CN1204662A - Single-component system based on coreactive polymers resulting in coatings which can be crosslinked at low temperature and their application in field of coatings - Google Patents
Single-component system based on coreactive polymers resulting in coatings which can be crosslinked at low temperature and their application in field of coatings Download PDFInfo
- Publication number
- CN1204662A CN1204662A CN 98102964 CN98102964A CN1204662A CN 1204662 A CN1204662 A CN 1204662A CN 98102964 CN98102964 CN 98102964 CN 98102964 A CN98102964 A CN 98102964A CN 1204662 A CN1204662 A CN 1204662A
- Authority
- CN
- China
- Prior art keywords
- monomer
- component system
- acrylamide
- weight
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 12
- 238000000576 coating method Methods 0.000 title claims description 11
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims abstract 6
- 239000000203 mixture Substances 0.000 claims description 43
- 239000000178 monomer Substances 0.000 claims description 35
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 17
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 11
- 239000003973 paint Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 6
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 claims description 4
- 125000006226 butoxyethyl group Chemical group 0.000 claims description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 4
- OPXLNXRRRDRHKG-UHFFFAOYSA-N C(CC(=O)C)(=O)OC.C(C(=C)C)(=O)O Chemical compound C(CC(=O)C)(=O)OC.C(C(=C)C)(=O)O OPXLNXRRRDRHKG-UHFFFAOYSA-N 0.000 claims description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000004753 textile Substances 0.000 claims description 3
- 239000002966 varnish Substances 0.000 claims description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 2
- JRIDTTRQXBIPKK-UHFFFAOYSA-N 2-methyl-n-(1,2,2-trimethoxyethyl)prop-2-enamide Chemical compound COC(OC)C(OC)NC(=O)C(C)=C JRIDTTRQXBIPKK-UHFFFAOYSA-N 0.000 claims description 2
- SRHUJGYCCSBDNR-UHFFFAOYSA-N C(#N)CC(=O)OCC.C(C=C)(=O)O Chemical compound C(#N)CC(=O)OCC.C(C=C)(=O)O SRHUJGYCCSBDNR-UHFFFAOYSA-N 0.000 claims description 2
- CSMCRYANOAOLJP-UHFFFAOYSA-N C(CC(=O)C)(=O)OC.C(=C)C(=O)O Chemical compound C(CC(=O)C)(=O)OC.C(=C)C(=O)O CSMCRYANOAOLJP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- KAEIFTQQDBDXIW-UHFFFAOYSA-N n-(1,2,2-trimethoxyethyl)prop-2-enamide Chemical compound COC(OC)C(OC)NC(=O)C=C KAEIFTQQDBDXIW-UHFFFAOYSA-N 0.000 claims description 2
- UMACUNWFNRWEOW-UHFFFAOYSA-N n-(1-hydroxy-2,2-dimethoxyethyl)-2-methylprop-2-enamide Chemical compound COC(OC)C(O)NC(=O)C(C)=C UMACUNWFNRWEOW-UHFFFAOYSA-N 0.000 claims description 2
- XWQDTJROXGIDKW-UHFFFAOYSA-N n-(1-hydroxy-2,2-dimethoxyethyl)prop-2-enamide Chemical compound COC(OC)C(O)NC(=O)C=C XWQDTJROXGIDKW-UHFFFAOYSA-N 0.000 claims description 2
- JEMGROUJSKACAT-UHFFFAOYSA-N n-(2,2-dibutoxy-1-hydroxyethyl)-2-methylprop-2-enamide Chemical compound CCCCOC(OCCCC)C(O)NC(=O)C(C)=C JEMGROUJSKACAT-UHFFFAOYSA-N 0.000 claims description 2
- ZCDKYXHHLCGQPT-UHFFFAOYSA-N n-(2,2-dibutoxy-1-hydroxyethyl)prop-2-enamide Chemical compound CCCCOC(OCCCC)C(O)NC(=O)C=C ZCDKYXHHLCGQPT-UHFFFAOYSA-N 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims 1
- 239000004815 dispersion polymer Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000839 emulsion Substances 0.000 abstract description 6
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- 239000004816 latex Substances 0.000 description 33
- 229920000126 latex Polymers 0.000 description 33
- 238000004132 cross linking Methods 0.000 description 10
- 238000007046 ethoxylation reaction Methods 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 238000007669 thermal treatment Methods 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 150000001299 aldehydes Chemical group 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- 206010013786 Dry skin Diseases 0.000 description 4
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000010985 leather Substances 0.000 description 3
- -1 papermaking Substances 0.000 description 3
- 229920006324 polyoxymethylene Polymers 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 150000001241 acetals Chemical group 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 229940075933 dithionate Drugs 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 238000005502 peroxidation Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a single-component system, which can be stably stored and comprises at least two common reactivity polymers which can low-temperature curable. The polymers are produced by polymerizing free radicals in water emulsion, and one of the polymers comprises aldehyde functional groups or masked aldehyde functional groups, another polymer comprises acetoacetic acid ethyl functional groups. The invention also relates to crosslinked films obtained by the method and used as coat.
Description
The present invention relates to be called as the waterborne compositions of latex, but said composition stable storing and comprise the coreactivity polymkeric substance of the film that can produce crosslinked at low temperature.The invention still further relates to the application of the crosslinkable film that obtains from described latex and these crosslinkable films in paint field.
These compositions can be used for coatings industry, especially can be used for paint, tackiness agent, papermaking, leather or textile industry.
The film-forming composition that is used for above-mentioned industrial circle contains the latex as tackiness agent usually.In some cases, these compositions need carry out back crosslinked performance, especially solvent resistance and mechanical property with the improvement coating that obtained, and reduce tackiness.
This cross-linking stage can adapt with working conditions and Application Areas.
The back crosslinkedly usually can cause some problem, for example the degraded of yellowing and film or production cost is increased.
Yet the crosslinked existing description when low temperature or middle temperature especially is being used for the paint of building industry, and this class paint must be in room temperature and sometimes even be lower than under the room temperature and use.On the other hand, the coating that is used for timber or leather or industrial paints need bear temperature.
But the crosslinked system of low temperature or middle temperature is usually based on the combination of two components, and this system has been used the copolymerization functional monomer in the process of composite adhesives, and adds crosslinked multifunctional dose after synthetic or during use.
As an example, EP 552,469, EP 555,774 and EP 653,469 have described and have used by the crosslinked functional monomer based on the etheric acid ethyl of polymeric amide.On the other hand, EP 581,466 has described with the crosslinked identical functional monomer of polyacetals.
And DE 4,219, and 384 have described and carry out crosslinked with azanol to the functionalized polymkeric substance of diacetone-acryloamide(DAA).US 5,468,800 and DE 4,439,457 described and carried out crosslinked to the polymkeric substance that contains urea/ureido functional group by polyacetals or polyacetal.
The main drawback of these systems is that latex adds the linking agent small molecules normally in the solution after synthetic to.Because these bulks of molecule and the partition ratio between water and organic phase (polymkeric substance), they can permeate in the polymkeric substance, cause precrosslink, and therefore make the storage of composition become difficult or even possible.Certainly, can add linking agent in use, but can make operation complicated more and cost is increased like this.
The problem that the present invention attempts to solve is to seek a kind of single-component system thus, and this system stable storing also can be by crosslinked at low temperature.
Our company has had been found that a kind of solution, promptly develops a kind of at least two kinds of polymkeric substance stabilized aqueous composition of (being called as the coreaction tackiness agent) that contains, and described polymkeric substance reacts at low temperature, when coalescent.
Composition of the present invention contains at least two kinds of functionalized tackiness agents, can mix after every kind of tackiness agent is synthetic, do not react between the functional group of carrying by one or another kind of tackiness agent in the storage process, and produce crosslinked film in low temperature or room temperature agglomeration process or after coalescent.
This combination of finding polymkeric substance is not conspicuous, only be not enough to during coalescent or after coalescent, just to react each other as above-mentioned functional group, because these functional groups must not react between the shelf lives, and its crosslinked kinetics must not disturbed the formation of the coalescent and film of particulate.
According to the present invention, the separately synthetic of these two kinds of functionalized polymkeric substance makes every kind of functional group obtain the good preservation of most probable, because polymerization temperature is usually greater than room temperature, let alone greater than the temperature of reaction of two kinds of tackiness agents.
But theme of the present invention is a kind of like this single-component system of the coreactivity polymkeric substance based on crosslinked at low temperature.Described system is made of the mixture of two kinds of adhesive dispersion at least, and every kind of adhesive dispersion obtains by letex polymerization in the aqueous medium of monomer composition.
Described tackiness agent is that the particle form of 50-500nm is disperseed with the mean diameter.
Particle of the present invention contains:
The adhesive A of the aldehyde functional group that has aldehyde functional group or shelter of-98-2%, preferred 95-5%;
The tackiness agent B that has etheric acid ethyl functional group of-98-2%, preferred 5-95%;
-0-50% at least a neither with adhesive A reaction also not with the adhesive C of tackiness agent B reaction.
Adhesive A is a kind of polymkeric substance that contains following composition:
At least a monomer A l that has the precursor group of aldehyde functional group or acetal functional group or aldehyde functional group of-0.5-10% (weight), preferred 1-8%;
At least a monomer that is selected from group I of 90-99.5% (weight), preferred 92-99%.
Monomer A l can be selected from aldehydes, as the aldehyde of propenal, Methylacrylaldehyde, formyl radical vinylbenzene, crotonic aldehyde and general formula I:
And the aldehyde of sheltering of general formula I I:
At general formula (I) with (II):
-R
1Represent hydrogen atom or methyl;
-R
2And R
3Be identical, represent C separately
1-C
8Alkyl, otherwise formation-CH together just
2-CR
4R
5-(CH
2)
n-group, n=0 or 1 in the base, R
4And R
5Can be identical or different, represent hydrogen atom or methyl separately;
-E represents O, NH or NR ＇ (R ＇=C
1-C
4Alkyl);
-G represents C
1-C
4Alkylidene residue or following residue:
R wherein
6Represent hydrogen atom or C
1-C
4Alkyl residue.
Preferred monomer A l is selected from:
-N-(2,2-dialkoxy-1-hydroxyethyl)-(methyl) acrylamide and N-(1,2,2-tri-alkoxy ethyl) (methyl) acrylamide, alkoxyl group one speech refers to C
1-C
4Alkoxyl group, for example:
N-(2,2-dimethoxy-1-hydroxyethyl) acrylamide;
N-(2,2-dimethoxy-1-hydroxyethyl)-Methacrylamide;
N-(1,2,2-trimethoxy ethyl) acrylamide;
N-(1,2,2-trimethoxy ethyl) Methacrylamide;
N-(2,2-dibutoxy-1-hydroxyethyl) acrylamide;
N-(2,2-dibutoxy-1-hydroxyethyl) Methacrylamide;
N-(1,2,2-three butoxyethyl group) acrylamide;
N-(1,2,2-three butoxyethyl group) Methacrylamide;
-4-acrylamido butyraldehyde dimethyl or diethyl acetal;
-methacrylamido acetaldehyde dimethylacetal;
-vinylformic acid diethoxy propyl ester;
-methacrylic acid diethoxy propyl ester;
-acryloyl oxopropyl-1, the 3-dioxolane;
-methacryloyl oxopropyl-1, the 3-dioxolane; And
-N-(1,1-dimethoxy fourth-4-yl) Methacrylamide.
According to advantageous manner of the present invention, Al is N-(2, a 2-dimethoxy-1-hydroxyethyl) acrylamide, is called Highlink DMH.
Group I is one group of neutral monomer, and this monomer can carry out polymerization by free radical method in the water-based emulsion that contains (methyl) vinylformic acid, vinylbenzene, vinyl etc.
Tackiness agent B is the polymkeric substance that contains following composition:
At least a monomers B 1 that contains etheric acid ethyl functional group of-0.1-10% (weight), preferred 1-8% (weight);
At least a monomer that is selected from group I of-90-99.9%, preferred 92-99%.
B1 is selected from the ethylenically unsaturated monomer that contains at least one etheric acid ethyl functional group.That can mention has these monomers:
-(methyl) vinylformic acid methyl aceto acetate;
-(methyl) vinylformic acid 2-ethyl cyanacetate;
-N-(2-etheric acid ethyl) (methyl) acrylamide;
-N-(2-acetyl acetamide ethyl) (methyl) acrylamide.
According to advantageous manner of the present invention, B1 is the methacrylic acid methyl aceto acetate, and this paper is referred to as AAEM later on.
Latex C contains at least a polymer of monomers that is selected from group I.
Every kind of tackiness agent is prepared separately according to emulsion polymerization technology known to a person of ordinary skill in the art.Therefore, preferably under inert atmosphere, when having radical initiator to exist, react.The initiator system that uses can be oxidation-reduction system, for example Na
2S
2O
8, (NH
4)
2S
2O
8/ Na
2S
2O
5, Na
2SO
3Or thermal initiation system, for example (NH
4)
2S
2O
8In the monomer total amount, the amount of employed initiator is 0.2-1.0% (weight), preferred 0.25-0.5% (weight).
According to the character of employed initiator system, emulsion polymerization of the present invention carries out under 65-85 ℃ temperature: for the oxidation-reduction system based on peroxidation dithionate and metabisulphite, temperature of reaction is 65-75 ℃; Based on the thermal initiation system of peroxidation dithionate, temperature of reaction is 70-85 ℃ for separately.
Dispersion of the present invention preferably makes according to the method for semi continuous, and this method can limit the drift that various monomers are taken place in composition because of reactive difference.In 3 hours 30 minutes to 5 hours time, monomeric introducing is usually to constitute the form of preemulsion with portion water and part surface promoting agent and to carry out.Although optional, it also is useful making the monomer of 1-15% become seed.The emulsification system that uses in the emulsion polymerization of the present invention is to select in the emulsifying agent scope with suitable hydrophilic value.Preferred system is made of the mixture of anion surfactant and nonionogenic tenside, the nonyl phenol vitriol of described anion surfactant such as sodium lauryl sulphate, ethoxylation, especially contain the aliphatic alcohol sulfate of nonyl phenol vitriol, dodecylbenzene sulfonate and ethoxylation of the ethoxylation of 20-25mol oxyethane, the nonyl phenol of described nonionogenic tenside such as ethoxylation, especially contain the nonyl phenol of ethoxylation of 10-40mol oxyethane and the Fatty Alcohol(C12-C14 and C12-C18) of ethoxylation.
In amount of monomer, the total amount of emulsifying agent is usually in the scope of 1-5% (weight), preferred 2-4% (weight).
Dispersion mixture of the present invention at room temperature makes.
Then, every kind of dispersion is analyzed, especially analyzed in the performance of 160 ℃ of other thermal treatments after 15 minutes to the performance of the film that obtained after the drying at room temperature and to identical film.
The performance of the film of being assessed is the mechanical property of solvent resistance and film, by measure under the room temperature in acetone dipping after 24 hours in the specimen percentage ratio (being called swelling index) of the percentage ratio of insolubles and the acetone that absorbed by the same test sample measure the solvent resistance of film, the mechanical property by the stretching test measurement film (determining rupture stress and the elongation when destroying).
The crosslinking degree of film and its excellent application performance can characterize by the amount of high as far as possible insolubles, alap swelling index and high as far as possible rupture stress and elongation at rupture.
It is crosslinked that the performance that the performance of the film that obtains by mixing is better than parent latex shows that the film in agglomeration process at room temperature exists, and the existence of the heat cross-linking of film will handle by comparative heat before and after the performance of mould be verified.
Under situation of the present invention, by the functionalized latex of the monomer that has acetal functional group (DMH) with will produce normal temperature crosslinked by mixing of the functionalized latex of the monomer that has etheric acid ethyl functional group (AAEM) and have the film that improves performance thus.
By being determined at 60 ℃ of performances that stored the film that 10 days mixture obtains, and the performance of the film that obtains with the mixture that newly makes compares, check latex mixture good preservation stability and prepare the possibility of single-component system thus.Also can check the stability of latex by the fundamental characteristics (being granular size, viscosity etc.) of monitoring latex.
Under situation of the present invention, the mixture before the thermal treatment and the performance of the film that obtains at the mixture of 160 ℃ of thermal treatments after 15 minutes are identical, no matter what kind of latex mixture carried out and handle (new system mixture or at 60 ℃ of mixtures of handling 10 days), this mixture has all showed good preservation stability.
The invention still further relates to the composition that is used to constitute crosslinkable coating, for example at the paint in building industry field, the varnish that is used for leather or finish paint, be used for the finish paint of textiles or be used for the protective varnish of timber, described composition be characterised in that it contain as defined above, as the coreactivity latex system of tackiness agent.
Following examples have been described the present invention, right rather than limiting the scope of the invention.In these embodiments, unless otherwise noted, described umber and per-cent are weight part and weight percent.
Synthesizing of embodiment 1 tackiness agent
Usually according to the semi-continuous polymerzation method, by add initiator solution and pre-emulsion and composite adhesives simultaneously and separately in the container bed material that is preheating to 75 ℃ (temperature of measuring in the reactor), reactor is equipped with circulating hot water, central stirrer and the condenser that is present in the sleeve pipe.
Some synthesizes in buffer medium and carries out, and in this case, introduces sodium bicarbonate in pre-emulsion.
The container bed material
54.00 parts in water
The aqueous solution 0.25 of the sodium alkyl sulfate of 32% ethoxylation
The aqueous solution 0.05 pre-emulsion of the Fatty Alcohol(C12-C14 and C12-C18) of 65% ethoxylation
Water 62.00
The aqueous solution 2.25 of the sodium alkyl sulfate of 32% ethoxylation
The aqueous solution 0.45 of the Fatty Alcohol(C12-C14 and C12-C18) of 65% ethoxylation
Monomer 100.00 initiator solutions
Water 6.00
Sodium Persulfate 0.30
Described consumption all uses the umber of active substance to represent.
Reaction process:
The container bed material is incorporated in the reactor, stirs evenly and be heated to 75 ℃.
When the temperature of container bed material reaches 75 ℃, in 4 hours, add pre-emulsion and initiator.
Mixture reacted 1 hour at 75 ℃ again.
With the mixture cool to room temperature, and filter by 100 microns filter cloth.
The performance of synthetic latex:
The performance of the synthetic product that obtains is as follows:
| Monomer | A | B |
| Ethyl propenoate AAEM Highlink DMH | 98 2 - | 98 - 2 |
| Solid content (%) pH diameter (nm) viscosity (mPas) | 44．3 2．0 112 225 | 43．8 3．2 149 ＜100 |
The methacrylic acid methyl aceto acetate is sold by Eastmann company.
Highlink DMH is sold by Hoechst company with the form of 50% the aqueous solution.
The cross-linking properties of embodiment 2 film crosslinked and that obtain by base-material latex
The percentage ratio (swelling index) (measuring 3 times mean value) of amount by measuring dipping insolubles in the specimen after 24 hours in acetone and the acetone that is absorbed is determined in the precrosslink degree of the every kind of latex film that obtains after 23 ℃ of dryings with through crosslinking degree after the heat of the film that 160 ℃ of thermal treatments obtained after 15 minutes again after the above-mentioned drying.
Specimen is of a size of 10 * 25mm, and thickness is between 1-2mm.
| Parameter | A | B |
| Swelling index (23 ℃) swelling index (160 ℃) | 4 40．4 | 4 6．8 |
| % insolubles (23 ℃) % insolubles (160 ℃) | 0 72．0 | 0 95．1 |
Latex A and latex B all do not have precrosslink, and the heat back cross-linking properties that latex A shows is low, and latex B shows excellent heat cross-linking performance.
Embodiment 3 coreactivity latex mixtures
The performance of known base-material latex, the various mixtures of preparation latex A and latex B under the room temperature, the film that is produced by these mixtures is drying under 23 ℃, the condition of 50%RH, and then 160 ℃ of thermal treatments after 15 minutes, its performance is carried out above-mentioned check.
| The mixture numbering | Latex A% | Latex B% | SI (25℃)％ | SI(160℃)％ | % insolubles (25 ℃) % | % insolubles (160 ℃) % |
| 1 | 100 | 0 | 4 | 40．4 | 0 | 72．0 |
| 2 | 75 | 25 | 29．5 | 21．1 | 77．7 | 78．5 |
| 3 | 55 | 45 | 24．3 | 12．6 | 78．2 | 84．5 |
| 4 | 50 | 50 | 35．2 | 11．8 | 71．3 | 84．2 |
| 5 | 25 | 75 | 18．4 | 10．5 | 85．5 | 91．4 |
| 6 | 0 | 100 | 4 | 6．8 | 0 | 95．1 |
The crosslinking degree that the film that the mixture of two kinds of latex produces shows is greater than the crosslinking degree of parent latex, reflected to have crosslinked under the room temperature.This crosslinked can being improved by thermal treatment.
Embodiment 4 mechanical propertys
According to iso standard 527, by tension test, the mechanical property of the film that will be obtained by mixture No.3 and the mechanical property of latex A and B compare.
| Film | 23 ℃ of dryings of elongation at rupture (%) | 23 ℃ of dryings of rupture stress (Mpa) | Destroy sharp long (%) 160 ℃ of thermal treatments | 160 ℃ of thermal treatments of rupture stress (Mpa) |
| A | 1800 | 0．14 | 820 | 0．24 |
| B | 1100 | 1．2 | 442 | 1．22 |
| Mixture No.3 | 1360 | 1．64 | 1060 | 2．4 |
The rupture stress of mixture has confirmed the crosslinking reaction under the low temperature much larger than the rupture stress of base-material latex.
Embodiment 5 stability in storagies
Mixture No.4 was placed 10 days at 60 ℃, then cool to room temperature.As stated above this latex is made new film 23 ℃ of dryings, the film that the anti-acetone before and after this film thermal treatment and new system mixture are obtained compares.
| Film | SI(23℃) | SI(160℃) | % insolubles (23 ℃) | % insolubles (160 ℃) |
| Mixture No.4 | 35．2 | 11．8 | 71．3 | 84．2 |
| Mixture No.4 (10 days 60 ℃) | 25．2 | 13．7 | 82．4 | 89．0 |
Latex is equal in the performance of the film that the performance of the film of 60 ℃ of accelerated deteriorations after 10 days obtains with new system latex basically.
Claims (9)
- Claims1. but based on the single-component system of the coreactivity aqueous polymer dispersion of the coating that can produce crosslinked at low temperature, described polymkeric substance is equivalent to the 10-30% (weight) of single-component system, and it is distributed in the polymer A of the aldehyde functional group that has aldehyde functional group or shelter of following scope :-2-98%, preferred 5-95% (weight); The polymer B that has etheric acid ethyl functional group of-2-98%, preferred 5-95% (weight);-0-50% (weight) neither with polymer A reaction also not with the polymkeric substance C of polymer B reaction, described polymkeric substance C is obtained by at least a monomer polymerization that is selected from group I, and the monomer of group I is made of neutral monomer and contains (methyl) acrylate, vinyl monomer, vinylbenzene and their derivative.
- 2. the single-component system of claim 1, wherein polymer A is obtained by letex polymerization by following monomeric mixture: the monomer A l of at least a aldehyde functional group that has aldehyde functional group or shelter of-0.5-10% (weight), preferred 1-8%; At least a monomer that is selected from group I of 90-99.5% (weight), preferred 92-99%.
- 3. claim 1 or 2 single-component system, wherein monomer A l is selected from :-N-(2,2-dialkoxy-1-hydroxyethyl)-(methyl) acrylamide and N-(1,2,2-tri-alkoxy ethyl) (methyl) acrylamide, alkoxyl group one speech refers to C 1-C 4Alkoxyl group, for example: N-(2,2-dimethoxy-1-hydroxyethyl) acrylamide; N-(2,2-dimethoxy-1-hydroxyethyl)-Methacrylamide; N-(1,2,2-trimethoxy ethyl) acrylamide; N-(1,2,2-trimethoxy ethyl) Methacrylamide; N-(2,2-dibutoxy-1-hydroxyethyl) acrylamide; N-(2,2-dibutoxy-1-hydroxyethyl) Methacrylamide; N-(1,2,2-three butoxyethyl group) acrylamide; N-(1,2,2-three butoxyethyl group) Methacrylamide;-4-acrylamido butyraldehyde dimethyl or diethyl acetal;-methacrylamido acetaldehyde dimethylacetal;-vinylformic acid diethoxy propyl ester;-methacrylic acid diethoxy propyl ester;-acryloyl oxopropyl-1, the 3-dioxolane;-methacryloyl oxopropyl-1, the 3-dioxolane; And-N-(1,1-dimethoxy fourth-4-yl) Methacrylamide.
- 4. the single-component system of claim 3, monomer A l wherein is N-(2, a 2-dimethoxy-1-hydroxyethyl) acrylamide.
- 5. the single-component system one of among the claim 1-4, wherein polymer B is to be obtained by aqueous emulsion polymerization by following monomeric mixture, and described monomer contains: at least a monomers B 1 that contains etheric acid ethyl functional group of-0.5-10% (weight), preferred 1-8% (weight); At least a monomer that is selected from group I of-90-99.5% (weight), preferred 92-99%.
- 6. the single-component system of claim 5, wherein monomers B 1 is selected from :-(methyl) vinylformic acid methyl aceto acetate;-(methyl) vinylformic acid 2-ethyl cyanacetate;-N-(2-etheric acid ethyl) (methyl) acrylamide;-N-(2-acetyl acetamide ethyl) (methyl) acrylamide.
- 7. the single-component system of claim 6, wherein B1 is the methacrylic acid methyl aceto acetate.
- 8. the single-component system one of among the claim 1-7 is characterized in that the coreactivity polymkeric substance is that the particle form of 50-500nm is disperseed with the diameter.
- 9. constitute the crosslinked film of coating, this coating is used for the processing of paper, timber or textiles as paint, varnish, finish paint or tackiness agent, and wherein this film can be obtained by coalescent by the single-component system of claim 1-8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98102964 CN1204662A (en) | 1997-04-29 | 1998-04-24 | Single-component system based on coreactive polymers resulting in coatings which can be crosslinked at low temperature and their application in field of coatings |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9705271 | 1997-04-29 | ||
| CN 98102964 CN1204662A (en) | 1997-04-29 | 1998-04-24 | Single-component system based on coreactive polymers resulting in coatings which can be crosslinked at low temperature and their application in field of coatings |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1204662A true CN1204662A (en) | 1999-01-13 |
Family
ID=5217660
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98102964 Pending CN1204662A (en) | 1997-04-29 | 1998-04-24 | Single-component system based on coreactive polymers resulting in coatings which can be crosslinked at low temperature and their application in field of coatings |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1204662A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100396741C (en) * | 2003-12-17 | 2008-06-25 | 陈良 | Resin composition for low-volatility aqueous paint and method for preparing same |
| CN101903416A (en) * | 2007-12-21 | 2010-12-01 | 巴斯夫欧洲公司 | Aqueous polymer dispersion, its preparation method and its use |
-
1998
- 1998-04-24 CN CN 98102964 patent/CN1204662A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100396741C (en) * | 2003-12-17 | 2008-06-25 | 陈良 | Resin composition for low-volatility aqueous paint and method for preparing same |
| CN101903416A (en) * | 2007-12-21 | 2010-12-01 | 巴斯夫欧洲公司 | Aqueous polymer dispersion, its preparation method and its use |
| CN101903416B (en) * | 2007-12-21 | 2015-01-14 | 巴斯夫欧洲公司 | Aqueous polymer dispersions and method for the production and use thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1062285C (en) | water resistant composition | |
| CN1021053C (en) | Method for preparing aqueous polymer emulsion in presence of hydroxyethyl fiber with improved hydrophobicity | |
| CN1124286C (en) | Process for the preparation of emulsions based on vinyl acetate resins, and aqueous adhesives | |
| CN1047782C (en) | Thermoset covering compsn. | |
| CN1117068A (en) | Emulsion adhesives | |
| CN1234060A (en) | Use of polymer dispersions as binding agents for sealing compounds and coating compound | |
| FR2497811A1 (en) | AQUEOUS DISPERSIONS OF POLYMERS AND THEIR APPLICATION IN PARTICULAR AS COATING COMPOSITIONS | |
| CN1137053A (en) | Water-dispersible powder composition for water resistant coatings | |
| CN87106519A (en) | Aqueous coating composition and method for coating a substrate | |
| CN1493601A (en) | A water-emulsion type fluorine-containing water and oil repellent agent and preparation method thereof | |
| JPS60221410A (en) | Surface modification of polymeric material | |
| RU2319717C1 (en) | Composition based on copolymer of terafluoroethylene and perfluoroalkyl vinyl ethers | |
| CN1394921A (en) | Water-proof composition and method capable of retaining active composition | |
| CN1132520A (en) | Aqueous polymer preparations | |
| JP3191978B2 (en) | Aqueous resin composition | |
| KR20010015684A (en) | Scrub resistant latexes | |
| CN111808228A (en) | Hyperbranched polyethyleneimine doped acrylic emulsion and preparation method thereof | |
| CN1204662A (en) | Single-component system based on coreactive polymers resulting in coatings which can be crosslinked at low temperature and their application in field of coatings | |
| CN1720223A (en) | Stabilised compositions containing polyfunctional aziridine compounds as hardening constituents | |
| JPH08100035A (en) | Water-base emulsion and its production | |
| JPH08134308A (en) | Aqueous emulsion and its production | |
| JP3029707B2 (en) | Curable resin composition | |
| JPH061928A (en) | Cationic micro-emulsion composition and its production | |
| CN1344419A (en) | Water miscible liquid polymer composition | |
| JP7129481B2 (en) | Aqueous dispersion, method for producing the same, coating composition and coating film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |