KR930007990A - Fluoroalkyl group-containing polymers, preparation methods thereof, surfactants, surface treatment agents and paint compositions - Google Patents

Abstract

In the present invention, one or two fluoroalkyl groups at one or both ends of the molecule are alkylten groups, a part of alkylene groups substituted with halogen, halogen, cyano group, alkylsulfonic acid group, aminosulfonic acid group, carboxylic acid group, carboxyl group, oxy A polymer comprising a fluoroalkyl group having a structure bonded to a part of an alkylene group substituted with a functional group such as a carbonyl group, an ether group, an epoxy group, and / or a part of a silicon group; A method for producing a polymer composed of a fluoroalkyl group by reacting a fluoroalkanoyl peroxide with a monomer composed of a functional group or a monomer composed of a silicone group; Surfactant consisting of a fluoroalkyl group and a carboxylic acid base; A surface treating agent composed of a polymer containing a fluorine group, a hydrolyzate thereof, a hydrolyzed condensate thereof and a mixture thereof; A coating composition composed of a polymer containing a fluoroalkyl group; As a result, polymers composed of these fluoroalkyl groups are excellent in water repellency, oil repellency and weather resistance because fluoroalkyl groups are introduced into the molecule through carbon-carbon bonds.

Description

Fluoroalkyl group-containing polymers, preparation methods thereof, surfactants, surface treatment agents and paint compositions

Since this is an open matter, no full text was included.

Claims (26)

General formula (I) [Wherein Z ¹ represents a hydrogen atom or a methyl group, and Z ² and Z ³ are the same or different groups and include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an alkylcarbonyloxy having 1 to 10 carbon atoms; Group is represented, R ¹ and R ² are the same or different, and represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² and R ⁴ are the same or different groups, a hydrogen atom, a halogen atom, a cyan Furnace group, alkyl sulfonic acid group of 1 to 4 carbon atoms, amide alkyl sulfonic acid group of 1 to 4 carbon atoms, -CO ₂ R ⁵ , -OCOR ⁶ , -OR ⁷ , -CO ₂ (CH ₂ CH (R ⁸ ) O m _4- ( ^{_{CH 2 CH (R 9) O}} ) m5 _{[CH 2 CH 2 (CH 2)} m7 O ] _m6 (R ^10), —CO ₂ CHCH ₃ OR ¹⁴ or —CO ₂ (CH ₂ ) _r —CHR ¹⁵ CHR ¹⁶ O [CO (CH ₂ ) _s CHR ¹⁷ (CH ₂ ) _t CHR ¹⁸ O] _u —H, is represented by R ^F _Is- (CH ₂ ) _n1 X or And m ₁ represents an integer of 1 to 1000, m ₂ and m ₃ represent an integer of 0 to 3000, and R ⁵ represents a hydrogen atom, sodium, potassium, ammonium or an alkyl group having 1 to 18 carbon atoms or 3 to 6 carbon atoms. A hydroxyalkyl group, R ⁶ and R ⁷ are the same or different and represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms, and R ⁸ , R ⁹ and R ¹⁰ are the same or different; As another group, a hydrogen atom or a methyl group is represented, R ¹¹ represents an alkylene group having 1 to 10 carbon atoms or-(CH ₂ CH ₂ O) pCH _2- , and R ¹² and R ¹³ are the same or different groups , A hydrogen atom or an alkyl group having 1 to 18 carbon atoms, R ¹⁴ represents an alkyl group having 1 to 18 carbon atoms, m ₄ represents an integer of 1 to 20, m ₅ and m ₆ represent an integer of 0 to 20, m ₇ represents 1 or 2, m ₈ represents an integer from 0 to 5, p represents an integer from 1 to 10, and R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are the same or different groups, Hydrogen atom or me Represents a and, r represents an integer of 0 to 2, s and t represents an integer of 0 to 3, and, and u represents an integer of 1 to 5, n ₁ denotes an integer of 1-10 , x represents a fluorine atom, a chlorine atom, a hydrogen atom, n ₂ represents an integer of 0 to 8, and m ₉ represents 0 or 1. However, when m ₉ = 0, Z ¹ is a hydrogen atom.] A fluoroalkyl group-containing polymer having a number average molecular weight of 500 to 1,000,000. The method according to claim 1, wherein the following general formula (II) … … … … … (Ⅱ) Wherein R ^F is — (CH ₂ ) _{n 1} X or n ₁ represents an integer of 1 to 10, x represents a fluorine atom, a chlorine atom and a hydrogen atom, n ₂ represents an integer of 0 to 8), and a fluoroalkane peroxide represented by the following general formula ( Ⅲ) CH ₂ = C (R ¹ ) (R ² ) (III) [In formula, R <^1> represents a hydrogen atom, a halogen atom, or a C1-C5 alkyl group, R <^2> represents a hydrogen atom, a halogen atom, a cyano group, a C1-C4 alkyl sulfonic acid group, a C1-C4 amide Alkylsulfonic acid group, -CO ₂ R ⁵ , -OCOR ⁶ , -OR ⁷ , -CO ₂ (CH | ₂ CH (R ⁸ ) O m _4- (CH ₂ CH (R ⁹ ) O) _{m5 [CH 2 CH 2 (CH 2)} m7 O ] _{^{m6 (R 10), -CO 2}} R 11 -CR 12 -CHR 13, -CO 2 -CO ₂ CHCH ₃ OR ¹⁴ or -CO ₂ (CH ₂ ) _r -CHR ¹⁵ CHR ¹⁶ O [CO (CH ₂ ) _s CHR ¹⁷ (CH ₂ ) _t CHR | ¹⁸ O] _u -H is represented, R ⁵ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or a hydroxyalkyl group having 3 to 6 carbon atoms, and R ⁶ and R ⁷ are hydrogen atoms as the same or different groups. , An alkyl group having 1 to 18 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms, R ⁸ , R ⁹ and R ¹⁰ represent the same or different groups and represent a hydrogen atom or a methyl group, and R ¹¹ represents 1 to C An alkylene group of 10 or — (CH ₂ CH ₂ O) pCH ₂ —, R ¹² and R ¹³ are the same or different, and represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and R ¹⁴ is 1 carbon atom. An alkyl group of ˜18, m ₄ represents an integer from 1 to 20, m ₅ and m ₆ represent an integer from 0 to 20, m ₇ represents 1 or 2, and m ₈ represents an integer from 0 to 50 P represents an integer of 1 to 10, R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are the same or different groups, represent a hydrogen atom or a methyl group, r represents an integer of 0 to 2, s and t are integers from 0 to 3 And u represents an integer of 1 to 5.)] or the following general formula (IV) CH ₂ = C (Z ¹⁾ [CO ₂ (CH _{2) 3] ^{m9 -Si (Z 1) 2 (}} Z 3) (Ⅳ) [Wherein Z ¹ represents a hydrogen atom or a methyl group, and Z ² and Z ³ are the same or different groups and include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an alkylcarbonyloxy having 1 to 10 carbon atoms; Group, and m ₉ represents 0 or 1, provided that when m ₉ = 0, Z ¹ is a hydrogen atom. Method for producing a fluoroalkyl group-containing polymer. General formula (Ⅴ) (Ⅴ) Wherein R ^F is-(CH ₂ ) _{n 1} X, Where Y represents a hydrogen atom, sodium, potassium or ammonium, R ¹⁹ represents a hydrogen atom or a methyl group, n ₁ represents an integer of 1 to 10, x represents a fluorine atom, a chlorine atom or a hydrogen atom And a fluoroalkyl group-containing surfactant having a number average molecular weight of 500 to 5000, wherein n ₂ represents an integer of 0 to 8 and m represents an integer of 1 to 250. General formula (Ⅵ) [Wherein Z ¹ represents a hydrogen atom or a methyl group, Z ² and Z ³ are the same or different groups and represent an alkyl group, an alkoxy group, or an alkoxycarbonyl group having 1 to 10 carbon atoms, and R ¹ and R ³ are the same; Or as another group, a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms, R ² and R ⁴ are the same or different groups and represent a hydrogen atom, a halogen atom, a cyano group, an alkyl sulfonic acid group having 1 to 4 carbon atoms, amide alkylsulfonate group having a carbon number of ^{_{1 ~ 4, -CO 2 R 5}} , -OCOR 6, -OR 7, -CO 2 (CH 2 CH (R 8) O m4 - (CH 2 CH (R 9) O) m5 [ _{CH 2 CH 2 (CH 2)} m7 O ] ^{_{m6 (R 10), -CO |}} 2 R 11 -CR ¹² -CHR ¹³ , —CO ₂ CHCH ₃ OR ¹⁴ or —CO ₂ (CH ₂ ) _r —CHR ¹⁵ CHR ¹⁶ O [CO (CH ₂ ) _s CHR ¹⁷ (CH ₂ ) _t CHR ¹⁸ O] _u —H, is represented by R ^F _Is- (CH ₂ ) _n1 X, M ₁ represents an integer of 1 to 1000, m ₂ and m ₃ represents an integer of 0 to 3000, and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms or a hydroxy alkyl group having 3 to 6 carbon atoms. R ⁶ and R ⁷ are the same or different, and represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms, and R ⁸ , R ⁹ and R ¹⁰ are the same or different groups, Represents a hydrogen atom or a methyl group, R ¹¹ represents an alkylene group having 1 to 10 carbon atoms or-(CH ₂ CH ₂ O) pCH _2- , and R ¹² and R ¹³ are the same or different groups and represent a hydrogen atom or An alkyl group having 1 to 18 carbon atoms is represented, R ¹⁴ represents an alkyl group having 1 to 18 carbon atoms, m ₄ represents an integer of 1 to 10, m ₅ and m ₆ represent an integer of 0 to 20, and m ₇ represents 1 Or 2, m ₈ represents an integer of 0 to 5, P represents an integer of 1 to 10, and R ¹⁶ , R ¹⁶ , R ¹⁷ and R ¹⁸ are the same or different groups and represent a hydrogen atom or Methyl group, n ₁ Denotes an integer from 1 to 10, x denotes a fluorine atom, a chlorine atom or a hydrogen atom, n ₂ denotes an integer of 0 to 8, r denotes an integer of 0 to 2, s and t Denotes an integer from 0 to 3, U denotes an integer from 1 to 5, and m ₉ denotes 0 or 1. However, when m ₉ = 0, Z ¹ is a hydrogen atom.] It is selected from the group consisting of a fluoroalkyl group-containing polymer having a number average molecular weight of 500 to 1000000, its hydrolyzate, its hydrolyzed condensate and mixtures thereof. Surface treatment agent using the ingredient to be an active ingredient. General formula (Ⅶ) Wherein R ^F is-(CH ₂ ) _{n 1} X, n ₁ represents an integer of 1 to 10, x represents a fluorine atom, a chlorine atom and a hydrogen atom, n ₂ represents an integer of 0 to 8), and a fluoroalkane peroxide represented by the following general formula ( Ⅲ) CH ₂ = C (Z ¹ ) [CO ₂ (CH ₂ ) ₃ ] _m9 -Si (Z ² ) ₂ (Z ³ ) (Ⅷ) Wherein, Z ¹ represents a hydrogen atom or a methyl group and, Z ² and Z ³ are, as the same or different groups, represents an alkyl group of 1 to 10 carbon atoms, an alkoxy group or alkylcarbonyloxy, and m ₈ is 0 or 1 Is displayed. However, when m ₉ = 0, Z ¹ is a hydrogen atom.] And the silicon monomer represented by the formula (1) and / or CH ₂ = C (R ²⁰ ) (R ²¹ ) (Ⅸ) [Wherein, R ²⁰ represents a hydrogen atom, a halogen atom carboxylic acid group or an alkyl group having 1 to 5 carbon atoms, and R ²¹ represents a hydrogen atom, a halogen atom, a cyano group, a carboxylic acid group, a phenyl group, a polmiloxy group, a hydroxyl group, or a carbon number 1-20 alkyloxycarbonyl group, C1-C4 hydroxyalkyloxycarbonyl group, C1-C18 alkylcarbonyloxy group, C1-C18 hydroxyalkylcarbonyloxy group, C1-C8 alkyl ether A group, an alkyl sulfonic acid group having 1 to 18 carbon atoms, an amide alkyl sulfonic acid group having 1 to 4 carbon atoms, a hydroxy alkyl ether group having 1 to 18 carbon atoms, Or —CO ₂ (CH ₂ ) _r —CHR ¹⁵ CHR ¹⁶ O [CO (CH ₂ ) _s, CHR ¹⁷ (CH ₂ ) _t CHR ¹⁸ O] _u —H, and R ¹¹ represents a carbon having from 1 to 10 carbon atoms. An alkylene group or — (CH ₂ CH ₂ O) pCH ₂ —, R ¹² and R ¹³ are the same or different, and represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and R ¹⁴ is 1 to 18 carbon atoms An alkyl group of m ₄ represents an integer of 1 to 20, m ₅ and m ₆ represent an integer of 0 to 20, m ₇ represents 1 or 2, m ₈ represents an integer of 0 to 5, p represents an integer of 1 to 10, R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are the same or different groups, represent a hydrogen atom or a methyl group, r represents an integer of 0 to 2, s and t represents an integer of 0 to 3 and u represents an integer of 1 to 5).] A fluorine having a number average molecular weight of 500 to 1000000 obtained by reacting a raw material component containing a radically polymerizable monomer represented by Alkyl group-containing polymer as an essential polymer component, Then, the coating composition characterized in that it contains 0.01 to 100% by weight. ※ Note: The disclosure is based on the initial application.