JPH0717717B2 - Polymer having alkoxysilyl group - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is useful as a coating material capable of stable water and oil repellency treatment on a surface of a substrate having a hydroxyl group such as glass by reacting with the surface. It relates to a novel reactive polymer.

[Prior art]

Fluorine-containing polymers have better corrosion resistance and chemical resistance than hydrocarbon-based polymers, and also have water and oil repellency, so these properties can be applied to antifouling materials and non-adhesive materials. Has been done.

[Problems to be Solved by the Invention] However, a polymer having a fluorine atom introduced into its main chain, such as polytetrafluoroethylene or polyvinylidene fluoride, is insoluble in a usual organic solvent, and therefore, for example, glass or When coating on a base material such as a metal, it is necessary to heat and melt and then press-bond the base material, and it is impossible to coat on a base material having a complicated top. Further, a polymer of a fluorinated acrylic ester or a fluorinated methacrylic ester is soluble in an organic solvent such as ethyl acetate, and by coating this polymer solution, water repellent treatment, antifouling treatment or optical fiber treatment of the fiber is performed. Although it is used as a coating material and the like, these polymers have ester bonds having hydrolyzability, so that performance deterioration such as water repellency and light transmittance cannot be avoided during long-term use.

Further, the fluorine-containing polymer has a problem in its adhesiveness to other substrates due to its low surface free energy.

The present inventors have conducted extensive studies in order to solve the above problems, and as a result, the polymer having an alkoxysilyl group of the present invention has high water repellency, oil repellency and permeability, as well as excellent coating property, stability, and substrate. It has been found that it has reactivity with, and has completed the present invention.

[Means for solving problems]

The polymer having an alkoxysilyl group of the present invention has the general formula (In the formula, R ¹ represents a hydrogen atom or a lower alkyl group,
R ² represents a hydrogen atom or a lower polyfluoroalkyl group, R ³ represents a polyfluoroalkyl group, and n is 0 to 2
Is an integer. ) And the general formula (In the formula, R ⁴ represents a hydrogen atom or a lower alkyl group,
R ⁵ and R ⁶ represent a lower alkyl group or a phenyl group, and A
Represents a divalent linking group, L is an integer of 0 to 5, m is 0 to
The integer of 2 and p represent the integer of 1-3. However, m + p =
It is 3. ) And a repeating unit having an alkoxysilyl group.

The lower polyfluoroalkyl group represented by R ² includes a difluoromethyl group, a perfluoromethyl group, an ethyl group substituted with 2 to 5 fluorine atoms, a propyl group substituted with 2 to 7 fluorine atoms, 2 To butyl group substituted with 9 fluorine atoms,
Particularly, a perfluoromethyl group and a perfluoroethyl group are preferable in terms of ease of introduction.

Examples of the polyfluoroalkyl group represented by R ³ include perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, perfluorodecyl group. A group, a difluoromethyl group, an ethyl group substituted with 2 to 4 fluorine atoms, a butyl group substituted with 2 to 8 fluorine atoms, a hexyl group substituted with 2 to 12 fluorine atoms, 3 Examples thereof include an octyl group substituted with 16 fluorine atoms and a 3-oxa-2-trifluoromethyl-2,4,4,5,5,6,6,6-octafluorohexyl group. Particularly, a poly (per) fluoroalkyl group in which the alkyl terminal is completely fluorinated is preferable in that it exhibits high water repellency and water repellency.

As a divalent linking group And the like (in the formula, R ⁷ represents a hydrogen atom or a lower alkyl group).

As a specific example of the repeating unit having an alkoxysilyl group Etc. can be shown.

The polymer having an alkoxysilyl group of the present invention has the general formula (Wherein R ¹ , R ² , R ³ and n are the same as above) and one or more kinds of monomers having an alkoxysilyl group are mixed to form a normal radical. It can be easily synthesized by copolymerization by a polymerization method. As a method used for the polymerization reaction, known methods such as bulk polymerization, solution polymerization and emulsion polymerization can be used. The radical polymerization reaction is quickly initiated simply by irradiation with heat, ultraviolet rays or addition of a radical initiator. Examples of the radical initiator preferably used in the reaction include organic peroxides such as dilauroyl peroxide and benzoyl peroxide, and azo compounds such as α, α′-azobisisobutyronitrile. The organic solvent that can be used in the polymerization reaction is preferably a soluble polymer to obtain a high molecular weight polymer, for example, benzene,
Toluene, chlorobenzene, tetrahydrofuran, carbon tetrachloride, chloroform, methyl ethyl ketone, fluorobenzene, hexafluorobenzene, N, N-dimethylformamide and the like can be used, but not limited thereto. The reaction is usually performed in the range of 40 ° C to 100 ° C.

As the monomer having an alkoxysilyl group that can be copolymerized, allyltriethoxysilane, allyltrimethoxysilane, methacryloyloxypropyltrimethoxysilane, acryloyloxybutyltriethoxysilane, 3-methacryloxypropyldimethylethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyldimethylethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinyltriethoxysilane, vinylitriphenoxysilane,
P- (trimethoxysilyl) styrene etc. can be illustrated. The composition of the repeating unit having an alkoxysil group contained in the polymer having an alkoxysilyl group is in the range of 1 mol% to 50 mol%, preferably 5 mol%.
~ 30 mol%. If the repeating unit is less than this, it does not react effectively with the base material, and if it is more than this, the water and oil repellency deteriorates.

The polymer of the present invention may contain, as the third repeating unit, a repeating unit having styrene, methyl acrylate, ethyl methacrylate or the like as a monomer, and in view of water repellency and oil repellency, The third repeating unit content is preferably 30 mol% or less.

The molecular weight of the polymer having an alkoxysilyl group of the present invention is
It is 1000 or more, preferably 5000 or more. Those having a molecular weight of 1,000 or less have poor film forming properties and do not exhibit sufficient water / oil repellency.

Hereinafter, the present invention will be specifically described with reference to Reference Examples, Examples, and Test Examples.

Reference example 1 1,2,3,3,3,4,4,4-heptafluoropropanol (18.0 g), tetra-n-butylammonium hydrogen sulfate (20.37 g) and benzene (300 ml) were placed in a three-necked flask and stirred under an argon stream. Next, add 17.5 ml of 50 wt% sodium hydroxide aqueous solution, stir for 15 minutes, and then add 9.15 g of p-chloromethylstyrene.
Was added and the mixture was stirred overnight at room temperature. A large amount of water was added to the reaction mixture, and the benzene layer was washed with water. This operation was repeated to wash the benzene layer and then dried over anhydrous magnesium sulfate, and benzene was distilled off under reduced pressure. The residue was purified by passing through a silica gel column using n-hexane as an eluent, and the yield was 56%.
To give p- (2,2,3,3,4,4,4-heptafluorobutyloxymethyl) styrene (OHF ₃ ).

Elemental analysis (%); Found: C; 49.34 H; 3.60 Calculated: C; 49.34 H; 3.48 IR (cm ^-1 ); 3000-2800,1610,1510 (aromatic ring), 1630 (CH
= CH ₂ ), 1205,1150 (CF). _{NMR (ppm) 3.83~4.13 (-OCH 2} CF 2), 4.63 5.15 ~ 5.89 (CH ₂ =), 6.50 ~ 6.90 (= CH), 7.17 ~ 7.49 Reference Example 2 Similar to Reference Example 1 except that alcohol was changed to 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecalfluorooctanol. P- (2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluooctyloxymethyl) styrene (OH
F ₇ ) was obtained with a yield of 50.9%.

Elemental analysis (%); Actual value: C; 39.5 H; 2.2 Calculated value: C: 39.6 H; 2.2 IR (cm ^-1 ); 2800 to 3000, 1610, 1510 (aromatic ring), 1630 (CH
_{= CH 2), 1210,1150 (C} -F), 1100~1080 (-O-). NMR (ppm): 3.8~4.11 (-CH 2 -, 2H), 4.6 (-CH 2 O-, 2
H), 5.2 ~ 5.9 (CH ₂ =, 2H), 6.5 ~ 6.9 (-CH =, 1H), 7.2
~ 7.5 (aromatic ring, 4H). Example 1 4.268 g (13.5 mmol) of OHF ₃ obtained in Reference Example 1 and 0.372 g of 3-methacryloyloxypropylmethoxysilane (MOS)
(1.5 mmol) was added to a glass polymerization tube which had been previously heated under reflux with a toluene solution of hexamethyldisilazane (1: 2 vol / vol) overnight. Tetrahydrofuran 10.5 ml as a solvent, α, α'-azobisisobutyronitrile 12.33 mg
Was added as a polymerization initiator, and this was degassed by a conventional method and then sealed under high vacuum (10 ^-5 mmHg or less). 29.5 at 60 ℃
The polymerization reaction was carried out with shaking for a while. The reaction mixture was poured into a large amount of methanol to precipitate the polymer. This was separated by filtration and dried to obtain 0.454 g of white solid (yield 9.8%). ¹ H
-NMR was confirmed to be OHF ₃ -MOS copolymer by measurement. The introduction rate of MOS calculated from the elemental analysis value was 9.4 mol%. Further, the molecular weight of the OHF ₃ -MOS copolymer obtained by GPC measurement was 2.3 × 10 ⁴ .

_{NMR (ppm / CFCl 2 CF 2} Cl); 0.27~0.67 (-SiCH 2 -), 0.97
~2.17,3.33~3.47 (-SiOCH _3), 3.47~4.13,4.30~4.7
0 6.17 ~ 7.27 Elemental analysis value (%); C; 49.30, H; 4.05 Example 2 OHF ₃ was replaced by OHF ₇ obtained in Reference Example 2, and the solvent was changed from THF to 1,4-bistrifluoromethylbenzene (BTB). A polymerization reaction was carried out in the same manner as in Example 1 to obtain an OHF ₇ -MOS copolymer having 7.7 mol% of MOS introduced therein at a yield of 26.7%. The molecular weight of this copolymer was 9.7 × 10 ³ .

_{NMR (ppm / CFCl 2 CF 2} Cl); 0.28~0,67 (-SiCH 2 -), 0.97
~2.20,3.40~3.48 (-SiOCH _3), 3.48~4.13,4.31~4.7
2 6.15 ~ 7.29 Test Example 1 200 mg of the OHF ₇ -MOS copolymer obtained in Example 2 was dissolved in 2 ml of BTB, and about 0.45 ml of the solution was cast on a clean glass plate of 18 × 24 mm and slowly heated at 50 ° C. The solvent was evaporated and a film was made on a glass plate. After further drying at 50 ° C. under reduced pressure overnight, 42 mg of the copolymer was coated on the glass. This was soaked in BTB for 30 minutes and then thoroughly dried.
When the weight of the insoluble matter attached to the glass plate was measured, it was 27 mg.
The reaction rate with the glass plate was 64%. The contact angle of the liquid droplet on the film surface on this glass plate was measured with a contact angle goniometer manufactured by Kyowa Kagaku Co., Ltd.
And 100.0 for methylene iodide.

The OHF ₇ -MOS copolymer film prepared by the same manner as in Test Example 2 Test Example 1 was allowed to stand overnight at saturated steam under 80 ° C.. Next, it was soaked in BTB for 30 minutes and then thoroughly dried. The reaction rate of this film with glass was 91%. The contact angle of the droplet on this film surface is 120.0 degrees with pure water and 1 with methylene iodide.
It was 00.0 degrees.

Except for using the OHF ₃ -MOS copolymer obtained in Example 1 in place of the Test Example 3 OHF ₇ -MOS copolymer in the same manner as in Test Example 2 to form a film, the reactivity test of the glass went. The reaction rate of this film with glass was 64%. The contact angle of droplets on the film surface is 115.0 degrees with pure water and 91.degree. With methylene iodide.
It was 5 degrees.

Comparative Example 1 OHF ₇ homopolymer was obtained in the same manner as in Example 2 except that MOS was not added. The molecular weight of the obtained polymer was 3.0 × 10 ⁴ .

Using this polymer, a polymer film was prepared on a glass plate in the same manner as in Test Example 1. When this film was treated under the same conditions as in Test Example 2, the film was almost completely dissolved in BTB and the contact angle of pure water was 30.5 degrees.

〔The invention's effect〕

The polymer of the present invention has an alkoxysilyl group that reacts with the surface of a base material having a hydroxyl group such as glass, firmly bonds to the surface of the base material, and exhibits high water and oil repellency. Therefore, it is useful as a stable water-repellent, oil-repellent treatment agent coating agent having a difficult peeling property.

Claims (2)

[Claims] 1. A general formula (In the formula, R ¹ represents a hydrogen atom or a lower alkyl group,
R ² represents a hydrogen atom or a lower polyfluoroalkyl group, R ³ represents a polyfluoroalkyl group, and n is 0 to 2
Is an integer. ) And the general formula (In the formula, R ⁴ represents a hydrogen atom or a lower alkyl group,
R ⁵ and R ⁶ represent a lower alkyl group or a phenyl group, and A
Represents a divalent linking group, L is an integer of 0 to 5, m is 0 to
The integer of 2 and p represent the integer of 1-3. However, m + p =
It is 3. ), The composition of the repeating unit having an alkoxysilyl group is in the range of 1 mol% to 50 mol%, and the molecular weight is 100.
A polymer having 0 or more alkoxysilyl groups. 2. The polymer having an alkoxysilyl group according to claim 1, wherein the composition of the repeating unit having an alkoxysilyl group is in the range of 5 mol% to 30 mol%.