DE1952585A1 - Fluorine-containing copolymer - Google Patents

Description

1339 Chestnut Street
Philadelphia, Pa. / UNITED STATES

Fluorine-containing copolymer

The present invention relates to new, valuable, fluorine-containing Copolymers, on polymeric mixtures of thermosetting, fluorine-containing Copolymers with non-fluorine-containing copolymers for use are suitable as coating preparations for solid substrates, and on tough, scratch-resistant, produced by heating or curing these coating preparations Films that make the coated substrate oleophobic (oil-repellent) and hydrophobic make (water-repellent).

Because of their low surface energies, fluorinated solids have the worst wettable and non-adhesive known surfaces. It was found that only the very outermost molecules on the surface of the solid need to be highly fluorinated in order to have a surface to result in extremely low surface energy. Hence it is for polymers Mixtures of fluorine-containing and non-fluorine-containing materials may be equally effective in making a surface oil and water repellent as a material consisting only of the fluorine-containing material, provided that the polymeric mixture hardens in such a way that the film surface olßophobic and hydrophobic properties are imparted. Mixtures of these fluorine-containing and non-fluorine-containing polymers are essential cheaper than the fluorine-containing polymers with the same coating thicknesses.

009817 / $ 1 01

The critical surface tension of a solid surface is characteristic of the oleophobic and hydrophobic properties of this surface. The crystal surface tension is determined by measuring the contact angles of wetting by a number of related liquids. Provided a treated surface is sufficiently smooth and clean, the equilibrium contact angle θ of a sessile drop of any pure liquid on the horizontal surface is a reproducible property measured by a goniometer at the solid / liquid / gas interface can be. Then a so-called "Zisman plot" of the cosine Q is made against the surface tension P of the liquids in the test series, and extrapolation gives the graphical section where cosine G equals 1, ie where Θ = Is zero (which defines a condition of full wetting). This graphical section is defined as the critical surface tension of wetting (dynes / cm). As shown in U.S. Naval Research Laboratory Report No. 6-324 dated Oct. 21, 1965, the use of any homologous series of liquids gives essentially the same value for the wetting crystal surface tension.

The aim of the present invention is to create new, fluorine-containing

Ϊ '■'"\ ■

Copolymers.

Another aim is to create coating preparations for solid substrates, the former consisting of a thermosetting polymer mixture of fluorine-containing copolymers and non-fluorine-containing copolymers, the non-fluorine-containing copolymers making up the majority of the polymers Form mixtures.

009817/1801

According to the invention, a thermosetting polymer mixture of a fluorine-containing copolymer and a non-fluorine-containing copolymer after application as a film on a solid substrate makes the coated surface of the solid oleophobic and hydrophobic and is resistant to heat and light, non-discoloring and durable.

In addition, according to the present invention, there is a method of coating solid substrates with a thermosetting polymer mixture of a fluorine-containing copolymer and a non-fluorine-containing copolymer created to provide a scratch-resistant, moisture- and solvent-resistant, stain-resistant, to give heat-resistant and corrosion-resistant film.

According to the invention, thermosetting polymeric mixtures are prepared by Mixing fluorine-containing copolymers and non-fluorine-containing copolymers. The thermosetting non-fluorine-containing copolymer comprises (1) a copolymer produced by reacting an aldehyde with an acrylic resin containing amide groups or (2) a copolymer produced by reacting at least one ethylenically unsaturated monomer with a monomer of the following structure:

CH ₂ = C (R ₁ ) CaM (referred to as structure I), where R ,, denotes H or CH- and M has the following meanings:
-OH;
-OCH ₂ C (R ₂ ) HOH, where R _{2 is} H or CH ₃ ;

-OCH ₉ CHCH ₉ ; or -OCH ₉ CH = CH ₀

\. / ■ 2 2

0 ·

The thermosetting, fluorine-containing copolymer is derived from reaction of (a) the functionally reactive monomer of the structure:

^CH 2 = C (Rj) COX (hereinafter referred to as structure II), in which R "

0 0 9 817/1801

ÖAD

is H or CHo and X has the following meaning: -NHR ^, where R ^ is H or a C ₁ to C ^ alkyl radical; -OH; . _

-OCH ₀ C (RjHOH;, where R- is H or CHo;

-OCH ₀ CHCH ₀ ; or -OCH ₀ CH = CH ₀ O

with (b) a monomer of the following structure:

RJ ⁵ (hereinafter referred to as Structure III), in which P for

-0OCCR ^ = CHo and R ₁ ^ means H or CH ₀ , and R "has the following meaning ο c ο J> 1

I has:

R ₉ (CF ₀ ) CH ₉ -, where R “denotes F or H and ¹ a is an integer between 1 and 20; .

(CFo) ₂ CRs ( ⁰ ^ b '^{wot> ei R} 8 ^{F or H} ^ if b = ο, and R _Q stands for F if B is an integer between 1 and 18; or _n (CC ^ F _1n ) CH ₀ -, where R _{n is} F or CF ₀ ... and η is an integer 7 ο lu / Zy η ώη + ι

is between 1 and k and where c- denotes an alicyclic structure;

and (c) an aldehyde when X is -NffiL.

The fluorine-containing copolymers according to the invention have a molecular weight below 10,000, preferably between 150 and 300. These fluorine-containing Copolymers are obtained in particular by reacting about 5-30% by weight of a functionally reactive monomer of structure II, preferably about 15% by weight, with about 70-95% by weight of the monomer of structure III and with an aldehyde when X of structure II is -NHR ^. The copolymers obtained are soluble in non-halogenated organic solvents, such as butanol or xylene or mixtures thereof, and contain sufficient

Fluorine of the appropriate structural form to make the copolymers oleophobic do.

009817/1801

8AD ORIGINAL

- 5 - 1955585

Aldehydes that are used to react with an acrylic resin containing amide groups Formation of a thermosetting, non-fluorine-containing polymer or with the fluorine-containing copolymer when X of structure II is -NHR ^ is used include formaldehyde, acetaldehyde, butyraldehyde, and furfural.

The thermosetting polymeric mixtures of the present invention, once applied to the desired solid substrate, can be cured at moderately elevated temperatures with or without an added catalyst. When the thermosetting mixtures according to the invention have cured, the surface, the air / film interface, is given the repellent properties of the fluorine-containing copolymer. It has been found that the thermosetting polymeric blends with only about 0.1 wt .- $ of the thermosetting fluorine-containing interpolymer are effective, _r to coatings on solid substrates such as metal, wood, concrete, glass and plastic e, sowohl.hydrophobe as also to impart oleophobic properties. Surprisingly, it is not necessary to use more than about 10 percent - to use $> of the thermosetting fluorine-containing interpolymer in the novel, thermosetting mixtures.. Nevertheless, higher or lower percentages of thermosetting, fluorine-containing copolymer can be used, the upper limit being determined by economic considerations. "

The present invention also includes dispersions or latices of the thermosetting, polymeric mixtures and materials treated with the thermosetting polymeric mixtures. The present invention also encompasses a process for treating solid substrates to achieve a scratch-resistant, moisture- and solvent-resistant, stain-resistant, heat-resistant and corrosion-resistant film. This procedure includes the Treatment of a solid substrate with the above-mentioned thermosetting,

00981771801,

polymeric mixture and heating the treated substrate to a temperature between about 75-20O ° C. for a period between about 10 minutes to about 10 hours.

A Fluorkomonomeren of structure III, whereupon% $ - As mentioned above, the thermosetting fluorine-containing copolymers are formed by copolymerizing (a) 5-30 wt .- ^ a functionally reactive monomers of the structure II with (b) 70-95 wt. an aldehyde is added when X is in structure

e.g.
II stands for -NHR ^. It can be the following, functionally reactive

Monomers of structure II are mentioned: CH ₂ CHCONH ₂ CH

CHoC (CHo) COOH CH ₂ CHCOOCh ₂ CH ₂ OH CH ₂ C (Ch ₃ ) COOCH ₂ CH ₂ OH

CHoCHCOOCHoCHO 2 2 _V / 2

e.g. '■

The following monomers of structure III are also mentioned:

CH ₀ C (CH JCOOCHo (CC ^ F ₁₁ ); where c- stands for «jrs alicyclic structure

CH ₉ C (CHo) COOCH (CFo) ο

£. J JC

CHoC (CHo) COOCHo (CFo), _L H

CJC £. ¹ V

CH ₂ CHC00CH ₂ (CF ₂ J ₆ H

CH ₂ C (CH ₃ ) COO (CF ₂ CH ₂ CHCOOCH ₂ Cf ₂ H

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CH ₂ C (CKo) C00CH ₂ (CC ^ ₁₀ ) CFo, where c- is an alicyclic structure.

The thermosetting, non-fluorine-containing copolymers which can be used according to the invention are prepared by reacting an aldehyde with acrylic resin containing ara.ügmppen, ^as listed in the table below. "AA" means an ethylenically unsaturated monomer with an amide group; "MA" means methyl acrylate; "ST" means styrene; "BM" means butyl methacrylate, "MM" means methyl methacrylate; "VT" means vinyltoluene; "A" means acrylonitrile; "EA" means ethyl acrylate; ¹¹ C "means chloroprene;" VC "means vinyl chloride; ¹¹ EHA" means ethylhexyl acrylate; and "B" means butadiene;

10 $ ΑΛ; 75% MA; 15 $ ST 15 i AA; 85 i RA $ 15 AA; 85 % MM-15 P AA; 85 i VT 15 % AA; 20 % A; 65 % EA 15% AA; ^ 2.5 i C; ^ 2.5 i ST 15 i AA; 25 % VC; $ 60 EA £ 20 AA; £ 40 Bi £ 40 ST '15 & AA; 25 i FM-, 60 ^ EA (the percentage is given in weight-76 in each case). .

The percentage of ethylene used in the above acrylic resins unsaturated monomers containing an amide group (e.g. acrylamide, methacrylamide etc.) can vary between about 3-25% by weight. Other monomers that polymerized with the ethylenically unsaturated, amide group-containing monomer are isobutyl acrylate, hexyl acrylate, octyl acrylate, dibut-ylraalest, etc. In general, those with. the ethylenically unsaturated, monomers containing an amide group are preferred to be polymerized monomers

00 98.17 / 18Qt

meren a single CH ₉ = C group in the end position.

Other non-fluorine-containing copolymers which can be used according to the invention include: (2-Hydroxy) propyl methacrylate copolymer, produced by reaction of methyl methacrylate, ethyl acrylate and (2-hydroxy) propyl methacrylate; Glycidyl methacrylate copolymer, produced by reacting methyl methacrylate, Glycidyl methacrylate and ethyl acrylate; and methacrylic acid copolymer, produced by reacting methyl methacrylate, ethyl acrylate and Methacrylic acid. These mixed polymers are produced by conversion from. at least one ethylenically unsaturated monomer with a monomer of structure I. Ethylenically unsaturated monomers include, for example, alkyl latex and methacrylates, such as methyl acrylate and methacrylate, propyl acrylate and methacrylate, Isoamyl acrylate and methacrylate, octadecyl acrylate and methacrylate and cetylacrylate and methacrylate; Vinyl esters of aliphatic acids, such as vinyl acetate, Vinyl caprylate and vinyl stearate; Styrene and alkyl styrenes such as methyl styrene j Vinyl halides such as vinyl fluoride and vinyl chloride; Vinylidene halides, like vinylidene fluoride and vinylidene chloride! Vinyl alkyl ketones such as , .Vinyl methyl ketone and vinyl ethyl ketone; and 1,3-butadiene.

Both the fluorine-containing and the non-fluorine-containing ones according to the invention Copolymers are easily produced by copolymerizing the corresponding Monomers according to known processes, such as solution polymerization and emulsion polymerization, using free radical polymerization initiators.

In the solution the combined monomers in a solvent at a concentration of about 15-70 are -.% Dissolved. The preferred solvents for the preparation of these copolymers are those in which all monomeric components and the resulting copolymer are soluble.

0 0 9817/1801

ORIGINAL

- J ■ "

• are borrowed. For example, isopropyl alcohol, n-butyl alcohol, xylene and dimethoxyethane can be used as Solvents can be used alone or in combination. Opposite

• t if necessary, relatively low-boiling solvents such as isopropyl

alcohol and acetone, a moderation of the reaction.

There may be a Mischpolymerisationstemperatur between about 25-150 C, are preferably employed between about 60-120 ⁰ C.. The reaction can be run for any desired duration, usually 1-4 hours.

Usually a catalyst is used as a copolymerization initiator in a concentration of 0.1-4% by weight of the reaction mixture is used. Suitable Catalysts are benzoyl peroxide, lauroyl peroxide, acetyl peroxide, cyclohexanone peroxide, tert-butyl peroxide, p-menthane hydroperoxide, tert-butyl hydroperoxide and cumene hydroperoxide. Azo catalysts, such as azobisisobutyronitrile, be used, it is usually convenient to use the initiator added batchwise to the mixture of all other ingredients at the desired reaction temperature in order to moderate the strongly exothermic reaction.

If a high solids, relatively low viscosity solution is to be prepared for coating purposes, it is normally desirable to use a chain modifier to control molecular weight. Preferred modifying agents are octyl mercaptan, decyl mercaptan, η- or tert-dodecyl mercaptan, usually in a concentration between 0.3-3 %. Other modifying agents can also be used, such as pentachloroethane, trichlorobromoethane and cumene.

The emulsion polymerization takes place in a * with a stirrer and external means reaction vessel provided for heating or cooling the charge. The monomers to be copolymerized are in a water solution of a surface

009817/1801

active agent emulsified to a given emulsion concentration of about 5-50 %. To achieve the interpolymerization in the presence of an added catalyst, the temperature is usually increased to about 30-70 ° C. Suitable catalysts include benzoyl peroxide, Laurylperoxyd, tert-butyl perbenzoate, i-Hydroxycyclohexylhydroperoxyd, tert-butyl peroxide, tert, -Butylhydroperoxyd, 3-Carboxvpropionylperoxyd, acetyl peroxide, 2,2'-AzQdIiSobutyramidindihydrochlorid, 2.2 ^I -Azodiisobutyronitril, 2.2 '-Azobis ^, ^ - diraethyl - ^ - raethoxyvaleronitril), matriur peroxide, barium peroxide, hydrogen peroxide, ammonium pereulphate, potassium persulphate etc. The catalyst concentration for the copolymerization is usually / between 0.01-2 %, based on the weight of the monomers.

Anionic, cationic or non-ionic emulsifiers can be used as surface-active agents to stabilize the emulsion during its formation and interpolymerization, but the cationic or non-ionic * surface-active agents are preferred. Anionic emulsifiers are, for example, alkyl-iC, - to C ^ o) sodium sulphate, sodium alkyl (C ₁ 2-C _l Q) benzene sulfonate, sodium alkyl naphthalene sulfonate, sodium salt of sulfated alkenyl (C ₁ -C ^ ₁ Q) acetate , Sodium oleate _r the sodium salt of sulfated methyl oleate and AimoniumperfXuoralkanoat. Useful cationic agents include DodecyltrmethylammoniiMacetat, Tromethyltetradecylammoniumchlorid, HexadecyltrimethylammoniumbroBiid, trimethyloctadecylammonium chloride, (Dodecyiniethylbenzyl) -triBiethylamnK> niiiacliLorid _t Benzyldodecyldiiuethylammöniumchlorid and N- £ 2- (DiäthylaBdno) -äthyl7-oleamidhydrochlorid.

Useful nonionic surfactants include condensation products of ethylene oxide with hexylphenol, isooctylphenol, hexadecanol, oleic acid

009817/1801

Alkane (C .-- Cr) thiols, alkyl (C ^ - C-, ο) amines, etc. Furthermore, small Amounts of chain transfer agents may be present during the interpolymerization, such as an alkanethiol having 1-12 carbon atoms.

Those which can be used according to the invention for the formation of the thermosetting copolymers Aldehydes include formaldehyde, acetaldehyde, butyraldehyde, and furfural. Formaldehyde, the preferred aldehyde, can be found in the form of paraformaldehyde, Hexamethylenetetramine or in alcohol or water solution can be used. It becomes an alcohol solution of formaldehyde, especially the n-butanol solution with about ^ + 0 $ aldehyde is preferred. Usually it is convenient at least 1.7 moles of formaldehyde per col of with the. Formaldehyde convertible monomers in To use mixed polymer, although amounts between about 0, ^ - 3 equivalents can be used.

Suitable substrates for applying the thermosetting polymeric mixtures of the present invention are solid materials such as tin plates, Sdwarzbledi, he phosphates steel, cold rolled steel, aluminum foil, wood, glass » Plastics, concrete and wall boards. Die.from the thermosetting polymers Coating preparations obtained from mixtures form on these solid substrates Films with excellent flexibility, adhesion and freedom of unwanted color formation. Furthermore, these excellent properties are combined with scratch resistance, moisture resistance, stain resistance, Grease resistance, heat resistance, detergent resistance and corrosion resistance are obtained. These properties make the invention thermosetting, buffing mixtures suitable as final coatings for Installation items such as stoves, refrigerators, air conditioners, washing machines and water heaters, and external surfaces such as wall coverings and canopies made of aluminum,

009817/1801

building

■ '". ^: - 12 - ■■" ■

The thermosetting polymeric blends of the present invention can can be applied by brushing, dipping, spraying, padding, rolling or any combination of these methods. The thermosetting polymeric blends are applied to a solid substrate, preferably from an organic solution upset.

The thermosetting, polymeric mixtures can be cured by heating the upper surface for 10 minutes to 10 hours to a temperature between about 75-200 G. Are shorter curing times or lower temperatures required, can the thermosetting polymeric f mixture prior to application to the surface, an acid catalyst, such as 0.1-1

$> Oxalic acid, trichloroacetic acid, p-toluenesulfonic acid or phosphoric acid can be added. As is to be expected from an addition of 0.5 wt .- $ phosphoric acid to result in a cure in 30 minutes at 90 C., which ertspricht a non-catalysed curing of 30 minutes at 17O ⁰ C.. The coated material obtained is water and oil repellent.

The following examples illustrate the present invention without restricting it. The following non-fluorine-containing copolymers are mentioned in the examples:
f copolymer A

In a 2-1 three-necked tube equipped with a stirrer, reflux condenser and thermometer

The following ingredients were given to round-bottom flasks:

Ethyl acrylate 225 g

Styrene 200 g

. Acrylamide 75 g

n-butanol 500 g

n-Dodecylnßrcaptan '12 ecm

0 0 9817/1801

ORiQlNAL

The mixture was then heated to reflux with an oil bath. . With stirring, a 50% solution of cumene hydro was added to the heated mixture peroxide added periodically in the following way:

Time; std 0 1.5-3 ^ .5 6. 7.5

Cumene hydro- _{£ £ 2 2}

peroxide; ecm

Conversion; # 0 "^ 6.2 56.9 67.9 81.3 90.1

After 9 hours the mixture was cooled and kept at room temperature overnight. The following ingredients were added to the cooled mixture:
Maleic anhydride 0.75 S

Butyl Formocel (^ O wt .- # formaldehyde, '~ _{?? t} -

53 Gewo -j6 n-butanol and 7 wt -. $ Water). ⁵

The mixture was then heated to 105 ° C. for 3 hours. After this time, 25 ecm of water and 200 ecm of organic solvent were distilled into a Dean-Stark trap. The remaining mixture was cooled to room temperature; it weighed 1077 g and had a total solids content of 50.2 #, Copolymer B

The following ingredients were mixed in a dropping funnel and added at 500 ecm refluxing n-butanol within 2 hours while rinsing with

Nitrogen added;

Methyl methacrylate 250 g

(2-hydroxy) propyl methacrylate 100 g

Ethyl acrylate 150 g

n-dodecylmereaptane 5 g

Cumene hydroperoxide x 5g

The mixture was then refluxed for a further h hours. The resulting mixture weighed 885 grams and had a total solids content of $ 56. The non-volatile residue was 500 g.

009817/1801

original

- mixed polymer C

The following ingredients were mixed in a dropping funnel and added to 500 g of refluxing xylene over a period of 3 hours:

Methyl methacrylate '250 g

Glycidyl methacrylate 100 g

- Ethyl acrylate 150 g n-dodecyl mercaptan 5 g Di-tert-butyl peroxide ■ 5g

The mixture was then refluxed for a further 3 hours. The resulting mixture had a total solids content of 50 ₁ 3 ί> and weighed 1005 g. The non-volatile residue was 500 g.
Copolymer D

The following ingredients became 125 g of reflux in 2 hours Xylene added:

Methyl methacrylate 90 g

Ethyl acrylate 90 g

Methacrylic acid 20 g

Di-tert-butyl peroxide 4g

n-dodecyl mercaptan 2g

The mixture was then refluxed for a further 2 hours. The resulting mixture had a total solids content of 57 * 3 %. The non-volatile residue was 200 g. . '

example 1

Into a 250 cc three-necked round bottom flask equipped with a reflux condenser, stirrer and dropping funnel 75 g of xylene were added. The xylene was washed with an oil bath heated to reflux temperature with a slow stream of nitrogen through the Flask was passed. Then, within 2 hours, it became the following Mixture added dropwise to the refluxing xylene:

009817/1801

Perfluorocyclohexane arbinol methacrylate ^ 5 E.

^ iethacrylic acid · 5 ■ K

n-dodecyl mercaptan 4 g

Di-tert-butyl peroxide 2 g

The mixture was refluxed for an additional 3 hours and then heated to 65 ° C. cooled down. 25 g of abs were added to the cooled mixture. Ethanol added, then the mixture was cooled to room temperature and decanted.

The resulting thermosetting polymeric material weighed 157.8 g, total solids content of 26.4 x. Ji and a non-volatile residue of 41.5 g · Its analysis was as follows: C = 41.76 $ \ H = 3.66- ^; S = 1.98 p \ F = $ 37.01

In different proportions a physical mixture of the thermosetting solution of Example 1 and copolymer A prepared, i. a mixture of the thermosetting, fluorine-containing copolymer and the

thermosetting, non-fluorine-containing copolymer. Then it became the thermosetting polymer mixture for about 20 minutes at about 150 ° C. in a compressed air oven to a hard, smooth film with excellent adhesion to the glass surface hardened. The following table shows the contact angles that were obtained when the water droplets and drops -of C, -C. ^ normal hydrocarbon solvents was on the surface of the cured film. The table also shows the critical surface tension obtained by plotting of the cosine of the contact angle versus the surface tension. ·

/ and applied to a smooth glass surface

009817/1801

i;?! BATH

Contact angle

$> fluorine content, -

Mixed polyra.in

mixture

normal hydrocarbon solvents on the surface of the cured film

Ί6

'12

'8th

Water critical surfaces

tension; Dyn / cra

co

100
88.3
72.7
69.5
53.5
27.6
17.2
12.8

2.9 0.0

56
50
54
51
57
52
58

52

23

62
48
48
47
50
• 56
55
50

^ 3
40
45
44
46

44
41

40 30 37 36 31 37 39 41

13 18

13 12

20th

13th

24 21

30th

90 22.1 95 21.0 90 21.2 90 21.5 107 21.7 102 21.5 105 21.5 109 21.5 100 21.4 28

ON I.

-. 1? Example 2

According to Example 1, methacrylic acid was reacted with the monomer CHoC (CHo) COOCH ₂ (CF ₂ ) J ¹ to form a thermosetting, fluorine-containing copolymer.

Then the obtained thermosetting, fluorine-containing copolymer was with the thermosetting, non-fluorine-containing copolymer A in different Mixed conditions. According to Example 1, contact angles and critical The surface tension of these thermosetting polymeric blends was determined and recorded in the following table:

009817/1801

Kont aktwin kel

ί fluorine content. Mixed polymer ■ in a mixture

n-hydrocarbon solution on surface. amusing films

Ί6

Ί4

^C 12 ^C io

'8 water critical surface tension; Dynes / cm

100
69.3
51.5
42.2

19.5
7.8
5.5
2.9
0.9
0.0

42

46 46

47 64 62 63 60 60 20

40 44 42 44 58 56 59 58 62

32

42

36

35

53

54

52 56

53

19 13

29 40 41 40 40 47

16 10 24 34 29 35 38 35

10

19 27 20 27 16 26

88 22.5 93 20.0 105 22.0 90 18.1 115 17.4 108 17.5 110 17.3 115 17.8 113 17.5

00

Example ß_

According to Example 1, methacrylic acid was _{mixed with the monomer GH 9} G (CHo) COOCH (CF) .H to form a thermosetting, fluorine-containing mixture

polymer implemented.

The thermosetting, fluorine-containing copolymer obtained was then in different proportions with the thermosetting, non-fluorine containing one Copolymer A mixed. Then, as in Example 1, contact angles were made and critical surface tension of these thermosetting polymeric blends

certainly.

$ .Fluorine content, η-hydrocarbon solvent on upper water critical mixed polymer in surface of the cured film surface mixture C ₁ / C, C ₁₀ C _1n Co Cr, C _A tension; ¹⁶ I ^ ^{U 1Q} ■ S / 6 dynes / cm

100
71.1 50 3o, i 8.7

40 34 10 - 42 41 38 25th __ 46 40 30th 10 41 40 34 25th 40 34 27 19th 39 30th 27 20th 38 25th 19th - 33 26th 14th - 16

87 26.1 - 87 25.8 90 24.5 84 24.2 87 22.5 90 23.5 81 22.9 83 24.5 84 26.0 81 28.0

1.6 0.5 0.3 ο, ο

Example 4

The following materials were put into one equipped with a stirrer, reflux condenser and thermometer provided 250 cc three-necked round-bottomed flask:

tv-'Hydrogen - perfluorobutyl methacrylate 22.5 g

ß-hydroxyethyl methacrylate 2.5 g

n-butanol 100 g

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Then the mixture was heated to reflux and the mixture was periodically added 3t5 g of n-dodecyl mercaptan and 2.0 g of guraol hydroperoxide were added.

After 6 hours at reflux, the mixture was cooled to about 65 ⁰ C., and to the cooled mixture were 25 g of abs. Ethanol added. It was then cooled to room temperature and decanted.

The resultant · thermosetting polymeric material weighed 115.9 g, had von.21,0 g a total solids content of 18.1 °] o and a non-volatile residue. His analysis was as follows: C = $ 41.24 \ H = $ 4.21; F = 28.34 %; S = $ 2.45.

According to Example 1, the physical blends of thermosetting Solutions of the copolymer A and Example 4 in different proportions ,, nits produced, applied to smooth glass surfaces and cured. The following table shows the contact angles and critical surface tension

these mixtures.

Contact angle

i fluorine-n-hydrocarbon solvent on water critical upper Lt f M ^ "v, surface of the cured films water critical upper hold .mix- -z -z - r - ^ - r - - surface tension

polymcin ° 16 ^υ ΐ4 ^υ 12 ⁰ Io ^υ 8 ^Ü 7 6 dynes / cm

100 59 55 50 32 29 15 ~ 103 20.4

46 41 39 23 16 - 103 20.3

51 46 39 28 22 15 100 20.0 57 .47 42 31 28 10 102 19.4

55 47 41 32 26 12 -. '19, 7

56 50 41 33 26 12 108 19.6 53 50 46 40 25 15 105 19.6

52 49 44 34 25 17 108 19.7 21 15 - - - - 81. 24.8

- ■; - - ■ - ■ - ■ 81 ^ 27

82.01 52 45.84 57 19.61 60 7.07 60 1.46 60 0.47 60 0.21 57 0.012 26th 0.000 • 15th

0098 17/1801

example

According to Example 4, β-hydroxyethyl _{methacrylate was reacted with the monomer CH 2} C (CH ^) COOCH ₂ (Gf ₂ ) KH to form a thermosetting, fluorine-containing copolymer.

The thermosetting, fluorine-containing copolymer obtained was then in different proportions with the thermosetting, non-fluorine containing one Copolymer A mixed. Then, as in Example 1, contact angles and critical surface tension of these mixtures was determined.

Contact angle

io fluorine content, η-hydrocarbon solvent on mixed polymer. Surface of the cured films water critical surface mixture Ow C ^ C ₁₂ C _1n Cg C " ^C 6 surface tension D.yn / cw

100 40 32 6th - - - 59.9 36 24 - - - 20.9 40 36 28 - - 6.9 4-7 38 32 26th - 2.8 52 4-3 35 32 19th 1.07 44 38 33 26th 15th 0.60 44 39 36 28 18th 0.49 40 35 35 21 17th 0.031 21 11th _- - - 0.000 - - - - - B e i s ρ i e 1

85 26th 80 26th 81 25th 83 23 90 21 92 21 90 21 90 ■ '21 81 26th 81 > 28

75 g of xylene were placed in a 250 cc three-necked round bottom flask equipped with a reflux condenser, stirrer and dropping funnel. The xylene was heated to reflux; then the following mixture was added dropwise within 2 hours:

Perfluorocyclohexane carbinol methacrylate 4-2.5 g

Glycidyl methacrylate 7.5 g

n-dodecyl mercaptan 4.0 g

Di-tort.-butyl peroxide 2.0 g

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The mixture was refluxed for an additional 4 hours, then to room temperature cooled and decanted.

The resulting thermosetting polymeric material weighed 121.3 grams and had a total solids content of 37.2 ⁽ yes and a non-volatile residue of 45.3 45.3 grams and the following analysis: C = 44.26 %; H = 3, 59 % i F = 34.16 p, S = 1.38 #.

The thermosetting, fluorine-containing copolymer obtained was in different Relationships with the thermosetting, non-fluorine-containing mixture " polymer A mixed. Then, as in Example 1, contact angles and

critical surface tension of these thermosetting polymeric mixtures

certainly.

Contact angle

% fluorine content. n-hydrocarbon solvents on krif h ob

Mixed polymer the surfaces of the cured films ", ..,

in mixes C ₁₆ C ₁ , C ₁₂ C ₁₀ C ₈ C ₇ 0, water "g ^ T» -

61 55 46 28 - - - 105 23

48.3 56 46 43 17 - - - 104 23

23.1 54 48 47 31 - - - 101 23

9.9 52 50 40 29 12 - - 104 22 ^:

) 1.53 57 53 49 32 104 23,

0.97 49 45 38 27 11 - - 103 23

0.045 35 29 23 - - - - 82 26

0.000 10 - - - - - -. 81 > 28

An extremely good resistance to Salzsprühmaterial and detergent was obtained when the thermosetting polymeric blend of this example primed to a film thickness of 0.033 ^"1 ^ ¹ ^ ^au aufsprühte and non-primed-steel panels and was cured 30 minutes at 150 ⁰ C..

009817/1801

example

The following materials were put into one with a stirrer, reflux condenser and 250cc 3-neck round-bottom flask fitted with a thermometer:

Hexafluoroisopropyl methacrylate 21.25 g

Acrylamide 3 »75 g

h-butanol 100 g

The mixture was then heated to reflux (about 117 ° C.), And in the following In this way, n-dodecyl mercaptan and cumene hydroperoxide were periodically mixed

admitted:

Time; std 0 1 2 3 k 5

n-dodecylmer- 3 2 2 110

captan; ecm -

Cumene hydroper- . _{First Λ} in

oxide; ecm ι ι ι ι ι ü

te

After 6 hours under reflux the mixture to 9O ⁰ C. was cooled, and the mixture abgeküiten the following ingredients were added:

Maleic anhydride 0.3 g

Butyl Fonnocel 20 ecm

The mixture was then heated to about 105 ° C. for 1 hour. heated. About 25 ecm of organic solvent and water were removed in a Dean-Stark trap. The remaining polymeric mixture was cooled to room temperature and decanted; it weighed 13.3 g and had a total solids content of 15.09 # and a non-volatile residue of 20.2 g. The thermosetting polymeric material showed the following analysis: C = 51.52 % \ H = 6, ^ 8 =; N = ■ 3.55 % ', F = 18.78 #;

009817/1801

In different proportions a physical mixture was made the ... heat-hardening solution of the copolymer A and Example 7 »that is, a Mixture of heat-curing, non-fluorine-containing and fluorine-containing copolymers ^ produced and applied to a smooth glass surface. Then the polymer mixture was about 20 minutes at about 150 ° C. in a compressed air oven to form a hard, smooth film with excellent adhesion to the glass surface hardened. The following table shows the contact angles obtained when placing drops of water and C ^ -C ^ normal paraffin Gave hydrocarbon solvents on the surface of the cured film. The table also shows the critical surface tension obtained by plotting of the cosine of the contact angle versus the surface tension.

Contact angle '

$ fluorine content . normal hydrocarbon solvents water ^C 14 ^C 12 ^C 10 ^C 8 ^G 7 ^C 6 90 critical waiter Mixed polymer
in mixture ^C 16 50 39 33 19th 89 surface tension
Dynes / cm 100 52 53 50 38 28 - 90 21.5 82.9 55 45 39 36 28 19th - 95 20.9 46.6 52 52 49 43 36 29 9 106 19.8 11.9 58 54 48 46 35 25th 9 100 19.1 3.24 60 56 50 45 39 29 10 103 19.3 1.72 58 54 48 43 39 27 12th 87 19.2 0.428 54 48 44 39 26th 10 - 83 19.0 0.093 51 25th 21 - - - - 20.5 0.0024 29 - - - - - 24.5 0.000 12th 8th 28 B e i s ρ i e 1

Into a 250 cc three-necked flask equipped with a stirrer, flow tube and thermometer the following materials were given:

Perfluorocyclohexane carbinol methacrylate 42.5 g

Acrylamide 7.5 g

n-butanol 100 g

0 0 9817/1801

Then the mixture was heated to reflux (about 17O ⁰ C), and in the following manner n-Dodecylmercaptan.als, chain transfer agent and a 50 # Cumolhydroperoxydlösung sodium were added as initiator to the mixture periodically: time; std 0 12 3 ^ 5

n-dodecyl mercaptan,. _ -.

ecm 5 ^^ 000

Cumene hydroper- ₁

oxydf ecm ■ ι ι ι ι ι ü

After 6 hours at reflux, the mixture was cooled to 9O ⁰ G., 'then

the following ingredients were added to the cooled mixture:

Maleic anhydride 0.2 g

Butyl Formocel 20 ecm

The mixture was then heated to about 105 ° C. for 1 hour. heated. Organic solvent and water were removed in a Dean-Stark trap and the resulting polymeric mixture was cooled to room temperature; it showed the following analysis: C = Ψ5Λ3 ii H = ^, 71 & N = 4.03 i \ F = 30.72 £; S = 2.61 #.

According to Example 7, physical mixture / thermosetting solutions of mixed polymer A and Example 8 in different proportions, applied to a smooth glass surface and cured. The following table shows the contact angles and critical surface tension these mixtures.

009817/1801

26 - ^C l4 9 ^C 12 ^C 10 31 ^G 7 ° 6 19th 5 2585 61 56 48 39 24 i> fluorine content.
Mixed polymer Contact angle 63 59 53 44. 32 -. water critical
surfaces in mixture n-hydrocarbon solvent on surface
area of the cured films. 65 62 57 51 34 26th tension;
Dynes / cm . 100 ^C 16 64 61 59 50 43 31 108 20.0 88 66 65 61 56 51 ' 45 32 - 19.4 19th 68 65 61 58 52 43 32 108 18.4 8.8 69 65 61 58 51 44 34 - 16.9 0.94 66 63 60 56 46 41 32 108 16.8 0.20 68 62 59 - 39 28 108 • 16.8 0.073 69 41 31 22nd - - -_ 112 16.8 0.064 68 113 17.1 0.050 66 89 17.7 0.0068 65 84 22.9 0.000
B is ρ ie 47 80 28 16 1

According to Example 8, acrylamide was _{mixed with the monomer CH 2} C (CHo) COOCH ₂ (CF ₂ ) J?
and then with formaldehyde to form a thermosetting fluorine-containing one
Copolymer implemented.

Then the thermosetting, fluorine-containing copolymer obtained was in:. different proportions with the thermosetting, non-fluorine containing one. Copolymer A mixed. Then, as in Example 7, the contact angles became and critical surface tension of these polymer mixtures is determined.

00 98 1 7 / 1.801

- 27 contact angles

% fluorine content, normal hydrocarbon solvents, water, critical upper mixed polyra. surface tension on the surface of the cured films

in mixture C ^ C ^ C ₁₂ C _1Q Cg C "Cg Dyn / cm

100 68 63 57 55 46 39 24 98, .. 18.1 .. '

87.9 68 67 63 59 49 35 30 96 17.2

14.1 67 63 60 56 49 44 35 85 _ 16.7

2.92 69 66 63 59 & ^ 5 3 ^ 105 16.9

1.57 70 63 57 54 54 48 .33 -. 16.7

0.436 72 69 65 62 57 46 37 113 16.7

0.101 71 62 57 56 56 37 35 H3 16.8

0.0061 36 32 25 15 - - - 113 23.6

0.000 16 - '- - - - ~ ' - / v 28

Example 10

According to Example 8, acrylamide was made with the monomer

CH ₂ C (CHo) COOCH ₂ (CF ₂ ) ^ H and then reacted with formaldehyde to form a thermosetting fluorine-containing copolymer.

The obtained, fluorine-containing copolymer was then in different Relationships with the thermosetting, non-fluorine-containing copolymer A mixed. Then, as in Example 7, the contact angle and the crystal surface tension became of these thermosetting polymeric blends.

0 0 9 8 17/1801

. - 28 -

Contact angle

# fluorine content, normal hydrocarbon solvent water Mixed polymer, on the surface of the cured films

in mixture C

16

Ί4 ^υ 12 ^υ 10 ^υ 8

critical surface tension dynes / cm

100

91.0

48.5

25.4
5.83
4.14
0.610
0.260
0.0444-0.000

35

43 48

47 51 54 46

45 34 10

35

36

46

45

7 22

31

18th

48 45 41

49 4? 35 43 42 39 41 39 32

26 19 ~ ~

88 82 88 98 90

example

11th

According to Example 8, acrylamide was made with the monomers CH ₂ CHCOOCH

24.6

24.3

23.3

21.5

19.9

20.0

21.0

21.7

25th

27

Λί and then

with formaldehyde to form a thermosetting, fluorine-containing copolymer

■ 1.

sates implemented.

The thermosetting, fluorine-containing copolymer obtained was then in different proportions with the thermosetting, non-fluorine containing one Copolymer A mixed. Then, as in Example 7, the contact angles became and critical surface tension of these thermosetting polymeric blends certainly.

009817/1801

_ 29 - ^C 14 ^C 12 ^C 10 ^C 8 10 ^C 6 water 1952585 47 42 32 22nd 20th __ % fluorine content.
Mixed polymer Contact angle ■ 46 43 36 23 27 -. 81 critical waiter
surface tension} in mixture 50 47 40 34 28 14th 90 Dynes / cm 100 48 46 42 36 25th 10 98 21.7 87.0 normal hydrocarbon solvents
on the surface of the cured films 50 47 42 31 29 10 · 87 20.5 30.9 ^C 16 51 46 36 32 22nd 11th 90 19% 8 5.84 51 53 50 44 36 - 12th 87 18.8 2.81 58 48 43 37 34 13th 90 18.9 2.55 53 29 24 16 - 90 19.2 0Λ70 52 &O 19.0 0.177 50 12th 81 19.0 0.024 53 23 »5 π nno 56 * V / 2ft B e i s ρ i 53 34 12th JLw
e 1

According to Example 8, acrylamide was made with the monomer

₂₂₂ ) _1Q H and then reacted with formaldehyde to form a thermosetting, fluorine-containing copolymer.

The obtained fluorine-containing copolymer was mixed with the thermosetting, non-fluorine-containing copolymer A in different proportions. Then like in example? Contact angle and critical surface tension
of these thermosetting polymeric blends.

009817/1801

- 30 contact angles

$ fluorine content. normal hydrocarbon solvents water critical top copolymer, on surface of cured films. surface tension

in mixture

^C l6 ^C 14 ^C 12 ^C I0 ^C 8

Dynes / cm

100
56.4

32.7
11.8

3.2

3.2

1.2

0.37

0.0015

0, (

54 47 42 36 26 20 59 55 46 40 34 28 57 50 47 43 37 30

50 47 40

61
62

59
61
27

56 49 44 36 53 49 44 36

35 29 29 28

54 55
19th

49 45 36 26 49 44 35 28

90 18.5 104 17.7 - 17.9 100 17.7 - 17.8 100 18.0 103 18.0 104 17.8 81

> 28

example

Eat

According to Example 8, acrylamide with the monomer CHpCHCOOCHgCJF, -, and then with foimaldehyde to form a thermosetting, fluorine-containing copolymer implemented. .

The thermosetting, fluorine-containing copolymer obtained was in different Relationships with the thermosetting, non-fluorine-containing copolymer A mixed. Then, as in Example 7, the contact angle and critical surface tension of these polymer mixtures were determined.

00981771801

Kont aktwin ke1 '^

$ fluo.rhalt. normal hydrocarbon solvents water critical upper mixed polymer. surface tension on the surface of the cured films

in mixture G ^ C ₁ ^ C ^ ₂ C ₁₀ C _Q C "Cg Dyn / cra

100 80 74 57 42 27 22 15

37.1 106 74 72 6o 43 30 30

66 65 48 42 39 29 71 61 52 47 34 27

67 65 50, 48 33 25 61 56 53 43 37 27 60 57 50 41 35 21 59 "56 52 37 27. 25 40 35 30 20 17 14

Example 14

According to Example 8, acrylamide with the monomer CH ₀ CHCOOCH ₀ C ₀ F ₁ - and then

<c c, a 3

with foimaldehyde to form a thermosetting, fluorine-containing copolymer implemented.

The thermosetting, fluorine-containing copolymer obtained was then mixed with the thermosetting, non-fluorine-containing copolymer A in different Mixed conditions. Then, as in Example 7, the contact angles and critical surface tension of these thermosetting polymeric blends was found.

21.0 81 11.5 71 9.1 73 1.3 61 0.47 61 0.25 68 0.04 30th 0.00 0

71 18.5 - 18.2 98 18.2 97 18.2 105 18.2 - 18.2 - 18.2 __ 18.0 90 18.5 72 > 27.8

0 0 9 8 17/1801

Contact angle Surface < ^C 12 ier cured films V ^C 6 water critical waiter ⁰ Jo fluorine content. normal hydrocarbon solvents ^C 14 ■ #. S. 0 ^C 8 surface tension Mixed polymer * on 70 50 45 37 - - Dynes / cm in mixture ^C 16 58 50 45 35 - - 73 20.9 100 73 53 50 48 28 15th - 90 20.9 40 58 54 48 44 31 21 95 20.9 23.2 58 53 49 43 32 .26 15th 77 20.3 11.0 57 52 46 43 34 25th 17th 70 20.2 5.3 57 48 48 41 32 26th 15th 80 18.0. 1.6 55 53 37 44 31 15th - 95 18.0 0.66 48 45 34 24 - 92 18.0 0.30 54 - - - 93 20.4 0.05 47 76 - 0.00 - B e i s ρ i e 1

According to Example 8, acrylamide was made with the monomer

CH ₂ C (CHo) COOGH ₂ (CC ^ F ₁₀ ) C ₂ F- (where c denotes an alicyclic structure) and then reacted with formaldehyde to form a thermosetting, fluorine-containing copolymer.

The thermosetting, fluorine-containing copolymer obtained was then mixed with the thermosetting, non-fluorine-containing copolymer A mixed. According to Example 7 was found critical surface tension of this mixture 18.1. ,

Got extremely good resistance to salt spray material and detergents when applying the thermosetting polymeric blend of this example to one Film thickness of 0.033 mm was sprayed onto primed and unprimed steel and battens and 30 minutes at 150 ° 0. hardened »

009817/1801

The coating preparations according to the invention can be used to form any desired Color pigments such as titanium dioxide, carbon black, etc., can be added. Furthermore you can the other ingredients commonly used in coating preparations, such as germicides, fillers, drying agents, silicones, etc., can also be added.

The thermosetting polymeric blends of the present invention can be used alone as Coating preparations for the treatment of solid surfaces or in combination with other resins can be used. Those for combined use with the thermosetting polymeric mixtures according to the invention »especially Suitable resins are e.g. phenol formaldehyde, epoxy resins, Mäamin formaldehyde, Urea-formaldehyde, cellulosic resins, vinyl resins, polyester resins and acrylic resins.

Those treated with the thermosetting polymeric blends of the invention Surfaces are given the following favorable properties, among others: * Oil and water repellency and reduced adhesion to wax, asphalt, Glues, dirt and similar materials. Lower coefficients of friction are found, which leads to reduced erosion of the coating * The result of curing of the thermosetting according to the invention Coatings made from polymeric mixtures are highly hatred Hardness, flexibility, adhesion, impact resistance, acid resistance, solvent resistance and resistance to salt spray As such, they have excellent outdoor aging durability and the ability to different substrates have exceptional surface properties, i.e. low coefficient of friction as well as exceptional repulsion of watery ones and organic media, to lend *

009817/1801

■ The thermosetting polymeric mixtures according to the invention can be used as agents sur release from the mold and used as color additives. Using The thermosetting polymers according to the invention provide as coating preparations Mixtures create an oil-resistant surface that does not soil to any degree comparable to that of the untreated surface. The unique surface properties continue to make the thermosetting polymeric blends exceptional suitable as a cover on rollers or spools for purposes where there is accumulation of batteries should be avoided from materials that would otherwise adhere tenaciously, such as a sheet of paper or cardboard.

009117/1801

Claims (1)

Claims 1, - Fluorine-containing copolymer, consisting of the copolymerization product the end (a) a functionally reactive monomer of the formula CH ₂ = C (R ₃ ) COX. in which R _{3 is} H or CH ₃ and X is NHR ^, OH, OCH ₂ C (R ₅ ) HOH, OCH ₉ CHCH ₀ or OCH ₉ CH = CH, where R _{k is} H or a C '-C . Alkyl radical and R, - Ho or CH «means, and (b) a monomer of the formula in which P stands for 00CCRg = CH ₂ and R ₄ . R ₇ (CF ₂ ) CH ₂ , (CF ₃ ) ₂ CRg (CF ₂ ) _b or R ₀ (C-CgF.) Is CH, where Rg is H or CH ₃ , R _{7 is} F or H, a is a is an integer between 1 and 20, Rg is F or H when b = 0, and Rg is F when b is an integer between 1 and 18, R- F or CF _0. "means η is an integer between 1 and k- , and y η <dn + i c- stands for an alicyclic structure. 2. Copolymer according to claim 1, characterized in that it comprises about 5-30 wt. -4 of the monomer CH ₂ = C (R ₃ ) COX. 3. Copolymer according to claim 1 and 2, characterized in that X is HER ₁ and .das copolymer is a copolymerization product of an aldehyde, the CH ₂ = C (R ₃ ) COX and the compound of the formula RP. 4. Copolymer according to claim 3, characterized in that the aldehyde Is formaldehyde, acetaldehyde, butyraldehyde or furfural 5 · - Thermosetting polymer mixture, consisting of a mixture of (A) the fluorine-containing copolymer according to claims 1 and 2 with the prerequisite that the copolymer is a thermosetting Mischpolyweriaations- 009817/1801 Ί952585 ■ - 36 -; ■■; product of an aldehyde, the compound of the formula CH ₂ = C (Ro) COX and the formula RJ ⁹ , when X is NHR ^, and (B) a thermosetting, non-fluorine-containing copolymer, produced by (1) reaction of an aldehyde with an acrylic resin containing amide groups or (2) reaction of at least one ethylenically unsaturated monomer with a monomer of the structure CH ₂ = C (R ₁ ) COM, where R. is H or CH1, M is OH, OCH ₂ C (R ₂ ) HOH, OCH ₂ CHCH ₂ or OCH ₂ CH = CH ₂ and R _{2 is} H or CH ₃ . t 6, - polymer mixture according to claim 5 »characterized in that the Alde hyd is formaldehyde, acetaldehyde, butyraldehyde or furfural. 7.- Polymeric mixture according to claim 5 and 6, characterized in that the amide group-containing Ac ^ lharz is a copolymer of an ethylenically unsaturated monomer with an amide group and at least one other monomer with a single CH ₂ = C group. 8.- A method for coating solid surfaces, characterized in that the polymeric, thermosetting mixture according to claim 5 to 7 on the solid surface applies and the coated surface for a duration between about 10 minutes to about 10 hours to a temperature of about 75-20O ⁰ C. heated. Process according to Claim 8, characterized in that the thermosetting "polymeric mixture is applied to the solid surface by spraying on an organic solution of this mixture . The patent attorney: 00 98 17/1801