CN110305403A - A kind of anti scuffing composite modified polypropylene material - Google Patents
A kind of anti scuffing composite modified polypropylene material Download PDFInfo
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- CN110305403A CN110305403A CN201910505684.3A CN201910505684A CN110305403A CN 110305403 A CN110305403 A CN 110305403A CN 201910505684 A CN201910505684 A CN 201910505684A CN 110305403 A CN110305403 A CN 110305403A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention discloses a kind of anti scuffing composite modified polypropylene materials, belong to technical field of polymer materials.The present invention wraps up Nano-meter SiO_2 with methyl methacrylate2Form enhancing component, melt blending composite material, cooperation is with vinyl acetate, styrene, linoleic acid etc. is latex material made from raw material heating reflux reaction, the stability of this composite system can be improved well, wherein, linoleic acid is the conjugated diene acid of 18 carbon, the flexibility and impact resistance after the effect of latex system can be improved in its backbone, the presence of carboxyl isopolarity functional group simultaneously, it may make the surface drying of this composite material, flexibility, wearability etc. effectively improves, the addition of styrene, phenyl ring rigid chain segment can be introduced in the molecular structure, auxiliary improves the wearability and mechanical performance of this system, mutually collaboration improves scratch resistance energy in the blending process.The present invention solves the problems, such as to commonly use PP composite material scratch resistance at present can be bad.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of anti scuffing composite modified polypropylene material.
Background technique
Polypropylene has good mechanical performance, and thermal stability is high, and processing performance is excellent, and crystallinity adjustable extent is big, anti-corruption
Corrosion can be good, cheap, and the advantages that can recycle, be widely used in industry, agricultural, building, health care,
The every field such as military science and technology, daily life.But PP is there is also many disadvantages, as the elasticity of melt during extrusion molding is big,
Non-Newtonianism is strong, molding shrinkage is big, the easy warpage of product etc., these defects limit the exploitation of PP new material, application.Therefore it needs
Polypropylene is modified to meet the needs of more areas.
The common method of polypropylene modification has chemical modification and physical modification at present.It is poly- that chemical modification mainly passes through change
The molecular structure of propylene improves the purpose of performance to realize, main means have copolymerization, grafting, crosslinking etc..The mode of physical modification
Mainly there are blending, filling, enhancing, surface modification etc., by changing polyacrylic molecular aggregation state structure to improve its performance.Its
It is middle filling and enhancing method because fill source extensively, the processing is simple, property regulation range is wide the advantages that be widely used, also because
This has developed miscellaneous PP composite material.The type of PP composite material has very much, but presses its strengthening material
Material and filler can be summarized as fiberglass reinforced, natural fiber enhancing or filling, Inorganic Fillers Filled three categories substantially.
Polypropylene is one of maximum general-purpose plastics of current dosage.Wherein application of the polypropylene material on automobile, oneself at
For one of the main direction of studying of auto industry components production domesticization.One defect of polypropylene material is that scratch resistance can be compared with
Difference, and this performance is the key performance of the automotive interior applications components such as instrument board, operation bench and door-plate epidermis, in addition, anti-
Scraping property is also automobile external application component, ATVs(all-terrain vehicle) etc. vehicles, durable goods and furniture etc. one of important performance.
Plastics and auto industry are finding solution actively just to improve the scratch resistance energy of polyolefine material.
Commonly improving the substance of polypropylene scratch resistance energy currently on the market is erucyl amide and oleamide, when them
When being added into thermoplastic, the surface of plastic product can be moved to, bloom generates a cured layer, reduces product
The coefficient of friction on surface also reduces the visibility of scratch simultaneously.However a problem existing for erucyl amide or oleamide is,
Under the irradiation of ultraviolet light, they can form high concentration accumulation in plastic product surface, adhesivity be brought, although this adhesivity
It can be dissociated after continuous ultraviolet light.Different light stabilizers is added in the plastic for the beginning of stickiness and disappears
Scattered speed has different influences, but light stabilizer itself is unrelated with this adhesivity, it will not prevent that gluing will not be caused
Property.That there are also against weathers is poor for other problems existing for erucyl amide or oleamide, paintability is bad, is applied to automobile external
Can haze etc..Relative to erucic acid class additive, another substance for improving scratch resistance is exactly that high molecular weight silicone is poly-
Object is closed, this polymer molecular weight is high, and it will not move to material surface thus can generate long-term scratch resistance energy, but such
Additive is expensive, and also can not effectively improve the scratch resistance energy of material in the case where few additive.Therefore it need to open
Send out the good modified polypropylene composite material of scratch resistance a kind of.
Summary of the invention
The technical problems to be solved by the invention: it bad can be asked for current common PP composite material scratch resistance
Topic, provides a kind of anti scuffing composite modified polypropylene material.
In order to solve the above technical problems, the present invention is using technical solution as described below:
A kind of anti scuffing composite modified polypropylene material, including following component: 5 ~ 8 parts of triethylene diamines, 1 ~ 4 part of stearic acid acyl
Amine, 6 ~ 10 parts of epoxy resin, 2 ~ 5 parts of antioxidants, further includes: 20 ~ 40 parts of composite polypropylene base-materials, the poly- cream of 12 ~ 25 parts of modifications
Acid material.
The preparation method of the composite polypropylene base-material, includes the following steps:
(1) 1:7 ~ 12 take Nano-meter SiO_2 in mass ratio2, methyl methacrylate be mixed, ultrasonication obtains dispersion liquid, takes
Azodiisobutyronitrile mixing is added in dispersion liquid 15 ~ 20:1 in mass ratio, is warming up to 75 ~ 90 DEG C, keeps the temperature, and filters, filter residue is taken to wash,
Polymer is obtained, after taking polymer 1:20 in mass ratio ~ 30 that polypropylene mixing is added, torque processing obtains composite S iO2Polypropylene
Material, it is spare；
(2) according to parts by weight, take 20 ~ 30 parts of reagent As, 10 ~ 20 parts of vinyl acetates, 10 ~ 20 parts of linoleic acid, 2 ~ 5 parts of styrene,
10 ~ 15 parts of plasticizer, 2 ~ 5 parts of emulsifiers, 1 ~ 4 part of sodium peroxydisulfate, 2 ~ 5 parts of iron nitrate solutions take acetic acid second prior to 45 ~ 60 DEG C
Alkene, linoleic acid and styrene are stirred, and obtain mix monomer, take mix monomer that reagent A, emulsifier, sodium peroxydisulfate stirring is added
Mixing, is heated to reflux in 60 ~ 80 DEG C, and iron nitrate solution mixing is added, is heated to reflux, cools down, and discharging obtains latex material, by quality
Composite S iO is taken than 4 ~ 8:3:12Polypropylene material, latex material, auxiliary material are mixed to get composite polypropylene base-material.
Reagent A in the step (2): 12 ~ 18:1 in mass ratio takes ethanol solution, NH4Cl mixes to get reagent A.
Plasticizer in the step (2): 6 ~ 10:1 in mass ratio takes triethyl citrate, dioctyl phthalate mixed
It closes to get plasticizer.
Emulsifier in the step (2): 5 ~ 8:1 in mass ratio take aliphatic amine polyoxyethylene ether, OP-10 mixing to get
Emulsifier.
Auxiliary material in the step (2): 1:1 ~ 3 take CaCl in mass ratio2, polyvinylpyrrolidine mixing to get auxiliary material.
The preparation of the polydactyl acid material: in 60 ~ 80 DEG C, 1:3 ~ 6:5 in mass ratio takes N- methyl chloride for imidazoles, allyl
Base chlorine, reagent B mixing, lead to nitrogen protection, and refluxing and pyrolyzing obtains reaction solution, extracts reaction solution reduced pressure, obtain concentrate, takes concentration
Object extraction takes inorganic phase 8 ~ 12:1 in mass ratio that auxiliary agent is added and is mixed, obtains mixture, take mixed liquor in mass ratio 6 ~ 10:
L- lactide is added in 3:1, dimethylamino naphthyridine is mixed, and is warming up to 90 ~ 100 DEG C, and heat preservation is stood, and is obtained treatment fluid, is taken processing
Liquid centrifugal treating collects centrifugation object washing, dry to get polydactyl acid material.
The reagent B: 7 ~ 10:3 in mass ratio takes dehydrated alcohol, acetone mixing to get reagent B.
The auxiliary agent: 4 ~ 8:1 in mass ratio takes citric acid solution, microcrystalline cellulose mixing to get auxiliary agent.
The antioxidant: 3 ~ 6:1 of mass ratio takes tert-butylhydroquinone, antiaging agent RD mixing to get antioxidant.
The present invention is compared with other methods, and advantageous effects are:
(1) present invention wraps up Nano-meter SiO_2 with methyl methacrylate2Being formed enhances component, melt blending composite material, herein
It can reduce Nano-meter SiO_2 in the process2The surface energy of particle, so that it can disperse well, the compatibility being able to ascend between interface,
Meanwhile cooperation is latex material made from raw material heating reflux reaction with vinyl acetate, styrene, linoleic acid etc., can be mentioned well
The stability of this high composite system, wherein linoleic acid is the conjugated diene acid of 18 carbon, and latex can be improved in backbone
Flexibility and impact resistance after system effect, and its special conjugated structure can improve the surface drying performance of system, and sub-
The addition of oleic acid can be such that the double bond quantity of the macromolecular end of the chain increases, and when solidification makes terminal double bond reaction compartment steric hindrance small, simultaneously
The presence of carboxyl isopolarity functional group, may make surface drying, flexibility, wearability of this composite material etc. to effectively improve；
(2) in preparation process of the present invention, the addition of styrene can introduce phenyl ring rigid chain segment in the molecular structure, and auxiliary improves
The wearability and mechanical performance of this system, using N- methyl chloride for imidazoles, allyl chloride as raw material, dimethylamino naphthyridine be catalysis
Agent is grafted on microcrystalline cellulose in polylactic acid using ring-opening polymerisation method, so that decreasing for the degree of polymerization of modifier, tough
Property be improved, and good with the compatibility of composite polypropylene base-material, mutually collaboration improves scratch resistance energy in the blending process；
(3) present invention is with organic principle and nano components interaction composite material processed, and reduces its surface energy, makes it very well
Dispersion, promote the compatibility between interface, cooperation with vinyl acetate, styrene, linoleic acid etc. is heated to reflux latex material processed, is promoted
The stability of this composite system improves the flexibility and impact resistance of latex system using the property of linoleic acid etc., and changes
The surface drying of kind system, flexibility, wearability, the introducing of phenyl ring can also assist the wearability and mechanical performance that improve this system,
In conjunction with using N- methyl chloride for imidazoles, allyl chloride as raw material, using processes such as ring-opening polymerisation, grafting, so that the polymerization of modifier
Degree decreases, and toughness is improved, and good with the compatibility of composite polypropylene base-material, in the blending process, mutually assists
With compound improvement scratch resistance energy, the present invention is mentioned for the problem that common PP composite material scratch resistance can be bad at present
It is significant to the improvement of scratch resistance energy for a kind of anti scuffing composite modified polypropylene material, it has a good application prospect.
Specific embodiment
Antioxidant: 3 ~ 6:1 in mass ratio takes tert-butylhydroquinone, antiaging agent RD mixing to get antioxidant.
Auxiliary material: 1:1 ~ 3 take CaCl in mass ratio2, polyvinylpyrrolidine mixing to get auxiliary material.
Reagent A: 12 ~ 18:1 in mass ratio takes the ethanol solution that volume fraction is 70%, NH4Cl mixes to get reagent A.
Reagent B: 7 ~ 10:3 in mass ratio takes dehydrated alcohol, acetone mixing to get reagent B.
Plasticizer: 6 ~ 10:1 in mass ratio takes triethyl citrate, dioctyl phthalate mixing to get plasticizer.
Emulsifier: 5 ~ 8:1 in mass ratio takes aliphatic amine polyoxyethylene ether, OP-10 mixing to get emulsifier.
Auxiliary agent: 4 ~ 8:1 in mass ratio takes the citric acid solution of concentration 0.1mol/L, microcrystalline cellulose mixing to get auxiliary agent.
The preparation method of composite polypropylene base-material, includes the following steps:
(1) 1:7 ~ 12 take Nano-meter SiO_2 in mass ratio2, methyl methacrylate be mixed, move to supersonic oscillations instrument in 28 ~
35 DEG C, 20 ~ 45min is handled with 50 ~ 65kHz frequency ultrasonic wave, obtains dispersion liquid, takes dispersion liquid 15 ~ 20:1 to be in mass ratio added even
The mixing of nitrogen bis-isobutyronitrile, is warming up to 75 ~ 90 DEG C, after keeping the temperature 40 ~ 60min, filters, takes filter residue to be washed with deionized 2 ~ 4 times, obtain
Polymer after taking polymer 1:20 in mass ratio ~ 30 that polypropylene mixing is added, moves to 170 ~ 190 DEG C of torque rheometer mixing, with
12 ~ 20min of processing is stablized in 40 ~ 60r/min torque, obtains composite S iO2Polypropylene material, it is spare；
(2) according to parts by weight, take 20 ~ 30 parts of reagent As, 10 ~ 20 parts of vinyl acetates, 10 ~ 20 parts of linoleic acid, 2 ~ 5 parts of styrene,
10 ~ 15 parts of plasticizer, 2 ~ 5 parts of emulsifiers, 1 ~ 4 part of sodium peroxydisulfate, 2 ~ 5 parts of concentration 0.1mol/L iron nitrate solution, prior to 45 ~
60 DEG C, take vinyl acetate, linoleic acid and styrene to be stirred, obtain mix monomer, take mix monomer be added reagent A, emulsifier,
Sodium peroxydisulfate is stirred 30 ~ 45min, after 60 ~ 80 DEG C are heated to reflux 40 ~ 60min, iron nitrate solution mixing is added, continues
In 60 ~ 80 DEG C of 1 ~ 3h of reflux, it is naturally cooling to room temperature, discharges, obtains latex material, 4 ~ 8:3:1 in mass ratio takes composite S iO2Poly- third
Alkene material, latex material, auxiliary material mixing, with 650 ~ 1000r/min magnetic agitation, 1 ~ 3h to get composite polypropylene base-material.
The preparation of polydactyl acid material: in 60 ~ 80 DEG C, 1:3 ~ 6:5 in mass ratio takes N- methyl chloride for imidazoles, allyl
Chlorine, reagent B are mixed in container, lead to nitrogen protection, and 3 ~ 6h of refluxing and pyrolyzing obtains reaction solution, are extracted reaction solution and are concentrated under reduced pressure in 70 ~ 90 DEG C
To the 35 ~ 50% of original volume, concentrate is obtained, concentrate is taken to be extracted with ether, takes inorganic phase 8 ~ 12:1 in mass ratio that auxiliary agent is added mixed
It closes, with 400 ~ 600r/min, 30 ~ 55min of magnetic agitation, obtains mixture, take mixed liquor 6 ~ 10:3:1 in mass ratio that L- third is added and hand over
Ester, dimethylamino naphthyridine are mixed evenly, and are warming up to 90 ~ 100 DEG C, and heat preservation stands 8 ~ 12h, obtains treatment fluid, take treatment fluid in
Centrifuge moves to 70 ~ 90 DEG C of vacuum after collecting centrifugation object washing 2 ~ 4 times with 3000 ~ 4000r/min, 15 ~ 25min of centrifugal treating
Drying box drying is to constant weight to get polydactyl acid material.
A kind of anti scuffing composite modified polypropylene material, according to the mass fraction, including following component: 5 ~ 8 parts of triethylenes two
Amine, 1 ~ 4 part of stearic amide, 6 ~ 10 parts of epoxy resin, 2 ~ 5 parts of antioxidants, 20 ~ 40 parts of composite polypropylene base-materials, 12 ~ 25 parts
Polydactyl acid material.
A kind of preparation method of anti scuffing composite modified polypropylene material, includes the following steps:
(1) according to the mass fraction, take 5 ~ 8 parts of triethylene diamines, 1 ~ 4 part of stearic amide, 6 ~ 10 parts of epoxy resin, 2 ~ 5 parts it is anti-
Oxidant, 20 ~ 40 parts of composite polypropylene base-materials, 12 ~ 25 parts of polydactyl acid material；
(2) prior to 55 ~ 70 DEG C, take triethylene diamine, antioxidant, composite polypropylene base-material in batch mixer, with 800 ~ 1100r/
Min 40 ~ 60min of magnetic agitation adds polydactyl acid material, stearic amide, epoxy resin mixing, moves to kneader kneading
After 1 ~ 3h, it is sent into double screw extruder, curtain coating is melted at 170 ~ 190 DEG C, natural cooling is to get anti scuffing composite modified poly- third
Alkene material.
Embodiment 1
Antioxidant: 3:1 in mass ratio takes tert-butylhydroquinone, antiaging agent RD mixing to get antioxidant.
Auxiliary material: 1:1 takes CaCl in mass ratio2, polyvinylpyrrolidine mixing to get auxiliary material.
Reagent A: 12:1 in mass ratio takes the ethanol solution that volume fraction is 70%, NH4Cl mixes to get reagent A.
Reagent B: 7:3 in mass ratio takes dehydrated alcohol, acetone mixing to get reagent B.
Plasticizer: 6:1 in mass ratio takes triethyl citrate, dioctyl phthalate mixing to get plasticizer.
Emulsifier: 5:1 in mass ratio takes aliphatic amine polyoxyethylene ether, OP-10 mixing to get emulsifier.
Auxiliary agent: 4:1 in mass ratio takes the citric acid solution of concentration 0.1mol/L, microcrystalline cellulose mixing to get auxiliary agent.
The preparation method of composite polypropylene base-material, includes the following steps:
(1) 1:7 takes Nano-meter SiO_2 in mass ratio2, methyl methacrylate be mixed, move to supersonic oscillations instrument in 28 DEG C, with
50kHz frequency ultrasonic wave handles 20min, obtains dispersion liquid, takes dispersion liquid 15:1 in mass ratio that azodiisobutyronitrile mixing is added, rises
Temperature is to 75 DEG C, after keeping the temperature 40min, filters, takes filter residue to be washed with deionized 2 times, obtain polymer, take polymer in mass ratio 1:
After 20 are added polypropylene mixing, 170 DEG C of torque rheometer mixing are moved to, processing 12min is stablized with 40r/min torque, is obtained compound
SiO2Polypropylene material, it is spare；
(2) according to parts by weight, take 20 parts of reagent As, 10 parts of vinyl acetates, 10 parts of linoleic acid, 2 parts of styrene, 10 parts of plasticizer,
2 parts of emulsifiers, 1 part of sodium peroxydisulfate, 2 parts of concentration 0.1mol/L iron nitrate solution take vinyl acetate, linoleic acid prior to 45 DEG C
It is stirred with styrene, obtains mix monomer, taken mix monomer that reagent A, emulsifier, sodium peroxydisulfate is added and be stirred 30min,
After 60 DEG C are heated to reflux 40min, iron nitrate solution mixing is added, continues at 60 DEG C of reflux 1h, is naturally cooling to room temperature, out
Material, obtains latex material, 4:3:1 in mass ratio takes composite S iO2Polypropylene material, latex material, auxiliary material mixing, are stirred with 650r/min magnetic force
1h is mixed to get composite polypropylene base-material.
The preparation of polydactyl acid material: in 60 DEG C, 1:3:5 in mass ratio takes N- methyl chloride for imidazoles, allyl chloride, reagent
B is mixed in container, leads to nitrogen protection, and refluxing and pyrolyzing 3h obtains reaction solution, extracts reaction solution and be concentrated under reduced pressure into original volume in 70 DEG C
35%, concentrate is obtained, concentrate is taken to be extracted with ether, takes inorganic phase 8:1 in mass ratio that auxiliary agent mixing is added, with 400r/min magnetic
Power stirs 30min, obtains mixture, takes mixed liquor 6:3:1 in mass ratio that L- lactide, dimethylamino naphthyridine mixing is added
It is even, 90 DEG C are warming up to, heat preservation stands 8h, obtains treatment fluid, and treatment fluid is taken, with 3000r/min centrifugal treating 15min, to receive in centrifuge
After collection centrifugation object is washed 2 times, 70 DEG C of vacuum ovens dryings are moved to constant weight to get polydactyl acid material.
A kind of anti scuffing composite modified polypropylene material, according to the mass fraction, including following component: 5 parts of triethylene diamines,
1 part of stearic amide, 6 parts of epoxy resin, 2 parts of antioxidants, 20 parts of composite polypropylene base-materials, 12 parts of polydactyl acid material.
A kind of preparation method of anti scuffing composite modified polypropylene material, includes the following steps:
(1) according to the mass fraction, 5 parts of triethylene diamines, 1 part of stearic amide, 6 parts of epoxy resin, 2 parts of antioxidants, 20 are taken
Part composite polypropylene base-material, 12 ~ 25 parts of polydactyl acid material；
(2) it prior to 55 DEG C, takes triethylene diamine, antioxidant, composite polypropylene base-material in batch mixer, is stirred with 800r/min magnetic force
40min is mixed, polydactyl acid material, stearic amide, epoxy resin mixing are added, after moving to kneader kneading 1h, is sent into double
Screw extruder melts curtain coating at 170 DEG C, and natural cooling is to get anti scuffing composite modified polypropylene material.
Embodiment 2
Antioxidant: 5:1 in mass ratio takes tert-butylhydroquinone, antiaging agent RD mixing to get antioxidant.
Auxiliary material: 1:2 takes CaCl in mass ratio2, polyvinylpyrrolidine mixing to get auxiliary material.
Reagent A: 16:1 in mass ratio takes the ethanol solution that volume fraction is 70%, NH4Cl mixes to get reagent A.
Reagent B: 8:3 in mass ratio takes dehydrated alcohol, acetone mixing to get reagent B.
Plasticizer: 8:1 in mass ratio takes triethyl citrate, dioctyl phthalate mixing to get plasticizer.
Emulsifier: 7:1 in mass ratio takes aliphatic amine polyoxyethylene ether, OP-10 mixing to get emulsifier.
Auxiliary agent: 6:1 in mass ratio takes the citric acid solution of concentration 0.1mol/L, microcrystalline cellulose mixing to get auxiliary agent.
The preparation method of composite polypropylene base-material, includes the following steps:
(1) 1:10 takes Nano-meter SiO_2 in mass ratio2, methyl methacrylate be mixed, move to supersonic oscillations instrument in 30 DEG C,
30min is handled with 55kHz frequency ultrasonic wave, obtains dispersion liquid, takes dispersion liquid 18:1 in mass ratio that azodiisobutyronitrile mixing is added,
80 DEG C are warming up to, after keeping the temperature 50min, filters, takes filter residue to be washed with deionized 3 times, obtain polymer, take polymer in mass ratio
After polypropylene mixing is added in 1:25,180 DEG C of torque rheometer mixing are moved to, processing 18min is stablized with 50r/min torque, must be answered
Close SiO2Polypropylene material, it is spare；
(2) according to parts by weight, take 25 parts of reagent As, 15 parts of vinyl acetates, 15 parts of linoleic acid, 4 parts of styrene, 13 parts of plasticizer,
4 parts of emulsifiers, 3 parts of sodium peroxydisulfates, 4 parts of concentration 0.1mol/L iron nitrate solution take vinyl acetate, linoleic acid prior to 50 DEG C
It is stirred with styrene, obtains mix monomer, taken mix monomer that reagent A, emulsifier, sodium peroxydisulfate is added and be stirred 35min,
After 70 DEG C are heated to reflux 50min, iron nitrate solution mixing is added, continues at 70 DEG C of reflux 2h, is naturally cooling to room temperature, out
Material, obtains latex material, 7:3:1 in mass ratio takes composite S iO2Polypropylene material, latex material, auxiliary material mixing, are stirred with 800r/min magnetic force
2h is mixed to get composite polypropylene base-material.
The preparation of polydactyl acid material: in 70 DEG C, 1:4:5 in mass ratio takes N- methyl chloride for imidazoles, allyl chloride, reagent
B is mixed in container, leads to nitrogen protection, and refluxing and pyrolyzing 4h obtains reaction solution, extracts reaction solution and be concentrated under reduced pressure into original volume in 80 DEG C
40%, concentrate is obtained, concentrate is taken to be extracted with ether, takes inorganic phase 10:1 in mass ratio that auxiliary agent mixing is added, with 500r/min magnetic
Power stirs 45min, obtains mixture, takes mixed liquor 8:3:1 in mass ratio that L- lactide, dimethylamino naphthyridine mixing is added
It is even, it is warming up to 95 DEG C, heat preservation stands 10h, obtains treatment fluid, and take treatment fluid in centrifuge with 3500r/min centrifugal treating 20min,
After collecting centrifugation object washing 3 times, 80 DEG C of vacuum ovens dryings are moved to constant weight to get polydactyl acid material.
A kind of anti scuffing composite modified polypropylene material, according to the mass fraction, including following component: 7 parts of triethylene diamines,
3 parts of stearic amides, 8 parts of epoxy resin, 3 parts of antioxidants, 30 parts of composite polypropylene base-materials, 20 parts of polydactyl acid material.
A kind of preparation method of anti scuffing composite modified polypropylene material, includes the following steps:
(1) according to the mass fraction, 7 parts of triethylene diamines, 3 parts of stearic amides, 8 parts of epoxy resin, 4 parts of antioxidants, 30 are taken
Part composite polypropylene base-material, 20 parts of polydactyl acid material；
(2) it prior to 60 DEG C, takes triethylene diamine, antioxidant, composite polypropylene base-material in batch mixer, is stirred with 900r/min magnetic force
50min is mixed, polydactyl acid material, stearic amide, epoxy resin mixing are added, after moving to kneader kneading 2h, is sent into double
Screw extruder melts curtain coating at 180 DEG C, and natural cooling is to get anti scuffing composite modified polypropylene material.
Embodiment 3
Antioxidant: 6:1 in mass ratio takes tert-butylhydroquinone, antiaging agent RD mixing to get antioxidant.
Auxiliary material: 1:3 takes CaCl in mass ratio2, polyvinylpyrrolidine mixing to get auxiliary material.
Reagent A: 18:1 in mass ratio takes the ethanol solution that volume fraction is 70%, NH4Cl mixes to get reagent A.
Reagent B: 10:3 in mass ratio takes dehydrated alcohol, acetone mixing to get reagent B.
Plasticizer: 10:1 in mass ratio takes triethyl citrate, dioctyl phthalate mixing to get plasticizer.
Emulsifier: 8:1 in mass ratio takes aliphatic amine polyoxyethylene ether, OP-10 mixing to get emulsifier.
Auxiliary agent: 8:1 in mass ratio takes the citric acid solution of concentration 0.1mol/L, microcrystalline cellulose mixing to get auxiliary agent.
The preparation method of composite polypropylene base-material, includes the following steps:
(1) 1:12 takes Nano-meter SiO_2 in mass ratio2, methyl methacrylate be mixed, move to supersonic oscillations instrument in 35 DEG C,
45min is handled with 65kHz frequency ultrasonic wave, obtains dispersion liquid, takes dispersion liquid 20:1 in mass ratio that azodiisobutyronitrile mixing is added,
90 DEG C are warming up to, after keeping the temperature 60min, filters, takes filter residue to be washed with deionized 4 times, obtain polymer, take polymer in mass ratio
After polypropylene mixing is added in 1:30,190 DEG C of torque rheometer mixing are moved to, processing 20min is stablized with 60r/min torque, must be answered
Close SiO2Polypropylene material, it is spare；
(2) according to parts by weight, take 30 parts of reagent As, 20 parts of vinyl acetates, 20 parts of linoleic acid, 5 parts of styrene, 15 parts of plasticizer,
5 parts of emulsifiers, 4 parts of sodium peroxydisulfates, 5 parts of concentration 0.1mol/L iron nitrate solution take vinyl acetate, linoleic acid prior to 60 DEG C
It is stirred with styrene, obtains mix monomer, taken mix monomer that reagent A, emulsifier, sodium peroxydisulfate is added and be stirred 45min,
After 80 DEG C are heated to reflux 60min, iron nitrate solution mixing is added, continues at 80 DEG C of reflux 3h, is naturally cooling to room temperature, out
Material, obtains latex material, 8:3:1 in mass ratio takes composite S iO2Polypropylene material, latex material, auxiliary material mixing, with 1000r/min magnetic force
3h is stirred to get composite polypropylene base-material.
The preparation of polydactyl acid material: in 80 DEG C, 1:6:5 in mass ratio takes N- methyl chloride for imidazoles, allyl chloride, reagent
B is mixed in container, leads to nitrogen protection, and refluxing and pyrolyzing 6h obtains reaction solution, extracts reaction solution and be concentrated under reduced pressure into original volume in 90 DEG C
50%, concentrate is obtained, concentrate is taken to be extracted with ether, takes inorganic phase 12:1 in mass ratio that auxiliary agent mixing is added, with 600r/min magnetic
Power stirs 55min, obtains mixture, takes mixed liquor 10:3:1 in mass ratio that L- lactide, dimethylamino naphthyridine mixing is added
Uniformly, 100 DEG C are warming up to, heat preservation stands 12h, obtains treatment fluid, takes treatment fluid in centrifuge with 4000r/min centrifugal treating
25min after collecting centrifugation object washing 4 times, moves to 90 DEG C of vacuum ovens dryings to constant weight to get polydactyl acid material.
A kind of anti scuffing composite modified polypropylene material, according to the mass fraction, including following component: 8 parts of triethylene diamines,
4 parts of stearic amides, 10 parts of epoxy resin, 5 parts of antioxidants, 40 parts of composite polypropylene base-materials, 25 parts of polydactyl acid material.
A kind of preparation method of anti scuffing composite modified polypropylene material, includes the following steps:
(1) according to the mass fraction, 8 parts of triethylene diamines, 4 parts of stearic amides, 10 parts of epoxy resin, 5 parts of antioxidants, 40 are taken
Part composite polypropylene base-material, 25 parts of polydactyl acid material；
(2) prior to 70 DEG C, take triethylene diamine, antioxidant, composite polypropylene base-material in batch mixer, with 1100r/min magnetic force
60min is stirred, polydactyl acid material, stearic amide, epoxy resin mixing are added, after moving to kneader kneading 3h, is sent into
Double screw extruder melts curtain coating at 190 DEG C, and natural cooling is to get anti scuffing composite modified polypropylene material.
Comparative example 1: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking composite polypropylene base-material.
Comparative example 2: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking polydactyl acid material.
Comparative example 3: the anti scuffing composite modified polypropylene composite material of Dongguan City company production.
Embodiment and comparative example are tested according to 9341.1 standard of GB/T1040.1-2006, GB/T, anti scuffing energy
Power then according to Ford standard FLTM BN 108-13 carry out, load 2N, by judge scrape specimen surface whiten degree come
Its scratch resistance energy is judged, degree of whitening is lower, indicates that the scratch resistance of material can be better.Test result is as shown in table 1.
Table 1
| Test item | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Impact strength (J/m) | 195 | 190 | 193 | 174 | 171 | 97 |
| Tensile strength (MPa) | 11.8 | 11.3 | 11.4 | 11 | 9.7 | 8.6 |
| Bending strength (MPa) | 43.6 | 42.3 | 43.2 | 40.1 | 39.8 | 30.4 |
| Heat distortion temperature (DEG C) | 120 | 115 | 117 | 111 | 113 | 96 |
| Anti scuffing whitens degree | Nothing is whitened | Nothing is whitened | Nothing is whitened | Whiten more apparent | Slightly whiten | Whiten obvious |
In summary, anti scuffing composite modified polypropylene material of the invention is more preferable compared to commercial product effect, mechanical property and
Scratch resistance is strong, is worth promoting.
The foregoing is merely preferred modes of the invention, are not intended to limit the invention, all in spirit and original of the invention
Within then, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of anti scuffing composite modified polypropylene material, according to the mass fraction, including following component: 5 ~ 8 parts of triethylene diamines,
1 ~ 4 part of stearic amide, 6 ~ 10 parts of epoxy resin, 2 ~ 5 parts of antioxidants, which is characterized in that further include: 20 ~ 40 parts are compound poly-
Propylene base-material, 12 ~ 25 parts of polydactyl acid material.
2. a kind of anti scuffing composite modified polypropylene material according to claim 1, which is characterized in that the composite polypropylene
The preparation method of base-material, includes the following steps:
(1) 1:7 ~ 12 take Nano-meter SiO_2 in mass ratio2, methyl methacrylate be mixed, ultrasonication obtains dispersion liquid, takes
Azodiisobutyronitrile mixing is added in dispersion liquid 15 ~ 20:1 in mass ratio, is warming up to 75 ~ 90 DEG C, keeps the temperature, and filters, filter residue is taken to wash,
Polymer is obtained, after taking polymer 1:20 in mass ratio ~ 30 that polypropylene mixing is added, torque processing obtains composite S iO2Polypropylene
Material, it is spare；
(2) according to parts by weight, take 20 ~ 30 parts of reagent As, 10 ~ 20 parts of vinyl acetates, 10 ~ 20 parts of linoleic acid, 2 ~ 5 parts of styrene,
10 ~ 15 parts of plasticizer, 2 ~ 5 parts of emulsifiers, 1 ~ 4 part of sodium peroxydisulfate, 2 ~ 5 parts of iron nitrate solutions take acetic acid second prior to 45 ~ 60 DEG C
Alkene, linoleic acid and styrene are stirred, and obtain mix monomer, take mix monomer that reagent A, emulsifier, sodium peroxydisulfate stirring is added
Mixing, is heated to reflux in 60 ~ 80 DEG C, and iron nitrate solution mixing is added, is heated to reflux, cools down, and discharging obtains latex material, by quality
Composite S iO is taken than 4 ~ 8:3:12Polypropylene material, latex material, auxiliary material are mixed to get composite polypropylene base-material.
3. a kind of anti scuffing composite modified polypropylene material according to claim 2, which is characterized in that in the step (2)
Reagent A: 12 ~ 18:1 in mass ratio takes ethanol solution, NH4Cl mixes to get reagent A.
4. a kind of anti scuffing composite modified polypropylene material according to claim 2, which is characterized in that in the step (2)
Plasticizer: 6 ~ 10:1 in mass ratio take triethyl citrate, dioctyl phthalate mix to get plasticizer.
5. a kind of anti scuffing composite modified polypropylene material according to claim 2, which is characterized in that in the step (2)
Emulsifier: 5 ~ 8:1 in mass ratio take aliphatic amine polyoxyethylene ether, OP-10 mix to get emulsifier.
6. a kind of anti scuffing composite modified polypropylene material according to claim 2, which is characterized in that in the step (2)
Auxiliary material: 1:1 ~ 3 take CaCl in mass ratio2, polyvinylpyrrolidine mixing to get auxiliary material.
7. a kind of anti scuffing composite modified polypropylene material according to claim 1, which is characterized in that the polydactyl acid
The preparation of material: in 60 ~ 80 DEG C, 1:3 ~ 6:5 in mass ratio takes N- methyl chloride to mix for imidazoles, allyl chloride, reagent B, leads to nitrogen
Protection, refluxing and pyrolyzing obtain reaction solution, extract reaction solution reduced pressure, obtain concentrate, concentrate is taken to extract, take inorganic phase by quality
Auxiliary agent is added than 8 ~ 12:1 to be mixed, obtains mixture, takes mixed liquor 6 ~ 10:3:1 in mass ratio that L- lactide, diformazan ammonia is added
Yl pyridines are mixed, and are warming up to 90 ~ 100 DEG C, and heat preservation is stood, and obtains treatment fluid, takes treatment fluid centrifugal treating, collect centrifugation object water
It washes, it is dry to get polydactyl acid material.
8. a kind of anti scuffing composite modified polypropylene material according to claim 7, which is characterized in that the reagent B: pressing matter
Amount takes dehydrated alcohol, acetone mixing to get reagent B than 7 ~ 10:3.
9. a kind of anti scuffing composite modified polypropylene material according to claim 7, which is characterized in that the auxiliary agent: pressing matter
Amount takes citric acid solution, microcrystalline cellulose mixing to get auxiliary agent than 4 ~ 8:1.
10. a kind of anti scuffing composite modified polypropylene material according to claim 1, which is characterized in that the antioxidant:
3 ~ 6:1 of mass ratio takes tert-butylhydroquinone, antiaging agent RD mixing to get antioxidant.
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