Use of polymeric reaction product Number:7,008,990 from the United States Patent and Trademark Office (PTO) owispatent

Title: Use of polymeric reaction product

Abstract: A reaction product (A) which can be prepared by reaction, under free radical conditions, of at least one monomer (a) capable of free radical reaction, in the presence of at least one free radical initiator and of a radical of the formula (III) ##STR1##
where R₁ to R₃, in each case independently of one another, are hydrogen, methyl or a radical-stabilizing and/or bulky group selected from an unsubstituted or substituted, linear or branched alkyl of two or more carbon atoms, cycloalkyl, alcohol, ether, polyether, amine, aralkyl radical, a substituted or unsubstituted aromatic, heterocyclic or olefinic hydrocarbon, a halogen atom, a substituted or unsubstituted, linear or branched alkenyl or alkynyl group, —C(O)R₅, —C(O)OR₅, —CR₅R₆—O—R₇, —O—C(O)R₅, —CN, —O—CN, —S—CN, —O—C═NR₅, —S—C═NR₅, —O—CR₅R₆—CR₇R₈NR₉R₁₀, —N═C═O, —C═NR₅, —CR₅R₆-Hal, —C(S)R₅, —CR₅R₆—P(O)R₇R₈, —CR₅R₆—PR₇R₈, —CR₅R₆—NR₇R₈, —CR₅R₆(OR₇)(OR₈), —CR₅R₆(OR₇)(NR₈), —CR₅R₆(NR₇)(NR₈), an anhydride, acetal or ketal group, —SO₂R₅, an amidine group, —NR₅C(S)NR₆, —NR₅C(S)—OR₆, —N═C═S, —NO₂, —C═N—OH, &md

Patent Number: 7,008,990 Issued on 03/07/2006 to Raether,   et al.

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Inventors:	Raether; Roman Benedikt (Limburgerhof, DE); Brinkmann-Rengel; Susanne (Ober-Olm, DE); Haremza; Sylke (Neckargemünd, DE)
Assignee:	Basf Aktiengesellschaft (Ludwigshafen, DE)
Appl. No.:	311378
Filed:	June 13, 2001
PCT Filed:	June 13, 2001
PCT NO:	PCT/EP01/06712
371 Date:	April 21, 2003
102(e) Date:	April 21, 2003
PCT PUB.NO.:	WO01/96408
PCT PUB. Date:	December 20, 2001

Foreign Application Priority Data

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Jun 16, 2000[DE]

100 29 694

Current U.S. Class:	524/457; 524/458; 525/64; 526/204
Current Intern'l Class:	C08K 3/20     (20060101)
Field of Search:	524/457,458 525/64 526/204

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References Cited [Referenced By]

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U.S. Patent Documents

6156858	Dec., 2000	Keoshkerian et al.
Foreign Patent Documents
2355252	Jun., 2000	CA.
2355620	Jul., 2000	CA.
198 58 708	Jun., 2000	DE.
198 60 011	Jun., 2000	DE.
199 09 752	Sep., 2000	DE.
199 30 067	Jan., 2001	DE.
199 30 664	Jan., 2001	DE.
199 30 665	Jan., 2001	DE.
00/39169	Jul., 2000	WO.
01/44327	Jun., 2001	WO.

Other References

Derwent Abstract XP002184006 (=JP 53 00 2579; Jan. 11, 1978). Hoering et al., Plaste und Kautschuk, Jan. 1985, 32(9), 326-329. Crivello et al., Polymer Bulletin, 1986, 16, 95-102. Otsu, Adv. Poly. Sci., 1998, 136, 75-137. Cacioli, J. Mac. Sci.-Chem., A23(7), 1986, 839-852. De Leon-Saenz et al., Macromol. Chem. Phys., 201, No. 1, 2000, 74-83.

Primary Examiner: Mulcahy; Peter D.
Attorney, Agent or Firm: Novak Druce & Quigg LLP

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Claims

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We claim:

1. Coating materials comprising a reaction product (A) which is prepared by means of a process comprising the following stage (i):

(i) Reaction, under free radical conditions, of a reaction mixture comprising at least one monomer (a), capable of free radical reaction, in the presence of at least one radical of the formula (III) ##STR7##

 where R₁ to R₃, in each case independently of one another, are hydrogen, methyl or a radical-stabilizing and/or bulky group selected from the group consisting of unsubstituted and substituted, linear and branched alkyl groups having two or more carbon atoms, cycloalkyl, alcohol, ether, polyether, amine and aralkyl radicals, substituted and unsubstituted aromatic, heterocyclic and olefinic hydrocarbons, halogen atoms, substituted and unsubstituted, linear and branched alkenyl and alkynyl groups, —C(O)R₅, —C(O)OR₅, —CR₅R₆—O—R₇, —O—C(O)R₅, —CN, —O—CN, —S—CN, —O—C═NR₅, —S—C═NR₅, —O—CR₅R₆—CR₇R₈NR₉R₁₀, —N═C═O, —C═NR₅, —CR₅R₆-Hal, —C(S)R₅, —CR₅R₆—P(O)R₇R₈, —CR₅R₆—PR₇R₈, —CR₅R₆—NR₇R₈, —CR₅R₆(OR₇)(OR₈), —CR₅R₆(OR₇)(NR₈), —CR₅R₆(NR₇)(NR₈), anhydride, acetal and ketal groups, —SO₂R₅, amidine groups, —NR₅C(S)NR₆, —NR₅C(S)—OR₆, —N═C═S, —NO₂, —C═N—OH, —N(R₅)═NR₆, —PR₅R₆R₇, —OSiR₅R₆R₇ and —SiR₅R₆R₇,

where R₅ to R₁₀, independently of one another in each case, are defined in the same way as R₁ to R₄, or two of the radicals R₁ to R₄ form a C₄- to C₇-ring which in turn may be substituted or unsubstituted and, optionally, contain one or more heteroatom,

with the proviso that

at least two of the radicals R₁ to R₃ are a radical-stabilizing and/or bulky group as defined above,

or a polymer (B) which is prepared by a process comprising the stage (ii):

(ii) Reaction of the reaction product (A) obtained in stage (i), under free radical conditions, in the presence of at least one monomer (b) capable of free radical hoinopolymerization or copolymerization,

and suitable additives (C) selected from the group consisting of

crosslinking agents, crosslinking catalysts, initiators, pigments, dyes, fillers, reinforcing fillers, rheology assistants, wetting agents, dispersants, antifoams, adhesion promoters, additives for improving substrate wetting, additives for improving surface smoothness, dulling agents, leveling agents, film-forming assistants, drying agents, antiskinning agents, light stabilizers, corrosion inhibitors, biocides, flameproofing agents, polymerization inhibitors, photoinhibitors and plasticizers.

2. Coating materials as claimed in claim 1, wherein the radical of the formula (III) is derived from at least one compound of the formula (I) ##STR8##

where R₁ to R₄, in each case independently of one another, are hydrogen, methyl or a radical-stabilizing and/or bulky group selected from the group consisting of unsubstituted and substituted, linear and branched alkyl group having two or more carbon atoms, cycloalkyl, alcohol, ether, polyether, amine and aralkyl radicals, substituted and unsubstituted aromatic, heterocyclic and olefinic hydrocarbons, halogen atoms, substituted and unsubstituted, linear and branched alkenyl and alkynyl groups, —C(O)R₅, —C(O)OR₅, —CR₅R₆—O—R₇, —O—C(O)R₅, —CN, —O—CN, —S—CN, —O—C═NR₅, —S—C═NR₅, —O—CR₅R₆—CR₇R₈NR₉R₁₀, —N═C═O, —C═NR₅, —CR₅R₆-Hal, —C(S)R₅, —CR₅R₆—P(O)R₇R₈, —CR₅R₆—PR₇R₈, —CR₅R₆—NR₇R₈, —CR₅R₆(OR₇)(OR₈), —CR₅R₆(OR₇)(NR₈), —CR₅R₆(NR₇)(NR₈), anhydride, acetal and ketal groups, —SO₂R₅, amidine groups, —NR₅C(S)NR₆, —NR₅C(S)—OR₆, —N═C═S, —NO₂, —C═N—OH, —N(R₅)═NR₆, —PR₅R₆R₇, —OSiR₅R₆R₇ and —SiR₅R₆R₇, where R₅ to R₁₀, independently of one another in each case, are defined in the same way as R₁ to R₅, or two of the radicals R₁ to R₄ form a C₄- to C₇-ring which in turn may be substituted or unsubstituted and may contain one or more heteroatoms,

with the proviso that

at least two of the radicals R₁ to R₄ are a radical-stabilizing and/or bulky group, as defined above, or the compounds are diphenylethylene, dinaphthylethylene, 4,4′-vinylidenebis(N,N′-dimethylaniline) 4,4′-vinylidenebis(aminobenzene) or cis- and trans-stilbene.

3. Coating materials as claimed in claim 1, wherein the radical of the formula (III) is derived from at least one compound of the formula (II): ##STR9##

where R₁ to R₄ and R₁₁ and R₁₂, in each case independently of one another, are hydrogen, methyl or a radical-stabilizing and/or bulky group selected from the group consisting of unsubstituted and substituted, linear and branched alkyl groups having two or more carbon atoms, cycloalkyl, alcohol, ether, polyether, amine and aralkyl radicals, substituted and unsubstituted aromatic, heterocyclic and olefinic hydrocarbons, halogen atoms, substituted and unsubstituted, linear and branched alkenyl and alkynyl group, —C(O)R₅, —C(O)OR₅, —CR₅R₆—O—R₇, —O—C(O)R₅, —CN, —O—CN, —S—CN, —O—C═NR₅, —S—C═NR₅, —O—CR₅R₆—CR₇R₈NR₉R₁₀, —N═C═O, —C═NR₅, —CR₅R₆-Hal, —C(S)R₅, —CR₅R₆—P(O)R₇R₈, —CR₅R₆—PR₇R₈, —CR₅R₆—NR₇R₈, —CR₅R₆(OR₇)(OR₈), —CR₅R₆(OR₇)(NR₈), —CR₅R₆(NR₇)(NR₈), anhydride, acetal and ketal groups, —SO₂R₅, amidine groups, —NR₅C(S)NR₆, —NR₅C(S)—OR₆, —N═C═S, —NO₂, —C═N—OH, —N(R₅)═NR₆, —PR₅R₆R₇, —OSiR₅R₆R₇ and —SiR₅R₆R₇,

where R₅ to R₁₀, independently of one another in each case, are defined in the same way as R₁ to R₄, or two of the radicals R₁ to R₄ form a C₄- to C₇-ring which in turn may be substituted or unsubstituted and, optionally, contain one or more heteroatoms,

with the proviso that

at least two of the radicals R₁ to R₄ are a radical-stabilizing and/or bulky group, as defined above.

4. Coating materials as claimed in claim 1, the radical of the formula (III) comprising the following combinations as radical-stabilizing and/or bulky groups:

at least one substituted or unsubstituted phenyl and —C(O)R₅;

at least one substituted or unsubstituted phenyl and —CN;

at least one substituted or unsubstituted phenyl and —C(O)OR₅;

independently of one another, at least two substituted or unsubstituted phenyl groups;

independently of one another, at least two —C(O)R₅; and

independently of one another, at least two —CN.

5. Coating materials as claimed in claim 1, the radical (III) being derived from the following compounds of the formula (I) or (II) or mixtures of two or more thereof:

1,1,4,4-tetraphenyl-1,3-butadiene

1,4-bis(2-methylstyryl)benzene

1,2,3,4,5-pentaphenyl-1,3-cyclopentadiene

1,2,3,4-tetraphenyl-1,3-cyclopentadiene

acenaphthylene

cis- and trans-alpha-methylstilbene

cis- and trans-4,4′-diphenylstilbene, diphenylethylene, dinaphthylethylene, 4,4′-vinylidenebis(N,N′-dimethylaniline), 4,4′-vinylidenebis(aminobenzene), cis- and trans-stilbene,

trans-trans- and trans-cis- and cis-cis-1,4-diphenyl-1,3-butadiene

alpha,omega-tetraphenylpolyethyne

diphenylfulvene

triphenylethene

tetraphenylethene

1-cyano-1-phenylethylene; 1-alkoxycarbonyl-1-phenylethylene; 1,1-dialkoxycarbonyl-2-ethylethylene; 1,1-dialkoxycarbonyl-2-phenylethylene, 1,1-dialkoxycarbonyl-2,2-dimethylethylene; 1,1-dialkoxycarbonylmethylethylene; 9-methylenexanthene; 9-methylenethioxanthene, 9-methylene-10-H-acridine, diphenylethylene, dinaphthylethylene, 4,4′-vinylidenebis(N,N′-dimethylaniline), 4,4-vinylidenebis(aminobenzene), cis- and trans-stilbene, 1,2-bis(trimethylsilyloxy)tetraphenylethane (TPSE), diethyl-2,3-dicyano-2,3-di(p-tolyl)succinate, hexaphenylethane, compounds of the structure (Ph₂CR₁—CR₁(Ph)₂, where Ph is substituted or unsubstituted phenyl and R₁ is selected from the group consisting of: hydrogen, ethyl, —C₂H₄—, —OC₆H₅, OSi(CH₃)₃, —OH, —OC(O)CH₃, —OCH₃, —CH₃, —CO₂C₂H₅, —CN; —OC(O)CH═CH₂, 1,1,2,2-tetraphenyl-1,2-diphenoxyethane (TPPA); 1,1,2,2-tetraphenyl-1,2-bis(trimethylsilyloxy)ethane (TPSA) and 1,2,2,2-tetraphenyl-1,2-dicyanoethane (TPCA); 1,2-diphenyl-1,2-dicyano-1,2-dimethylethane.

6. Coating materials as claimed in claim 1, which are prepared in the presence of a low molecular weight base selected the group consisting of NaOH, KOH, ammonia, diethanolamine, triethanolamine, mono-, di- and triethylamine, dimethylethanolamine and a mixture of two or more thereof.

7. Resin materials comprising a reaction product (A) which is prepared by means of a process comprising the following stage (i):

(i) Reaction, under free radical conditions, of a reaction mixture comprising at least one monomer (a), capable of free radical reaction, in the presence of at least one radical of the formula (III) ##STR10##

 where R₁ to R₃, in each case independently of one another, are hydrogen, methyl or a radical-stabilizing and/or bulky group selected from the group consisting of unsubstituted and substituted, linear and branched alkyl groups having two or more carbon atoms, cycloalkyl, alcohol, ether, polyether, amine and aralkyl radicals, substituted and unsubstituted aromatic, heterocyclic and olefinic hydrocarbons, halogen atoms, a substituted and unsubstituted, linear and branched alkenyl and alkynyl groups, —C(O)R₅, —C(O)OR₅, —CR₅R₆—O—R₇, —O—C(O)R₅, —CN, —O—CN, —S—CN, —O—C═NR₅, —S—C═NR₅, —O—CR₅R₆—CR₇R₈NR₉R₁₀, —N═C═O, —C═NR₅, —CR₅R₆-Hal, —C(S)R₅, —CR₅R₆—P(O)R₇R₈, —CR₅R₆—PR₇R₈, —CR₅R₆—NR₇R₈, —CR₅R₆(OR₇)(OR₈), —CR₅R₆(OR₇)(NR₈), —CR₅R₆(NR₇)(NR₈), anhydride, acetal and ketal groups, —SO₂R₅, amidine groups, —NR₅C(S)NR₆, —NR₅C(S)—OR₆, —N═C═S, —NO₂, —C═N—OH, —N(R₅)═NR₆, —PR₅R₆R₇, —OSiR₅R₆R₇ and —SiR₅R₆R₇,

where R₅ to R₁₀, independently of one another in each case, are defined in the same way as R₁ to R₄, or two of the radicals R₁ to R₄ form a C₄- to C₇-ring which in turn may be substituted or unsubstituted and, optionally, contain one or more heteroatom,

with the proviso that

at least two of the radicals R₁ to R₃ are a radical-stabilizing and/or bulky group as defined above,

or a polymer (B) which is prepared by a process comprising the stage (ii):

(ii) Reaction of the reaction product (A) obtained in stage (i), under free radical conditions, in the presence of at least one monomer (b) capable of free radical homopolymerization or copolymerization,

and additives selected from the group consisting of lubricants,

antistatic agents, antioxidants, heat stabilizers, ultraviolet absorbers, pigments, dyes, nucleating agents, rubbers, fillers, dulling agents, brightening compositions, flameproofing agents, blowing agents, mold release agents and mineral oil.

8. Resin materials as claimed in claim 7, wherein the radical of the formula (III) is derived from at least one compound of the formula (I): ##STR11##

where R₁ to R₄ and R₁₁ and R₁₂, in each case independently of one another, are hydrogen, methyl or a radical-stabilizing and/or bulky group selected from the group consisting of unsubstituted and substituted, linear and branched alkyl groups having two or more carbon atoms, cycloalkyl, alcohol, ether, polyether, amine and aralkyl radicals, substituted and unsubstituted aromatic, heterocyclic and olefinic hydrocarbons, halogen atoms, substituted and unsubstituted, linear and branched alkenyl and alkynyl groups, —C(O)R₅, —C(O)OR₅, —CR₅R₆—O—R₇, —O—C(O)R₅, —CN, —O—CN, —S—CN, —O—C═NR₅, —S—C═NR₅, —O—CR₅R₆—CR₇R₈NR₉R₁₀, —N═C═O, —C═NR₅, —CR₅R₆-Hal, —C(S)R₅, —CR₅R₆—P(O)R₇R₈, —CR₅R₆—PR₇R₈, —CR₅R₆—NR₇R₈, —CR₅R₆(OR₇)(OR₈), —CR₅R₆(OR₇)(NR₈), —CR₅R₆(NR₇)(NR₈), anhydride, acetal and ketal groups, —SO₂R₅, amidine groups, —NR₅C(S)NR₆, —NR₅C(S)—OR₆, —N═C═S, —NO₂, —C═N—OH, —N(R₅)═NR₆, —PR₅R₆R₇, —OSiR₅R₆R₇ and —SiR₅R₆R₇, where R₅ to R₁₀, independently of one another in each case, are defined in the same way as R₁ to R₄, or two of the radicals R₁ to R₄ form a C₄- to C₇-ring which in turn may be substituted or unsubstituted and, optionally, contain one or more heteroatoms,

with the proviso that

at least two of the radicals R₁ to R₄ are a radical-stabilizing and/or bulky group, as defined above, or the compounds are diphenylethylene, dinaphthylethylene, 4,4′-vinylidenebis(N,N′-dimethylaniline), 4,4′-vinylidenebis(aminobenzene) or cis- and trans-stilbene.

9. The resin material as claimed in claim 7, wherein the radical of the formula (III) is derived from at least one compound of the formula (II): ##STR12##

where R₁ to R₄ and R₁₁ and R₁₂, in each case independently of one another, are hydrogen, methyl or a radical-stabilizing and/or bulky group selected from unsubstituted and substituted, linear and branched alkyl groups two or more carbon atoms, cycloalkyl, alcohol, ether, polyether, and amine aralkyl radicals, substituted and unsubstituted aromatic, heterocyclic and olefinic hydrocarbons, halogen atoms, substituted and unsubstituted, linear and branched alkenyl and alkynyl groups, —C(O)R₅, —C(O)OR₅, —CR₅R₆—O—R₇, —O—C(O)R₅, —CN, —O—CN, —S—CN, —O—C═NR₅, —S—C═NR₅, —O—CR₅R₆—CR₇R₈NR₉R₁₀, —N═C═O, —C═NR₅, —CR₅R₆-Hal, —C(S)R₅, —CR₅R₆—P(O)R₇R₈, —CR₅R₆—PR₇R₈, —CR₅R₆—NR₇R₈, —CR₅R₆(OR₇)(OR₈), —CR₅R₆(OR₇)(NR₈), —CR₅R₆(NR₇)(NR₈), anhydride, acetal and ketal groups, —SO₂R₅, amidine groups, —NR₅C(S)NR₆, —NR₅C(S)—OR₆, —N═C═S, —NO₂, —C═N—OH, —N(R₅)═NR₆, —PR₅R₆R₇, —OSiR₅R₆R₇ and —SiR₅R₆R₇, where R₅ to R₁₀, independently of one another in each case, are defined in the same way as R₁ to R₄, or two of the radicals R₁ to R₄ form a C₄- to C₇-ring which in turn may be substituted or unsubstituted and, optionally, contain one or more heteroatoms,

with the proviso that

at least two of the radicals R₁ to R₄ are a radical-stabilizing and/or bulky group, as defined above.

10. The resin material as claimed in claim 7, the radical of the formula (III) comprising the following combinations as radical-stabilizing and/or bulky groups:

at least one substituted or unsubstituted phenyl and —C(O)R₅;

at least one substituted or unsubstituted phenyl and —CN;

at least one substituted or unsubstituted phenyl and —C(O)OR₅;

independently of one another, at least two substituted or unsubstituted phenyl groups;

independently of one another, at least two —C(O)R₅; and

independently of one another, at least two —CN.

11. The resin material as claimed in claim 7, the radical (III) being derived from the following compounds of the formula (I) or (II) or mixtures of two or more thereof:

1,1,4,4-tetraphenyl-1,3-butadiene

1,4-bis(2-methylstyryl)benzene

1,2,3,4,5-pentaphenyl-1,3-cyclopentadiene

1,2,3,4-tetraphenyl-1,3-cyclopentadiene

acenaphthylene

cis- and trans-alpha-methylstilbene

cis- and trans-4,4′-diphenylstilbene, diphenylethylene, dinaphthylethylene, 4,4′-vinylidenebis(N,N′-dimethylaniline), 4,4′-vinylidenebis(aminobenzene), cis- and trans-stilbene,

trans-trans- and trans-cis- and cis-cis-1,4-diphenyl-1,3-butadiene

alpha,omega-tetraphenylpolyethyne

diphenylfulvene

triphenylethene

tetraphenylethene

1-cyano-1-phenylethylene; 1-alkoxycarbonyl-1-phenylethylene; 1,1-dialkoxycarbonyl-2-ethylethylene; 1,1-dialkoxycarbonyl-2-phenylethylene, 1,1-dialkoxycarbonyl-2,2-dimethylethylene; 1,1-dialkoxycarbonylmethylethylene; 9-methylenexanthene; 9-methylenethioxanthene, 9-methylene-10-H-acridine, diphenylethylene, dinaphthylethylene, 4,4′-vinylidenebis(N,N′-dimethylaniline), 4,4′-vinylidenebis(aminobenzene), cis- and trans-stilbene, 1,2-bis(trimethylsilyloxy)tetraphenylethane (TPSE), diethyl-2,3-dicyano-2,3-di(p-tolyl)succinate, hexaphenylethane, compounds of the structure (Ph₂CR₁—CR₁(Ph)₂, where Ph is substituted or unsubstituted phenyl and R₁ is selected from the group consisting of: hydrogen, ethyl, —C₂H₄—, —OC₆H₅, OSi(CH₃)₃, —OH, —OC(O)CH₃, —OCH₃, —CH₃, —CO₂C₂H₅, —CN; —OC(O)CH═CH₂, 1,1,2,2-tetraphenyl-1,2-diphenoxyethane (TPPA); 1,1,2,2-tetraphenyl-1,2-bis(trimethylsilyloxy)ethane (TPSA) and 1,2,2,2-tetraphenyl-1,2-dicyanoethane (TPCA); 1,2-diphenyl-1,2-dicyano-1,2-dimethylethane.

12. The resin material as claimed in claim 7, which is prepared in the presence low molecular weight base selected from the group consisting of NaOH, KOH, ammonia, diethanolamine, triethanolamine, mono-, di- or triethylamine, dimethylethanolamine or a mixture of two or more thereof.

13. Aqueous dispersion containing a reaction product (A) which is prepared by means of a process comprising the following stage (i):

(i) Reaction, under free radical conditions, of a reaction mixture comprising at least one monomer (a), capable of free radical reaction, in the presence of at least one radical of the formula (III) ##STR13##

 where R₁ to R₃, in each case independently of one another, are hydrogen, methyl or a radical-stabilizing and/or bulky group selected from the group consisting of unsubstituted and substituted, linear and branched alkyl groups having two or more carbon atoms, cycloalkyl, alcohol, ether, polyether, amine and aralkyl radicals, substituted and unsubstituted aromatic, heterocyclic and olefinic hydrocarbons, a halogen atoms, substituted and unsubstituted, linear and branched alkenyl and alkynyl groups, —C(O)R₅, —C(O)OR₅, —CR₅R₆—O—R₇, —O—C(O)R₅, —CN, —O—CN, —S—CN, —O—C═NR₅, —S—C═NR₅, —O—CR₅R₆—CR₇R₈NR₉R₁₀, —N═C═O, —C═NR₅, —CR₅R₆-Hal, —C(S)R₅, —CR₅R₆—P(O)R₇R₈, —CR₅R₆—PR₇R₈, —CR₅R₆—NR₇R₈, —CR₅R₆(OR₇)(OR₈), —CR₅R₆(OR₇)(NR₈), —CR₅R₆(NR₇)(NR₈), anhydride, acetal and ketal groups, —SO₂R₅, amidine groups, —NR₅C(S)NR₆, —NR₅C(S)—OR₆, —N═C═S, —NO₂, —C═N—OH, —N(R₅)═NR₆, —PR₅R₆R₇, —OSiR₅R₆R₇ and —SiR₅R₆R₇,

where R₅ to R₁₀, independently of one another in each case, are defined in the same way as R₁ to R₄, or two of the radicals R₁ to R₄ form a C₄- to C₇-ring which in turn may be substituted or unsubstituted and, if required, may contain one or more heteroatom,

with the proviso that

at least two of the radicals R₁ to R₃ are a radical-stabilizing and/or bulky group as defined above, or a polymer (B) which is prepared by a process comprising the stage (ii):

(ii) Reaction of the reaction product (A) obtained in stage (i), under free radical conditions, in the presence of at least one monomer (b) capable of free radical homopolymerization or copolymerization,

or a mixture of(A) and (B).

14. The dispersion as claimed in claim 13, wherein the radical of the formula (III) is derived from at least one compound of the formula (I) ##STR14##

where R₁ to R₄, in each case independently of one another, are hydrogen, methyl or a radical-stabilizing and/or bulky group selected from the group consisting of unsubstituted and substituted, linear and branched alkyl groups having two or more carbon atoms, cycloalkyl, alcohol, ether, polyether, amine and aralkyl radicals, a substituted and unsubstituted aromatic, heterocyclic and olefinic hydrocarbons, a halogen atoms, a substituted and unsubstituted, linear and branched alkenyl and alkynyl groups, —C(O)R₅, —C(O)OR₅, —CR₅R₆—O—R₇, —O—C(O)R₅, —CN, —O—CN, —S—CN, —O—C═NR₅, —S—C═NR₅, —O—CR₅R₆—CR₇R₈NR₉R₁₀, —N═C═O, —C═NR₅, —CR₅R₆-Hal, —C(S)R₅, —CR₅R₆—P(O)R₇R₈, —CR₅R₆—PR₇R₈, —CR₅R₆—NR₇R₈, —CR₅R₆(OR₇)(OR₈), —CR₅R₆(OR₇)(NR₈), —CR₅R₆(NR₇)(NR₈), anhydride, acetal and ketal groups, —SO₂R₅, amidine groups, —NR₅C(S)NR₆, —NR₅C(S)—OR₆, —N═C═S, —NO₂, —C═N—OH, —N(R₅)═NR₆, —PR₅R₆R₇, —OSiR₅R₆R₇ and —SiR₅R₆R₇,

where R₅ to R₁₀, independently of one another in each case, are defined in the same way as R₁ to R₄, or two of the radicals R₁ to R₄ form a C₄- to C₇-ring which in turn may be substituted or unsubstituted and may contain one or more heteroatoms,

with the proviso that

at least two of the radicals R₁ to R₄ are a radical-stabilizing and/or bulky group, as defined above, or the compounds are diphenylethylene, dinaphthylethylene, 4,4′-vinylidenebis(N,N′-dimethylaniline) 4,4′-vinylidenebis(aminobenzene) or cis- and trans-stilbene.

15. The dispersion as claimed in claim 13, wherein the radical of the formula (III) is derived from at least one compound of the formula (II): ##STR15##

where R₁ to R₄ and R₁₁ and R₁₂, in each case independently of one another, are hydrogen, methyl or a radical-stabilizing and/or bulky group selected from the group consiting of unsubstituted and substituted, linear and branched alkyl groups having two or more carbon atoms, cycloalkyl, alcohol, ether, polyether, amine and aralkyl radicals, substituted and unsubstituted aromatic, heterocyclic and olefinic hydrocarbons, halogen atoms, substituted and unsubstituted, linear and branched alkenyl and alkynyl groups, —C(O)R₅, —C(O)OR₅, —CR₅R₆—O—R₇, —O—C(O)R₅, —CN, —O—CN, —S—CN, —O—C═NR₅, —S—C═NR₅, —O—CR₅R₆—CR₇R₈NR₉R₁₀, —N═C═O, —C═NR₅, —CR₅R₆-Hal, —C(S)R₅, —CR₅R₆—P(O)R₇R₈, —CR₅R₆—PR₇R₈, —CR₅R₆—NR₇R₈, —CR₅R₆(OR₇)(OR₈), —CR₅R₆(OR₇)(NR₈), —CR₅R₆(NR₇)(NR₈), an anhydride, acetal and ketal groups, —SO₂R₅, an amidine groups, —NR₅C(S)NR₆, —NR₅C(S)—OR₆, —N═C═S, —NO₂, —C═N—OH, —N(R₅)═NR₆, —PR₅R₆R₇, —OSiR₅R₆R₇ and —SiR₅R₆R₇,

where R₅ to R₁₀, independently of one another in each case, are defined in the same way as R₁ to R₄, or two of the radicals R₁ to R₄ form a C₄- to C₇-ring which in turn may be substituted or unsubstituted and, optionally, contain one or more heteroatoms,

with the proviso that

at least two of the radicals R₁ to R₄ are a radical-stabilizing and/or bulky group, as defined above.

16. The dispersion as claimed in claim 13, the radical of the formula (III) comprising the following combinations as radical-stabilizing and/or bulky groups:

at least one substituted or unsubstituted phenyl and —C(O)R₅;

at least one substituted or unsubstituted phenyl and —CN;

at least one substituted or unsubstituted phenyl and —C(O)OR₅;

independently of one another, at least two substituted or unsubstituted phenyl groups;

independently of one another, at least two —C(O)R₅; and

independently of one another, at least two —CN.

17. The dispersion as claimed in claim 13, the radical (III) being derived from the following compounds of the formula (I) or (II) or mixtures of two or more thereof:

1,1,4,4-tetraphenyl-1,3-butadiene

1,4-bis(2-methylstyryl)benzene

1,2,3,4,5-pentaphenyl-1,3-cyclopentadiene

1,2,3,4-tetraphenyl-1,3-cyclopentadiene

acenaphthylene

cis- and trans-alpha-methylstilbene

cis- and trans-4,4′-diphenylstilbene, diphenylethylene, dinaphthylethylene, 4,4′-vinylidenebis(N,N′-dimethylaniline), 4,4′-vinylidenebis(aminobenzene), cis- and trans-stilbene,

trans-trans- and trans-cis- and cis-cis-1,4-diphenyl-1,3-butadiene

alpha,omega-tetraphenylpolyethyne

diphenylfulvene

triphenylethene

tetraphenylethene

1-cyano-1-phenylethylene; 1-alkoxycarbonyl-1-phenylethylene; 1,1-dialkoxycarbonyl-2-ethylethylene; 1,1-dialkoxycarbonyl-2-phenylethylene, 1,1-dialkoxycarbonyl-2,2-dimethylethylene; 1,1-dialkoxycarbonylmethylethylene; 9-methylenexanthene; 9-methylenethioxanthene, 9-methylene-10-H-acridine, diphenylethylene, dinaphthylethylene, 4,4′-vinylidenebis(N,N′-dimethylaniline), 4,4′-vinylidenebis(aminobenzene), cis- and trans-stilbene, 1,2-bis(trimethylsilyloxy)tetraphenylethane (TPSE), diethyl -2,3 -dicyano-2,3-di(p-tolyl)succinate, hexaphenylethane, compounds of the structure (Ph₂CR₁—CR₁(Ph)₂, where Ph is substituted or unsubstituted phenyl and R₁ is selected from the group consisting of: hydrogen, ethyl, —C₂H₄—, —OC₆H₅, OSi(CH₃)₃, —OH, —OC(O)CH₃, —OCH₃, —CH₃, —CO₂C₂H₅, —CN; —OC(O)CH═CH₂, 1,1,2,2-tetraphenyl-1,2-diphenoxyethane (TPPA); 1,1,2,2-tetraphenyl-1,2-bis(trimethylsilyloxy)ethane (TPSA) and 1,2,2,2-tetraphenyl-1,2-dicyanoethane (TPCA); 1,2-diphenyl-1,2-dicyano-1,2-dimethylethane.

18. The dispersion as claimed in claim 13, which is prepared in the presence of a low molecular weight base selected from the group consisting of NaOH, KOH, ammonia, diethanolamine, triethanolamine, mono-, di- and triethylamine, dimethylethanolamine and a mixture of two or more thereof.

19. A method of applying a coating material comprising a reaction product (A) or a mixture of two or more thereof or a polymer (B) as claimed in claim 1,

comprising the step of dipping, spraying, knife coating, brushing, roller coating, or pouring in the form of a liquid curtain the coating material onto a substrate selected from the group consisting of films, sheets, fibers, metal sheets, woven fabrics, shaped articles of metal, glass, wood, paper, plastics, leather, mineral substrates, and composite materials thereof.

20. A method for preparing a resin material comprising a reaction product (A) or a polymer (B) as claimed in claim 7,

comprising the step of mixing, optionally subsequent roll-milling and kneading (plasticization) and, optionally, subsequent granulation the reaction product (A) or the polymer (B) with additives and optionally further polymers.

21. A method for preparing a pigment formulation comprising a reaction product (A) or a polymer (B) as claimed in claim 13 as a dispersant

comprising the step of mixing a pigment together with one or more dispersant(s) in the presence of water and predispersing in a suitable apparatus, wherein a mixture is obtained, subsequently milling the mixture obtained in a mill in order to establish the desired pigment particle size distribution, adding further assistants, and

finally preparing the final formulation by adding corresponding amounts of water, optionally one or more humectants, and optionally further assistants, mixing and then fixing by means of a filtration apparatus with fines removal in the range from 10 to 1 μm.

22. A method for preparing

finishes coating materials,

toners,

cosmetics,

resin material,

retention aids for papermaking,

solubilizers in pharmaceutical and cosmetic formulations,

incrustation inhibitors and/or soil-release polymers in detergents,

filtration assistants and for protecting and clarifying beverages,

disinfectants,

elastomeric binders in printing plates,

a dispersant, preferably in inkjet pigment formulations,

an assistant in a tablet matrix,

an assistant in the plasticizing of concrete,

biodegradable polymers for, for example, materials for implants, surgical suture materials and garbage bags,

water-soluble adhesives,

adhesives for floor coverings,

thickeners of aqueous or predominantly aqueous systems,

sheets, moldings, foams and fibers,

pressure-sensitive adhesive materials,

solid or liquid adhesives,

for producing self-cleaning surfaces of articles,

as stain inhibitors in solid and liquid formulations,

plastics used in automotive construction, in the household sector, for leisure articles, in the production of road signs, window profiles, lamp covers, garden furniture, boats, surfboards, toys, in the packaging sector, in the production of massage apparatuses and housings therefor, in the production of medical equipment, in the production of equipment for information processing and transmission, in the production of extensive wall elements, in transport containers, in housings for electrical equipment, in moldings for the construction sector or in grating covers

comprising the step of mixing a reaction product (A) which is prepared by means of a process comprising the following stage (i):

(i) Reaction, under free radical conditions, of a reaction mixture comprising at least one monomer (a), capable of free radical reaction, in the presence of at least one radical of the formula (III) ##STR16##

 where R₁ to R₃, in each case independently of one another, are hydrogen, methyl or a radical-stabilizing and/or bulky group selected from the group consisting of unsubstituted and substituted, linear and branched alkyl groups having two or more carbon atoms, cycloalkyl, alcohol, ether, polyether, amine and aralkyl radicals, substituted and unsubstituted aromatic, heterocyclic and olefinic hydrocarbons, halogen atoms, a substituted and unsubstituted, linear and branched alkenyl and alkynyl groups, —C(O)R₅, —C(O)OR₅, —CR₅R₆—O—R₇, —O—C(O)R₅, —CN, —O—CN, —S—CN, —O—C═NR₅, —S—C═NR₅, —O—CR₅R₆—CR₇R₈NR₉R₁₀, —N═C═O, —C═NR₅, —CR₅R₆-Hal, —C(S)R₅, —CR₅R₆—P(O)R₇R₈, —CR₅R₆—PR₇R₈, —CR₅R₆—NR₇R₈, —CR₅R₆(OR₇)(OR₈), —CR₅R₆(OR₇)(NR₈), —CR₅R₆(NR₇)(NR₈), anhydride, acetal and ketal groups, —SO₂R₅, amidine groups, —NR₅C(S)NR₆, —NR₅C(S)—OR₆, —N═C═S, —NO₂, —C═N—OH, —N(R₅)═NR₆, —PR₅R₆R₇, —OSiR₅R₆R₇ and —SiR₅R₆R₇,

where R₅ to R₁₀, independently of one another in each case, are defined in the same way as R₁ to R₄, or two of the radicals R₁ to R₄ form a C₄- to C₇-ring which in turn may be substituted or unsubstituted and, optionally, contain one or more heteroatom,

with the proviso that

at least two of the radicals R₁ to R₃ are a radical-stabilizing and/or bulky group as defined above or a polymer (B) which is prepared by a process comprising the stage (ii):

(ii) Reaction of the reaction product (A) obtained in stage (i), under free radical conditions, in the presence of at least one monomer (b) capable of free radical homopolymerization or copolymerization,

with suitable additives.

23. The coating materials defined in claim 1, wherein the radical of the formula (III) is generated by cleavage of a compound of formula (I) or (II) ##STR17## ##STR18##

in which R₁ to R₄ and R₁₁ and R₁₂, in each case independently of one another, are hydrogen, methyl or a radical-stabilizing and/or bulky group defined in claim 8, and at least two of the radicals R¹ to R⁴ in formula (I) and and at least two to the radicals R¹ to R⁴ in formula (II) are radical-stabilizing and/or bulky groups.

24. The resin materials defined in claim 7, where the radical of the formula (III) is generated by cleavage of a compound of formulae (I) or (II) ##STR19## ##STR20##

in which R₁ to R₄ and R₁₁ and R₁₂, in each case independently of one another, are hydrogen, methyl or a radical stabilizing and/or bulky group defined in claim 8, and at least two of the radicals R¹ to R⁴ in formula (I) and and at least two of the radicals R¹ to R⁴ in formula (II) are radical-stabilizing and/or bulky groups.

25. The aqueous dispersion defined in claim 13, wherein the radical of the formula (III) is generated by cleavage of a compound of formulae (I) or (II) ##STR21## ##STR22##

in which R₁ to R₄ and R₁₁ and R₁₂, in each case independently of one another, are hydrogen, methyl or a radical-stabilizing and/or bulky group defined in claim 8, and at least two of the radicals R¹ to R⁴ in formula (I) and and at least two to the radicals R¹ to R⁴ in formula (II) are radical-stabilizing and/or bulky groups.

---

Description

---

The present invention relates to various uses of a reaction product (A) which was prepared by reaction, under free radical conditions, of at least one monomer (a), capable of free radical reaction, in the presence of at least one free radical initiator and of a radical of the formula (III), as defined below.

The technical field of the present invention is the use of reaction products or polymers which were prepared by free radical polymerization in many applications in various technical fields, such as inkjet inks, cosmetics, coating materials and engineering materials.

The reaction products (A) or polymers (B) used within the scope of the present invention are known per se or form the subject of a parallel application of the Applicant.

In this context, reference may be made to DE 198 58 708.2 and the prior art cited therein. The preparation of the polymers used according to the invention has moreover been the subject of numerous scientific investigations.

A free radical chain polymerization or copolymerization with an ω-unsaturated oligo(methyl methacrylate) with ethyl acrylate, styrene, methyl methacrylate, acrylonitrile and vinyl acetate as copolymers is described in a scientific article in J. Macromol. Sci. Chem. A 23 (7) (1986), 839-852.

Furthermore, free radical chain polymerizations and copolymerizations using 1,2-(trimethylsilyloxy)tetraphenylethane are described in Macromol. Chem. Phys. 201 (2000), 74-83, methyl methacrylate, styrene, phenyl acetate, butyl acrylate and glycidyl methacrylate being used as monomers there.

An overview of free radical chain polymerizations using in particular tetraphenylethane (derivatives) is given by Otsu and Matsumoto in Advances in Polymer Science 136, 75-137, and in Polymer Bulletin 16 (1986), 95-102.

Furthermore, Harwood et al. in Macromol. Symp. 111 (1996), 25-35 report on NMR investigations into random, block and graft copolymers using NMR-sensitive initiators and macroinitiators. Inter alia, the reaction of a methyl methacrylate/stilbene mixture and the properties of the polymer resulting therefrom are described there.

The abovementioned scientific papers are concerned exclusively with the reaction mechanism on which free radical chain polymerization is based or relate to investigations into the structure of the resulting products. Possible uses of the reaction products or polymers discussed therein are not mentioned.

It is an object of the present invention to demonstrate the numerous potential uses of such specific reaction products or polymers prepared by free radical chain polymerization. The reaction products and polymers described herein are of considerable interest since the chosen method of preparation makes it possible to establish the properties of these products in a specific manner with regard to the wide range of potential uses, in particular by the preparation of block structures by means of free radical polymerization.

In the context of the present invention, a block copolymer is understood as meaning a polymer which has at least two polymer blocks characterized by different monomer compositions. In the context of the present invention, different monomer compositions is understood as meaning that at least two regions of the block copolymer have different monomer compositions. In the context of the present invention, it is possible for the transition between two blocks to be continuous, i.e., for there to exist between two blocks a zone which has a random or regular sequence of the monomers constituting the blocks. In the context of the present invention, however, it is also envisaged that the transition between two blocks is essentially discontinuous. An essentially discontinuous transition is understood as meaning a transition zone which has a substantially shorter length than at least one of the blocks separated by the transition zone. It is possible for a block to be based only on one type of monomer. However, it is also envisaged that a block is composed of two or more monomers. In a preferred embodiment of the present invention, the chain length of such a transition zone is less than 1/10, preferably less than 1/20, of the block length of at least one of the blocks separated by the transition zone.

In the context of the present invention different monomer compositions is furthermore understood as meaning that the monomers constituting the respective block differ in at least one feature, for example in their linkage to one another, in their conformation or in their constitution. If, as described above, a block is composed of more than one type of monomer, in the present context different blocks of the block copolymer can, for example, also differ by having different concentrations of the monomers constituting a block in each case. In the context of the present invention, block copolymers preferably used are those which have at least two blocks whose monomer compositions differ at least in the constitution of the monomers.

We have found that the abovementioned and further objects are achieved by the use of a reaction product (A) which can be prepared by means of a process comprising the following stage (i):

• (i) Reaction, under free radical conditions, of a reaction mixture comprising at least one monomer (a), capable of free radical reaction, in the presence of at least one radical of the formula (III) ##STR2##
  where R₁ to R₃, in each case independently of one another, are hydrogen, methyl or a radical-stabilizing and/or bulky group selected from an unsubstituted or substituted, linear or branched alkyl of two or more carbon atoms, cycloalkyl, alcohol, ether, polyether, amine, aralkyl radical, a substituted or unsubstituted aromatic, heterocyclic or olefinic hydrocarbon, a halogen atom (Hal), a substituted or unsubstituted, linear or branched alkenyl or alkynyl group, —C(O)R₅, —C(O)OR₅, —CR₅R₆—O—R₇, —O—C(O)R₅, —CN, —O—CN, —S—CN, —O—C═NR₅, —S—C═NR₅, —O—CR₅R₆—CR₇R₈NR₉R₁₀, —N═C═O, —C═NR₅, —CR₅R₆-Hal, —C(S)R₅, —CR₅R₆—P(O)R₇R₈, —CR₅R₆—PR₇R₈, —CR₅R₆—NR₇R₈, —CR₅R₆(OR₇)(OR₈), —CR₅R₆(OR₇)(NR₈), —CR₅R₆(NR₇)(NR₈), an anhydride, acetal or ketal group, —SO₂R₅, an amidine group, —NR₅C(S)NR₆, —NR₅C(S)—OR₆, —N═C═S, —NO₂, —C═N—OH, —N(R₅)═NR₆, —PR₅R₆R₇, —OSiR₅R₆R₇ or —SiR₅R₆R₇, where R₅ to R₁₀, independently of one another in each case, are defined in the same way as R₁ to R₄, or two of the radicals R₁ to R₄ form a C₄- to C₇-ring which in turn may be substituted or unsubstituted and, if required, may contain one or more heteroatoms,
  with the proviso that
• at least two of the radicals R₁ to R₃ are a radical-stabilizing and/or bulky group as defined above,
  • as a component in coating materials,
  • in finishes and coating materials,
  • as a component in toners,
  • as a component in cosmetics,
  • as a component in resin material,
  • as a component in retention aids for papermaking,
  • as a component in solubilizers in pharmaceutical and cosmetic formulations,
  • as incrustation inhibitors and/or soil-release polymers in detergents,
  • as a component in filtration assistants and for protecting and clarifying beverages,
  • as a component in disinfectants,
  • as a component in elastomeric binders,
  • in printing plates,
  • as a dispersant, preferably in inkjet pigment formulations,
  • as an assistant in a tablet matrix,
  • as an assistant in the plasticizing of concrete,
  • as biodegradable polymers for, for example, materials for implants, surgical suture materials and garbage bags,
  • as a component in wallpaper adhesive,
  • as a component of plastics used in automotive construction, in the household sector, for leisure articles, in the production of road signs, window profiles, lamp covers, garden furniture, boats, surfboards, toys, in the packaging sector, in the production of massage apparatuses and housings therefor, in the production of medical equipment, in the production of equipment for information processing and transmission, in the production of extensive wall elements, in transport containers, in
  • housings for electrical equipment, in moldings for the construction sector or in grating covers, and
    the use of a polymer (B) which can be prepared by a process comprising the stage (ii):
• (ii) Reaction of the reaction product (A) obtained in stage (i), under free radical conditions, in the presence of at least one monomer (b) capable of free radical homopolymerization or copolymerization,
  • as a component in coating materials,
  • in finishes and coating materials,
  • as a component in toners,
  • as a component in cosmetics,
  • as a component in resin material,
  • as a component in retention aids for papermaking,
  • as a component in solubilizers in pharmaceutical and cosmetic formulations,
  • as a component in incrustation inhibitors and/or soil-release polymers in detergents,
  • as a component in filtration assistants and for protecting and clarifying beverages,
  • as a component in disinfectants,
  • as a component in elastomeric binders,
  • in printing plates,
  • as a dispersant, preferably in inkjet pigment formulations,
  • as an assistant in a tablet matrix,
  • as an assistant in the plasticizing of concrete,
  • as biodegradable polymers for, for example, materials for implants, surgical suture materials and garbage bags,
  • as a component in wallpaper adhesive,
  • as a component of plastics used in automotive construction, in the household sector, for leisure articles, in the production of road signs, window profiles, lamp covers, garden furniture, boats, surfboards, toys, in the packaging sector, in the production of massage apparatuses and housings therefor, in the production of medical equipment, in the production of equipment for information processing and transmission, in the production of extensive wall elements, in transport containers, in housings for electrical equipment, in moldings for the construction sector or in grating covers.

Preferably, the radical of the formula (III) is derived from at least one compound of the formula (I) ##STR3##

• where R₁ to R₄, in each case independently of one another, are hydrogen, methyl or a radical-stabilizing and/or bulky group selected from an unsubstituted or substituted, linear or branched alkyl of two or more carbon atoms, cycloalkyl, alcohol, ether, polyether, amine, aralkyl radical, a substituted or unsubstituted aromatic, heterocyclic or olefinic hydrocarbon, a halogen atom, a substituted or unsubstituted, linear or branched alkenyl or alkynyl group, —C(O)R₅, —C(O)OR₅, —CR₅R₆—O—R₇, —O—C(O)R₅, —CN, —O—CN, —S—CN,