CN1082574A - Modified poly propylene powdered coating and preparation method - Google Patents
Modified poly propylene powdered coating and preparation method Download PDFInfo
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- CN1082574A CN1082574A CN 92109066 CN92109066A CN1082574A CN 1082574 A CN1082574 A CN 1082574A CN 92109066 CN92109066 CN 92109066 CN 92109066 A CN92109066 A CN 92109066A CN 1082574 A CN1082574 A CN 1082574A
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Abstract
A kind of modified poly propylene powdered coating that is used for the metal base coating contains (mass fraction) 65～95 crystal polypropylenes (A) with unsaturated carboxylic acid and acid anhydrides and organo-peroxide modification, 33～5 parts of polyethylene (B), 2～10 parts of blends that ethylene-alpha-olefin-non-conjugated diene hydrocarbon ter-polymer rubber (C) is formed.It is filmed and has excellent sticking power and high resistance to impact shock.It is anticorrosion to be used for chemical pipeline, pail pack, pond groove etc., and the protection and the decoration of automobile bicycle assembly parts, building net frame member, electric insulation device, net grid etc. also can be used for modified thermoplastic, improve the blending effect and the processing fluidity of each component.
Description
The present invention relates to a kind of modified poly propylene powdered coating and preparation method.In more detail, it is the blend of forming with polypropylene, polyethylene, ethylene-alpha-olefin-non-conjugated diene hydrocarbon ter-polymer rubber, after unsaturated carboxylic acid and acid anhydrides and organo-peroxide modification, make a kind of TPO powder coating that contains polarity carboxylic group, slight crosslinked and branch chain.It is mainly used in metallic conduit pipe fitting, chemical industry pail pack, the chemical industry pond groove etc. anticorrosion, the protection and the decoration of automobile bicycle part, family daily necessity, hardware tool handle, building net frame member, electric insulation device, net grid etc., it also can be used for blending effect and the processing fluidity that other thermoplastics of modification improves each component.
In plastics industry, particularly ripe with polyethylene and the polyacrylic technology of modified rubber, add rubber and improve its shock resistance effectively, add polyethylene and improve its processing fluidity.Bibliographical information is arranged, contain the blend of slight crosslinked ternary ethylene-propylene copolymer-polypropylene system, can make each component phase interface bonding force enhancing in the polypropylene blend that is modified, mechanical property significantly improves.
As everyone knows, use unsaturated carboxylic acid and acid anhydrides, particularly maleic acid, MALEIC ANHYDRIDE, acrylic acid-grafted polypropylene or polyethylene to be widely used in hot melt adhesive, can obtain the sticking power certain with metal.Yet use still can not reach the ideal adhesion effect as powder coating.
Japan publication JP59,202,845 disclose, with Resins, epoxy is bottom, is the middle layer with the polypropylene and the rubber blend of maleic anhydride modified, is the surface layer compound coating with Co-polypropylene, shock resistance, sticking power, high thermal resistance of coating etc. have been improved, but present method construction technology is comparatively complicated, only is suitable for the application of the workpiece of simple shape such as steel pipe etc.
Europe publication EP360,646 disclose, in the polypropylene of maleic anhydride modified, add ethylene-alpha-olefin copolymer, vinyl cycloalkane polymer and metal oxide or oxyhydroxide, making films has kept high sticking power, and still, its Vicat softening point only can reach 133 ℃, although because the existence of metal oxide or oxyhydroxide has improved adhesion effect, its elongation has been subjected to obvious influence.
The objective of the invention is to overcome above-mentioned deficiency of the prior art, a kind of blend powders resin that contains the modified polypropene of slight crosslinked and branch chain is provided, it can make the mixed effect of each component of blend improve greatly, guarantees higher mechanical properties.
Another object of the present invention is to the polarity carboxylic group is introduced each component in the blend simultaneously, particularly introduce ethylene-alpha-olefin-non-conjugated diene hydrocarbon copolymer, its sticking power of filming with metal is improved greatly.
Another purpose of the present invention is to make a kind of polyolefins powder paint, and it is filmed at aspects such as shock-resistance temperature tolerance, elongations all than more excellent, and has and decorate preferably and protection effect.
Modified polypropene blend as the coating use, be not only required in the degree of mixing that homogeneous is arranged in the atomic little scope, and consider that the unlikely levelling and the surperficial gloss of filming in the melting process that influences of slight crosslinked and branch chain in blend, modified poly propylene powdered coating of the present invention comprise and contain (mass fraction):
65～95 crystal polypropylenes (A)
33～5 parts of polyethylene (B)
2～10 parts of ethylene-alpha-olefin-non-conjugated diene hydrocarbon terpolymers (C)
Be grafted with (0.01～5) * 10 in the composition of the present invention
-4The carboxyl composition of mol/g.When content less than 0.01 * 10
-4The adhesion effect of filming during mol/g is poor, when greater than 5 * 10
-4Film coated surface unfairness glossiness is poor during mol/g, therefore, carboxyl-content must be controlled, its measuring method is a soluble modified above-mentioned composition blend in the dimethylbenzene that refluxes, adding KOH-methyl alcohol-dimethylbenzene standardized solution reacts under reflux state, using HCL-Virahol standardized solution residual titration then under the condition of heat, is indicator with phenolphthalein-ethanolic soln.
Contain slight crosslinked and branch chain composition in the modified poly propylene powdered coating constituent of the present invention.This composition produces under dynamic condition, and it is scattered in the blend system equably, is still keeping thermoplastic characteristics, and it has improved the mechanical property of blend effectively, can have a strong impact on film melt-flow levelling and glossiness if this composition is crossed at most.The principle of the present invention's control is that the melt flow rate (MFR) of blend does not have obvious decline after the modification.
Any and combination of unsaturated carboxylic acid that the present invention adopts and acid anhydrides as maleic acid, FUMARIC ACID TECH GRADE, vinylformic acid, MALEIC ANHYDRIDE etc., is preferably MALEIC ANHYDRIDE and vinylformic acid.
The organo-peroxide that the present invention adopts is a radical initiator, any and combination at 90～170 ℃ of transformation period organo-peroxide that is 1h, being preferably in 110～150 ℃ of transformation period is 1h, as benzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5 pair (tert-butyl peroxy base) hexane, lauroyl peroxide, peroxidation N-BUTYL ACETATE, peroxidized t-butyl perbenzoate, peroxidation (the 2 ethyl hexanoic acid tert-butyl ester) ditertiary butyl peroxide etc.
The crystalline polypropylene that the present invention adopts is the crystallization homo-polypropylene.Crystalline ethylene-propylene-based block copolymer.Any and combination of crystalline ethylene-random copolymer of propylene.Their melt flow rate (MFR) (MFR) is 3～50g/10min, is preferably 5～30g/10min.If MFR is less than 3, then the film coated surface levelling property is poor, when MFR greater than 50, the mechanical property of then filming is obviously not enough.If use its consumption of crystallization homo-polypropylene should be controlled at 65～85 parts, can obtain good comprehensive performances.If use the crystallinity ethylene-propylene copolymer, then its consumption should be controlled at 80～95 parts, and polyacrylic consumption can be decided according to the difference of its ethylene content, the then higher control of ethylene content height, and content is low then should to be controlled in lower limit.
The polyethylene that the present invention adopts is any and combination of high density polyethylene(HDPE), new LDPE (film grade), linear low density polyethylene, their melt flow rate (MFR) (MFR) is 3～50g/10min, be preferably 5～30g/10min, if MFR greater than 50, then makes the mechanical degradation of filming, if MFR is less than 3, then modified effect is not good, and the levelling property of filming is poor, and its usage quantity is 5～33 parts, can guarantee that ethylene total content is 10～35% according to the ethylene content in the propene polymer.
Ethylene-alpha-olefin-non-conjugated diene hydrocarbon ter-polymer rubber that the present invention adopts is a thermoplastic elastomer, therein ethylene, alhpa olefin is any ratio, alhpa olefin is the alkene such as the propylene of 3～8 carbon atoms, 1-butylene, the 1-amylene, the 1-hexene, the 1-heptene, any and combination of 1-octene and 1-decene, non-conjugated diene monomers content is 0.001～10%, operable diene monomers is 1, the 4-hexadiene, dicyclopentadiene, the vinylidene norbornylene, first is any and combination of norbornylene again, its Mooney viscosity of rubber is 10～100, is preferably 30～80.
Any and combination of the various additives that the present invention adds according to concrete purposes is as oxidation inhibitor, stablizer, pigment etc.Oxidation inhibitor as 1010, CA, 2246, DSTP, DLTP etc., stablizer such as UV-327, UV-531, triazine-5, carbon black, ZnO, TiO2 etc., pigment such as carbon black, phthalocyanine blue, phthalein viridescent, cadmium yellow etc.
The solvating agent that the present invention adopts is a boiling point greater than any and combination of 90 ℃ aromatic hydrocarbons and alkane as toluene, xylol, ethylbenzene, propyl benzene, mixing trimethylbenzene, and alkane such as heptane, octane, nonane and decane are preferably xylol.
Any and combination of the non-solvating agent that the present invention adopts as ethanol, acetone, methylethylketone and water etc., is preferably water.
Purpose of the present invention can reach by following measure, i.e. the preparation method of modified poly propylene powdered coating of the present invention.
In the there-necked flask that agitator and reflux exchanger are housed, add dimethylbenzene successively, polypropylene, polyethylene and ethylene-propylene-vinylidene norbornene terpolymer, dimethylbenzene: (polypropylene+polyethylene+vinylidene norbornene terpolymer)=1: (0.1～0.25) (weight ratio), stir, under the refluxing xylene state, dissolve 1～3h, add MALEIC ANHYDRIDE and dicumyl peroxide then and continue at reaction 1～3h under the refluxing xylene state, treat to add big water gaging stirring 1～2h under normal temperature behind the naturally cooling, it is centrifugal to put into whizzer, and filter cake moves in the kneader and adds additive and mediates.Mixture moves in the drying machine and carries out drying, sieves powder at last and promptly obtains modified poly propylene powdered coating of the present invention by 0.18mm sieve aperture (i.e. 80 orders).
The modified poly propylene powdered coating that the present invention makes, appearance luster basically identical, the full 0.18mm sieve aperture of crossing of loose nothing caking, melt flow rate (MFR) is 8.5g/10min, volatile content is less than 0.7% under the melt temperature, powder has excellent flowing, be suitable for various coating processs, construction technology is easy, is customer satisfaction system thermoplastic powder coating.
Its film coated surface of modified poly propylene powdered coating of the present invention is smooth smooth, have excellent decoration and protection effect, stripping strength is greater than 3.2KN/m, impact strength-40 is ℃ greater than 5J, yield tensile strength is 24MPa, elongation is 450%, and Vicat softening point is 140 ℃, and ball indentation hardness is 40MPa.
It films modified poly propylene powdered coating of the present invention and has good Corrosion Protection, 50% sulfuric acid of ability below 100 ℃, 40% sodium hydroxide, the corrosion of 36% hydrochloric acid and saturated sodium chloride solution, the erosion of organic solvents such as ability acetone, ethanol under the normal temperature.
The related Performance Detection standard of process of the present invention sees attached list 1.The specimen preparation condition is undertaken by relevant regulations in the standard, and the fluidized bed coating sample is by 240～280 ℃ of preheatings, and 5～20min plastifies 200 ± 5 ℃, and the condition of 30～60min is carried out.
Modified poly propylene powdered coating embodiment of the present invention is as follows:
Embodiment 1
In reactor, add dimethylbenzene (industrial goods) 550g, crystallization homo-polypropylene (A) [MFR is 8.8g/10min] 85g, new LDPE (film grade) (B) [MFR is 8.1g/10min] 10g, ethylene-propylene-vinylidene norbornene terpolymer (C) [mooney viscosity is 50] 5g, calorify dimethylbenzene and return dissolving 1h under the state, add MALEIC ANHYDRIDE 1.5g, dicumyl peroxide 0.16g, under the refluxing xylene state, stir 2h, be cooled to room temperature and add entry 500～1000g stirring 1h under normal temperature, filter again.
With filter cake and antioxidant 1010 0.5g, DSTP 0.4g, carbon black 0.5g moves in the kneader and mediates 15min in 2000rpm.Move into baking oven dry 4h under 80 ℃ and vacuum condition, sieve powder at last by the 0.18mm sieve aperture, the modified poly propylene powdered coating performance that obtains sees attached list 2.
Embodiment 2～3
Provide the proportioning of A, B, C component by subordinate list 2, other processing parameter is constant, repeats embodiment 1, and the modified poly propylene powdered coating performance that obtains sees attached list 2.
Claims (9)
1, a kind of modified poly propylene powdered coating that is used for the metal base coating is characterized in that containing (mass fraction):
Blend system with unsaturated carboxylic acid and acid anhydrides and organo-peroxide modification contains 65～95 crystal polypropylenes (A), 33～5 parts of polyethylene (B), 2～10 parts of ethylene-alpha-olefin-non-conjugated diene hydrocarbon ter-polymer rubbers (C), (0.01～5) * 10
-4Grafting unsaturated carboxylic acid and the acid anhydrides thereof of mol/g.
2, by the described modified poly propylene powdered coating of claim 1, it is characterized in that its said modification is meant that unsaturated carboxylic acid and acid anhydrides and organo-peroxide thereof carry out chemical modification at the same time or separately to A, B, three kinds of polymkeric substance of C in the blend.
3,, it is characterized in that its said crystalline polypropylene (A) is crystallization homo-polypropylene, crystalline ethylene-propylene-based block copolymer by the described modified poly propylene powdered coating of claim 1.Any and combination of crystalline ethylene-random copolymer of propylene, its melt flow rate (MFR) is 3～50g/10min, is preferably 5～30g/10min.
4,, it is characterized in that of any and combination of its said polyethylene (B) for high density polyethylene(HDPE), new LDPE (film grade), linear low density polyethylene by the described modified poly propylene powdered coating of claim 1.Its melt flow rate (MFR) is 3～50g/10min.Be preferably 5～30g/10min.
5, by the described modified poly propylene powdered coating of claim 1, it is characterized in that its said ethylene-alpha-olefin-non-conjugated diene hydrocarbon terpolymer is a thermoplastic elastomer, therein ethylene, alhpa olefin are any ratio, diene content is 0.001～10%, Mooney viscosity of rubber is 10～100, is preferably 30～80.
6,, it is characterized in that its said unsaturated carboxylic acid and acid anhydrides thereof are meant maleic acid, MALEIC ANHYDRIDE and acrylic acid any and combination by the described modified poly propylene powdered coating of claim 1.
7, by the described modified poly propylene powdered coating of claim 1, it is characterized in that its said organo-peroxide is a radical initiator, in any and combination of 90～170 ℃ of transformation period organo-peroxide that is 1h, being preferably in 110～150 ℃ of transformation period is 1h.
8,, it is characterized in that it can add other various additives such as oxidation inhibitor, stablizer, pigment etc. by the described modified poly propylene powdered coating of claim 1.
9, a kind of preparation method who is used for the modified poly propylene powdered coating of metal base coating is characterized in that:
A dissolves blend with solvating agent under 90～170 ℃ of conditions, add unsaturated carboxylic acid and acid anhydrides and organo-peroxide, and reaction makes modified blends solution under 90～170 ℃ of conditions.
B behind the naturally cooling, adds a large amount of non-solvating agents, makes the resin precipitating come out and filter.
C will mediate in above-mentioned filter cake and the various additive adding high-speed mixer, and then carries out drying.
D sieves, by 0.18mm or littler sieve aperture.Promptly get modified poly propylene powdered coating of the present invention.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92109066 CN1082574A (en) | 1992-08-07 | 1992-08-07 | Modified poly propylene powdered coating and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92109066 CN1082574A (en) | 1992-08-07 | 1992-08-07 | Modified poly propylene powdered coating and preparation method |
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| CN1082574A true CN1082574A (en) | 1994-02-23 |
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| CN 92109066 Pending CN1082574A (en) | 1992-08-07 | 1992-08-07 | Modified poly propylene powdered coating and preparation method |
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|---|---|---|---|---|
| CN102052543A (en) * | 2009-11-10 | 2011-05-11 | 上海海隆防腐技术工程有限公司 | Composite polyethylene (PE) powder thermally sprayed anticorrosion coating for petroleum and natural gas pipe |
| CN102112563A (en) * | 2008-07-28 | 2011-06-29 | 纳幕尔杜邦公司 | Powder coating composition for thermoplastic composites |
| CN102850857A (en) * | 2012-09-28 | 2013-01-02 | 四川仁智油田技术服务股份有限公司 | Steel pipeline anticorrosive material and preparation method of steel pipeline anticorrosive material |
| CN103254695A (en) * | 2013-04-09 | 2013-08-21 | 刘庆芳 | Powder coating with high density polyethylene as main ingredient and preparation method thereof |
| CN103497600A (en) * | 2013-09-03 | 2014-01-08 | 安徽普源分离机械制造有限公司 | Insulating powdery paint for electromagnetic wire |
| CN103497549A (en) * | 2013-09-24 | 2014-01-08 | 安徽锐视光电技术有限公司 | High-adhesion polyethylene powder coating |
| CN103589288A (en) * | 2013-10-12 | 2014-02-19 | 安徽蓝润自动化仪表有限公司 | Epoxy anticorrosive paint for circuit board as well as preparation method thereof |
| CN103773126A (en) * | 2014-01-15 | 2014-05-07 | 芜湖市宝艺游乐科技设备有限公司 | Radiating paint with good peeling resistance |
| CN104693949A (en) * | 2015-03-18 | 2015-06-10 | 黄山贝诺科技有限公司 | Thermoplastic powder coating and preparation method thereof |
| CN105219175A (en) * | 2015-11-04 | 2016-01-06 | 国网河南南召县供电公司 | A kind of shaft tower impregnating material |
| CN107201092A (en) * | 2017-07-24 | 2017-09-26 | 谢泳江 | A kind of preparation method of epoxidation crosslinked polypropylene powdery paints |
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1992
- 1992-08-07 CN CN 92109066 patent/CN1082574A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102112563A (en) * | 2008-07-28 | 2011-06-29 | 纳幕尔杜邦公司 | Powder coating composition for thermoplastic composites |
| CN102052543A (en) * | 2009-11-10 | 2011-05-11 | 上海海隆防腐技术工程有限公司 | Composite polyethylene (PE) powder thermally sprayed anticorrosion coating for petroleum and natural gas pipe |
| CN102850857B (en) * | 2012-09-28 | 2014-12-03 | 四川仁智油田技术服务股份有限公司 | Steel pipeline anticorrosive material and preparation method of steel pipeline anticorrosive material |
| CN102850857A (en) * | 2012-09-28 | 2013-01-02 | 四川仁智油田技术服务股份有限公司 | Steel pipeline anticorrosive material and preparation method of steel pipeline anticorrosive material |
| CN103254695A (en) * | 2013-04-09 | 2013-08-21 | 刘庆芳 | Powder coating with high density polyethylene as main ingredient and preparation method thereof |
| CN103254695B (en) * | 2013-04-09 | 2015-12-23 | 刘庆芳 | A kind of take high density polyethylene(HDPE) as powder coating of major ingredient and preparation method thereof |
| CN103497600A (en) * | 2013-09-03 | 2014-01-08 | 安徽普源分离机械制造有限公司 | Insulating powdery paint for electromagnetic wire |
| CN103497600B (en) * | 2013-09-03 | 2016-05-04 | 安徽普源分离机械制造有限公司 | A kind of coating material of insulating powder in use for electromagnetic wire |
| CN103497549A (en) * | 2013-09-24 | 2014-01-08 | 安徽锐视光电技术有限公司 | High-adhesion polyethylene powder coating |
| CN103589288A (en) * | 2013-10-12 | 2014-02-19 | 安徽蓝润自动化仪表有限公司 | Epoxy anticorrosive paint for circuit board as well as preparation method thereof |
| CN103589288B (en) * | 2013-10-12 | 2016-03-23 | 安徽蓝润自动化仪表有限公司 | A kind of wiring board epoxy anticorrosive paint and preparation method thereof |
| CN103773126A (en) * | 2014-01-15 | 2014-05-07 | 芜湖市宝艺游乐科技设备有限公司 | Radiating paint with good peeling resistance |
| CN104693949A (en) * | 2015-03-18 | 2015-06-10 | 黄山贝诺科技有限公司 | Thermoplastic powder coating and preparation method thereof |
| CN104693949B (en) * | 2015-03-18 | 2017-07-14 | 黄山贝诺科技有限公司 | thermoplastic powder coating and preparation method thereof |
| CN105219175A (en) * | 2015-11-04 | 2016-01-06 | 国网河南南召县供电公司 | A kind of shaft tower impregnating material |
| CN107201092A (en) * | 2017-07-24 | 2017-09-26 | 谢泳江 | A kind of preparation method of epoxidation crosslinked polypropylene powdery paints |
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