CN110330723A - One kind is automobile-used to exempt from spraying composite material and preparation method thereof - Google Patents
One kind is automobile-used to exempt from spraying composite material and preparation method thereof Download PDFInfo
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- CN110330723A CN110330723A CN201910660348.6A CN201910660348A CN110330723A CN 110330723 A CN110330723 A CN 110330723A CN 201910660348 A CN201910660348 A CN 201910660348A CN 110330723 A CN110330723 A CN 110330723A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K9/10—Encapsulated ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0812—Aluminium
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
Automobile-used exempt from spraying composite material, raw material composition are as follows: acrylic resin, filler, metal-powder, straight chained alkyl hydrochlorate, cyclopentadiene, antioxidant the present invention relates to a kind of；Wherein metal-powder uses double wrapped, and inner layer is thermosetting resin cladding, outer layer is silicon dioxide nano powder cladding.The invention further relates to a kind of methods for preparing the material simultaneously.The present invention uses double wrapped aluminium powder, the setting of inner layer for reducing metal-powder thermal coefficient, to reduce the appearance of weld bond；The silicon dioxide nano powder of outer layer can prevent metal-powder and inner layer generation in high-temperature process from physically or chemically changing.The addition of straight chained alkyl hydrochlorate simultaneously is conducive to improve the compatibility of powder and polypropylene base, reduces the generation of current mark；The addition of cyclopentadiene can play the role of crosslinking, improve the hardness of material entirety；The characteristic of cyclopentadiene high temperature depolymerization simultaneously, is unaffected the high temperature process of acrylic resin.
Description
Technical field
The present invention relates to vehicle material field, more particularly to a kind of automobile-used exempt from spraying composite material and preparation method thereof.
Background technique
With the continuous development of automobile industry, the application of new material, new technology provides new think of for the exploitation of components
Road.Automobile interior exterior decorations plastic product generallys use paint spraying, and not only process is many and diverse, and very big pollution is also resulted in environment.
Exempting from sprayed on material is that metal powder is added in raw materials for plastics production, and directly injection molding can make product that the material for spraying appearance be presented
Material.Nowadays, some interior exterior trims exempt from spray piece and have gradually replaced spray painting part to enter market.Exempt from the applying to a certain degree of sprayed on material
On simplify the moulding process of inner and outer decorative parts of automobile, improve product competitiveness, be beneficial to the development of Chinese automobile plastics.
But automobile-used at present exempt from sprayed on material there is also this some shortcomings: as material injection will appear at finished product rear surface it is molten
The problem of appearance such as wiring, current mark；The hardness for exempting from sprayed on material simultaneously still wants solution party far short of what is expected, current compared with metallic paint
Method is that crosslinking agent is added；But the addition of crosslinking agent leverages materials hot working performance, to affect the injection molding of material
Performance.
Summary of the invention
The present invention overcomes the deficiencies in the prior art, provide the injection-molded finished no current mark of one kind, weldless line and hardness height, together
When good automobile-used of material hot-workability itself exempt from sprayed on material and preparation method thereof.
In order to achieve the above objectives, the technical solution adopted by the present invention are as follows: provide it is a kind of it is automobile-used exempt from spraying composite material,
Be characterized in that: prepare the composite material raw material composition are as follows: acrylic resin, filler, metal-powder, straight chained alkyl hydrochlorate,
Cyclopentadiene, antioxidant；The metal-powder uses double wrapped, and inner layer is thermosetting resin cladding, outer layer is dioxy
SiClx nano-powder cladding；The general formula of the straight chained alkyl hydrochlorate is AMX, and wherein A is C15-C25Straight chained alkyl, M is acid group,
X is metal ion.
As a preferred embodiment, the acrylic resin, filler, metal-powder, straight chained alkyl hydrochlorate, cyclopentadiene,
The proportion of antioxidant are as follows: acrylic resin 70-80 mass parts, filler 15-20 mass parts, metal-powder 2-8 mass parts, straight chain
Alkyl hydrochlorate 2-6 mass parts, cyclopentadiene 2-5 mass parts, antioxidant 1-3 mass parts.
As a preferred embodiment, the metal-powder is aluminium powder.
As a kind of more preferable scheme, the thermosetting resin is polyacrylate or phenolic resin.
As a preferred embodiment, the acid group is carboxylate radical or sulfonate radical.
As a kind of more preferable scheme, the metal ion is one of sodium, potassium, magnesium.
Prepare the above-mentioned automobile-used method for exempting from spraying composite material the present invention also provides a kind of, it is characterised in that: including with
Lower step:
(1) metal-powder is added in the organic solution of thermosetting resin, high-speed stirred 1- under conditions of 700-1000rpm
2.5h；Be placed at a temperature of 160-180 DEG C, distillation drying 3-5min, obtain resin clad metal powder；
(2) resin clad metal powder, nano silica powder are weighed respectively by the quality proportioning of 1:0.8-1.2, stirring is equal
It is even；Obtained mixture is put into high shear dispersion machine processing 15-25min, obtains the metal-powder of double-coating；
(3) double-coating metal-powder, the straight chained alkyl acid that acrylic resin, filler, step (2) obtain are weighed after according to the ratio
Salt, cyclopentadiene, antioxidant are uniformly mixed；Uniformly mixed raw material is passed through in extruder and is melted, is squeezed out；
(4) cooling extruded blank；
(5) it is granulated, obtains automobile-used exempting from spraying composite material.
As a preferred embodiment, in the step (1), the concentration of thermosetting resin organic solution is 30-40wt%；Gold
The quality proportioning for belonging to powder and thermosetting resin organic solution is 1:3-5.
As a kind of more preferable scheme, in the step (1), solvent in thermosetting resin organic solution is ethyl alcohol, different
One kind of propyl alcohol, ethyl acetate.
As a preferred embodiment, in the step (2), resin clad metal powder, nano silica powder exist
It is stirred 2-4h under 200-450rpm revolving speed and is uniformly mixed.
The beneficial technical effect of the present invention lies in: the injection-molded finished no current mark of one kind, weldless line and hardness height are provided, together
When good automobile-used of material hot-workability itself exempt from sprayed on material and preparation method thereof.
(1) metal-powder that uses of the present invention for inner layer is thermosetting resin, outer layer is the double of silicon dioxide nano powder
Layer package metal-powder；The setting of inner layer for reducing metal-powder thermal coefficient, to reduce the appearance of weld bond；Outer layer
Silicon dioxide nano powder, have good heat resistance, by metal-powder be wrapped in wherein, for improve metal-powder and in
The temperature tolerance of layer prevents metal-powder and inner layer generation in high-temperature process from physically or chemically changing.
(2) addition of straight chained alkyl hydrochlorate is conducive to improve the compatibility of powder and polypropylene base, reduces the production of current mark
It is raw.
(3) addition of cyclopentadiene can play the role of crosslinking, be intertwined with acrylic resin, improve material
Expect whole hardness；The characteristic of cyclopentadiene high temperature depolymerization simultaneously, is unaffected the high temperature process of acrylic resin.
Specific embodiment
The invention will be further described combined with specific embodiments below.Following embodiment is only used for clearly illustrating
Technical solution of the present invention, and not intended to limit the protection scope of the present invention.
Embodiment 1
The present invention provides it is a kind of it is automobile-used exempt from spraying composite material, prepare the raw material composition of the material are as follows: 70 matter of acrylic resin
Measure part, 20 mass parts of filler, 2 mass parts of metal-powder, 4 mass parts of cetyl potassium sulfonate, 2 mass parts of cyclopentadiene, antioxygen
2 mass parts of agent.
Wherein: acrylic resin 230 DEG C at a temperature of, the lower flow rate of 2.16kg load is 35-50g/min.
Filler is the talcum powder coated using epoxy resin, and modified talcum powder is more easier and acrylic resin phase
Hold, the partial size of talcum powder is at 10-15 μm.
Metal-powder is aluminium powder, using double wrapped；Its inner layer is phenolic resin cladding, outer layer is silica nanometer powder
Body cladding.Inner layer is used to improve the reduction thermal coefficient of aluminium powder, to reduce the appearance of weld bond；The silica nanometer of outer layer
Powder has good heat resistance, aluminium powder is wrapped in wherein, for improving the temperature tolerance of aluminium powder and inner layer, is prevented in high temperature
Aluminium powder and inner layer generation physically or chemically change when processing.
The addition of cetyl potassium sulfonate is conducive to improve the compatibility of powder and polypropylene base, reduces the production of current mark
It is raw.
Cyclopentadiene (CPD) has crosslinked at low temperature, the performance of high temperature depolymerization；When dimerization reaction occurs under room temperature automatically
(Diels-Alder reaction), which generates dicyclopentadiene (DCPD), crosslinks molecular structure, is wrapped in acrylic resin
Together, the hardness of material entirety is improved；When temperature is to 170 DEG C, dicyclopentadiene occurs inverse Diels-Alder and reacts, depolymerization
Cyclopentadiene is formed, to will not influence the high temperature process of acrylic resin.
Antioxidant is Hinered phenols antioxidant.
This automobile-used spraying composite material of exempting from is prepared using following steps:
(1) aluminium powder is added to (the matter of the organic solution of aluminium powder and phenolic resin in the organic solution of the phenolic resin of 30wt% concentration
Amount proportion is 1:3), high-speed stirred 2.5h under the conditions of 700rpm；Be placed at a temperature of 160 DEG C, distillation drying 5min, removal
Make phenolic resin in aluminium powder surface-crosslinked package while organic solvent, obtains resin cladding aluminium powder；Phenolic resin organic solution
In solvent be ethyl alcohol；
(2) resin cladding aluminium powder, nano silica powder are weighed respectively by the quality proportioning of 1:0.8；Under 200rpm revolving speed
It is stirred 4h；By obtained mixture be put into high shear dispersion machine processing 15min, make material bear it is huge impact, compression,
Shearing force simultaneously generates localized hyperthermia, and two kinds of materials are fused into spheric granules, obtains the aluminium powder of double-coating；
(3) double-coating aluminium powder, cetyl sulfonic acid that acrylic resin, filler, step (2) obtain are weighed after according to the ratio
Potassium, cyclopentadiene, antioxidant are uniformly mixed；Uniformly mixed raw material is passed through in double screw extruder and is melted, is squeezed out；It squeezes out
Each work area temperature of machine are as follows: 180 DEG C of an area, two 200 DEG C of areas, three 200 DEG C of areas, four 210 DEG C of areas, five 210 DEG C of areas, six 210 DEG C of areas, seven
225 DEG C of area, eight 230 DEG C of areas, nine 230 DEG C of areas, ten 230 DEG C of areas；Raw material residence time in double screw extruder is 1-2min；Pressure
Power is 15MPa；
(4) blank squeezed out, using 15 DEG C of circulating water；
(5) it is granulated, obtains automobile-used exempting from spraying composite material.
Embodiment 2
The present invention provides it is a kind of it is automobile-used exempt from spraying composite material, prepare the raw material composition of the material are as follows: 80 matter of acrylic resin
Measure part, 15 mass parts of filler, 8 mass parts of metal-powder, 6 mass parts of octadecyl carboxylic acid sodium, 2 mass parts of cyclopentadiene, antioxygen
3 mass parts of agent.
Wherein: acrylic resin, filler, cyclopentadiene, the performance of antioxidant and effect and embodiment 1 are identical.
Metal-powder is similarly aluminium powder, using double wrapped；Its inner layer is polyacrylate resin cladding, remaining and implementation
Example 1 is identical.
The addition of octadecyl carboxylic acid sodium is conducive to improve the compatibility of powder and polypropylene base, reduces the production of current mark
It is raw.
This automobile-used spraying composite material of exempting from is prepared using following steps:
(1) aluminium powder is added to (the organic solution of aluminium powder and polyacrylate in the organic solution of the polyacrylate of 40wt% concentration
Quality proportioning be 1:5), high-speed stirred 2h under the conditions of 1000rpm；Be placed at a temperature of 170 DEG C, distillation drying 4min,
Make polyacrylate in aluminium powder surface-crosslinked package while removing organic solvent, obtains resin cladding aluminium powder；Polyacrylate
Solvent in organic solution is ethyl acetate；
(2) resin cladding aluminium powder, nano silica powder are weighed respectively by the quality proportioning of 1:1.2；Under 450rpm revolving speed
It is stirred 3h；Obtained mixture is put into high shear dispersion machine processing 20min, obtains the aluminium powder of double-coating；
(3) double-coating aluminium powder, octadecyl carboxylic acid that acrylic resin, filler, step (2) obtain are weighed after according to the ratio
Sodium, cyclopentadiene, antioxidant are uniformly mixed；Uniformly mixed raw material is passed through in double screw extruder and is melted, is squeezed out；It squeezes out
Each work area temperature of machine are as follows: 185 DEG C of an area, two 205 DEG C of areas, three 205 DEG C of areas, four 215 DEG C of areas, five 215 DEG C of areas, six 215 DEG C of areas, seven
220 DEG C of area, eight 225 DEG C of areas, nine 225 DEG C of areas, ten 225 DEG C of areas；Raw material residence time in double screw extruder is 1-2min；Pressure
Power is 18MPa；
(4) blank squeezed out, using 10 DEG C of circulating water；
(5) it is granulated, obtains automobile-used exempting from spraying composite material.
Embodiment 3
The present invention provides it is a kind of it is automobile-used exempt from spraying composite material, prepare the raw material composition of the material are as follows: 75 matter of acrylic resin
Measure part, 20 mass parts of filler, 5 mass parts of metal-powder, 2 mass parts of eicosyl sulfonate, 5 mass parts of cyclopentadiene, antioxygen
1 mass parts of agent.
Wherein: acrylic resin, filler, metal-powder, cyclopentadiene, the performance of antioxidant and effect and embodiment 1
It is identical.
The addition of eicosyl sulfonate is conducive to improve the compatibility of powder and polypropylene base, reduces the production of current mark
It is raw.
This automobile-used spraying composite material of exempting from is prepared using following steps:
(1) aluminium powder is added to (the matter of the organic solution of aluminium powder and phenolic resin in the organic solution of the phenolic resin of 35wt% concentration
Amount proportion is 1:4), high-speed stirred 1h under the conditions of 800rpm；Be placed at a temperature of 180 DEG C, distillation drying 3min, removal has
Make phenolic resin in aluminium powder surface-crosslinked package while solvent, obtains resin cladding aluminium powder；In phenolic resin organic solution
Solvent be isopropanol；
(2) resin cladding aluminium powder, nano silica powder are weighed respectively by the quality proportioning of 1:1；It is stirred under 400rpm revolving speed
Mix mixing 2h；Obtained mixture is put into high shear dispersion machine processing 25min, obtains the aluminium powder of double-coating；
(3) double-coating aluminium powder, eicosyl sulfonic acid that acrylic resin, filler, step (2) obtain are weighed after according to the ratio
Sodium, cyclopentadiene, antioxidant are uniformly mixed；Uniformly mixed raw material is passed through in double screw extruder and is melted, is squeezed out；It squeezes out
Each work area temperature of machine are as follows: 190 DEG C of an area, two 210 DEG C of areas, three 210 DEG C of areas, four 220 DEG C of areas, five 220 DEG C of areas, six 220 DEG C of areas, seven
225 DEG C of area, eight 230 DEG C of areas, nine 230 DEG C of areas, ten 230 DEG C of areas；Raw material residence time in double screw extruder is 1-2min；Pressure
Power is 18MPa；
(4) blank squeezed out, using 5 DEG C of circulating water；
(5) it is granulated, obtains automobile-used exempting from spraying composite material.
Comparative example 1
This comparative example is essentially identical compared with Example 1, the difference is that:
1, preparing the metal-powder in the automobile-used raw material composition for exempting from spraying composite material is the common aluminium powder without double-coating.
Specific raw material proportioning: 70 mass parts of acrylic resin, 20 mass parts of filler, 2 mass parts of common metal powder, 16
4 mass parts of alkyl sulfonic acid potassium, 2 mass parts of cyclopentadiene, 2 mass parts of antioxidant.
2, without step (1) and (2) in the automobile-used method for exempting from spraying composite material preparation；
Specific steps are as follows:
(1) acrylic resin, filler, aluminium powder, cetyl potassium sulfonate, cyclopentadiene, antioxidant mixing are weighed according to the ratio
It is even；Uniformly mixed raw material is passed through in double screw extruder and is melted, is squeezed out；Each work area temperature of extruder are as follows: 180 DEG C of an area,
Two 200 DEG C of areas, three 200 DEG C of areas, four 210 DEG C of areas, five 210 DEG C of areas, six 210 DEG C of areas, seven 225 DEG C of areas, eight 230 DEG C of areas, nine areas 230
DEG C, ten 230 DEG C of areas；Raw material residence time in double screw extruder is 1-2min；Pressure is 15MPa；
(2) blank squeezed out, using 15 DEG C of circulating water；
(3) it is granulated, obtains automobile-used exempting from spraying composite material.
Comparative example 2
This comparative example is essentially identical compared with Example 1, the difference is that:
1, preparing in the automobile-used raw material composition for exempting from spraying composite material does not include cetyl potassium sulfonate and other straight chained alkyls acid
Salt.
Specific raw material proportioning: 70 mass parts of acrylic resin, 20 mass parts of filler, 2 mass parts of common metal powder, ring penta
2 mass parts of diene, 2 mass parts of antioxidant.
Comparative example 3
This comparative example is essentially identical compared with Example 1, the difference is that:
1, preparing in the automobile-used raw material composition for exempting from spraying composite material does not include cyclopentadiene.
Specific raw material proportioning: 70 mass parts of acrylic resin, 20 mass parts of filler, 2 mass parts of common metal powder, 16
4 mass parts of alkyl sulfonic acid potassium, 2 mass parts of antioxidant.
Performance test:
Exempt from spraying composite material by automobile-used provided by embodiment 1-3 and comparative example 1-3 on injection (mo(u)lding) machine and inject
Sample preparation is formed, and is tested for the property.
Tensile strength test: reference standard: ISO527-2；Test condition: span 50mm.
Bending strength test: reference standard: ISO178；Test condition: span 64mm, speed 14mm/min.
Notch impact strength test: reference standard: ISO179-1；Test condition: span 40mm, notch depth 1/3D.
Shrinking percentage test: reference standard: ISO2577-2007.
Shore hardness D: reference standard: GB/T 2411-1980.
Testing result:
Embodiment 1: tensile strength: 18Mpa；Bending modulus: 1800Mpa；Notch impact strength test: 15kJ/m2；Shrinking percentage:
0.8%；Hardness: 2H；Appearance: without current mark, weldless line.
Embodiment 2: tensile strength: 17Mpa；Bending modulus: 1800Mpa；Notch impact strength test: 16kJ/m2；It shrinks
Rate: 1.0%；Hardness: 2H；Appearance: without current mark, weldless line.
Embodiment 3: tensile strength: 15Mpa；Bending strength: 1700Mpa；Notch impact strength test: 14kJ/m2；It shrinks
Rate: 0.9%；Hardness: 2H；Appearance: without current mark, weldless line.
Comparative example 1: tensile strength: 15Mpa；Bending strength: 1700Mpa；Notch impact strength test: 13kJ/m2；It shrinks
Rate: 1.0%；Hardness: 2H；Appearance: there are weld bond, the metal equation of light.
Comparative example 2: tensile strength: 13Mpa；Bending strength: 1550Mpa；Notch impact strength test: 11kJ/m2；It shrinks
Rate: 1.0%；Hardness: 2H；Appearance: there is current mark.
Comparative example 3: tensile strength: 12Mpa；Bending strength: 1500Mpa；Notch impact strength test: 10kJ/m2；It shrinks
Rate: 1.3%；Hardness: 1H；Appearance: without current mark, weldless line.
According to testing result it can be found that:
(1) there is weld bond in surface compared with Example 1 for comparative example 1 injection-molded finished, this is because without resin package
Caused by metal-powder thermal coefficient is higher；And metal-powder thermal coefficient reduces after thermosetting resin wraps up, to eliminate
Weld bond；Comparative example 1 is injection-molded finished poor compared to the finished metal gloss of embodiment 1 simultaneously；This is because metal powder
Body (aluminium powder), which is had occurred in melting extrusion due to high temperature, the physical changes such as softens, while chemistry also has occurred with vapor etc.
Reaction, to affect the gloss of metal-powder；After silicon dioxide nano powder resistant to high temperature package, metal-powder is heat-resisting
Performance boost is influenced to become smaller by high temperature.
(2) comparative example 2 it is injection-molded finished compared with Example 1, there is current mark in surface and mechanical property is poor；It is main former
Because being: the compatibility of metal-powder and polypropylene matrix is poor, to not only create current mark and affect mechanical property；And it is straight
The addition of alkyl group hydrochlorate improves the compatibility of metal-powder and polypropylene matrix, does not remove only current mark and improves mechanics
Performance.
(3) shrinking percentage is higher compared with Example 1 for comparative example 3 injection-molded finished, and surface hardness is smaller；This is because ring
Pentadiene can play the role of crosslinking, be intertwined with acrylic resin, improve the hardness of material entirety；Ring simultaneously
The characteristic of pentadiene high temperature depolymerization, will not influence the processing of entire material.
Based on the above description of the preferred embodiments of the present invention, through the above description, related personnel completely can be with
Without departing from the scope of the technological thought of the present invention', various changes and amendments are carried out.The technical scope of this invention
It is not limited to the contents of the specification, it is necessary to determine the technical scope according to the scope of the claims.
Claims (10)
1. one kind is automobile-used to exempt from spraying composite material, it is characterised in that: prepare the raw material composition of the composite material are as follows: polypropylene tree
Rouge, filler, metal-powder, straight chained alkyl hydrochlorate, cyclopentadiene, antioxidant；The metal-powder uses double wrapped, inner
Layer is thermosetting resin cladding, outer layer is silicon dioxide nano powder cladding；The general formula of the straight chained alkyl hydrochlorate is AMX,
Middle A is C15-C25Straight chained alkyl, M is acid group, and X is metal ion.
Automobile-used exempt from spraying composite material 2. according to claim 1, it is characterised in that: the acrylic resin, filler, gold
Belong to the proportion of powder, straight chained alkyl hydrochlorate, cyclopentadiene, antioxidant are as follows: acrylic resin 70-80 mass parts, filler 15-20
Mass parts, metal-powder 2-8 mass parts, straight chained alkyl hydrochlorate 2-6 mass parts, cyclopentadiene 2-5 mass parts, antioxidant 1-3
Mass parts.
Automobile-used exempt from spraying composite material 3. according to claim 1, it is characterised in that: the metal-powder is aluminium powder.
Automobile-used exempt from spraying composite material 4. according to claim 3, it is characterised in that: the thermosetting resin is polypropylene
Acid esters or phenolic resin.
Automobile-used exempt from spraying composite material 5. according to claim 1, it is characterised in that: the acid group is carboxylate radical or sulphur
Acid group.
Automobile-used exempt from spraying composite material 6. according to claim 5, it is characterised in that: the metal ion is sodium, potassium, magnesium
One of.
7. a kind of automobile-used method for exempting from spraying composite material prepared as described in claim 1-6 is any, it is characterised in that: including
Following steps:
(1) metal-powder is added in the organic solution of thermosetting resin, high-speed stirred 1- under conditions of 700-1000rpm
2.5h；Be placed at a temperature of 160-180 DEG C, distillation drying 3-5min, obtain resin clad metal powder；
(2) resin clad metal powder, nano silica powder are weighed respectively by the quality proportioning of 1:0.8-1.2, stirring is equal
It is even；Obtained mixture is put into high shear dispersion machine processing 15-25min, obtains the metal-powder of double-coating；
(3) double-coating metal-powder, the straight chained alkyl acid that acrylic resin, filler, step (2) obtain are weighed after according to the ratio
Salt, cyclopentadiene, antioxidant are uniformly mixed；Uniformly mixed raw material is passed through in extruder and is melted, is squeezed out；
(4) cooling extruded blank；
(5) it is granulated, obtains automobile-used exempting from spraying composite material.
8. according to claim 7 prepare the automobile-used method for exempting from spraying composite material, it is characterised in that: the step (1)
In, the concentration of thermosetting resin organic solution is 30-40wt%；The quality proportioning of metal-powder and thermosetting resin organic solution
For 1:3-5.
9. according to claim 8 prepare the automobile-used method for exempting from spraying composite material, it is characterised in that: the step (1)
In, the solvent in thermosetting resin organic solution is one kind of ethyl alcohol, isopropanol, ethyl acetate.
10. according to claim 7 prepare the automobile-used method for exempting from spraying composite material, it is characterised in that: the step (2)
In, resin clad metal powder, nano silica powder are stirred 2-4h under 200-450rpm revolving speed and are uniformly mixed.
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