JPS5910685B2 - SBR latex industrial antifoaming agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an emulsion-type antifoaming agent for the SBR production process by emulsifying a specific polyether polyol and a selected emulsifier in water.

When producing SBR, styrene-butadiene monomer is emulsion polymerized using an activator such as fatty acid soap or rosin acid soap, and then unreacted monomers are distilled off under reduced pressure or steam distillation. Due to foaming problems, work is seriously hindered. For this purpose, the special public
As shown in Japanese Patent Publication No. 6-17202 and Japanese Patent Publication No. 51-959, antifoaming agents such as silicone and polyether are generally used. Emulsion type antifoaming agents are widely used especially for the purpose of improving workability during use, but conventionally silicone,
Emulsion-type antifoaming agents such as wax, mineral oil, polyether, metal soap, and silica are known, but they lack emulsification stability and cause problems such as clogging of piping from the antifoaming agent storage tank to the polymerization reaction system. None of the powers have been satisfactory in terms of sustainability. The object of the present invention is to improve these drawbacks and provide an emulsion-type antifoaming agent for the SBR manufacturing process that has excellent initial foam-breaking properties and sustained defoaming power, and has a stable emulsified state. The antifoaming agent of the present invention is an aqueous emulsion type, and has a molecular weight of 2000 to 8 as an essential component.
000 polyether polyol (I) and H
Polyhydric alcohol fatty acid ester with LB of 2 to 8 (■-1
) one or more polyether polyols with HLB of 13 or more (H-2-1), polyoxyethylene sorbitan fatty acid esters with HLB of 13 or more (-2-2), and HLB
One or more compounds (-2) with an HLB of 13 or more selected from polyoxyethylene polyol fatty acid esters (Kawa-2-3) with a HLB of 13 or more, and castor oil or hydrogenated castor with an HLB of 5 to 14. Oil polyoxyalkylene glycol ether (H-3-1), HLB is 5-1
4 polyoxyalkylene glycol mono(alkyl)
Aryl ether (H-3-2), phosphoric acid ester of polyoxyalkylene glycol mono(alkyl)aryl ether with HLB of 5 to 14 (-3-3), and HLB
is mixed with one or more compounds (-3) having an HLB of 5 to 14 selected from phosphoric acid esters (-3-4) of polyoxyalkylene glycol monoalkyl ethers having an average HLB of 5 to 14. - 11 mixtures U).

In addition, throughout this specification, the HLB calculation method is Glyphin for fatty acid esters of polyhydric alcohols, polyoxyethylene polyol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and mono(alkyl)aryl ethers of polyoxyethylene glycol. (Gr.
iffin) method, polyether polyols are HLB
= 0.0980x + 4.02 (where x is the cloud point of the 1096 aqueous solution (°C)), and for other substances, refer to the Surfactant Handbook (published on July 5, 1960, published by Sangyo Tosho Co., Ltd.) The value measured by the HLB measurement method described on page 319 was used. Various conventionally known polyether polyols (1) can be used as the polyether polyol (1) used in the present invention, such as water, ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, engineered ethylene diamine, Molecular weight 2 obtained by adding alkylene oxide, such as propylene oxide, butylene oxide, etc., to an active hydrogen-containing compound, such as phenol Al4,4'-diaminodiphenylmethane, etc.
Examples include polyether polyols having antifoaming properties of 000 to 80,001, preferably 3,000 to 8,000.

Further, it is preferable that the polyether chain contains no oxyethylene groups as much as possible, but it may contain a small amount of oxyethylene groups that does not substantially affect the antifoaming properties.

Furthermore, the polyhydric alcohol fatty acid ester (-1) with an HLB of 2 to 8, the compound (-2) with an HLB of 13 or more, and the compound (-3) with an HLB of 5 to 14 used in the present invention are all themselves It is a known compound. Examples of the polyhydric alcohol used to obtain the polyhydric alcohol fatty acid ester (-1) include the same polyhydric alcohols as exemplified above in the explanation of the polyether polyol (1), and examples of the fatty acid include lauric acid and palmitic acid. acid, stearic acid, oleic acid, oil fatty acid, tall oil fatty acid, soybean oil fatty acid, beef tallow fatty acid, etc. having 8 to 22 carbon atoms, preferably 12
~20 fatty acids are exemplified.

Further, as fatty acids, fatty acids having the same number of carbon atoms obtained from hydrocarbons etc. by chemical synthesis can also be used. These fatty acids are also used when obtaining polyoxyethylene sorbitan fatty acid ester (-2-2) or polyoxyethylene polyol fatty acid ester (-2-3).

Polyether polyol with HLB of 13 or more (-2-1
) are generally referred to as Pluronic type or Tetronic type polyether chains in which the polyether chain is a polyoxyethylene/polyoxypropylene block polyether chain, and particularly preferred are polyether chains with a molecular weight of 2,000 to 20,000. It is of a certain degree. Preferred polyoxyalkylene glycol mono(alkyl)aryl ethers (-3-2) include nonylphenol polyoxyethylene adduct, paracumylphenol polyoxyethylene adduct, octylphenol polyoxyethylene adduct, dinonylphenol polyoxy Ethylene adducts or all or one of these polyoxyethylene chains
Examples include those in which the moiety is replaced with an oxypropylene chain. Preferred phosphoric esters of polyoxyalkylene glycol mono(alkyl)aryl ether (H-3-3) and phosphoric esters of polyoxyalkylene glycol monoalkyl ether (H-3-4) have 8 to 8 carbon atoms. It has 30 alkylaryl or alkyl groups.

Examples of the polyoxyalkylene glycol ether (-3-1) of castor oil or hydrogenated castor oil include those obtained by adding ethylene oxide and/or propylene oxide to castor oil or hydrogenated castor oil.

Polyhydric alcohol fatty acid ester (]f-1), a compound with an HLB of 13 or more (-2), and a compound with an HLB of 5 to 14 (-3) should be mixed so that the average HLB is 5 to 11. However, it is undesirable to have a mixing ratio in which only one component is extremely high or low, and in practice, the weight ratio is polyhydric alcohol fatty acid ester (-1) 4
Compound (-2) with HLB of 13 or more
50 preferably about 15 to 44 (f), HLB 5 to 1
Compound (H-3) of No. 4 is preferably adjusted within a range of 1 to 10%, preferably 2 to 6%.

The composition of the present invention comprises a polyether polyol (1) and a mixture () having an average HLB of 5 to 11 in a weight ratio of 100:5.
~100:40, preferably 100:10-100:3
It is preferable that the content be at a ratio of 0.

One preferred method for obtaining the composition of the present invention is a mixture of polyether polyol (1) and an average HLB of 5 to 11 (
) and then mixed with water and emulsionized using a suitable method. Water can be added in several stages before it is actually used as an antifoaming agent, such as first creating an emulsion in which water accounts for approximately 1/2 of the weight, and then adding water at the site of use. The undiluted solution can be diluted and used. The solid content concentration in SBR latex at which the composition of the present invention exhibits an antifoaming effect is 0.
00101) to 0.1(f), but no matter how little the composition of the present invention has a negative effect on latex,
Since there is also the problem of wastewater treatment soil, the practical concentration is 0.
The content is preferably about 0.001 to 0.05%.

Formulation example 1 Various compounds other than water, 44 parts by weight of polyether polyol (glycerin base MW = 3000) and average HLB
7. Sorbitan monooleate (HLB4
．． 3) Take 4 parts, 1.5 parts of polyoxyethylene sorbitan monostearate (HLBl4.9), and 0.5 parts of hydrogenated castor oil polyoxyethylene adduct (HLB6.6) and heat to 60-70°C. Dissolve and stir to homogenize using a homomixer.

Gradually add 50 parts of warm water at about 60℃ and change from W/O type to O/O type.
A test product 1 is obtained by phase inversion emulsification into W type to obtain an emulsion. Formulation example H Polyether polyol (glycerin base MW = 40
00) 44 parts by weight and 4.5 parts of sorbitan monooleate (HLB 4.3), Pluronic F-68 (polyether polyol block polymer manufactured by Asahi Denka Kogyo Co., Ltd.) and HLB 5.0 to give an average HLB of 6.6. 4) 1.0 copy,
Take 0.5 part of Gafuak LE5OO (polyoxyethylene alkyl or alkylaryl ether phosphate, manufactured by Toho Chemical Co., Ltd., HLB 9.5) and homogenize it by stirring at about 60-70°C in the same way as in Formulation Example 1. After that, add hot water at about 60°C. 50
This is used as a test product in which an emulsion is obtained by gradually adding 50% of the emulsion and performing phase inversion emulsification.

Blend Example: 45 parts by weight of polyether polyol (trimethylolpropane base MW=4000), 3 parts of sorbitan monooleate (HLB 4.3), and 1 part of sorbitan monostearate (HLB 4.7) to give an average HLB of 6.3. 2
5 parts, polyethylene glycol (600) oleate (
1.0 part of HLBl3.5) and 0.25 part of nonylphenol polyoxyethylene adduct (HLBl3.3) are heated at about 60-70°C and stirred uniformly using a homomixer.

A test product was obtained by gradually adding 49.5 parts of warm water at about 60°C to carry out phase inversion emulsification to obtain an emulsion. EXAMPLE A defoaming power test was conducted using each test product and a comparative product.

Comparative product A is polyether polyol-based 50 (F
Comparative product B, which is an emulsion type antifoaming agent, is a silicone emulsion with a solid content concentration of 20%. Comparative product C is a commercially available antifoaming agent based on self-emulsifying polyether with a solids content of 100%.

The results of performance tests such as defoaming power and emulsion stability are shown in Tables 1 and 2.

The defoaming power test was carried out by taking 200 d of latex before recovery of SBR unreacted monomers into a 1 t measuring cylinder with a diameter of 5 cm, and aerating the latex from the bottom at 10 t/min to determine the change in foam amount over time.

Measurement Conditions: 50°C 0 Each defoaming power sample was left at 5°C, 25°C, and 40°C for one month using an air constant temperature bath, and the condition was visually judged.

O Good emulsifying property × Separation occurs

Claims (1)

[Scope of Claims] 1. As essential components, (I) a polyether polyol with a molecular weight of 2,000 to 8,000, (II) a polyhydric alcohol fatty acid ester with an HLB of 2 to 8 (II-1), a polyether polyol, and a polyol. A compound (II-2) with an HLB of 13 or more selected from the group consisting of oxyethylene sorbitan fatty acid ester and polyoxyethylene polyol fatty acid ester, and polyoxyalkylene glycol ether of castor oil, which may be hardened, polyoxyalkylene glycol A compound having an HLB of 5 to 14 selected from the group consisting of mono(alkyl)aryl ether of Average HLB obtained by mixing one or more compounds from each group of II-3)
Aqueous emulsion type SB containing a mixture of 5 to 11
R latex industrial antifoaming agent.