JP2006265452A - Method for modifying spherical polymer material by liquid-phase chemical reaction and modified spherical polymer material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To modify a spherical polymer material by imparting functionality thereto, particularly to introduce a reactive active species or a reactive functional group while retaining the high molecular weight and mechanical properties or the spherical shape of the material. <P>SOLUTION: The method for modifying the polymer material comprises an active species introduction step for introducing the reactive active species into the spherical polymer material by causing a first compound, which is excitable by an active radiation thereby to form a reactive species, to exist as a liquid phase and irradiating the compound with the active radiation in the coexistence of the spherical polymer material. The method may further comprise a functional group conversion step of causing the spherical polymer material to react with a second compound bearing a reactive functional group to convert the reactive active species into the reactive functional group. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for modifying particles made of natural or synthetic polymers. More particularly, the present invention relates to a method for modifying a spherical polymer material in which a reactive functional group or a polar functional group for imparting functionality to a polymer particle is introduced, and a spherical modified polymer material.

  Conventionally, in order to introduce a reactive functional group or a polar functional group in order to impart functionality to a polymer material, in the case of a synthetic polymer, a functional group is previously added to a polymerizable monomer (monomer) serving as a repeating unit. There are two methods: a method in which a polymerization reaction is carried out after introduction of a polymer, and a method in which a polymer material is dissolved in a solvent and introduced by a reaction between a compound having a functional group to be introduced and a polymer. Functionality includes wettability (hydrophilicity, water repellency), polarity and the like. Regarding the modification of polymer materials by introducing functional groups into these polymer materials and the method thereof, for example, a functional polymer (edited by Kyoritsu Publishing Co., Ltd., July 1974) It is stated in the books such as the first edition).

  However, in the method of introducing the monomer into the polymerizable monomer (monomer) in advance, the introduced functional group inhibits the polymerization reaction, the degree of polymerization does not increase, or the introduced functional group reacts during the polymerization. There are problems such as reducing the amount of solvent, lowering the solvent solubility of the polymer material to which the corner function is added by creating a crosslinked structure by reaction, and making it difficult to change the shape such as molding in order to increase the thermal softening temperature. there were.

  Furthermore, depending on the polymerization reaction, there is a problem that the functional group to be introduced does not exhibit a sufficient function because it is present in the material as a non-uniform block.

  In addition, the method of introducing a functional group by dissolving a polymer material in a solvent and reacting with a low molecular compound having a functional functional group can be used only for a material that dissolves in the solvent, and has a functional group to be introduced. If the low molecular weight compound is not dissolved in the same solvent as the polymer material, the reaction will not proceed well, and even if the functional group introduction reaction proceeds, the solubility in the reaction solvent will decrease with the progress of the reaction, resulting in precipitation, etc. There is also a problem that a sufficient amount of functional groups cannot be introduced.

  In addition to the above, a method of surface modification after forming a polymer material into a structure such as a film, a fiber or a fabric woven by spinning using fibers, or a knitted knitted fabric has been widely performed in various fields. ing. As the method, there is a method in which polar groups are generated on the surface of a polymer structure (polymer material) by treatment such as electron beam, plasma, corona discharge in the presence of a gas such as nitrogen, oxygen, helium and argon. For example, Patent Documents 1 and 2 describe a method for improving the wettability of an aqueous dye solution during printing by plasma treatment of the surface of the fabric.

  This method is effective in improving the wettability of the fabric surface with the aqueous dye solution, but a sufficient amount of functional groups for imparting a function cannot be introduced. Furthermore, there is a problem that desired reactivity or polar functional groups cannot be introduced.

Also disclosed is a method for improving the adhesion by a method in which the surface of a film made of polyethylene terephthalate is subjected to corona discharge treatment in air and a coating film is formed on the treated surface. In this method, the film surface is modified and the adhesiveness is improved by the interaction with the coating film, but a desired functional group cannot be introduced.

  In addition, in these conventional methods, there is a problem that foreign matters such as dust are easily attracted due to charging during processing, and the surface is contaminated. Furthermore, the sustainability of the effect was short and it had to be used in the next step immediately after treatment. Further, the modification was only on the polymer surface, and the effect could not be exerted on the inside or the back side of the material.

  In addition, a technique for efficiently improving the polarity of the surface by actively irradiating the fabric surface with ultraviolet rays in the presence of ozone has been disclosed, but a sufficient amount of polar groups has not been introduced, and its effect There is a problem with the sustainability of the product, and a desired functional group cannot be introduced.

  There is also a method using photo-CH activation. C—H activation is a means for directly introducing a functional group by cleaving an inactive C—H bond such as a saturated hydrocarbon, such as chlorine substitution into natural gas. It hits. Usually, a metal catalyst or the like is used, but there is a method based on a photochemical reaction mechanism. Although these reactions are well known as organic synthetic chemistry reactions, they are not widely used industrially because of the difficulty in controlling the reaction position. However, examples of use include photonitrosation of cyclohexane in Toray's caprolactam synthesis.

  However, in such a method based on a photochemical reaction mechanism, a reaction of a low-molecular compound is mainly carried out, so that diffusion or mixing of molecules occurs sufficiently even in a liquid phase. In order to sufficiently cause molecular diffusion in the solid-liquid state, the solid-gas state has a higher diffusion rate than the solid-liquid state, and not only the surface but also the internal reforming of the polymer material can be efficiently performed.

  Accordingly, one of the present inventors has developed a method for modifying a polymer material using a photochemical reaction by a solid-gas phase reaction (Patent Document 3). However, the surface functional group concentration introduced by modification may be insufficient depending on the application. In particular, it has been difficult to introduce reactive functional groups uniformly and at a high concentration on the surface of spherical particles made of a polymer material.

JP-A-2-47378 JP-A-4-1533381 JP-A-9-316126

  The problem to be solved by the present invention is to perform modification for imparting functionality to the spherical polymer material, in particular, while maintaining the high molecular weight and mechanical properties of the material and maintaining the spherical shape. In this state, a reactive active species or a reactive functional group or a polar functional group (both these groups are also simply referred to as “reactive functional groups”) is introduced.

  Further, the amount of functional groups to be introduced is introduced not only on the surface but also inside the particles as needed, as compared with the prior art, and it is possible to provide a spherical polymer material having a long-lasting effect. It is a problem.

  As a result of intensive studies to solve the above problems, in the present invention, the surface or internal modification of the spherical polymer material is generated in a liquid phase of a specific compound, and this reactive active species is polymerized. The present inventors have found that it is effective to introduce it into a material and to convert it into various reactive functional groups or polar functional groups.

The above-described problems of the present invention have been solved by the following means.
Item 1) The reactive property of the spherical polymer material is obtained by irradiating active radiation in the coexistence of the spherical polymer material in the presence of the first compound that is excited by actinic radiation to generate a reactive active species as a liquid phase. A method for modifying a polymer material, comprising an active species introduction step of introducing an active species.

Preferred embodiments of the above reforming method are listed below.
Item 2) A functional group that converts the reactive active species into the reactive functional group by reacting the spherical polymer material into which the reactive active species has been introduced with a second compound having a reactive functional group Item 1. The method for modifying a spherical polymer material according to item 1 including a conversion step,
Item 3) The reactive functional group is terminated with at least one group selected from the group consisting of —COCl, —COOH, —OH, —SH, —NH ₂ , —R ₁ NH, and —R ₁ R ₂ N. The method for modifying a spherical polymer material according to item 1) or 2), which is a group contained in
Item 4) The method for modifying a spherical polymer material according to any one of Items 1) to 3), wherein the first compound is oxalyl halide,
Item 5) The spherical height according to any one of Items 1) to 4), wherein the second compound is a compound having active hydrogen capable of reacting with a carbonyl halide group introduced into a spherical polymer material or water. Modification method of molecular material,
Item 6) The method for modifying a spherical polymer material according to any one of Items 1) to 5), wherein the first compound is oxalyl dichloride and / or oxalyl bromide,
Item 7) The method for modifying a spherical polymer material according to any one of Items 1) to 6), wherein the active radiation is ultraviolet light,
Item 8) The method for modifying a spherical polymer material according to any one of Items 2) to 7), wherein the functional group conversion step is performed in an organic solvent,
Item 9) The method for modifying a spherical polymer material according to any one of Items 2) to 8), wherein the functional group conversion step is performed in a gas phase of the second compound.
Item 10) The method for modifying a spherical polymer material according to any one of Items 2) to 9), wherein the second compound has two or more reactive functional groups in the molecular structure.

The above problems of the present invention have been solved by means described in the following item 11).
Item 11) A spherical modified polymer material, wherein the reactive active species generated by the first compound excited by actinic radiation is a spherical polymer material introduced on the particle surface.

Preferred embodiments of the above spherical modified polymer material are listed below.
Item 12) A spherical modified polymer material having a reactive functional group obtained by converting a reactive active species of the modified spherical polymer material according to Item 11),
Item 13) The reactive functional group is —COCl, —COBr, —COOH, —OH, —SH, —NH ₂ , —R ₁ NH, and —R ₁ R ₂ N (R ₁ and R ₂ are independently A hydrogen atom, an alkyl group, or an aryl group.) The spherical modified polymer material according to Item 11) or 12), which is a group selected from the group consisting of: and a group covalently bonded to the polymer material;
Item 14) The spherical modified polymer material according to any one of Items 11) to 13), wherein the reactive active species is -COCl or -COBr.

  According to the present invention, a reactive active species such as a carbonyl halide group can be introduced into a polymer material having a spherical shape such as PET fine particles, PE fine particles, or PP fine particles, and this group can be converted by a subsequent reaction. It can be derivatized to other reactive functional groups.

Means for solving the above problems will be specifically described below.
As a result of intensive studies to solve the above-described problems related to the modification of polymer materials, the present inventors have found that most of the polymer materials have a saturated or unsaturated hydrocarbon structure. We found that the problem can be solved by using. Various types of polymer materials can be obtained by introducing reactive species into the C—H bonds of the polymer material by photo-CH activation and performing photochemical reaction in the liquid phase in order to modify its properties. That is, it is possible to modify even a fiber, a woven fabric, a film, particularly a polymer material having a particle shape.

That is, the present invention provides a spherical polymer material by irradiating actinic radiation in the presence of a spherical polymer material in the presence of a first compound that is excited by actinic radiation to generate a reactive active species as a liquid phase. The present invention relates to a method for modifying a spherical polymer material, comprising an active species introduction step for introducing the reactive active species.
The present invention also relates to a modified polymer material characterized in that it is a spherical polymer material into which a reactive active species generated by a first compound excited by actinic radiation is introduced.
Here, the average particle diameter of the spherical particles is preferably 0.1 to 1,000 μm, more preferably 0.5 to 500 μm, and particularly preferably 1 to 100 μm. Here, the average means a number average.
The spherical particles include a substantially spherical shape close to a spherical shape in addition to a true spherical shape. Here, the substantially spherical shape means a shape of 100 to 140, preferably 105 to 130, according to a shape factor SF-1. The shape factor SF1 is an average value of the shape factors, and is calculated by the following method. That is, an optical microscope image of spherical particles dispersed on a slide glass is taken into a Luzex image analyzer through a video camera, and SF1 is obtained from the peripheral length and projected area for 100 or more toners by the following formula to obtain an average value. It is a thing. In the formula, ML represents the maximum length of toner particles, and A represents the projected area of the particles.

  Hereinafter, in order to facilitate understanding of the present invention, an example using a chlorocarbonylation reaction of C—H by a photochemical reaction of oxalyl dichloride will be shown as one embodiment. This reaction is a reaction that occurs through a reactive active species (radical species) that occurs photochemically, and is stoichiometrically as shown in Formula (1).

ここで、Ｒは球状高分子材料中の炭素原子残基を示す。

Here, R represents a carbon atom residue in the spherical polymer material.

  This reaction is effective for chlorocarbonylation of hydrocarbon groups in various polymer materials. For example, in a compound having the basic structure of polyethylene terephthalate, a product in which carbon atoms such as methylene chains are chlorocarbonylated. Is obtained.

  In general, any kind of actinic radiation can be used as the actinic radiation used for C—H activation as long as it is an actinic radiation that excites the first compound to generate a reactive species (radical species). For example, electron beams such as γ rays, β rays, and X rays, radiation, ultraviolet rays, and the like can be exemplified. Among these, use of ultraviolet rays is preferable from the viewpoint of safety because it can be downsized without being restricted by the place of use. The ultraviolet light preferably contains a UV wavelength component that is absorbed by the first compound that is a radical generation source.

  The first compound that generates the reactive active species may be any compound that generates the reactive active species by being excited by the above-described active energy rays, but various compounds other than those shown in the examples are used. It goes without saying that the present invention is effective in addition to the exemplified compounds, and the scope of the invention is not limited to the examples. Examples of the first compound include thionyl chloride, thionyl bromide, sulfuryl chloride, sulfuryl bromide and the like.

  In the solution containing the first compound, the first compound itself is preferably used neat as it is, and an inert solvent may be used if necessary. Examples of the inert solvent include halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride.

  In order to change the properties of the polymer material using the reactive species after introduction, the first compound is preferably oxalyl halide, more preferably oxalyl chloride and oxalyl bromide, and particularly preferably oxalyl dichloride. Oxalyl dichloride and oxalyl dibromide are liquid at room temperature and can be processed in a liquid phase by being introduced into the reaction processing vessel as it is.

  As the atmospheric gas in the liquid phase reaction, air can be used, but in order to stably perform the treatment, an inert gas such as nitrogen, helium, or argon is preferable in order to control humidity and oxygen content. Moreover, dry nitrogen is preferable from the ease of handling. The atmospheric gas pressure during the treatment is not particularly problematic, but a sufficient effect can be obtained by the normal pressure treatment. In view of simplicity of the apparatus, atmospheric pressure treatment is preferable.

As the polymer material to be modified, a natural polymer material or a synthetic polymer material can be used. The form is not particularly limited, and examples thereof include fibers, fabrics, films, and particles. As the state of the fabric, a woven fabric or a knitted fabric made of vegetable fiber, animal fiber, artificial fiber, or the like can be used. Plant fibers include cotton and hemp fabrics, animal fibers are silk and wool fabrics, and artificial fibers are classified as recycled artificial fibers, viscose rayon, polynosic rayon, copper ammonium rayon, protein Examples thereof include fabrics such as series. Moreover, the cloth which consists of a polyamide, a polyimide, a polyurethane, a polyvinyl alcohol, polyacryl, polyester, a polypropylene, a vinyl chloride, vinylidene chloride etc. which are classified into the synthetic fiber in an artificial fiber is mentioned. Any of these fabrics can be used in the form of fibers, woven fabrics and knitted fabrics. The fiber yarns constituting them may be in the form of filaments or staples. These fibers can be used singly or in combination of two or more kinds of blends, woven fabrics, and knitted fabrics. That is, it can be used in any case as long as it has a C—H bond in the molecular structure of the polymer material constituting these fibers.
In particular, the modification method by the liquid phase method of the present invention effectively works on polyolefin-based spherical polymer materials such as polypropylene and polyethylene that are difficult to modify by the conventional gas phase method.

  The polymer material can be applied not only to particles but also to non-woven fabrics, films, fibers, or plate-like materials. Examples of the material for forming these include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethylene, polypropylene, polyimide, polyamide, vinyl chloride, and vinylidene chloride. Moreover, it can be used also for composite materials, such as blend of these polymeric materials, and bonding. Examples of these composite materials include films obtained by mixing the respective materials, plates, those having different materials for the front and back surfaces of the films and the plates bonded together, or films obtained by applying a polyurethane resin or the like to the PET surface.

The reactive active species introduced into the polymer material can be converted into a reactive functional group as necessary. That is, in the modification method of the present invention, the reactive active species is reacted with the reactive functional group by reacting the polymer material into which the reactive active species has been introduced with the second compound having a reactive functional group. You may give the functional group conversion process converted into.
As this 2nd compound, the organic compound or water which has active hydrogen which can react with the halogenated carbonyl group etc. which were introduce | transduced into the polymeric material can be illustrated.
Further, the present invention is characterized in that the range of compounds that can be used for the polymer material can be expanded by changing the surface functional group of the modified polymer material. That is, it is possible to change the functional group on the surface by reacting the reactive active species introduced first with the second compound and converting it into a compound having a reactive functional group covalent bond. For example, the acid chloride residue represented by Formula 1 can be further reacted with amines, alcohols, thiol compounds or water to convert the residue. At that time, when the reaction is carried out in the presence of a basic compound, the introduction rate can be improved.

  Further, at this time, it is preferable to use the first compound having two or more reactive functional groups or polar functional groups in the molecular structure because the surface functional group can be a desired residue. A plurality of functional groups or polar groups may be the same or different, but the same functional group is preferable in order to make the surface state the same functional group.

  Examples of the second compound include amines such as ethylenediamine and triethylenediamine, glycols such as ethylene glycol, diethylene glycol and butanediol, and compounds having different functional groups such as diethanolamine and hydroxyethylamine. The present invention is not limited to the exemplified compounds, and any compound having a functional group that reacts with a reactive active species can be used.

  The reaction for converting to a reactive functional group is preferably carried out in an organic solvent. As the organic solvent, it is preferable to use a solvent inert to the conversion reaction, such as petroleum hydrocarbon solvents such as benzene, toluene, xylene, hexane and heptane, and halogenated hydrocarbons such as methylene chloride and chloroform tetrachloride. The treatment can be performed by dissolving the second compound in a solvent and immersing it in the surface of a polymer material that has been modified to have an acid chloride residue or the like. At this time, for dehydrochlorination, tertiary amines such as triethylamine and pyridine and alkaline reagents such as sodium hydroxide and sodium alkoxide may be allowed to coexist and then washed with water to remove by-products.

  Further, this reaction can be achieved even in a gas phase in which the second compound is introduced as a gas. Such a second compound can be used as long as it has a low boiling point and a relatively high vapor pressure, or can be easily converted into a gaseous state by heating, and does not require a treatment such as washing. Have Among such second compounds, compounds that can be reacted in the gas phase in a gaseous state can be compounds such as ethylenediamine.

Specific effects will be described below with reference to examples.
Examples in the case where the polymer material is a microsphere are shown below, but the present invention is not limited to these examples.

Example 1
500 g of microspheres (average particle diameter 18 μm, SF-1 = 110) made of polypropylene having a particle diameter of 5 to 30 μm were synthesized by the melt phase separation method described in JP-A-2001-114901. Of this, 0.5 g was taken and loaded into a quartz glass rotary reaction vessel, and 0.2 g of oxalyl dichloride solution was added to switch to a nitrogen gas atmosphere. Then, after irradiating with ultraviolet rays generated from a 32 W low-pressure mercury lamp for 20 minutes, nitrogen gas was allowed to flow for 10 minutes at a temperature of 50 ° C. to 100 ° C. to remove residual oxalyl dichloride in the reaction mixture, and a sample was collected.

(Example 2)
A sample was collected by treating under the same conditions except that polyethylene particles were used instead of polypropylene particles in Example 1.

(Comparative Example 1)
A sample was collected by treating under the same conditions as in Example 2-1, except that oxalyl dichloride gas was used in place of the oxalyl dichloride solution so that the partial pressure was 100 mmHg and the Ar partial pressure was 660 mmHg.

  The samples of Examples 1 and 2 and Comparative Example 1 were subjected to reflection FT-IR, and the characteristic absorption of the carbonyl chloride group was measured from the surface infrared spectrum. Further, each sample was immersed in 100 ml of water at 50 ° C. for 30 minutes, the sample was filtered, and the characteristics of the filtrate were measured with a litmus paper. Further, the sample separated by filtration was formed into pellets with a tablet molding machine, water droplets were placed on the surface, and the contact angle, which is an index of wettability, was measured. The results are shown in Table 1.

  From the above results, even in the case of microspheres in which the polymer material is in the form of particles, more carbonyl chloride groups and the like are introduced into the material in the liquid phase reaction of the present invention than in the gas phase reaction, and hydrolysis is performed with water. It can be seen that the residual liquid is strongly acidic. The effectiveness of the liquid phase reaction is also reflected in the contact angle indicating wettability.

Claims (14)

The reactive active species is introduced into the spherical molecular material by irradiating active radiation in the presence of the spherical polymer material in the presence of the first compound that is excited by the active radiation to generate the reactive active species as a liquid phase. A method for modifying a spherical polymer material, comprising the step of introducing an active species. A functional group conversion step of converting the reactive active species into the reactive functional groups by reacting the spherical polymer material into which the reactive active species have been introduced and a second compound having a reactive functional group; A method for modifying a spherical polymer material according to claim 1. A group having a reactive functional group terminated with at least one group selected from the group consisting of —COCl, —COOH, —OH, —SH, —NH ₂ , —R ₁ NH, and —R ₁ R ₂ N The method for modifying a spherical polymer material according to claim 1 or 2. The method for modifying a spherical polymer material according to any one of claims 1 to 3, wherein the first compound is oxalyl halide. 5. The spherical polymer material according to claim 1, wherein the second compound is a compound having active hydrogen capable of reacting with a carbonyl halide group introduced into the spherical polymer material or water. Quality method. The method for modifying a spherical polymer material according to any one of claims 1 to 5, wherein the first compound is oxalyl dichloride and / or oxalyl bromide. The method for modifying a spherical polymer material according to claim 1, wherein the active radiation is ultraviolet light. The method for modifying a spherical polymer material according to any one of claims 2 to 7, wherein the functional group conversion step is performed in an organic solvent. The method for modifying a spherical polymer material according to any one of claims 2 to 8, wherein the functional group conversion step is performed in a gas phase of the second compound.   The method for modifying a spherical polymer material according to any one of claims 2 to 9, wherein the second compound has two or more types of reactive functional groups in the molecular structure.   A spherical modified polymer material, which is a spherical polymer material into which a reactive active species generated by a first compound excited by actinic radiation is introduced.   A spherical modified polymer material having a reactive functional group obtained by converting a reactive active species of the modified spherical polymer material according to claim 11. The reactive functional group is —COCl, —COBr, —COOH, —OH, —SH, —NH ₂ , —R ₁ NH, and —R ₁ R ₂ N (R ₁ and R ₂ are independently hydrogen atoms, The spherical modified polymer material according to claim 11 or 12, which is a group selected from the group consisting of an alkyl group or an aryl group, and a group covalently bonded to the polymer material.   The spherical modified polymer material according to claim 11, wherein the reactive active species is —COCl or —COBr.