JP2008174756A - Polymeric material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymeric material that forms a colloid or a gel that can be used in treatment, combustion or recovery of oil. <P>SOLUTION: A method for preparing a first polymeric compound comprises providing a compound of formula (I) (wherein A and B are the same or different, and at least one of them comprises a relatively polar atom or group; and R<SP>1</SP>and R<SP>2</SP>independently comprise relatively non-polar atoms or groups) or a salt thereof in a solvent in which ethene itself is generally insoluble and reacting groups C=C in the compound with one another to form a polymeric structure. The first polymer compound may be reacted with a second polymer compound (e.g., polyvinyl alcohol, collagen or the like) to produce the colloid or gel that can be used in the treatment, combustion or recovery of the oil. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to polymeric materials, but not exclusively, particularly to polymeric materials formed at least in part from 1,2-substituted ethene compounds, such as substituted styrylpyridinium compounds.

  British Patent Application Publication No. 2030575 (Agency of Science and Technology) discloses a styrylpyridium salt having a formyl group or an acetal group on a styrylphenyl group, polyvinyl alcohol or partially saponified poly A photosensitive resin prepared by reacting with vinyl acetate is disclosed. In the resin, the —CH═CH— group has photosensitivity, and therefore the resin can be used in screen printing, for example, when it is known that it exhibits high sensitivity.

  The present invention is based on the discovery of the surprising properties of 1,2-substituted ethene compounds of the kind described above that can prepare polymeric materials having a variety of useful properties.

（式中、ＡおよびＢは、同じまたは異なっており、および少なくとも一方が比較的極性の原子または基を含み、およびＲ^１およびＲ^２は、独立して、比較的非極性の原子または基を含む。）
で表される化合物またはその塩を、エテン自体が一般に不溶性の溶媒中で供給し、前記化合物中のＣ＝Ｃ基を互いに反応させてポリマー構造を形成することから成る第１ポリマー化合物を調製する方法が提供される。 According to a first aspect of the invention, the formula:

Wherein A and B are the same or different, and at least one contains a relatively polar atom or group, and R ¹ and R ² independently represent a relatively non-polar atom or group. Including)
Or a salt thereof is supplied in a solvent in which ethene itself is generally insoluble, and a C═C group in the compound is reacted with each other to form a polymer structure. A method is provided.

Preferably R ¹ and R ² are independently selected from a hydrogen atom or an optionally substituted, preferably unsubstituted alkyl group. Preferably R ¹ and R ² represent the same atom or group. Preferably, R ¹ and R ² represent a hydrogen atom.

  Preferably, the solvent is a polar solvent. Preferably, the solvent is an aqueous solvent. More preferably, the solvent consists essentially of water.

  Preferably, the compound of formula I is supplied in the solvent at a concentration at which molecules of the compound aggregate. Aggregation of compounds of Formula I may be indicated or inferred from the results of various analytical methods described below, and one or more of such analytical methods may be used. Preferably, said compound of formula I is provided in a solvent or above a concentration suggested as being the aggregation point of the compound by appropriate vapor pressure measurements.

The molecules of Compound I are believed to form aggregates or micelles in the solvent that have C═C bonds aligned with each other such that the molecules are effectively aligned substantially parallel to each other.
Preferably, the molecule is aligned with groups A and B adjacent to each other.

  Said compound of formula I may be provided in a solvent at a concentration of at least 0.5% by weight, preferably at least 1.0% by weight, more preferably at least 1.5% by weight.

  The group C = C in the compound preferably causes a reaction in the photochemical reaction. Preferably, the method comprises inducing a photochemical reaction, suitably using ultraviolet light. Preferably, light having a wavelength of up to 500 nm is used in the previous method.

  Preferably, A and B are independently selected from optionally substituted alkyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkynyl groups, aromatic and heteroaromatic groups. When the group A or B has a cyclic structure, a 5-membered ring or more, preferably a 6-membered ring is preferred.

  More preferably, A and B are independently selected from 5-membered, or more preferably 6-membered, optionally substituted aromatic and heteroaromatic groups, with 6-membered groups being particularly preferred. Preferred heteroatoms of the heteroaromatic group include a nitrogen atom, an oxygen atom and a sulfur atom, and an oxygen atom and particularly a nitrogen atom are preferred. Preferred heteroaromatic groups contain only one heteroatom. Preferably, the particular or said heteroatom is located farthest from the attachment position of the group C═C and the heteroaromatic group. For example, if the heteroaromatic group is comprised of a 6-membered ring, the heteroatom is preferably supplied in the 4-position with respect to the position of attachment of the group C = C to the ring.

  Unless otherwise specified, the optionally substituted groups described herein, eg, groups A and B, are halogen atoms and optionally substituted alkyl groups, acyl groups, acetal groups, hemiacetal groups, acetals Alkyloxy group, hemiacetal alkyloxy group, nitro group, cyano group, alkoxy group, hydroxyl group, amino group, alkylamino group, sulfinyl group, skillsulfinyl group, sulfonor group, alkylsulfonyl group, sulfonate group, amide group, alkylamide May be substituted with groups, alkylcarbonyl groups, alkoxycarbonyl groups, halocarbonyl groups and haloalkyl groups. Preferably up to 3, more preferably up to 1 optional substituents may be provided on the optionally substituted group.

  Unless otherwise specified, alkyl groups may have up to 10 carbon atoms, preferably up to 6, more preferably up to 4, with methyl and ethyl groups being particularly preferred.

  Preferably, A and B each represent a polar atom or group. Preferably, A and B each represent an optionally substituted aromatic or heteroaromatic group, wherein the “p” orbital of said aromatic group is aligned with the “p” orbital of the group C═C. Preferably A and B represent different atoms or groups.

Preferably one of the groups A and B includes an optional substituent including a carbonyl group or an acetal group, particularly preferably a formyl group. The other of the groups A and B includes an optional substituent which is an optionally substituted alkyl group, preferably an unsubstituted C _1-4 alkyl group (eg, particularly preferably a methyl group).

（式中、Ｘは、１〜６の整数であり、および各Ｒ^３は、独立して、アルキル基またはフェニル基であるかまたは合わせてアルカレン基を形成する。）
で表される基で置換されたフェニル基を表す。 Preferably, the group A is preferably in the 4-position with respect to the group C═C, a formyl group or the formula:

(Wherein X is an integer from 1 to 6 and each R ³ is independently an alkyl group or a phenyl group or together forms an alkane group.)
The phenyl group substituted by group represented by these is represented.

（式中、Ｒ^４は、水素原子またはアルキル基またはアラルキル基を表し、Ｒ^５は、水素原子またはアルキル基を表し、およびＸ⁻は、強酸イオンを表す。）
の基を表す。 Preferably, the group B has the formula:

(In the formula, R ⁴ represents a hydrogen atom, an alkyl group or an aralkyl group, R ⁵ represents a hydrogen atom or an alkyl group, and X ⁻ represents a strong acid ion.)
Represents a group of

  Preferred compounds of formula I for use in the present invention include those disclosed in British Patent Application Publication No. 2030575, page 3, lines 8 to 39, into which the compound is inserted.

  The compounds of formula I in the use according to the invention may be prepared in the same way as disclosed in GB-A-2030575, and such preparation methods are also inserted here.

（式中、Ａ、Ｂ、Ｒ^１およびＲ^２は、上述と同様のものであり、およびｎは、整数である。）
で表される新規な第１ポリマー化合物が提供される。 The present invention also extends to a novel first polymer compound that can be prepared by the method of the first aspect.
According to a second aspect of the invention, the formula:

(In the formula, A, B, R ¹ and R ² are the same as described above, and n is an integer.)
A novel first polymer compound represented by the formula:

  According to a third aspect of the present invention, the composition comprises supplying the first polymer compound of the first or second aspect together with the second polymer compound in a solvent and thoroughly mixing them. Are provided.

  Preferably, the second polymer compound includes one or more functional groups that can react with the first polymer compound, preferably in an acid catalyzed reaction. The reaction is preferably a condensation reaction. Preferably, the second polymer compound includes a functional group selected from an alcohol, a carboxylic acid, a carboxylic acid derivative (eg, ester), and an amine group. Preferred second polymer compounds include optionally substituted, preferably unsubstituted polyvinyl alcohol, polyvinyl acetate, polyalkylene glycols (eg, polypropylene glycol) and collagen (and any component thereof).

  Preferably, the second polymer compound is a solid under normal conditions. Preferably, the thorough mixing is performed at an elevated temperature. Preferably, the mixing is performed in the same solvent in which Compound I was prepared. The mixture may further include a polymer compound that may be of the same type as the second polymer compound described above.

It has been found that the weight ratio of the first polymer compound to the second polymer compound (or the total weight of the second polymer compound and the further compound) in the mixture has a significant effect on the properties of the composition to be prepared. ing. The weight ratio of the first polymer compound to the second polymer compound may be in the range of 0.01 to 100, preferably 0.05 to 50, more preferably 0.3 to 20.
Preferably, water is removed from the composition to produce a solid material, for example in the form of a film.

According to a fourth aspect of the present invention, there is provided a composition comprising the first polymer compound of the first or second aspect and the second polymer compound described in the third aspect.
Preferably, the composition is provided in solid form.

  According to a fifth aspect of the present invention, a material comprising supplying the mixture prepared in the third aspect or the mixture of the fourth aspect in a solvent and reacting the first and second polymer compounds with each other For example, a method of making a colloid or gel is provided.

The reaction may be acid catalyzed, and thus the method may include providing an acid into the mixture. It has been found that the concentration of acid used affects the rate of colloid / gel formation. Preferably at least 0.05% by weight of acid is used, more preferably at least 0.1% by weight. Either organic or inorganic acids may be used. Preferred acids include p-toluene sulfonic acid, hydrochloric acid, phosphoric acid, sulfonic acid and naphthalene sulfuric acid.
The concentration of the mixture used affects whether a colloid or a gel is formed. A viscoelastic colloidal solution is formed when the weight percent of the solid composition of the first and second polymer compounds of the solid composition is about 2 weight percent or less. On the other hand, if the concentration exceeds about 2% by weight, a gel is formed.

  Another active component may be incorporated into the colloid or gel prepared as described in the fifth aspect by adding the active component as appropriate prior to the reaction between the first polymer compound and the second polymer compound. . Preferred active ingredients include antibacterial agents such as iodine / iodine mixtures, cetyltrimethylammonium bromide and neomycin sulfate. Sheet materials may be made incorporating active ingredients, and products prepared as described herein have been found to be biocompatible so that the sheet material is ready for combustion processing. May be used.

  It has been found that when the oil (or oily) comes into contact with the reaction mixture of the fifth aspect, up to 50% by weight of the oil can be emulsified by the mixture and the resulting gel retains the oil in a solid matrix. . Accordingly, in a sixth aspect, the present invention provides a method for collecting and / or isolating and / or emulsifying an oil (or oily) comprising the reaction mixture of the fifth aspect. Or oily) is introduced into the material (eg, the gel formed).

  The invention extends to colloids or gels that can be prepared by the method of the fifth aspect.

  According to a seventh aspect, there is provided a novel third polymeric compound comprising a reaction product of a second polymeric material as described herein and a compound of formula IV.

  Any aspect or example feature of the invention disclosed herein may be combined with any other aspect or example feature described herein.

  Specific embodiments of the invention will now be described by way of example with reference to the accompanying drawings.

Physico-chemical experiment of 4- (4-formylphenylethenyl) -1-methylpyridinium methosulfonate (SbQ)
Various physico-chemical experiments were conducted on the experimentally purified SbQ aqueous solution samples as follows.
i. The surface tension measurement-dropping profile measurement procedure was used.
ii. Vapor pressure measurement-performed using a Knauer vapor pressure osmometer calibrated with Analar NaCl solution.
iii. Energy analysis of the structure of the minimized SbQ molecule in water—performed using the Hyperchem® molecular model package based on MM ⁺ force fielding calculations.
iv. Conductivity measurements-performed using a Wayne Kerr B905 automatic measurement bridge.
v. Density measurements-were performed as described in European Polymer Journal, 1987, pages 23, 711 to give apparent molar volume values.
vi. Light Scattering Measurement—A Sofica Photogoniometer Model 42000 modified to use a Uniphase 1 mW HeNe laser operating at 543 nm.
vii. Dilution heat measurement--LKB flow micro calorimeter 2107-121 / 127 was used.

Result:
According to FIG. 1, the Δt / C ratio represents the temperature difference between the solvent reference probe and the solution probe at a concentration C (g / kg). The plot represents two linear regions, both of which have good correlation coefficients of 0.996 and 0.998 and intersect at a concentration value of 1.25% by weight. The portion of the range where the solution concentration was low was used in the usual manner to obtain a SbQ number average molecular weight value 341 close to the expected value 335. The difference in slope at higher concentrations suggests that the formation of aggregates of SbQ molecules occurred at concentrations above 1.25 wt%.

Analysis using the Hyperchem package expects a very flat structure. Such a structure for a molecule consists of four SbQ molecules as shown in FIG. 2, with the molecules stacked in order in the hydrophobic region of the molecule and alternating aldehyde and —N—CH ₃ groups. In view of this, the possibility of producing aggregates exhibiting minimized energy in water is naturally taken into account.

  Taking the difference between the intercepts in FIG. 1 for the two concentration regions as attributed to the aggregate yields a molecular weight of about 2800 for the SbQ aggregate, which is the critical concentration for a change of 1.25 wt% or near 0.04M Suggests that the aggregate stack is composed of about 8 monomer units.

  According to the surface tension measurements in FIG. 3, the pattern shown is a typical pattern for surfactant micellization, with a transition point occurring at about 0.06M. Therefore, this trace is actually a rod-like micelle in which SbQ aggregates having a critical micelle concentration (cmc) of 0.04 to 0.06 M are stacked.

  The molar conductivity in FIG. 4 also represents the expected pattern of micelle-forming species, including the change in slope at cmc occurring at 0.04M.

  According to FIG. 5, the steep change in slope seen at 0.04M indicates that SbQ molecules adopt a more compact shape above this concentration, more precisely when they aggregate to form micelles. It means you can predict what will happen.

  According to FIG. 6, the sudden increase in scattering that occurs as the concentration approaches 0.04M indicates the development of larger particles (ie, micelles).

  According to FIG. 7, the measurement of the heat of dilution shows a steep change in the gradient (in this case a change at 0.035M) and also shows the main change in the solution state of the solute from the monomer to the generated micelles. ing.

  It should be appreciated from the above that the close correlation between the concentration dependent properties of all experimental measurements is a sufficient confirmation of the presence of monomer-micelle equilibrium in an aqueous solution of SbQ. This property is useful in the following examples.

ポリマー化合物IIは新規であると考えられる。 Example 1
Poly (1,4-di (4- (N-methylpyridinyl))-2,3-di (4- (1-formylphenyl) butylidene) (Compound II shown below)
An aqueous solution exceeding 1% by weight of SbQ was exposed to ultraviolet light. As a result, a photochemical reaction occurs between the carbon-carbon double bonds of adjacent 4- (4-formylphenylethenyl) -1-methylpyridinium methosulphate molecules (I) in the aggregate. As shown, the polymer [poly (1,4-di (4- (N-methylpyridinyl))-2,3-di (4- (1-formylphenyl) butylidene (II)]] was formed. It should be appreciated that the anion of II is omitted for clarity.

Polymer compound II is believed to be novel.

Example 2
Preparation of Blends with Compound II Conventional methods for the preparation of gels are outlined below.
13 g of 88% hydrolyzed poly (vinyl alcohol) having a molecular weight of 300,000 was dissolved in 87 g of a 2 wt% solution of Compound II. Poly (vinyl alcohol) was added slowly with stirring at a constant rate to disperse the powder. Final dissolution was achieved by holding the solution at a temperature of 60 ° C. for 6 hours. The resulting poly (vinyl alcohol) / poly (1,4-di (4- (N-methylpyridinyl))-2,3-di (4- (1-formylphenyl) butylidene) solution was filmed on a PTFE sheet The solid blend is light stable and can be stored in a desiccator until needed.

実施例２に記載のフィルムを、酸（例えば、ｐ−トルエン硫酸）も含む水中に再度溶解することもある。これは、以下のスキームに従って、酸触媒化アルドール縮合反応を生じさせる。 Example 3
Gel preparation

The film described in Example 2 may be redissolved in water that also contains an acid (eg, p-toluene sulfuric acid). This results in an acid catalyzed aldol condensation reaction according to the following scheme.

  The concentration of film used affects the properties of the resulting gel. For example, at concentrations above 2.5% by weight, a firm gel is formed. Furthermore, the gel time depends on the concentration of acid used. 0.1% by weight acid gives a gel time of 16 hours, while 1% by weight acid gives a gel time of 10 minutes.

Properties of the gel prepared by the following procedure described herein 1. Gels formed with 2.5 to 13% by weight of poly (vinyl alcohol) do not melt or display a visual trace of shape change when heated to 100 ° C. At higher temperatures, the gel “carbonizes” but does not burn.
2. The gel is stiff and optionally transparent.
3. The time required for gelation can be controlled by changing the concentration of acid used to catalyze the gelation reaction. With different gel times, different shaped gels can be integrally formed by simply pouring the reaction mixture into the mold. There is almost no shrinkage of the material during gel formation.
4). Gels are insoluble in all common organic solvents, but some swell considerably. Gels are also insoluble in aqueous solutions.
5. Instead of the poly (vinyl alcohol) described in Examples 2 and 3 only, a mixture of 50% by weight collagen and 50% by weight poly (vinyl alcohol) can be used to produce a hard gel. The gel produced exhibits organic solvent resistance and limited swelling in water.
6). After the addition of an acid that catalyzes the gelling reaction in Example 3, up to 50% by weight of oil may be emulsified with the reaction mixture. The gel that is formed retains the oil in a solid matrix.
7). Gels can be made using a solvent mixture containing up to 50% by weight of polypropylene glycol 400. The swelling properties of the resulting gel in water are controlled by the amount of polypropylene glycol in the solvent.
At a concentration of less than 8.2% by weight, a viscoelastic solution is produced and the viscosity is increased 10 times compared to the unreacted mixture. This property is used in the collection of tertiary oil because the reaction mixture is poured into a crevice in the well and the viscoelasticity of the cross-linked polymer solution improves as the reaction proceeds, allowing the crevice to remain open. It has the possibility of
Both the gels of Examples 1-3 and the gels described above can rapidly disintegrate due to the periodate cleavage process of the poly (vinyl alcohol) chain. The resulting solution is low viscosity and easily washed with water. In the case of emulsified oil, the above 6. These gels can collect oil because periodate splitting results in gel disintegration.
The reader's attention is directed to all articles and documents submitted in conjunction with or prior to this specification in conjunction with this application and all articles and documents that are publicly viewed with this specification. Insert the contents of all such articles and documents here.

  All features disclosed in this specification (including the appended claims, abstracts, and drawings) and / or every step of a disclosed method or process must include at least such features and / or steps. Unless some are incompatible combinations, they may be combined.

  Each feature disclosed in this specification (including the appended claims, abstract and drawings) may be replaced with an alternative feature serving the same, equivalent or similar purpose unless otherwise indicated. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.

  The present invention is not limited to the details of the foregoing aspects. The invention includes novel features, novel combinations of features disclosed herein (including the appended claims, abstract and drawings), or novel steps of the disclosed method or process. To anything or new combinations.

2 is a graph showing vapor pressure measurement as a function of concentration at 37 ° C. of an aqueous solution of 4- (4-formylphenylethenyl) -1-methylpyridinium methosulfonate (SbQ). It is a representative example of the expected energy minimization structure of four molecules in water. FIG. 6 is a graph representing surface tension measurement of SbQ solution as a function of concentration at 25 ° C. FIG. 4 is a graph showing the molar conductivity of the SbQ solution as a function of concentration at 25 ° C. FIG. 6 is a graph showing the apparent molar volume value as a function of concentration at 25 ° C. of an SbQ solution. FIG. 5 is a graph representing Rayleigh scattering at 90 ° as a function of concentration at 25 ° C. for an SbQ solution. FIG. FIG. 6 is a graph showing the heat of dilution of SbQ solution as a function of concentration at 25 ° C. FIG.

Claims (12)

A third polymer material containing a reaction product of the first polymer material and the second polymer material, wherein the first polymer material has the formula:

Wherein A and B are the same or different, and at least one contains a relatively polar atom or group, and R ¹ and R ² independently contain a relatively nonpolar atom or group. , N is an integer.)
A third polymer material, characterized in that Wherein A is an optionally substituted aromatic group, B is an optionally substituted heteroaromatic group, and one of the groups A and B includes any substituent, including a carbonyl or acetal group. , R ¹ and R ² are independently selected from a hydrogen atom, a methyl group or an ethyl group, and n is an integer. 3. The group of claim 2, wherein one of the groups A and B includes an optional substituent that includes a carbonyl or acetal group, and the other of the groups A and B includes an optional substituent that is a _C1-4 alkyl group. 3 polymer material. A phenyl group in which the group A is substituted by a formyl group or the formula:

(Wherein X is an integer from 1 to 6 and each R ³ is independently a C _1-4 alkyl or phenyl group, or together form an alkane group.)
The 3rd polymer material in any one of Claims 1-3 which shows the phenyl group substituted by group represented by these. Group B has the general formula:

(Wherein R ⁴ represents a hydrogen atom or an alkyl or aralkyl group, R ⁵ represents a hydrogen atom or an alkyl group, and X ⁻ represents a strongly acidic ion, and each alkyl group of R ⁴ or R ⁵ represents a carbon number. 4 or less, including an alkyl group contained in the aralkyl group.)
The 3rd polymer material in any one of Claims 1-4 represented by these.   The third polymer material according to any one of claims 1 to 5, wherein the second polymer material contains a functional group selected from an alcohol, a carboxylic acid, a carboxylic acid derivative, and an amine group.   The third polymer material according to any one of claims 1 to 6, wherein the second polymer material is selected from optionally substituted polyvinyl alcohol, polyvinyl acetate, polyalkylene glycol and collagen.   The third polymer material according to any one of claims 1 to 7, wherein the second polymer material is polyvinyl alcohol.   A composition comprising: feeding a first polymeric material according to any of claims 1-8 together with a second polymeric material according to any of claims 1-8 into a solvent and thoroughly mixing them. Preparation method.   A composition comprising the first polymer material and the second polymer material according to claim 1.   A method of producing a third polymeric material, wherein a mixture of first and second polymeric materials is provided in a solvent and both are reacted with each other.   An oil is brought into contact with the reaction mixture containing the first and second polymer materials according to any one of claims 1 to 8 and the first and second polymer materials are reacted to be introduced into a third polymer material from which oil is formed. A method for collecting, isolating or emulsifying oil, characterized in that

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