphenylphosphite and triethylphosphite; phosphorus such as diphosphine such as bis (diphenylphosphino) ethane and bis (diphenylphosphino) propane It is desirable to polymerize the allene derivative represented by the formula (I) in the presence of a compound; a nitrogen compound such as bipyridyl; an arsenic compound such as triphenylarsine.

The polymerization of the allene derivative represented by the formula (I) is preferably carried out in the presence of a solvent. Examples of the solvent include alcohols such as ethanol and methanol; aromatic hydrocarbons such as toluene; polar aprotic solvents such as dimethyl sulfoxide and dimethylformamide; pyrrole; halogenated hydrocarbons such as chloroform and dichloromethane. One type of solvent may be used, or two or more types may be mixed and used.
In view of the stability of the catalyst and the solubility of the resulting precursor, ethanol, methanol, and dimethyl sulfoxide are preferred.

The polymerization temperature is preferably in the range of −80 to 120 ° C., more preferably in the range of −40 to 80 ° C., and still more preferably in the range of 0 to 60 ° C.
The polymerization of the allene derivative represented by the formula (I) is preferably carried out in an inert gas atmosphere such as nitrogen or argon.

  The precursor obtained by the above-described polymerization reaction can be obtained by, for example, re-precipitation, solvent removal under heating, solvent removal under reduced pressure, solvent removal with steam (steam stripping), and the like. It can be separated and obtained from the reaction solution by a normal operation during separation. Moreover, you may use for the hydrogenation reaction mentioned later in the form of the reaction mixture which this precursor melt | dissolved in the solvent if desired.

  The hydrogenation reaction of the precursor is preferably carried out in the presence of a catalyst. Examples of the catalyst used in the hydrogenation reaction of the precursor include known ones such as a ruthenium catalyst, a palladium catalyst, a platinum catalyst, a nickel catalyst, and a titanium catalyst, but the structural unit (3 ) And the total amount of the structural unit (4)], and considering the prevention of elimination of a hydroxyl group that may be protected by a protecting group, a ruthenium catalyst is more preferable. Moreover, as a catalyst form, a known catalyst such as a homogeneous catalyst or a supported catalyst can be used. However, since the catalyst of the present invention produced by hydrogenation and the catalyst may be efficiently separated, the homogeneous system may be used. A catalyst is preferred.

  Examples of the ruthenium catalyst include ruthenium black; ruthenium trichloride, ruthenium tribromide, ruthenium carbonyl, ruthenium acetylacetonate, benzene ruthenium (II) chloride dimer, dichloro (p-cymene) ruthenium (II) dimer. Homogeneous catalysts such as tri (triphenylphosphine) ruthenium (II) chloride; ruthenium catalysts supported on activated carbon, silica, alumina, silica-alumina, zirconium oxide, titanium oxide, ion exchange resin, etc. it can. Although depending on the reaction substrate and hydrogenation conditions, if the hydrogenated polymer is precipitated during the hydrogenation reaction, the risk of the catalyst used being mixed into the polymer after hydrogenation is reduced. It is preferred to use a homogeneous catalyst. These catalysts may use a single thing, and may mix and use 2 or more types. If necessary, triphenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tricyclohexylphosphine, 1,4-di (diphenylphosphino) butane, 1,3-di (diphenylphosphino) propane, 1, Phosphorus compounds such as 2-di (diphenylphosphino) ethane; and phosphorus compounds such as phosphites such as triphenyl phosphite and tributyl phosphite may be added and used as a cocatalyst. The amount of catalyst used is optimally different depending on the type of catalyst used, so it is difficult to uniquely define it. However, when the above-mentioned homogeneous ruthenium catalyst is used, it is included in the precursor. It is usually in the range of 0.0001 to 0.1 mol in terms of ruthenium atom per 1 mol of unsaturated bond, and in the range of 0.001 to 0.05 mol in terms of economy and reaction rate. Preferably there is. Furthermore, when using phosphine and phosphites, it is preferable to use usually 0.1 to 10 mol of these compounds per 1 mol of ruthenium atom.

  The hydrogenation of the precursor is preferably carried out in the presence of a solvent that does not inhibit the reaction. Examples of the solvent that can be used include alcohols such as methanol, ethanol, and isopropanol; saturated hydrocarbons such as hexane, heptane, and octane; and aromatic hydrocarbons such as toluene and xylene. Although there is no restriction | limiting in particular in the usage-amount of a solvent, Usually, it exists in the range of 1-1000 weight times with respect to the weight of a precursor. The hydrogen pressure in the hydrogenation reaction is not particularly limited, but is usually in the range of 0.1 to 10 MPa, and preferably in the range of 1 to 5 MPa. Furthermore, the reaction temperature is usually in the range of 0 to 140 ° C, and preferably in the range of 20 to 100 ° C.

  In the polymer of the present invention obtained by hydrogenation, a hydroxyl group or a hydroxyl group protected by a protecting group in the precursor is generally not changed by hydrogenation, but is converted to another functional group depending on reaction conditions. It doesn't matter.

  The polymer of the present invention can be produced, for example, by placing a precursor in a pressure-resistant container, then adding a solvent, dissolving the precursor in the solvent, and then adding a catalyst such as a ruthenium catalyst and the like to the obtained solution. Correspondingly, a co-catalyst such as phosphines and phosphites is added, the atmosphere in the container is replaced with nitrogen, and further replaced with hydrogen. Then, hydrogen is supplied into the container, adjusted to a predetermined pressure, and set to a predetermined temperature. Can be implemented.

After completion of the reaction, the hydrogenated polymer can be separated from the reaction solution by a normal isolation and purification operation when the polymer is isolated from the solution. For example, known methods such as reprecipitation, solvent removal under heating, solvent removal under reduced pressure, and solvent removal by steam (steam stripping) are employed.
Depending on the reaction substrate and hydrogenation conditions, if a hydrogenated polymer is precipitated during the hydrogenation reaction, it can be isolated by a relatively simple isolation procedure such as decantation, filtration, or centrifugation. The intended polymer can be obtained.

When the polymer of the present invention has a hydroxyl group protected by a protecting group in the structural unit, deprotection may be performed by a known method according to the protecting group, such as hydrolysis, if desired. Further, it may be converted from one protecting group to another according to a known method.
Furthermore, when the polymer of the present invention has a hydroxyl group in the structural unit, the hydroxyl group may be protected with a protecting group by a known method, if desired.
Further, when the polymer of the present invention has a carbon-carbon double bond in the structural unit [when it has the structural unit (1) and / or the structural unit (2)], part or all of the double bond is Modification may be performed using a known method such as an addition reaction.

  The polymer of the present invention can be used alone, or polyamide, polyurethane, polyester, polycarbonate, polyoxymethylene resin, acrylic resin, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyolefin, polystyrene, styrene block It can also be used as a composition blended with another polymer such as a copolymer. When used as a composition, stabilizers, lubricants, pigments, impact resistance improvers, processing aids, crystal nucleating agents, reinforcing agents, colorants, flame retardants, weather resistance improvers, UV absorbers, antioxidants, Various additives such as hydrolysis resistance improvers, fungicides, antibacterial agents, light stabilizers, antistatic agents, silicone oils, antiblocking agents, mold release agents, foaming agents, fragrances; glass fibers, polyester fibers, etc. Various fibers; fillers such as talc, mica, montmorillonite, smectite, silica, and wood powder; optional components such as various coupling agents can be blended as necessary.

Stretched film comprising a polymer of the present invention can be used in various applications of the gas barrier film, such as various packaging materials for food packaging materials.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the examples.

Reference Example 1 (Synthesis of hydroxymethylallene)
4-chloro-2-butyne produced by reacting 16.4 g (0.22 mol) of propargyl chloride, 12.8 g (0.20 mol) of n-BuLi and 7.2 g (0.24 mol) of formaldehyde 1-ol was isolated by vacuum distillation. 12.6 g (0.121 mol) of 4-chloro-2-butyn-1-ol was obtained (yield: 60%).
Next, the obtained 4-chloro-2-butyn-1-ol was reacted with 4.6 g (0.12 mol) of LiAlH ₄ to synthesize hydroxymethylallene. The product was isolated and purified by distillation under reduced pressure to obtain 4.4 g (0.063 mol) of hydroxymethylallene (yield: 53%).

Reference Example 2 (Synthesis of polyhydroxymethyl allene)
In a nitrogen atmosphere, 0.20 ml of a 0.1 M concentration of bis (1,5-cyclooctadiene) nickel in toluene in a polymerization tube [containing 0.02 mmol of bis (1,5-cyclooctadiene) nickel And 20 μl of 1.0 M allyl chloride in toluene solution (containing 0.02 mmol of allyl chloride) and stirring, then 30 μl of 1.0 M tributylphosphine in toluene solution [0.03 Containing 2.0 millimoles of tributylphosphine] and 2.0 ml of ethanol were added and stirred to prepare a catalyst solution.
To the obtained catalyst solution, 0.07 g (1 mmol) of hydroxymethylallene obtained in Reference Example 1 was added at 25 ° C. in a nitrogen atmosphere and stirred for 10 hours. After confirming the disappearance of hydroxymethylallene by gas chromatography, the reaction solution was dropped into benzene, and the resulting precipitate was filtered to obtain 0.067 g of a hydroxymethylallene polymer (yield: 95%). ).

As a result of ¹ H-NMR (300 MHz) measurement, the obtained polymer is a polymer composed of a structural unit (1) in which X is a hydroxyl group and a structural unit (2) in which X is a hydroxyl group, and the ratio thereof. Was found to be structural unit (1) / structural unit (2) = 60/40 (molar ratio).

In 5 ml of pyridine, 1.5 g of acetic anhydride was added to 0.067 g of the hydroxymethylallene polymer obtained above and reacted at 35 ° C. for 5 hours to acetylate the hydroxyl group in the molecule. By reprecipitation using a mixture of water and methanol [water / methanol = 2/1 (volume ratio)], a polymer in which the hydroxyl group was protected with an acetyl group was obtained in a yield of 98%. It was confirmed that the hydroxyl group was quantitatively acetylated by ¹ H-NMR (300 MHz) measurement.
When the obtained acetylated polymer was analyzed by GPC, it was found that the number average molecular weight (polystyrene conversion) was 5500, and the molecular weight distribution (Mw / Mn) was 1.2.

Example 1
In an autoclave made of hastelloy having an internal volume of 100 ml, 0.07 g of the polymer of hydroxymethylallene obtained in Reference Example 2 was taken, 50 ml of methanol, 0.0006 g (3 μmol) of ruthenium trichloride, and triphenylphosphine 0 .0012 g (4.6 μmol) was added, and the atmosphere in the autoclave was purged with nitrogen, followed by hydrogen substitution, and further hydrogen was supplied to adjust the hydrogen pressure in the autoclave to 5 MPa. Hydrogenation was carried out by stirring the autoclave at 60 ° C. for 6 hours. After cooling to room temperature, the precipitated polymer was filtered off to obtain 0.065 g of polymer (hereinafter, this polymer is abbreviated as polymer (I)). Analysis by ¹ H-NMR (300 MHz) confirmed that no carbon-carbon double bonds remained and the carbon-carbon double bonds were hydrogenated. Moreover, the disappearance of the hydroxyl group was not observed. From this, the polymer (a) is a polymer composed of the structural unit (3) in which X is a hydroxyl group and the structural unit (4) in which X is a hydroxyl group, and the ratio is the structural unit (3) / It was found that the structural unit (4) = 60/40 (molar ratio).

  The polymer (a) obtained above was dissolved in a mixture of tetrahydrofuran and methanol [tetrahydrofuran / methanol = 1/3 (volume ratio)], and the resulting solution was placed on a polytetrafluoroethylene plate (base material). And dried at 80 ° C. overnight, and then peeled off from the substrate to obtain a film having a thickness of 15 μm.

Evaluation of film flexibility The film obtained above was subjected to a pantograph-type biaxial stretching apparatus manufactured by Toyo Seiki Seisakusho Co., Ltd., and subjected to simultaneous biaxial stretching at 90 ° C. and a stretching ratio of 3.5 × 3.5 times. went. When the appearance of the stretched film was visually evaluated, it was found that no unevenness and local uneven thickness were observed, the stretchability was good, and the film was highly flexible.

Example 2
In an autoclave made of Hastelloy having an internal volume of 100 ml, 0.07 g of the polymer of hydroxymethylallene obtained in Reference Example 2 was taken, and 50 ml of methanol, 0.0012 g of tri (triphenylphosphine) ruthenium (II) chloride (1 .3 micromol) was added, and the atmosphere in the autoclave was purged with nitrogen, followed by hydrogen substitution, and further hydrogen was supplied to adjust the hydrogen pressure in the autoclave to 5 MPa. The temperature in the autoclave was set to 60 ° C. and stirred for 6 hours to carry out a hydrogenation reaction. After cooling to room temperature, the precipitated polymer was separated by filtration to obtain 0.065 g of a polymer. ^When analyzed by ¹ H-NMR (300 MHz), the conversion rate of carbon-carbon double bonds was 78%. Moreover, the disappearance of the hydroxyl group was not observed.

Reference example 3
In an autoclave made of Hastelloy having an internal volume of 100 ml, 0.07 g of the polymer of hydroxymethylallene obtained in Reference Example 2 was taken, and 50 ml of methanol, 5% palladium on carbon (5% E106KR / w made by Degussa) 0. 001 g (0.5 micromol) was added, and the atmosphere in the autoclave was replaced with nitrogen, followed by replacement with hydrogen, and further hydrogen was supplied to adjust the hydrogen pressure in the autoclave to 5 MPa. Hydrogenation was carried out by stirring the autoclave at 90 ° C. for 6 hours. After cooling to room temperature, the precipitated polymer was filtered off to obtain 0.051 g of polymer. ^When observed by ¹ H-NMR (300 MHz), the conversion rate of the double bond was 81%, and it was confirmed that the carbon-carbon double bond was hydrogenated. However, since no residual hydroxyl group was observed, it was found that the polymer of the present invention was not obtained.

As shown in the above examples, it can be seen that the polymer of the present invention has appropriate flexibility.
Therefore, it can be seen that the polymer of the present invention is very useful when a packaging material such as a packaging film having excellent bag forming processability is produced.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the stretched film which consists of a novel polymer which can be induced | guided | derived from the polymers of allenes, such as hydroxymethyl allene, is provided .

Claims (4)

The following formulas (1) to (4)

(In the formula, X represents a hydroxyl group, a hydroxyl group protected by a protecting group, or a hydrocarbon group having a hydroxyl group or a hydroxyl group protected by a protecting group. X in formulas (1) to (4) are the same as each other. may be different even.) Ri or the structural unit Rana represented by,
The content (molar ratio) of structural units other than the structural units (1) to (4) is 40 mol% or less with respect to the total of the structural units (1) to (4),
The ratio (molar ratio) is a method for producing a stretched film made of a polymer satisfying the following relational expression (A) :
[Total amount of structural unit (1) and structural unit (2)] / [Total amount of structural unit (3) and structural unit (4)] = 70/30 to 0/100 (A)
The following formula (1) and / or formula (2)

(Wherein X represents a hydroxyl group, a hydroxyl group protected by a protecting group, or a hydrocarbon group having a hydroxyl group or a hydroxyl group protected by a protecting group. X in formulas (1) and (2) are the same as each other) Or may be different.) A method for producing a stretched film comprising a polymer, wherein the carbon-carbon double bond of the polymer comprising the structural unit represented by formula (1) is hydrogenated. The stretching comprising the polymer according to claim 1, wherein the molecular weight distribution (Mw / Mn) defined by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is in the range of 1.0 to 2.5. A method for producing a film . The production method according to claim 1 or 2 , wherein the hydrogenation is carried out in the presence of a homogeneous catalyst.
The method according to claim 3 , wherein the homogeneous catalyst is a ruthenium catalyst.