[Technology]
Mutual citations and related application (s)
This application claims the benefit of priority based on the date of Korea Patent Application No. 10-2016-0179851 27 December 2016, and all information disclosed in the literature of Korea that the patent application is included as part of the specification.
The present invention relates to a polymer and a method of manufacturing the cyano-containing group.

- that the technical background of the invention;

In producing the secondary battery, and as a way to improve the stability of a battery using the SRS (safety reinforced separator). The SRS was coated as the inorganic particles to a polymer film such as PE (polyethylene), PP (polypropylene). The inorganic particles may retain functions to prevent the heat shrinkage of the polymer film and keeping separated the anode and the cathode the form of a membrane at high Ndo.

On the other hand, if the binder is used it is to attach the inorganic particles in the polymer film during manufacture SRS. Binders currently used for this purpose, there are a polymer having a 2-cyanoethyl group. The polymer addition to the adhesive serves to attach the inorganic particles to the polymer film and the dispersing agent acts to help the dispersion of inorganic particles to coat the inorganic particles to the polymer film.

When no inorganic particles are uniformly distributed in the polymer film for small areas that inorganic particles are not distributed is likely to cause thermal shrinkage. Therefore, there is a need to develop a useful as an adhesive binder and a dispersant.

[Contents of the present invention;

[Problems to be solved;

The present invention provides a _ containing polymer cyanoethyl group.

The present invention also provides a process for the preparation of cyano-containing polymeric group.

[Solving means of a problem]

Will be cyano Describes the ethyl group-containing polymer increases and a method according to the specific implementation of the invention below.

According to one embodiment of the invention, as the polymer containing a cyano group, with respect to the total repeating units contained in the polymer - 0CH 2 CH 2 C0NH 2 it includes a repeating unit that includes and their ions to less than 1.0%, -0CH 2 CH 2 C00H, and a repeating unit containing a counter-ion. The cyano group-containing polymer comprising more than 0%, is provided.

The inventors have experimental results, the polymer had a small content of the specific functional group-cyano-containing group is used as a binder for use SRS (safety re i nforced separator) to improve the dispersibility of the inorganic particles, enhance the adhesion of the inorganic particles to the polymer film check Sikkim, thereby completing the present invention.

In this specification defines the content of the specific functional group contained in the polymer in a proportion of the repeating unit containing a particular functional group to the total repeating units contained in the polymer. At this time, the total repeating units contained in the authentication-polymer refers to increasing polymer the number of the total repeating units of the polymer on average contained (that is, jeunghap degrees), and a repeating unit including a specific ¾ functional group to the polymer is the average including the It means the number of the repeating unit containing a particular functional group. For example, the polymer having a degree of polymerization of 100 -0CH 2 CH 2 C0NH 2 , if the repeating unit containing the average, contain one by one, with respect to the total repeating units contained in the polymer -0CH 2 CH 2 C0NH 2 containing a repeating unit 1. It is defined as a polymer containing 0%.

The cyano group-containing polymer is -0CH 2 CH 2 C0匪2 may or may not include or ion and a very small amount thereof.

. Concretely, the cyano group-containing polymer is, with respect to the total repeating units contained in the polymer eu - 0CH 2 CH 2 C0NH 2 and a recurring unit containing a counter ion 1. 0% or less, or may include from 0% to 1.0%. It is - improving the dispersion of inorganic particles in such a range to be able to claim i provides a binder capable of fixing a uniform radish water particles in a polymer film.

The _0CH 2 CH 2 C0NH 2 is to introduce cyanoethyl group to the polymer through the cyanoethylated reaction (cyanoethyl at i on), it may be a functional group introduced due to side reactions. The -0CH 2 CH 2 C0丽2 in accordance with the cyano group-containing polymer is placed environment -0CH 2 CH 2 C0NH 3 + black is -0CH 2 CH 2 C0NH _ may be in the form. therefore. -0CH 2 CH 2 C0NH 2 and the counter ion of -0CH 2 CH 2 C0丽3 + and -0CH 2 CH 2 can be the total content of the repeating unit containing the C0NH- exhibit the above effect be part of the above range.

The cyano group-containing polymer may or may not include black has a -0C¾C¾C00H and their ions in a very small amount.

Specifically, the cyano group-containing polymer, -0CH on the total repeating units contained in the polymer 2 CH 2 may include a repeating unit that includes C00H and their ions is 2.0% or less or 0% to 2.0% . Within this range improves the dispersibility of the inorganic particles and thereby can provide a binder capable of fixing even out the inorganic particles to the polymer film.

The - 0CH 2 C C00H may be cyanoethylated reaction, the functional groups introduced due to side reactions when euho through (cyanoethyl at i on) to introduce cyanoethyl group to the polymer. The -0CH 2 CH 2 C00H is a cyano group-containing environment in accordance with the no-polymer is placed -0CH 2 CH 2 C00 " may be in the form Thus, -. 0C CH 2 repeating units containing C00H and its ion -0C¾C C00 the total content of the can exhibit the aforementioned effect belong within the above range.

The cyanoethyl group-containing polymer is, for example, cyanoethyl pullulan, cyanoethyl selreul as agarose, cyanoethyl dihydroxypropyl pullulan, cyanoethyl hydroxide as hydroxyethyl selreul agarose cyanoethyl-hydroxypropyl cellulose, cyanoethyl-dihydroxydiphenyl as hydroxypropyl selreul agarose cyano or cyano, such as ethyl acetate polysaccharide or starch furnace black may be cyanoethyl polyvinyl alcohol. Of these, cyanoethyl polyvinyl alkoeul can be fixed strongly "the inorganic particles in a polymer film, a flexible hard advantages are here to be bent even if broken or peeled off the separator.

If the cyano group-containing polymer is a cyanoethyl polyvinyl alkoeul, to may comprise a repeating unit represented by formula (1).

Formula 1

In addition, cyanoethyl polyvinyl alkoeul the degree of substitution of cyanoethyl group ο 100 ) to a, if not may include a repeating unit represented by the following formula (2).

[

In addition, the cyanoethyl polyvinyl alcohol can not, with or very small amount of a repeating unit represented by the following formulas (3) and (4).

In the above formula 3 and 4, m is an integer from 1 to 3, n is 0 or 1. Specifically, the cyano group-containing polymer 1 is a repeating unit represented by the formula (3) for the total amount of repeating units represented by the above formula 1-4. 0% or less, i.e. 0 to 1. Including 0%, and the repeating unit represented by the Formula 42. 0% or less, i.e. 0 to 2. It may include 0%. Cyano group-containing polymer can provide that implements the above-described effect in this range.

Meanwhile, according to another embodiment of the invention, there is provided a method for producing a composition containing a small cyanoethyl group content of the above-described specific functional group polymer.

Specifically, the cyano production method of containing polymer group comprises the steps of producing a containing cyanoethyl group polymer from containing half male functional group through-containing reactive functional polymer and cyano cyanoethylated reaction of ethyl dobip precursor (cyanoethylat ion) polymer to include a yo, wherein the solubility of the reactants. it is possible to suppress the portion banung held by the above-described specific functional group is created as a good level. Than it is possible to specifically, the addition of the cyanoethylated solvent that Ra is less than 6, which is calculated in response to for formula (1).

[Equation 1 i

(Ra) 2 = 4 (S D2 - 5 D1 ) 2 + (d P 2 - S P 1 ) 2 + (d H 2 - d H j) 2

In the formula 1,

δ 02 , δ Ρ2 and δ Η2 is half male functional group-containing polymer and a cyano group introduced into the precursor 100- X: according to the solubility parameter, solubility parameter and a hydrogen bonding due to the polarity of the common combined heunhap water dispersion in a molar ratio of X the solubility parameter, wherein the X is either an ethyl a-cyano measured at the point in time at which screen replacement ratio, δοι, δ Ρ1 solubility parameter, polarity by and ^ is a dispersion of a solvent system that is used for cyanoethylated banung at the any one time It is the solubility parameter of the solubility parameter and a hydrogen bonding by eu

Ra is the distance between the solvent and solute Hansen solubility parameters. The lower the Ra value smaller solutes due to high degree of solvent and solute affinity can be easily dissolved in a solvent.

Thus, in the production method using such a Ra maintains a good level of solubility ¾ reaction.

S in the expression 1 D , and δρ δ Η each dispersion (dispersion force) solubility parameter, solubility parameter and a hydrogen by a polar (dipolar intermolecular force) by the ' means a solubility parameter by combining (hydrogen bonding). In the above formula 1 5 D2 , δ Ρ2 and δ Η2 shall represent the solubility parameters of the reaction at a given point in time. In addition to the actual cyanoethylated reacted banung water, precursor and the product was collected in process contains various by-products are. Accordingly, the use of a water banung collected directly in the reaction's progress as the physical properties of all measurements of the reaction product has a low accuracy, reliability and repeatability problems. ■ I.

The present inventors then cyanoethylated measuring the substituted at any point in time, and mixing the cyanoethylated replacement ratio containing half male functional group at a ratio of Daewoong the polymer and the cyano group introduced into the precursor, and thus-not obtained , is by calculating the solubility parameter of the mixture was used as a physical property, which represents the solubility parameter of the seat at the time of reaction-specific. For example, cyanoethyl at any one time Chemistry

If the substitution rate is 30%, the solubility parameter of the reaction at the point O is taken the place of the male half-functional group containing polymer and a cyano group introduced into the precursor to the solubility parameter of a mixture prepared by mixing in a molar ratio of 70:30.

On the other hand, δ 01 , δ Ρ1 and 5 }) 1 is the solubility parameter according to the cyanoethylated solubility parameter, solubility parameter and a hydrogen bonding due to the polarity of the dispersing ability of a solvent system (solvent system) is used to banung.

The solvent system is " cyano dissolved does not directly participate in the ethylation banung precursor graphite is contained the solvent used for dispersing. Furthermore, the solvent system, the cyanoethylated reaction and is directly involved in the normal temperature (about 25 ° indicate the liquid at C) the other precursor dissolved black may also be included that can be dispersed in the precursor. The precursor compound black is common solvent the solubility parameter of a mixture of any two or more materials, such as system can be calculated by the following equation 2.

[Formula 2]

δ [common compound] = {(δ [# ¾i ] * a) + (.δ [ substance 2 ] * b) + ... + (Δ [substance n ] * n)} / (a + b + --- + n)

In the formula 2 a, b, ... n are each material 1, material 2,. A weight ratio of substance n eu

The formula (2) is a formula to obtain the heunhap water solubility parameters, including the material of the n kinds, the solubility parameters for each substance (δ [substances ιμ δ [substance 2] , ··· δ [substances η] ) to the weight of each substance ratio (a, b, ... n) for dividing the sum of values obtained by multiplying the sum of the increased proportion of the total material heunhap the solvent also can be calculated with parameters.

To contain the reactive functional group, the polymer may be a hydroxyl group-containing polymer. More specifically, as-containing polymer wherein the semi male functional group, pullulan, cellulose / dihydroxypropyl pullulan, hydroxypropyl as hydroxyethyl selreul as agarose, hydroxypropyl selreul agarose, dihydroxy ethoxy a profile selreul such as agarose or starch using a polysaccharide, or using a polyvinyl alcohol when it is possible to manufacture a wide range which contains the above cyano group polymer.

The cyanoethyl group: by introducing glass spheres may be used various types of precursors known in the art. In particular, the cyano group introduced precursor may be acrylonitrile.

The cyanoethylated banung may proceed under a base catalyst.

' To the base catalyst is sodium hydroxide (NaOH),' sodium carbonate (NaC0 3 may be used) or a common compound.

The manufacturing method has the cyanoethylated reaction solvent showing a high solubility to the precursor and the product was used in can be used. In one embodiment, the method for producing the water (distilled water), an alcohol solvent, a ketone solvent is between, sulfoxide solvents H acids or their heunhap solvent may be used. Specifically, the alcohol solvents include methyl alcohol, ethyl alcohol, n- propyl alcohol, isopropyl alkoeul, n- butyl alcohol, isobutyl alcohol, t- butyl alcohol. n- pentyl alkoeul. n- haeksil may be used snout alcohol or a common compound, the ketone solvent as may be used such as methyl ethyl ketone, or acetone may be used is a mixture thereof, in the sulfoxide solvent is dimethylsulfoxide acids.

The cyanoethylated banung is about 10 to 60 ° can be carried out at a temperature of C is approximately 40 minutes to 500 minutes. It is possible to minimize the portion banung that a specific functional group is created above within this range.

In the production method of the solvent is added so that the Ra is less than 6, which is calculated by the formula 1 while cyanoethylated reaction as described above. The kind and amount of solvent to be added may be determined depending on the kind of precursor used and the contents, cyanoethylated banung replacement ratio, and the type and amount of solvent put into the initial.

In one embodiment, a method for producing a cyanoethyl polyvinyl alcohol through the production method in detail.

By the cyanoethyl poly (vinyl alcohol) to prepare a polymer containing the reactive functional group is increased using polyvinyl alcohol, the cyano group introduced precursor may be acrylonitrile.

Therefore, cyano production process of the furnace ethyl replicon (vinyl alcohol) is made in a common compound acrylonitrile, polyvinyl alcohol, an acrylic, a mixture of a base catalyst and a first solvent, and adding a second solvent to the heunhap water cyanoethylated banung increase the above-described specific. The functional group content may provide a less-cyanoethyl polyvinyl alkoeul.

In this specification, the solvent injected before reaction in order to distinguish the solvent to be added in the reaction solvent and the former committed banung is "first solvent 1 , and written in. The reaction of

The solvent to be added is described as "the 0.2 solvent. The first solvent is not only one type of solvent, and collectively refer to two or more of the mixed solvent, the second solvent is also known as one type of the two or more mixed solvents as well as solvent.

The first solvent may be appropriately selected Ra is represented by the formula 1 is less than 6.

Specifically, cyanoethylated substitution rate of the reaction initially is because it is 0%, δ in formula (1) 02 . δ Ρ2 and δ Η2 include polyvinyl alcohol: substitutes the solubility parameter according to the solubility parameter, solubility parameter and a hydrogen bonding due to the polarity of the dispersion of (polyvinyl alcohol and the molar ratio of acrylonitrile 0 = 100). Eu solubility parameter according to the solubility parameter, solubility parameter and a hydrogen bonding due to the polarity of the dispersion of the polyvinyl alkoeul respectively MPa 15.90 1/2 , 8.10 MPa 1/2 and 18.80 MPa 1/2 so. 5 1 of formula D2 , δ Ρ2 and δ Η2 15.90 in. It substitutes 8.10 and 18.80.

Then, the equation 15 of D1 , δ Ρ1 and δ Η1 there and acrylonitrile showing a liquid at room temperature and solubility of the solubility parameter, solubility parameter and a hydrogen bonding due to the polarity of the dispersing ability of a solvent system including a first solvent, It is substituted into a parameter. Thus, it is calculated by the formula 1. So that the lever is Ra of less than 6 may be selected Took a suitable first solvent.

With the first solvent can be used water (distilled water), alcohol solvents, ketone solvents, sulfoxide solvents, or acids thereof heunhap solvent. Specifically, in the alcohol solvents include methyl alkoeul, ethyl alcohol, n- propyl alcohol, isopropyl alcohol, n- butyl alcohol, isobutyl alcohol, butyl alcohol t_. n- pentyl alcohol n- haeksil alcohol or may be a mixture thereof rounded, in the flow Kerron solvent is methyl ethyl ketone . And acetone or a mixture thereof or the like, to the sulfoxide flow solvents may be used such as dimethyl sulfoxide. Among them, as the first solvent is water may be used alone. If said if in the first solvent used is a mixture of water and an organic solvent, it may be used in an under portion 100 increase more than 0 parts by weight to 100 parts by weight of an organic solvent with an acrylic-nitrile

The select the proper solvent in a solvent, polyvinyl alcohol, acrylonitrile, combined with a base catalyst and a first solvent traces, which from about 10 to 60 ° and at a temperature of C and stirred for about 40 minutes to 500 minutes cyanoethylated banung can proceed. The cyanoethylated may be a Ra value that is calculated by the formula 1 during the banung monitored by the addition of a second solvent so that Ra is not more than 6.

Specifically, it is possible through the H-NMR obtain a cyanoethylated replacement ratio in the cyanoethylated reaction. More specifically, when the hydroxyl groups of the polyvinyl alcohol substituted by a cyano group, -CH 2 peak corresponding to the CN is observed at 2.5 to 2.8 ppm, of poly (vinyl alcohol) derived from the main chain is -CH 2 - peak corresponding to 1.3 to be observed at 2.0 ppm. Thus, over the area percentage of the peak observed at 2.5 to 2.8 ppm to the area of the peak observed at 1.3 to 2.0 ppm can be obtained cyanoethylated substitution rate.

[Equation 3]

Cyanoethylated degree of substitution (%): : (peak area of 2. 5 2.8 ppm) I (peak area of 1.3 - 2.0 ppm) * 100

Subsequently, cyano heunhap obtain a water solubility parameter of common sum of the precursor at a ratio of Daewoong the ethylation substitution rate. For example. Preparing a precursor mixture, and the formula 2: Through mye be able to calculate the solubility parameter of the precursor heunhap § cyanoethylated replacement ratio of the polyvinyl alcohol The results are shown in Table 1 below.

[Table 1]

60 40 60 15.96 10.92 11.60

70 30 70 15.97 11.39 10.40

80 20 80 15.98 11.86 9.20

90 10 90 15.99 12.33 8.00

100 0 100 16.00 12.80 6.80

* PVA: polyvinyl alcohol; AN: Acrylonitrile

And, calculate the solubility parameter of the solvent system at the time. , And substituting these values ​​in the formula (1) determine the Ra value and, if the Ra value increases can be added to lower the Ra value, the appropriate second solvents.

For example, cyanoethyl poly (vinyl alcohol) in the production method of may be added to an alcohol solvent, ketone solvent, sulfoxide solvents, or acids thereof heunhap solvent to the second solvent. Specifically, in the alcohol solvents include methyl alcohol, ethyl alcohol. Ol, n- propyl alcohol, isopropyl alcohol, n- butyl alcohol. Alkoeul isobutyl, t- butyl alcohol, n- pentyl alcohol, n- haeksil alkoeul or may be used in common in these compounds such as, in the ketone solvent may be used methyl ethyl ketone, acetone or a mixture thereof, wherein a sulfoxide solvent flow may be used, such as dimethyl sulfoxide.

In addition, cyanoethyl poly (vinyl alcohol) in the production method of the cyanoethylated replacement ratio can by the addition of a second solvent twice or more in the range of 25% to 85% to control the Ra of the above formula 1 is less than 6.

Specifically, cyanoethyl poly In the production process of the vinyl alcohol cyanoethylated replacement ratio is added to the second solvent is from 25% to 35% range portion of 30 to 70 parts by weight based on 100 parts by weight of a first solvent, and cyanoethyl Chemistry the degree of substitution can be added to the second solvent is from 45% to 55% in the range from 30 to 130 parts by weight based on 100 parts by weight of a first solvent to adjust the Ra of the above formula 1 is less than 6. Further, if necessary, cyanoethylated degree of substitution can be added to the low-12 solvent from within the 75% to 85% of the first portion of 30 to 130 parts by weight based on 100 parts by weight of solvent. Although the in-cyano details the method of producing the polyvinyl acetate alkoeul, the production method of the present invention may be utilized in the method of manufacturing a polymer-containing furnace variety of cyano group. Polymers containing a cyano group prepared according to the production method of the present invention is -0CH 2 CH 2 C0NH 2 and -0CH 2 CH 2 containing a functional group such as a very small amount of C00H, or do not include the SRS (safety re inforced separator) use is used as a binder to improve the dispersibility of the inorganic particles, it is possible to enhance the adhesive force of the inorganic particles to the polymer film.

On the other hand, according to another embodiment of the invention, there is provided a secondary battery comprising a separation membrane and the separation membrane comprising a containing less cyanoethyl group content of the above-described specific functional group polymer. The separator and the secondary battery can be produced by the present method invention is known in the art that, but uses a group containing the above-described cyano-polymer.

The separation membrane is a polymer film; Inorganic particles distributed on the polymer film; And this comprises a binder for fixing the inorganic particles to the polymer film the content of a particular functional group described above as the binder may include a small cyano group-containing polymer.

The cyano group-containing polymer is -0CH CH 2 C0N¾ and - 0CH 2 CH 2 to not contain or contains a functional group of a very small amount C0OH ^ enhance the dispersion and adhesion of inorganic particles to inorganic particles uniformly on a polymer film sikimyeo distribution may be tightly coupled. In addition, the secondary battery can exhibit excellent stability, including such separation membranes.

【Effects of the Invention】

Cyano-containing group polymer according to one embodiment of the invention is cyano the amount of the other functional group other than an ethyl group is extremely less used as a binder for use SRS (safety re inforced separator) to improve the dispersibility of the inorganic particles, the inorganic material for the polymer film It can enhance the adhesion of the particles.

- specific information for carrying out the invention;

Operation of the invention through a specific embodiment of the invention below, the effect of " more

It will be described in detail. However, it is not limited thereto whatsoever that any means the scope of the invention set forth by way of illustration of the invention.

Example 1: Preparation of cyano group-containing polymer

20% by weight of a polyvinyl alcohol aqueous solution to the reaction vessel 100 g (polyvinyl alcohol

20 g, distilled water 80 g), NaOH aqueous solution of 30% by weight of 2 g (NaOH 0.6 g, distilled water, 1.4 g) and placed 150 g acrylonitrile 30 ° the mixture was stirred at C was carried out the cyanoethylated banung.

Then, through the H-NMR monitoring the cyanoethylated replacement ratio, cyanoethylated when the substitution rate is 30%. 30 g acetone was charged to the reaction vessel.

Referring to Table 1, cyanoethylated percent substitution is when 30%, S in the formula 1, D 2 is 15.93 MPa 1/2 , and, δ Ρ2 is 9.51 MPa 1/2 and, δ Η2 is 15.20 MPa 1 / 2 is identified to be. On the other hand, cyanoethylated replacement ratio is then added the acetone is 30% when s of formula 1 D1 , δ Ρ1 and δ Η ι respectively MPa 15.78 1/2 , 13.54 MPa 1/2 and 18.19 MPa 1/2 respectively. Substituting the solubility parameter value of the above formula 1 cyanoethylated when the substitution rate is 30%. Ra is identified to be less than 6 to 5.03.

Cyano, continue the ethylation banung was added an additional 30 g of acetone in the reaction vessel when the cyano-ethylated substitution rate was 50%.

Referring to Table 1, cyanoethylated percent substitution is when 50%, S in the formula 1, D 2 is 15.95 MPa 1/2 , and, δ Ρ2 is 10,45 MPa 1/2 , and, δ Η2 is 12.80 MPa 1/2 a. Further, cyanoethylated replacement ratio is then added the acetone is 50% when s of formula 1 D1 , δ Ρ1 and ^ are each MPa 15.75 1/2 , 13.22 MPa 1/2 and 17.19 MPa 1/2 , respectively. Substituting these values for the solubility parameters of the formula 1, when the cyanoethylated substitution rate is 50%, Ra is the ½ confirmed to be less than 6 to 5.20. ' -

After 30 minutes, acetic acid was added to 3 g of the reaction vessel, and 3000 g of distilled water

It was added to precipitate a reaction product. And re-dissolving the polymer was precipitated in acetone, 200 g and, by putting it in distilled water to 3000 g was reprecipitated a cyano group-containing polymer. The cyanoethylated banung kept to less than 6 by monitoring the Ra value of the entire process was confirmed.

Example 2: Preparation of cyano group-containing polymer

Banung the temperature in Example 1 50 ° to prepare a cyano group-containing polymer in the same manner as in Example 1 except that the control in C. The cyanoethylated banung kept to less than 6 by monitoring the Ra value of the entire process was confirmed.

Example 3: Preparation of cyano group-containing polymer

Example 1 cyanoethylated replacement ratio was prepared in the cyano group-containing polymer when the 80%, except for the container that a banung In an additional 100 g of acetone in the same manner as in Example 1 at. The Ra values ​​in the cyanoethylated banung entire process is maintained at about 5. 52 it was confirmed that less than 6.

Example 4: Preparation of cyano group-containing polymer

Polyvinyl alkoeul aqueous solution of 20% by weight of the banung vessel 100 g (polyvinyl alkoeul 20 g, distilled water 80 g). NaOH aqueous solution of 30% by weight of 2 g (NaOH 0.6 g, distilled water, 1.4 g) and placed 150 g acrylonitrile 30 ° the mixture was stirred at C was carried out the cyanoethylated reaction.

And, it was charged with dimethyl sulfoxide, 50 g of the vessel when the banung through the H-NMR monitoring the cyanoethylated replacement ratio, cyanoethylated replacement ratio has been 30%.

Referring ol Table 1 above. Cyanoethylated percent substitution is when 30%, S in the expression 1 D 2 is 15.93 MPa 1/2 , and, δ Ρ2 is 9.51 MPa 1/2 and, δ Η2 -15. 20 MPa 1/2 is identified to be. On the other hand, ^ cyano ethylated replacement ratio is the back 30% eoteul as dimethyl sulfoxide and then added to 5 of the formula 1 D1 , '' δ Ρ1 and 5 111 are each MPa 16.29 1/2 , 14.41 MPa 1/2 , and MPa 17.96 1/2 respectively. The . Substituting the solubility parameter value to the above equation 1 cyanoethylated when the substitution rate is 30%, Ra is identified to be less than 6 to 5.67.

Cyano 100 g of dimethyl sulfoxide in the reaction vessel was further charged into the furnace when the ethylation reaction continues to proceed to the replacement ratio cyanoethylated was 50%.

Referring to Table 1-ol, cyanoethylated when the substitution of 50%, 5 1 of the formula D2 is 15.95 MPa 1/2 , and, δ Ρ2 1 coming from 45 MPa 1/2 , and, δ Η2 is 12.80 MPa 1/2 a. Further, cyanoethylated substitution rate is 50% when it is added after the dimethylsulfoxide 5 of the formula 1 D1 , δ Ρ1 and ^ are each MPa 16.86 1/2 , 14.97 MPa 1/2 and 16.00 MPa 1/2 respectively. Substituting these values for the solubility parameters of the formula 1, when the cyanoethylated replacement ratio is 50¾, is identified to be less than six by Ra is 5.83.

To continue the cyanoethylated banung was added to the cyanoethylated added 100 g of isopropyl alcohol to the reaction vessel when the substitution rate is 80%.

To Table 1 True: if high, cyanoethylated substitution rate is, the expression 1≤ 5 when 80% D2 is 15.98 MPa 1/2 , and, δ Ρ2 is 11.86 MPa 1/2 , and, δ Η 2 is 9.20 MPa 1/2 a. Further, cyanoethylated substitution rate is 80% when it is added after the isopropyl alcohol 5 of the formula 1 D1 , δ Ρ1 and δ Η1 respectively MPa 17.43 1/2 , 14.56 MPa 1/2 and 13. 55 MPa 1.2 , respectively. Substituting these values for the solubility parameters of the formula 1, when the cyanoethylated substitution rate is 80%, it is confirmed to be a 1 is less than 6 to 5.88.

After 30 minutes, acetic acid was added to 3 g of the reaction vessel was added 3000 g of distilled water to precipitate the product banung. And re-dissolve the polymer during precipitation to ¾ O seron 200 g and, by putting it in distilled water to 3000 g was reprecipitated a cyano group-containing polymer. The cyanoethylated reaction is maintained at less than 6 monitors the Ra value of the entire process was confirmed.

Comparative Example 1: Preparation of No-cyano group-containing polymer

Into 100 g of acrylonitrile banung vessel theta 7% polyvinyl alcohol aqueous solution 100 g, NaOH aqueous solution of 30% by weight of the weight of 2 g, and acrylic 50 ° and stirred for 1 hour at C was carried out the cyanoethylated banung. Cyano by monitoring the no-ethylation reaction cyanoethylated this replacement ratio was found to be 6 yisangim results of the measurement of the Ra of the formula (1) when 50% 12.32.

Then, the addition of acetic acid 3 g of the banung vessel was added 3000 g of distilled water to precipitate the product banung. And re-dissolving the polymer was precipitated in acetone and 200 g, which distilled water. 3000 were charged into a g was reprecipitated a cyano group-containing polymer.

Comparative Example 2: Preparation of No-cyano group-containing polymer

In the cyanoethylated replacement ratio with distilled water 100 g of the banung container when the 30% in Example 1, except that the cyanoethylated replacement ratio is put into distilled water 100 g of the banung container when 50% conducted in the same manner as in example 1 to prepare a cyano group-containing polymer. Comparative Example 2 cyanoethylated a replacement ratio is the result 16.21 as measured for Ra. Of the formula (1) when 30%, cyanoethylated substitution rate of 6 yisangim to 50%, results 21.24 measure the Ra of the formula 1 when work in this It was confirmed.

Comparative Example 3: Preparation of No-cyano group-containing polymer

In banung vessel placed 200 g acrylonitrile, polyvinyl alcohol, 100 g, NaOH 10 g and acrylic 70 was added to acetone and 400 mL (316.4 g) and distilled water 300 mL ° and stirred to C was performed to cyanoethylated banung eu

After 30 minutes, a cyano were no ethylated substitution rate is 60% when the work input of acetone and 100 mL (79. 1 g) and continue the cyanoethylated banung. Acetone was added 8.41 Results of calculating the Ra of the former (1). Appeared as a result of after acetone In calculating the Ra of the formula 1 is 6.99 Ra was confirmed that 6 or later.

After 30 minutes, acetic acid was added to 3 g of the banung vessel was added 3000 g of distilled water to precipitate a reaction product. And re-dissolving the polymer was precipitated in acetone, 200 g and, by putting it in distilled water to 3000 g was reprecipitated a cyano group-containing polymer.

Test example: cyano group-containing polymer and characteristics of the structure make evaluation

(1) determine the structure of the cyano group-containing polymer

Examples and Comparative -0CH the introduction of a cyano group-containing polymer prepared in Example 2 CH 2 C0NH 2 and repeating units including a counter ion and -0CH 2 the content of the repeating unit containing a counter ion and C¾C00H H- confirmed by NMR and IR spectrum, and the results are shown in Table 2. It is shown. Specifically, H-匪R spectrum from 2.2 to 2.3 and the peak area of the IR spectrum of the 1570 cnf observed in ρρηι 1 observed in - through the area of the peak corresponding to the C00 to the repeating units included in each polymer-0CH 2 CH 2 C0NH 2 and the repeating unit with eu 0CH comprising a counter ion 2 CH 2 and calculated the content of the repeating unit containing C00H and followed thereof.

[Table 2]

(unit : )

2-cyano-ethyl i -containing polymer characterization

- to evaluate the combined common dispersing ability and adhesiveness to the above embodiment and a cyano group-containing polymerizable theta produced in Comparative Example and the inorganic particles. Specifically, a cyano group-containing polymer is 0.7, and average particle diameter, BET is 4 m 2 a / g of alumina 10: To a slurry of 90 weight percentage of the combined common.

Then, the cyanoethyl group to determine the dispersion containing the polymer using the dispersion stability spreader (UMiSi zer) a slurry was prepared in while rotating the 200 rpm 25 ° and measuring the sedimentation rate of the alumina in C, and the results It is shown in Table 3 below. The more excellent in dispersing ability of the cyano group-containing polymer is precipitated is slowly alumina is well dispersed.

Cyano group-containing polymer in order to evaluate the adhesion, to the indicated to thereby prepare the electrode is bonded to one surface of the separator assembly in the same way and there is a separator is peeled off from the electrode measures the force required in Table 3. The

Specifically, the artificial graphite, carbon black, CMC, binder 96: 1: 1: 1 in a weight ratio of 2 was prepared eumguk slurry mixed with water. Coating the cathode slurry on a copper foil having a thickness of ί, Ο卿and 80 ° after drying at least 1 hour at C was prepared by rolling the anode (pressing).

It was then applied to one of a cyano group-containing polymer and inorganic particles schemes Blair Dr Slurry the de »used in the polyethylene porous base material prepared in the above and dried to prepare a porous membrane coating chungyi formed.

The negative electrode and the separator and bonding it in the lamination equipment, the saempol the using UTM equipment there is a separation of the adhesive surface 100 隱 / niin speed as the electrode and the separator (porous coating charging) to determine the force required.

[Table 3]

Referring to Table 3, in Examples 1 to a precipitation rate of 4, the dispersibility of the lower inorganic particles than in Comparative Examples 1 to 3 it was confirmed improvements that, in Example 1 to compare the electrode adhesion at 4 Examples 1 to 3 high ground chamryeok of inorganic particles are confirmed to be improved compared to. Accordingly, -0CH 2 CH 2 C0NH 2 , and - Using a small-containing functional group such as cyanoethyl group 0C C¾C00H polymer is confirmed can be implemented excellent dispersing ability and adhesive force.

[Claims]
[Claim 1]
A polymer containing a cyano group,
With respect to the total repeating units contained in the polymer -0CH 2 CH 2 C0NH 2 and comprising a repeating unit containing a counter ion to not more than 1.0% and, - 0CH 2 CH 2 C00H, and a repeating unit containing a counter ion 2.0% cyano group-containing polymer containing less than.

[Claim 2]

The method of claim 1, wherein the cyano group-containing polymer is 0 cyanoethyl polyvinyl alcohol which, cyano group-containing polymer.

[Claim 3]

The method of claim 2, wherein the cyano group-containing polymer to below, includes a repeated five unit represented by the following for repeating the total amount of units represented by the formula (i) to 4 formula (3) by more than 1.0% of the formula (4) containing repeating units to more than 2.0%, a cyano group-containing polymer increases:

[Formula 2]

In the above formula 3 and 4, m is an integer from 1 to 3, n is 0 or 1.

[Claim 4]

Through the cyanoethylated reaction of the free reactive functional group-containing polymer and a cyano group-containing polymer precursor from male half functional group comprising a step of producing a cyanoethyl group-containing polymer,

The cyanoethylated banung formula 1 is added to Ra and the solvent is less than 6, which is calculated by, a cyano group-containing polymer for a method for producing:

[Equation 1]

(Ra) 2 = 4 (S D2 - d 0 j) 2 + (d P 2 - S P 1 ) 2 + (d H 2 - d H j) 2

In the formula 1,

S D2 , δ Ρ2 and δ Η2 mole of X: is half male functional group-containing polymer and a cyano group introduced into the precursor 100-χ. The solubility parameters of the solubility parameter, solubility parameter and a hydrogen bonding due to the polarity of the common combined heunhap water dispersion in a ratio, wherein the X is a cyanoethylated replacement ratio measured at any point in time, οΐ δ, δ Ρ! And δ Η1 is the solubility parameter of the solubility parameter, solubility parameter and a hydrogen bonding due to the polarity of the dispersing ability of the solvent system used in the cyanoethylated banung at the any one time.

[5.]

The method of claim 4 wherein the cyanoethylated banung is from 10 to 60 ° C The silver sseseo min to 40, process for producing a cyano group-containing polymer is no progress of 500 minutes.

[Claim 6]

The method of claim 4, wherein the polyvinyl alcohol, acrylonitrile, a common combined to prepare a mixture of a base catalyst and a first solvent, and adding the second solvent in the heunhap water cyanoethylated reaction, from the polyvinyl alcohol-cyano for producing a polyvinyl alcohol acetate. The method of the cyano group-containing polymer increases.

[7. The

The method of claim 6, wherein the second solvent stream alkoeul solvent, ketone solvent, sulfoxide solvent, or a method of producing a stream thereof contains, cyano group to add the polymer to the solvent heunhap.

[Claim 8]

Claim 6, cyanoethylated substitution rate a method of preparing a composition containing twice the second solvent, the cyanoethyl group to add more than in the range 25% to 85% polymer to.

[9.]

Claim 6, cyanoethylated substitution ratio of 25% to 35% within the range the second solvent to the first solvent per 100 parts by weight added in an amount of 30 to 70 parts by weight, and cyanoethylated substitution rate of 45% and at the 55 % range in the second " solvent for the first solvent 100 parts by weight of the production method of the cyano group-containing polymer, which added in an amount of from 30 to 130 parts by weight with respect to.

[10.]

A polymer film;

Inorganic particles distributed on the polymer film; And

The polymer film comprises a binder, and the fixing the inorganic particles, the binder is a cyano, a separator comprising a polymer-containing group according to claim 1.

[11.]

Secondary battery comprising a separator according to claim 10, wherein all.