JPS58192852A - Vinyl ester and preparation thereof - Google Patents

Abstract

NEW MATERIAL:A vinyl ester of formula I (n is 0 or an integer; m is an integer). USE:A monomer capable of giving a polymer capable of acting effectively as a water and oil repellent and imparting the sufficient water and oil repellency to fibers on application thereto without deteriorating the feeling, hue, etc. PROCESS:A carboxylic acid of formula II and vinyl ester of a lower aliphatic fatty acid e.g. vinyl acetate or vinyl propionate, in a molar excess, are refluxed in the presence of a catalyst of mercury acetate and concentrated sulfuric acid, etc. and subjected to the ester interchange reaction to give the aimed compound of formula I . The carboxylic acid of formula II is obtained by polymerizing hexafluoroproylene oxide in the presence of a catalyst, e.g. cesium fluoride, and a solvent, e.g. diglyme, and hydrolyzing the resultant acid fluoride of formula III. COF2, CF3COF, C2F5COF, etc. are used as an initiator for the polymerization reaction to give various compounds of formula II (m has various values).

Description

[Detailed description of the invention] The present invention relates to vinyl esters and methods for producing the same.

In detail, vinyl ester as a monomer that provides a polymer tube that can act as a water- and oil-repellent and its production method E1m is a vinyl ester consisting of a polymer having a perfluoroalkyl group in O@@. Oil agents have been known for a long time,
For example, Japanese Patent Publication No. 49-35348 discloses a compound in which a fluoroalkyl group-containing polymerizable monomer is copolymerized with a diacetone acrylamide compound or its -CH20R fermentation conductor, and if necessary, vinyl chloride. In Japanese Patent Publication No. 4'7-9416, a water and oil repellent consisting of a polymer is disclosed in which a methacrylic acid ester having a perfluoroalkyl group at the end of the ester group is converted into 2-ethyl syl methacrylate, and in the ester group A water and oil repellent agent made of a copolymer of a (meth)acrylic acid ester containing a hydroxyl group and N-methylol acrylamide is loaded on the 9111 chain. The co-coalescence with the perfluoroalkyl group takes advantage of the unique characteristics of the perfluoroalkyl group, that is, its lack of affinity with substances that do not have a perfluoroalkyl group, and its extremely low surface tension. Copolymerize monomers,
It is used in water and oil repellents as a copolymer with improved other required physical properties. For example, in the case of the copolymer described in the above-mentioned Japanese Patent Publication No. Shoban-2 No. 9416, I/CVi, perfluoroalkyl group-containing Methacrylic acid ester provides wrinkle and water-retaining properties, 2-ethylhexyl methacrylate provides water repellency and flexibility, and hydroxyl group-containing (meth)acrylic ester and N-methylol acrylamide provide adhesion to fibers, etc. It is copolymerized for the purpose of adding it to the copolymer.

In general, water and oil repellents are used as treatment agents for textiles, etc., but homopolymers with perfluoroalkyl groups in their side chains are rigid and long-chain, so they are crystalline. However, when such crystalline polymers are applied to fibers, they may become stiff and stiff.
Also, since it is a crystalline polymer, if you apply it to colored fabrics, the dried water/oil repellent film will not become transparent, and the fabrics, etc. In fact, H cannot be used in homopolymer form, since this would impair the color of the H.

III. In order to avoid these drawbacks that occur when monomers having a perfluoroalkyl group at Polymers are generally modified by copolymerization, but even if the modification is successful, the proportion of perfluoroalkyl group-containing monomer components in the copolymer decreases. As a result, water and oil repellency, which is the most desired property, is often impaired, and conventionally, there have been few water and oil repellents that simultaneously satisfy both water and oil repellency and other physical properties. The present inventor has found that the N! + As a result of extensive studies in search of Nine Emperors coalescence by reducing a property and crystallinity, a polymer having a poly(perfluoroalkylene glycol) group in the @ chain,
It was discovered that even when a single polymer is applied to fabrics, it exhibits sufficient water and oil repellency without impairing the texture or color.
Its water and oil repellency 4! A copolymer can be formed at a pressure within a range that does not impair E, and in this case, the washing resistance is j!
The present invention thus provides a vinyl ester as a monomer that provides a polymer capable of acting as a water and oil repellent and a method for producing the same.

Accordingly, the present invention relates to vinyl esters, which are represented by the general formula where ΩFiO and fC are integers and m is an integer.

The present invention also relates to a method for producing a vinyl ester represented by the general formula, wherein the vinyl ester is carvone #l! represented by the general formula (where n and m are as defined above). It is produced by carrying out a lower fatty acid vinyl transesterification reaction.

The synthesis of the carboxylic acid represented by the above general formula (1) is carried out by polymerizing hexafluoropropylene oxide in the presence of a catalyst such as cenium fluoride and a solvent such as diglyme or acetonitrile according to the method described in Japanese Patent Publication No. 10061/1983. When the resulting acid fluoride @) is hydrolyzed in the absence of a catalyst, O(,"F'3C)'3, which is carried out by K, is obtained when hexafluoropropylene ochind is independently combined with , above 1: An acid fluoride represented by the formula (1) is obtained, but COF2, c) r:!・ is used as the initiator of the reaction.
When a reaction is carried out in the presence of these compounds using foto, C2F, COF, Subsequent hydrolysis gives the corresponding carboxylic acid.

The acid fluoride d1 obtained by combining hexanefluoroglohylene is mixed with the number of D, although it is -1,
They are obtained by distillation n −0~1, k~3 and 4~
It can be divided into 1 minute each of 6. In addition, by changing the polymerization conditions in 10, it is possible to obtain a certain degree of Ffr desired Ωθ.
It is also possible to use acid nosodides with a number, for example, nLv
If you try to use a small number of acid fluoride dice, you will have to withdraw the 1ν of the electric medium from the VC, or increase the reaction 1M degree. When Fr, J K f'i, hexafluoro) Robile 7 oya/do 100 y was combined with V(0'CT blood) in the presence of 1 fluoride, 5 g of cenium catalyst and 201 hyacetonitrile, the resulting acid was obtained. Fluoride′!@ is n −, ) −
There is a mixture of 4 fractions, which can be separated into the following fractions by F1 distillation.

I□-(No7g n -115417 n -24'Z 3 El ++ 3 182g r+-4106j In addition, the acid fluoride obtained by removing tC remains a mixture of the number of n'4r in each cypress. or as a fraction thereof, it is subjected to a hydrolysis reaction and converted to the corresponding carboxylic acid (1).

Ester cross-reaction with carboxylic acid/carboxylic acid VC is used as a low-fat vinyl ester, such as vinyl acetate, vinyl propionate, etc., and general VFi
Vinyl acetate is used.

In the transesterification reaction, a general method can be applied as is, but for example, a low-fat vinyl ester with a permolar number of fat is added to a carboxylic acid, and a catalyst such as vinegared rice and water is added. After the reaction is completed, the mixture is refluxed, the excess lower fatty acid vinyl ester is distilled off, and the target vinyl ester is then separated by distillation.

In the single-coupling reaction of vinyl esters, a general radical method can be used. That is, in the case of emulsification, for example, oftatecyldimethylamine salt tf! In the case of bath IQ]k, aromatic compounds, ketones, alcohols, halogenated hydrogen ash, etc. etc. are used as the electrolyte, and anohisinobutyronitrile, peroxide, etc. are used as the hemopolymerization initiator, and the breast reaction is initiated.

Vinyl esters can be used alone or in combination as water and oil repellents with desired properties, but they can also be used as water and oil repellents in the form of co-electrochemical combinations with vinyl compounds.

As other vinyl compounds that can be used as the basic unit, various compounds such as Fushimi are used. ◇ 0) Vinyl compounds having a hydrocarbon group having 4 or more carbon atoms;
For example, butyl acrylate, butyl methacrylate, octyl acrylate, octyl methacrylate, 2-ethylhexyl acrylate, quinol acrylate, quinol acrylate, etc.; Rogge/Miyaari vinyl compounds, such as Hanawa (L) , hiniritene chloride,
2-Chlorethylvinyl-vinyl, vinyl bromide, vinyl fluoride, vinyliso7 fluoride, etc.; enene compounds, such as chlorogrene, inogren, butanene, etc.: these vinyl compounds and diene compounds are about 99% by volume Below, preferably about 90% or more, preferably about 7%
It is used at a rate of 5% by volume or less, and contributes to improving the flexibility of the rice cooker body, improving the solubility in rogenated bath additives, etc.

(2) Vinyl compounds containing active groups such as hydroxyl groups, amide groups, amine groups, carboxyl groups, acid groups, and sulfonic acid groups, such as 2-hydroquinoethyl acrylate, 2-hydroxyethylnotacrylate, etc. These vinyl compounds include ,F)001~1olHk amount%
, preferably about QO5-5% blood pressure, preferably Fir
It is used at a ratio of +01 to 2 IIL, and the presence of the active group in the vinyl compound improves the adhesion of the electrolyte to delicate materials, paper, leather, etc.

(3,1 low M perfluoroalkyl group-containing sulfuryl group; A
Compounds such as 2.2.2- )') fluoroethyl acrylate, 1. ],,1. 843-hexafluoro-2-nolopyl acrylate and the like.

These vinyl compounds have a content of about 10-90%, preferably about 20-80%, preferably about 30-6%.
Used in a proportion of 0% blood volume, they improve the water and oil repellency and softness of the polymer, respectively.

The preparation of Sōzuga oil is carried out in the form of a diluted aqueous solution of the anastomoses, and in the case of analyzing the mixture of the mucous in an aqueous medium by the emulsification method or the suspension method. When using the legal method or the FG solution method, 7L of diluted organic solvents are used.

For treatment of shakusui oil, the fC prepared in this way is used for each machine M1. It is performed on board processing @ of textiles or blends of these *cloths, pulp products, leather, etc.

Next, the present invention will be explained with reference to examples.

Examples Carvone represented by the above general formula (1) (n -1
, m-3) 100g (0201 mol) K1 acetate vinyl 2
00y (233 mol), mercury acetate L6Sl+ and fa
Sulfur 1! J&Q15- was added and refluxed for 3 hours, neutralized, and then filtered.7) Vinyl acetate was distilled off to give a boiling point of 85-1.
05℃/Q 5111MHg fraction 7g4p (yield 69
From the results of NMR spectrum, infrared leg absorption spectrum measurements, and elemental analysis of this fraction, this fraction was found to contain 0F-N with IR (CF
3COOH external standard): 6-8 ppm (CF,,C
F, )55 ppm (CF30F20F, O)6
5 ppm (CF) ) (-h+, iR: 4.5 to 5 ppm and 7 to 15 ppm (vinyl ester group) infrared absorption spectrum; 1810 cm (varnish f group) 7-part analysis: = 1 calculation i d C: 2a 28%, H: 019%, F: 6
188% actual subvalue, ;:2al'7%, H:045%,
F: 61.03%: lI5 Examples Deionized water 220b heated to 50-60°C ()
10 voices j) K,) Limeter octatenor f7 7-nium chloride 15 parts gold power [1e, the above implementation Fl and 1e
f1 The compound represented by the following formula, attended by God's method.
5. N-Methylolacine 1) Add 7100 parts of Ruamide C151N and acetate, mix with a colloid mill, and stir. When the inside of reaction 6 was mixed with 9 elementary particles, the radical 1 was started under reflux conditions, and the azo/inobutyramidine salt 11i4iQO5b was added thereto. After 4 hours, the copolymerization reaction 1G was completed. Stir. Milky white aqueous Latinx t; Served, its solid content is very high RJ2:!
, 2% of electric power, and 11% of the direct cross-cutting had progressed completely.

The obtained aqueous Radex was diluted with water to give a dilution of about 0.051! to 1
% solids III Arashi KpA and soak the real cotton cloth therein. After soaking for 5 minutes, the cloth was taken out, water was thoroughly removed using a dehydration roll, and then dried at 175°C for 5 minutes.
The cotton fabric thus treated with the copolymer was subjected to a water repellency test, an oil repellency test, a bulge test, and a straightness test as follows.

[Water repellency test]

Drop a drop of water on the treated cotton cloth and observe the condition after 5 minutes and evaluate the water repellency Water droplet condition: 100 No moisture adhesion observed on the surface 190 Slight moisture adhesion observed on the surface 80 Partial adhesion and turbidity is observed on the surface 70 Moisture and turbidity is observed on the surface 50 Moisture and turbidity is observed on the entire surface 0 Moisture and turbidity is observed on the entire surface 0 [Oil repellency test] Treated book Drop one drop of the test liquid (mixed liquid with a specific proportion shown in the table below) on the cotton cloth and observe the state of wave transmission for 5 minutes.If the dropped test liquid is retained on the cloth, KFi , further tested with a test solution containing a large amount of n-heptane,
On the other hand, if it is not held on the cloth, use K, and then Nujol TM
Test with a test solution containing a large amount of Then, using the test liquid at the limit that can be retained on the cloth, it was evaluated as f-0 based on the oil-resistance evaluation in the following table.In addition, when retaining 100% Nujol in the oil-repellent bandage is 50.If 100% Nujol is not retained, let it be fO.

150 0
100140 10
90130
20 80120
．． 30
'70110 40
60, l('+Q
50 5090
60
408θ 70
3070 80
2060
90 10 go 0
100
00 (100% Nujol hole retention side) [Cleanability test] The treated hole was soaked in water containing 01 t% of neutral Nisso soap and 51 t% of lime QO.
Stir at 80° C. for 40 minutes and rinse fCC for 1030 seconds.

This operation was repeated three times and the water and oil repellency was evaluated.

[Rigidity test]

Based on the JrBL-109615 method, the stiffness and softness of the feet were measured 1,
Then calculate the flexibility according to the following formula: The closer the softness value is to 1, the closer it is to untreated cloth, and the smaller the number of im, the harder it is.

The results are shown in the following table: Surface water repellency 100 Oil repellency 150 Er, ll1 l resistance (water repellency) 80 (Oil repellency) 130 Flexibility 098 Touch Good procedure amendment (voluntary) 1981 lθ
February 27, 1, Display of the case 1982 Patent No. 75686 2 Name of the invention Vinyl ester and its manufacturing method 3 Person making the amendment Relationship to the case Name of the patent applicant Shuu Mekto N Co., Ltd. 4, Representative Address: 50 Ato Pill, 1-2'-7 Shiba Daimon, Minato-ku, Tokyo
Column 6 of Detailed Description of the Invention in Specification No. 1, Contents of Amendment (1) Correct "Formula (H)" in the second line of page 7 to "Formula (4)".

(3) Correct "1 Flexibility" in the second line directly below No. 17 to "Flexibility".

Claims (1)

[Claims] A vinyl ester represented by the general formula (where nFiOl or the number U, m is an integer). General formula (where n and m are as defined above) 03 Claim #M in which vinyl acetate is used as the lower fatty acid vinyl ester
Method 0 for producing vinyl ester according to item 2