JPS5815942A - Stabilization of cationic vinyl monomer - Google Patents

Abstract

PURPOSE:To prevent the degradation of the titled compound useful as a raw material monomer of a cationic polymer during storage, transport and production, and to effect remarkable stabilization of the compound without lowering the polymerization reactivity, by adding a cyclic amino compound to the cationic vinyl monomer. CONSTITUTION:A cationic vinyl monomer of formulaI(R1 is H or CH3; R2 and R3 are 1-4C alkyl, etc., R4 is H, 1-4C alkyl, etc.; A is O or NH; B is 1-4C alkylene, etc.; X is anionic counter ion) is stabilized with a cyclic amino compound of formula II[R5-R8 are alkyl, etc.; X is group of formula III (R9 is alkyl, etc.), etc.]such as 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1- oxyl. The amount of the compound of formula II to be added is 0.1-1,000ppm, preferably 1-50ppm. The monomer prepared by the process has sufficiently high degradation resistance and improved stability, and can be converted to a high quality polymer extremely easily, in high conversion, without loss of the polymerization activity of the cationic monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for stabilizing cationic vinyl monomers. More specifically, it relates to a stabilization method that dramatically improves the stability of cationic vinyl monomers by preventing deterioration during storage, transportation, or production without impairing their polymerization reactivity.

Cationic vinyl monomers are used as fiber modifiers, water treatment agents,
It is widely used as a raw material monomer for cationic polymers, which have uses such as paper chemicals, adhesives, and pharmaceutical and cosmetic products. In particular, the cationic vinyl monomer represented by the general formula (1) described later has excellent radical polymerization reactivity and is relatively easily available industrially, so it is widely used. However, these are highly polymerizable and have poor stability during storage, transportation, and manufacturing processes, and may cause unexpected thickening and Bobcon polymerization due to external temperatures, natural light, shock, and contact with trace amounts of metals (especially iron, etc.). This may cause problems and deterioration in quality.

Conventionally, in order to prevent the polymerization of the cationic vinyl monomer represented by the general formula (1), stabilizers such as hydroquinone, hydroquinone 7-methyl ether, and t-butylcatechol have been added. However, even if a large amount of this type of stabilizer is added, storage stability is not always satisfied.

JP-A-58-147022 describes dtA, uru)-tetraalkyA/-N-heterocyclic compounds such as triacetonamine and 4-dimethylamino-2,2,6,6-tetmethylpiperidine. A method has been proposed in which the compound is added to a cationic vinyl monomer.

However, these compounds cannot be said to be sufficiently effective in preventing deterioration or improving stability (for example, under harsh conditions).
The problem has not been fully resolved yet.

Furthermore, JP-A-58-144519 describes a method in which a salt of N-nitrosophenylhydroxylamine is added to a cationic vinyl monomer. However, since this substance has an extremely large inhibiting effect on radical polymerization, the polymerization of the cationic vinyl monomer (1) is seriously inhibited. It may become easier to form, or a very long induction period and long polymerization time may become necessary during polymerization 1.

In view of the current situation, the present inventors have developed a method that improves the deterioration prevention effect of cationic vinyl monomers and does not cause any adverse effects such as inhibition of polymerization when producing a polymer by radically polymerizing the monomers. As a result of intensive research aimed at this purpose, we have arrived at the present invention. That is, the present invention is based on the general formula (where & is H or CH3; R3s'3 is each an independent KIEu alkyl group having a prime number of 1 to 4 or a hydroxyalkyl group having 2 to 4 carbon atoms, the peak is H, and the carbon i number is t~ 4
alkyl group, hydroxyalkyl group or benzyl group having 2-4 carbon atoms; A is an oxygen atom or NH; B is an alkylene group having 1-4 carbon atoms or a hydroxyalkylene group having 2-4 carbon atoms; X- is anionic It is a counter ion. ) to the cationic vinyl monomer represented by the general formula [wherein R7s Ra , Rr and R8 are the same or different alkyl groups, and R5 and & or R7 and R8
together with the carbon atom to which they are attached R9Rh.

This is a method for stabilizing cationic vinyl monomers, which is characterized by adding a mono-amino compound.

In the general formula (2), the alkyl group of R5+ 穐* R7 and R8 is a lower alkyl group such as a methyl group,
Examples include ethyl group and butyl group. Examples of Rg, R1, methyl group, ethyl group, butyl group, and examples of cyclic amino compounds (oxyls) include the following compounds.

[1] Compound 4-benzoyloxy-2,2,6,6-titramethylpiberidine-1-oxyl 4-acetoxy- where X is O10-C-R9-CH2-C-c[(,- Compound 4-dimethylamino-2,2,6,6-tetramethylpiperidine-l-oxyl[3]X is R9RI.

1 4,4-dimethoxy-2,2,6,6-titrame ≠ rubiberidine-1-oxyl 2,2,6,6-tetramethylpiperidine-1-oxyl-4-medirow 17 (4'-oxoimidazolidine) -5'-spiro-1''-cyclohex[5]X is R1+ ■ CH2-, N Compound 16 of -CH2-
Compounds where +CH2+1 Among these, preferred is 4-benzoyloxy-2
・2,6,6-titramethylpiperidine=1-oxyl; 4-acetoxy-2, ・2,6,6-tetramethylpiperidine-l-oxyl; 4-dimethylamino-2,2
・6,6-tetramethylbiperidine-l-oxyl; 4
, 4-dimethoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and mixtures of two or more thereof.

Cationic vinyl represented by general formula (1) in the present invention! Examples of the lemonomer include those similar to the monomer represented by the general formula (1) described in JP-A-54-102888. R2゜R3 of general formula (1) in the present invention
, R, , B and
R1°R of general formula (1) in Specification No. 102888
The descriptions of 3, R4, B and X can be applied as they are.

The present invention is effective for the cationic vinyl monomer represented by the general formula (1), but the effect of preventing deterioration or improving stability differs slightly depending on the structure of the monomer. In terms of the greater effect, preferred in the general formula fl) are an oxygen atom as A and a methyl group as R1. R2* R3 is preferably an alkyl group having 1 to 4 carbon atoms, and R and H are preferably alkyl groups having 1 to 4 carbon atoms. crow.

Particularly preferred R3 and R4 are methyl and ethyl groups. Moreover, as B, an ethylene group is preferable.

As X-, halogen ions, CH30S03- and H8O are preferred, and halogen ions are particularly preferred. Among Harome surihi, CA''' is preferred.

Specific examples of the cationic vinyl monomer represented by the general formula (1) are also the same as the monomers described in JP-A-54-102388, and this description can be quoted as is. For example, the following.

(i-p, ) Quaternary nitrogen-containing (meth)acrylate (1) (meth)acryloyloxyalkylate, realkylammonium salt (2) (meth)acryloyloxyhydroxyalkyl trialkyl Ann Moniu
Salt (2-A) Salt of tertiary nitrogen-containing (meth)acrylate and acid (1) Salt of dialkylaminoalkyl/L/(meth)acrylate (2) Dialkylaminohydroxyanolekyl/L/(meth)acrylate ) Acrylate salt (a-A) Quaternary nitrogen-containing (meth)acrylamide (1) (meth) acrylamide
Alkylammonium salt (2) (meth)acrylamidohydroxyalkyltrialkylammonium salt (4-A>Salt of 8N nitrogen-containing (meth)acrylamide and acid (1) dialkylaminoalk) V (meth) ) acrylamide salt (2) dialkyl/raaminohydroxya! Salt of Rekyl (meth)acrylamide The cationic vinyl monomer represented by the general formula (1) may be in any known form such as solid, solution, emulsion, or slurry, but the state in which it coexists with water is In the present invention, this is the most effective and preferred method. In this case, the amount of water is usually 0.01 to 10 times by weight, preferably 0.01 to 10 times the weight of the cationic vinyl monomer represented by general formula (1).
．． It is 1 to 5 times, more preferably 0.2 to 2 times.

In the present invention, the amount of the cyclic amino compound added is usually 0.1-1.000 ppm, preferably 0.55 ppm based on the cationic vinyl monomer represented by the general formula (1).
-500 ppm, particularly preferably 1 to 50 ppm. Addition amount is 0. The effect is small below lppm;
Moreover, when the amount exceeds 1,000 ppm, the influence on polymerization becomes large.

As a method for adding the cyclic amino compound, the cation flJ
=, a method of adding it as it is to the vinyl monomer and a method of adding it as an aqueous solution are mentioned.

In addition to being added to the cationic vinyl monomer represented by general formula (1), the cyclic amino compound may be added during the production of the cationic vinyl monomer.

In the present invention, in addition to the cyclic amino compound, arehahydroquinone monomethyl ether, hydroquinone t
It may be used in combination with known polymerization inhibitors such as 71-tylcatechol, p-phenylenediamine, and phenothiazine.

The cationic vinyl monomer represented by the general formula (1) to which the stabilization method of the present invention is applied can be polymerized alone or together with other vinyl monomers other than the cationic vinyl monomer represented by the general formula (1) by a known (co)polymerization method. It can be made into a (co)polymer by Other vinyl monomers other than the heptamine of general formula (1) that can be used in producing the (co)polymer include monomers described in JP-A-54-102888, such as hydrophilic nonionic vinyl monomers. Monomers, other hydrophilic cationic vinyl monomers, hydrophilic anionic vinyl monomers, and the hydrophilic anionic vinyl monomer stabilized according to the present invention can be polymerized by conventional methods. For example, it can be carried out by a method using a radical polymerization initiator, radiation, or the like. Among these, methods using radical polymerization initiators such as water-soluble persulfates (sodium persulfate, ammonium persulfate, etc.) and azo compounds (azobisisobutyronitrile, azobisdimethylvaleronitrile, etc.) are preferred.

Further, the polymerization can be carried out by known methods such as aqueous solution polymerization, emulsion polymerization, suspension polymerization, and precipitation polymerization. In the case of aqueous solution polymerization, for example, the monomer is made into an aqueous solution (monomer concentration is, for example, 10 to 90% by weight), and after purging the system with an inert gas, a radical polymerization initiator is added,
This can be carried out by polymerizing usually at about 0 to 80°C for several hours. In the case of emulsion polymerization, for example
This can be carried out by the method described in Japanese Patent No. 102388.

The Nanatsumar obtained according to the present invention undergoes deterioration even under severe conditions (e.g. external temperature during storage, transportation or manufacturing process).
It is effective in preventing unexpected thickening or polymerization due to natural light, impact, etc. or improving stability, and is effective in preventing the polymerization of cationic vinyl monomers. A high-quality cationic polymer with a high polymerization rate can be obtained very easily without any inhibition.

The (co)polymer produced using the cationic vinyl monomer to which the stabilization method of the present invention is applied can be widely used as a fiber modifier, water treatment agent, flocculant, paper agent, adhesive, etc. I can do it.

The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 Methacrylyloxyethyltrimethylammonium chloride was made into an 80% aqueous solution, and 4-benzoyloxy-
A stabilized cationic vinyl monomer is obtained by uniformly dissolving 2,2,6-6-titramethylpiberidine-1-oxy)V 5 I)pm.

Stability tests and polymerization tests were conducted on this product.

For comparison, 4-benzoyloxy-2.2.6.
Similar tests were conducted on those without 6-tetramethylpiperidine-1-oxyl and those in which hydroquinone monomethyl ether, benzophenone, urea, cuperone, and triacetonamine were each added and dissolved individually in the same manner. The test method is as shown below.

The test results are shown in Table-1.

(Stability test) 100 parts of the sample (monomer aqueous solution) was placed in a glass sample bottle, the system was sufficiently replaced with nitrogen by blowing nitrogen gas at room temperature, the bottle was sealed, and the bottle was left in a constant temperature bath at 60°C. The presence or absence of polymer formation over time was investigated.

The polymerization initiation point is the point at which a glass rod shows stringiness when immersed in the sample and pulled up.

(Polymerization Test) A sample was placed in a glass polymerization vessel equipped with a thermometer, a nitrogen gas blowing tube, a stirrer, and a cooling tube, and the system was purged with nitrogen by blowing nitrogen at room temperature while stirring. Next, this was maintained at 50°C, and azobisisodecylonitrile was added to the cationic vinyl monomer in an amount of 0.2% by weight, and the polymerization behavior (induction period) and polymerization rate were checked.

□ Table-1 As is clear from Table-1, 4-benzoyloxy-2.2
-6,6-titramethylpiveridine-1-oxyl has an extremely large stabilizing effect and has little effect on polymerizability.

Example 2 Methacrylyloxyethyltrimethylammonium sulfate was made into a 70% aqueous solution, stabilizers as listed in Table 2 were added thereto, and stability tests and polymerization tests were conducted in the same manner as in Example 1. . The results are shown in Table-2.

Claims (1)

[Claims] 1. General formula (in the formula, R3 is H or CH3; R2 and R3 are each a German alkyl group, a hydroxyalkylene group having 2 to 4 carbon atoms, or a benzyl group; A is an oxygen atom or NHiB is a carbon A cationic vinyl monomer represented by the general formula [wherein R5+ R6+ Ry and R8 are the same or are different alkyl groups, R5 and 8 or R7 and R
8 and the carbon atoms to which they are bonded jointly O
Spider X is a group -CH2-C-CH2-, -(3H2-C-C
H2-. -CH2-○-C[(2-* dimension an2y7;" 1. E(, Fe1Jt, 14+i Ry, l<, 12
r-1esAFli&? -Ai horse and Ro. 1d A method for stabilizing a cationic vinyl monomer, which comprises adding a cyclic amino compound represented by an alkyl group or a phenyl group. 2. The stabilization method according to claim 1, wherein the amount of the cyclic amino compound added is 0.1 to 1000 ppm based on the cationic vinyl monomer.