DE3028302C2 - Linear interpolymers, processes for their preparation and use - Google Patents

Description

CH ₂ -CH ₂ -N

IV ₂

wherein R, and R> have the same meanings as in the preceding claims, or instead of: · ο Monomers of the formula (C) of a monomer of the following formula (H)

H ⁽⁾

wherein R ₁ , R. and X have the same meanings as in the preceding claims? n hafejr ». and 10 to 98 wt. ".. of a monomer of the formula (D)

R, R ₃

C = C

H C = O

R ₄ O

wherein R., R ₁ and R ^ have the same meanings as in the preceding claims, polymerized, and optionally the linear mixed polymer of the monomers of the formulas (C) and (D) with an acid of the formula HX (in which X has the same meaning as ir. the preceding claims), the amounts of the monomers being used in such a ratio that the linear copolymer has a nitrogen content of 0.2 to 10% by weight.

6. Use of the copolymers according to one of the preceding claims as a component for the cathodic electrophoretic painting.

The invention relates to a new nitrogen-containing linear acrylic copolymer, a process for its manufacture and its use.

Applying b / w. Deposition of a coating substance on the surface of a metallic material (the iils electrode is to be coated) by electrophoresis is known as the electrocoat process or electrophoresis Painting refers to and is largely used for covering or coating motor vehicle bodies used. A distinction is made between two methods in electrophoretic painting; while viewing anodis Electrophorelic painting is the material to be coated as anode and cathodic Electrophorelic painting uses the material to be coated as a cathode. Of these two I

Methods are offered by cathodic electrophoretic painting, in which the I to be coated is the cathode

Metal is used, the great advantage that the metal does not dissolve as an ion. An example! for a cathodic electrophoretic painting composition currently in use is the composition obtained by reacting an epoxy resin with a secondary amine to convert the epoxy groups to alpha-dialkylaminobeta-hydroxyethyl groups.
DE-OS 20 08 643 describes the polymerization of aryl vinyl benzamines of the formula

CH = CH ₂

described with aminoalkyl acrylates. In order to form a stable emulsion, according to this teaching, the mixed polymer must be converted into its tetraalkylammonium salt by alkylation with, for example, a benzyl halide or a dialkyl sulfate or with an acid, for example a mineral acid or a water-soluble organic acid, in an amount equivalent to the nitrogen atoms in the mixed polymer. ' to change. Because of the low basicity of the mixed polymer, an acid with a relatively high acidity must be used, as a result of which the emulsion has a corrosive effect on the devices to be used and is limited in its applications. Furthermore, a relatively high temperature is required to cure a coating made from such a copolymer.
The invention relates to linear copolymers with 2 to 90% by weight of recurring units of the formula (A) below:

-CH ₂ -CH-

[1 R ₁ (A)

wherein R, and R _2, which may be the same or different, each represents a hydrogen atom, a C, ₂ "-Alkylrcsl, a Q-io-CycIoalkylrest, a Qg-alkenyl group, a C ^ u-aminoalkyl radical, a C ₆ _ ₂₀ -Aryl radical or a C ₇ _i ₂ -arylalkyl radical,

where - ^! The recurring units of the formula (A) can be wholly or partially replaced by their acid addition salts of the formula (A ') below:

-CH ₂ -CH-

I " _R (A ')

CH ₂ -CH ₂ -N ^ R ₂

νθ \

^X H

wherein Ri and R ₂ have the same meaning as in the formula (A) have (but if at least one of R, and R ₂ is a C, _ ₁₅ aminoalkyl radical is, this as - (CH _{2) M5} - N ⁺ H ₃ X "Radical is present), and where X is an acid radical consisting of halogen atoms, 'h SO ₄ -, HSO ₄ -, NO ₃ -, Ίϊ CrO ₄ -, ClO ₄ -, H ₂ PO ₄ -, R., - COO . - and R | "SO, - Restcn existing group (wherein R a c._ ₂₀ alkyl radical, a Q ^ - aryl group or a C- _(;, -lJytlroxyalkylrest bedeuiet and R _n, a methyl radical, an ethyl radical. or a C ₆ _ means _2n -aryl), and IO to 98 wt .-% of recurring units of the following formula (B):

R ₅ R ₃

M) - CH- C -

OR ₄

where R _{3 is} a hydrogen atom, a methyl radical, a carboxymethyl radical, a haloalom or a - CH ₂ COOR ₆ radical (WOrJn R _{6 is} a hydrogen atom, a C _1. , - alkyl radical or a C ₇ , ₇ -arylalkyl radical means) or a C |. ", - alkoxy or CVni-acyloxy radical. R _{1 is} a hydrogen atom. a C, ...-

Alkylrcst, a C ₁ κ, -C'ycloalkylrest, a Ci-io-Ilalogencycloalkylrest, a C ₆ . ₂ |, aryl radical, a C _b - llalogcnarylalkylrcst ₂ n, a C ₇ _, ₂ arylalkyl radical, a C |. , j-haloalkyl radical, a C, _ | ₂ -hydroxyalkyl radical, a (ij-alkoxyalkyl radical, a tetrahydrofurfuryl radical, a glycidyl radical or a radical

- (CH ₂ - CH ₂ - O—) "- R,

(wherein R ₇ is a C ₁ alkyl group, and /, is an integer of 1 to 30), a C, - means _2n -Dialkylaminoalkylrcst or a C ₆ ju-llalogenarylrest and

R «denotes a hydrogen atom or a —COOR ₁₁ radical (in which R _s denotes a hydrogen atom or a Ci-J ₀ alkyl radical), the recurring units of the formula (B) being replaced by recurring units of the formula (E) below:

Y
-CH ₂ -C- (E)

in which Y denotes a hydrogen atom, a methyl radical or a halogen atom and Z denotes a phenyl radical, a nitrile radical, a —CO - R ₈ radical, an - O - CO - R _s radical (in which R ₈ denotes a C ₁ _, i-alkyl radical ) or a halogen atom, and / or can be partially replaced by repeating units of the formula (F) below:

R ₅ R ₃

CH-CH

CH ₂ -CH ₂ -NC = O (F)

IV ₁ K4U

in which R ₁ , R ₃ , R ₄ and R _{5 have} the meanings given above, based on the total weight of the repeating units of the formulas (A) and (B), and by a content of about 0.2 to about 10% by weight nitrogen, based on the weight of the linear copolymer.

UiC residues R | and R ₂ in the formula (A) preferably denote a C6-20-Äryircsi which is unsubstituted or substituted by 1 to 3 alkyl radicals. The remainder of R ₃ in the form! (B) preferably denotes a methoxy-ethoxy, acctoxy or benzoyloxy radical. The radical R ₄ in the formula (B) is preferably a C _t - _2n -aryl radical which is unsubstituted or is substituted INEM alkyl group, a C ₅ - ₂ o-MonohaIogenarylrest, C ₆ _ ₂₀ -Dihalogcnarylrest or a C _f) - ₂ u-Tr'haloaryl radical; a Q ^ - monohaloalkyl or Ci-u-dihaloalkyl radical; or a C | ,, - Monohydroxyalkylrest or C ^^ - Dihydroxyalkylrest.

Specific examples of R ₁ and R 2 in the above formula (A) are hydrogen atoms; C 1-20 -alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, η-butyl, isobutyl, sec-butyl. tert-butyl, n-pentyl, isopentyl, n-hydroxyl. n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-dodecyl, n-tetradecyl, n-hexadecyl and n-ociadecyl groups; Ci ι ,, - Cycloalkyl radicals such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl radicals; C _{3 S} -alkenyl radicals, such as allyl, crotyl and hexenyl radicals; C1-5 aminoalkyl radicals, such as aminoethyl, aminopropyl, aminohexyl and aminododecyl radicals; C (, - ₁₅ -aryl radicals such as phenyl, tolyl, Trirrethylphenyl-, diethyl phenyl, naphthyl and Biphenyireste and C ₇ _ ₁₂ arylalkyl radicals such as benzyl, a-phenethyl - ,. / - Phcnäthyl-? and phenyl-tert-butyl radicals. Of these radicals, the Q - ^ - alkyl radicals and the Cj - ^ - aminoalkyl radicals are preferred in view of the easy accessibility of the starting _{monomers; the C, H} -alkyl radicals and C _1-8 -aminoalkyl radicals are particularly preferred.

According to a preferred embodiment of the invention, one of the radicals R. and R ₂ in the above formula (A) is a hydrogen atom; particularly preferably one of the two radicals R ₁ and R _{2 is} a hydrogen atom and the other is a C | -20-alkyl radical, in particular a C ₂ -iralkyl radical. According to a further preferred embodiment of the invention, the radicals R ₁ and R ₂ in the above formula (A) are Cj-g-alkyl radicals. Preferred combinations of the radicals R _{1 and R 2 of} the formula (A) are, for example, R 1 = H and R ₂ = C ₂ H ₅ , HC ₁ H ₇ or ISO-C ₃ H ₇ ; R ₁ = R ₂ = CH ₃ or C ₂ H ₅ ; R ₁ = CH ₃ and R ₂ = CH ₂ CH ₂ NH ₂ ; and R ₁ = R ₂ = CH ₂ CH ₂ NH _2. "

The - CH ₂ - CH ₂ - NR ₁ R ₂ radical of the formula (A), which is attached to the linear copolymer, can be in any position relative to the

- CH ₂ - CH radical

which builds up the main chain of the linear copolymer. The copolymers in which the - CfI ₂ - CH ₂ - NR, R ₂ radical is in the para position to the

- CH ₂ -CH radical

όΌΙ

is located, offer the advantage that the preparation of the starting monomers is simple.

Specific examples of the group R of the above formula (B) are hydrogen atoms, methyl groups and alkoxycarbonylmethyl groups such as methoxycarbonylmethyl, ethoxycarbonylmethyl and benzyloxycarbonylmethyl groups; and halogen atoms such as chlorine and bromine atoms. Particularly preferred examples of the radical R 1 are hydrogen atoms and methyl radicals. Specific examples of the R ₄ residues are hydrogen atoms; C, _:! , -Alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, η-butyl, isobutyl, sec-butyl, tert-butyl, n-octyI, 2-AthyIric-Ay! - , n-decyl, n-dodecyl, n-hexadecyl and n-octadecyl radicals: Cj-io-cycloalkyl radicals, such as cyclohexyl, trimethylcyclohexyl and cyclooctyl radicals; C 1-10 aryl radicals such as phenyl, propylphenyl, butylphenyl, amylphenyl and naphthyl radicals; CT. ^ - arylalkyl such as benzyl; Ci-ij-haloalkyl radicals, such as chloromethyl, chloroethyl, dichloropropyl, bromoethyl, bromopropyl and fluoroethyl radicals; C, u-hydroxyalkyl radicals, such as hydroxyethyl and hydroxypropyl radicals; C ₂ _ | ₃ -alkoxylalkyl, such as methoxyethyl, methoxypropyl, methoxybutyl, ethoxyethyl and ethoxypropyl; Tetrahydrofurfuryl residues; Glycidyl residues; - (CH, - CH ₂ - O) ,, - R, radicals, in which R _{7 is} a methyl radical; and C, _ _2ü -Dialkylaminoäthylreste, such as Dimethylaminoüthyl- and Diiithylaminoäthylreste.

Preferred radicals R, are hydrogen atoms, C | - | _2- hydroxyalkyl radicals, in particular Hydroxyiithylrestc; Cj-jo-Dialkylaminoalkylreste, especially Dimethylaminoäthylreste or Diethylaminoäthylreslc. F. A specific example of the radical R ₅ is a hydrogen atom.

Preferred combinations of the radicals R ₁ , R ₄ and R ₅ are listed below in brackets (R ₁ , K ₁ , K ₅ ) and are, for. B .:

(H ₁ CH ₃₁ H), (H, C ₂ H ₅ , H), (H, C ₄ H ,, H), (H, C, H ₁₇ , H) (H, CH ₂ CH ₂ OH, H ), i-

(H ₁ H ₁ H) ₁ ZH ₁ CH ₂ -CH ₂ N (CHj) ₂₁ H /, (CH ₃ , CHj, H), (CH ₃ , C ₂ H ₅₁ H), (CH ₃₁ C ₄ H ₉₁ H), $

(CH ₃ , C ₁ H ₁₇ , H), (CH ₃ , C. ₂ H ₂₅ , H), (CH ₃₁ C ₁₁ H ₃₇₁ H), (CH _3l cyclo-C ₆ H, "H), (CH ₃₁ H ₁ H) ₁ ||

(CH ₃₁ CHjCH ₂ OH ₁ H) ₁ ZCH ₃ , CH ₂ CH ₂ N (CHj) ₂ , H /, / CH ,, -CH ₂ -CH-CH ₂ , HV i |

/ CH ₃₁ CH ₂ -CH- (CH ₂ ), - O, H \, / H, CH ₂ -CHjN (CjHs) ₂₁ H / and / CH ₃ , ί)

{ I __J ) I.

CH ₂ CH ₂ N (C ₂ Hs) ₂ , H /. |

Particularly preferred combinations of the radicals R ₃ , R ₄ and R ₅ are: ||

(H, CH ₃ , H) ₁ (H ₁ C ₂ H ₅ , H), (H, C ₄ H ₉ , H), (H, C ₅ H ₁₇ , H), ff

(H, CHjCH ₂ OH ₁ HVH, CH ₂ -CHjN (CHj) ₂ , H /, (CH ₃ , CH ₃ , H), (CH ₁ , C 3 H ₅ , H), |

(CH ₃ , C ₄ H ,, H), (CH ₃ , C ₈ H ₁₇ , H) ₁ (CH ₃₁ CHJCHJOH ₁ H) ₁ ZCHj ₁ CH ₂ CHjN (CHj) ₂₁ HZ ₁ |

■ »o M

/ H ₁ CH ₂ -CHjN (CjHs) ₂₁ H / and / CHj, CHjCH ₂ N (CjH _s ) j, H /. fj

The radicals R ,, R _21, Ri _1, R ₄ and R ₅ are in each case not limited to a specific radical, but can be a;

Mean mixture of at least two different radicals. ^

The interpolymer of the invention typically has from 0.2 to 10% by weight nitrogen based on weight j «j

of the mixed polymer. A preferred amount of nitrogen is 0.3 to 7 weight percent based on the weight of the U

Copolymers; a particularly preferred amount of nitrogen is 0.5 to 5 wt% based on weight | (

of the mixed polymer. Sj

The amount of repeating units of the formula (B) in the copolymer is typically in | j

Range from 10 to 98% by weight, preferably in the range -on 20 to 97% by weight and in particular in the range from ß _t

30 to 96% by weight based on the total weight of the repeating units of the formulas (A) and (B). %

The number average molecular weight of the copolymer of the invention is not limited and is typically

usually in the range from 1,000 to 500,000. §

Some of the recurring units of the formula (B) can be replaced by recurring units of the formula (E) §§

be replaced. Ij

Y
-CH ₂ -C- (E)

I.

wherein Y represents a hydrogen atom, a methyl radical or a halogen atom, e.g. B. Ci or Br ₁ and /. a phenyl radical, a nitrile residue, a - CO - Rg radical, an - O - CO - R ₈ radical ₁ in which R _{8 is} a C ₁ , - alkyl radical, e.g. B. a methyl, ethyl, propyl, butyl, hexyl or octyl radical; or represents a halogen atom, / _ B. Cl or Br,
and / or by repeating units of the formula (F)

-ClI -CH- <f *>

R ₅ R ₅

\ / CH-CH

CH ₂ -CH ₂ -NC = O

R ₁ R ₄ O

(F) ^s

wherein R ₁ , R ₃ , R. and R _{5 have} the above meanings. ίο

The mixed polymer of the invention can be prepared by using a monomer mixture with 2 to 90 wt .- '/ n of a monomer of the formula (C)

Ri

CH ₂ -CH ₂ -N

CH ₂ = CH-

(Cj

where R | and R _{2 have} the above meanings, or instead of the monomer of the formula (C) a monomer of the following formula (H)

R ₁

CH ₂ = CH-

CH ₂ -CH, -N® <-R _{2 χ} θ \ H

20th

(H) 25

wherein R ₁ , R ₂ and X have the above meanings,
and 10 to 98% by weight of a monomer of the formula (D)

R ₃

C = C

C = O

(D)

R ₄ O

wherein R ₃ , R ₄ and R _{5 have} the above meanings, polymerizes,

and optionally the linear mixed polymer from the monomers; of the formulas (C) and (D) with an acid of the formula HX (in which X has the same meaning as in the preceding claims),
the amounts of the monomers being used in such a ratio that the linear copolymer has a nitrogen content of 0.2 to 10% by weight.

A preferred amount of the monomer of formula (D) is in the range of 20 to 97% by weight based on the Total weight of the monomer of the formula (C) and the monomer of the formula (D). A particularly preferred one The amount of the monomer of formula (D) is in the range of 30 to 96% by weight based on the total weight of the monomer of the formula (C) and the monomer of the formula (D).

! • line method for producing the monomer of the form! (C) is in Makromol. Chem., Vol, 177, No. 11, pp. 3255 to 3263 (1976) and Vol. 179, pp. 2069 to 2073 (1978), and Japanese Patent Applications (OPI) 1 00 489/1979 and 11 539/1980.

Examples of monomers of formula (C) are

[2- (ethylamino) ethyl] styrenes, [2- (isopropylamino) ethy [] styrenes, [2- {n-propylamino) ethyl] styrenes, [2- (dimethylamino) ethyl] styrenes , [2- (diethylamino) ethyl] styrenes, [2- (sec-butylamino) ethyl] styrenes, [2- (cyclohexylamino) ethyl] styrenes, [2- (allylamino) ethyl] styrenes , [2- (benzylamino) ethyl] styrenes, {2- [bis (2-aminoethyl) amino] ethyl} styrenes (ie R ₁ = R ₂ = CH ₂ - CH ₂ - NH ₂ ) and {[2-Aminoethylmethyl) amino] ethyl} styrenes (ie R ₁ = CH ₃ , R ₂ = CH ₂ - CH ₂ - NH ₂ ).

Examples of monomers of the formula (D) are unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, alpha-chloroacrylic acid, itaconic acid, maleic acid and fumaric acid; Acrylates such as inclusion of alkyl acrylates of methyl, ethyl, butyl and octyl acrylates; Cycloalkyl acrylates such as cyclohexyl and trimethylcyclohexyl acrylates; Aryl acrylates including phenyl and amylphenyl acrylates; Inclusion of haloalkyl acrylates of chloroethyl acrylate, dichloropropyl and bromopropyl acrylates; Hydroxyalkyl acrylates including of Hydroxyäthyl- and Bishydroxymethylpentylaciylaten; Alkoxyalkyl acrylates including methoxyethyl and ethoxypropyl acrylates; and cyclic ether acrylates including glycidyl and tetrahydrofurfuryl acrylates; Methacrylates, such as alkyl methacrylates including methyl, ethyl, butyl, octyl, Decyl and octadecyl methacrylates; Cycloalkyl methacrylates including cyclohexyl methacrylate; Aryl methacrylates including phenyl, butylphenyl and naphthyl methacrylates; Arylalkyl methacryl

30th

40

45

50

55

60

65

late including benzyl methacrylates; Haloalkyl methacrylates including Chlormcthyk Fluonithyl and bromoethyl methacrylate: n; Halocycloalkyl methacrylates including chloro cycloalkyl methacrylate; Haloaryl methacrylate including chlorophenyl and tribromophenyl methacrylates; Hydroxyaikyimethacrylate including Hyciroxypropylmethacrylal; Alkoxyalkyl methacrylates including ethoxyethyl and methoxybutyl methacrylates; Methacrylates of cyclic ethers with the addition of glycidyl and tetrahydrofurfuryl methacrylates; and methacrylates of methoxypolyäthylcntilycolen; α-chloroacrylates including butyl and ethoxyethyl-α-chloroacrylates; inclusion of a-alkoxyacrylate of methyl-a-methoxyacrylate, cyclohexyl-a-ethoxyacrylate, ethyl-ff-acetoxyacrylate and ethyl-a-bcr. zoyloxyacrylate; unsaturated carboxylates such as itaconates including dibutyl itaconate; Fumarate under

ίο inclusion of dimethyl fumarate; Maleates including diethyl maleate and dioctyl malcal. Of these Compounds are preferred acrylic acid, methyl acrylate, butyjacrylate, 2-ethylhexyl acrylic, Hydroxyülhylacry-

lat, methacrylic acid, methyl methacrylate. Butyl methacrylate, 2-ethylhexyl methacrylate, dimethylaminoethyl methacrylate and tetrahydrofurfuryl methacrylate.

It is also possible to use styrene, vinyl chloride, acrylonitrile, vinylidene chloride, Use methyl vinyl ketone or vinyl acetate.

If R ₂ in the formula (C) of the monomers is a hydrogen atom, there is an addition reaction between some monomers of the formula (D) and the monomers of the formula (C) mentioned to form monomers of the formula (G)

Ri

CH ₂ -CH ₂ -NR ₃

CH ₂ = CH ^ X \ _H -ciT (G)

R ₅ C = O

R ₄ O

This reaction can occur when R | of the monomers of formula (C) is not a bulky hydrocarbon resin, e.g. B. is an n-alkyl radical, and R ₅ in the formula (D) of the monomers is a hydrogen atom. When a monomer of formula (G) has been formed, it acts as a copolymerizable component.

The polymerization according to the invention can be either an ionic polymerization or a act radical polymerization; the polymerization is preferably carried out in the presence of a radical initiator or a radical source carried out. The polymerization can either be as bulk polymerization or as Solution polymerization or as suspension polymerization or as emulsion polymerization will.

Examples of usable radical sources are azo compounds, such as azotisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile) and Ι, Γ-azobiscyclohexane-l-carbonitrile; Hydroperoxides, such as tert-butyl hydropcroxide; Persulfates such as potassium persulfate and ammonium persulfate; and peroxides such as benzoyl peroxide, lauroyl peroxide and dilauroyl peroxide.

The molecular weight of the copolymers can be determined by the amount of radicals added,; elle or by solution polymerization using a solvent or a chain transfer agent rules.

The amount of free radical source used will range from about 0.05 to about 10 percent by weight based on des Total weight of the monomer mixture. A preferred range is about 0.2 to about 5 weight percent.

Examples of solvents or chain transfer agents that can be used are aromatic Hydrocarbons such as toluene, ethylbenzene, cumene and diphenylmethane; halogenated hydrocarbons, such as carbon tetrachloride and chloroform; aliphatic alcohols such as n-butanol and isopropanol; and mercaptans, like n-butyl mercaptan. The amount of the solvent or the chain transfer agent is not limited. The weight ratio of the solvent or chain transfer agent to the monomer mixture, that can be used ranges from about 0.1 to about 40, and preferably from about 1 to about 20.

The Polymerisaticnstemperatur is 0 to about 15O ⁰ C and preferably 40 to 100 ⁰ C.

The isolation and purification of the copolymers obtained from the monomers used, and if necessary of the solvent can be carried out by various known methods. In the Solution polymerization, the reaction mixture is poured into a medium that contains the mixed polymer formed does not dissolve, the mixed polymer precipitates, the mixed polymer is filtered and the mixed polymer is washed with water. The reaction mixture can also be subjected to steam distillation by adding steam to the reaction mixture blown in with heat and the solvent and unreacted monomers are distilled off. at the suspension polymerization is the finely divided copolymer obtained from the reaction mixture Separated by filtration and washed with sufficient water to remove the suspending agent and suspending aid to wash out, which adhere to the surface of the copolymer.

In the linear copolymers according to the invention, the recurring units of the formula (A) can be completely or partially replaced by recurring units of the formula (A ") ,

-CH ₂ -CH-

CH ₂ -CH ₁ -N ³ ^ -R ₂
^Λ Η

wherein R ₁ and R _{2 have the} same meaning as in formula (A), but if at least one of the radicals R, io |

and R ₂ is a C, _iS aminoalkyl, this is a - before N ⁺ H ₃ X radical (CH _2), - -, _5; where X denotes an acid radical which is formed from halogen atoms, ¹ A SO ₄ -, HSO ₄ -, NO ₃ -, ¹ Z ₂ CrO ₄ -, ClO ₄ -, H ₂ PO ₄ -, R ₉ - COO radicals (in which R _{9 is} a C | -2 _U alkyl, C ₆ _ ₁₅ aryl group or a hydroxyalkyl Ci_i represents _0), and Ri has chosen ₀ SOJ residues existing group (wherein R ₁₀ is a methyl radical, an ethyl radical or a C ₆ - _2O -aryl radical). \ s

Such a modified interpolymer can be produced by mixing the interpolymer with repeating Reacting units of the formula (A) and (B) according to the invention with an acid of the formula HX. The resulting mixed polymer is soluble or dispersible in water.

Usable acids of the formula HX are not particularly limited; Examples are mineral acids such as hydrochloric acid, Sulfuric acid, nitric acid, chromic acid, perchloric acid and phosphoric acid; aliphatic carboxylic acids, such as acetic acid, propionic acid, butyric acid and caproic acid; Hydroxycarboxylic acids such as glycolic acid and Lactic acid; Dicarboxylic acids such as malonic acid and adipic acid, aromatic carboxylic acids such as benzoic acid, Phthalic acid and salicylic acid; Alkanesulfonic acids such as methanesulfonic acid and ethanesulfonic acid; and aryl sulfonic acids, such as benzenesulfonic acid, toluenesulfonic acid and laurylbenzenesulfonic acid. Of these acids will be organic carboxylic acids preferred.

Acetic acid, lactic acid and hydroxyacetic acid are particularly preferred acids.

The amount of acid of the formula HX that can be used is not limited and is typically in Be; aich from about 0.1 to about 5 moles per nitrogen atom of the interpolymer. A preferred amount of acid of the formula HX ranges from about 0.3 to about 2 moles per nitrogen atom of the interpolymer.

The reaction or neutralization with the acid can be carried out by using the mixed polymer the acid mixes; however, a solvent is preferably used if the acid is solid or if the Amount of acid is less than equimolar. Preferred solvents are water-soluble organic liquids, like alcohols including methanol, ethanol and propano! and ketones including acetone and methyl ethyl ketone. The amount of solvent to be employed is typically in the range of about 10 to about 300% by weight based on the weight of the copolymer according to the invention. A preferred one The amount ranges from about 20 to about 150 weight percent based on the weight of the interpolymer.

The neutralization temperature is typically in the range from about -20 to about 200 ^° C. and preferably in the range from about 10 to about 150 ^° C.

In addition, copolymers with recurring units of the formula (A ') and (B) can be prepared by a monomer mixture with a monomer of the formula (H)

R,
CH ₂ - CH ₂ - N® <^ R ₂

H ⁽ⁿ⁾

wherein R ₁ , R ₁ and X have the above meanings, and polymerizes a monomer of the formula (D).

Monomers of the formula (H) can be prepared by reacting monomers of the formula (C) with an acid of the Formula HX in the same way as when neutralizing a copolymer having repeating units of formulas (A) and (B) neutralized.

In this polymerization of a monomer mixture of monomers of the formulas (H) and (D), a radical polymerization is preferably used as in the case of the polymerization of the monomer mixture with the monomers of the formulas (C) and (D); a solution polymerization is preferably carried out in a highly polar solvent. When using water, it is possible to use a redox initiator such as persulfate / hydrogen sulfite including potassium persulfate / sodium hydrogen sulfite, or chlorate / sulphite including sodium chlorate / sodium sulfite, in addition to the water-soluble radical sources mentioned.

The structure of the copolymer obtained can be determined by various conventional methods, /. H. Elemental analysis, IR absorption spectrum analysis and NMR spectrum analysis. The amount of unshelted After completion of the polymerization, monomers are quantitatively determined by gas or liquid chromatography analyzed; one can see the chemical composition of the interpolymer from the result to calculate. The molecular weight of the copolymer is determined by viscosity measurement, gel permeation chromatography, Light diffraction measurement, osmometry and vapor pressure cosmometry.

Copolymers with recurring units of the formula (A) and (B) according to the invention are used as a component / useful for forming coating films. Namely, it was found that the coating films have a Have approved / calibrated strength or resistance. A coating film can be obtained by that one dissolves a copolymer according to the invention in a solvent, the solution on a material applied and then the solvent evaporated.

l-emcr can be the mixed polymer according to the invention, in which the repeating units of the formula

(A) are completely or partially replaced by recurring units of the formula (A ¹ ), use as a component for cathodic electrophoretic painting. Cathodic electrophoretic painting from an aqueous solution or dispersion is particularly preferred.

The monomer (C) used according to the invention has one more methylene group than the monomer used in DE-OS 20 08 643 and thus shows a higher basicity than the latter. If, for example, the radical R _{1 is a hydrogen atom and the radical R 2 is} an isopropyl radical, the pKa value of the monomer (A) according to the invention or of the monomer according to the known teaching has the following values:

Monomer pKa

7.75

15 CH ₂ = CH-

_ _ 8.60

²⁰ CH ₂ = CH

Due to the strong basicity of the linear copolymer according to the invention, which is caused by the monomer of the formula (C), quaternization is not necessary for the production of a stable emulsion carry out by alkylation, and you can use an acid in less than the equivalent amount (based on the nitrogen atoms in the copolymer). One can also for the linear according to the invention Mixed polymeric acids with a lower acidity than salt-forming reagent due to their high basicity of the mixed polymer. This also increases the pH of the emulsion, which is achieved through neutralization obtained, and the emulsion can be handled in the neutral range, which extends its applicability and reduces the corrosion of the devices used.

The temperature necessary for curing coatings formed from the linear copolymer is lower in the case of the copolymer according to the invention than that of the copolymers of DE-OS 20 08 643.
The production of some starting monomers is described below:

35

Preparation example 1 | j

p- [2- (Isopropylamino) -ethyI] -styrene %

1

In a 2-1 three-necked flask in which the air had been replaced by nitrogen and which you could use with a Ruhgj

rer, a thermometer and a reflux condenser, 744 ml of purified Tetrahydro- ff were used

furan from a dropping funnel and then added 86 ml of isopropylamine with stirring and also added 20 ml of f j

of all 2 η n-butyllithium solution to the mixture. The color of the solution changed from colorless to pale | 5

yellow. The flask was placed in a thermostatic bath which was kept at 30 ^° C., and 148 ml of p- $ were added with stirring

Divinylbenzene to the mixture, which turned the color of the reaction mixture to orange. The reaction ||

continued under the same conditions for 3 hours. After the reaction, 1 ml of methanol was added to the ||

Reaction mixture and added the mixture to 2 l of water. The solution obtained was then extracted twice j $ j

with η-hexane, the oily phase was dried over magnesium sulfate overnight, then distilled and received 118 g * $

of a distillate with a boiling point of about 67 ° C / 0.09 moar. This distillate was identified as p- [2- (Iso- Aj

propylamino) ethyl] styrene using the analytical results below. '§I

Froton NMR spectrum: [100 MHz, solvent CDCI ₃ , standard substance: tetramethylsilane (TMS)] |

Delta value: 0.8 (1 H), 0.96 (doublet, J = 7 Hz, 1 H), 2.6-2.9 (multiples, 5 H), 5.1 (doublet, J = IIHz, I. 1H), 5.6 (doublet, J = 18 Hz, 1H), 6.6 (double doublet, 1H), 7.0-7.35 (multiples, 4H). : ■ j

Note: J shows a coupling constant and nH corresponds to π hydrogen atoms. ^

IR absorption spectrum (liquid film): _r , |

3300, 1630, 1510, 1470, 1380, 1080,990,910,835 cm ' ¹ . vj

Preparation example 2 V

p- [2- (ethylamino) ethyl] styrene ■

In a 200 ml stainless steel autoclave fitted with a stirrer, i

80 ml of η-hexane, which had been dried over metallic sodium and subjected to distillation. ;

10 ^

The autoclave was then cooled sufficiently from the outside with a mixture of dry ice and methanol. A bomb containing ethylamine was connected to the autoclave and ethylamine was introduced into the autoclave. From the change in the weight of the bomb before and after it was introduced, it was determined that 6.3 g of ethylamine had been introduced. While the mixture was stirred, 8.4 ml of a 15% n-hexane solution of n-butyllithium was introduced. Thereafter, a solution of 18.2 g of p-divinylbenzene dissolved in 40 ml of dry η-hexane was added to the mixture. The autoclave was placed in a water bath kept at 25 ° C and stirring was continued for 5 hours. To the reaction mixture was added 0.5 g of methanol and the resulting mixture was added to 200 ml of water. The solution obtained in this way was extracted twice with η-hexane, and the oil was dried ^; ge phase over magnesium sulfate overnight, then distilled and obtained 14.7 g of a distillate with a boiling point of 72 to 73 ° C./0.41 mbar. This distillate was a single compound as confirmed by gas chromatography. This distillate showed the following analytical results:
IR absorption spectrum:

3280, 1620, 1510, 1120, 985, 900, 820 cm " ¹ .

Proton NMR Spectrum: (100 MHz, solvent CDCl ₃ , standard substance TMS)

Delta value: 0.80 (singlet, 1H), 1.04 (triplet, J = 7.2 Hz, 3H), 2.55 (quartet, J = 7.2 Hz, 2H), 2.6 -2.8 (Multiplet, 4H), 5.08 (doublet, J = 10.5 Hz, 1H), 5.60 (doublet, J = 17.8 Hz, 1H), 6.56 (double Düblet »J = 10.5 and 17.8 Hz, 1 H), 6.9-7.3 (multiplet, 4 H). '

With the help of the results mentioned, the product was identified as p- [2- (ethylamino) ethyl] styrene.

Production example 3

p- [2- (dimethylamino) ethyl] styrene

A magnetic stirrer and 100 g. The outside of the flask was cooled with a liquid mixture of methanol and dry ice. After methanol which had been cooled with dry ice was passed through the condenser, the end of the condenser was connected to a bomb containing dimethylamine and dimethylamine was introduced into the flask. From the change in the weight of the bomb before and after the introduction of dimethylamine, it was found that 115.4 g of dimethylamine had been introduced. While the solution of dimethylamine in n-hexane was stirred with the magnetic stirrer, 77 g of a solution of n-butyllithium (15%) in n-hexane was added dropwise to the mixture from the one dropping funnel at a rate such that the internal temperature of the piston did not rise about -60 ⁰ C and a yellowish solution was obtained. Thereafter, a nüssige mixture of 435 g of dry n-hexane and 332 g of p-divinylbenzene this was added dropwise to the solution from the other dropping funnel at such a rate that the internal temperature of the flask did not rise above -60 ⁰ C, to give a light green Reaction solution. After completion of the addition of the liquid M ischung, agitation was continued 3.5 hours, and as a result, the inner temperature of the flask rose to -20 ⁰ C. When, a part of the product as a sample and a quantitative analysis took the p-divinylbenzene When subjected to gas chromatography, the amount of p-divinylbenzene found was 15% of the original amount, and the reaction was terminated with 10 ml of methanol. 11% of water were added to the reaction mixture and the mixture was extracted twice with n-hexane, the oily phase was dried over magnesium sulphate overnight and then distilled to give 250 g of the distillate with a boiling point of 75 to 80 ° C./0.5 mbar. This product was a single compound as confirmed by gas chromatography. This compound showed the following analytical values.

50 Terminal analysis for compound C | ₂ H _i7 N:

Calculated (%): C82.23, H 9.78, N 7.99

Found (%): C 82.08, H 9.86, N 8.07

IR absorption spectrum:

2920, 2740, 1620, 1500, 1440, 1250, 1130, 1030, 980, 890, 820 cm " ¹
Proton NMR spectrum: (solvent CDCI ₃ , standard substance TMS)

Delta value: 2.07 (singlet, 6H), 2.2-2.7 (4H), 5.00 (doublet, J = 11 Hz, 1H), 5.50 (doublet, J = 18 Hz, 1H), 6.55 (double doublet, J = 11 Hz and J = 18 Hz, 1H), 6.8-7.3 (4H).

Production example 4

ί p- [2- (diethylamino) ethyl] styrene

/ 5 p- [2- (diethylamino) ethyl] styrene was prepared according to the method described in Makromol. Chem., 177, 3255-3263 (1976) (Tsuruta et al.).

'. "IR absorption spectrum:

1800, 1620, 1505, 1195, 1060, 980, 895, 820 cm " ¹ .

■ · "Elementary analysis:

* C 82.65%, H 10.58%, N 6.80%

The invention is explained in more detail below by means of examples.

.15 Example 1

, In a separable flask or separable flask with a content of 2 l, which you can use with a stirrer, a

* Thermometer and a reflux condenser, 1014 g of toluene, 102.8 g of methyl methacrylate, 17.7 g of p- [2- (isopropylamino) ethyl] styrene from preparation example 1.41.7 g of 2-ethylhexyl methacrylate and 2 , 5 g 2,2'-azob: sisobutyrop.! Iri! and carried out the reaction while heating the mixture at kii ' ^s C for 18 hours with stirring. After the reaction, the unreacted monomers were stirred up quantitatively by gas chromatography and it was established that 11.6% of the methyl methacrylate and 12.8% of the 2-ethylhexyl methacrylate had not been converted, but that all of the p- [2- (isopropylamino) -alhyl] -styrene was reversed. The reaction mixture was then subjected to steam distillation by introducing steam from a steam generator into the mixture and distilling off the unreacted monomers and the toluene. The obtained product was cooled, pulverized, dried, and 130 g of a copolymer was obtained. This copolymer shows the following analytical values.

< Elemental analysis:

Found (%): C 65.9, H 9.1, O 24.0, N 0.9.

IR absorption spectrum:

Characteristic absorptions at
2930, 1720, 1450, 1280, 1230, 980, 960, 740 cm " ¹ .

Proton NMR spectrum [CDCl ₃ solvent; Standard substance tetramethylsilane (TMS)]

Delta value (ppm): 0.8 ~ 1.2 (J = 6 Hz), 1.2 ~ 1.7, 1.7 2.3, 2.7 ~ 3.1, 3.65, 3, 8 ~ 4.1, 6.9 ~ 7.3.
Intrinsic viscosity / eta / (chloroform solution): 0.04i.

Example 2

1300 g of cumene, 11.3 g of [2- (isopropylamino) ethyl] -strol from Merslcllungs'üebeispiel 1, 47 g of methyl methacrylate, 93.1 g of n-octyl methacrylate and 7 were placed in a 2 liter separating flask , 5 g of 2,2'-azobisisobutyronitrile. After nitrogen was introduced into the flask for 2 minutes at 20 ⁰ C, to shut the flask heated at 80 ⁰ C for 18 hours and then the reaction mixture subjected to steam distillation aufgleichc manner as in Example 1. The mixed polymers obtained showed the following analytical Values.

Elemental analysis:

Found (%): C 69.6, H 10.2, O 19.6, N 0.6.

IR absorption spectrum:

Characteristic absorptions at 2940, 1720, 1470, 1230, 1150 cm "'.

Intrinsic viscosity / eta / (chloroform solution): 0.022.

Example 3

A solvent, methyl methacrylate, p- [2- (isopropylamino) -iithyl- !: iyrene and 2.2 '-Azobisisobutyronitrile in the amounts shown in Table 1 and carried out the reaction while heating the mixture at 70 ⁰ C for 5 hours. After the reaction, unreacted monomers were quantitatively analyzed by gas chromatography. The results are shown in Table 1.

T; ibclle I

attempt

solvent

(G)

MMA ¹ ) IAES ² ) AIBN ^J )

(G)

(G)

Around Around Mixed polymer: reason change change viscosity from from Elementary (eta) MMA ¹ ) IAES ² ) analysis 0.095 (%) Butt) (%) 72.6 100 C: 64.8 H: 8.5 O: 25.1 0.187 N: 1.7 92.0 100 C: 62.7 H: 8.2 O: 28.3 N: 0.9

Carbon tetrachloride 4080

Isopropyl alcohol 1344

Cumene 2687

252

220

220

53

26.5

21.9

100

0.108

C: 62.3
H: 8.3
O: 28.6

N: 0.8

') MMA: methyl methacrylate;

² ) IAIiS: p- [2- (isopropylamino) ethy!) - styrene; ¹ I AIBN: 2,2'-azobisisobutyronitrile.

Experiment No. 2:

IR absorption spectrum: Characteristic absorptions at 2930, 1720, 1480, 1440, 1380, 1230, 1190, 1140, 980, 830, 750 cm '.

l'roton NMR spectrum: solvent CDCI ₃ ; Standard substance TMS (tetramethylsilane): dclla value (ppm): 0.4 ~ 1.7, 1.7 - 2.6, 2.6 ~ 3.3, 3.8, 7 ~ 7.3.

The reaction mixture was then added to hexane, the amount of which was three times the volume of the reaction mixture was, a copolymer precipitated, the copolymer was separated by filtration and dried it under reduced pressure. The result of the elemental analysis of the copolymer and the basic viscosity of the interpolymer are shown in Table 1. Also are for the copolymers that you are trying No. 2, the results of the IR absorption spectrum analysis and the NMR spectrum analysis in Table 1 shown.

Example 4

4 g of a partially saponified polyvinyl alcohol, which had a degree of saponification of 88% and a viscosity (in a 2% strength aqueous solution) of, were dissolved in a 2 l separable flask fitted with a stirrer, a thermometer and a reflux condenser 23 x 10 " ³ Pa · s (23 eps), and Sg sodium chloride in 800 ml of pure water. To the mixture was added a mixture of 73.6 g of ethyl methacrylate, 17.7 gp- [2- (n-propylamino) - ethyl] -styrene, which is analogous to preparation example 1 was prepared, 69.7 g of 2-ethylhexyl acrylate and 1.6 g of 2,2'-azobis (2,4-dimethylva! eronitril) bet 60 ⁰ C with stirring, and sat heating under stirring at 60 ⁰ C for 2 h, BTI 70 ⁰ C for 2 h and then at 80 ⁰ C for 4 hours continuously. After the reaction, the product was washed thoroughly with warm water, dried it and obtained 140 g of a mixed polymer with a Particle diameters from 50 to 400 µm.

The result of the elemental analysis of this copolymer is shown below:

Elemental analysis:
rounded (%): C 69.0, H 9.9, O 20.2, N 0.9.

Example! 5

500 g of hexane, 30 g of methyl methacrylate, 56.7 g of p- [2- (isopropylamino) ethyl] styrene were placed in a 1 l separable flask, which had been provided with a stirrer, a thermometer and a reflux condenser, which had been prepared in the same way as in Preparation Example 1, and 2.6 g of 2,2'-azobisisobutyronitrile, and the mixture was heated at 70 ^° C. for 18 hours while stirring. After the reaction, the reaction mixture, which was a homogeneous liquid, was externally cooled with a dry ice / methanol mixture, and a white precipitate was obtained. The precipitate formed was separated off with a glass filter in the cooled state. The result of the elemental analysis of the dry product thus obtained is given below:

Element analysis:
Found (%): C 71.1, H 8.92, O 15.97, N 4.0.

13th

Zo JUZ

Example 6

The monomers according to Table 2, toluene as the solvent in an amount according to Table 2 and 2 g of 2,2'-azobisisobutyronitrile were used in a! -I separating flask which had been provided with a stirrer, a thermometer and a reflux condenser. The reaction was carried out by heating the mixture at 70 ^° C. for 18 hours with stirring. The reaction mixture was then subjected to steam distillation, partly by introducing steam from a steam generator into the reaction mixture, and unconverted monomers and toluene were removed. The obtained copolymer was cooled, pulverized and dried; the results of the elemental analysis of the copolymer are shown in Table 2.

Table 2 toluene
(G) Monomer (C)
(G) Monomer (D)
(G) lilcmcnlar-
analysc attempt
No. 340 m- [2- (ethylamino) -
äthyij-styroi 5ö Ethyl acrylate 50 C: 71.6
ti: 9.0
O: 15.3
N: 4.2 1 269 p- [2- (dimethylamino) -
ethyl] styrene 40 Cyclohexyl methacrylate 60 C: 76.4
H: 9.7
O: 10.3
N: 3.7 2 293 p- [2- (diethylamino) -
ethyl] styrene 60 Hydroxyethyl acrylate 40 C: 71.0
H: 9.1
O: 15.6 3

N: 4.3

Example 7

The monomers according to Table 3, 500 g of benzene as solvent and a free radical source according to Table 3 were used in a 1-1 separable flask fitted with a stirrer, a thermometer and a reflux condenser .15. The reaction was carried out by heating the mixture at 60 ^° C. for 20 hours with stirring. Thereafter, the reaction mixture was subjected to steam distillation by introducing steam from a steam generator into the reaction mixture, and unreacted monomer and benzene were removed. The obtained mixed polymer was cooled, pulverized and dried; the results of elemental analysis of the copolymer are shown in Table 3.

Table 3

Attempt no.

Monomer (C) (g)

Monomer (D)

(G)

2 (g)

Radical source
(G)

Elemental analysis

p- [2- (allylamino) ethyl] styrene 25

m- [2- (isopropylamino) ethy!] - styrene 4

p- [2- (ethylamino) ethyl] styrene 14

p- [2- (Isopropylamino) ethyl] styrene 18

Methyl acrylate 50

N, N-diethylaminoethyl methacrylate 30

Tetrahydrofurfuryl methacrylate 56

Acrylic acid 40

n-butyl methacrylate 25

n-butyl acrylate 66

Methyl methacrylate 30

2-ethylhexyl methacrylate 42

Benzoyl peroxide
2

Lauroyl peroxide
1

2,2'-azobisisobutyronitrile 2

2,2'-azobisisobutyronitrile 2

C: 70.3 H: 9.0 O: 18.2 N-2.5

C: 66.2 H: 9.7 O: 21.4, N: 2.6

C: 64.2 H: 8.1 O: 26.5 N: U

C: 67.9 H: 9.3 O: 21.3

N: 1.5

14th

Example 8

A mixture of monomers, a solvent and 0.4 g of 2,2'-azobisisobutyronitrile was placed in a 200 ml glass tube according to Table 4, closed the glass tube and placed it in a water bath at 80 ° C. for 18 hours. Thereafter, the glass tube was opened, the reaction mixture was subjected to steam distillation and removed Solvents and unreacted monomers. The results of the elemental analysis and the infrared absorption spectrum analysis of the copolymer obtained are shown in Table 4.

Table 4

Attempt no.

Monomer Cres (C)

Monomer (D)

(G)

Solution center! (G)

Elemental analysis

IR absorptions

"Ι

p- [2- (sec-butyl- n-octadecylmeth- Ethylbenzene C: 78.4 710, 960, amino) -äthylj- acrylate 24 130 H: 12.6 1140, 1230 styrene 1 N: 0.5 1460, 1720 p- [2- (diethyl Lauryl methacrylate Benzene 120 C: 76.4 720, 1150, amino) ethyl] - 23 H: 12.6 1240. 1470 styrene 2 N: 0.7 1730 Example 9

In a 200 ml three-necked flask was placed a mixture of monomers, a solvent and 0.3 g of 2,2'-A / .obisisobutyronitril shown in Table 5 and the mixture was heated at 80 ⁰ C for 24 hours with stirring. Thereafter was added the reaction mixture in 11 η-hexane, cooled with a liquid mixture of dry ice and methanol, separating the precipitate obtained by filtration and dried it under vacuum at 7O ⁰ C overnight. The result of elemental analysis of the copolymer obtained is shown in Table 5.

Table 5

attempt
No. Monomer (C) Monomer (D)
] 2 solvent Elementary-
anulyse (G) (G) (G) (G) Ck) 1 p- [2- (cyclohexyl-
amino) ethyl] -
styrene 4.5 Dimethyl
itakonat 21 Styrene 4.5 Toluene 140 C: 63.9
H: 6.8
O: 28, t>
N: 1.0 2 p- (2- [bis- (2-amino-
ethyl) -amino] -äthyl} -
styrene 3 Phenyl acrylate
27 Ethylbenzene 140 C: 73.6
H: 5.2
O: 19.0
N: 1.9 3 p [2- (benzylamino) -
ethyl] styrene 6 Methylmeth-
acrylate 18 Acrylonitrile 6 Isopropanol 130 C: 63.8
H: 7.4
O: 22.0
N: 6.1 4th m- [2- (dimethyl-
amino) ethyl] -
styrene 8 Glycidyl
methacrylate 24 Toluene 140 C: 62.5
H: 7.5
O: 28.1
N: 2.3 5 m- [2- (isopropyl-
amino) ethyl] -
styrene 6 Dimethyl
fumarate 24 sec-butanol 130 C: 56.2
H: 6.8
O: 35.2
N: 1.6

Application example 1

To 9.2 g of isopropanol was added 21.5 g of the copolymer ai, see Example 1 and made the mix is homogenous by being heated at 70 ⁰ C. Thereafter, 1 g of lactic acid of 72% purity was added to the mixture, and the resulting mixture was stirred until it became homogeneous. 31.7 g of this mixed solution were dissolved in 98 ml of water to form a solution with a pH of 6.6 and a specific conductivity of 1540 μ / ohm cm. A direct current was applied to this solution, one being treated with zinc phosphate

Using a steel plate of 4 x 10 cm as a cathode and a stainless steel anode, became the copolymer deposited electrically or electrophoretically on the cathode at a voltage of 250 V. Of the The resulting coating had the following properties.

Erichsen (mrn) *):

Cross-section or cross-cut test

(Remainder or residue / 100) **):

Impact resistance (Du Pont) (cm) **) [500gX 1.27 cm (1/2 in)]:

7.0
100
50

Remarks:

*): JIS Z-2247 *): JIS K-5400

Application example 2

The formation of the electrophoretic precipitate was carried out using a mixed solution in accordance with table ό in the same way as in the application example i. The properties of the coating obtained are shown in Table 7.

Table 6

Attempt no.

Mixed polymer (g)

Acid (g)

solvent
(G)

Water (g)

1 No. 2 ¹ ) 23.9 lactic acid (purity 72%) 0.63

2 No. 3 25, is lactic acid (purity 72%) 1.9

') No. 2 denotes the mixed polymer from Example 2 No. 3 denotes the mixed polymer from Example 3.

Isopropanol
Isopropanol

10.5
15th

240 200

Table 7 attempt attempt number 1 No. 19 4000 1700 Specific conductivity (jl / Ohmcm) 4.6 5.2 PH value 7.2 6.8 Erichsen test (mm) *) 100 100 Cross cut test (Residue / 100) **) 50 50 Impact resistance Du Pont

(cm) **) [1 kg x 1.27 cm (1/2 in)]

Remarks:

*). **): The same meaning as in application example 1

Application example 3

10 g of the copolymer from Example 1 were dissolved in 10 g of isopropanol, the solution was applied as a coating to a steel plate which had been treated with zinc phosphate and dried at 50 ^° C. for 10 minutes. The coating had the following properties.

Erichsen test (mm) *): 6.5

Cross cut test (residue / 100) **): 100

Impact strength Du Pont (cm) **)

[500 g X 1,27 cm (1/2 in)]: 50

Remarks:

*), **): Same meaning as in application example 1.

Comparative experiment

A linear copolymer according to the invention was dissolved, an epoxy compound modified with an amine

Binding and a blocked polyisocyanate in a solvent, brought the mixture as a coating on a Steel plate on. dried to form a coating, whereupon the coating was cured by heating. To the A linear copolymer was produced for comparison, using isopropylaminoethylstyrene instead (according to the invention) Isopropylaminomethylstyrene (DE-OS 30 46 242) used and in the same way made a coating.

Interpolymer (A) (comparative) parts by weight

1. isopropylaminomethylstyrene '3.9

Methyl methacrylate 51.4

2-ethylhexyl methacrylate 34.7

Mixed polymer (B) (according to the invention)

Isopropylaminoethylstyrene 15

Methyl methacrylate 51

2-ethylhexyl methacrylate 34

Coating composition with (A) or (B)

Mixed polymer (A) or mixed polymer (B) 30

epoxy compound modified with amine ¹ ) 23

blocked polyisocyanate-) 47

Dibiiiylzirsrsiaurai 3

¹ 1 l: pn \ yhar / vom Bisphenol-A-diglycidyläiher-T \ ρ with ^ neni epoxyäi. equivalent to 450 to 500.

') M; in blocked toluil diisocyanal to lift with 1/2 equivalent of 2-. \ Ttn Ihexanol and then put it with 1 /.' -Viuiva- ! Cnt irimelhylnlpropane.

The heating temperature for the coatings made from the two copolymers was determined. The results are shown in Table 8 below.

10

15th

Table 8 Coating L bcr / ugs- Hardening / together- / together- temperature ( ⁰ C) set / ung (A) sel / ung (Bi ("..I ¹ I C, I ¹ I. 9 5 175 12th 6th 165 23 16 155

.'0

-IO

Ί The gch.irteten over / ug was extracted with acetone,
and one calculated the percentage of the ungch ^ irlclen
Amount from the (iewichlsveränderune

The table shows that the coating composition (B) according to the invention can be used at a lower Temperature in comparison to the known coating composition! Z.i: rig (A) can harden.

60

17th

Claims (5)

Patent claims: 1. Linear copolymers, characterized by 2 to 90% by weight of repeating units of the following formula (A): -CH ₂ -CH- wherein R, and R ₂ , which can be the same or different, each represent a hydrogen atom, a C | ₂₀ alkyl, C ₃ _ _I0 -CycIoalkylrest, a C ₃ _ _g alkenyl, a C, _, ₅ -aminoalkyl, a C ^ ₆ aryl or a C ₇ _i ₂ arylalkyl mean wherein the repeating units of the formula (A) are represented by their acid addition salts of the following Formula (A *) can be replaced in whole or in part:
20th -CH ₂ -CH- R, ^ΙΛΙ CH ₂ - CH ₂ - N® / r _2
χ θ \
^Λ Η wherein R _f and R _{2 have the} same meaning as in the formula (A) (if, however, at least one of the radicals R ₁ and R _{2 is} a C |., ₅ -aminoalkyl radical, this as - (CH ₂ ) |., ₅ - N ⁺ H ₃ X "radical is present), and where X is an acid radical selected from the group consisting of halogen atoms, '/, SO ₄ -, HSO ₄ -, NO ₃ -, V ₂ CrO ₄ -, CIO ₄ -, H ₂ PO ₄ -, R ₉ - COO and R, ₀ SO ₃ radicals (where R _{9 is} a Ci - ^ - alkyl radical, a QI ₅ - aryl radical or a Qm-hydroxyalkyl _{radical and R 10 is} a methyl radical, an ethyl radical or a Q ₁ , "- Arylresl"); and 10 to 98 wt .-% of repeating units of the formula (B) below: K.5 K ₃ - CH-C - I (B) C = O OR ₄ where R _{3 is} a hydrogen atom, a methyl group, a carboxymethyl group, a halogen atom or a - CH ₂ COOR ₆ group (where R _{6 is} a hydrogen atom, a Ci_ | ₀ -alkyl group or a CV, ₂ -arylalkyl group) or a C | - | _U alkoxy or Ci-io acyloxy, R ₄ a Wasserstofl'ator.i, C _{1 2} "alkyl, C ₃ - | ₀ -cycloalkyl radical, a Qi-io- _{halocycloalkyl radical, a Q- 2} "-aryl radical, a Q,>" - _{haloaryia'kyl radical, a C 7} -i ₂ -aryl a! Kylrcst, a Ci-u-ilalogenalkyl radical, a C | ^ -Hydroxyalkyl radical, a C ₂ - | ₂ -Alkoxyalkyl radical, a tetrahydrofurfuryl radical, a glycidyl radical or a radical - (CH ₂ - CH ₂ - O -) "- R ₇ (where R _{7 is} a C |. ₈ -alkyl radical and η is an integer from 1 to 30 ), a C ₃ _ ₂₀ -Dialkylaminoalkylrest or C ₆ _ ₂₀ -Halogenarylrest and
R _{5 is} a hydrogen atom or a - COORg radical (where R _{8 is} a hydrogen atom or a -C>"- alkyl radical), wherein the repeating units of the formula (B) are replaced by repeating units of the following Formula (E): Wl I -CH ₂ -C- (Ii) where Y is a hydrogen atom, a methyl radical or a halogen atom and Z is a phenyl radical, a nitrile radical, a - CO - R "radical, an - O - CO - R ₁₁ radical (where R _{8 is} a C,. Alkyl radical) or a halogen atom, and / or can be partially replaced by repeating units of the formula below (Fl: (F) -CH ₂ -CH- where R ,, R ;, R, and R _{5 have} the meanings given above, based on the total weight of the recurring units of the formulas (A) and (B), and by a content of 0.2 to 10% by weight nitrogen! * based on the weight of the linear interpolymer. 2. Mixed polymers according to claim 1, characterized by a nitrogen content of 0.3 to 7, preferably 0.5 to 5% by weight, based on the weight of the polymer. 3. Mixed polymers according to one of the preceding claims, characterized by 20 to 97, preferably 30 to 96% by weight of recurring units of the formula (B) according to Claim i, based on the Total weight of the recurring units of formulas (A) and (B) according to claim 1. 4. Mixed polymers according to one of the preceding claims, characterized by a number average the molecular weight of the copolymer from 1,000 to 500,000. 5. Process for the production of ip.earen copolymers according to one of the preceding claims, by using a monomer mixture with 2 to 90% by weight of a monomer of the formula (C) R ₁