JPH02229542A - Inverse-phase and its production - Google Patents

Abstract

PURPOSE:To obtain an inverse-phase emulsion having high shelf stability over a long period of time, low viscosity and high flowability by using specified five kinds of surfactants. CONSTITUTION:An inverse-phase emulsion of a water-soluble or hydrophilic polymer is obtd. by using sorbitan fatty acid ester having 3-5 HLB, a nonionic oil-soluble surfactant having >=2,000mol.wt., a nonionic oil-soluble surfactant having <2,000mol.wt. and 8-10 HLB, a water-soluble polyoxyethylene- polyoxypropylene deriv. and a nonionic water-soluble surfactant having 12-14 HLB. The emulsion has low viscosity, high flowability and shelf stability over a long period of time and is rapidly dispersed in water and dissolved by phase inversion.

Description

[Detailed description of the invention] A) Field of industrial application for the purpose of the invention> The present invention has excellent long-term storage stability, low apparent viscosity and good fluidity, and is suitable for phase inversion bath dissolution into water. Soura is very fast and has excellent workability compared to conventional products.Water bathability or hydrophilicity 1
This invention relates to reverse-phase emulsions of coalescence, and is widely used in the paper manufacturing industry, the construction industry, and various industries that require wastewater treatment.

It is supplied to the market in the form of a phase emulsion (water-in-oil emulsion) for use in the treatment of <<prior art>> drilling mud, conditioning agent for drilling mud, oil-water flooding, etc. Among these, reverse phase emulsion products are more easily dispersed in water than powdered and paste products.
It is widely used because it melts quickly and it is easy to use continuous melting equipment.

A general method for producing a reversed phase emulsion is disclosed in Japanese Patent Application Laid-open No. 1973-
No. 10644, Japanese Unexamined Patent Publication No. 52-39417, etc. For example, a water-in-oil emulsifier (H
Using a hydrophobic organic dispersion medium containing LB3-6),
A water-in-oil emulsion of an aqueous solution of the unsaturated monopolymer is made, and 0.0% of the weight of the phase in which the initiator is dissolved is prepared. A reverse phase emulsion can be obtained by method K, in which the emulsion is heated in the presence of 2 to 0.2% of a peroxide polymerization initiator to polymerize the monomers. However, the reversed phase emulsions produced by these methods do not have long-term storage stability;
Since the polymer particles settle in 3 to 6 months, K must be stirred and dispersed again when used, and there is a risk that the functionality will be significantly reduced. In addition, the emulsion has several drawbacks such as high apparent viscosity and poor fluidity.

In addition, a phase inversion accelerator is required to rapidly and uniformly disperse the water-soluble or hydrophilic polymer in water in these reversed phase emulsions and to cause phase inversion and dissolution.
In 27, water-soluble surfactants such as polyoxyethylene (20 mol) alkyl fluorols,
Polyoxyethylene (20 moles), oleyl ether, polyoxyethylene (20 moles), stearyl ether, etc. are used. There is also a description of a one-component reverse phase emulsion in which it is added in advance to the emulsion after polymerization, but these reverse phase emulsions have a limit in solubility for uniform dispersion in water. Furthermore, since it has the disadvantage that it is difficult to obtain satisfactory long-term storage stability and fluidity, improvements in this area are desperately needed.

<<The Problem to be Solved by the Invention>> As mentioned above, the present invention improves the drawbacks of the conventional reverse phase emulsion carbonate, and has good storage stability over a long period of time, low viscosity, and good fluidity. Another object of the present invention is to provide a reversed phase emulsion in which a water-soluble or hydrophilic polymer is rapidly dispersed and dissolved in water through phase inversion, and maintains good workability over a long period of time.

(Example) Structure of the Invention and Means for Solving the Problems As a result of extensive research into surfactants used during polymerization or added after polymerization, the present inventors have discovered the following specific surfactants. It was found that a reversed phase emulsion containing the agent achieves the above-mentioned improvement objective, and based on this knowledge, the present invention was completed. That is, the present invention relates to a water-soluble or hydrophilic polymer reverse phase emulsion characterized by containing the following surfactants 1) to 5), and a method for producing the same.

1) Sorbitan fatty acid ester of HLH3-5.

2) Nonionic oil-soluble surfactants with molecules ii2000 or more.

3) A nonionic oil-soluble surfactant with a molecular weight of less than 2000 and an HLB of 8 to 10.

4) Water-soluble polyoxyethylene polyoxypropylene derivative.

5) Nonionic water-soluble surfactants other than 4) above iLB12 to 14.

The above-mentioned reversed phase emulsion of the present invention has a lower apparent viscosity and good fluidity than conventional reversed phase emulsions, has long-term storage stability, and has the advantages of being able to be quickly dispersed and dissolved in water through phase inversion. It has many features.

The reversed phase emulsion of the present invention contains five types of surfactants, and these surfactants are used during polymerization or added after polymerization.

Details of the five surfactants used in the reversed phase emulsion of the present invention are as follows.

1) Sorbitan fatty acid ester of iLB5-5 O Sorbitan fatty acid ester consists of sorbitan and lauric acid,
It is an ester with palmitic acid, stearic acid, and oleic acid, and is often a mixture of mono-, di-, and triesters, etc., and the HLB varies depending on the ratio, and the one used in the present invention is one with iL83-5. This nrubitan fatty acid ester is used during polymerization, and is preferably used in an amount of 0.5 to 6 parts per 100 parts by weight of monomer.
．． 0 parts by weight, particularly preferably 1.0 to 2.0 parts by weight. If the amount used is less than 0.5 part by weight, it will be difficult to maintain the stability of the emulsion. The amount is preferably 60 to 70% by weight of the total amount of surfactant used.

Commercially available sorbitan fatty acid esters used in the present invention include Rheodol AO-10, AU-15, and As-1.
0, SP-010, SP-SIO (all manufactured by Kao ■)
, Newcol 3-80 (manufactured by Nippon Nyukazai ■), and Cadenax SO-86 (manufactured by Lion ■).

2) Nonionic oil-soluble surfactant with a molecule t2 0 0 0 or more.

A high molecular weight surfactant having a weight average molecular weight of 2,000 or more and preferably soooo or less is preferably used, such as a block type polymer or a graft type polymer having a hydrophilic group and a hydrophobic group. Specifically, K is poly(12 Polyester-polyoxyethylene condensates such as monopolyoxyethylene-poly(12-hydroxystearic acid), polyoxyethylene-polyoxypropylene condensates such as polyoxyethylene-polyoxypropylene-polyoxyethylene, etc. , graft-type polymers made by copolymerizing lipophilic monomers such as ethylenediamine and polyoxyethylene-polyoxypropylene condensates, polyethylene glycol monomethacrylate and styrene, methyl methacrylate, ethyl methacrylate, and methyl acrylate. Can be done.

These surfactants are also used in the formulation, and the amount used is preferably 1.0 to 6.0 parts by weight, more preferably 1.0 to 4.0 parts by weight per 100 parts by weight of the single product. toX
If the quantity is too high, the stability of the emulsion during and after polymerization will deteriorate, and if it exceeds 6.0 wtg, the viscosity of the emulsion will increase, reducing dispersion or dissolution rate during phase inversion. It becomes like this.

Commercially available surfactants include No1 Perm B
-246, B-261 (both manufactured by ICI)
, Tetronik T-701, TR-702, TR-7
04, Pluronik L-101, L-121 (all made by Asahi Denka Kogyo ■), Emulgen'P-250 (Kao ■)
(manufactured by).

5) Nonionic oil-soluble surfactants with molecules [less than 2000} iL88-10.

Specific examples of the surfactant include polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene rubitan m fatty acid ester, etc. Preferred for the present invention are polyoxyethylene alkyl It is phenyl ether.

These surfactants are used as K phase inversion accelerators during polymerization and after polymerization, and the amount used is *-i.
0.1 to 10 tons per 100 tons of body weight during polymerization
S is more preferably 2 to 7 parts by weight, and the amount added after polymerization is more preferably 5 to 7 parts by weight than 1 to 8 parts by weight. The stability of the product cannot be maintained, and the dispersion or dissolution rate becomes slow.
Too much tAr of the emulsion. Mobility deteriorates.

Commercially available surfactants include Emulgen 10
4}', 105, 904, 905, 404, Reodore SP-1, 10% TW-8106 (all Kao Large)
, Ribonox NC-58, Dopanox 2 3 C-
C, 23D1 Rheox LC-38, LC-40 (all Lions, Newcol 150, 562
(all made by H Hon Emulsifier ■) etc.

4) Water-soluble polyoxyethylene polyoxy-1-robilene.

The polyoxyethylene polyoxy-1-robilene derivative in the present invention is a surfactant represented by the following general formula.

R}'h -(J-(EO)n ・(PO)mX In the above formula, ethylene oxide and propylene oxide have a block diagram, and the bond between the ethylene oxide block and the flobylene oxide block is the reverse of the formula above. Those in which the number of added moles n and m are preferably 10 to 25 are preferred, and those in which R is an alkyl group having 5 to 10 carbon atoms or a styryl group are preferred.

These conductors are used as phase inversion promoters after polymerization,
Its usage is 1~aMLt per 100 parts by weight of all monomers.
It is preferably 4 to 6N, more preferably 4 to 6N. If the amount used is less than 1 part sweet part, its effectiveness as a phase inversion accelerator will be low, and if it is used in excess of 8 parts by weight, the storage stability of the emulsion may be impaired.

As a commercially available surfactant, Emulgen L-40 (manufactured by Kao ■) can be mentioned.

5) A nonionic water-soluble surfactant with an HLB of 12 to 14 other than 4) above.

Examples of nonionic water-soluble surfactants with HLB of 12 to 14 include polyoxyethylene alkyl 7-enyl ether, polyoxyethylene alkyl ether, and polyoxyethylene lupitan fatty acid ester. It is ethylene nonylphenyl ether.

These surfactants are used as phase inversion accelerators after polymerization, and the usage rate is 1 to sx per 100 parts by weight of the entire monomer.
Preferably, it is its.

If the amount is less than 1 part by weight, the phase inversion rate may be slow and the apparent viscosity of the reversed phase emulsion may not be low.
If the emulsion exceeds the ft part, the stability of the emulsion may be impaired and the fluidity may also be impaired due to thickening, so it is preferable to avoid using the emulsion for toilet use.

Commercially available surfactants include Emulgen 109.
P, 108, 420, 916, 911, P 1-2
0 '1', Rheodor '1'W-1,120 (all manufactured by Kao ■), Newcol 8 6 4, 1100
(All manufactured by Nippon Nyukazai ■), Ribonox NC-10
0, NC-95, (JC-95, OC-100, Dovanox 251 (all manufactured by Lion ■).

As a method for obtaining the reversed phase emulsion of the present invention,
An inert hydrophobic organic solvent K After polymerization, a monomer aqueous solution that gives a water-bathable or hydrophilic polymer is dispersed in the presence of the above-mentioned surfactant, and polymerization is carried out using an oil-soluble radical initiator. A specific method is used.

The monomer that provides water-bathability or hydrophilic polymerization is preferably acrylamide, methacrylamide, sodium acrylate, sodium methacrylate alone, or a mixture thereof. It is also preferable for the present invention to use a single substance such as +L maleic acid, itaconic acid, vinyl sulfonate, styrene sulfonate, dimethylamino methacrylate, etc. in small amounts. Note that a small amount refers to 30ii of all single units.
Refers to i% or less. The monomer concentration in producing the reversed phase emulsion is preferably such that the polymer concentration in the final reversed phase emulsion is 20% by weight to 5% by weight. If the # degree is less than 20!it%, it is uneconomical due to the cost of transporting the product, and if it is more than 50!it%, the fluidity and stability of the emulsion may be impaired.Polymer in a reverse phase emulsion The molecular weight is preferably a polymer having a weight average molecular weight of 100,000 or more because of the required property of reverse phase emulsion 1K that the polymer can be quickly dispersed and dissolved in water, but from 1000 to soooooooo
A polymer having a molecular weight within this range can be used as a reversed phase emulsion that exhibits the effects of the present invention.

Hydrophobic organic solvents used in reversed phase emulsions include:
There are a wide range of examples including hydrophobic aliphatic or aromatic hydrocarbon liquids, vegetable or animal oils, and modified oils of these oils. Preferred among these are aliphatic hydrocarbon liquids such as mineral oil, kerosene, naphtha, paraffin and isoparaffin, and aromatic hydrocarbon liquids such as benzene, toluene and xylene. Particularly preferred are solvents such as kerosene, Exol 80, Exol 100, Isopar M (all manufactured by Ekun Chemical ■), and Surtrex 60 (manufactured by Mobil Oil ■).

There are no particular restrictions on the oil-soluble radical initiator used to polymerize the monomers, and examples include azo compound initiators such as azobisimptilonitrile and azobisdimethylpaleronitrile, penzoyl peroxide, t-butyl peroxide,
Organic peroxides such as t-butyl hydroperoxide and imptyryl peroxide are used.

Effects> Conventionally, methods for improving the stability of reversed-phase emulsions include reducing the particle size, increasing the surfactant concentration, and increasing the viscosity of the emulsion to delay particle sedimentation. However, both methods impair the fluidity of the emulsion blind. Also, emulsi g/
In order to speed up the phase inversion dissolution rate of K, water-soluble surfactants are added during and after polymerization to make the phase inversion of water-in-oil emulsions to oil-in-water emulsions as easy as possible. However, in this method using only a water-soluble surfactant, the long-term storage stability of the reverse phase emulsion cannot be maintained, and the emulsion may gel or its fluidity may decrease.

Therefore, it has been extremely difficult to obtain a reversed phase emulsion that is superior in all three aspects of stability, fluidity, and solubility. Nevertheless, due to the surfactant combination 7 mentioned above, by using part of the oil-soluble surfactant as the phase inversion surfactant, the particles do not settle at all at room temperature and freeze. Stable even when thawed (for example, even if it loses its fluidity at temperatures below 0°C and becomes frozen, it can be brought back to room temperature without stirring and returned to the original emulsion, and its original physical properties are also maintained. Compared to conventional reversed phase emulsions, which do not suffer any damage, it is possible to obtain a reversed phase emulsion with excellent stability. Furthermore, this reversed phase emulsion had excellent fluidity with an apparent viscosity of 100 PS or less, and also had an extremely fast dissolution rate in which the hydrophilic polymer was quickly dissolved when added to water. The reason why the reversed phase emulsion obtained by the present invention has such characteristics is not clear, but the surfactants conveniently used in the present invention do not exhibit the desired effect alone. In addition, the use of surfactants with a wide range of properties from oil-soluble to water-bathable, and the use of characteristic surfactants (polymer surfactants) This is thought to be due to the delicate balance of the combination of agents, polyalkylene oxide derivatives).

EXAMPLES> The present invention will be described in more detail with reference to Examples below, but the technical scope of the present invention is not limited by Example K.

In addition, the measurement method of emulsion viscosity and the evaluation of phase inversion viscosity in the examples were performed by the method described below.

・Measurement method of emulsion viscosity Adjust the solid content to 30% and measure with a Pruckfield viscometer at 25°C and 60 rpm.

・Evaluation of phase inversion viscosity: Dissolve the reversed phase emulsion in water to obtain a water bath solution of 91% polymer purity.

For example, 5 g of a reverse phase emulsion with a solid content of 60 wt.
rpm). The viscosity 5 minutes after adding it to water (
(Measure with stirring stopped) and measure the viscosity one day later (viscosity was measured using a Pruckfield viscometer at 25°C and 30 rpm).
).

Example 1> ・Oil phase adjustment oil・・・・・・・・・ Kerosene
100g surfactant... Emulgen 9 0 5 (
HLB9.2) 6g Hiberma B-2 46 (HLH5~6) 3g Rheodol AU-15 (}iL813.2) 1g ・Aqueous phase adjustment Acrylamide Sodium acrylate Ion exchange water ・Phase inversion surfactant Emulgun 905 4g Emulgen 911 (HLB15.1) 4g 70g 30g 100g Emulgen L-404g ・Initiator V-70 (Wako Pure Chestnut) 0.2g Toluene 15g Dissolve the above surfactant in kerosene, adjust the oil phase to P4, Separately, prepare an aqueous phase by dissolving acrylamide in a 23% aqueous solution of sodium acrylate. The oil phase was placed in a jacketed glass reactor, and the oil phase was added thereto under high speed stirring (500-700 rpm).
) was slowly added to the aqueous phase, and stirring was continued for 10 minutes to prepare an emulsion. After that, the stirring number was set to 15 O rpm.
The internal temperature was adjusted to 30° C., and a nitrogen atmosphere was created in the reactor using a nitrogen bubbling trap. Next, 0.2 g of a radical initiator (V-70 Wako Pure Chemical Industries, Ltd.) dissolved in 15 g of toluene was added to the reactor to initiate polymerization. After polymerization was carried out for 3 hours, the temperature was adjusted to 30° C. or lower and the above phase inversion surfactant was added.

The results are shown in Table 1. From these results, the reversed phase emulsion composition obtained in Example 1 had no aggregates at all during polymerization, the emulsion viscosity was very low at 36 cps, and the fluidity was good, and the phase inversion rate was also high after 3 minutes. The phase inversion viscosity is quite close to the phase inversion viscosity after one day, so it can be said that the phase inversion viscosity is fast.

The evaluation of aggregates during polymerization in this table is ◎: No aggregates Δ: Partially aggregated ×: Aggregate or gelation of polyester It becomes.

Examples 2 to 5, Comparative Examples 1 to 4> Polymerization was performed by the method described in Example 1 while changing the surfactant composition.

The composition and properties regarding the reversed phase emulsion are shown in Table 1K.

Example 6> Emulgen 905 (}iLB9.2) was mixed with Emulgen 10.
The procedure is the same as in Example 1 except that 4P (HLB9.6) is used.

Comparative Example 5> Emulge 905 (HLB9.2) was mixed with Emulge y903.
The same procedure as in Example 1 was carried out except that (HLB7.8).

Comparative Example 6> Emulgen 905 (HLB9.2) was converted into Emulgen PM-
Example 1 except that 20T (HLB1 2.2)
Apply the same pressure.

Example 7> Rheodol IW-L12 was used as a nonionic water-soluble surfactant.
The pressure was the same as in Example 1 except that the pressure was set to 0 (HLB 13.3).

Example 8> Adding a nonionic water-soluble surfactant to Holie Margay P1-2
The same procedure as in Example 1 was carried out except that it was set to 0T (HLB12.2).

Comparative Example 7> A nonionic water-soluble surfactant was used as Emulgen 930 (HL
The procedure is the same as in Example 1 except that H1 5.1).

Example 9 Molecule! Nonionic soluble surfactants of 2,000 or more are called Tetronic 704 (ethylenediamine-boritulopyrene oxide-polyethylene oxide, K.,, etc.) and Kazuhiro Go, Kagyo, Yu.). Other than that, K is the same as in Example 1.
do.

Example 10 The organic solvent was Isovar M (manufactured by Exxon), and the initiator was Isophityryl peroxide (manufactured by NOF ■).
．． The pressure was the same as in Example 1 except that the pressure was 2 g.

Example 11> The aqueous phase was mixed with 100 g of acrylamide and Og of sodium acrylate.
The procedure of Example 1 was repeated, except that 100 g of water and 0.1 g of the oil bath surfactant Emulgen 905 (HLB92) added during polymerization were used.

Example 12> 80g of kerosene. The aqueous phase was made of 20 g of acrylamide, 80 g of sodium acrylate, and 120 g of water, and 1 portion of Emulgen 905 (HLB9.2) added during polymerization was added.
The properties of the emulsions of Examples 6 to 12 and Comparative Examples 5 to 7 are shown in Tables 2 and 3.

01 Effects of the Invention As detailed above, the present invention K is able to obtain a reverse phase emulsion with excellent stability, fluidity and solubility. There is a huge contribution to be made to various industries that require processing.

Claims (1)

[Scope of Claims] 1. A water-bathable or hydrophilic polymer reversed-phase emulsion characterized by containing the following surfactants 1) to 5). 1) Sorbitan fatty acid ester with HLB of 3 to 5. 2) Nonionic oil-soluble surfactant with a molecular weight of 2000 or more. 3) A nonionic oil-soluble surfactant with a molecular weight of less than 2000 and an HLB of 8 to 10. 4) Water-soluble polyoxyethylene polyoxypropylene derivative. 5) A nonionic water-soluble surfactant with an HLB of 12 to 14 other than 4) above. 2. After emulsion polymerization of water-soluble or hydrophilic monomers in an oil phase using the surfactants 1) to 3) described in claim 1, 3)～
4) A method for producing a reverse phase emulsion of a water-soluble or hydrophilic polymer, which comprises adding a surfactant.