Synthesis of improved binders and modified tacticity
View Patent ↗The invention relates to a process for preparing polymers for coating applications by polymerizing esters of acrylic acid or of methacrylic acid or vinyl aromatics or other free-radically polymerizable vinyl compounds or monomer mixtures composed predominantly of such monomers by means of a continuous polymerization process. In particular, the invention relates to a solvent-free preparation process for polymers, through which the binder can be prepared for coating applications with superior processing properties, very good thermal stability, improved pigment wetting and a higher gloss.
1. A process for preparing a (meth)acrylate-based binder, the process comprising:
continuous bulk polymerizing a monomer present in a mixture composed exclusively of said monomer, an initiator, optionally, a chain transfer reagent, and not more than 10% by weight of a solvent in a kneading apparatus to obtain a polymer; and
thermally treating said polymer obtained from said continuous bulk polymerizing at a temperature of more than 160° C. in a device downstream from said kneading apparatus, thereby obtaining a binder having a thermal stability of up to 214° C.,
wherein
said continuous bulk polymerizing is carried out in said kneading apparatus at a temperature of from 20 to 250° C.,
said binder is a polymer having a tacticity obtained by said continuous bulk polymerizing carried out at said temperature.
2. The process for preparing a binder according to claim 1 , wherein
said continuous bulk polymerizing is carried out at a temperature of from 100 to 250° C.; and
said monomer is exclusively methacrylic acid, an ester of methacrylic acid, or a combination thereof.
3. The process for preparing a binder according to claim 1 , wherein said thermally treating is carried out at a temperature of more than 180° C.
4. The process for preparing a binder according to claim 1 , wherein said thermally treating is carried out at a temperature of more than 160° C. and at an internal pressure of from 1 to 800 mbar.
5. The process for preparing a binder according to claim 1 , wherein said thermally treating is carried out at a temperature of more than 160° C. and at an internal pressure of from 5 to 400 mbar.
6. The process for preparing a binder according to claim 1 , wherein said thermally treating is carried out at a temperature of more than 160° C. and at an internal pressure of from 10 to 100 mbar.
7. The process for preparing a binder according to claim 1 , wherein said thermally treating is carried out at a temperature of more than 180° C. and at an internal pressure of from 1 to 800 mbar.
8. The process for preparing a binder according to claim 1 , wherein said thermally treating is carried out at a temperature of more than 180° C. and at an internal pressure of from 5 to 400 mbar.
9. The process for preparing a binder according to claim 1 , wherein said thermally treating is carried out at a temperature of more than 180° C. and at an internal pressure of from 10 to 100 mbar.
10. The process for preparing a binder according to claim 1 , wherein said initiator is present in said monomer mixture in an amount of from 0.1 to 5% by weight relative to the total weight of the monomer mixture.
11. The process for preparing a binder according to claim 1 , wherein said initiator is selected from the group consisting of azobisisobutyronitrile; 1,1′-azobis(cyclohexanecarbonitrile); 2-(carbamoylazo)isobutyronitrile; tert-butyl peroctoate; di(tert-butyl)peroxide; di(tert-amyl)peroxide; tert-butyl peroxy(2-ethylhexyl)carbonate; octanoyl peroxide; decanoyl peroxide; lauroyl peroxide; benzoyl peroxide; monochlorobenzoyl peroxide; dichlorobenzoyl peroxide; p-ethylbenzoyl peroxide; tert-butyl perbenzoate; azobis(2,4-dimethyl)valeronitrile; and a combination thereof.
12. The process for preparing a binder according to claim 1 , wherein said initiator is present in said monomer mixture in an amount of from 0.1 to 5% by weight relative to the total weight of the monomer and is selected from the group consisting of azobisisobutyronitrile; 1,1′-azobis(cyclohexanecarbonitrile); 2-(carbamoylazo)isobutyronitrile; tert-butyl peroctoate; di(tert-butyl)peroxide; di(tert-amyl)peroxide; tert-butyl peroxy(2-ethylhexyl)carbonate; octanoyl peroxide; decanoyl peroxide; lauroyl peroxide; benzoyl peroxide; monochlorobenzoyl peroxide; dichlorobenzoyl peroxide; p-ethylbenzoyl peroxide; tert-butyl perbenzoate; azobis(2,4-dimethyl)valeronitrile; and a combination thereof.
13. The process for preparing a binder according to claim 1 , wherein said chain transfer reagent is present in said monomer mixture and is selected from the group consisting of n-butyl mercaptan; n-octyl mercaptan; n-dodecyl mercaptan; tert-dodecyl mercaptan; mercaptoethanol; thioglycolic acid; isooctyl thioglycolate; lauryl thioglycolate; an aliphatic chlorine compound; an enol ether; dimeric α-methylstyrene; and a combination thereof.
14. The process for preparing a binder according to claim 1 , wherein said chain transfer reagent is present in said monomer mixture in an amount of up to 8% by weight relative to the total weight of said monomer and is selected from the group consisting of n-butyl mercaptan; n-octyl mercaptan; n-dodecyl mercaptan; tert-dodecyl mercaptan; mercaptoethanol; thioglycolic acid; isooctyl thioglycolate; lauryl thioglycolate; an aliphatic chlorine compound; an enol ether; dimeric α-methylstyrene; and a combination thereof.
15. The process for preparing a binder according to claim 1 , wherein said monomer consists of at least one of methyl (meth)acrylate; ethyl (meth)acrylate; n-butyl (meth)acrylate; isobutyl(meth)acrylate; tert-butyl (meth)acrylate; pentyl(meth)acrylate; 2-ethylhexyl(meth)acrylate; stearyl(meth)acrylate; lauryl(meth)acrylate; cyclohexyl(meth)acrylate; isobornyl(meth)acrylate; benzyl (meth)acrylate; phenyl(meth)acrylate; naphthyl(meth)acrylate; a mono(meth)acrylate of an ether; a polyethylene glycol; a polypropylene glycol; and a mixture of at least two of tetrahydrofurfuryl methacrylate, methoxy(m)ethoxyethyl methacrylate, 1-butoxy-propyl methacrylate, cyclohexyloxymethyl methacrylate, benzyloxymethyl methacrylate, furfuryl methacrylate, 2-butoxyethyl methacrylate, 2-ethoxyethyl methacrylate, allyloxymethyl methacrylate, 1-ethoxybutyl methacrylate, 1-ethoxyethyl methacrylate, ethoxymethyl methacrylate, poly(ethylene glycol) methyl ether(meth)acrylate and poly(propylene glycol) methyl ether(meth)acrylate.
16. The process for preparing a binder according to claim 1 , wherein said monomer consists of at least one of 1-hexene; 1-heptene; vinylcyclohexane; 3,3-dimethyl-1-propene; 3-methyl-1-diisobutylene; 4-methyl-1-pentene; acrylonitrile; styrene; α-methylstyrene; α-ethylstyrene; vinyltoluene; p-methylstyrene; monochlorostyrene; a dichlorostyrene; a tribromostyrene; a tetrabromostyrene; 2-vinylpyridine; 3-vinylpyridine; 2-methyl-5-vinylpyridine; 3-ethyl-4-vinylpyridine; 2,3-dimethyl-5-vinylpyridine; vinylpyrimidine; 9-vinylcarbazole; 3-vinylcarbazole; 4-vinylcarbazole; 2-methyl-1-vinylimidazole; vinyloxolane; vinylfuran; vinylthiophene; vinylthiolane; a vinylthiazole; a vinyloxazole; anisoprenyl ether; maleic anhydride; maleimide; methylmaleimide; cyclohexylmaleimide; divinylbenzene; vinylpiperidine; 1-vinylimidazole; N-vinylpyrrolidone; 2-vinylpyrrolidone; N-vinylpyrrolidine; 3-vinylpyrrolidine; N-vinylcaprolactam; N-vinylbutyrolactam; a hydrogenated vinylthiazole; a hydrogenated vinyloxazole; methyl (meth)acrylate; ethyl (meth)acrylate; n-butyl (meth)acrylate; isobutyl(meth)acrylate; tert-butyl (meth)acrylate; pentyl(meth)acrylate; 2-ethylhexyl(meth)acrylate; stearyl(meth)acrylate; lauryl(meth)acrylate; cyclohexyl(meth)acrylate; isobornyl(meth)acrylate; benzyl (meth)acrylate; phenyl(meth)acrylate; naphthyl(meth)acrylate; a mono(meth)acrylate of an ether; a polyethylene glycol; a polypropylene glycol; and a mixture of at least two of tetrahydrofurfuryl methacrylate, methoxy(m)ethoxyethyl methacrylate, 1-butoxy-propyl methacrylate, cyclohexyloxymethyl methacrylate, benzyloxymethyl methacrylate, furfuryl methacrylate, 2-butoxyethyl methacrylate, 2-ethoxyethyl methacrylate, allyloxymethyl methacrylate, 1-ethoxybutyl methacrylate, 1-ethoxyethyl methacrylate, ethoxymethyl methacrylate, poly(ethylene glycol) methyl ether(meth)acrylate and poly(propylene glycol) methyl ether(meth)acrylate.
17. The process for preparing a binder according to claim 1 , wherein said monomer is a combination of methyl methacrylate and n-butyl methacrylate, said initiator is tert-butyl peroxy(2-ethylhexyl)carbonate, and said chain transfer reagent is present and is ethylhexylthioglycolate.