JP3463339B2 - Method for producing copolymer solution - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a method for producing a copolymer solution.
About. More specifically, containing a polyfluoroalkyl group
(Meth) acrylate and a monomer copolymerizable therewith
To prepare a copolymer solution by copolymerizing
About the law. [0002] 2. Description of the Related Art Polyfluoroalkyl group-containing (meth)
Relate and copolymerizable monomer with organic solvent
To produce a solvent-based water and oil repellent by copolymerizing
It has been proposed. In that case, the organic solvent
Hydrogenated hydrocarbons, aromatic hydrocarbons, ethers, keto
Compounds, acetates, etc. are used.
No. 3759, JP-A-61-291676-7, JP-A-5-7842
No. 5). [0003] However, the impact on the global environment, workers
Nowadays, safety is becoming important,
The use of solvents is becoming very difficult. Immediately
In the case of halogenated hydrocarbons, the ozone layer of the earth
There are problems such as destruction and groundwater contamination, and other solvents mentioned above
In the case of, work due to toxicity, odor, low flash point, etc.
Safety concerns to transporters, transport and storage volumes by law
There is a problem of target restrictions. In addition, a solvent-based water / oil repellent is used.
The diluent used in this process also contains aromatic hydrocarbons.
Water-repellent for cleaning
Oil repellents should not contain aromatic hydrocarbons
Is indispensable. Therefore, it is natural that aliphatic or
The use of alicyclic hydrocarbon solvents is conceivable.
(Meth) acrylates containing polyalkyl groups and copolymers
When copolymerizable with polymerizable monomers in these solvents
In many cases, a large amount of precipitate is generated during the polymerization reaction,
Result. [0006] SUMMARY OF THE INVENTION The object of the present invention is to
Fluoroalkyl group-containing (meth) acrylate and the same
And a copolymerizable monomer with an aliphatic or alicyclic hydrocarbon
Copolymerized in solvent, solvent-based water and oil repellent by itself
For producing a copolymer solution effectively used as an agent
Is to provide. [0007] SUMMARY OF THE INVENTION The object of the present invention is as follows.
Polyfluoroalkyl group-containing (meth) acrylate and
The monomer copolymerizable therewith is converted to glycol dialkyl ether.
Or aliphatic or alicyclic carbonization with a flash point of 21 ° C or higher
Copolymerization in a mixed solution of hydrogen solvent to produce a copolymer solution
Achieved by building. The resulting copolymer solution
Is a solvent-based water and oil repellent with a flash point of 21 ° C or higher.
Agent may be formed. [0008] Polyfluoroalkyl group-containing (meth) acryl
The rate is a general formula CH_Two= CRCOOR´Rf R: hydrogen atom or methyl group R ': C1-C10 alkylene group Rf: C4-20 polyfluoroalkyl group And may contain other halogen atoms The following are examples of compounds represented by
I can do it. CH_Two= CRCOO (CH_Two)_TwoC₆F₁₃ CH_Two= CRCOO (CH_Two)_TwoC₈F₁₇ CH_Two= CRCOO (CH_Two)_TwoC_TenF_{twenty one} CH_Two= CRCOO (CH_Two)_TwoC₁₂F_{twenty five} CH_Two= CRCOO (CH_Two)_Two(CF_Two)₆CF (CF_Three)_Two CH_Two= CRCOOCH_TwoC₇F_Fifteen CH_Two= CRCOOCH_TwoC₉F₁₉ CH_Two= CRCOOCH_Two(CF_Two)_TenH CH_Two= CRCOOCH_Two(CF_Two)_TenCF_TwoCl CH_Two= CRCOOCH_TwoCF (CF_Three) (OC_ThreeF₆)_ThreeOC_ThreeF₇ [0009] These polyfluoroalkyl group-containing (meth
Examples of the comonomer copolymerized with (t) acrylate include:
For example, vinyl halide, vinylidene halide, acrylic
Lonitrile, methacrylonitrile, acrylic acid, methac
Alkyl, acrylic or methacrylic acid,
Chloroalkyl, aryl or allyl esters, styrene
Len, α-methylstyrene, alkyl vinyl ether,
Halogeno alkyl vinyl ether, alkyl vinyl keto
, Butadiene, isoprene, chloroprene, polyal
Acrylate or methacrylate of kylene glycol
G, acrylamide, N-methylolacrylamide, N-
n-alkoxymethylacrylamide, 2-hydroxyethyl
Methacrylate phosphate ester and the like.
Preferably vinylidene chloride, acrylic acid or methacrylic
Benzyl, cyclohexyl, higher alkyl, glycylic acids
Ester such as jill, N-methylolacrylamide, 2-
Chloroethyl vinyl ether and the like are used. these
Are generally about 10-70% by weight, preferably
It is copolymerized in a proportion of about 20 to 60% by weight. [0010] The copolymerization reaction is carried out by azobisisobutyronitrile.
Compound represented by benzoyl peroxy
Side, cumyl peroxide, dialkyl peroxy
Organic peroxides represented by dicarbonates, etc.
Solution weight at a temperature of about 40-120 ° C in the presence of a polymerization initiator of
It is done legally. Fat used as solvent for solution polymerization reaction
As the aromatic or alicyclic hydrocarbon, n- or i-
So-decane, undecane, dodecane, tridecane, etc.
Or n-propylcyclohexane, n-butylcyclohexa
Flash point of methane, cyclodecane, decahydronaphthalene, etc.
Is 21 ° C. or higher. An aliphatic hydrocarbon, an alicyclic hydrocarbon or
Use commercially available petroleum hydrocarbon solvents consisting of these mixtures
For example, Shell Japan products
Series 70, 71, 72, D40, D70, D1
00 or Shell Bright Sol, Idemitsu Kosan Products Iso
Software, IP solvent series 1620, 20
28, 2835, 25, 3 of the Super Sol FP series
0, 38, Nikko Petrochemical Nikko White N-1
0, Nippon Petroleum Products DrySol HaiActually use software etc.
You can also. The solution polymerization reaction involves the reaction of these hydrocarbon solvents.
The presence of glycol dialkyl ether
Requires the coexistence of satellites. Glycol glycol
As a tell, the general formula R¹O (R^TwoO) nR^Three R¹, R^Three: C1-C6 alkyl group R^Two: C2-4 alkylene group n: positive integer, preferably 1-3 Is generally used. Specifically, for example, ethylene glycol
Diethyl ether, dibutyl ether, diethylene glycol
Chole dimethyl ether, diethyl ether, Djibouti
Diether, triethylene glycol dimethyl ether
Toluene, diethyl ether, dipropylene glycol
Tyl ether, diethyl ether, dipropyl ether
Dimethyl ether of dibutylene glycol, diethyl
And the like. These glycol dialkyl ethers
Is about 5 to 90% by weight, preferably about
It is used by mixing at a ratio of 10 to 80% by weight. Also this
These mixtures, as reaction solvents, are generally based on the total monomer weight.
It is used in an equivalent to about 10 times the amount. Such conditions
If the copolymerization reaction is performed under
A polymer solution is obtained. Copolymer solution obtained as a result of solution polymerization reaction
Can itself be used as a water and oil repellent.
The water- and oil-repellent treatment using this is performed by using the obtained copolymer solution.
Solids concentration of commercial petroleum solvents for cleaning (para
Fin type, paraffin-naphthene mixed type, paraffin-na
0.5% by weight)
After diluting to the appropriate concentration, cotton, hemp, wool, silk, polyet
Stele, polyamide, acrylic, polyolefin, recycled
Various fibers such as cellulose, or woven or
Apply dipping, spraying, or any other means of application to textile products, etc.
It is done by doing. Then air dry at room temperature
Even though water and oil repellent effects are exhibited, at about 80 to 180 ° C
Heating for about 0.5 to 10 minutes will further reduce the effect.
Demonstrated step by step. [0017] According to the present invention, a polyfluoroalkyl group-containing (meth) ac
Solution and monomer copolymerizable with it
And a solvent-based water and oil repellent consisting of a copolymer solution.
In preparation, halogenated hydrocarbons and aromatic hydrocarbons
Without the use of aliphatic or alicyclic hydrocarbons in the polymerization reaction
When used as a solvent, a smooth copolymerization reaction can be performed.
No, but coexist with glycol dialkyl ether
Allows the copolymerization reaction to proceed smoothly
Can be. The resulting copolymer solution is itself water-repellent.
It can be used as an oil repellent.
Class 2 petroleum and above, easy to store and handle
Aliphatic or alicyclic hydrocarbons with a flash point of 21 ° C or higher
Can be used. The water and oil repellents of the present invention
Necessary not only for leaning but also for aerosol
To fully satisfy these essential conditions.
You. [0019] 【Example】 [Table 1](Monomer) FAA: Perfluoroalkylethyl acrylate (Perf
Average for mixtures containing 6,8,10,12 fluoroalkyl groups
Is 9) VdCl: vinylidene chloride BzMA: Benzyl methacrylate CHA: cyclohexyl acrylate LMA: Lauryl methacrylate SA: Stearyl acrylate GMA: Glycidyl methacrylate MAA: N-methylol acrylamide CEVE: 2-chloroethyl vinyl ether (Glycol dialkyl ether) EGDEE: Ethylene glycol diethyl ether DEGDME: Diethylene glycol dimethyl ether TEGDME: Triethylene glycol dimethyl ether DPGDME: Dipropylene glycol dimethyl ether (Hydrocarbon solvent) n-D: n-decane n-PCH: n-propylcyclohexane S70: Shellsol 70 ISS: Isole Soft The monomers shown in Table 1 above, glycol di
Of alkyl ethers and aliphatic or cycloaliphatic hydrocarbons
A mixture of a predetermined amount (g) and 5 g of azobisisobutyronitrile
Into a glass reaction vessel with a cooling tube with a capacity of 500 ml.
After stirring under a stream of nitrogen gas, copolymerize at 60 ° C for 24 hours
Reaction, all solids concentration of about 15 wt% copolymer
A solution was obtained. Each of the obtained copolymer solutions is adjusted to have a solid content concentration of
Petroleum-based solvent (Shell Bright Sol) to be 0.5% by weight
With water and oil repellents A to Q (Examples) and R to V (specific ratio).
Comparative example, except that in SV, a large amount of precipitate was generated during the copolymerization reaction.
And no polymer was obtained). these
Test cloth (cotton broad 40, polyester) in water and oil repellent
Amundsen or nylon taffeta) for about 10 seconds,
After being sufficiently squeezed with a mangle, it was dried at 80 ° C. for 10 minutes.
The following items were tested for this water- and oil-repellent treated cloth.
Was. Flash point: Measured by JIS K-2265 tag closed type Aromatic component amount: Measured according to JIS K-2536 Water repellency evaluation: Measured according to JIS L-1092 Oil repellency evaluation: Measured by AATCC Test Method 118 The results obtained are shown in Table 2 below. What
Here, the amount of the aromatic component was 0 in all cases.                                   Table 2  Water repellent flash pointWater repellency Oil repellency Oil repellent (℃) cotton polyester Nylon cotton polyester Nylon   A 35 100 100 100 6 7 6   B 46 〃 〃 〃 〃 〃 〃 〃   C 〃 〃 〃 〃 〃 〃 〃   D 〃 〃 〃 〃 〃 〃 〃 〃   E 35 90 〃 〃 5 6 5   F 50 80 〃 90 〃 〃 〃   G 35 100 〃 100 6 7 6   H 50 90 〃 〃 5 6 5   I 38 〃 〃 〃 〃 〃 〃   J 45 〃 〃 〃 〃 〃 〃   K 50 100 〃 〃 6 7 6   L 35 90 〃 〃 5 6 5   M 42 100 〃 〃 〃 〃 〃   N 50 〃 〃 〃 〃 〃 〃   O 35 90 〃 〃 6 7 6   P 〃 〃 〃 〃 5 〃 5   Q 42 80 〃 〃 〃 〃 〃   R 35 0 50 50 2 52

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Claims (1)

(57) [Claim 1] A polyfluoroalkyl group-containing (meth) acrylate and a monomer copolymerizable therewith are formed from glycol dialkyl ether and an aliphatic or alicyclic compound having a flash point of 21 ° C or higher. A method for producing a copolymer solution, comprising copolymerizing in a mixed solution of a hydrocarbon solvent.