WO1986005792A1

WO1986005792A1 - Dispersant for reversed phase suspension polymerization

Info

Publication number: WO1986005792A1
Application number: PCT/JP1986/000162
Authority: WO
Inventors: Shoji Ohtani; Yasunori Hosokawa; Yutaka Yasuda
Original assignee: Kao Corporation
Priority date: 1985-04-05
Filing date: 1986-04-04
Publication date: 1986-10-09
Also published as: GB8624298D0; GB2181140B; NL8620116A; JPS61231004A; GB2181140A; DE3690157T1

Abstract

Reversed phase suspension polymerization is conducted by adding an aqueous solution of a water-soluble, ethylenically unsaturated monomer to a hydrophobic solvent inert to polymerization in the presence of a dispersant comprising a polymer obtained by addition reaction of alpha-olefin or alkyl vinyl ether to N-vinyl cyclic amide polymer to obtain stable small granules of the polymer.

Description

6/05792 丄逆逆 Dispersant for reversed-phase suspension polymerization

[Industrial applications]

The present invention relates to a dispersant used when performing a reversed-phase suspension polymerization by adding a water-soluble aqueous diethylene unsaturated monomer solution to a polymerization-inactive and hydrophobic solvent. It is a dispersant for reversed-phase turbid polymerization that can stably maintain a polymerization system.

[Conventional technology]

As a method of polymerizing a water-soluble ethylenically unsaturated monomer, a so-called reverse-phase suspension polymerization method in which a monomer is suspended and dispersed in a hydrophobic solvent and polymerized is well known. In carrying out this method, it is important to properly select a dispersant that can stabilize the polymerizing monomers and prevent or reduce agglomeration of the polymer particles. It is a point. In other words, productivity can be significantly improved by selecting a suitable dispersant. / 05792 ^

It is possible to obtain a polymer having uniform physical properties.

Examples of dispersants used in reverse-phase emulsion polymerization of water-soluble ethylenically unsaturated monomers include: sorbitan monostearate, sorbitan monooleate, and ethoxylated aliphatic alcohol. Non-ionic surfactants such as mid and dariscelin fatty esters are known (JP-B-54-30710, etc.).

Further, in addition to the above, for example, a water-treated maleic acid product of a resin having an aryl (A11 yl) group, and a polymerization charge having a lipoxyl group having an affinity for an organic solvent. High molecular compounds such as lipophilic textile derivatives are known (JP-A-57-74309).

[Problems to be solved by the invention]

However, when the former group (non-ionic surfactant) is used, the resulting polymer becomes fine particles, which causes problems such as generation of dust in the separation and drying steps. Taking 05792 3

Can be difficult to handle. When the latter group of dispersants is used, the resulting polymer is in the form of small agglomerates, and although the above-mentioned disadvantages can be improved, the polymer particles and the wall of the polymer are stirred or mixed during the polymerization operation. It is inevitable that a large part of the reacted fumer will be lost as unusable polymerized plant deposits due to the stickiness caused by the tomato. Generally, removing the polymerized / adhered matter of the water-soluble ethylenically unsaturated herb requires a great deal of effort from dogs, resulting in efficient production of granular polymer.

[Means for solving the problem]

As a result of intensive studies to solve the above-mentioned problems, the present Kiyoshi et al. Found that using a polymer having a specific structure as a fu position repeatedly as a dispersant in reverse-phase turbidity polymerization provided fine particles. The present inventors have found that a small granule containing no polymer can be obtained stably, and have completed the present invention.

That is, the present invention provides: (CH CH-R ₃ , N

c-C—— CH ₂ ——

(Where R _t and R ₂ have the following combinations:

One

You. That is, the combination c with R _z , R ₂ ) is (H, .H), (H, CH ₃ ), (H, C ₂ oH ₅ ), (CH ₃ , C ₂ H ₅ ) (H, It is any one of the group consisting of a straight-chain or branched alkyl group having 6 or more carbon atoms) and (H, an alkoxyethyl group having 6 or more carbon atoms). R ₃ and R each represent H or a straight or branched alkyl group having 6 or more carbon atoms or an alkoxyethyl group having 6 or more carbon atoms. _n represents an integer of 1 to 3. ]

It is intended to provide a dispersant for reversed-phase suspension polymerization comprising an oil-soluble polymer having a structure represented by the following formula:

The repetition of the above-mentioned steel structure means that adjacent constituent units have the same set of R, R ₂ R ₃ and R ₄ . It does not mean that for the corresponding constituent units (similarly R _Z , ₃ R :) may be different from each other.

The dispersant for reversed-phase suspension polymerization of the present invention is a dispersant for reversed-phase suspension polymerization, which comprises a balance between a polar amide moiety and a nonpolar alkyl or alkoxyethyl moiety. Good performance as an agent.

The reversed phase dispersant of the present invention can be produced, for example, by the following method. That is,

(CH. ₂ ^ K CH ₂

R C C = 0

I

CH = CH _Z

(R ', R "each _{_{H, CH 3, C 2 H}} S sac lichen Zureka represents a single 1. N Table to an integer of 1 to 3.)

A polymer of at least one N-Bull ring amide represented by is converted to a «-olefin or carbon having 6 or more carbon atoms by using a peroxide compound. It can be produced by alkylation or alkoxyethylation with an alkyl vinyl ether having an alkyl group of several or more. More specifically, a polymer of N-Bull cyclic amide is dissolved in a suitable solvent, for example, n-hexano-one-mole, n-amirea-reco-one-mele, methicole-soft-birketone, etc. , Or -olefin or alkylbutyl ether and a peroxide compound such as di-t-Bu-peroxide, t-Bu-no- The reaction is carried out at a temperature of 80 to 200, preferably 90 to 140, for 10 to 40 hours in the presence of idlo / hydroxy acid, etc., and the solvent is removed under reduced pressure. Unreacted or-refined molybdenum can be used as a dispersing agent even with 1 ter. Even if it is produced by a method other than this method, the performance as a dispersant for reversed-phase suspension polymerization does not change, so any method may be used.

In addition, the reversed phase polymerization polymerization dispersant of the present invention, Two

7

A portion (unit) other than the above-mentioned repeated position may be included as long as the performance as a dispersant for the turbid polymerization is not hindered. Examples of the monomer capable of constituting such a portion include: unsaturated monocarboxylic acid ester such as alkyl methacrylate or alkyl acrylate having an alkyl group having 6 or more carbon atoms, dianolequinolate, Non-encapsulated rosin compounds such as dianolequinolefumarate and diaquinolose tancone, monomers having an aromatic ring such as propylene diester, styrene, and alkylstyrene, alkyl vinylinolenate, Examples thereof include anolex lesbininolates and mixtures thereof. "-Refin can also be used.

The の -vinyl cyclic amide polymers which can be used in the production of the dispersant for reversed phase polymerization of the present invention by the above-mentioned method include Ν-vinyl viridone and Ν-Bulle-5. -Alkylpyrrolidone, Ν-vinylbiperidone, Ν-vinyl-6-alkylbiperidone, ビ -bulcaprolactam, Ν-bi Polymers of nil-7-alkynorecaprolactam. In particular, an N-vinylpyrrolidone polymer is preferable because a poly (vinylpyrrolidone) having a market δ can be used as it is. These polymers of Ν-Bull ring amide can be suitably used as long as they have an average molecular weight of 1,000 to 100,000, more preferably 5,000 to 500,000.

In addition, as the orifice that can be used in the above method, any straight or branched one having 6 or more carbon atoms may be used. Numbers between 10 and 20 are more preferred. If the number of carbon atoms is smaller than 6, the produced dispersant has insufficient oil solubility and loses its performance as a dispersant. Examples of the olefin having 10 to 20 carbon atoms include eicosene, and commercially available ones can be used. Alkyl vinyl ethers that can be used in the above method include any alkyl vinyl ether having an alkyl group having 6 or more carbon atoms. 9

Alkyl ether having an alkyl group having 10 to 20 carbon atoms, such as vinyl dodecyl ether, is more preferable. When the alkyl group has less than 6 carbon atoms, the produced dispersant has insufficient oil solubility and cannot function as a dispersant.

When the polymer is subjected to reverse-phase suspension polymerization using the dispersant for reverse-phase turbid polymerization of the present invention, the appropriate amount of the dispersant to be used is usually 0.0 to 10% by weight based on the polymer. %, Preferably 0.05 to 5.0% by weight.

When the dispersant for reversed-phase suspension polymerization of the present invention is used, as a solvent for reversed-phase suspension polymerization, in principle, any solvent having polymerization inertness and water-insoluble property can be used. is there. In consideration of the removal of the heat of polymerization and the drying step of the obtained polymer, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons or mixed solutions thereof having a point of 30 to 200 are preferred. In particular, it is especially useful for San, benzene, toluene or a mixed solvent thereof is preferably used.

As the water-soluble ethylenically unsaturated polymer which can be polymerized by reverse phase suspension polymerization to which the dispersant of the present invention is applied, various compounds can be mentioned. For example, acrylic acid or metaacrylic alkali metal salt, ammonium salt, ammonium salt, acrylylamide or methacrylamide or water-soluble N-substituted acrylic acid Mid or metal lubricated or vinyl imid

_,

Dazoisure, bininolepyridine, bininolepyrrolidone or styrene sulfonate, alkali metal salt of vinyl sulfone, and the like. In addition to these, 2-hydroxyl-ethyl methacrylate-hydroxy-2-ethyl methacrylate, dimethylaminoethyl methacrylate, methylethyl methacrylate Noethyl and the like can be mentioned. These fumers can be used in any combination of one or more kinds. In addition, other water-soluble monomers are used as long as hydrophilicity is not impaired. / 05792

丄 1

It can also be copolymerized.

Further, if necessary, a water-soluble crosslinking agent having two or more polymerizable unsaturated groups, such as, for example, methylene bisacrylinoleamide, or a functional group of an ethylenically unsaturated fumer may be used. Using a water-soluble cross-linking agent having two or more functional groups that can react with, for example, ethylene glycol diglycidyl ether, crosslinks during (co) polymerization of the above monomer or after polymerization撟 It is also possible to react. -The monomer concentration of the aqueous monomer solution in the present invention can be changed in a wide range, but generally 15 to 80% by weight is preferable.

Also, the ratio of the amount of the aqueous solution of fumer and the amount of the polymerization-inactive and hydrophobic solvent can be changed over a wide range, but usually, the ratio by volume is 1: 1 to 1: 1: A range of 4 is preferred. For the polymerization of fumer, a water-soluble radisol polymerization initiator such as a peroxide, a hydroperoxide, or an azo compound is used in a known amount. 6/05792

12

Used in These polymerization initiators can be used as a mixture of two or more kinds.Furthermore, redox polymerization initiation is performed by adding chromion, sulfite, hydroxylamine, hydrazine and the like. It can also be used as an agent.

(Operation)

The dispersant for reverse phase polymerization of the present invention has a polar amide moiety and a nonpolar alkyl or alkoxymethyl group moiety, and is suitable for reverse phase polymerization. In practice, the dispersant is regularly oriented at the oil-water interface and stabilizes both interfaces, so it is considered that the reversed-phase suspension polymerization system is stably maintained. ' 〔Example〕 '

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to only these Examples.

The dispersants used in the examples are listed below. / 05792

13

Dispersant A

In a 500 m1 four-necked round-bottomed flask equipped with a stirrer, an overflow condenser, and a nitrogen gas inlet, 30 g (0.27 equivalent) of polyvinylidene lidone K-90 (manufactured by GAF) and 225 ml of n- Hexanol, 75.7 g (0.27 mol) a-eicosene and 4 g of di-Bu-peroxide were added. After substituting with nitrogen gas, reacting at a temperature of 125 to 130 for 30 hours, π-hexanol is distilled off under reduced pressure, and a waxy polymer / cc-refined mixture is obtained. I got Its IV was 205, which was dissolved in hexane.

Dispersant B

In the same apparatus as used for dispersant A, 55.5 g (0.5 eq.) Of Boli-Burpipone lidone K-30 (manufactured by GAF), 150 ml of n-hexanol, and commercially available C ₁₆ -C 92.3 g (0. mol) of _{1 S or-} refin (Diaren 168, manufactured by Mitsubishi Chemical) and 5. lg of di-t-Bu-baroxide were added, and the mixture was replaced with nitrogen gas. 12 / 05792 14

The reaction was performed at 5-130'c for 20 hours. After an additional 2.5 g of peroxide was added, the reaction was performed for 10 hours. The n-hexanol and unreacted oil were distilled off under reduced pressure to obtain a pale yellow viscous liquid. Its IV was 5.6, which was dissolved in cyclohexane.

Dispersant C

Polyvinylvinylidone K-30 55.5 g (0.5 equivalent), n-hexanol 100 g, vinyl dodecyl ether 106.3 g (0.5 mol), and di- After adding 10 g of t-Bu-baxide and reacting for 1 hour at a temperature of 120 to 140, the hexane and unreacted vinyl dodecyl ether are removed under reduced pressure to give a pale yellow viscous solution. A thick liquid was obtained. Its IV was 6.0, which was dissolved in cyclohexane.

Dispersant D

Alkylation product of GAF's polypyrrolidone (ANTALON V-216) / 05792

Fifteen

Dispersant E

GAF Polybutylpyrrolidone alkylated product (Antalon V-220)

Example 1

250 ml of cyclohexane and 1.2 g of dispersant A were charged into a 500 ml four-neck round bottom flask equipped with a stirrer, reflux condenser, dropping funnel and nitrogen gas inlet, and dissolved by blowing nitrogen gas. Oxygen was expelled and the temperature was raised to 75. Separately, 30 g of acrylic acid was neutralized by dissolving 13.4 g of 98% caustic soda in 40 g of ion-exchanged water while externally cooling 30 g of acrylic acid in a flask φ. Next, after adding and dissolving potassium persulfate O.lg, nitrogen gas was blown in to remove oxygen present in the aqueous solution. This solution was added dropwise to the four-necked flask in 3′0 minutes to carry out polymerization. After completion of the dropwise addition, the mixture was kept at 75 and the reaction was further continued for 1 hour. Thereafter, the hexane solvent Sik b 'were evaporated flashing pressure, 80 remaining ivy polymer portion: If you减圧dried at L00, the center particle size of 150 to 300 mu _m small granular of / 05792 16

Polysodium acrylate was obtained. The amount of the dressing in 揎 was 0.5 g.

Examples 2 to 5

In Example 1, polymerization was performed using Dispersant B, Dispersant C, Dispersant D, and Dispersant E instead of Dispersant A, respectively. Table 1 shows the center particle size and the amount of the attached poly (sodium polyacrylate). table 1

Example 6

In Example 1, 25 g of sodium vinyl sulfonate was used instead of acrylonitrile as the aqueous solution of ethylenically unsaturated fumer, and this was ion-exchanged. When the monomer dissolved in 75 g of water replacement was used, small particles of sodium polyvinylsulfonate having a center particle diameter of 130 to 350 m were obtained. The amount of deposits in the area was 0.8 g.

Comparative example

The polymerization was carried out according to Example 1. However, when 1.2 g of sorbitan monostearate was used in place of dispersant A, only a particulate polymer having a center particle size of 30 to 7.0 μm was obtained. The amount of deposits in the reaction tank was 0.9 g.

[Effectiveness of development]

As specifically shown in the examples, when producing the polymerized ^ using the dispersant for reversed-phase, turbid polymerization of the present invention, almost no occurrence of polymer aggregates was observed. In addition, the produced polymer has a center particle diameter of 100 to 350'in.Working throughout the entire process of polymerization and production, the productivity can be significantly improved. it can. For example, when the dispersant for reverse-phase turbid polymerization of the present invention is used, the polymerization of the polymer into a polymerization apparatus or a stirrer can be performed. Since the amount of adhesion can be extremely small, the polymerization apparatus can be used continuously.

Claims

O 86/05792

19

Next formula

(CH ₂ hr CH-R ₃

I

… Α-blue

C -CH ₂

Wherein, R ,, R ₂ has a set ¾ wheel alignment as follows. That is, the combination of and R ₂ (Ri, R ₂ ) is (H, H), (H, CH ₃ ), (H, C ₂ H ₅ ), (CH ₃ , C ₂ H ₅ ), CH, carbon number A straight or branched alkyl group having 6 or more) or (H, an alkoxyethyl group having 6 or more carbon atoms). [5 _3, R ₄ is Ku linear if having 6 or more H or carbon respectively represent one or branched alkyl group or having 6 or more alkoxy Echiru group sac Chiizure carbon. n represents an integer of 1 to 3. ] A dispersant for reversed phase suspension polymerization comprising a polymer having a structure represented by the following formula as a repeating unit. _2. The dispersant according to claim 1, wherein the alkyl group and the alkoxysilyl group representing Ri. R ₂ , R ₃ and R ₄ have 6 to 20 carbon atoms. 2. The dispersant according to claim 1, wherein the polymer further comprises another repeating unit. When the polymer is converted to an N-Bull ring polymer or 3. The dispersant according to claim 1, wherein the dispersant is obtained by an addition reaction of an alkyl vinyl ether.

5. The dispersant according to claim 4, wherein the polymer of the N-Bull cyclic amide has an average molecular weight of 1,000 to 1,000,000.

5. The dispersant according to claim 4, wherein the α-olefin or alkylbutyl ether has an alkyl group having 6 or more carbon atoms.

A method for performing reverse phase emulsion polymerization by adding a water-soluble aqueous ethylenically unsaturated monomer solution to a polymerization-inactive and hydrophobic solvent in the presence of the dispersant according to claim 1.

The method according to claim 7, wherein the dispersant is present in an amount of 0.1 to 10% by weight based on the monomer.

The monomer is contained in the aqueous monomer solution at 15 to 80% by weight, and the volume ratio of the monomer and monomer aqueous solution to the solvent is 1: 1 to 1: 4. How to record.

The method according to claim 7, wherein the polymerization inert and hydrophobic solvent is an aliphatic hydrocarbon or an alicyclic hydrocarbon having a boiling point of 30 to 200 ° C, or a mixed solvent thereof. .