JPS62131003A - Cationic copolymer and its production - Google Patents

Abstract

PURPOSE:To obtain a cationic copolymer having cationic groups in good efficiency, by reacting a polyvinyl alcohol polymer with a specified compound. CONSTITUTION:This cationic copolymer essentially consists of structural units of formulas I as II and having a content of (I) of 0.05-20mol%, a content of (II) of 99.5-80mol and a degree of polymerization of 50-10,000. In formula I, R1 is H or methyl, A is a group through which the -CONH group is connected with B and is 2C or higher alkylene, branched alkylene, hydroxyalkylene or phenylene, B is a group of formula II or IV, R2, R3 and R4 are each H or a lower alkyl and X<-> is an anion. The above cationic copolymer can be obtained by reacting the hydroxyl groups of a polyvinyl alcohol polymer with a compound of formula V (wherein R1, A, B and R2-R4 are as defined above) in the presence of a basic catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel cationic copolymer and a method for producing the same. The novel cationic copolymer obtained in the present invention is
In addition to the conventional uses of polyvinyl alcohol (hereinafter abbreviated as PVA), it can also be used as a polymer flocculant, a paper manufacturing agent that increases paper strength, improves sizing properties, and improves yield, a sizing agent for warp sizing, a fiber dyeability improver, and electrostatic charging. Inhibitor, ion conversion resin, emulsion 1 emulsion stabilizer, surface sizing agent for paper, binder for pigment coating, binder for inorganic fibers, rust preventive, anti-mold agent, stabilizer for suspension polymerization, cement mortar admixture,
It is expected to be used as an adhesive for paper, fiber, plastic, wood, etc.

[Conventional technology]

In recent years, cationic polymers have been used as polymer flocculants, paper strength agents, etc., sizing agents for warp sizing, antistatic agents,
It is attracting attention as a raw material base for textile dyeability improvers, antibacterial agents, and ion-convertible resins.

PVA has long been used as a surface sizing agent for paper and for warp sizing of I1 fibers to improve its strength, but recently it has been used as an internal addition method to improve paper strength, sizing properties, water repellency, and filler yield. I was suddenly filled with anticipation.

As a method for introducing a PVA0 cationic group, the following methods have been disclosed as conventional methods.

A, Method of post-modifying 44-go A) % Kosho No. 30-5563, Tsutsuboku no Shibunshu, 34
843 (1977), the introduction of amino groups by aminoacetalization of PVA.

mouth) Bulletin of Chemic
al 5ociety of Japan.

47 2990 (1974), and then the acrylamide unit is subjected to Hofmann decomposition to introduce an amino group.

c) Japanese Patent Publication No. 57-34842 discloses a method for producing cationic PVA containing a quaternary ammonium salt by reacting glycidyltrimethylammonium chloride with PVA in the presence of an alkali catalyst. There is also a report of reacting 6-chloro-2-hydroxynolopyltrimethylammonium chloride, which has a glycidyl group opened, with PVA.

2) Journal of the Chemical Society of Japan, 1975 (11) p-1995
Then, react PVA with epichlorohydrin, and then react with polyethylene polyamine to form cationic pvA? r
llteil.

B. Copolymerization method If reported in Kobunshi Kagaku, 8 467 (1951), cationic PVA is obtained by saponifying a comonomer of vinyl acetate and vinylpyridine.

(Note) Special @ 4 Publication No. 14504 of 1982, Japanese Patent Application Publication No. 56-8 of 1983
No. 841) and JP-A No. 56-118997, a copolymer of aminoalkyl (meth)acrylamide, aminoalkyl (meth)acrylate (or its quaternary ammonium salt) and vinyl acetate is saponified to obtain cationic properties. I have a PVA meeting.

[Interlude in trying to invent or solve]

The method of converting the cation group by post-denaturation of the MIJ method A had the following points.

(1) Shihashi involves a crosslinking reaction, and the cylindrical molecule compound tends to gel.

(2) The reaction rate is extremely low compared to the amount of monomer charged.

(3) It is generally difficult to produce products with a certain degree of modification.

On the other hand, method B, which involves the combination of two compounds, overcomes the above-mentioned drawbacks and makes it possible to industrialize the process in terms of cost.

+21 In the comonomerization of aminoalkyl (meth)acrylamide and vinyl intoxicant, judging from the reactivity ratio of the monomers, a homopolymer of aminoalkyl (methacrylamide) is very easily formed, and On the other hand, the proportion of cationic Seizo units contained in the comonomer with vinyl acetate is very low.

(3) Aminoalkyl (meth)acrylates and their quaternary ammonium salts are also produced industrially, and these monomers are either co-merged with vinyl esters, especially vinyl esters, or their co-merged In the process of saponifying PVA, the ester bonds of the cationic structural units are also saponified at the same time, making it impossible to introduce cationic groups into PVA.

To put it simply, in the conventional technology, the cationizing agent had low reactivity or was easily accompanied by a crosslinking reaction, and the cationic group was detached due to the instability of the cation@structural unit.
At present, it has not been possible to efficiently introduce cationic groups.

[Means for solving problems]

The present invention has the following structural units +11 and (■) as essential components, ill is 0.05 to 20 mol%, and 111 is 99.9 mol%.
A cationic copolymer having a molecular weight of 5 to 80 mol % and a molecular weight of 50 to 10,000, and a method for producing the same.

0CH2CHR4CONH-A-B (R1 is a hydrogen atom or a methyl group, A is a group connecting -CONH and B, B is an aqueous atom or a lower alkyl group, xQ is an anion.) OH The above lit, lll+ In addition to using structural units as essential components, small amounts of other structural units (e.g., vinyl ester units represented by acetic vinyl, olefin units represented by ethylene, and alkyl vinyl ether units) are also used. It's okay to be there.

The cationic copolymer 1'l of the present invention and the pyA-based 1 polymer were treated with a base catalyst to give a general 2〇H2=CR4C0NH-
It is obtained by Michael addition of AB (where R1, A, and B are the same as above).

The reaction formula is shown by the following formula.

OHOHC0NH-A-B OH0CH2CHR4CONH-A-B (R1, A, B
(same as above) Among the compounds represented by the general formula CH2-CRI, C0NH-A-B A is a group that connects 100NH and B, and any group that can be used as a stable bond can be used. Examples thereof include a hydroxyalkylene group, a branched alkylene group, a phenylene group, and an alkylene group having 2 or more carbon atoms.

R1 is a water-based atom or a methyl group, and usually a water-based atom is preferred. B means an aqueous atom or lower alkyl: j1=, and θ means all anions forming a base with ammonium nitrogen.

R5I, R3, and R4 are all preferably methyl groups for normal purposes, but methylol groups can be used for special purposes, and lower alkyl groups having an aminoalkyl group can be used for the purpose of improving cation density.

As a substitute, C-β, Bro, Ωdera's halogen ion 7 or n CH30S030% CH3-C6H4-8
C-ρ is particularly preferable from the viewpoint of safety and physical properties. After B, it can be quaternized using a quaternizing agent such as an alkyl halide, dimethyl mi, or methyl p-toluenesulfonate.

The PVA-based monomer used in the present invention includes (1) all PVA having a degree of polymerization and saponification, vinyl esters represented by vinyl acetate, and a small amount of other polymerizable monomers, etc. Modified PVA such as a saponified product of a comonomer with (for example, ethylene, isobutylene, etc.) [alpha]-olefin, alkyl vinyl ether, (meth)acrylamide, etc.] may also be mentioned.

PVA union o31 degree VC tweet lrx 50~1
0000゜good-! Those with L<h200 to 6500 are used.

There is no particular limit to the saponification degree (70 to 100 to 10,000 as long as the properties of PVA are not impaired).

General formula CH2=CHR1 (R,, A, B are the above and 〇〇N
Examples of compounds represented by H-A-B are dimethylaminopropylacrylamide, acrylamidepropyltrimethylammonium chloride, N-(1,1-dimethyl-6-dimethylaminoglovir)acrylamide, and trimethyl-6- (1-acrylamido-1,1-dimethylzolobyl) ammonium chloride, N-(1,1-dimethyl-3-dimethylaminobutyl) acrylamide, trimethyl-6-(1-acrylamido-1,1-dimethylbutyrin ammonium) Chloride, N-(1-methyl-
1,6-diphenyl-3-soethylaminopropyl) methacrylamide, etc. Among these, the following two types of compounds are preferable in terms of availability and reactivity: cH2=cH-C0NHCH2CH2CH2N (CH3
)2(dimethylaminepropylacrylamide)■ CH2=CH-C0NHCH2CH2CH2N(CH3
) 3Q older brother (acrylamidopropyltrimethylammonium chloride) PVA-based offshore body and general formula CH2=CR4 (R1,
The reaction of the compound represented by C0NI (-A-B A and B are the same as above) is carried out in the presence of a base catalyst, and the base catalyst used at this time is hydroxide) IJium, potassium hydroxide, etc. Preferred are alkaline earth metal hydroxides such as alkali metal hydroxides, calcium hydroxide, and barium hydroxide, and alkali metal maple alkoxides such as sodium methoxide, potassium methoxide, and sodium butoxide. In addition, 6th class amines such as triethylamine can also be used.

The reaction is carried out by preparing a solution of 1 to 30 mol of the PVA system 1 in a solvent such as water, dimethyl sulfoxide, dimethyl formamide, etc. base, 10-250 mol% CH
2-CRY (R4% A % Bu Previous C0
NH-A-B [same as above], further add 1 hydroquinone, hydroquinone monomethyl ether, etc. as a thread-preventing agent, and 2
Either react at a temperature of 0°C to 80°C for 10 minutes to 20 hours, and precipitate the reactant by placing it in excess acetone, methanol, ethanol, n-propanol, etc., or add an acid such as acetic acid, hydrochloric acid, sulfuric acid, etc. It is also possible to neutralize by adding (an aqueous solution of various acids may also be used) and take out the reactant. Depending on the combination of reaction mixtures, conditions other than those described above, such as reaction temperature, reaction concentration, catalyst concentration, reaction time, etc., may be selected when carrying out the above reaction. Furthermore, monoisomers such as PvA can also be reacted in a heterogeneous system in an inert medium such as benzene, toluene, hexane, etc.

General formula in the present invention CH2=CR4(R1, A%C0
The reaction needle of NH-A-B (B is the same as above) can be adjusted as desired by selecting appropriate reaction conditions, but from 0.05 to
20 mol %, particularly preferably 1 to 10 mol %. For example, at 0.05 mol%, it shows a light cationic state.1.
If the amount exceeds 20 mol%, the cationic effect will not be increased even though it is a cationized substance.

〔Example〕

Examples of the present invention will be described below, but the present invention is not limited to the following examples.

In examples, unless otherwise specified, % is N.

Moreover, the degree of polymerization and the degree of saponification were measured in accordance with JIS p-6726.

Example 1 In a 1 ton separable flask, 10I PVA (manufactured by Denki Kagaku Kogyo Co., Ltd. -17.1, degree of 1700, degree of saponification 99.5)
mole%)? 90.9 ion 5c dissolved in water, 5
Hydroxide of N) 20ml of IJum aqueous solution, 22g of dimethylaminopropylacrylamide, 0% hydroquinone
．． 02, F was added and reacted at 65°C for 3 hours with stirring. After the reaction, the reaction solution was poured into acetone and the precipitate was separated into four jars, and further washed with methanol to remove the catalyst and unreacted monomers. Knowledge body was removed.

The reaction rate with respect to the charged cationic compound was 10.3. The Hl-NMR spectrum of the reaction product thus obtained is shown in FIG. 2.73 ppm was attributed to the protons of the two methyl groups of the dimethylamino group of the Michael-added dimethylaminoprobyl acrylamide unit, and it was confirmed from the absorption intensity that the content was 6.6 mol%.

The NMR suppression was as follows.

Trimethylsilylpropionic acid-d,- as a reference substance
) 9 Q in a hydrogen aqueous solution to which IJium salt was added.
MHz Hl-NMR (Japan Denshi Wave FX-90Q)
was measured.

Example 2 1017) PVA (11 Kikagaku Kogyo aK-24,1 concentration 2400, saponification degree 99.5 mol%) 5N sodium hydroxide 101, acrylamide propyl trimethyl ammonium chloride 11 g' (Except that Example 1 was added) The reaction was carried out at 65'G for 5 hours in the same manner as above, and the entire reactant was taken out.The reaction rate with respect to the charged cationic compound was 18.
It was 6%. The reaction product thus obtained is HA −
The complete NMR spectrum is shown in Figure 2. 6. It was confirmed that i 6 ppm was attributed to the protons of 6 methyl groups attached to the nitrogen atom of the quaternary ammonium salt, and the absorption intensity was 4.6 molar.

Example 6 1011 t:D PVA (Denki Kagaku Kogyo HK-05
, degree of polymerization 600, degree of saponification 99.5 mol%) 5N sodium hydroxide 51, trimethyl-6-(1-acrylamido-1,1-dimethylpropyl)ammonium chloride 11.9. The reaction was carried out at 60° C. for 3 hours in the same manner as in Example 1 (b) except that 0.01° of hydroquinone monomethyl ether was added. The reaction rate with respect to the charged cationic compound was 8.8%.

It was confirmed that the protons of the six methyl groups attached to the nitrogen atom of the quaternary ammonium salt increased and decreased to 3.16 ppm, and the absorption intensity was 1.8 mol% tea.

Example 4 Ethylene-vinyl alcohol comonomer of 101 (x f
v:y%*6.5 mol, saponification degree 99.
5 molar concentration, 1 degree 1600)' was dissolved in 90 g of dimethyl sulfoxide and %5N sodium hydroxide bath solution 10
1. 44 g of dimethylaminopropylacrylamide and 0.04 ykl of hydroquinone were added, and the mixture was reacted at 70°C for 2 hours with stirring. After the reaction, add an equivalent amount of acetic acid to neutralize, and pour the reaction solution into acetone to collect the filtrate.
The mixture was separated and thoroughly washed with methanol to remove the catalyst and unreacted monomer. The reaction rate with respect to the charged cationic compound was 6.8%. 2.73 ppm fl of the Hl-NMR spectrum of the reaction product thus obtained.
This was attributed to the protons of two methyl groups in the dimethylamino group of the Michael-added dimethylaminopropylacrylamide unit, and it was confirmed from the absorption intensity that it was contained at 8.3 moles.

Example 5 and Comparative Example 1 The fixation rate t of the cationic copolymers obtained in Examples 1 to 4 to pulp was investigated.

2.4% L-BKP slurry with 0.0% to pulp.
4% cationic copolymer k 1! After adding rS and stirring for 2 minutes, the mixture was filtered through a 100 mesh wire mesh and then through filter paper/166. **For 10 wounds, 4 hours of water bath solution 15 hours, 12-
KI (12.7 g - 25.9/l) solution 31 is added and diluted to a total of 50 Wu;

The constant N rate was determined by measuring the maximum absorption wavelength of 670 to 680 nm and the absorbance of the blank. In addition, as a comparative example, the fixing rate was also determined for PVA K-17 manufactured by Denki Kagaku Kogyo. The results are shown in the table.

Examples 1 to 4 showed pot fixation rates of 90% or more, while Comparative Examples showed almost no fixation of 8%.

The fact that the product of the present invention is effective on pulp and exhibits a fixation rate indicates that the introduced cationic groups are stably retained.

Table Comparative Example 2 10g of PVA (made by Kikagaku Kogyo -17, m time 1
700, degree of saponification 99.5 mol) 5N sodium hydroxide 10WLls Glycidyltrimethylammonium chloride 10.1% except that 60
A modified cationic polymer was synthesized after reacting for 115 hours. 3.14 ppm was determined by the protons of three methyl groups attached to both thread atoms of the quaternary ammonium salt, and the absorption intensity was determined to be 0.14 ppm. It has been confirmed that 9 morchi palaces are being used.

In addition, the reaction rate with respect to the charged cationic compound was 6.1%.
The reaction rate was extremely low compared to the reaction rate of the present invention.

〔Effect of the invention〕

(1) It was confirmed that the cationic comonomer of the present invention is a new substance.

(2) Due to the high reactivity of the cationic compound that combines PVA thread and heavy threads, cationic groups can be formed efficiently, and the crosslinking reaction can be carried out even after the reaction, and the amide group in the cationic compound can also be formed during the reaction. Will not be desorbed (can be stably retained).

[Brief explanation of drawings]

Figure 1 shows Hi + NMR of Example 1, and Figure 2 shows Example 2.
It is a spectrum diagram.

Claims (2)

[Claims] (1) The following structural units (I) and (II) are essential components, (I) is 0.05 to 20 mol%, and (II) is 99% by mole.
A cationic copolymer containing 95 to 80 mol% and having a degree of polymerization of 50 to 10,000. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (R_1 is a hydrogen atom or methyl group, A is -CONH and B
A group connecting , which represents alkylene, branched alkylene, hydroxyalkylene, or phenylene having 2 or more carbon atoms,
B is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, R_2, R_3, R_4 are hydrogen atoms or lower alkyl groups, X^■ indicates an anion) ▲ Mathematical formula, There are chemical formulas, tables, etc. ▼ (II) (2) In the presence of a basic catalyst, the hydroxyl group of the polyvinyl alcohol polymer has a general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (R_1 is a hydrogen atom or methyl group, A is -CONH and B
A group connecting , which represents alkylene, branched alkylene, hydroxyalkylene, or phenylene having 2 or more carbon atoms,
B is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R_2, R_3, R_4 are hydrogen atoms or lower alkyl groups, and X^■ represents an anion. ) A method for producing a cationic copolymer, characterized by reacting it with a compound represented by: