JPS5921640A - Preparation of zinc acrylate - Google Patents

Abstract

PURPOSE:To obtain the titled substance easily in high yield, by reacting acrylic acid with a zinc compound in a solvent in the absence of water, adding a solution prepared by dissolving stearic acid under heating to the reaction solution or a filtered material thereof to form a slurry, and drying the resultant slurry under reduced pressure. CONSTITUTION:Acrylic acid is reacted with a powdery zinc compound, e.g. zinc acetate or zinc carbonate, in a solvent, e.g. methanol or benzene, in the absence of water, and a solution prepared by dissolving 5-20pts.wt. stearic acid, based on 100pts.wt. acrylic acid, underheating is added to the resultant reaction solution or the stearic acid is added to the reaction solution heated at 70-90 deg.C and stirred. The resultant mixture is then dried under reduced pressure to give the titled substance. The acrylic acid may contain a little amount of water without problems, and even the contamination due to a polymerication inhibitor, e.g. hydroquinone, causes no problem.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a zinc salt of acrylic acid, and more particularly, the present invention relates to a method for producing a zinc salt of acrylic acid. ``After carrying out the reaction in a solvent, a solution of stearic acid dissolved in the solvent by heating is added to the reaction solution or to the filtrate to form a slurry, which is then dried under reduced pressure. The present invention relates to a method for producing zinc monoacrylate salt.

Conventionally, there is a well-known method of reacting acid and zinc compound in a solvent, removing the solvent under reduced pressure after the reaction is completed, or filtering and drying under reduced pressure to obtain zinc acid. There is. According to this method, the reaction product sticks to the inner wall of the reactor 2g or during stirring, or forms large lumps, causing process problems. Furthermore, when the solvent is removed under reduced pressure, the solvent contained in the produced zinc acrylate (IJ) is scattered, but at the same time, the zinc acrylate is also violently removed.
The problem was that the recovery of the solvent was difficult and the economic loss was large.

The present inventor has conducted various studies as a method for overcoming the drawbacks described in , and found that after the reaction between acrylic acid and zinc compound in a solvent is completed, a solvent is added to the reaction solution or to the filter/dental movement. Next to the 100% acrylic acid added in the
゛ Add a solution prepared by heating and dissolving 45 to 2-fpgJ parts of stearic acid, or 70'C-9
Add stearic acid to the reaction solution heated to 0°C +sHf+
It was found that by drying under reduced pressure, the defects described in 1- were overcome and the desired powdery solid (!) was obtained in 2. +
Completed investigation.

Thus, the invention is an industrially viable method for overcoming the drawbacks of the conventional adhesive method.
It provides the power method, operation and control (1"/1" of control).
The present invention provides a method for producing high-yield acrylic acid zinc powder.

+ As the solvent used in the invention, hydrocarbon compounds are suitable, and in Shell Isu Example and 17, methanol, benzene,
Examples thereof include l·no1/ene, xylene, n-hebutane I, 11-hegisan, and the like.

The acrylic acid used in the present invention is 11n monoacrylic acid which has not been dissolved in water, but it may contain a slight amount of &. Furthermore, acrylic 11/hydro[1 quinone contained in acid.

High 1 and 1 ginone monomethyl ether etc. polymerization prevention + I:
Wll's confusion does not cause any trouble.

The zinc compound used in the present invention is
．． 'Use 1 +1-f-. ! 111
Examples include zinc oxide, hydroxide, zinc oxide, lead, and carbonic acid! An example is along 411.

iX1' response of acrylic acid and zinc compound? Crystal Iθ゛ is especially 1 grudge, 1 te l <) LJ) tet (H squid, II
T*1. <c, 90'CL'sF is desirable.

Anti-"l't,?!tA /l is soil") Sieve < tc and some market reactions are 10U product Jun'e < f, 7ro.

1.nl of stearin [17 each] was heated and dissolved in Z medium.
'lY: You can go to t'1 at night to complete the reaction of stearic acid (5 degrees).
can.

L゛1: 119 pages of the invention will be explained using an actual MQ example.

Example 1! LIHi7600 g J: TOTVEN200
0mOtowo5 p i7) し A"1) Formula)'/','
IC7 (9S Ki'l' Nit1 included, Kagimazena r arm 1% cloudy, next Ni Y acrylic acid 1θ6Qg 30
'-) between 7'morning F' L=te city 11 c wheat, always? 0 minutes 1-'-! : l, i,, sa→J-ta. 1 to 1 Oa of stearic acid to toluene
[] 0yn() plus IHI and 711) ~ 50 and i+
o % solution: l+'r l, t i')\liquid'<e 4
' + 11, then 3 Q If > Stir, make slurry "black, ' 4 + 'ia, coated with tearic acid. Then 50?; , 120 ~ 60 + 11H
Heat for 3 hours at α's reduced pressure F, distill out the produced water and toluene, and dry. -]'Ivy. 21-tinged with stearic acid -≠-祠←←Aku IJ) acid lI + r lead 1
620g was obtained. There were three heating areas on the skin. When drying under reduced pressure, <1: Made acrylic +4? Almost no scattering of lead was observed, and no solidity was observed on the inner wall of the reactor. In addition, even in the drying device, the child remained sore and no lumps were observed.

, -Jf is the same for all of the following embodiments 2 and 66.

Example 2 1400 g of acid and 1960 mO of toluene were mixed at 10
The mixture was poured into a jacket-type Nigu (e) and thawed to homogenize. Next, while continuing the mixed operation, acrylic acid 247
After heating 7g for 60 minutes at 71MF, 40~50''C,
The reaction was carried out for 1 hour. After the reaction, stearic acid 37
Add 6g and raise the temperature to 75 while kneading.
The 0 minute stirred product was coated with stearic acid. Next 300~200 ffa+og nont*I [Fte 2 o'clock 1fl17+11+? ! t.

Then, the produced water and toluene were distilled, dried in a vacuum chamber, and 570 g of acrylic acid [111 lead] was added. , - of the IQ product) rlA'! H reduction is 0.25
'Ih 7=A-).

Example + for j17 +, 'lj' (2260g and May / -
, rv 200 +mp.

And 10C fil jacket type --- goo 1 fil
Add 4000 g of acid, 130 minutes, and mix the slurry with drops. Ta. /1m F't'z1 hour anti-1, I-1':<f'r/)7',:('2
, warm IQ 40% 50 c nitestearic acid (320
Add 1. Knead with: 1-tingt<? jw.

;I will not be able to reach Jihakuket'-(I mountain, l crystal pull 7D(
-After distilling Megnol, from Nigu +(
Drying was carried out using a low +1 to N drying method for 2r+ and 40't. -11 Sen 4 Aku'J / Citric Acid 111 Lead 629
I got 0B7. Heating ii and IA was 25 kan.

Example 4 60 g of zinc oxide and 1500 ml of n-hexane were placed in a glass 2e colben equipped with a 4-bean stirrer, a droplet, and a cooling condenser. 106 g of IJ) acid was stirred for 40 minutes while stirring at 71°C, and the reaction was carried out at 55 to 65'C for 4 hours. After the reaction was completed, the product was taken out from the Kolben and filtered with a vacuum filter. .

Transfer the 11 plants to a mortar and add stearin lv116gc.
A 40° C. solution obtained by heating and dissolving 100 ytre of n-hexane was added, kneaded for 40 minutes, and heated with hot air at 50° C. for 1 hour to dry. 11 pieces of diacrylic acid
1) 157 g of lead was obtained. The weight loss on heating was 0.3%.

Example: 5e of 900g of zinc oxide and 3000yne of benzene
After the jacket was formed, the mixture was charged into a W mixer and stirred and mixed to make it suspended.Next, acrylic acid 1590 was added dropwise for 60 minutes while stirring and mixed, and the reaction was carried out as usual for 60 minutes. After completion of the reaction, stearic acid sogv benzene 50
Add 0 m(lk) and heat-dissolved solution at 45-5 G'C, stir and mix for 0 minutes, reduce the pressure of the resulting slurry to 275-11011 JH, and jacket with 50-C T-grade water. The product was heated for 2 hours to distill out the produced water and benzene, and continued drying to produce 492 g of lead in 1 liter of acrylic acid coated with stearic acid. , 0.25 ton.

Example 6 560 g of zinc oxide and 3000 g of xylene were stirred in a clear microwave, 11 cold [Panto, cold Jill condensate →)-1]
Add 425g of acrylic acid to a 5e kolben in a sintered glass and stir for 30 minutes to make a suspension. The reaction was carried out for an hour. After the reaction was completed, the product was taken out from a kolben, filtered for 1" (11 degrees) using an empty filter mixer, and the volatile content was reduced to 0.5 °C or more with hot air at 50'C. Add 1 more of this product I to a jacket type Nigu, add 69.5g of stearin H to 450ynQ of xylene, and heat at 45-50'C.
The resulting slurry was heated under a reduced pressure of 150 to 50 mMHg for 2 hours, heated for 2 hours, and mixed with xylene for 30 minutes. Distilled, continued drying, and coated with stearic acid Aku IJ 7 acid! 1 [944 g of lead was obtained. The volatile matter of the obtained product was 0.3.

Example 7 When 601 parts of zinc acrylate obtained in Example 1 was kneaded with 100 parts of polybutadiene using a 6-inch roll, no agglomerates were observed in the rubber, and no adhesion to the roll surface was observed. was hardly recognized.

Comparative Example 1 The same operation as in Example 1 was carried out except that after the completion of one reaction, stearic acid was added to toluene and a heated solution was added to coat the product.

When drying under reduced pressure was carried out after the completion of the reaction, the acid salts were significantly scattered and entered the distilled solvent, making its recovery difficult. In addition, it is quite complicated to recover the zinc oxide (IJ) scattered in the reactor, clean the reactor, and remove the reactant solidified on the inner wall of the reactor.
) Zinc chloride also sticks and there is a lot of loss due to scattering (1,120
It was gr. As it dried, it was partially observed that it formed into large lumps, and it was quite difficult to crush them.

Comparative Example 2 Aku IJ obtained in Comparative Example 1)
17. When 30% IV part of the crushed material was kneaded with 100 parts by weight of polybutadiene rubber using a 6-inch roll, a significant amount of agglomerates of 5 silks were formed in the comb, and the roll Adhesion to the surface was also significant.

Patent Applicant: Sumitomo Rubber Industries, Ltd. -] Three consecutive TE documents (spontaneous) 1. Indication of [1982 Patent Application No. 118069 2, Name of the invention, Process for manufacturing zinc acrylate 3, Relationship with the amended matters + 1] Attached is the patent applicant's specification 5, the full text of the statement of contents of the amendment. First, correct it as follows.

Details-) 1. Name of the invention 2. Process for producing lead III acrylate 2. Permit request 21.
This is a method for producing zinc acrylate, which is characterized by adding and stirring stearin 11ρ (drying).

6 Light 11L1 details, detailed explanation ＼ Komei is related to the production method of zinc salt of acrylic acid, and furthermore, Nl: L, < is the reaction of anrihanoic acid and 1lli lead compound) to produce the acrylic eye 2 jllj complex by force. 5. Incubate once, add water to the solution and react in a solvent, then add stearic acid to the solution, stir, and dry) 11 ^・Special?acrylic acid 1
The present invention relates to a method for manufacturing it-in.

? ! After that, acrylic acid and 1111 lead compound were reacted in a solvent, and after completion of T'y, the solvent was removed under reduced pressure, and 11. ) The method of drying the bending resistance Ff, acrylic I, and increasing the bending resistance W) is well known. According to this method, the reaction product is 1. (Written by Yaura Shocking L (Kajjf
f Shifukori friendki lumpy? This causes a problem, and the munimari mata ζ becomes extremely convex.

Also, when the solvent is removed under reduced pressure, the acrylic acid produced
) v1 The solvent contained in Shunzinc scatters, but at the same time, zinc acrylate also scatters violently, so it is difficult to collect (・
However, the problem was that it was difficult to recover the solvent, resulting in heavy economic losses.

For those who are uncertain, the above-mentioned shortcomings should be taken into consideration, and +j
li /4r, + 7 After the reaction of acrylic acid and 111 lead compound in medium was completed, 100 parts f of acrylic acid added to medium #I was added to the reaction solution. Heat 1 part of stearic acid f'? I
1llvL.

Add and stir the melted τfk, or 40υ~9o゛c
Heat to 1. It was found that by adding stearic acid to the two reaction surfaces, stirring, and then drying, the above-mentioned deficiency could be overcome and the desired shape 1-11 could be obtained, and the present invention was completed.

Thus, the present invention provides a method for preparing zinc acrylate powder that is extremely advantageous for the T industry and overcomes the drawbacks of conventional manufacturing methods, and is extremely easy to operate and control, and has a high yield. When compounded into rubber with acrylic acid 1111 lead powder initiator, heating (・) reaction [7.
Although it acts as a cross-linking agent, the oxide tends to decompose under acidic conditions, and stearic acid is compounded into rubber and its fl'1 polymers. It is known that it acts as an organic acid.

Therefore, the addition of stearic acid (in a fluid system) is undesirable from the viewpoint of the quality of the vulcanizate, and it has not been done in the past. Like m
By adding stearic acid, which was considered unsuitable for oxide vulcanization systems, during production of water-based 1; IITI example: When used as a co-crosslinking agent in zinc white and oxide (historically composed of co-crosslinked ml and polybutadiene) as a fossil conditioner, the physical properties are significantly reduced due to the decomposition of the peroxide. Contrary to the expectation, the sum of the obtained balls is
So1. It was &L<good.

Furthermore, it was also observed that the vulcanized physical properties (e.g., inner core hardness, toughness (!'I:)) were further improved compared to vulcanizates made using acrylic 1Ili lead made without the addition of stearic acid. The feel and sound of the two-piece golf ball produced using this golf ball when hit were sufficiently satisfactory as a golf ball.

The solvent used in the present invention includes many hydrocarbon compounds, and specific examples thereof include methanol, benzene, toluene, xylene, n-hebuta7, and n-hexane.

The acrylic acid used in the present invention is undiluted Acrylic acid with normal water, but may contain some amount of water. Furthermore, the mixed pressure of polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether/V contained in acrylic acid does not cause any problem.

The zinc compound used in the present invention is commonly used as a powdery solid. Specific examples of zinc compounds include zinc oxide, zinc hydroxide, a-lead carbonate, and zinc bicarbonate.

The reaction humidity between acrylic acid and the zinc compound is not limited to Y or ν, but is preferably 90° C. or higher.

If the reaction temperature is too high, some polymerization reaction force will be generated and the purity of the product will be poor.

Stearic acid may be added to a hot solution of a solvent, or stearic acid may be added to a solution after the reaction has been completed.

Hereinafter, the present invention will be explained with reference to Examples.

Example 1 600 g of r faecal zinc and 2000 m (l) of Toluev were placed in a 5e jacket type mixer, suspended while stirring, and then 10 boys of acrylic acid were added dropwise over 30 minutes to mix. The reaction was carried out for 60 minutes using an e-trowel at room temperature. After the reaction, 130v of stearic acid was added to 100v of toluene.
In addition to m1, a solution heated and dissolved at 45-50°C was added, stirred for 50 minutes, and the slurry was strained to coat the product with stearic acid. Then 50'C, 12
It was heated for 3 hours under a reduced pressure of 0 to 6 Q mmHf to distill out the produced water and toluene and was dried. 162 mF of acrylic former lead lead coated with stearic acid was obtained. The loss on heating was 03. During vacuum drying, there was almost no scattering of the generated lead acrylate, and no solidity was observed on the inner wall of the reactor.The particles remained 1111 even after drying. , no lumps were observed.

〆The same 4f can be said for everything from Example 2 of F to red.

Example 2 1,400 g of zinc oxide and 1,960 g of toluene
The mixture was placed in a 0e jacket type Nigu and kneaded to make it homogeneous. Next, while continuing the kneading operation, acrylic acid 247
71 for 60 minutes, the reaction was carried out at 40-50'C for 1 hour. After the reaction was completed, 576 g of stearic acid was added, the temperature was raised to 75° C. while kneading, and the mixture was stirred for 30 minutes to coat the product with stearic acid. Next 3
The mixture was heated for 2 hours at a reduced pressure F of 00 to 200 mHg to distill off the produced water and toluene, and continued drying to obtain 3720 g of lead a acrylate. The heating loss of this product was 025.

Example filtered zinc oxide 2260f and methanol 2000me 1
Pour into a jacket-type Nigu with a capacity of 0e, knead to make a slurry of IJI, and then add 4000p of acrylic acid.
It was dripped in 30 minutes. After reacting for 1 hour, 820 g of -C stearic acid was added at a temperature of 40 to 50'C, kneaded, and coated. Next, steam was introduced into the jacket, and methanol was added at a temperature of 70'C. After distilling the
It was taken out from the kneader and dried in a low temperature dryer at 40°C. Zinc acrylate 6290f was obtained. The loss on heating was 0.25%.

Example 4 Oxidation if! l'AI 900 y and benzene 30 (]
Once the jacket was formed, put it into a mold mixer, stir 11 (1), make the mixture cloudy for 11W, then add 159Qg of acrylic acid with 50% of the juice and stir for 1 hour. (1, +:・□, / Crystal 1 iron, O minute anti-[11\, row -'').Anti U, −
Heat the melt at 45 to 50°C, add 80% water, stir at 60°C, heat the melt at 7M, (If 1"
) Add the slurry to 275 to 100 kg).
Pour 500 quarts of crystal water into the jacket and heat for 2 hours for 11 minutes. nu? Iy,) 1st water and benzene were distilled, and 1st water and benzene were distilled, and 1st and 2nd steps were added to the stearic acid coded 4929 page. (The volatilization rate of the product was 025.

Is this the same procedure as in Example 1, except that after the reaction is complete, a solution of stearic acid dissolved by heating is added to coat the product? Nia: “Rita.

When drying under reduced pressure is carried out after completion of the test, acrylic acid 1111 is significantly scattered and enters the distilled solvent, making recovery difficult. Also, acrylic acid +l scattered inside the reactor.
i Collection of lead and cleaning of the reactor Ij ☆ Also, the inner wall of the reactor e solidification T
Removal of the reactants caused by EI' is quite complicated, and the acrylic acrylic 1st turn is also difficult to remove, and there is a lot of loss due to failure. As it dried, it was observed that 1- and 1- and 1- and 1- and 1- and 1- and 1- and 1- and 1- and 1- and 1-- and 1-- and 1--= 1X were observed to form a large lump when dried, and that H) Ili' was quite difficult to form.

Comparative Example 2 Acrylic acid obtained in Comparative Example 1! II! Grind 1-1 to 10 to 17A in a lead-like 1icL vessel, add 11 parts of 30 to polybutadiene, and 6 to 10 to 1A full.
When kneaded using an inch D-ru, the agglomerates of O5 and V appear to be in the middle! 1-Serial 1, 7, father V1-The adhesion to the surface is also remarkable.

Claims (1)

[Claims] A method for producing a zinc salt of acrylic acid, which comprises reacting acrylic acid with a zinc compound and then adding stearic acid to the reaction solution.