1. A process for the preparation of a latex comprising the steps of:
a) radical aqueous emulsion polymerization of a reaction mixture, to obtain a latex, said reaction mixture comprising at least one ethylenically unsaturated monomer, at least one radical polymerization initiator and at least an effective amount of a surface-active block copolymer comprising at least one hydrophilic block and at least one hydrophobic block which is prepared by a living preparation process using a transfer agent, the said copolymer exhibiting:
a number-average molecular mass of between 2 000 and 20 000 gmol,
a glass transition temperature of the hydrophobic block of less than 30 C., and greater than -100 C., and
a surface tension of less than 60 millinewtons per metre (mNm), measured at a concentration in demineralized water of less than or equal to 104 moll at 20 C. and under one atmosphere,
the transfer agent having been rendered inert with respect to the said radical polymerization, and
b) recovery of the latex thus obtained.
2. The process according to claim 1, wherein the copolymer exhibits:
a number-average molecular mass of between 4 000 and 16 000 gmol,
a glass transition temperature of the hydrophobic block of less than 25 C., and
a surface tension of less than 50 millinewtons per metre.
3. The process according to claim 1, wherein the transfer agent is selected from the group consisting of dithioesters, thioethers-thiones, dithiocarbamates and xanthates.
4. The process according to claim 1, wherein the block copolymer is prepared by a process comprising the following steps:
aa) as a first implementation, bringing into contact to obtain a polymer:
at least one ethylenically unsaturated monomer,
at least one source of free radicals, and
at least one transfer agent of formula (I):
3
wherein:
R represents an R20-, R2R2N- or R3- group with:
R2 and R2, which are identical or different, representing:
(i) an alkyl, acyl, aryl, alkene or alkyne group,
(ii) an optionally aromatic, saturated or unsaturated carbonaceous ring, or
(iii) a saturated or unsaturated heterocycle, groups and rings (i), (ii) and (iii) being optionally substituted,
R3 representing H, Cl, an alkyl, aryl, alkene or alkyne group, an optionally substituted, saturated or unsaturated (hetero)cycle, an alkylthio, alkoxycarbonyl, aryloxycarbonyl, carboxyl, acyloxy, carbamoyl, cyano, dialkyl- or diarylphosphonato, dialkyl- or diarylphosphinato group, or a polymer chain,
R1 represents
(i) an optionally substituted alkyl, acyl, aryl, alkene or alkyne group
(ii) a carbonaceous ring which is saturated or unsaturated and which is optionally substituted or aromatic, or
(iii) an optionally substituted, saturated or unsaturated heterocycle or a polymer chain,
bb) repeating, at least once, the above operation of bringing into contact using:
different monomers from the preceding implementation, and
instead of the precursor compound of formula (I), the polymer resulting from the preceding implementation, and
cc) rendering the transfer agent inert at the end of the polymerization.
5. The process according to claim 4, wherein the transfer agent of formula (I) is a dithiocarbonate selected from the group consisting of the compounds of following formulae (IA), (IB) and (IC):
4
wherein:
R2 and R2represent
(i) an alkyl, acyl, aryl, alkene or alkyne group,
(ii) an optionally aromatic, saturated or unsaturated carbonaceous ring, or
(iii) a saturated or unsaturated heterocycle, groups and rings (i), (ii) and (iii) being optionally substituted,
R1 and R1 represent
(i) an optionally substituted alkyl, acyl, aryl, alkene or alkyne group,
(ii) a carbonaceous ring which is saturated or unsaturated and which is optionally substituted or aromatic, or
(iii) an optionally substituted, saturated or unsaturated heterocycle or a polymer chain, and
p is between 2 and 10.
6. The process according to claim 4, wherein step cc) comprises masking of active chemical functional groups of the transfer agent by means of a masking agent or destruction of the transfer agent by a hydrolysis or oxidation reaction by metal catalysis or by use of primary radicals.
7. The process according to claim 4, wherein the hydrophilic block derives from hydrophilic monomers selected from the group consisting of:
unsaturated ethylenic mono- and dicarboxylic acids,
monoalkyl esters of the dicarboxylic acids of the type mentioned with alkanols preferably having 1 to 4 carbon atoms and their N-substituted derivatives,
amides of unsaturated carboxylic acids, and
ethylenic monomers comprising a sulphonic acid group and its alkali metal or ammonium salts.
8. The process according to claim 7, wherein the hydrophilic block derives from hydrophilic monomers selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, 2-hydroxyethyl acrylate or methacrylate, acrylamide, methacrylamide, vinylsulphonic acid, vinylbenzenesulphonic acid, alpha-acrylamidomethylpropanesulphonic acid, 2-sulphoethyl methacrylate, 2-acrylamido-2-methylpropanesulphonic acid and styrenesulphonate.
9. The process according to claim 4, wherein the hydrophobic block derives hydrophobic monomers selected from the group consisting of:
esters of acrylic acid and of methacrylic acid with hydrogenated or fluorinated C1-C12 alcohols,
vinyl nitriles having from 3 to 12 carbon atoms,
carboxylic acid vinyl esters,
vinyl halides,
vinylamine amides, and
unsaturated ethylenic monomers comprising a secondary, tertiary or quaternary amino group, or a heterocyclic group comprising nitrogen.
10. The process according to claim 9, wherein the hydrophobic block derives hydrophobic monomers selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl versatate, vinyl propionate,-vinylformamide, vinylacetamide, vinylpyridines, vinylimidazole, dimethylaminoethyl acrylate or methacrylate, di-tert-butylaminoethyl acrylate or methacrylate, and dimethylaminomethylacrylamide or -methacrylamide.
11. The process according to claim 10, wherein the polymerization of the copolymer is carried out in tetrahydrofuran or in a linear, cyclic or branched C1-C8 aliphatic alcohol.
12. The process according to claim 11, wherein the alcohol is methanol, ethanol, cyclohexanol or ethylene glycol, and wherein the hydrophilic monomer is acrylic acid (AA), acrylamide (AM), 2-acrylamido-2-methylpropanesulphonic acid (AMPS) or styrenesulphonate (SS).
13. The process according to claim 1, wherein said process comprises the following steps:
aaa) a stable aqueous preemulsion comprising starting ethylenically unsaturated monomers and the surface-active block copolymer is prepared,
bbb) a reaction mixture comprising a conventional surfactant, an initiator and water is introduced into a radical polymerization reactor comprising two openings and from 1 to 10% by weight of preemulsion prepared in step aaa) is added to the said mixture,
ccc) the reaction mixture obtained at the end of stage bbb) is heated to a temperature of between 40 and 90 C., for the purpose of generating a seed formed of latex particles in dispersion in the water,
ddd) the preemulsion obtained in stage aaa) is added with an additional amount of initiator via the two separate openings of the reactor to produce the latex, and
eee) optionally, the latex obtained in stage ddd) is heated at a temperature of between 40 and 90 C.
14. The process according to claim 13, wherein:
in step bbb) of preemulsion prepared is of between 3 and 7%,
in step ccc), the temperature is of between 60 and 80 C, and
in optional step eee), the temperature is of between 60 and 80 C.
15. The process according to claim 1, wherein the ethylenically unsaturated monomer or monomers are selected from the group consisting of styrene, styrene derivatives, butadiene, chloroprene, (meth)acrylic esters and vinyl nitrites.
16. The process according to claim 1, wherein use is made of 0.5to 5% by weight of the surface-active block copolymer with respect to the total weight of water employed during the polymerization of the latex, or of 1to 8% by weight of the surface-active block copolymer copolymer with respect to the total weight of the monomers employed during the polymerization of the latex.
17. The process according to claim 16, wherein use is made of 1to 4% by weight of the surface-active block copolymer with respect to the total weight of water employed during the polymerization of the latex, and of 2to 5% by weight of the surface-active block copolymer with respect to the total weight of the monomers employed during the polymerization of the latex.
18. The process according to claim 13, wherein use is made of 0.5to 5% by weight of the surface-active block copolymer with respect to the total weight of water employed during the polymerization of the latex, or of 1to 8% by weight of the surface-active block copolymer copolymer with respect to the total weight of the monomers employed during the polymerization of the latex.
19. The process according to claim 18, wherein use is made of 1to 4% by weight of the surface-active block copolymer with respect to the total weight of water employed during the polymerization of the latex, and of 2to 5% by weight of the surface-active block copolymer with respect to the total weight of the monomers employed during the polymerization of the latex.
20. Formulations intended for applications in the field of building materials, of paper, of paints or of adhesives, comprising the latex prepared according to the process of claim 1.
The claims below are in addition to those above.
All refrences to claim(s) which appear below refer to the numbering after this setence.
What is claimed is:
1. A circular saw blade, comprising:
a circular body having a peripheral edge;
a plurality of curved slots spaced along the peripheral edge, each slot having an open outer end connecting with the peripheral edge, and defined by essentially parallel, continuously-curved sidewalls leading away from the peripheral edge; and
a cutting segment fixed to the peripheral edge between at least some of the adjacent slots.
2. The circular saw blade of claim 1, wherein the slots are essentially parallel to one another.
3. The circular saw blade of claim 1, wherein the slots extend inward from the peripheral edge by from about 0.5 inches to about 2 inches.
4. The circular saw blade of claim 1, wherein the outer ends of the slots lie along radii of the body.
5. The circular saw blade of claim 1, wherein the outer ends of the slots are at an angle to radii of the body.
6. The circular saw blade of claim 5, wherein the angle is up to about 30 degrees.
7. The circular saw blade of claim 1, wherein there are from 4 to 75 segments.
8. The circular saw blade of claim 7, where each segment is from about 1 inch to about 2 inches long in the peripheral direction.
9. The circular saw blade of claim 1, wherein the slots all have essentially the same radius of curvature.
10. The circular saw blade of claim 9, wherein the slot radius of curvature is from about 1 inch to about 3 inches.
11. The circular saw blade of claim 1, wherein the slots have a width of from about 0.125 inches to about 0.250 inches.
12. The circular saw blade of claim 1, wherein the circular body has a nominal diameter of from about 4 inches to about 36 inches.
13. The circular saw blade of claim 1, wherein the segments comprise diamond particles in a metal matrix.
14. The circular saw blade of claim 1, wherein the segments have a peripheral length essentially the same as the peripheral distance between the open outer ends of adjacent slots.
15. The circular saw blade of claim 1, wherein the segments have ends that are essentially parallel to a radius of the body.
16. The circular saw blade of claim 1, wherein the segments have curved ends.
17. The circular saw blade of claim 16, wherein the radius of curvature of the segment ends in substantially the same as the radius of curvature of the adjacent slots.
18. The circular saw blade of claim 1, wherein the center of curvature of the slot is behind its open outer end in the direction of blade rotation.
19. The circular saw blade of claim 1, wherein the center of curvature of the slot is ahead of its open outer end in the direction of blade rotation.
20. A circular saw blade, comprising:
a circular body having a peripheral edge;
a plurality of curved slots spaced along the peripheral edge, each slot having an open outer end connecting with the peripheral edge, and defined by essentially parallel, continuously-curved sidewalls leading away from the peripheral edge, the slots all having essentially the same radius of curvature and being essentially parallel to one another; and
a cutting segment fixed to the peripheral edge between each pair of adjacent slots.