CN1580165A - High temperature resistance anticorrosive polyolefin composition and its use - Google Patents
High temperature resistance anticorrosive polyolefin composition and its use Download PDFInfo
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- CN1580165A CN1580165A CN 03150344 CN03150344A CN1580165A CN 1580165 A CN1580165 A CN 1580165A CN 03150344 CN03150344 CN 03150344 CN 03150344 A CN03150344 A CN 03150344A CN 1580165 A CN1580165 A CN 1580165A
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 45
- 239000000203 mixture Substances 0.000 title claims description 38
- 238000000576 coating method Methods 0.000 claims abstract description 76
- 239000011248 coating agent Substances 0.000 claims abstract description 72
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000002844 melting Methods 0.000 claims abstract description 26
- 230000008018 melting Effects 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 17
- 229920002521 macromolecule Polymers 0.000 claims abstract description 8
- 238000010285 flame spraying Methods 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 54
- 239000000463 material Substances 0.000 claims description 46
- -1 polypropylene Polymers 0.000 claims description 36
- 229920000573 polyethylene Polymers 0.000 claims description 34
- 239000004698 Polyethylene Substances 0.000 claims description 28
- 229910000077 silane Inorganic materials 0.000 claims description 27
- 239000004743 Polypropylene Substances 0.000 claims description 12
- 229920001155 polypropylene Polymers 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 10
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 9
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
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- 238000001175 rotational moulding Methods 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 239000000049 pigment Substances 0.000 claims description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
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- 239000004677 Nylon Substances 0.000 claims description 3
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- 239000011521 glass Substances 0.000 claims description 3
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 3
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- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
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- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
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- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 235000010215 titanium dioxide Nutrition 0.000 claims description 3
- 239000010456 wollastonite Substances 0.000 claims description 3
- 229910052882 wollastonite Inorganic materials 0.000 claims description 3
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- 238000012360 testing method Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
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- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 3
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- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
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- 229910000831 Steel Inorganic materials 0.000 description 2
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 238000012856 packing Methods 0.000 description 2
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- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- CXURGFRDGROIKG-UHFFFAOYSA-N 3,3-bis(chloromethyl)oxetane Chemical compound ClCC1(CCl)COC1 CXURGFRDGROIKG-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
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- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000011074 autoclave method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- ZZHNUBIHHLQNHX-UHFFFAOYSA-N butoxysilane Chemical class CCCCO[SiH3] ZZHNUBIHHLQNHX-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
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- 230000007423 decrease Effects 0.000 description 1
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- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
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- VXHFNALHLRWIIU-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)OC(=O)C(C)(C)C VXHFNALHLRWIIU-UHFFFAOYSA-N 0.000 description 1
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- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates dusty combination of polyolefin that can be able to bear high temperature and antisepticise. The application in the coating area is also given. This combination contains 1,50wt%-98.95wt% silicane cross linking with polyolefin. 2, 0.5wt%-50wt% polar macromolecule. 3, 0.5wt%-50wt% others macromolecule. 4, 0.5wt%-10wt% filling. The polyolefin combination can be used to shape anticorrosion coating at the bottom of the metal in the methods of rolling mold, fluidized bed method, electrostatic, blast flame spraying or melting.
Description
[technical field]
The present invention relates to poly-polyolefin compositions of a kind of high-temperature resistant anti-corrosive and uses thereof.More specifically, the present invention relates to a kind of graft polyolefin composition of high-temperature resistant anti-corrosive and in the purposes of coatings art.
[background technology]
Plastics are because its superior unreactiveness and other good comprehensive performances have obtained extensive application in the protection against corrosion field.Plastics have following application in anticorrosion engineering: plastics anticorrosion structure material, plastic apparatus (comprising various towers, storage tank, basin, reactor, plating tank, heat exchanger etc.), tubing system, plastic lining, plastic coating.The present invention just relates to use polyethylene dedicated modified materials and the using method thereof of making plastic coating.
Material with making coatings at first need be ground into powder; be equipped with suitable filler, flow agent, pigment etc.; adopt rotation-formed method such as rotational moulding or various spraying method evenly to be coated in nonmetallic surfaces such as metallic surface such as iron and steel or concrete, as the protective layer of base material.
Nowadays the plastic powders that uses on market has various thermoplastics powder and thermosetting resin powder.Wherein thermoplastic powder mainly contains common polythene powder, polypropylene powder, polyamide powder, ethylene/acrylic acid or ethylene/methacrylic acid (EAA, EMAA) powder, ethylene/vinyl acetate multipolymer (EVA) powder, penton powder, polyphenylene sulfide (PPS) powder; The thermosetting resin powder coating has epoxy powder, polyester powder, acrylic clear powder, epoxy/polyester powder etc.
Polyethylene coating has superior corrosion resistance, pharmaceutical chemicalss such as anti-non-oxidizing acid (example hydrochloric acid, dilute sulphuric acid), alkaline-resisting, salt tolerant class, the performance of anti-polar organic matter (alcohol, ketone); At room temperature anti-common solvent.But polyethylene coating non-refractory, the maximum operation (service) temperature of new LDPE (film grade) are 60 ℃, and the high density polyethylene(HDPE) maximum operation (service) temperature also can only reach 70 ℃.Polyethylene coating is the corrosion of concentrated sulfuric acid resistant, concentrated nitric acid and other strong oxidizer not, and bad mechanical strength is not wear-resisting, and weathering resistance is also not enough.Polyethylene powders generally all uses new LDPE (film grade), because the melt viscosity of new LDPE (film grade) is low, and good fluidity, the easier levelling of coating, and also the coating stress cracking is little.
The mesh network that forms behind the polyethylene crosslinking has improved high and low temperature resistance, resistance to chemical attack, the ESCR of material, has therefore obtained widespread use in fields such as wire cable insulating, cold and hot water pipelines.The production of crosslinked polyethylene has cross-linking radiation, peroxide crosslinking, crosslinked with silicane.Consider when using making coatings, crosslinked should occur in coating and form after, be silane cross-linking method so the present invention adopts.The preparation method of typical organosilane crosslinked polyethylene has the two-step approach of DOWCORNLING, and is open in US3646155; The single stage method of MAILLEFER, open in US4117195.Two kinds of methods have been widely used in the production of cross-linked polyethylene pipe, electric wire.But the crosslinked polyethylene that is applied to coating does not still have relevant patent and product.Polyethylene is nonpolar polymer, puts forth effort not by force with covering of substrate such as metal, and therefore the coating that forms easily comes off, and the nook of especially large-scale product is because the difference of Thermal Contraction Coefficient often forms defectives such as hole.Therefore in US6455630, disclosed in the powder of polyethylene etc. and added powder such as a certain amount of modified with polar polyethylene, polypropylene.
Therefore in view of above situation,, need a kind of high temperature resistant and be able to bear strong corrosion and the coated powder of good adhesion arranged with metal base in coatings art.
[summary of the invention]
The corrosion protection coating polyolefin compositions that the purpose of this invention is to provide a kind of ability acid with strong oxidizing property such as the vitriol oil, concentrated nitric acid;
Another object of the present invention provides the corrosion protection coating polyolefin compositions of a kind of at high temperature (more than 80 degrees centigrade) anti-strong acid, highly basic, salt, organic solvent;
A further object of the present invention provides and can improve and the good polyolefin compositions of metal base adhesion effect.
In order to achieve the above object, provide following composition:
Silane graft polyolefin: 50～98.95% (weight percents)
The preparation method is: by the polyethylene of 100 weight parts or based on polyethylene with other the mixture of polyolefine material such as polypropylene, polystyrene, ethylene vinyl acetate, 0.1～5 weight part silane, 0.01～0.5 weight part radical initiator is extruded acquisition by frit reaction in twin screw or single screw extruder.
Polarity polymer: 0.5～50%
Such material can be maleic anhydride grafted polyethylene, acrylic acid-grafted polyethylene, chlorinatedpolyethylene, ethylene vinyl acetate, ethylene acrylic acid co polymer etc. or their mixture.
Other family macromolecule: 0.5～50%
Such material can be common polythene, polypropylene, polystyrene, polyvinyl chloride, nylon, polyester etc.
Filler: 0.05～10%
Such material can be glass microsphere, titanium dioxide, lime carbonate, talcum powder, wollastonite, silicon-dioxide, barium sulfate etc.
Other relevant auxiliary agent such as oxidation inhibitor, ultraviolet screening agent etc.
And other relevant pigment etc., can add as required.
The polyolefin compositions that the present invention relates to is applicable to that rotational moulding method, fluidized bed process, electrostatic spraying, flame spraying, hot meltblown etc. form the high-temperature resistant anti-corrosive coating in the metallic surface.
Polyolefin compositions of the present invention, gel fraction more can not be taken at below 10% below 15% before being used to be coated with formable layer, can be taken at below 5%.After forming coating, full cross-linked reaction back gel fraction is 30%～80% in 90 ℃ hot water.
The macromolecular material that is adapted to coating need have good flowability, could guarantee that like this material can form the bright and clean smooth of surface at the abundant levelling of substrate surfaces such as metal in molten state.An index that characterizes the melt fluidity of macromolecular material is exactly a melting index.In disclosed various patents about crosslinked polyethylene, or in the actual production, the melting index of organosilane crosslinked polyethylene material is less, this is because material mainly is used as hot-water line or CABLE MATERIALS, therefore when selecting polyethylene, need consider other physical and mechanical properties of material, less than 1g/min, the melting index of the silane grafted material in CN1195673 among the disclosed embodiment is also less than 1 as the melting index of silane grafted material among the disclosed embodiment in US3075948.So low melting index is not suitable for coating processing.Therefore among the present invention by add melting index big and with the silane grafted polyethylene consistency preferably macromolecular material improve the melt fluidity of whole composition, make its melting index more than 1g/min, preferably more than 2g/min, more preferably more than 3g/min.
The common polythene powder is owing to be nonpolar polymer, and a little less than the bonding force of metallic coating, the coating of formation easily comes off, under the especially long-time situation about using.As nooks such as containers, easier because thermal contraction forms the hole.After polyethylene coating damages, because coating and matrix surface are the state of peeling off, there is gas, during repairing, when gases are heated, they expand is overflowed by coating, makes coating have pore.Silane grafted polyethylene issues unboiled water in the effect of water and separates the formation hydroxyl, can further react the formation crosslinking structure between these hydroxyls, and unreacted oh group can good adhering to take place with the substrate of metal isopolarity.The present invention has simultaneously also adopted the sticking power of substrates such as further adding polarity polymer raising and metal, though this polarity polymer can react with the hydroxyl that forms after the organosilane crosslinked polyethylene hydrolysis, finally can reach certain degree of crosslinking but a certain amount of polarity polymer adds material, not influence the erosion resistance of coating.
The graft polyolefin composition need be advised the order into 60-200, preferably at the 80-200 order through grinding to granularity is the processing that 40-200 purpose powder just can be applied to coating.The thickness of granularity have influence on powder feeding in the spraying evenly or the levelling of the coating of rotational moulding etc., coating fine and closely woven, thin more powder is then processed easy more, and the fusion plastification of powder is abundant more, the minimum zero defect coat-thickness that is easy to get more, meticulous powder also causes loss of powder easily certainly.The configuration of surface of powder also has influence on the homogeneity of powder feeding, in the process of lapping of material, because frictional heat, the material deliquescing deforms on shear direction easily, and length-to-diameter ratio is excessive, powder is not spherical, twines easily between the powder to cause the flowability of powder poor.The employing cooled with liquid nitrogen is ground, and plastics become fragile then that the fineness and the mode of appearance of powder can both be improved under the condition of deep cooling.
The matrix polyethylene that is used for graft polyolefin of the present invention is various high density polyethylene(HDPE)s, new LDPE (film grade), linear low density polyethylene or their mixture.
High density polyethylene(HDPE) be low, in or use various catalyzer under the high pressure, as Zieglar type catalyzer with based on the catalyzer of chromium, with various polymerization processs, the ethene polymers that makes as vapour phase polymerization, letex polymerization and suspension polymerization.
New LDPE (film grade) is meant with tubular process method or autoclave method, the ethene polymers that makes by the high-pressure free radical polymerization.
Preferably, polyolefin compositions of the present invention be melting index more than 1g/10min, preferable more than 2g/10min, preferably select more than the 3g/10min.
Being used for organic unsaturated silane of the present invention is the compound that general formula R R ' SiY2 represents, wherein R is a univalent unsaturated hydrocarbon radical, and Y is hydrolyzable organic group, and R ' is the monovalence alkyl of non-aliphatic unsaturated hydrocarbon base, and perhaps R ' is identical with Y.
The preferred organic unsaturated silane that uses is identical with Y and be expressed as those compounds of general formula R SiY3 for R ' wherein, vinyltrimethoxy silane for example, vinyltriethoxysilane, vinyl three butoxy silanes, allyltrimethoxysilanis and allyltriethoxysilane.With respect to 100 parts of polyolefinic weight, the consumption of the silane of adding is 0.1～5 weight part, preferred 0.7～3 weight part.When this amount less than 0.1 the time, can not take place enough crosslinked; When it surpassed 5 weight parts, precrosslink was excessive, the coating defectiveness of formation, and also cost is too high.
Being used for radical initiator of the present invention can be various organo-peroxides and peresters, dicumyl peroxide for example, di-t-butyl peroxide, tertiary butyl sec.-propyl superoxide, dibenzoyl peroxide, 2,5-dibutyl-2, two (dual-tert-butyl peroxide) hexanes of 5-, the peroxidation trimethylacetic acid tert-butyl ester and peroxidation-two-thylhexoic acid tert-butyl ester.With respect to 100 parts of poly weight, the amount of the radical initiator of adding is 0.01～0.5 weight part, preferred 0.05～0.2 weight part.When this measured less than 0.01 weight part, the crosslinked with silicane reaction was carried out insufficiently; When it surpassed 0.5 weight part, directly excessive by the degree of crosslinking of its generation, the surface appearance of coating was also bad.
The preparation process of silane grafted polyethylene all is fully aware of for the engineering staff who is familiar with the plastics field, is disclosing in a large amount of patents about the production method of this grafted material.Here it is pointed out that in this patent in the grafting process, can add other polyolefine material, can improve melting index as polyacrylic adding to adjust the correlated performance of material.Strict restriction is wanted in the precrosslink that is used for the silane graft polyolefin material of coating, and the melting index of grafted material will improve as far as possible, therefore want entering of strict restriction water in producing, raw material will carry out drying before adding twin screw extruder, polyethylene should select melting index bigger, the melting index of preferably controlling silane graft polyolefin material is more than 1g/10min, preferable at 2g/10min, optimum more than 3g/10min, the gel fraction of silane graft polyolefin more can be taken at below 10% below 15%, and is best below 5%, material has good flowability in the time of could guaranteeing like this to form coating, and coating is smooth, fine and close.
Among the present invention, the polar macromolecule material that adds will have good consistency with the silane graft polyolefin, and desirable have maleic anhydride grafted polyethylene, acrylic acid-grafted polyethylene, chlorinatedpolyethylene, ethylene vinyl acetate, ethylene acrylic acid co polymer etc. or their mixture.The introducing of polar macromolecule material forms its polar group of back and metal base has good adhesive power in coating on the one hand, and the polar group water absorbing capacity impels moisture to be deep into material internal on the other hand, impels the hydrolysis of silane graft polyolefin.Preferred polarity polymer has maleic anhydride grafted polyethylene, ethylene acrylic acid co polymer melting index to select more than 6.Polarity polymer add-on can account between 0.5～50% (weight ratio) of whole composition, preferably between 0.5～30% (weight ratio), most preferably between 0.5～20% (weight ratio).
The adding of other family macromolecule is the flowability of adjustable material on the one hand, second can regulate other mechanical and physical performance of material such as snappiness, hardness etc., such material that can add is more as common polythene, polypropylene, polystyrene, polyvinyl chloride, nylon, polyester etc.
The adding of other inorganic powder filler such as glass microsphere, titanium dioxide, lime carbonate, talcum powder, wollastonite, silicon-dioxide, barium sulfate etc. also can improve the performance of material, its consumption can add suitable consumption according to different needs between 0.02～10%, more can be taken between 0.05～5%.
An amount of adding of pigment, other functional agent is conspicuous for being familiar with the person skilled in art, but be pointed out that here, pigment etc. should be dry and should not be contained the material that can react with organosilane crosslinked polyethylene, could guarantee like this in the processing of said composition stores, to keep stable, not crosslinked in advance.
According to the present invention, the preparation process the first step of said composition powder is the production of silane graft polyolefin, adopting general twin screw extruder or single screw extrusion machine melt blending to extrude pelletizing gets final product, the silane graft polyolefin pellet that obtains can carry out the polymeric powder, filler after the crushing screening classification is pulverized with other then etc. and carry out the mechanical-physical blend, technology such as also silane grafted polyethylene material and certain other component such as other macromolecular material etc. can be carried out that the twin screw extruder melt blending is pulverized again again.Mechanical blending, melt blending can suitably be selected according to the different of material.
The composition powder that obtains according to the present invention adopts before use every wet packing, could eliminate in the storage engineering crosslinked owing to the material of the effect generation of airborne moisture like this.
According to the present invention, said composition is applicable to rotational moulding method, fluidized bed process, electrostatic spraying, flame spraying, hot meltblown etc. and forms the high-temperature resistant anti-corrosive coating at substrate surfaces such as metals.
[embodiment]
Following examples are used to illustrate the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
Get 100 parts 80 order silane graft polyolefins, make as follows: 100 parts polyethylene (swallowization 18D, melting index 7.0g/10min, 190 ℃, 2.16kg), 0.1 portion dicumyl peroxide, 2 parts of vinyltriethoxysilanes obtain silane grafted polyethylene material (melting index, gel fraction see Table) by double-screw melt blending, with 5 parts of maleic anhydride grafted polyethylene (percentage of grafting 0.8%, melting index 6g/10min), and 5 parts of polypropene blended extruding pelletizations, get 80 order powder by liquid nitrogen cryogenics pulverizer crushing and classification then; 2 part of 1250 order talcum powder.Mechanical blending.
Embodiment 2
100 parts of example one described silane graft polyolefins, 10 parts of maleic anhydride grafted polyethylenes (percentage of grafting 0.8%, melting index 6g/10min), 5 parts of polypropylene carry out the melt blending extruding pelletization, carry out the pulverize at low temperature classification then and get 80 order powder, add 2 part of 1250 order talcum powder, technology is with example 1 thereafter.Test result sees Table.
Embodiment 3
100 parts of example one described silane graft polyolefins, 5 parts of maleic anhydride grafted polyethylene (percentage of grafting 0.8%, melting index 6g/10min), 5 parts of high density polyethylene(HDPE)s, carry out the melt blending extruding pelletization, carry out the pulverize at low temperature classification then and get 80 order powder, add 2 part of 1250 order talcum powder, technology is with example 1 thereafter.Test result sees Table.
Embodiment 4
100 parts of example one described silane graft polyolefins, 10 parts of maleic anhydride grafted polyethylene (percentage of grafting 0.8%, melting index 6g/10min), 5 parts of high density polyethylene(HDPE)s, carry out the melt blending extruding pelletization, carry out the pulverize at low temperature classification then and get 80 order powder, add 2 part of 1250 order talcum powder, technology is with example 1 thereafter.Test result sees Table.
Embodiment 5
100 parts of silane graft polyolefins, make as follows: 100 parts of polyethylene (swallowization 18D, melting index 7.0g/10min, 190 ℃, 2.16kg), 20 parts of polypropylene, 0.1 portion dicumyl peroxide, 2 parts of vinyltriethoxysilanes obtain silane grafted polyethylene material (melting index by double-screw melt blending, gel fraction sees Table), 10 parts of maleic anhydride grafted polyethylene (percentage of grafting 0.8%, melting index 6g/10min), 5 parts of polypropylenes carry out the melt blending extruding pelletization, carry out the pulverize at low temperature classification then and get 80 order powder, add 2 part of 1250 order talcum powder, technology is with example 1 thereafter.Test result sees Table.
Comparative example:
Directly polyolefine used in the example 1 is carried out the pulverize at low temperature classification gets 80 order powder, adds 2 part of 1250 order talcum powder mechanical blending.Carry out flame plating according to example 1 method then, flame plating technology is suitably regulated, and mainly is that pre-heating temperature decreases.The performance test results sees Table.
The product that obtains in the foregoing description is made the thick soft steel test specimen of 0.5cm as substrate, and sandblasting is carried out to degree of cleaning Sa2.5, roughness R in the surface
z20～40 μ m adopt the pre-heat extraction of oxygen/acetylene torch powder spraying system (FS-4 type, Wuhan Inst. of Material Protection) surface moisture; spraying, plasticizing, powder feeding gas is pressurized air, pressure 0.4Mpa; powder feed rate 3～5kg/h, it is thick to form the fine and close continuously about 0.5mm of coating.The test specimen that has sprayed carries out performance test after room temperature after the cooling is placed a week.The results are shown in Table.
Adopt the flame plating technology of general common polythene: workpiece surface pre-treatment, workpiece surface preheating, priming operation, plastic-blasting, plasticizing, coating aftertreatment, coating check.Workpiece surface passes through oil removing, goes pre-treatment such as embroidery and sandblast, has increased surface-area, can improve the defective that bonding strength reduces coating.The purpose of priming operation generally is to improve the bonding strength of coating and matrix surface, and the crosslinked polyethylene among the present invention can be without priming operation.Workpiece surface need preheat to certain temperature, mainly is in order to remove surperficial moisture and other gas, to make molten plastic soak into matrix surface fully, and improves the levelling of melted powder.Pre-warmed temperature can not be too high, and too high temperature material can decompose, the coating yellowing, and the preheating temperature that this invention is adopted should be no more than 120 ℃ about 100 ℃, can adopt infrared rays tester rapid detection.After preheating temperature reaches, spray, spray distance should be moderate, and the flow of combustion-supporting gas, combustion gas, shielding gas, powder feeding is regulated, to obtain smooth slick coating.In spraying, with plastic spraying gum to fully the fusing or the coatingsurface of levelling heat, make it fusing, levelling.Coating after the spraying is carried out naturally cooling and is handled, and being cooled to that room temperature is qualified after testing must the finished product.
Above-mentioned the invention will be further described with flame spraying, and embodiment only plays a part to further specify, rather than limits the present invention by any way, more is not that said composition is limited in the flame plating field.In addition, product among the present invention is acted on metal base with rotation-formed method of rotational moulding and dip-coating method, also obtained very good effect.
The present invention relates to following concrete Performance Detection:
Outward appearance adopts appearance method, and whether observation plastic coating surface has crackle, pin hole, peels off with matrix, bubbling, leakage spray and surperficial yellowing coking etc., and whether the surface smooth smooth, solid colour.
Coating adhesion is handled adherometer column cap and coating adhesive face to degree of cleaning Sa2.5, roughness R with reference to ASTMC633 and GB/T5210-85
z20～40 μ m put into baking oven and are heated to 220 ℃, take out column cap, sandblast face is immersed the 3990EMAA of Du Pont powder, be stained with one deck EMAA, put into baking oven plasticizing 30 seconds then, be placed on coatingsurface to be measured behind the sandblast face of the treating EMAA powder smelting levelling, add the 330g briquetting on the column cap.After treating that column cap cools off fully, detect coating adhesion with Elcometer108 type hydraulic pressure adherometer.
The accurate weighing 0.3g of the mensuration of degree of crosslinking is dry, and sample encases with 100 order copper mesh, at 130 ℃ of extraction 6h that conflux, takes out the sample bag with dimethylbenzene, and vacuum-drying is calculated as follows gel content (gel%) to constant weight
gel％＝[W1-(W2-W3)]/W1×100
W1 is the quality of sample in the copper mesh of packing in the formula, W2 for extraction before sample and copper mesh heavy amount, W3 for extraction after sample and copper mesh heavy amount.
Melt index determination is pressed ASTMD1238-98 test, 190 ℃ of test conditions, 2.16kg.
Effect compares:
| 1 | 2 | 3 | 4 | 5 | Comparative example 1 | |
| Grafts melting index (k/10min) | 4.3 | 4.3 | 4.3 | 4.3 | 5.6 | 7.0 |
| The grafts gel fraction | 5％ | 5％ | 5％ | 5％ | 3.6％ | 0 |
| The coating gel fraction | 65％ | 58％ | 63％ | 56％ | 50％ | 0 |
| Outward appearance | Coating is smooth, neat, smooth | Coating is smooth, neat, smooth | Coating is smooth, neat, smooth | Coating is smooth, neat, smooth | Coating is smooth, neat, smooth | Coating is smooth, neat, smooth |
| Sticking power Mpa | 6.02 | 6.32 | 6.18 | 6.45 | 6.72 | 3.50 |
| Medium-resistance: | ||||||
| 98% sulfuric acid (7 days, 23 ℃) | Coating is intact | Coating is intact | Coating is intact | Coating is intact | Coating is intact | The coating yellowing, surface irregularity |
| 40% sulfuric acid (7 days, 85 ℃) | Coating is intact | Coating is intact | Coating is intact | Coating is intact | Coating is intact | Breakdown of coating, acid accumulator penetration is serious to metallic corrosion |
| 40% sulfuric acid (7 days, 23 ℃) | Coating is intact | Coating is intact | Coating is intact | Coating is intact | Coating is intact | Coating is intact |
Other conversion of the present invention and improvement, for reading this area of the present invention ordinary skill, it is conspicuous falling, though, above the present invention is described in detail with a general description of the specific embodiments, but on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, not departing from the these modifications or improvements basically of spirit of the present invention, all belong to the scope of protection of present invention.
Claims (10)
1. the polyolefin compositions of a high-temperature resistant anti-corrosive comprises:
(1) the silane graft polyolefin of 50-98.95wt%;
(2) the polarity polymer of 0.5-50wt%;
(3) other family macromolecule of 0.5-50wt%;
(4) the inorganic powder filler of 0.05-30wt%;
Wherein, described other family macromolecule is selected from common polythene, polypropylene, polystyrene, polyvinyl chloride, nylon or polyester; The melting index of said composition is more than 1g/10min.
2. according to the polyolefin compositions of claim 1, wherein the melting index of polyolefin compositions is more than 1g/10min, preferably more than 3g/10min.
3. according to the polyolefin compositions of claim 1, wherein said silane cross-linked polyolefin preparation method is: be the mixture of polyolefine materials such as main body and other polypropylene, polystyrene, ethylene vinyl acetate by the polyethylene of 100 weight parts or with the polyethylene, 0.1～5 weight part silane, 0.01～0.5 weight part radical initiator is extruded acquisition by frit reaction in twin screw extruder or single screw extrusion machine.
4. according to the polyolefin compositions of claim 3, wherein said radical initiator is selected from various organo-peroxides or peresters.
5. according to the polyolefin compositions of claim 1, wherein said polarity polymer is selected from maleic anhydride grafted polyethylene, the maleic anhydride grafted polypropylene that rubs, acrylic acid-grafted polyethylene, acrylic acid-grafted polypropylene, chlorinatedpolyethylene, ethylene vinyl acetate, ethylene acrylic acid co polymer or their mixture.
6. according to each polyolefin compositions among the claim 1-2, wherein said inorganic powder filler is selected from glass microsphere, titanium dioxide, lime carbonate, talcum powder, wollastonite, silicon-dioxide or barium sulfate.
7. according to the polyolefin compositions of claim 1, also comprise oxidation inhibitor, ultraviolet screening agent and pigment.
8. according to the polyolefin compositions of claim 1, be not used to be coated with the preceding gel fraction of formable layer, more can be taken at below 10%, can be taken at below 5% below 15%.
According to the polyolefin compositions of claim 1 after forming coating in 90 ℃ hot water full cross-linked reaction afterwards gel fraction 30%～80%.
10. form the high-temperature resistant anti-corrosive coating according to each polyolefin compositions powder among the claim 1-9 in the metallic surface with rotational moulding method, fluidized bed process, electrostatic spraying, flame spraying, hot meltblown etc.
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