CN1246405C - Improved coating and coating composition - Google Patents

Improved coating and coating composition Download PDF

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Publication number
CN1246405C
CN1246405C CN 02142585 CN02142585A CN1246405C CN 1246405 C CN1246405 C CN 1246405C CN 02142585 CN02142585 CN 02142585 CN 02142585 A CN02142585 A CN 02142585A CN 1246405 C CN1246405 C CN 1246405C
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monomer
pnp
coating
crosslinked polymer
polymer nano
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CN1407044A (en
Inventor
R·S·贝克利
R·M·布兰肯希普
A·B·布朗
J·T·布朗
S－J·周
A·G·埃勒玛
S·J·菲茨沃特
R·H·戈尔
E·J·兰根梅尔
D·P·罗拉
W·H·麦克雷德
J·W·尼利
G·H·雷德利克
C·施瓦茨
F·J·辛德勒
R·V·斯隆
D·W·惠特曼
M·R·温克尔
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Rohm and Haas Co
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Rohm and Haas Co
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Abstract

Provided are improved coatings, polymeric dispersions, and polymeric composites, which include PNPs. Also provided are methods for forming improved coatings, polymeric dispersions, and polymeric composites, which include PNPs. The PNPs have polymerized units of at least one multi-ethylenically-unsaturated monomer have a mean diameter of from 1 to 50 nanometers. PNPs having polymerized units of at least one multi-ethylenically-unsaturated monomer and at least one surface-active monomer are also provided.

Description

Improved coating and coating composition
The present invention relates to a kind of improved coating and a kind of improved fluid-coating composition.Specifically, the present invention relates to a kind of dry coating that contains crosslinked polymer nano granules (after this with " PNP " expression), described dry coating is compared with the dry coating that does not contain described PNP, has a kind of anti-tack that is improved, print resistance, scuff resistance, scrub resistance, wear-resistant photosensitiveness, anti-dirt retention, sticking power, gloss, flexible, snappiness, shock resistance, time of drying, coalescing agent requirement, water tolerance, chemical-resistant, anti-biodeterioration and stain resistance in the following performance at least.The invention still further relates to the fluid-coating composition of a kind of PNP of containing, described fluid-coating is compared with the fluid-coating that does not contain described PNP, has a kind of being improved in the following performance at least: japanning pitch time (paint open time), rheological and stability.The invention still further relates to PNP with surface active groups.The invention still further relates to the polymer composites and the polymeric dispersions that contain PNP.The invention still further relates to the method for the improved coating, fluid-coating composition, polymeric dispersions and the polymer composites that are used to provide the described PNP of containing.
" coating " described herein comprises the composition that is applied on the various base materials, they are classified as building coats usually, for example unglazed coating, semigloss coating, glossy coating, priming paint, finish paint, stain seal coat, be used for porous substrate such as chalk surface, concrete and marmorean perviousness sealing lacquer, elastic coating, thick coating layer, caulk compound and sealing agent; Industry coating, for example sheet material peace plate coating, transportation means coating, furniture coating and coiled material coating; Maintenance coatings, for example bridge and basin coating and traffic paint; Leather coating and treatment agent; The floor care coating; Paper coating; The personal care coating for example is used for hair conditioning, skin, nail and weaving and fabric coating nonwoven and pigment printing slurry; And bonding coat, for example pressure sensitive adhesive and wet-and do-laminating adhesive.For a long time, people are seeking the coating that at least a performance is improved always, for example anti-tack, print resistance, scuff resistance, scrub resistance, wear-resistant photosensitiveness, anti-dirt retention, sticking power, gloss, flexible, snappiness, shock resistance, time of drying, coalescing agent requirement, water tolerance, chemical-resistant, anti-biodeterioration and stain resistance." coating composition " described herein and " fluid-coating composition " is meant such composition, after being applied on the base material, adopting heating or need not heat and be dried or when allowing drying, can form a kind of coating.People are also seeking to have the rheological of at least a performance such as needs and the coating composition that the thickening material effect is improved always.
It is the tackiness agent that the band carboxyl functional group metal organic nanometer granule reaction of 5-200 nanometer forms that WO200075244 discloses by the tackiness agent of one or more band oxide compound functional groups and average particle size particle size.
People are desirable to provide coating and the coating composition with at least a improvement performance as described herein.Have been found that now containing mean diameter can provide this improvement for the coating composition of the PNP of 1-50 nanometer with by the coating that coating composition forms, described PNP contains at least a polyenoid key unsaturated monomer as polymerized unit.
Aspect first, provide a kind of improved coating of the present invention, comprise that coating and mean diameter are the PNP of 1-50 nanometer, described PNP contains at least a polyenoid key unsaturated monomer as polymerized unit.
Aspect second of the present invention, a kind of method that is used for obtaining to improve coating is provided, may further comprise the steps: forming mean diameter is the PNP of 1-50 nanometer, and described PNP contains at least a polyenoid key unsaturated monomer as polymerized unit; Contain the coating composition of described PNP with formation.
Aspect the 3rd of invention, a kind of method that is used for forming polymeric dispersions is provided, may further comprise the steps: forming mean diameter is the PNP of 1-50 nanometer, and described PNP contains at least a polyenoid key unsaturated monomer as polymerized unit; A kind of reaction mixture that comprises described PNP and at least a ethylenically unsaturated monomer is provided; With make described reaction mixture stand at least a body, solution, gas phase, emulsion, microemulsion or suspension polymerization condition.
Aspect the 4th of the present invention, a kind of PNP is provided, comprise the polymerized unit of at least a polyenoid key unsaturated monomer and at least a surface active monomer, the mean diameter of described PNP is the 1-50 nanometer.
Aspect the 5th of the present invention, a kind of polymer composites is provided, comprising: mean diameter is the PNP of 1-50 nanometer, described PNP contains at least a polyenoid key unsaturated monomer as polymerized unit; With contain the polymkeric substance of at least a ethylenically unsaturated monomer as polymerized unit.
Term used herein " dispersion " is meant and comprises at least two discrete phases, wherein one is dispersed in the physics attitude of successive second among mutually mutually.
Term described herein " molecular weight " when describing described PNP, is meant the apparent molecular weight that adopts the standard gel permeation chromatography to be obtained, for example, adopt the THF solvent at 40C, 3Plgel Columns (PolymerLabs), 100 dusts, 10^3, the 10^4 dust, 30cm is long, 7.8mm ID, 1mil/min, 100 microlitres inject volume, adopt Polymer Labs CALIBRETM software calibration to narrow polystyrene standards.
Term used herein " Tg " is meant second-order transition temperature, and it is to adopt dsc (" DSC ") to measure.
Following abbreviation used herein has the following meaning, have in addition in the context offer some clarification on except: the C=centigradetemperature; μ m=micron; The UV=ultraviolet ray; The rpm=rotations per minute; The nm=nanometer; The J=joule; The cc=cubic centimetre; The g=gram; The wt%=weight percentage; The L=liter; The mL=milliliter; The MIAK=methyl isoamyl ketone; The MIBK=methyl iso-butyl ketone (MIBK); The BA=butyl acrylate; AA=vinylformic acid; The MAA=methacrylic acid; PS=particle size=average particulate diameter; PMA=gathers (methyl acrylate); The CyHMA=cyclohexyl methacrylate; EG=ethylene glycol; The DPG=dipropylene glycol; DEA=diethylene glycol ethyl ether acetic ester; BzA=vinylformic acid benzene methyl; BzMA=methacrylic acid benzene methyl; MAPS=MATS=methacrylic acid (trimethoxy-silylpropyl) ester; OFPMA=methacrylic acid octafluoro amyl group ester; Ropyl methacrylate; PETTA=tetramethylolmethane four/triacetate; PPG4000DMA=polypropylene glycol 4,000 two (methacrylic acid) ester; DPEPA=Dipentaerythritol five acrylate; TMSMA=methacrylic acid (trimethyl silyl) ester; MOPTSOMS=methacryloxypropyl two (trimethylsiloxy group) methyl-monosilane; MOPMDMOS=3-methacryloxypropyl methyl dimethoxy oxosilane; TAT=triallyl-1,3,5-triazines-2,4, and 6-(1H, 3H, 5H)-triketone; The IBOMA=isobornyl methacrylate; The PGMEA=propylene glycol methyl ether acetate; PEGMEMA475=polymethyl acrylic acid (Ethylene Glycol Methyl ether) ester, Mw=475; EUG=oxymethoxyallylbenzene (4-allyl group-2-methoxyphenol); With PGDMA=two (methacrylic acid) propylene glycol ester.
Term " (methyl) vinylformic acid " comprises vinylformic acid and methacrylic acid, and term " (methyl) acrylate " comprises acrylate and methacrylic ester.Similarly, term " (methyl) acrylamide " is meant acrylamide and Methacrylamide." alkyl " comprises straight chain, branching and cycloalkyl.
These defined all scopes all be comprise head and the tail and be combinative.
The object of the invention is coating composition, coating, the polymeric dispersions that is formed by coating composition and the polymer composites that contains PNP, described PNP has the polymerized unit of at least a polyenoid key unsaturated monomer, described PNP has the mean diameter of 1-50 nanometer, and the method that is used for preparing them.The object of the invention also is to have the PNP of the polymerized unit of at least a polyenoid key unsaturated monomer and at least a surface active monomer, and described PNP has the mean diameter of 1-50 nanometer.
Although be used for the average particulate diameter that the PNP of the various different embodiments of the present invention has the 1-50 nanometer usually,, they preferably have 1-40nm, 1-30nm more preferably, be preferably 1-20nm again, further be preferably 1-10nm, most preferably be the average particulate diameter of 2-8nm.
Described PNP is that the radical polymerization by at least a polyenoid key unsaturated monomer forms.Normally, unless otherwise prescribed, be benchmark with described PNP weight, described PNP contains at least a polymeric polyenoid key unsaturated monomer of at least 1% weight.With described PNP weight is benchmark, nearly and comprise 100% polymerization polyenoid key unsaturated monomer, can be used for effectively among the particle of the present invention.The amount of preferred polymeric polyenoid key unsaturated monomer is the 1%-80% of described PNP weight, and the 1%-60% of more preferably described PNP weight most preferably is the 1%-25% of described PNP weight.
Can be used for suitable polyenoid key unsaturated monomer of the present invention and comprise two-, three-, four-or higher polyfunctional ethylene linkage unsaturated monomer, for example trivinylbenzene, divinyl toluene, divinyl pyridine, divinyl naphthalene and divinyl dimethylbenzene; And such as glycol diacrylate, Viscoat 295, diethylene glycol divinyl ether, the trivinyl hexanaphthene, allyl methacrylate (" ALMA "), ethylene glycol bisthioglycolate (methacrylic acid) ester (" EGDMA "), glycol ether two (methacrylic acid) ester (" DEGDMA "), propylene glycol two (methacrylic acid) ester, propylene glycol diacrylate, trimethylolpropane trimethacrylate (" TMPTMA "), Vinylstyrene (" DVB "), 2,2-dimethylpropane-1, the 3-diacrylate, 1, the 3-butylene glycol diacrylate, 1,3-butyleneglycol two (methacrylic acid) ester, 1, the 4-butylene glycol diacrylate, diethylene glycol diacrylate, glycol ether two (methacrylic acid) ester, 1, the 6-hexanediyl ester, 1,6-hexylene glycol two (methacrylic acid) ester, tripropylene glycol diacrylate, triglycol two (methacrylic acid) ester, Viscoat 335HP, the Macrogol 200 diacrylate, Tetraglycol 99 two (methacrylic acid) ester, polyoxyethylene glycol two (methacrylic acid) ester, ethoxylated bisphenol a diacrylate, ethoxylation dihydroxyphenyl propane two (methacrylic acid) ester, Polyethylene Glycol-600 two (methacrylic acid) ester, poly-(butyleneglycol) diacrylate, pentaerythritol triacrylate, trimethylolpropane tris oxyethyl group triacrylate, glyceryl propoxy-triacrylate, tetramethylol methane tetraacrylate, tetramethylolmethane tetramethyl-acrylate, Dipentaerythritol monohydroxy five acrylate, divinyl silane, trivinyl silane, dimethyl divinyl silane, the divinyl methyl-monosilane, methyl trivinyl silane, phenylbenzene divinyl silane, the divinyl phenyl silane, the trivinyl phenyl silane, the divinyl aminomethyl phenyl silane, tetrem thiazolinyl silane, dimethyl vinyl sily oxide, poly-(ethylene methacrylic radical siloxane), poly-(vinyl hydride siloxane), poly-(phenyl vinyl siloxanes) and their mixture.
Can be attached to that the suitable ethylene linkage unsaturated monomer as copolymerization units includes but not limited among the described PNP: (methyl) vinylformic acid, (methyl) acrylamide, (methyl) alkyl acrylate, vinyl-acetic ester, (methyl) vinylformic acid alkenyl esters, aromatics (methyl) acrylate, vi-ny l aromatic monomers, nitrogenous compound and their thip-analogues, P contained compound are as (methyl) vinylformic acid (phospho ethyl) ester (" PEM "), and the vinyl monomer that replaces.
Usually, being used for described (methyl) of the present invention alkyl acrylate is (methyl) vinylformic acid (C 1-C 24) alkyl ester.Suitable (methyl) alkyl acrylate includes but not limited to: (methyl) vinylformic acid " low cut " alkyl ester, (methyl) vinylformic acid " middle cut " alkyl ester and (methyl) vinylformic acid " high cut " alkyl ester.
(methyl) vinylformic acid " low cut " alkyl ester be typically those wherein alkyl contain (methyl) alkyl acrylate of 1-6 carbon atom.The low cut alkyl ester of suitable (methyl) vinylformic acid includes but not limited to: methyl methacrylate (" MMA "), methyl acrylate, ethyl propenoate, propyl methacrylate, butyl methacrylate (" BMA "), butyl acrylate (" BA "), Propenoic acid, 2-methyl, isobutyl ester (" IBMA "), the own ester of methacrylic ester, cyclohexyl methacrylate, cyclohexyl acrylate and their mixture.
(methyl) vinylformic acid " middle cut " alkyl ester is (methyl) alkyl acrylate that those alkyl contain 7-15 carbon atom typically.The cut alkyl ester includes but not limited in suitable (methyl) vinylformic acid: vinylformic acid (2-ethylhexyl) ester (" EHA "), methacrylic acid (2-ethylhexyl) ester, methacrylic acid octyl group ester, methacrylic acid decyl ester, (" IDMA " is based on (the C of branching for methacrylic acid isodecyl ester 10) the alkyl isomer mixture), methacrylic acid undecyl ester, lauryl methacrylate (being also referred to as the methacrylic acid Lauryl Ester), methacrylic acid tridecyl ester, methacrylic acid tetradecyl ester (being also referred to as methacrylic acid myristyl ester), methacrylic acid pentadecyl ester and their mixture.Suitable mixture comprises methacrylic acid (dodecyl-pentadecyl) ester (" DPMA "), the methacrylic ester of the straight chain of a kind of dodecyl, tridecyl, tetradecyl and pentadecyl and the mixture of branched isomer; And methacrylic acid (lauryl-myristyl) ester (" LNA ").
(methyl) vinylformic acid " high cut " alkyl ester is (methyl) alkyl acrylate that those alkyl contain 16-24 carbon atom typically.The suitable high cut alkyl ester of (methyl) vinylformic acid includes but not limited to: methacrylic acid cetyl ester, methacrylic acid heptadecyl ester, methacrylic acid stearyl, methacrylic acid nonadecyl ester, methacrylic acid cosyl ester, methacrylic acid eicosyl ester and their mixture.The useful mixture of the high cut alkyl ester of (methyl) vinylformic acid includes but not limited to: methacrylic acid (hexadecyl-eicosyl) ester (" CEMA "), and it is a kind of mixture of being made up of methacrylic acid cetyl ester, stearyl, cosyl ester and eicosyl ester; And methacrylic acid (hexadecyl-octadecyl) ester (" SMA "), it is a kind of mixture of being made up of methacrylic acid cetyl ester and stearyl.
Cut and high cut alkyl ester monomer in above-mentioned (methyl) vinylformic acid, normally by the standard esterification process, adopt the long chain aliphatic of technical grade to prepare, these commercially available alcohols are the mixture of the alcohol of the different chain length that contains 10-15 or 16-20 carbon atom in alkyl.These pure examples are for deriving from the catalytic ALFOL alcohol of multiple Ziegler of Vista Chemical (being Sasol now) Company, be ALFOL 1618 and ALFOL 1620, derive from the catalytic multiple NEODOL alcohol of Ziegler of Shell Chemical Company, be that NEODOL 25L and natural deutero-alcohol is as Proctor﹠amp; The TA-1618 of Gamble and CO-1270.Therefore, for the present invention, (methyl) alkyl acrylate not only comprises specified each (methyl) alkyl acrylate product, also comprises (methyl) alkyl acrylate and the mixture of specified specific (methyl) alkyl acrylate of the quantity of preponderating.
Can be used for (methyl) of the present invention alkyl acrylate monomer, can be a kind of single monomer, also can be the mixture that has different number carbon atoms at described moieties.And, can be used for described (methyl) of the present invention acrylamide and (methyl) alkyl acrylate monomer, can randomly be substituted.(methyl) acrylamide of suitable optional replacement and (methyl) alkyl acrylate monomer include but not limited to: (methyl) vinylformic acid (hydroxyl (C 2-C 6) alkyl) ester, (methyl) vinylformic acid (dialkyl amido (C 2-C 8) alkyl) ester, dialkyl amido (C 2-C 6) alkyl (methyl) acrylamide.
(methyl) alkyl acrylate monomer of useful replacement is the material that those materials that have one or more hydroxyls in described alkyl group, particularly those wherein said hydroxyls are positioned at described alkyl group β-position (2-position).Wherein substituted alkyl is (C branching or non-branching 2-C 6) (methyl) acrylic acid hydroxy alkyl ester monomer of alkyl is preferred.Suitable (methyl) acrylic acid hydroxy alkyl ester monomer includes but not limited to: methacrylic acid (2-hydroxyethyl) ester (" HEMA "), vinylformic acid (2-hydroxyethyl) ester (" HEA "), methacrylic acid (2-hydroxypropyl) ester, methacrylic acid (1-methyl-2-hydroxyethyl) ester, 2-hydroxypropyl acrylate, vinylformic acid (1-methyl-2-hydroxyethyl) ester, methacrylic acid (2-hydroxyl butyl) ester, vinylformic acid (2-hydroxyl butyl) ester and their mixture.Preferably (methyl) acrylic acid hydroxy alkyl ester monomer is HEMA, methacrylic acid (1-methyl-2-hydroxyethyl) ester, methacrylic acid (2-hydroxypropyl) ester and their mixture.The two kinds of monomeric mixtures in back are commonly referred to as " hydroxypropyl methacrylate " or " HPMA ".
Other can be used for replacement of the present invention (methyl) acrylate and (methyl) acrylamide monomer is those materials that have dialkyl amido or dialkyl aminoalkyl in described alkyl group.(methyl) acrylate that this class replaces and the example of (methyl) acrylamide include but not limited to: methacrylic acid (dimethyl aminoethyl) ester, vinylformic acid (dimethyl aminoethyl) ester, (N, the N-dimethyl aminoethyl) Methacrylamide, (N, the N-dimethylaminopropyl) Methacrylamide, (N, N-dimethylamino butyl) Methacrylamide, (N, N-diethylamino ethyl) Methacrylamide, (N, N-diethylamino propyl group) Methacrylamide, (N, N-diethylamino butyl) Methacrylamide, N-(1,1-dimethyl-3-oxo butyl) acrylamide, N-(1,3-phenylbenzene-1-ethyl-3-oxo butyl) acrylamide, N-(1-methyl isophthalic acid-phenyl-3-oxo butyl) Methacrylamide, with 2-hydroxyethyl acrylamide, the N methacrylamide of amino-ethyl ethylidene-urea, N-methylacryoyloxyethyl morpholine, the N-maleimide of dimethylaminopropyl amine and their mixture.
(methyl) acrylate monomer that can be used for other replacement of the present invention is a silicon-containing monomer, as γ-propyl group three (C 1-C 6) alkoxysilyl (methyl) acrylate, γ-propyl group three (C 1-C 6) alkyl silyl (methyl) acrylate, γ-propyl group two (C 1-C 6) alkoxyl group (C 1-C 6) alkyl silyl (methyl) acrylate, γ-propyl group two (C 1-C 6) alkyl (C 1-C 6) alkoxysilyl (methyl) acrylate, vinyl three (C 1-C 6) alkoxysilyl (methyl) acrylate, vinyl two (C 1-C 6) alkoxyl group (C 1-C 6) alkyl silyl (methyl) acrylate, vinyl (C 1-C 6) alkoxyl group two (C 1-C 6) alkyl silyl (methyl) acrylate, vinyl three (C 1-C 6) alkyl silyl (methyl) acrylate and their mixture.
The vi-ny l aromatic monomers that can be used as unsaturated monomer of the present invention includes but not limited to: vinylbenzene (" STY "), alpha-methyl styrene, Vinyl toluene, time-vinyl toluene, vinyl xylene, ethyl vinyl benzene, vinyl naphthalene, ethene dimethylbenzene and their mixture.Described vi-ny l aromatic monomers also comprises their corresponding counterparts that replaces, and as halogenated derivative, promptly contains one or more halogen groups, as fluorine, chlorine or bromine; With nitro, cyano group, (C 1-C 10) alkoxyl group, halo (C 1-C 10) alkyl, (C 1-C 10) carbalkoxy, carboxyl, amino, (C 1-C 10) the alkylamino derivative etc.
Can be used as the nitrogenous compound of unsaturated monomer of the present invention and their thip-analogues includes but not limited to: vinyl pyridine such as 2-vinyl pyridine or 4-vinylpridine; Low alkyl group (C 1-C 8) the N-vinyl pyridine that replaces such as 2-methyl-5-vinylpyrine, 2-ethyl-5-vinyl pyridine, 3-methyl-5-vinyl pyridine, 2,3-dimethyl-5-vinyl pyridine and 2-methyl-3-ethyl-5-vinyl pyridine; Methyl substituted quinoline and isoquinoline 99.9; The N-vinylcaprolactam; The N-vinyl butyrate lactam; The N-vinyl pyrrolidone; Vinyl imidazole; The N-vinylcarbazole; N-vinyl succinimide; (methyl) vinyl cyanide; Adjacent-,-or right-amino-benzene ethene; Maleimide; N-vinyl-oxazolidones; N, N-dimethyl aminoethyl-vinyl ether; Ethyl-2-cyanoacrylate; Vinylacetonitrile; N-vinyl phthalic imidine; N-vinyl pyrrolidone such as N-vinyl-sulphur-pyrrolidone, 3-methyl isophthalic acid-vinyl pyrrolidone, 4-methyl isophthalic acid-vinyl pyrrolidone, 5-methyl isophthalic acid-vinyl pyrrolidone, 3-ethyl-1-vinyl pyrrolidone, 3-butyl-1-vinyl pyrrolidone, 3,3-dimethyl-1-vinyl pyrrolidone, 4,5-dimethyl-1-vinyl pyrrolidone, 5,5-dimethyl-1-vinyl pyrrolidone, 3,3,5-trimethylammonium-1-vinyl pyrrolidone, 4-ethyl-1-vinyl pyrrolidone, 5-methyl-5-ethyl-1-vinyl pyrrolidone and 3,4,5-trimethylammonium-1-vinyl pyrrolidone; Vinyl pyrrole; Vinyl aniline, branched alkane hydroxyl carboxylic acid (versatic) vinyl ester and vinyl piperidines.
The vinyl monomer that can be used as the replacement of unsaturated monomer of the present invention includes but not limited to: allyl monomer, vinyl-acetic ester, vinyl formamide, vinylchlorid, vinyl fluoride, bromine ethene, vinylidene chloride, vinylidene fluoride and inclined to one side sym-dibromoethane.
Being used for described PNP of the present invention can prepare by letex polymerization, corpuscle emulsion, microemulsion, suspension polymerization, non-aqueous dispersion polymerization or solution polymerization process.Herein " solution polymerization " be meant the radical addition polymerization in water-based or non-aqueous media (it is a polymer solvent)." polymer solvent " is that the uncrosslinked polymkeric substance of expression will be soluble in described polymerization reaction medium herein, for containing the polymkeric substance that is lower than about 20wt.% polyenoid key unsaturated monomer, it can be according to the solubleness of the polymkeric substance for preparing under the identical conditions that does not have described cross-linking monomer, or based on dissolubility picture described herein selecting for use of polymerisation medium predicted.
Described PNP can prepare in non-aqueous solvent.The example of this kind solvent includes but not limited to: hydro carbons such as alkane, hydrofluoric ether and aromatic hydrocarbon, ether, ketone, ester, alcohol and their mixture.Specially suitable solvent comprises dodecane, sym-trimethylbenzene, dimethylbenzene, diphenyl ether, gamma-butyrolactone, ethyl acetate, ethyl lactate, propylene glycol monomethyl ether, caprolactone, 2-heptanone, methyl iso-butyl ketone (MIBK), diisobutyl ketone, propylene glycol monomethyl ether and alkyl alcohol such as decyl alcohol, the trimethyl carbinol and Virahol (" IPA ").
The preparation of described PNP can be at first with the solvent tailing, and the perhaps mixture of solvent and partial monosomy is fed in the reactor that disposes agitator, thermometer and reflux exchanger.Described monomer feed generally is made up of by suitable proportion monomer, initiator and chain-transfer agent.Described solvent or solvent/monomer tailing are stirred and heated to the about 125 ℃ temperature of about 55-under nitrogen protection.After described tailing charging reaches the temperature that is enough to initiated polymerization, be reflected under the needed temperature of reaction keeping, with described monomer or remaining monomer, in 15 minutes-4 hours time, add in the described reactor.After adding monomer mixture, other initiator feed that will be in solvent is in described reaction and/or keep for some time.
Described PNP can adopt letex polymerization to be prepared.Can be used for the preparation of emulsion polymer of the present invention, normally earlier the emulsion feed to of water and partial monosomy is disposed in the reactor of agitator, thermometer and reflux exchanger.Typically, described monomer emulsion is made up of by suitable proportion monomer, tensio-active agent, initiator and chain-transfer agent.The initial charge of monomer emulsion is joined in the suitable reactor, under nitrogen protection, be stirred and heated to about 125 ℃ of about 55-.After reaching the temperature that is enough to initiated polymerization in the seed charging, be reflected under the needed temperature of reaction keeping,, in 15 minutes-4 hours time, add in the described reactor described monomer emulsion or remaining monomer emulsion.After adding monomer emulsion, with other initiator feed in described reaction and/or keep for some time.
In replacement scheme, described letex polymerization can be undertaken by intermittent mode.In this batch technology, described emulsion polymer is by water, monomer, tensio-active agent, initiator and chain-transfer agent with suitable proportion, under agitation is fed in the reactor under the nitrogen protection and preparation.Described monomer emulsion is heated to the about 125 ℃ temperature of about 55-to carry out polyreaction.After the interpolation of finishing monomer emulsion, other initiator feed that will be in solvent is in described reaction and/or keep for some time.
Suitable PNP for example comprises: HEMA/DEGDMA, MMA/DEGDMA, MMA/MAPS/DEGDMA, MMA/MAPS/PETTA, MMA/MAPS/PPG4000DMA, MMA/MAPS/DPEPA, MAPS/DEGDMA, BA/DEGDMA, MMA/MAPS/TMPTMA, MMA/MAPS/DVB, STY/MAPS/DVB, BA/MAPS/DVB, BA/TMSMA/DVB, BA/MOPTSOMS/DVB, BA/MOPMDMOS/DVB, BA/MAPS/TAT, ALMA/BA/DVB, IBOMA/MAPS/DVB, IBOA/MAPS/DVB, BA/DVB, BA/PGDMA, BA/ALMA, BA/TMPTMA, BA/DPEPA, EHA/DVB, EHA/ALMA, EHA/TMPTMA, EHA/DPEPA, STY/DVB, STY/ALMA, EHA/STY/ALMA, MMA/BA/ALMA, STY/MMA/DVB, MMA/ divinyl/STY, MMA/EA/ALMA, BA/ALMA/MATS, STY/MATS/DVB, MMA/BA/MATS, STY/MMA/MATS/DVB, MMA/BA/MATS/ALMA, BzA/TMPTMA, BzA/DVB, IDMA/BzMA and MMA/ALMA/MATS.
The control of particle size and distribution can realize by kind and the method quantity and the reaction conditions such as selective solvent, the type of selecting initiator, overall solids content, initiator level, polyfunctional monomer and quantity, chain-transfer agent.Particle size (average particulate diameter) can adopt standard dynamic light scattering technical measurement, and wherein related function can adopt the LaPlace transformation approach, is converted into the hydrokinetics size as CONTIN.
The initiator that can be used for Raolical polymerizable of the present invention for instance, comprises in the following substances one or more: peroxyester, dialkyl peroxide, alkyl hydroperoxide, persulphate, azo initiator, redox initiator etc.Useful radical initiator includes but not limited to: benzoyl peroxide, Peroxycaprylic acid tertiary butyl ester, peroxide PIVALIC ACID CRUDE (25) tert-pentyl ester, cumene hydroperoxide and azo-compound such as azo isobutyronitrile and 2,2 '-azo-two (2-methylbutyronitrile).Preferred radical initiator is a peroxide PIVALIC ACID CRUDE (25) tert-pentyl ester.The consumption of described radical initiator is generally the 0.05-10wt% of total monomer weight.
Chain-transfer agent can be chosen wantonly to be used for preparing and can be used for polymkeric substance of the present invention.For example, suitable chain-transfer agent comprises: alkyl sulfhydryl such as lauryl mercaptan and aromatic hydrocarbons such as toluene with active hydrogen.
Described PNP " apparent weight-average molecular weight " is generally 5,000-1, and 000,000, be preferably 10,000-500,000, more preferably 15,000-100,000." apparent weight-average molecular weight " described herein reflected described PNP particulate size.The GPC elution time of described PNP provides measuring of apparent weight-average molecular weight, and does not need absolute weight-average molecular weight to measure.
Described PNP also can carry out the functionalized processing in back.Functionalized processing can adopt any technology known in the art to carry out after this class.The post polymerization of described PNP is functionalized to be favourable, for example, makes other component compatibility in PNP and the coating composition.
Wish that described PNP is an accumulative that disperse or non-, and be can disperse, can be miscible or additionally compatible basically in the coating composition and the exsiccant coating of fluid state.
The consistency of described PNP and surplus coating composition, typically by their solubility parameter such as δ d relatively, δ p, the Van Krevelen parameter of δ h and δ v and definite.Referring to for example, people's such as Van Krevelen Properties of Polymers.Their Estimation and Correlation with Chemical Structure, Elsevier Scientific Publishing Co., 1976; People's such as Olabisi Polymer-Polymer Miscibility, Academic Press, NY, 1979; People's such as Coleman Specific Interactions and the Miscibility of Polymer Blends, Technomic, 1991; And A.F.M.Barton, CRC Handbook of Solubility Parameters And Other Cohesion Parameters, 2 NdEd., CRC Press, 1991.δ d disperses interactional measuring, and δ p is measuring of polar interaction, and δ h is measuring of interaction of hydrogen bond, and δ v is measuring of dispersion and polar interaction.This class solubility parameter can adopt as Group Contribution Method (the groupcontribution method) and calculate, and also can measure by measurement cloud point of polymer materials in the mixed solvent system of being made up of soluble solvent and insoluble solvent.Be based on the weight percent of solvent in the solubility parameter of cloud point.Typically, to a plurality of cloud points of described Materials Measurement, be defined as the solubility parameter zone (scope) of described material by the determined central section of these cloud points.
In some embodiments of the present invention, the solubility parameter of described PNP and coating composition medium can be a broadly similar.In these embodiments, described PNP in described coating composition/and described coating composition between consistency be improved and described PNP being separated and/or accumulative possibility occurrence step-down in described coating.Preferably, the solubility parameter of described PNP and coating composition medium, particularly δ h and δ v mate basically.Those skilled in the art can understand, and except that solubility parameter, other performance of PNP also can influence the consistency of PNP in coating.
Described PNP can use with the form of the dispersion in polymerization solvent, perhaps they can be by for example vacuum-evaporation, be deposited in the non-solvent and separated with spray-dired method.At after separating, PNP can follow redispersion among the medium that is suitable for being incorporated in the coating composition.
As those skilled in the art were known, dispersion that can be by making described PNP or described PNP and other dissolved or dispersive polymkeric substance and/or other coatings additive(s) mixed, and positive-negative-positive is incorporated among the coating composition.Described coating composition can comprise water-based or nonaqueous medium.Described coating composition can contain conventional coatings additive(s), as tackifier, pigment, emulsifying agent, linking agent, monomer, oligopolymer, polymkeric substance, solvent, coalescing agent, buffer reagent, neutralizing agent, thickening material or rheology modifiers, wetting Agent for Printing Inks, wetting agent, biocide, softening agent, defoamer, tinting material, wax and oxidation inhibitor.
Solids content in the improvement coating of the present invention, by volume can be about 10-about 85%.In water-borne coatings, its viscosity typically be 0.05-2000Pa.s (50cps-2,000,000cps), its adopts Brookfield viscometer to measure; The viscosity variation that is fit to different end-use and methods for using thems is sizable.
Described coating can adopt conventional coating process to be coated with, for example, brushing or roller coat, air atomizing spraying, gas help spraying, no gas blowout mist, the spraying of high appearance low pressure, gas to help no gas blowout mist, curtain coating, roller coat, inverse roller coating, intaglio plate coating, offset printing, ink-jet, bubble jet and electrostatic spraying.
Described coating can be applied on the base material, for example, comprise plastics, timber, metal, leather, fabric or non-woven fabrics, hair, skin, nail, the paper of sheet material and film, surface, cement matrix and the pitch base material of precoating, base material can carry out or not carry out pre-treatment, as priming paint.
Coating on described base material carries out drying or allows its drying at 10-200 ℃ typically.
With respect to the same combination that does not have described PNP, coating of the present invention has at least a following improvement performance: anti-tack, print resistance, scuff resistance, scrub resistance, wear-resistant photosensitiveness, anti-dirt retention, snappiness, water tolerance, chemical-resistant and stain resistance, they can be by guaranteeing distinctive hard being achieved of described PNP.When described Tg is lower than room temperature, hard PNP can be higher than needed crosslinked being achieved of whole invention and (promptly adopts and be higher than 5 by providing, preferably be higher than 10, more preferably be higher than 15, at least a polyenoid key unsaturated monomer that preferably is higher than 20 percent by weight again prepares described PNP).Another kind of replacement scheme is, hard PNP can by adopt the monomer (for example methacrylic acid and vi-ny l aromatic monomers) can produce high-tg polymer make described PNP Tg greater than room temperature (promptly greater than 25C, be preferably greater than 50C, more preferably greater than 100C) and be achieved.Preferably, hard PNP combines highly cross-linked in combination and can produce the monomer of high-tg polymer, so that the sufficiently high hardness of improving coating property to be provided.
With respect to the same combination that does not have described PNP, have the water-proof coating of improvement, also can provide by guaranteeing the distinctive hydrophobic nature of described PNP.The weight percentage of the polymerized unit of the described PNP by guaranteeing to be derived from hydrophobic monomer, with total PNP weight is benchmark, be at least 20 weight %, preferably be at least 40 weight %, more preferably be at least 50 weight %, preferably be at least 70 weight % again, most preferably be at least 80 weight %, the PNP of hydrophobic nature can be provided.The hydrophobic monomer that can be used for embodiment of the present invention, the water solubility in the time of 25 ℃ (the perhaps weight average water solubility of hydrophobic monomer mixture) generally is lower than 10%, preferably is lower than 5%, more preferably less than 2%, further preferably is lower than 1%." water solubility " is the solubleness in water when being illustrated in 25C herein." weight average water solubility " is meant when selecting for use more than a kind of second monomer, by every kind second monomeric water solubility and its water solubility that obtains based on the product addition calculation of the weight fraction of second total monomer weight herein.The solubleness of monomer in water is known.For example, can be at " PolymerHandbook " (second edition, J.Brandrup, E.H.Immergut, Editors, JohnWiley﹠amp; Sons) and " Merck Index " (Eleventh Edition, Merck﹠amp; Co., (Rahway, N.J. find these data in U.S.A.) to Inc..The data of typical monomers are as follows:
The solubleness (%, 25 ℃) of monomer in water
Methyl methacrylate 1.35
Jia Jibingxisuanyizhi 0.46
Butyl methacrylate 0.03
Ethyl propenoate 2.0 (20C)
Vinylformic acid (2-ethylhexyl) ester 0.01
Methacrylic acid (2-hydroxyethyl) ester dissolves each other fully
Vinylbenzene 0.029
Vinyl cyanide 7.30
Vinyl-acetic ester 2.3
Acrylamide 20.4
In one embodiment of the invention, will contain the coating that is dissolved in the polymkeric substance in the polymer solvent, and mix with PNP, the second-order transition temperature of described PNP is higher than the second-order transition temperature of described polymkeric substance.The coating that forms by described coating composition, with respect to the same combination that does not have described PNP, at least a being improved in the following performance: anti-tack, print resistance, scuff resistance, scrub resistance, wear-resistant photosensitiveness, anti-dirt retention, snappiness, water tolerance, chemical-resistant and stain resistance.
In one embodiment of the invention, will contain the coating that is dissolved in the Synolac in the Synolac solvent, the PNP that is higher than the second-order transition temperature of described polymkeric substance with second-order transition temperature mixes.The coating that forms by described coating composition, with respect to the same combination that does not have described PNP, at least a being improved in the following performance: time of drying, anti-tack, print resistance, scuff resistance, scrub resistance, wear-resistant photosensitiveness, anti-dirt retention, snappiness, water tolerance, chemical-resistant and stain resistance.
In one embodiment of the invention, will contain the coating that is dissolved in the polymkeric substance in the polymer solvent, the PNP that is lower than the second-order transition temperature of described polymkeric substance with second-order transition temperature mixes.The coating that forms by described coating composition, with respect to the same combination that does not have described PNP, at least a being improved in the following performance: scrub resistance, snappiness, flexible, water tolerance, chemical-resistant and stain resistance.
In one embodiment of the invention, to contain the polymkeric substance that is dispersed in the aqueous medium, as the water-borne coatings of particle size greater than the Emulgating polymers of 50 nanometers, the PNP that is higher than the second-order transition temperature of described polymkeric substance with second-order transition temperature mixes.The dry coating that forms by described coating composition, with respect to the same combination that does not have described PNP, at least a being improved in the following performance: anti-tack, print resistance, scuff resistance, scrub resistance, wear-resistant photosensitiveness, anti-dirt retention, snappiness, time of drying, water tolerance, chemical-resistant and stain resistance.
In one embodiment of the invention, contain the polymkeric substance that is dispersed in the aqueous medium,, in the presence of PNP, prepare as the water-borne coatings of particle size greater than the Emulgating polymers of 50 nanometers.The described polymkeric substance that is dispersed in the aqueous medium can be by various polymerisation process preparation, as letex polymerization, corpuscle emulsion, microemulsion, suspension polymerization, non-aqueous dispersion polymerization or solution polymerization.The dry coating that forms by described coating composition, with respect to the same combination that does not have described PNP, at least a being improved in the following performance: anti-tack, print resistance, scuff resistance, scrub resistance, wear-resistant photosensitiveness, anti-dirt retention, snappiness, time of drying, water tolerance, chemical-resistant and stain resistance.
In one embodiment of the invention, will contain the polymkeric substance that is dispersed in the aqueous medium such as the coating of emulsion polymer, the PNP that is lower than the second-order transition temperature of described polymkeric substance with second-order transition temperature mixes.The dry coating that forms by described coating composition, with respect to the same combination that does not have described PNP, at least a being improved in the following performance: scrub resistance, anti-tack, anti-dirt retention, snappiness, flexible, water tolerance, chemical-resistant and stain resistance.
In one embodiment of the invention, will contain the polymkeric substance that is dispersed in the aqueous medium such as the coating of emulsion polymer, and mix with PNP, described PNP is to provide as the dispersion form in the solvent of emulsion polymer coalescing agent.The dry coating that forms by described coating composition, with respect to the same combination that does not have described PNP, at least a being improved in the following performance: scrub resistance, snappiness, flexible, coalescing agent consumption, water tolerance, chemical-resistant and stain resistance.
In one embodiment of the invention, provide a kind of containing to have functional substance in the above, for example the coating of the PNP of oxidation inhibitor or white dyes.For instance, the function corresponding monomer by in the PNP preparation process, introducing, the afterreaction by PNP or by suitable substance is appended on the PNP as absorption, hydrogen bond etc. with physical method, and described functional substance is provided.With respect to the coating that does not have described PNP, described PNP has more effectively utilized described functional substance.Be combined in greater than the coating on the particle of 50nm with respect to functional substance wherein, described PNP has also more effectively utilized described functional substance.
In one embodiment of the invention, will contain the polymkeric substance that is dispersed in the aqueous medium,, mix with the PNP of composition with the fluorochemical monomer that comprises copolymerization or silicon-containing monomer as the coating composition of emulsion polymer.Dry coating by described coating composition forms with respect to the same combination that does not have described PNP, has improved stain resistance, anti-biodeterioration (for example, mildew resistance, microbial resistance and anti-algae property) and chemical-resistant.
In one embodiment of the invention, will contain the polymkeric substance that is dispersed in the aqueous medium, and, and have the PNP that contains the monomeric composition of aldehyde active group that comprises at least a copolymerization and mix as the coating composition of emulsion polymer.Dry coating by described coating composition forms with respect to the same combination that does not have described PNP, has improved sticking power for Synolac.
In one embodiment of the invention, improvement coating of the present invention is in fluid state.
" containing aldehyde active group monomer " described herein is meant a kind of like this monomer, in the homogeneous solution that contains described monomer of 20 weight % and equimolar amount formaldehyde, under any pH value of 1-14,25 ℃ among one day, the level of response between described monomer and formaldehyde is all greater than 10% mole.Containing the unsaturated monomer to the aldehyde active group of ethylene linkage for example comprises: the etheric acid vinyl acetate; (methyl) vinylformic acid (acetoacetoxy groups ethyl) ester; (methyl) vinylformic acid (acetoacetoxy groups propyl group) ester; acetoacetic acid allyl ester; (methyl) vinylformic acid (acetoacetoxy groups butyl) ester; (methyl) vinylformic acid (2; 3-two (acetoacetoxy groups) propyl group) ester; the vinyl aceto-acetamide; acetoacetoxy groups ethyl (methyl) acrylamide; 3-(2-vinyl oxygen ethylamino)-propionic acid amide; N-(2-(methyl) acrylyl oxy-ethyl)-morpholone mai-2; 2-methyl isophthalic acid-vinyl-2-tetrahydroglyoxaline; 2-phenyl-1-vinyl-2-tetrahydroglyoxaline; (methyl) vinylformic acid (2-(3-oxazolidinyl) ethyl) ester; N-(2-ethylene oxy ethyl)-2-Jia Ji oxazolidine; 4; 4-dimethyl-2-Yi Bing Xi oxazolin; (methyl) vinylformic acid (3-(4-pyridyl) propyl group) ester; 2-methyl-5-vinyl-pyridine; 2-vinyloxy group ethamine (2-vinoxyethylamine); 2-vinyloxy group ethylethylenediamine; 3-aminopropyl vinyl ether; 2-amino-2-methyl propyl vinyl ether; the amino butyl vinyl ether of 2-; (methyl) vinylformic acid (tertiary butyl amino-ethyl) ester; 2-(methyl) acryloxy ethyl dimethyl-β-propionyl trimethyl-glycine; the diethanolamine mono vinyl ether; neighbour-aniline vinyl thioether; (methyl) acryloxy kharophen ethyl ethylidene-urea; (methyl) vinylformic acid (ethylidene urea groups ethyl) ester; (methyl) acrylamido ethyl-ethylidene-urea; (methyl) acrylamido ethyl-ethylene thiourea; N-((methyl) acrylamido ethyl)-N1-methylol ethylidene-urea; N-((methyl) acrylamido ethyl)-N1-methoxymethyl ethylidene-urea; N-formamido group ethyl-N1-vinyl ethylidene-urea; N-vinyl-N1-amino-ethyl-ethylidene-urea; N-(ethylidene urea groups ethyl)-4-amylene acid amides; N-(ethylene thiourea base-ethyl)-10-hendecene acid amides; ethylidene urea groups-ethyl fumaric acid butyl ester; ethylidene urea groups-ethyl fumarate dimethyl; N-(ethylidene urea groups-ethyl) dibenzyl fumarate; N-(ethylidene urea groups-ethyl) Malaysia acid benzyl ester; N-ethylene oxy ethyl ethylidene-urea (N-vinoxyethylethylene-urea); N-(ethylidene urea groups ethyl) crotonamide; urea groups amyl group vinyl ether; (methyl) vinylformic acid (2-urea groups ethyl) ester; N-2-(allyl amino formyl radical) amino-ethyl imidazolidone; 1-(2-((20 hydroxyls-3-(2-propenyloxy group) propyl group) amino) ethyl)-2-imidazolidone; ethylidene urea groups ethyl unlined garment health acid amides; methylene-succinic acid list ethylidene urea groups ethyl ester; methylene-succinic acid diethylidene urea groups ethyl ester; undecylenic acid (ethylidene urea groups ethyl) ester; ethylidene urea groups ethyl undecylene acid amides; vinylformic acid (2-(3-hydroxy methylimidazole alkane ketone-2-base-1) ethyl) ester; N-acryloxy Wan Ji oxazolidine; amidoalkyl vinyl alkylidene group urea; containing the monomer of the active amino of aldehyde and contain the ethylene linkage unsaturated monomer of aziridine (aziridene) functional group as methacrylic acid (dimethyl aminoethyl) ester.By the following PNP that contains the preparation of the monomer of aldehyde active group is particularly preferred: methacrylic acid (2-(2-oxo-1-imidazolidyl) ethyl) ester, 1-[2-[[2-hydroxyl-3-(2-propenyloxy group) propyl group] amino] ethyl]-the 2-imidazolidone, the Methacrylamide of 2-methyl-just-[2-(2-oxo-1-imidazolidyl) ethyl], 2-butylene diacid two [2-(2-oxo-1-imidazolidyl) ethyl] ester, carboxylamine ([2-(2-oxo-1-imidazolidyl) ethyl]-2-propenyl) ester, AAEM and their mixture.
In this embodiment, described can be to the aldehyde active group by the synthetic described PNP of the monomer of aldehyde active group being introduced among the composition of described PNP with containing.For instance, the described monomer that contains the aldehyde active group can prepare the PNP that has the aldehyde active group with polyenoid key unsaturated monomer and ethylene linkage unsaturated monomer.The described monomeric concentration that contains the aldehyde active group is benchmark with the total monomer weight, typically is 1-99%, more typically is 5-90%, typically is 10-80% more.
The PNP (" to the active PNP of aldehyde ") that employing contains the monomer preparation of aldehyde active group is useful for improving the sticking power of finally filming for base material.For instance, emulsion-based coating can be prepared by latex polymer, and with composite to the active PNP of aldehyde.Described containing can be by means of the active PNP of aldehyde being joined among the formulation for coating material, to improve the sticking power of coating for base material to the monomer of aldehyde active group.Similarly, the polymerization of monomer emulsion latex also can carried out in the presence of the active PNP aldehyde.Being used for improving the described of adhesion strength the concentration of the active PNP of aldehyde in described formulation for coating material typically is 0.1-5 weight %, more typically is 0.2-4 weight %, typically is 0.5-3 weight % more, typically is 1-2 weight % most.
In one embodiment, contain the polymkeric substance that is dispersed in the aqueous medium, as the coating of anionic polymerization thing, can be in the volatile alkali mixing of nonionic state with the described PNP that guarantees of PNP with the monomeric component of promotion exsiccant that comprises at least a copolymerization and sufficient amount.Promote the monomeric example of exsiccant to comprise the ethylene linkage unsaturated monomer of the amido that contains alkalescence.The monomeric example that this class contains alkaline amido is disclosed in US5, and 527,823 and US5,804,627.Useful especially monomer comprises DMAEMA, DMAPMA and OXEMA (methacrylic acid (2-(3-oxazolidinyl) ethyl) ester), and their mixture.Therefore, " promoting exsiccant PNP " is useful for the drying or the curing speed that improve coating, particularly for negatively charged ion latex base coating.
In this embodiment, the dry group of described promotion can be by with promoting the synthetic described PNP of exsiccant functional monomer to be incorporated among the composition of described PNP.Various promotion exsiccant functional monomers can be used for preparing the PNP with promotion exsiccant group with polyenoid key unsaturated monomer and other optional ethylene linkage unsaturated monomer.The dry functional monomer's of described promotion concentration is benchmark to be used for the total monomer weight of synthetic described PNP, typically is 1-99 weight %, more typically is 5-90 weight %, typically is 10-80 weight % more.The concentration of the dry PNP of described promotion in described formulation for coating material, should be enough to shorten the time of drying of described coating, be benchmark with the negatively charged ion raw material equivalent in the described formulation for coating material, and its quantity typically is 20-500%, more typically be 50-250%, typically be 75-150% more.
In one embodiment of the invention, to contain the coating that is dissolved in the polymkeric substance in the solvent, mix with the PNP of the surface active monomer that comprises at least a copolymerization, described surface active monomer is that for example fluoromonomers, silicon-containing monomer or poly-(oxyalkylene) fragmental molecule amount are 100-5, the monomer of containing of 000g/mol poly-(oxyalkylene) (as containing poly-(oxyethane) pulsating monomer), or their mixture.In this embodiment, the weight percentage that is used for preparing the surface active monomer of described PNP is 1-90%, is preferably 2-75%, and more preferably 5-50% is more preferably 10-40%.The PNP that contains fluorine, silicon and poly-(oxyalkylene) group also can prepare by making the PNP and fluorine, silicon and poly-(oxyalkylene) chemical segment (they can carry out chemical reaction with the active group of the described PNP) reaction that contain active group.Dry coating by described coating composition forms with respect to the same combination that does not have described PNP, has the performance of the improved bio-accumulation of anti-the pollution of the sea.Although the Tg to the PNP that uses in the present embodiment does not limit,, in some applications, preferred Tg is lower than 25C, more preferably less than 0C, is more preferably and is lower than-25C, to reduce the ability of pollution of the sea bioadhesion to the coatingsurface.
In one embodiment of the invention, provide not stained/anti-fouling coating, they do not need expensive environmentally harmful biocide or silicon resin base coating.These coatings be by with have the acidiferous monomer that comprises copolymerization crosslinked PNP blended coating composition and provide as the component of (methyl) vinylformic acid and at least a fluoromonomers or siliceous resin monomer or their mixture, with described coating composition coated substrate, solidify or dry described coating, and adhere to poly-(oxyalkylene) molecule on described curing or exsiccant coating.Poly-(oxyalkylene) molecule, particularly poly-(oxyethane) (" PEO ") molecule attached can reduce the absorption of biomolecules on these surface modified substrates significantly on final coating.There is the multiple different PE0 that adheres to can be applicable in the embodiment of the present invention to the method on the base material, they are disclosed in people's such as Ostuni ASurvey of Structure-Property Relationships of Surfaces that Resist theAdsorption of Protein, Langmuir, 17,5605-5620 (2001).But the existence of acid in the body basement membrane can make absorption owing to water cause the reduction (being water sensitivity) of film properties.Therefore, by surface active monomer (for example, F and Si) with acidiferous monomer (for example, MAA or AA) PNP for preparing, provide spissated acidic site at described coatingsurface, they can be used to carry out grafting, but they do not have contribution for the water sensitivity of coating.In this embodiment, the weight percentage that is used to prepare the surface active monomer of described PNP is 1-90%, is preferably 2-30%, and more preferably 5-25% is more preferably 10-25%.In this embodiment, the weight percentage that is used to prepare the acidiferous monomer of described PNP is 1-90%, is preferably 2-30%, and more preferably 5-25% is more preferably 10-25%.
Although be not subjected to the constraint of particular theory, but believe that described PNP moves to described curing or exsiccant coatingsurface and provide sour binding site at described coatingsurface, sour subsequently binding site again with poly-(oxyalkylene) component, as poly-(oxyethane) (" PEO ") component grafting, a kind of to form " PEO thicket ", they can the deposition of arrestin matter on described coatingsurface.Resulting not stained/anti-fouling coating is durable in use, and more current silicon resin base coating is easier to coating, and the same combination of described with respect to not having " PEO thicket " has the performance of the improved biological accumulation of anti-the pollution of the sea.
In one embodiment, the tackiness agent of not stained/anti-fouling coating can be low Tg, crosslinkable polymkeric substance, wherein is mixed with the PNP that contains surface active groups and sour binding site.Although do not wish to be subjected to the constraint of particular theory, believe that the PNP in this type coating may be moved to air interface, and provide can be used for surface treatment subsequently (for example, but grafting position PEO).In the present embodiment, " low Tg " be meant and preferably be lower than 0C by the Tg that is lower than 25C, more preferably less than-25C.
In one embodiment of the invention, the mean diameter of the PNP that provides is the 1-50 nanometer, be preferably 1-40nm, 1-30nm more preferably, be more preferably 1-20nm, further be preferably 1-10nm, most preferably be 2-8nm, described PNP has at least a polyenoid key unsaturated monomer and at least a surface active monomer as polymerized unit, to form " surfactivity PNP ".In an alternate embodiment, described surfactivity PNP contains the polymerized unit that is derived from acid mono in addition.In another embodiment, described surfactivity PNP contains poly-(oxyalkylene) in addition, preferably contains PEO.Poly-(oxyalkylene) can be incorporated among the PNP as mentioned above.These PNP build in multiple different being used for of preparation, the material and the coating of electronics and transport field are useful.For example, contain the surfactivity PNP of poly-(oxyalkylene), can be used to improve the antibiont deposition property on building and transportation coating.Surfactivity PNP also can be used to preparation as US6,271,273 described porogens.
In one embodiment of the invention, a kind of polymkeric substance that is dispersed in the aqueous medium that contains as the paper coating compositions of emulsion polymer, mixes with functionalized PNP.The dry coating that forms by described coating composition, with respect to the same combination that does not have described functionalized PNP, have improved absorption of inks ability and/or impression persistence, for example comprise: water tolerance, anti-biography seal property (offsetresistance) and resistant damage property.Described coating paper can preferably be used as the ground of ink jet printing.
In one embodiment of the invention, provide a kind of coating composition, it contains already through being impregnated with the PNP of functionalized reagent such as agronomy activeconstituents and static inhibitor, and described reagent is insoluble basically in the medium of described coating composition.By the dry coating that described coating composition forms, show the surface that wherein said functionalized reagent can be discharged into described coating with controlled rate of release, this speed partly is subjected to the influence of the second-order transition temperature of described PNP.
In one embodiment of the invention, provide a kind of composition, it contains the PNP that is impregnated with functionalized reagent such as lubricant or silicone resin already.In washing and exsiccant wash cycle, the PNP of described modification is deposited on the textile materials, and described functionalized reagent is distributed on the textile materials.
In one embodiment of the invention, provide a kind of composition, it contains the PNP that is impregnated with functionalized reagent such as lubricant or silicone resin already.The PNP of this modification can be used in personal-care supplies such as shampoo or the lotion.
In one embodiment, provide a kind of method that forms polymeric dispersions.The polymeric dispersions of the present embodiment provides by following steps: form PNP; A kind of described PNP and at least a monomeric reaction mixture of containing is provided; With make described reaction mixture stand at least a body, solution, gas phase, emulsion, corpuscle emulsion or suspension polymerization condition.In this embodiment, described PNP dissolves or is dispersed in monomer or the monomer mixture, and is used for the polyreaction that is used for preparing polymeric dispersions subsequently.Any can all can employing by the polymeric monomer is preferably the ethylene linkage unsaturated monomer.Although be used for the polymerization that PNP of the present invention can be combined in any kind, comprise emulsion, corpuscle emulsion, body, solution, gas phase, suspension and their combination, but, preferably comprise suspension polymerization, corpuscle emulsion polymerization, micro-emulsion polymerization and letex polymerization, so that polymeric dispersions to be provided with the post-polymerization type.
Although can use any amount of PNP to prepare polymeric dispersions,, preferably, based on monomer weight, the PNP consumption is 1-90%, is preferably 1-75%, more preferably 1-50% is more preferably 1-30%, further is preferably 1-20 weight %.
Wetting ability PNP can advantageously be used for preparing the polymeric dispersions that adopts emulsion polymerization technology.The example of wetting ability PNP is a kind of PNP that contains the 50MMA/20BA/10DEGDMA/20PEGMEMA475 polymerized unit, and the numerical value before the wherein said monomer mark is the weight fraction of the described polymerized unit of expression.Under corpuscle emulsion polymerization and diffuse-aggregate situation, preferred PNP is not highly soluble in water.PNP in described polymeric dispersions, can with the interpolymer interaction that formed afterwards, can not interact yet.Interaction can comprise that for example covalent bonding, acid/alkali interact and charge transfer interacts.For the application in water based polymerization reaction, described PNP preferably is dispersed in the water or in the mixture of water/solvent.Be included in the PNP in this polymer dispersion, the comparative polymer particle that is directly formed by emulsion or suspension polymerization can obtainablely be formed, can provide a kind of wideer can obtainable compositing range, promptly too hydrophobic or hydrophilic components too for direct polymerization can be introduced by adding the PNP that is formed by solution polymerization.Described particle dispersion is incorporated in a kind of coating composition, has at least a improved performance by its coating that forms.Described particle dispersion also can be used to form polymer complex.
In one embodiment of the invention, the PNP solubilized be dispersed in monomer or monomer mixture in, and be used for subsequently be used for prepare among the polyreaction of polymer complex.The monomer that is adopted can be any monomer mixture that can be used to form polymeric material, is preferably the ethylene linkage unsaturated monomer.The polyreaction of any kind comprises emulsion, corpuscle emulsion, body, solution, gas phase, suspension and their combination, all can be used to prepare described polymer complex.
Although can use any amount of PNP to prepare described polymer complex,, preferably, based on monomer weight, the PNP consumption is 1-90%, is preferably 1-75%, more preferably 1-50% is more preferably 1-30 weight %.Described polymer complex also can adopt before this, and the method for preparing polymeric dispersions described in the embodiment obtains.
In one embodiment of the invention, PNP is used for emulsion polymerization technique, is used for improving the performance (for example, improved stability) of resulting emulsion polymer particle dispersion.In this embodiment, improved stability is meant that having reduced described emulsion polymer particle becomes unstable and become not dispersive possibility, promptly by flocculation, agglomeration, formation gel and similar procedure, interacts two or more polymer beads.Described PNP can be used as the stablizer of water-base emulsion polymerization and aqueous-based polymers dispersion.In the present embodiment, described PNP contains acid or other hydrophilic functional group.Preferably, described PNP adopts acidiferous monomer to prepare.Preferably, described acid content is high enough to provide a static charge layer around described PNP.With the acid content of the suitable PNP of used as stabilizers, can estimate by the acid content of known typical case's " peracid " polymkeric substance as the letex polymerization stablizer, for example, as US4, described in 845,149.
Typically, the PNP that can be used as stablizer in aqueous dispersion such as the emulsion polymerization, the unit that contains at least a acidiferous monomer that is derived from 1-99 weight % or one-tenth acid reagent, be preferably 5-95 weight %, 8-75 weight % more preferably, be more preferably 15-60 weight %, further be preferably 20-40 weight %.Although any acidiferous monomer all can adopt, typically, described acidiferous monomer can pass through the Raolical polymerizable copolymerization.In this class acidiferous monomer, vinylformic acid and methacrylic acid are preferred the employings.Typically, can be used as the described PNP of stablizer, contain the unit of at least a polyenoid key unsaturated monomer that is derived from 1-50 weight %, be preferably 2-40 weight %, more preferably 3-20 weight % is more preferably 5-15 weight %.Preferably, the acid functional group of described PNP is with suitable neutralization bases such as oxyhydroxide (for example, sodium hydroxide, potassium hydroxide), amine be preferably ammonia and neutralize.More preferably, this class PNP be can with the solvent of water coexistence in prepare, neutralize with alkali, in water, dilute before the described emulsion polymerization implementing.More preferably, described can with the solvent of water coexistence, when being used for the stable emulsion polyreaction, from described PNP dispersion, remove at least in part, preferably from described PNP dispersion, remove substantially fully.
Although as mentioned above, this class PNP stablizer only needs to contain acid mono and polyenoid key unsaturated monomer, but, should be understood that, described PNP can randomly contain up to 85 weight % stem from neither acidiferous monomer neither polyenoid key unsaturated monomer the unit of other ethylene linkage unsaturated monomer.Similarly, the described PNP that can be used as stablizer also can contain optional functional monomer, includes but not limited to the functional monomer such as hydroxyl, acetylacetic ester, acrylamide, acrylamide/formaldehyde adducts, urea groups, amine etc.
PNP of the present invention can be at the emulsion polymerization that carries out according to the method for known employing " peracid " polymerization stabilizer (so-called " resin-carried type emulsion polymerization ", for example referring to US4,845,149 and US6,020,061) middle with used as stabilizers (being dispersion agent).The amount ranges of PNP in emulsion polymerization as dispersion agent is as follows: 5-80, be preferably 10-60, and most preferably be the PNP of 15-40 weight %, be benchmark with described PNP and described emulsion polymer solid gross weight.
In these suitable emulsion polymer compositions, any emulsion polymer, multipolymer, multistage multipolymer, multipolymer (narrow sense), core-shell polymer etc. all can adopt PNP of the present invention stable.Although any ethylene linkage unsaturated monomer all can adopt, preferred stabilized emulsion polymer is by at least a the preparing in (methyl) acrylate and the vi-ny l aromatic monomers.
When implementing to contain the emulsion polymerization of PNP stablizer of the present invention, all typical emulsion polymerization compositions, condition and method all can adopt, for example, can there be (perhaps not existing) in any known emulsion polymerization emulsifying agent (soap), initiator, temperature, chain-transfer agent, type of reactor and solids content etc.Employing has the improvement of coating of the emulsion polymer preparation of PNP stablizer, and expection is embodied among the following performance: japanning pitch time, gloss, controlled rheological, stability, water tolerance, block resistance, heat resistanceheat resistant stopping property and anti-dirt retention.
In one embodiment of the invention, can envision the mixture of emulsion polymer latex particle and PNP stablizer, be preferred although adopt PNP as the emulsion polymer latex particle of stablizer preparation.
In one embodiment, the PNP that contains remaining degree of unsaturation handles under polymerizing condition with other monomer subsequently, contains the PNP of at least a second section polymkeric substance with formation.Described second section polymkeric substance can have functional performance, and as promoting bonding, waterproof, it can pass through as US5, and 330,537 described amphiphilic polymers are realized.Described second section polymkeric substance also can have surface-active performance by introducing surface active monomer.Described compound PNP is incorporated in a kind of coating composition, has at least a improved performance by its formed coating.
In one embodiment, coating is used as leather treatment, so that the process for tanning of a kind of tanning and retanning leather to be provided.A kind of method of the skin of tanning is provided, and described skin carries out rotary drum via this method in the pH value is the aqueous buffer solution that contains PNP of 3-7 (being preferably 3.5-4.5) handles.In the present embodiment, preferred described aqueous buffer solution is made up of sodium acetate and acetate, and preferred ratio between two is 1: 1.Obtain a kind of leather of tanning through this, it is Full Featured.In the ending of its time limit of service, this leather can adopt the quality impairment to environment very little or do not have the burning of infringement and/or bury and/or the method for burying of digging pit is handled.In the eco-friendly process for tanning of this class, described PNP preferably contains the halogen atom that is lower than 1 weight %, more preferably less than 0.5 weight % halogen atom, is more preferably and is lower than 0.2 weight % halogen atom, most preferably is lower than 0.1 weight % halogen atom.It also is easy to be decomposed into amino acid by chemistry and enzyme method, to be used as fertilizer and/or animal-feed.
In one embodiment, be dispersed in the PNP in the solvent, can be used as preparation heat pipe oligopolymer and can allow the isolating medium of 100% solid oligomer/PNP.This provides the PNP in oligopolymer " solvent ".Described PNP has quite high molecular weight, still, and may be as disperse phase to the few of contribution of total viscosity.For example for the reaction of polymeric polyisocyanate, the hydroxy radical content of described PNP is preferably lower than the hydroxy radical content of described oligopolymer.Similarly, other cross-linking chemistry material comprises for example epoxy amine or carboxylicesters, and uv/eb solidifies (origoester acrylate) and other material, can be based on the mixture of oligopolymer/PNP.
In one embodiment, contain the water-based paint compositions of associative thickener and PNP and the emulsion polymer adhesives of choosing wantonly, pigment and/or other paint assistant agent, do not have the same combination of described PNP, better thickening effectiveness can be provided.Various associative thickeners are known in the art, and can be used among the present invention with PNP.Preferred associative thickener comprises at least a in the following type: hydrophobic modified urethane, the soluble emulsion of hydrophobic modified alkali, hydrophobic modified Natvosol, hydrophobic modified polyvinyl alcohol and hydrophobic modified polyacrylamide and their variant.The weight percent of described associative thickener and described PNP is a benchmark with the gross weight of water-based paint compositions, preferably is at least 0.02, more preferably is at least 0.05, is more preferably and is at least 0.1.Typically, the scope of the weight ratio of described PNP and described associative thickener is 1-99: 99-1, is preferably 5-95: 95-5; 10-90: 90-10 more preferably is more preferably 20-80: 80-20, further be preferably 30-70: 70-30, and most preferably be 40-60: 60-40.Typically, the weight percent of described associative thickener and described PNP is at most 20, preferably is at most 10, more preferably is at most 5 weight %, is benchmark with the gross weight of described water-based paint compositions.The viscosity of described water-based paint compositions is at least 0.2 pool, preferably is at least 0.5 pool, more preferably is at least 1 pool, is more preferably to be at least 2 pools.Typically, the viscosity of described water-based paint compositions is at most 50 pools, preferably is at most 20 pools, more preferably is at most 10 pools.Although be not subjected to the constraint of mechanism, it is believed that described PNP can provide additional bridging site by described associative thickener.
Following embodiment is used for further describing all respects of the present invention.
Embodiment 1 preparation PNP
On a 500mL reactor, assemble thermopair, temperature regulator, purgative gas inlet, have water cooling reflux exchanger, agitator and feed hopper that purgative gas exports.Add the 201.60g monomer mixture in described feed hopper, it is made up of petroleum spirit (Luperox 554-M-75) solution of the peroxide PIVALIC ACID CRUDE (25) tert-pentyl ester of 18.00g methyl methacrylate (100% purity), 2.00g diethylene glycol dimethacrylate (100% purity), 1.60g 75% and 180.00g diisobutyl ketone (" DIBK ").Then with nitrogen the reactor that contains 180.00g DIBK was purged 30 minutes, the content with reactor is heated to 75 ℃ then.When the content in the described reactor reaches 75 ℃, the monomer mixture in the described feed hopper is joined in the described reactor equably with 90 minutes.After described monomer mixture interpolation finishes 30 minutes, two parts of aliquots containigs of appending were joined wherein at interval in 30 minutes, and this five equilibrium sample is made up of petroleum spirit (Luperox 554-M-75) solution and the 2.00g DIBK of the peroxide PIVALIC ACID CRUDE (25) tert-pentyl ester of 0.06g 75%.After adding second part of aliquots containig of appending, the content in the described reactor kept 2.5 hours down at 80 ℃, and reaction is finished.The polymkeric substance that obtains filters and collects by separating with the heptane precipitation, and dry under vacuum, obtains white powder.This material is dissolved in the propylene glycol monomethyl ether again.The particle size distribution of the PNP of Xing Chenging is 0.8-5.0nm like this, and recording its mean sizes by the dynamic laser light scattering method is 1.4nm, and it is 22642g/mol that GPC records its apparent molecular weight, and number-average molecular weight is 14601g/mol, and its Mw/Mn is 1.6.
Embodiment 2 prepares PNP, promptly a kind of AAEM/ALMA multipolymer by semi-batch emulsion polymerization process
Mixture by 17g deionized water, 8.85g 28%w/w solid ammonium lauryl sulfate (" ALS "), 12.4g methacrylic acid (acetoacetyl oxygen ethyl) ester (" AAEM ") and 1.78g allyl methacrylate (" ALMA ") is made monomer emulsion.Then in a reactor, prepare 600g deionized water, 15.0g 28%w/w solid ALS and 0.15g and be dissolved in ammonium persulphate (" APS ") in the 1mL deionized water.Described reactor is carrying out being heated to 90 ℃ under the purging condition with nitrogen.Half of described monomer emulsion joins in the described reactor under the 200rpm rotating speed stirs.After 20 minutes, with the monomer emulsion adding of remainder.Described still temperature was kept 30 minutes at 90 ℃, be cooled to 55 ℃, then 0.02g tert-butyl hydroperoxide (" t-BHP ") is dissolved in the solution of 1mL deionized water and the solution that 0.010g sodium sulfoxylate formaldehyde (" SSF ") is dissolved in the 1mL deionized water, joins wherein respectively.Cool to room temperature is followed in described reaction, and described emulsion is filtered respectively by 400 and 100 eye mesh screens.
Described sample is separated from water by lyophilize, prepares the frangible runny powder of a kind of white.Resulting white powder is with a large amount of second distillations and deionized water washing, to remove most tensio-active agent.
Embodiment 3 prepares PNP-AAEM/ALMA multipolymer by the discontinuous emulsion polymerization method
The mixture that monomer emulsion is made up of 17g deionized water, 8.85g 28%w/w solid ALS, 12.4g AAEM and 1.78g ALMA makes in a bottle.Then in a reactor, prepare 600g deionized water, 15.0g 28%w/w solid ALS and 0.15g and be dissolved in APS in the 1mL deionized water.Described reactor is heated to 90 ℃ in nitrogen purging.Described monomer emulsion all joins in the described reactor under the 200rpm rotating speed stirs once.After 30 minutes, cool off described reactor to 75 ℃, the solution that then 0.02g t-BHP is dissolved in the 1mL deionized water joins wherein.Further cooling is described is reacted to 55 ℃, and the solution that 0.010g SSF is dissolved in the 2mL deionized water is joined wherein.Cool to room temperature is followed in described reaction, and described emulsion is filtered respectively by 400 and 100 eye mesh screens.
Embodiment 4 prepares PNP by progressively addition polymerization method
Monomer emulsion is by 100g water, 1.60g 28%w/w solid ALS, 68g ethyl propenoate (" EA) ", the mixture formed of 17g methyl methacrylate (" MMA "), 12.5g Vinylstyrene (" DVB ") and 5g methacrylic acid (" MAA ") makes.The reactor that will contain 445g water, 22.2g 28%w/w solid ALS and 0.37g APS is heated to 85 ℃ under nitrogen atmosphere.Described monomer emulsion was fed in the described still with 90 minutes.After charging finished, described being reflected at kept under 85 ℃ 30 minutes, was cooled to 65 ℃ then.After cooling, add 1.33g 10% ferrous sulfate (FeSO4).After 1 minute, add 0.2g 70%t-BHP, after 2 minutes, add 0.10g 100% saccharosonic acid (" IAA "), described reaction continues 15 minutes.Second system of appending adds in the identical timed interval by identical sequence.Cool to room temperature is followed in described reaction, and filters by 400 and 100 eye mesh screens.
The multiple different PNP of embodiment 5 preparations
PNP forms shown in table 5.1.These polymkeric substance are according to the preparation of the universal program of embodiment 1-4.Abbreviation " Mw " expression weight-average molecular weight, term " Mn " expression number-average molecular weight.The ratio of term " Dist " expression Mw/Mn.Apparent molecular weight is that employing standard GPC method measures as solvent with tetrahydrofuran (THF).
Table 5.1PNP polymkeric substance is formed
Sample 5- Form Ratio Mw Mn Dist
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 HEMA/DEGDMA MMA/DEGDMA MMA/DEGDMA MMA/DEGDMA MMA/DEGDMA MMA/MAPS/DEGDMA MMA/MAPS/DEGDMA MMA/MAPS/DEGDMA MMA/MAPS/DEGDMA MMA/MAPS/DEGDMA MAPS/DEGDMA MMA/MAPS BA/DEGDMA MMA/MAPS/PETTA MMA/MAPS/PPG4000DMA MMA/MAPS/DPEPA MMA/MAPS/TMPTMA MMA/MAPS/DEGDMA MMA/MAPS/DEGDMA MMA/MAPS/DVB MMA/MAPS/DVB MMA/MAPS/DVB MMA/MAPS/DVB MMA/MAPS/DEGDMA MMA/MAPS/DEGDMA MMA/MAPS/DVB STY/MAPS/DVB BA/MAPS/DVB BA/MAPS/DVB BA/TMSMA/DVB BA/MOPTSOMS/DVB BA/MOPMDMOS/DVB BA/MAPS/TAT ALM/BA/DVB IBOMA/MAPS/DVB BA/DVB BA/PGDMA BA/ALMA BA/TMPTMA BA/DPEPA EHA/DVB EHA/ALMA EHA/TMPTMA EHA/DPEPA STY/DVB STY/ALMA EHA/STY/ALMA EHA/STY/ALMA MMA/DEGDMA 90/10 90/10 90/10 90/10 90/10 70/20/10 80/10/10 60/30/10 40/50710 20/70/10 90/10 88.9/11.1 90/10 80/10/10 80/10/10 80/10/10 80/10/10 75/10/15 85/10/5 10/60/30 20/60/20 25/60/15 30/60/10 20/70/10 30/60/10 10/80/10 30/60/10 30/60/10 10/80/10 10/80/10 10/80/10 10/80/10 10/80/10 10/80/10 10/80/10 90/10 90/10 90/10 90/10 90/10 90/10 90/10 90/10 90/10 90/10 90/10 20/70/10 45/45/10 90/10 19073 644 771 10640 12819 43667 166432 11683 15965 51007 95613 110422 35249 35105 331732 38455 499094 312848 674730 97530 363561 12201 223436 26797 104529 39638 103945 22642 11183 221 3989 4254 8091 9047 7404 3484 7424 29065 12003 19814 7438 7003 29918 12320 36317 16102 30989 12154 37553 5182 29309 8242 15967 16306 18702 14601 1.7 2.9 1.9 2.5 1.6 4.8 22.5 3.4 2.2 1.8 8.0 5.6 4.7 5.3 11.1 3.1 13.7 19.4 21.8 8.0 9.7 2.4 7.6 3.3 6.5 2.4 5.6 1.6
Embodiment 6 introduces the suspension polymerization of PNP
Raw material Feed weight (gram)
Solution #1
Deionized water 67.10
Pharmagel 4.75
Solution #2
Deionized water 414.00
Padmac 21.30
NaCl 93.30
Monomer/PNP mixture
MMA 333.00
PNP 16.65
Benzoquinones 0.018
The dodecyl superoxide 3.30
The afterreaction additive
Triton CF-32 3
Preparation consists of the PNP of 80BA/10MMA/10DEGDMA in MIBK, and solids content is 5%.The 1000g sample of this composition is placed in 2 liters of flasks, adopts rotatory evaporator under reduced pressure to remove MIBK.Preparation solution #1 in a beaker, and under agitation be heated to 60 ℃, all dissolve up to pharmagel.Solution #2 stirs under room temperature in a beaker, all dissolves up to Padmac and NaCl.Then, under agitation, solution #1 is added among the solution #2.Then, by the 333.00g methyl methacrylate is placed in the beaker with 0.018g benzoquinones and 3.30g dodecyl superoxide, prepare described monomer mixture; This mixture at room temperature stirred 20 minutes, and described benzoquinones and dodecyl superoxide are dissolved fully.Described Padmac/ pharmagel mixture then joins reactor, stirs 10 minutes under 245rpm.Described monomer/PNP mixes anti-then joining wherein, forms monomer dispersion in described reactor.Then temperature of reactor was brought up to 65 ℃ with 1 hour, to cause described monomeric polyreaction.Temperature can allow to reach 74 ℃, maintains this temperature by adding cold water then.After heat release finished, temperature was kept 15 minutes at 74 ℃.Then, add 0.6mL TritonCF-32 to reactor, temperature is brought up to 90 ℃, continues 2 hours.At last, cool off described reactor, filter and collect product to room temperature.
Embodiment 7 preparation suspension polymers
Repeat the method for embodiment 6, difference is to adopt the PNP that consists of 54MMA/36BA/10DEGDMA for preparing in MIBK, and solids content is 5%.
The preparation of comparative example A's suspension polymer
Raw material Feed weight (gram)
Solution #1
Deionized water 67.10
Pharmagel 4.75
Solution #2
Deionized water 414.00
Padmac 21.30
NaCl 93.30
Monomer mixture
MMA 333.00
Benzoquinones 0.018
The dodecyl superoxide 3.30
The afterreaction additive
Triton CF-32 3
Preparation solution #1 in a beaker, and under agitation be heated to 60 ℃, all dissolve up to pharmagel.Solution #2 stirs under room temperature in a beaker, all dissolves up to Padmac and NaCl.Then, under agitation, solution #1 is added among the solution #2.Then, by the 333.00g methyl methacrylate is placed in the beaker with 0.018g benzoquinones and 3.30g dodecyl superoxide, prepare described monomer mixture; This mixture at room temperature stirred 20 minutes, and described benzoquinones and dodecyl superoxide are dissolved fully.Described Padmac/ pharmagel mixture then joins reactor, stirs 10 minutes under 245rpm.Described monomer mixture then joins wherein, forms monomer dispersion in described reactor.Then temperature of reactor was brought up to 65 ℃ with 1 hour, to cause described monomeric polyreaction.Temperature can allow to reach 74 ℃, maintains this temperature by adding cold water then.After heat release finished, temperature was kept 15 minutes at 74 ℃.Then, add 0.6mL Triton CF-32, temperature is brought up to 90 ℃, continue 2 hours to described reactor.At last, cool off described reactor, filter and collect product to room temperature.
The corpuscle emulsion of embodiment 8 preparation polymkeric substance/PNP mixtures
Preparation consists of the PNP of 90MMA/10DEGDMA in MIBK, and solids content is 5%.Get the 1000g sample of this composition, be placed in 2 liters of flasks, adopt rotatory evaporator under reduced pressure to remove described MIBK.
Component Consumption (g)
BA 20.9
MMA 13.9
PNP 1.05
Deionized water 144.4
Sodium lauryl sulphate (SLS) 0.62
N-Hexadecane 1.5
Potassium Persulphate (KPS) 0.0705
Sodium bicarbonate 0.021
Said mixture is placed in the reactor, and homogenizing 30 minutes obtains a kind of stable corpuscle emulsion.Then, temperature is brought up to 75C, continue 2 hours, with the described styrene monomer of polymerization.Behind cool to room temperature, described material is filtered and characterizes.
The corpuscle emulsion of embodiment 9 preparation polymkeric substance/PNP mixtures
Method according to embodiment 8 prepares a kind of corpuscle emulsion, and difference is to adopt the PNP that consists of 54MMA/26BA/10DMAPMA/10DEGDMA for preparing in MIBK, and solids content is 5%.
Comparative Examples B does not contain the corpuscle emulsion polymer latex of PNP
Component Consumption (g)
Vinylbenzene 34.8
Deionized water 144.4
Sodium lauryl sulphate (SLS) 0.62
N-Hexadecane 1.5
Potassium Persulphate (KPS) 0.0705
Sodium bicarbonate 0.021
Said mixture is placed in the reactor, and homogenizing 30 minutes obtains a kind of stable corpuscle emulsion liquid.Then, temperature is brought up to 75 ℃, continue 2 hours, with the described styrene monomer of polymerization.Behind cool to room temperature, described material is filtered and characterizes.
Embodiment 10 letex polymerizations are to form polymkeric substance/PNP mixture
Preparation consists of the PNP of 50MMA/20BA/10DEGDMA/20PEGMEMA475 in MIBK, and final solids content is 5%.Get the 1000g sample of PNP, be placed in 2 liters of flasks, adopt rotatory evaporator under reduced pressure to remove described MIBK.To wherein adding 335g MMA and 600g BA, stir described mixture till it evenly.
On one 3 liters four neck round-bottomed flasks the mechanical paddle agitator of configuration, be used for monitor temperature thermopair, reflux exchanger, be used for the device and the nitrogen atmosphere of heating and cooling.In described flask, add the 400g deionized water, and be heated to 85 ℃.Be equipped with monomer pre-emulsion by 280g deionized water, 11g Sodium dodecylbenzene sulfonate (23% the aqueous solution), the above-mentioned monomer of making/PNP mixture and the 15g Dutch treatment.Add in reaction flask that 4g is dissolved in ammonium persulphate in the 20g deionized water and 100nm seed latex and the total amount of 16g (based on solid) is the deionized water of 29g.Described pre-emulsion and 1.5g are dissolved in the ammonium persulphate in the 45g deionized water, join wherein with 3 hours.As required, carry out heating and cooling, to keep temperature of reaction at 83 ℃.After adding end, with the described pre-emulsion container of 30g deionized water rinsing, washing lotion is added among the described flask.After 30 minutes, cool off described flask to 60 ℃.When temperature is cooled to 55 ℃, be dissolved in FeSO in the 5g deionized water to wherein adding 0.008g 47H 2O is then with 1 hour, to wherein dripping the 0.40g 70% tert-butyl hydroperoxide aqueous solution that is dissolved in the 45g deionized water and the 0.25g sodium formaldehyde sulphoxylate that is dissolved in the 45g deionized water.Reaction mixture to 45 ℃ is regulated the pH value with 14g14% ammoniacal liquor.Behind cool to room temperature, filter described emulsion polymer.The emulsion polymer of present embodiment consist of 60BA/33.5MMA/5PNP/1.5AA.
Comparative Examples C preparation does not contain the emulsion polymer of PNP
Do not adopt PNP, repeat the method for embodiment 3.Contain and comprise that average particulate diameter is embodiment 6-7, the 8-9 of PNP of 1-100 nanometer and the coating of 10 polymkeric substance, with respect to the coating of the same composition of the polymkeric substance that contains comparative example A, B and C respectively, expection has at least a following performance: higher intensity, lower viscosity, better block resistance and better film-forming properties.
Embodiment 11-A adopts the leather of PNP composition to handle (tanning)
PNP T is a kind of 15% in pimelinketone (90EUG/10TMTPA) that be present in.Its average particle size particle size that records is 1.5 nanometers.All percentage ratio all is based on the weight of pickling raw material.
From the pickling raw material of the 1.2mm thickness of local tannery, adopt ordinary method to neutralize.A slice pickled skin (100G.) is put in 1 gallon of glass jar, and 5% sodium chloride aqueous solution with 200% makes it floating.Seal described glass jar, content wherein overturn 15 minutes under room temperature in rotating the paint can mixing tank, to wash this raw material.Decant washings, recording its pH is～3.5.Soft pickled skin in the glass jar then makes it floating with fresh 100% 5% salts solution that provides, and the anhydrous sodium acetate of adding 2% in this system.Seal described glass jar, this system of overturning continuously 4 hours is with the described fur that neutralizes.After this time, the pH of body lotion is～4.5, shows that it contains acetate and sodium acetate is 1: 1 damping fluid.Adopt standard method of test to measure the shrinkage temperature of described neutral skin, find that it typically is 60 ℃.Then, 5% salts solution that in described cylinder, adds PNP T (50g) and other 50%.Seal described cylinder, and manually shake to make its content homogenizing fast.Observe a kind of spumescence three-phase system, it is similar to the system that the tanner obtains when adopting kerosene that wet pelt is carried out degreasing.Described glass jar and content thereof then overturn 24 hours under room temperature in described paint can mixing tank.After this, stop upset.From cylinder, take out described fur.It has hard/plentiful feel, and its thickness is measured as 1.8 millimeters, represents the filling capacity that described tanning is handled.Estimating and measure the shrinkage temperature of fur after handling, is 93 ℃.This high shrinkage temperature shows that PNPT is converted into a kind of stable leather with fur, thereby has confirmed the tanning ability of PNP T.Described leather then cuts into 2 equal portions.Adopt usual means, portion is cutd open 2 thin slices into the 0.9 millimeter thickness that equates along its plane.Do not run into glued and the irregular problem of operation.Described 3 leathers are carried out dry air.Each all has white/opaque color, is softish very, all is the aesthetic complete pleasant that, and shows that they have good being used for and produce potentiality as footwear and ornament furnishings and so on commodity.Above-mentioned exhausted two-phase owse is analyzed as follows, to measure the residual volume of described PNP tanning agent.It is put in 250 milliliters of separating funnels, collect top loop hexanone layer.With the deionized water wash of equivalent once, to remove residual acetic acid.Use anhydrous magnesium sulfate drying then.Get an aliquots containig (20G.) of this pimelinketone solution, dry in being heated to 60 ℃ baking oven.Residue weight is 1g.Adopt HPLC that this resistates is analyzed, determine that it is mainly natural animal grease/fat.Therefore, PNP T 100% is absorbed by described fur basically.
Embodiment 11-B 100% solid polyurethane binder
Be prepared as follows the premixture of PNP dispersion, monomer and initiator:
PNP (85BA/15HEA, 10nm particle, 15% acetone soln) 1000g
Butyl acrylate 255g
Hydroxyethyl acrylate 45g
Two (tertiary butyl) superoxide 5.7g
Described mixture under 250C and 3500psi, according to the described program of EP1010706, stands polymeric reaction condition in a tubular reactor.Product solution in the acetone carries out stripping in a wiped film evaporator, to obtain 10nm PNP polyvalent alcohol 100% " solid " dispersion in described oligomer polyol " solvent ".Resulting polyhydric alcohol composition can be used to substitute conventional polyether glycol, polyester polyol or the acrylic polyol in 2 parts of polymeric polyisocyanate cure adhesives or the coating.Expect that resulting coating composition has lower viscosity than reference frame before coating, and because the reinforced effects of described PNP provides improved intensity after curing.
Embodiment 11-C has the coating composition of the thickening effectiveness of raising
The viscosity of 5 pools to be provided in order feeding water, to need the ACRYSOL RM-825 (associative thickener, Rohm and Haas Company) of 2wt%.Only needing the mean diameter that contains 50wt%RM-825 solid and 50wt% of adding 0.2wt% in water is the mixture of the PNP (40%BA, 40%MMA and 10 Viscoat 295s) of 4nm, just can obtain the viscosity of 5 pools.Except having efficiently in aqueous formulation, mixture of the present invention has very low susceptibility for the change of described aqueous formulation.
PNP described in embodiment 12 following tables is by the synthetic method described in the universal program of embodiment 1-4, (contains having surface active monomer FOr SiMonomer) MEK (15-21% solid) in prepare.
The PNP monomeric unit is formed, weight %
PNP OFPMA MATS BA MMA TMPTMA Granular size, average
12-a 5 51 34 10 5.2nm
12-b 10 48 32 10 5.9nm
12-c 20 70 10 3.7nm
12-d 30 60 10 4.6nm
Polymeric film is by making PARALOID B-82 (a kind of low acid acrylic acid resinoid that contains, can obtain by Rohmand Haas Company) mix with these each PNP that is dispersed among the MEK, dilute with MEK or acetone, and on base material curtain coating and drying and forming-film and prepare formation.Surfactivity F on described film surface and the distribution of Si, (it adopts VG-XPS to measure) is recorded in the following table.
Film # PNP#/thinner F or the Si weight % in total coating Form (weight %) at the atom that film surface records
F O C Si
12-A Nothing/MEK (contrast) 0.000 0.0 37.9 62.1 0.0
12-B 12-a/MEK 0.025 2.4 35.2 62.4 0.0
12-C 12-b/MEK 0.051 6.1 33.9 60.0 0.0
12-D 12-c/MEK 0.101 14.3 29.1 56.6 0.0
12-E 12-d/MEK 0.034 0.0 35.4 62.1 2.5
12-F Nothing/acetone (contrast) 0.000 0.0 37.9 62.1 0.0
12-G 12-a/ acetone 0.025 2.7 36.1 61.2 0.0
12-H 12-b/ acetone 0.051 4.2 36.1 59.7 0.0
12-I 12-c/ acetone 0.101 11.1 32.3 56.6 0.0
12-J 12-d/ acetone 0.034 0.0 35.3 62.2 2.5
Result in this table shows, the surface concn of active element and the surface concn of described PNP are evenly distributed in desired concentration in whole film matrix according to described PNP, exceed a lot.
Embodiment 13 testing films stop the performance of algal grown
The film of the MEK dilution film of preparation embodiment 12 on slide glass, and be suspended in 4 ounces of glass jars that 90ml growth medium (algal grown fresh water medium derives from Carolina Biological Supply Company) is housed.Described growth medium is inoculated with the not clear green algal cultures that 10ml takes from the fish jar.In the test formerly, described algae proof has very strong adhesive capacity for untreated slide glass.Described film is cultivated in～150RPM, 30 ℃, impeller under illumination (F20W T12CW).The observed value of algal grown covers percentage ratio with area and represents, record once continues to observe for three weeks weekly.Growth medium upgrades termly, so that provide fresh nutrient for described algae.Described slide glass is placed in second cylinder subsequently, and under light other five weeks of vigorous stirring.Measure the area percent that is covered by algae of each film, and be reported in the following table.
Derive from the film of embodiment 12 The weight % of F in PNP Film is by algae area coverage %
Exposure duration/week
1 2 3 4 5 6 7 8
12-A Contrast (0.000%) 0 0 0 5 7.5 15 50 50
12-B 0.025％ 0 0 0 10 15 15 20 25
12-C 0.051％ 0 0 0 5 5 10 10 20
12-D 0.101％ 0 0 0 10 10 15 20 25
The result shows in the table, has the film of surfactivity PNP, does not have the base material polymer of described PNP, has the ability that stronger resistant is decreased.
Embodiment 14PNP is that (15-21% solid) prepares in the MEK with surface active monomer (monomer that contains F or Si) and acidiferous monomer (MAA or AA) as shown in the table.
Embodiment The PNP monomeric unit is formed, weight % Granular size is average
OFPMA MATS BA MMA MAA AA TMPTMA
A 10 42 28 10 10 5.1nm
B 10 42 28 10 10 5.0nm
C 30 50 10 10 4.2nm
D 30 50 10 10 23.8nm
The PNP of embodiment 15. embodiment 14 with do not contain acid acrylic acid polymer coating prescription and mix, be convenient to follow-up PEO grafted and have the coating of the acidic site that is concentrated in coatingsurface to provide, still, they do not have water sensitivity.The PNP of embodiment 14 mixes with PARALOID B-82 (Rohm andHaas Company) according to the composition shown in the following table.
Coating composition # PNP# B-82 (g) PNP (g) MEK (g) The weight ratio of PNP/B-82, wt% (s/s) Theoretical microequivalent COOH/ slide glass
15-A 14-A 12 1 10 3.26 2.44
15-B 14-B 12 1 10 3.26 4.29
15-C 14-C 12 1 10 3.26 3.65
15-D 14-D 12 1.3 10 3.19 4.24
Every kind of coating composition (15-A ,-B ,-C and-D) be coated on two slide glasss with the 25mil wet thickness.Dry air is after a couple of days, is placed in the big furnace pot that fills PEO solution by the slide glass that described film is covered, and carries out grafting with one in every group of slide glass, and described PEO solution composition is as follows:
Deionized water 90g
PEO 3350 10g 2990μM
TEA 18.1mg 179μM
Imide 30.6mg 160μM
Adopt a large amount of excessive PEO and～11 times of excessive imide.Reaction was carried out 1 hour, afterwards, and slide glass rinsing 1.5 hours in the mobile deionized water, then other 1.5 hours of rinsing in the immobilized deionized water.After the dry air of a few hours, they are placed in the room temperature vacuum drying oven spend the night.Described PEO grafted and grafting contrast coating not according to the testing method of embodiment 13, are tested the performance of anti-algal grown.After all around, each film is because the area percent that algal grown is capped is 0-10%.
Embodiment 16-27 is used for the PNP of letex polymerization
Embodiment 16: the PNP of methyl methacrylate/methacrylic acid/Viscoat 295 (70/20/10wt%) is to be prepared from via following solution polymerization: assemble thermopair, thermoswitch, Purge gas inlet on 5 liters of reactors, have water-cooled reflux condenser, agitator and the monomer feed pipeline of purified gas outlet.Add the monomer mixture (A) of 450.00g in an isolating container, it is made up of 315.00g methyl methacrylate (MMA), 90.00g methacrylic acid (MAA) and 45.00g Viscoat 295 (TMPTA).Add initiator mixture (B) in an other container, it is made up of petroleum spirit (Triganox125-C75) solution and the 112.50g Virahol of the 75% peroxide PIVALIC ACID CRUDE (25) tert-pentyl ester of 18.00g.The 2325.00g Virahol is fed in the described reactor.Using the nitrogen purging reactor after about 30 minutes, heating makes described reactor content be warmed up to 79 ℃.When reactor content reaches 79 ℃, the dual raw material of described monomer mixture (A) and described initiator mixture (B) is joined in the described reactor.Described two kinds of mixtures adopt fresh feed pump in 120 minutes, charging equably.After adding described monomer and initiator raw material, described material was kept 30 minutes at 79 ℃, add three parts of first parts of appending initiator then, this appends initiator and is made up of the solution and the 22.50g Virahol of the petroleum spirit (Triganox 125-C75) of 9.00g 75% peroxide PIVALIC ACID CRUDE (25) tert-pentyl ester.Second part of interpolation of appending initiator carried out after first part is appended the initiator interpolation in 30 minutes.Similarly, the interpolation that last portion appends initiator is to carry out after second part is appended 30 minutes that initiator adds.The polymerization temperature that described material is followed at 79 ℃ continues other 2.5 hours, so that monomer is all transformed.After insulation finishes, 50% the NH of described material by 42.5g 4The mixture that the OH aqueous solution and 450.00g water are formed neutralizes.Polymers soln after the neutralization is transferred in the rotatory evaporator, under full chamber vacuum (full house vacuum) in～35 ℃ of stripping solvents.After removing whole solvents, it is～40% that described material water further is diluted to polymkeric substance content in water.Particle size determination is～5.0nm.Resulting water-based PNP dispersion can be used as the stablizer of emulsion polymerization.
Embodiment 17: the 295.3g deionized water is joined one dispose in side arm, condenser, agitator and thermopair 2 liters, 4 neck round-bottomed flasks.Then, in described round-bottomed flask, add in 160.6g (effective concentration 51.6% in the water) ammonia and the acrylic PNP that crosses, pH is 8-9 (70MMA/20MAA/10TMPTA, particle size makes according to embodiment 16 less than 10nm-), and uses used as stabilizers.Content in the described flask is heated to 85C under nitrogen purging, add the monomer mixture of 6.8g then, and this mixture is made up of the thiohydracrylic acid butyl ester of vinylformic acid (2-ethylhexyl) ester of 145.9g vinylbenzene, 185.7g and 0.35g.After described flask adds the 6.8g monomer mixture, in described flask, add ammonium persulfate solution (the 0.33g ammonium persulphate is dissolved in the 3g secondary ions water (di-ionized water)) immediately, the content in the described flask was kept 15 minutes at 85C.After keeping 15 minutes, other a ammonium persulfate solution (the 1.0g ammonium persulphate is dissolved in the 17.8g water) is joined in the flask, and the monomer mixture of remainder was joined in the flask with 150 minutes., a kind of ammonium persulphate is advanced section's solution (the 1.2g ammonium persulphate is dissolved in the 29.9g water) altogether added in the described flask in the time of 60 minutes in described monomer mixture charge with 120 minutes.In the time of 140 minutes, temperature of reaction is elevated to 87C in described monomer mixture charge.After described monomer mixture charge was finished, the content in the described flask kept under 87C other 60 minutes.Afterwards, cool off content in the described flask, and filter by the stacked screen cloth group of 100/325 purpose to 25C, obtain can the amount of ignoring the polymkeric substance that condenses.The solids content of resultant filtering emulsion polymeric product is 48.1%, and pH is 8.3, and particle size is 700nm, and viscosity is 1340cps.
Embodiment 18-27: the PNP in being listed in the table below is according to the described methods preparation of embodiment 17, and is used among the emulsion polymerization by embodiment 16 is described.Adopt the different PNP that form, cause the difference of the latex and the improvement aspect of performance that they show of different particle sizes.Resulting emulsion polymer, compare with the comparable emulsion polymer that does not have these PNP to make, can be used to prepare the coating of rheology, stability, water tolerance, block resistance, temperature resistant encapsulation and/or anti-dirt retention with the improved pitch time of painting, gloss, needs.
PNP table as emulsion stabilizer
Embodiment Form Particle size (nm)
17 70MMA/20MAA/10TMPTA 10
18 80MMA/10AA/10TMPTA 10
19 75MMA/20AA/5ALMA 8
20 35MMA/35BA/20AA/10TMPTA 8
21 30MMA/30BA/30AA/10TMPAT 10
22 60BA/30AA/10TMPTA 10
23 20MMA/402-EHA/30AA/10TMPTA 10
24 30Sty/30MMA/20AA/10TMPTA/10AAEM 10
25 70MMA/20PEM/10TMPTA 15
26 20BA/60AA/20TMPTA 15
27 80AA/20TMPTA 20

Claims (10)

1. one kind is improved coating, comprise: coating composition and mean diameter are the crosslinked polymer nano granules of 2-8 nanometer, wherein said polymer nano granules contains the unit as at least a polyenoid key unsaturated monomer of being derived from of at least 10 weight % of polymerized unit, with at least a copolymerization units, this copolymerization units stems from least a in the following monomer: contain monomer to the aldehyde active group, promote exsiccant monomer, surface active monomer and acidiferous monomer, described promotion exsiccant monomer to be selected to contain the amino ethylenically unsaturated monomer of at least one alkalescence; Described surface active monomer is selected from fluoromonomers, silicon-containing monomer and the monomer that contains poly-(oxyalkylene); Described acidiferous monomer is selected from vinylformic acid and methacrylic acid monomer.
2. the described improvement coating of claim 1, wherein said coating is to be in fluid state.
3. one kind provides the method for improving coating, may further comprise the steps:
Forming mean diameter is the crosslinked polymer nano granules of 2-8 nanometer, and described crosslinked polymer nano granules contains at least a polyenoid key unsaturated monomer as polymerized unit;
Form a kind of coating composition that contains described crosslinked polymer nano granules; With
At least a poly-(oxyalkylene) molecule of grafting on the exsiccant coating,
Wherein said crosslinked polymer nano granules comprises (a) derived from one of at least at least a copolymerization units in the following monomer: contain the monomer to the active group of aldehyde; Be selected from the promotion exsiccant monomer that contains the amino ethylenically unsaturated monomer of at least one alkalescence; Be selected from fluoromonomers, silicon-containing monomer and contain poly-(oxyalkylene) monomeric surface active monomer; With at least a copolymerization units derived from least a acidiferous monomer that is selected from vinylformic acid and methacrylic acid monomer; (b) derived from least a copolymerization units of at least a surface active monomer, described surface active monomer is selected from fluoromonomers, silicon-containing monomer and contains the monomer of poly-(oxyalkylene); (c) derived from least a copolymerization units of at least a acid mono.
4. the described method of improving coating that provides of claim 3, further comprising the steps of:
Be coated with described coating composition to base material; With
Dry described coating composition.
5. method that forms polymeric dispersions may further comprise the steps:
Forming mean diameter is the crosslinked polymer nano granules of 2-8 nanometer, and described crosslinked polymer nano granules contains at least a polyenoid key unsaturated monomer as polymerized unit;
A kind of reaction mixture is provided, and it contains described crosslinked polymer nano granules and at least a ethylene linkage unsaturated monomer; With
Make described reaction mixture stand at least a body, solution, gas phase, emulsion, corpuscle emulsion, microemulsion or suspension polymerization condition.
6. the method for the described formation polymeric dispersions of claim 5 wherein makes before described mixture stands polymerizing condition, and described crosslinked polymer nano granules is dispersed in and contains among the water.
7. crosslinked polymer nano granules, the polymerized unit that comprises at least a polyenoid key unsaturated monomer and at least a surface active monomer, described surface active monomer is selected from fluoromonomers, silicon-containing monomer and contains the monomer of poly-(oxyalkylene), and the mean diameter of described crosslinked polymer nano granules is the 2-8 nanometer.
8. polymer complex comprises:
Mean diameter is the crosslinked polymer nano granules of 2-8 nanometer, and described crosslinked polymer nano granules contains at least a polyenoid key unsaturated monomer as polymerized unit; With
Contain the polymkeric substance of at least a ethylene linkage unsaturated monomer as polymerized unit.
9. one kind provides the method for improving coating, may further comprise the steps:
Forming mean diameter is the crosslinked polymer nano granules of 2-8 nanometer, and described crosslinked polymer nano granules comprises at least a polyenoid key unsaturated monomer as polymerized unit; With
Formation comprises the coating composition of described crosslinked polymer nano granules.
10. improved coating, comprise that coating composition and mean diameter are the crosslinked polymer nano granules of 2-8 nanometer, described crosslinked polymer nano granules comprises at least a polyenoid key unsaturated monomer as polymerized unit, wherein said crosslinked polymer nano granules comprises at least a copolymerization units as polymerized unit, and this copolymerization units is derived from the acidiferous monomer that is selected from vinylformic acid and methacrylic acid monomer.
CN 02142585 2001-03-30 2002-03-29 Improved coating and coating composition Expired - Fee Related CN1246405C (en)

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