JPH07228613A - Emulsifying dispersion agent for polymerization - Google Patents

Abstract

PURPOSE:To obtain an emulsifying dispersion agent composed of a polyoxyalkylene propenylphenyl ether phosphate (salt), giving an emulsion exhibiting high stability, forming a film having excellent physical properties and free from problem of contamination of waste water with the residue. CONSTITUTION:This emulsifying dispersion agent for polymerization is composed of a compound of formula I [R<1> is H or methyl; R<2> is 1-propenyl or isopropenyl; A is a 2-4C alkylene; (n) is 1-100; X is group of formula II, III or TV; M is H, an alkali metal, an alkaline earth metal, ammonium or an alkanolamine]. In the formula, A is preferably ethylene or propylene and (n) is preferably 1-50. The agent is applied in the emulsion polymerization of acrylic monomer, aromatic monomer, etc., and the suspension polymerization of styrene or vinyl chloride.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an emulsion dispersant for polymerization which is used as an emulsifier in emulsion polymerization and as a dispersant in suspension polymerization.

[0002]

Conventionally, as emulsifiers for emulsion polymerization, alkyl sulfate ester salts, alkylbenzene sulfonate salts, dialkyl sulfosuccinate ester salts, polyoxyalkylene alkyl (aryl) ether sulfate ester salts, etc. Nonionic surfactants such as anionic surfactants, polyoxyalkylene alkyl (aryl) ethers, polyoxyethylene polyoxypropylene block copolymers, polyoxyethylene sorbitan fatty acid esters, etc. are used alone or in a mixture. However, the stability of the emulsion and the properties of the film produced from the emulsion are not always sufficiently satisfactory, and many problems to be solved remain. That is, there is a problem in polymerization stability of the emulsion, mechanical stability of the obtained emulsion, chemical stability, freeze-thaw stability, pigment miscibility, storage stability, etc.,
Regarding mechanical stability, there remain problems to be improved.

Further, when a polymer film is prepared from an emulsion, the emulsifier used for the polymerization remains in the polymer film in a free state, which causes problems such as poor water resistance and adhesiveness of the film.

Further, when the polymer is taken out from the emulsion by means of salting out or the like, a large amount of an emulsifier is contained in the waste water, which causes river pollution, so that a great deal of labor is required for the treatment of removing the emulsifier from the waste water. Become.

From this point of view, in order to solve the problems of the conventional emulsifiers, a number of patents relating to new emulsifiers generally called reactive emulsifiers have been proposed.

Reactive emulsifiers include nonionic and anionic ones. For example, as anionic reactive emulsifiers, JP-B-46-12472 and JP-A-54-1
No. 44317, Japanese Patent Publication No. 46-34894, Japanese Patent Publication No. 56
-29657, JP-A-51-30285, and JP-B-4.
No. 9-46291 and the like, which have been tried as emulsifiers for emulsion polymerization of various monomers.
However, these reactive emulsifiers often have insufficient stability during emulsion polymerization when used alone as an emulsifier, and polymerization does not proceed smoothly unless they are used in combination with conventional emulsifiers. It has a problem that it cannot be fully exhibited.

On the other hand, as a dispersant for suspension polymerization, anionic surfactants such as sodium lauryl sulfate and sodium dodecylbenzene sulfonate have been conventionally used. However, like these emulsifiers for emulsion polymerization, when the polymer is taken out after the polymerization, many dispersants are contained in the wastewater, which causes river pollution. Labor is required.

The object of the present invention is to solve the above-mentioned problems, the stability of the emulsion and the physical properties of the polymer film prepared from this emulsion are excellent, and the polymer produced remains in the waste water after separation. There is a need to provide a difficult emulsion dispersant for polymerization.

[0009]

The present invention provides an emulsion dispersant for polymerization comprising a compound represented by the following general formula (I).

[0010]

[Chemical 2]

A in the above general formula is an alkylene group having 2 to 4 carbon atoms, for example, ethylene, propylene, butylene, isobutylene and the like. From the viewpoint of emulsifying and dispersing performance, ethylene and propylene are preferable. (AO) _n and (OA) _n are, for example, ethylene oxide (E
O), propylene oxide (PO), butylene oxide or isobutylene oxide may be a single adduct, a block adduct, a random adduct, or a mixture thereof. n is an integer of 1 to 100, and is preferably in the range of 1 to 50 from the viewpoint of emulsion dispersion performance. R ¹ is a hydrogen atom or a methyl group. R ² is a 1-propenyl group or an isopropenyl group. M is a hydrogen atom; an alkali metal atom such as sodium or potassium; calcium,
An alkaline earth metal atom such as magnesium; ammonium; an alkanolamine group such as monoethanolamine, triethanolamine, etc., and a mixed system thereof may be used.

The emulsifying dispersant of the present invention can be synthesized by adopting a known method. For example, by adding alkylene oxide to allylphenol or isopropenylphenol under an alkaline catalyst at high temperature and high pressure, a polyoxyalkylenepropenylphenyl ether is obtained, to which a known sulfating agent or phosphorylating agent is added. The reaction can be carried out to obtain a sulfuric acid ester (salt) and a phosphoric acid ester (salt) (neutralizing with a basic substance if necessary). Phosphate ester (salt)
May be a mixture of a monoester (salt) and a diester (salt), the ratio of which is determined by the amount of water and the amount of phosphorylating agent contained in the reaction system of the phosphoric acid esterification reaction.

The emulsifying dispersant for polymerization of the present invention has a propenyl group in the hydrophobic group portion of its molecule, and therefore has excellent copolymerizability with a polymerizable monomer, particularly a vinyl monomer, and is easily incorporated into a polymer component. Therefore, the amount of the emulsifier existing in a free state in the polymer film prepared from the polymer emulsion produced by the polymerization is remarkably reduced, and the water resistance and the adhesive property of the film are extremely excellent. Further, foaming of the polymer emulsion, mechanical stability, etc. are remarkably improved.

As the monomer to which the emulsifying dispersant of the present invention is applied, various monomers can be used in emulsion polymerization. For example, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, acrylic monomers such as acrylonitrile, acrylamide, hydroxyethyl acrylate, and aromatics such as styrene and divinylbenzene. Examples include monomers, vinyl ester monomers such as vinyl acetate, halogen-containing monomers such as vinyl chloride and vinylidene chloride, conjugated diolefin monomers such as butadiene, isoprene and chloroprene, and ethylene, maleic anhydride and methyl maleate. The emulsifiers of this invention can be used in the emulsion polymerization of one or more of these monomers. Preferred are acrylic monomers, aromatic monomers, and conjugated diolefin monomers.

In suspension polymerization, it is used as a monomer such as styrene, vinyl chloride, acrylonitrile, methyl methacrylate and methyl acrylate. Preferred are styrene and vinyl chloride.

The emulsifying dispersant of the present invention may be used alone or in combination of several kinds. Moreover, you may use together with the conventional reactive emulsifier (For example, polyoxyethylene propenyl nonylphenol sulfuric acid ester salt, 1-allyloxy-2- polyoxyethylene-3-nonylphenoxy sulfuric acid ester salt). When used in combination with such a conventional reactive emulsifier, it has the effect of improving stability.

The polymerization initiator may be a conventionally known one, and examples thereof include hydrogen peroxide, potassium persulfate, ammonium persulfate, t-butylperoxybibalate, azobisisobutyronitrile and benzoyl peroxide. .

Examples of the polymerization accelerator include sodium hydrogen sulfite, ferrous ammonium sulfate and the like.

In the emulsion polymerization, the amount of the emulsifying dispersant used in the present invention is usually 0.1 to 20% by weight, preferably 0.2 to 5.0% by weight, more preferably 100 to 50% by weight, based on all monomers. Is 0.5 to 3.0% by weight. If it is less than these ranges, the emulsion dispersion stability will be poor, and if it exceeds the ranges, the physical properties of the polymer will be poor. In suspension polymerization, 10 to 1000 ppm, preferably 100 to 300, based on all monomers.
It is ppm. If it is less than these ranges, the dispersion stability will be poor, and if it exceeds it, a preferable polymer particle size cannot be obtained.

Although a good aqueous resin dispersion can be obtained by using the emulsifying dispersant of the present invention alone, it is emulsified when other emulsifying dispersant (other than the above reactive emulsifying agent) or a protective colloid agent is used in combination. This has the effect of improving dispersion stability. When another emulsifying dispersant or protective colloidal agent is used in combination, the proportion of the emulsifying dispersant of the present invention used is preferably 10 to 95%. If it is less than 10%, the water resistance of the polymer is not improved, and if it exceeds 95%, the meaning of using it in combination is diminished.

Further, when a compound in which X is a hydrogen atom in the above general formula (I) is used in combination with the emulsifying dispersant of the present invention,
Has the same effect.

The aqueous resin dispersion obtained by applying the emulsifying dispersant of the present invention should be applied to wood, metal, paper, cloth, concrete, etc. as an adhesive, coating agent, impregnation reinforcing agent, etc. You can

[0023]

EXAMPLES The present invention will be specifically described below with reference to examples. (%, Parts are based on weight.) Production Example 1 (Production of emulsifying dispersant [A]) In a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube, 94 g of phenol (1.0 mol) and 40 g of NaOH ( (1.0 mol) and 210 g of acetone were charged, and the internal temperature was raised to 40 ° C. with stirring. Next, allyl chloride 76.
5 g (1.0 mol) was added dropwise over 1 hour, and after the addition was completed, the reaction was carried out at 40 ° C. for 2 hours. Next, the reaction product was filtered to remove by-produced NaCl, and then acetone was removed under reduced pressure to obtain 130 g (yield 97.0%) of allyl phenyl ether.

67 g of this allyl phenyl ether (0.
(5 mol) was charged into an autoclave, and the mixture was held at 150 ° C. for 5 hours while stirring to carry out a rearrangement reaction to obtain allylphenol. Next, after once cooling to room temperature, 1.4 g of NaOH as a catalyst was added, and the inside of the autoclave was replaced with N _2, and then 290 g (5.0) of propylene oxide (PO) at 130 ° C. under a pressure of 1 to ² kg / cm ^2. Mol) to give 2- (1-propenyl) phenol P.
O-average 10-mol addition product 357g was obtained. Allyl group is P
At the time of O addition reaction, it was changed to a 1-propenyl group.

Next, an average of 10 moles of this 2- (1-propenyl) phenol PO adduct 357 g (0.5 mole)
Was charged into a reaction vessel equipped with a stirrer and a thermometer,
Charge 48.5 g (0.5 mol) of sulfamic acid, 1
The reaction was carried out at 30 ° C. for 2 hours to obtain 2 which is the emulsifying dispersant of the present invention.
405.5 g of a sulfuric acid ester ammonium salt of a 10-mol adduct of-(1-propenyl) phenol PO was obtained.

Production Example 2 (Production of Emulsified Dispersant [B]) In a reaction vessel equipped with a stirrer, a thermometer and a reflux tube, 94 g (1.0 mol) of phenol, 40 g (1.0 mol) of NaOH and 210 g of acetone were added. Was charged, and the internal temperature was raised to 40 ° C. with stirring. Next, allyl chloride 76.
5 g (1.0 mol) was added dropwise over 1 hour, and after the addition was completed, the reaction was carried out at 40 ° C. for 2 hours. Next, the reaction product was filtered to remove by-produced NaCl, and then acetone was removed under reduced pressure to obtain 130 g (yield 97.0%) of allyl phenyl ether.

67 g of this allyl phenyl ether (0.
(5 mol) was charged into an autoclave, and the mixture was held at 150 ° C. for 5 hours while stirring to carry out a rearrangement reaction to obtain allylphenol. Next, after cooling once to room temperature, 1.4 g of NaOH as a catalyst was added, and the inside of the autoclave was replaced with N _2, and then 58 g (1.0) of propylene oxide (PO) at 130 ° C. under a pressure of 1 to ² kg / cm ^2. Mol) and then ethylene oxide (EO) 17
6 g (4.0 mol) was added to obtain 301 g of a 2- (1-propenyl) phenol PO 2 mol EO 8 mol adduct. The allyl group was changed to a 1-propenyl group in the PO / EO addition reaction.

Next, 301 g (0.5 mol) of this 2- (1-propenyl) phenol PO2 mol EO8 mol adduct was charged into a reaction vessel equipped with a stirrer and a thermometer, and the internal temperature was raised to 70.degree. 1.8 g of water (0.
(1 mol). Subsequently, phosphoric anhydride 24.1 g
After adding (0.17 mol) over 30 minutes, 70-
The reaction was carried out at 75 ° C. for 7 hours to obtain 326.9 g of phosphoric acid ester of 2- (1-propenyl) phenol PO 2 mol EO 8 mol adduct which is the emulsifying dispersant of the present invention. The ratio (molar ratio) of the monoester and diester of this phosphoric acid ester was measured by NMR (phosphorus), and the result was monoester / diester = 80/20.

Production Example 3 (Production of Emulsifying Dispersant [E]) p-isopropenylphenol 134 was placed in an autoclave.
g (1.0 mol) and 48% KOH 3.0 as catalyst
After being charged with g and dehydrated under reduced pressure at 120 ° C., the inside of the autoclave was replaced with N ₂ . Next, ethylene oxide (E
O) 440 g (10.0 mol) was gradually added to 130 ° C.
Then, the addition reaction was carried out under the condition of a pressure of 1 to ² kg / cm ² to obtain 574 g of p-isopropenylphenol EO average 10 mol adduct.

Next, 287 g (0.5 mol) of this p-isopropenylphenol EO average 10 mol adduct was charged into a reaction vessel equipped with a stirrer and a thermometer, and then 48.5 g (0. 5 mol), 130 ° C
For 2 hours to obtain 335.5 g of a sulfuric acid ester ammonium salt of a 10-mole adduct of p-isopropenylphenol EO, which is an emulsifying dispersant of the present invention.

Production Example 4 (Production of Emulsifying Dispersant [I]) 67 g of p-isopropenylphenol was placed in an autoclave.
(0.5 mol) and 6.0 g of 48% KOH as catalyst
Was charged and dehydrated under reduced pressure at 120 ° C., and then the inside of the autoclave was replaced with N ₂ . Next, 1-2 kg / c at 130 ° C
Propylene oxide (PO) 1 under m ² pressure
After adding 45 g (2.5 mol), 330 g (7.5 mol) of ethylene oxide (EO) was added, and p-
542 g of an adduct of 5 mol of isopropenylphenol PO and 15 mol of EO was obtained.

Next, 542 g (0.5 mol) of this p-isopropenylphenol PO 5 mol EO 15 mol adduct.
Was charged into a reaction vessel equipped with a stirrer and a thermometer, the internal temperature was raised to 70 ° C., and 4.5 g (0.25
Mol). Subsequently, 35.5 g of phosphoric anhydride (0.
25 mol) over 30 minutes and then 70-75 ° C
Was reacted for 7 hours. After completion of the reaction, 3000 g of water was added to dilute, neutralized with 40.0 g (1.0 mol) of NaOH, and phosphoric acid monohydrate of adduct of p-isopropenylphenol PO 5 mol EO 15 mol EO was used as an emulsifying dispersant of the present invention. 604 g (solid content) of ester sodium salt was obtained.

Examples 1 to 7 and Comparative Examples 1 to 4 (emulsification weight)
In the following emulsion polymerization formulation, emulsion polymerization was carried out using the emulsifiers [A] to [F] of the present invention represented by the following formula (manufactured in the same manner as in Manufacturing Examples 1 to 4) to obtain an emulsion. The physical properties and the physical properties of the polymer film obtained from the emulsion were tested. As a comparative example, an example of a conventional emulsifier (the anionic reactive emulsifier used in Comparative Example 3 is represented by the following formula) was also tested. The results are shown in Table 1.

[0034]

[Chemical 3]

[0035]

[Chemical 4]

[0036]

[Chemical 5]

[Emulsion Polymerization Formulation] 5 parts of an emulsifier was dissolved in 295 parts of water and the temperature was raised to 70 ° C. Next, 20 parts of monomer and 0.5 part of ammonium persulfate are added to carry out prepolymerization,
After 10 minutes from the start of polymerization, 180 parts of the monomer was added dropwise over 3 hours to carry out polymerization. Next, the mixture was aged at the polymerization temperature for 1 hour and then cooled, and the emulsion was taken out to obtain a test sample.

Next, this test sample was applied to a glass plate and dried at room temperature for 24 hours to prepare a polymer film.

[0039]

[Table 1]

Polymerization stability of the emulsion in Table 1,
The mechanical stability and the water resistance of the polymer film were evaluated as follows.

[Polymerization stability] After completion of the polymerization, the emulsion was filtered through a 150-mesh stainless mesh, and the agglomerates remaining on the stainless mesh were thoroughly washed with water and then weighed.
This weight was evaluated as a percentage of the weight of the charged monomers. When this percentage was 0.5% or less: ⊚: 0.5 to 2%: ◯: 2 to 5%: Δ: 5% or more: ×

[Mechanical Stability] 5 by a Marlon type mechanical stability tester under the conditions of 10 kg / cm ² and 1000 rpm.
After treating the emulsion for a minute, the coagulated product was filtered through a stainless steel mesh of 80 mesh, the coagulated product remaining on the stainless steel net was thoroughly washed with water, and the weight thereof was measured. This weight was evaluated as a percentage of the weight of the charged monomers. When this percentage was 0.5% or less: ⊚: 0.5 to 2%: ◯: 2 to 5%: Δ: 5% or more: ×

[Water resistance of polymer film] The polymer film formed on a glass plate was immersed in water to evaluate the whitening condition of the film. After 1 hour, no whitening at all: ◎ After 1 hour, slightly whitening: ○ Whitening within 10 to 30 minutes: △ Immediate whitening: evaluated as ×.

Examples 8 to 11 and Comparative Example 5 (emulsification weight)
If) was dissolved mixed emulsifier 5 parts of the composition shown in Table 2 to 295 parts of water was heated to 80 ° C.. To this, 20 parts of a mixed monomer of n-butyl acrylate / styrene = 7/3 and 0.3 part of ammonium persulfate were added and prepolymerized to start polymerization 1.
It takes about 3 hours from 0 minutes to the mixed monomer 18 having the above composition.
0 part was dropped. Then, the mixture was aged at 80 ° C. for 1 hour and then cooled, and the emulsion was taken out to obtain a test sample.

Further, this test sample was applied to a glass plate and dried at room temperature for 24 hours to prepare a polymer film.

The physical properties of the emulsion thus obtained and the physical properties of the polymer film obtained from the emulsion are shown in Table 2. Table 2 also shows examples of conventional emulsifiers as comparative examples.

Emulsifiers [G] to [I] of the present invention shown in Table 2
The reactive emulsifiers [1] and [2] are represented by the following formula.

[0048]

[Chemical 6]

[0049]

[Table 2]

The polymerization stability of the emulsion and the water resistance of the polymer film in Table 2 were evaluated in the same manner as in Table 1. The foamability of the emulsion was evaluated as follows.

[Foamability] 50 ml of an emulsion diluted twice with distilled water was placed in a 100 ml measuring cylinder with a stopper.
It was put in, shaken vigorously up and down 30 times at 25 ° C., and evaluated by the amount of foam after 1 minute of standing. When the amount of bubbles was 0 to 5 ml: ⊚ 5 to 10 ml: ∘ 10 to 30 ml: Δ When 30 ml or more: ×

Examples 12 to 16 (Emulsion Polymerization) By the same emulsion polymerization formulation as in Examples 1 to 7, the emulsifiers [A], [B], [E], [G] and [J] of the present invention (see below). Was used for the emulsion polymerization, and the physical properties of the obtained emulsion and the physical properties of the polymer film obtained from the emulsion were tested. The results are shown in Table 3.
It was shown to.

[0053]

[Chemical 7]

[0054]

[Table 3]

Examples 17 and 18 and Comparative Example 6 (suspension weight)
In a 1000 ml autoclave, deionized water 450
g, partially saponified polyvinyl acetate (dispersant) 180 m
g, 300 g of vinyl chloride monomer, 75 mg of t-butylperoxybibalate, and 60 mg of the dispersants [A] and [E] of the present invention as a dispersant for suspension polymerization (sodium lauryl sulfate ester in Comparative Example 6). ,
Polymerization was carried out at 58 ° C. for 5 hours.

The vinyl chloride polymer slurry produced was filtered off, and the amount of the dispersant for suspension polymerization contained in the aqueous layer was determined by the Epton method, which is a method for determining an anion activator. The results are shown in Table 4. From these results, it is understood that the dispersant of the present invention, when copolymerized with vinyl chloride, hardly remains in the water layer, and therefore the load thereof when the waste water is treated can be reduced.

[0057]

[Table 4]

[0058]

When the emulsion dispersant for polymerization of the present invention is used as an emulsifier for emulsion polymerization to emulsion-polymerize a monomer, the polymerization stability is good, the foaming of the obtained emulsion is low, and the mechanical stability is improved. . In addition, the polymer film obtained from this emulsion has significantly improved water resistance.

When the emulsion dispersant for polymerization of the present invention is used for emulsion polymerization or suspension polymerization, the amount of free dispersant in the produced emulsion or slurry can be reduced and the load of waste water generated from the manufacturing process can be reduced. be able to.

Claims (1)

[Claims] 1. An emulsion dispersant for polymerization comprising a compound represented by the following general formula (I). [Chemical 1]