CN103113663B - A kind of damage resistant polypropylene composite with self-regeneration function and preparation method thereof - Google Patents
A kind of damage resistant polypropylene composite with self-regeneration function and preparation method thereof Download PDFInfo
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- CN103113663B CN103113663B CN201110366136.0A CN201110366136A CN103113663B CN 103113663 B CN103113663 B CN 103113663B CN 201110366136 A CN201110366136 A CN 201110366136A CN 103113663 B CN103113663 B CN 103113663B
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Abstract
The invention discloses a kind of have can self-regeneration function damage resistant polypropylene composite and preparation method thereof, it comprises the component of following percetage by weight: polypropylene 28-91.8, heat stabilizer 0.1-1, lubricant 0.1-1, flexibilizer 2-20, scratches renovation agent 1-10, inorganic mineral powder 5-40. This present invention product, DL (5min)≤1.5 after 4N power scratches, DL (10min)≤0.5, DL (30min)≤0.05. This material has after surface is subject to slightly scratching, and under natural daylight, exposes after 10-30min, under normal temperature state, cut is had the function of rapid self-regeneration. Can be used for the occasion that automotive trim, household appliances shell etc. are higher to damage resistant requirement.
Description
Technical field
The present invention relates to a kind of damage resistant polypropylene composite with self-regeneration function and preparation method thereof,Be specifically related to the automotive trim higher with the requirement of effects on surface damage resistant or household appliances shell polypropylene multipleCompound and preparation method thereof.
Background technology
Automotive interior material or home electric appliance material in use inevitably can produce slight scuffingOr cut, damages to the outward appearance of product, thereby affect consumer's use mood. At present in automobileDecorations polypropylene composite generally adopts and adds the inorganic filler such as talcum powder and increase rigidity and the heat resistance of material,Add rubber simultaneously and improve toughness and the lower temperature resistance of material, but adding of inorganic filler or rubber no matterIt is more obvious that capital makes material be subject to slightly scratching rear surface cut.
For reducing this cut effect visually producing, damage resistant polypropylene composite generally adopts and adds at presentAdd the damage resistant such as amide-type and silicone auxiliary agent, the principle of this raising damage resistant is that damage resistant auxiliary agent is at materialSurface forms a kind of superficial layer, improves the smooth degree of material surface, thereby is standing material after slight scuffingThe brightness at cut place changes not obvious. But the defect of this damage resistant modification technology is, adds damage resistantAfter auxiliary agent, can not eliminate physics cut, and physics cut can be more obvious, just optical effect is not obvious.
Summary of the invention
The object of the invention is for provide a kind of have can self-regeneration damage resistant polypropylene composite, withOvercome the above-mentioned defect that prior art exists.
Another object of the present invention is the preparation method for this polypropylene composite is provided.
There is a damage resistant polypropylene composite for self-regeneration function, by weight percentage, its componentAnd content:
It is the homopolymerization PP, copolymerization PP of 1-20 ten thousand or the mixture of two kinds that described polypropylene is selected molecular weight.
Described heat stabilizer is selected from phenols, amine, phosphorous acid esters, half Hinered phenols, acryloyl group officialThe mixture of one or more in compound class and the calixarenes of energy group and monothioester.
Described lubricant is selected from low molecule ester class, metal soap, stearic acid complex ester class, amide-typeThe mixture of one or more.
Described flexibilizer is selected from high density polyethylene (HDPE), low density polyethylene (LDPE), LLDPE, secondThe ethylene-butadiene-styrene copolymer of alkene-acetate ethylene copolymer, hydrogenation, s-B-SThe SBS of triblock copolymer, hydrogenation, ethene-α-ethylene-octeneThe mixture of one or more of copolymer, ethylene-propylene diene copolymer and polyurethane.
Described scuffing renovation agent is A+B binary combination system, wherein A be shitosan, carboxylic acidified chitosan,Benzoylation shitosan, cyanoethyl shitosan, hydroxypropyl chitosan, hydroxyethyl chitosan, N-carboxy methylationThe western Buddhist alkali of benzaldehyde of shitosan, shitosan, N-ethyl chitosan, N-succinylated chitosan, N-are suitableOne in butylene two acylation chitosans, N-phthaloyl chitosan and N-Acetylated Chitosans or severalKind mixture, B be oxirane, expoxy propane, epoxychloropropane, epoxy butane, epoxy iso-butane,The mixture of one or more in 7-oxa-bicyclo[4.1.0 and cyclopentane epoxide.
Described inorganic filler be selected from calcium carbonate, talcum powder, kaolin, mica, wollastonite, glass microballoon,The mixture of one or more in ceramic fine bead and barium sulfate.
The preparation method of the above-mentioned damage resistant polypropylene composite with self-regeneration function, concrete steps are as follows:
By polypropylene, heat stabilizer, lubricant, flexibilizer, scuffing renovation agent, inorganic filler in draw ratioBe that in the double screw extruder of 40: 1, melting mixing is disperseed, extruding pelletization, finally obtains product.
Described melting mixing is disperseed, and extrusion temperature is 170-240 DEG C.
The present invention adopts the efficient scuffing renovation agent of a kind of A (alkylene oxide hydro carbons)+B (shitosan class) combinationImprove the anti-scratch ability of polypropylene composite. Concrete principle is to be subject to after small scuffing when material, polypropyleneShitosan class material in compound and alkylene oxide hydro carbons material issue third contact of a total solar or lunar eclipse chemical reaction in the effect of natural daylightRepair impaired cut.
Product of the present invention, is subject to after slight scuffing at material surface, after natural light irradiation 10-30min, and normal temperatureUnder state, there is the function of rapid self-regeneration. DL (5min)≤1.5 after 4N power scratches, DL (10min)≤0.5，DL(30min)≤0.05。
Detailed description of the invention
Further set forth technical characterstic of the present invention below in conjunction with specific embodiment.
Embodiment 1
By 31.2 kilograms of polypropylene, 0.9 kilogram of phenols heat stabilizer Irganox1010 (CIBA company), 0.9Kilogram processing aid calcium stearate, 18 kilograms of POEs, 9 kilograms scratch renovation agent, 40 kilogramsIn the double screw extruder that calcium carbonate is 1: 40 in draw ratio, melting mixing is disperseed, and extrusion temperature is 200 DEG C,Extruding pelletization, finally obtains product.
Product of the present invention, is subject to after slight scuffing at material surface, after natural light irradiation 10-30min, normalUnder temperature state, there is the function of rapid self-regeneration. DL (5min)=1.3 after 4N power scratches, DL (10min)＝0.4，DL(30min)＝0.04。
Embodiment 2
By 78 kilograms of polypropylene, 0.7 kilogram of phenols heat stabilizer Irganox1010 (CIBA company), 0.3Kilogram processing aid zinc stearate, 2 kilograms of ethylene-propylene copolymers, 4 kilograms scratch renovation agents, 15 kilograms of talcum powderIn the double screw extruder that is 1: 40 in draw ratio, melting mixing is disperseed, and extrusion temperature is 200 DEG C, extrudes and makesGrain, finally obtains product.
Product of the present invention, is subject to after slight scuffing at material surface, after natural light irradiation 10-30min, normalUnder temperature state, there is the function of rapid self-regeneration. DL (5min)=1.2 after 4N power scratches, DL (10min)＝0.3，DL(30min)＝0.03。
Embodiment 3
By 69 kilograms of polypropylene, 0.5 kilogram of phenols heat stabilizer Irganox1010 (CIBA company), 0.5Kilogram processing aid EBS, 7 kilograms of SEBS, 3 kilograms scratch renovation agents, 20 kilograms of wollastonites in draw ratioBe that in the double screw extruder of 1: 40, melting mixing is disperseed, extrusion temperature is 200 DEG C, and extruding pelletization is finalObtain product.
Product of the present invention, is subject to after slight scuffing at material surface, after natural light irradiation 10-30min, and normal temperatureUnder state, there is the function of rapid self-regeneration. DL (5min)=1.1 after 4N power scratches, DL (10min)＝0.2，DL(30min)＝0.02。
Embodiment 4
By 91 kilograms of polypropylene, 0.2 kilogram of phenols heat stabilizer Irganox1010 (CIBA company), 0.8Kilogram processing aid calcium stearate, 2 kilograms of LLDPEs, 1 kilogram scratch renovation agent, 5 kilogramsIn the double screw extruder that kaolin is 1: 40 in draw ratio, melting mixing is disperseed, and extrusion temperature is 200 DEG C,Extruding pelletization, finally obtains product.
Product of the present invention, is subject to after slight scuffing at material surface, after natural light irradiation 10-30min, and normal temperatureUnder state, there is the function of rapid self-regeneration. DL (5min)=1.0 after 4N power scratches, DL (10min)＝0.15，DL(30min)＝0.03。
Embodiment 5
By 54 kilograms of polypropylene, 0.6 kilogram of phenols heat stabilizer Irganox1010 (CIBA company), 0.4Kilogram processing aid EBS, 10 kilograms of high density polyethylene (HDPE)s, 5 kilograms scratch renovation agents, 30 kilograms of barium sulfateIn the double screw extruder that is 1: 40 in draw ratio, melting mixing is disperseed, and extrusion temperature is 200 DEG C, extrudes and makesGrain, finally obtains product.
Product of the present invention, is subject to after slight scuffing at material surface, after natural light irradiation 10-30min, and normal temperatureUnder state, there is the function of rapid self-regeneration. DL (5min)=1.1 after 4N power scratches, DL (10min)＝0.25，DL(30min)＝0.02。
Claims (8)
1. a damage resistant polypropylene composite with self-regeneration function, is characterized in that: by weight hundredProportion by subtraction meter, its component and content:
Described scuffing renovation agent is A+B binary combination system, wherein A be shitosan, carboxylic acidified chitosan,Benzoylation shitosan, cyanoethyl shitosan, hydroxypropyl chitosan, hydroxyethyl chitosan, N-carboxy methylationThe western Buddhist alkali of benzaldehyde of shitosan, shitosan, N-ethyl chitosan, N-succinylated chitosan, N-are suitableOne in butylene two acylation chitosans, N-phthaloyl chitosan and N-Acetylated Chitosans or severalKind mixture, B be oxirane, expoxy propane, epoxychloropropane, epoxy butane, 7-oxa-bicyclo[4.1.0 andThe mixture of one or more in cyclopentane epoxide.
2. the damage resistant polypropylene composite with self-regeneration function according to claim 1, its spyLevy and be: it is the mixed of the homopolymerization PP, copolymerization PP of 1-20 ten thousand or two kinds that described polypropylene is selected molecular weightCompound.
3. the damage resistant polypropylene composite with self-regeneration function according to claim 1, its spyLevy and be: described heat stabilizer is selected from a kind of or several in phenols, amine, phosphorous acid esters and calixarenesThe mixture of planting.
4. the damage resistant polypropylene composite with self-regeneration function according to claim 1, its spyLevy and be: described lubricant be selected from low molecule ester class, metal soap and amide-type one or moreMixture.
5. the damage resistant polypropylene composite with self-regeneration function according to claim 1, its spyLevy and be: described flexibilizer be selected from high density polyethylene (HDPE), low density polyethylene (LDPE), LLDPE,The ethylene-butadiene-styrene copolymer of ethylene-vinyl acetate copolymer, hydrogenation, styrene-butadiene-benzene secondSBS, the ethylene-alpha-octylene of alkene triblock copolymer, hydrogenation are commonThe mixture of one or more of polymers, ethylene-propylene diene copolymer and polyurethane.
6. the damage resistant polypropylene composite with self-regeneration function according to claim 1, its spyLevy and be: described inorganic filler is selected from calcium carbonate, talcum powder, kaolin, mica, wollastonite, glassThe mixture of one or more in microballon, ceramic fine bead and barium sulfate.
7. prepare the damage resistant polypropylene composite with self-regeneration function claimed in claim 1 for one kindMethod, is characterized in that: concrete steps are as follows:
By polypropylene, heat stabilizer, lubricant, flexibilizer, scuffing renovation agent, inorganic filler in draw ratioDisperse for melting mixing in the double screw extruder of 40:1, extruding pelletization, finally obtains product.
8. preparation method according to claim 7, is characterized in that: extrusion temperature is 170-240 DEG C.
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| CN103113663B true CN103113663B (en) | 2016-06-15 |
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| CN106147010A (en) * | 2015-04-13 | 2016-11-23 | 深圳市联创科技集团有限公司 | Irradiating through ultraviolet light can the PP composite material and preparation method thereof of selfreparing |
| CN106398085A (en) * | 2016-09-09 | 2017-02-15 | 博硕科技(江西)有限公司 | Scratching-resistant halogen-free flame-retardant TPE injection molding material and preparation method thereof |
| CN106496814A (en) * | 2016-10-13 | 2017-03-15 | 广东省石油化工研究院 | A kind of and secondary Overmolded surface damage resistant TPV compositions of nylon base and preparation method thereof |
| CN109705762A (en) * | 2018-12-31 | 2019-05-03 | 湖北德威包装科技有限公司 | Easy uncoiling CPP protective film |
| CN111499965B (en) * | 2019-01-30 | 2022-12-02 | 江苏金发科技新材料有限公司 | Self-repairing scratch-resistant polypropylene nano material for automobile clothes and preparation method thereof |
| CN111718539B (en) * | 2020-05-26 | 2023-06-16 | 江苏金发科技新材料有限公司 | Self-repairing polypropylene material and preparation method thereof |
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