CN109134993A - A kind of wear-resistant polyolefin composite material and preparation method for rapid shaping - Google Patents
A kind of wear-resistant polyolefin composite material and preparation method for rapid shaping Download PDFInfo
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- CN109134993A CN109134993A CN201710457812.2A CN201710457812A CN109134993A CN 109134993 A CN109134993 A CN 109134993A CN 201710457812 A CN201710457812 A CN 201710457812A CN 109134993 A CN109134993 A CN 109134993A
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- C—CHEMISTRY; METALLURGY
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The present invention provides a kind of wear-resistant polyolefin composite material and preparation methods for rapid shaping, are made of following raw material: 100 parts of resin matrix, 5~45 parts of ultrashort glass, 2~10 parts of compatilizer, 0.5~2.5 part of coupling agent, 0.1~0.5 part of heat stabilizer, 0.05~0.25 part of antioxidant, 0.05~0.25 part of lubricant.Wear-resistant polyolefin composite material prepared by the present invention for fusion stacking rapid shaping has the characteristics that high-intensitive, high heat resistance and high abrasion, the shaping speed of product is further increased simultaneously, furthermore production equipment according to the present invention and process for producing composite material are simple, can directly using and be extended to fusion stacking rapid shaping field, and prepare the component that there is certain wearability to require.
Description
Technical field
The present invention relates to rapid shaping material modification field, specially a kind of wear-resistant polyolefin for rapid shaping is compound
Material and preparation method thereof.
Background technique
Fusion stacking molding, using heater strip as heat source, passes through the side of heating melting using Filamentous or fibrous material as raw material
Formula completes material building in the form that stratiform is accumulated.Such rapid shaping technique simple process, does not generate poison gas or change in the process
Pollution is learned, is highly suitable for the modeling and reverse R&D work at product development initial stage, may be directly applied to working environment.Melting layer
The product most common raw material of rapid shaping technique is synthetic rubber, oily wax or pure resin material, therefore product after molding is in mechanics
Intensity, heat resistance and shaping speed are convenient insufficient, and furthermore the wearability of material is very poor, are unfavorable for the initial stage test of component
And research and development.
Summary of the invention
The present invention is prepared for innovatively with ultrashort glass improved polyalkene composite material for the wear-resisting poly- of rapid shaping
Alkene composite material.
To achieve the above object, the invention adopts the following technical scheme:
A kind of wear-resistant polyolefin composite material for rapid shaping includes following components and parts by weight content: resin base
100 parts of body, 5~45 parts of ultrashort glass, 0.5~2.5 part of coupling agent, 0.1~0.5 part of heat stabilizer, resists by 2~10 parts of compatilizer
0.05~0.25 part of oxygen agent, 0.05~0.25 part of lubricant.
Preferably, the resin matrix is polyethylene or copolymer polypropylene.
Preferably, the ultrashort Length of Glass Fiber is 10~150 μm.
Preferably, the compatilizer is maleic anhydride grafted polyethylene or maleic anhydride inoculated polypropylene.
Preferably, the coupling agent is gamma-aminopropyl-triethoxy-silane or γ-(2,3- the third oxygen of epoxy) propyl three
Methoxy silane.
Preferably, the heat stabilizer is epoxy stearate or epoxy tetrahydrophthalic acid ester.
Preferably, the antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, three
[2.4- di-tert-butyl-phenyl] phosphite ester or the double octadecyls of thio-2 acid.
Preferably, the lubricant is ethylidine bis-stearamides or pentaerythritol stearate.
A kind of preparation method of the wear-resistant polyolefin composite material for rapid shaping comprising the steps of:
(1) by 100 parts of resin matrix, 5~45 parts of ultrashort glass, 2~10 parts of compatilizer, 0.5~2.5 part of coupling agent, heat
0.1~0.5 part of stabilizer, 0.05~0.25 part of antioxidant and 0.05~0.25 part of lubricant are uniformly mixed, and it is mixed to be placed in high speed
Conjunction machine disperses 10~30 minutes；
(2) by the raw material after dispersion by after melting, plasticizing, extrusion, traction, being made for fast rapid-result in extruder
The wear-resistant polyolefin composite material of type.
Composite material is configured to test bars through fusion stacking molding mode.
The invention has the following advantages:
1, ultrashort glass is after coupling agent treatment, can improve and the combination effect of resin matrix, effectively reduces material
The probability that defect occurs, perfect internal structure, can effectively improve whole mechanical strength；
2, for compared with polyolefin resin, ultrashort glass has apparent heat-resisting advantage, can significantly improve after introducing compound
The heat resistance of material；
3, after ultrashort glass is dispersed in resin matrix, the abrasion of basis material can be effectively reduced, improve wearability；
4, in fusion stacking forming process, the fibrous structure of ultrashort glass can effectively play a supporting role, and show
The shaping speed for accelerating composite material is write, molding cycle is shortened.
Therefore the wear-resistant polyolefin composite material prepared by the present invention for fusion stacking rapid shaping has high-intensitive, high
The features such as heat-resisting and high abrasion, while further increasing the shaping speed of product.Furthermore production equipment according to the present invention and
Process for producing composite material is simple, can directly using and be extended to fusion stacking rapid shaping field, and prepare have it is certain resistance to
The component that mill property requires.
Specific implementation method
The content of present invention is further detailed below with reference to specific example, but it is to this hair that the embodiment, which is not,
The simple restriction of bright connotation, it is any to should belong to based on simple change made by true spirit or equivalent replacement
Within scope of the present invention.
After the sample of preparation is adjusted under 23 DEG C, 50% humidity environment, be respectively adopted ASTM D638, ASTM D648 and
ASTM D1242 detects tensile strength, heat distortion temperature and wearability, and records shaping speed.
Specific embodiments of the present invention are as follows:
Example 1
(1) be equipped with raw material in the following proportions: 100 parts of polyvinyl resin matrix, length is 5 parts of ultrashort glass of 10 μm, phase
Hold 2 parts of agent maleic anhydride grafted polyethylene, 0.5 part of coupling agent gamma-aminopropyl-triethoxy-silane, heat stabilizer epoxy is stearic
0.1 part of acid esters, 0.02 part of pentaerythritol ester of antioxidant four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid], antioxidant three
0.03 part of phosphite ester of [2.4- di-tert-butyl-phenyl], 0.05 part of lubricant ethylidine bis-stearamides are placed in high-speed mixer
Dispersion 10 minutes；
(2) by the raw material after dispersion by after melting, plasticizing, extrusion, traction, being made for fast rapid-result in extruder
The wear-resistant polyolefin composite material of type.
Composite material is configured to test bars through fusion stacking molding mode.Composite property is shown in Table one.
Example 2
(1) be equipped with raw material in the following proportions: 100 parts of polyvinyl resin matrix, length is 15 parts of ultrashort glass of 10 μm, phase
4 parts of agent maleic anhydride grafted polyethylene of appearance, 1 part of coupling agent gamma-aminopropyl-triethoxy-silane, heat stabilizer epoxystearic acid
0.2 part of ester, 0.04 part of pentaerythritol ester of antioxidant four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid], antioxidant three
0.06 part of phosphite ester of [2.4- di-tert-butyl-phenyl], 0.1 part of lubricant ethylidine bis-stearamides are placed in high-speed mixer point
It dissipates 15 minutes；
(2) by the raw material after dispersion by after melting, plasticizing, extrusion, traction, being made for fast rapid-result in extruder
The wear-resistant polyolefin composite material of type.
Composite material is configured to test bars through fusion stacking molding mode.Composite property is shown in Table one.
Example 3
(1) be equipped with raw material in the following proportions: 100 parts of polyvinyl resin matrix, length is 25 parts of ultrashort glass of 10 μm, phase
Hold 6 parts of agent maleic anhydride grafted polyethylene, 1.5 parts of coupling agent gamma-aminopropyl-triethoxy-silane, heat stabilizer epoxy is stearic
0.3 part of acid esters, 0.06 part of pentaerythritol ester of antioxidant four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid], antioxidant three
0.09 part of phosphite ester of [2.4- di-tert-butyl-phenyl], 0.15 part of lubricant ethylidine bis-stearamides are placed in high-speed mixer
Dispersion 20 minutes；
(2) by the raw material after dispersion by after melting, plasticizing, extrusion, traction, being made for fast rapid-result in extruder
The wear-resistant polyolefin composite material of type.
Composite material is configured to test bars through fusion stacking molding mode.Composite property is shown in Table one.
Example 4
(1) be equipped with raw material in the following proportions: 100 parts of polyvinyl resin matrix, length is 35 parts of ultrashort glass of 10 μm, phase
8 parts of agent maleic anhydride grafted polyethylene of appearance, 2 parts of coupling agent gamma-aminopropyl-triethoxy-silane, heat stabilizer epoxystearic acid
0.4 part of ester, 0.08 part of pentaerythritol ester of antioxidant four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid], antioxidant three
0.12 part of phosphite ester of [2.4- di-tert-butyl-phenyl], 0.2 part of lubricant ethylidine bis-stearamides are placed in high-speed mixer point
It dissipates 25 minutes；
(2) by the raw material after dispersion by after melting, plasticizing, extrusion, traction, being made for fast rapid-result in extruder
The wear-resistant polyolefin composite material of type.
Composite material is configured to test bars through fusion stacking molding mode.Composite property is shown in Table one.
Example 5
(1) be equipped with raw material in the following proportions: 100 parts of polyvinyl resin matrix, length is 45 parts of ultrashort glass of 10 μm, phase
Hold 10 parts of agent maleic anhydride grafted polyethylene, 2.5 parts of coupling agent gamma-aminopropyl-triethoxy-silane, heat stabilizer epoxy is stearic
0.5 part of acid esters, 0.1 part of pentaerythritol ester of antioxidant four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid], antioxidant three
0.15 part of phosphite ester of [2.4- di-tert-butyl-phenyl], 0.25 part of lubricant ethylidine bis-stearamides are placed in high-speed mixer
Dispersion 30 minutes；
(2) by the raw material after dispersion by after melting, plasticizing, extrusion, traction, being made for fast rapid-result in extruder
The wear-resistant polyolefin composite material of type.
Composite material is configured to test bars through fusion stacking molding mode.Composite property is shown in Table one.
Example 6
(1) it is equipped with raw material in the following proportions: 100 parts of acrylic resin copolymer matrix, the ultrashort glass 5 that length is 150 μm
Part, 2 parts of compatilizer maleic anhydride inoculated polypropylene, 0.5 part of propyl trimethoxy silicane of coupling agent γ-(2,3- the third oxygen of epoxy),
0.1 part of ester of heat stabilizer epoxy tetrahydrophthalic acid, antioxidant four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid]
0.02 part of pentaerythritol ester, double 0.03 part of the octadecyls of antioxidant thio-2 acid, lubricant pentaerythritol stearate 0.05
Part, it is placed in high-speed mixer and disperses 10 minutes；
(2) by the raw material after dispersion by after melting, plasticizing, extrusion, traction, being made for fast rapid-result in extruder
The wear-resistant polyolefin composite material of type.
Composite material is configured to test bars through fusion stacking molding mode.Composite property is shown in Table one.
Example 7
(1) it is equipped with raw material in the following proportions: 100 parts of acrylic resin copolymer matrix, the ultrashort glass 15 that length is 150 μm
Part, 4 parts of compatilizer maleic anhydride inoculated polypropylene, 1 part of propyl trimethoxy silicane of coupling agent γ-(2,3- the third oxygen of epoxy),
0.2 part of ester of heat stabilizer epoxy tetrahydrophthalic acid, antioxidant four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid]
0.04 part of pentaerythritol ester, double 0.06 part of the octadecyls of antioxidant thio-2 acid, lubricant pentaerythritol stearate 0.1
Part, it is placed in high-speed mixer and disperses 15 minutes；
(2) by the raw material after dispersion by after melting, plasticizing, extrusion, traction, being made for fast rapid-result in extruder
The wear-resistant polyolefin composite material of type.
Composite material is configured to test bars through fusion stacking molding mode.Composite property is shown in Table one.
Example 8
(1) it is equipped with raw material in the following proportions: 100 parts of acrylic resin copolymer matrix, the ultrashort glass 25 that length is 150 μm
Part, 6 parts of compatilizer maleic anhydride inoculated polypropylene, coupling agent γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane 1.5
Part, 0.3 part of ester of heat stabilizer epoxy tetrahydrophthalic acid, [the β-(3,5- di-tert-butyl-hydroxy phenyl) third of antioxidant four
Acid] 0.06 part of pentaerythritol ester, double 0.09 part of the octadecyls of antioxidant thio-2 acid, lubricant pentaerythritol stearate
It 0.15 part, is placed in high-speed mixer and disperses 20 minutes；
(2) by the raw material after dispersion by after melting, plasticizing, extrusion, traction, being made for fast rapid-result in extruder
The wear-resistant polyolefin composite material of type.
Composite material is configured to test bars through fusion stacking molding mode.Composite property is shown in Table one.
Example 9
(1) it is equipped with raw material in the following proportions: 100 parts of acrylic resin copolymer matrix, the ultrashort glass 35 that length is 150 μm
Part, 8 parts of compatilizer maleic anhydride inoculated polypropylene, 2 parts of propyl trimethoxy silicane of coupling agent γ-(2,3- the third oxygen of epoxy),
0.4 part of ester of heat stabilizer epoxy tetrahydrophthalic acid, antioxidant four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid]
0.08 part of pentaerythritol ester, double 0.12 part of the octadecyls of antioxidant thio-2 acid, lubricant pentaerythritol stearate 0.2
Part, it is placed in high-speed mixer and disperses 25 minutes；
(2) by the raw material after dispersion by after melting, plasticizing, extrusion, traction, being made for fast rapid-result in extruder
The wear-resistant polyolefin composite material of type.
Composite material is configured to test bars through fusion stacking molding mode.Composite property is shown in Table one.
Example 10
(1) it is equipped with raw material in the following proportions: 100 parts of acrylic resin copolymer matrix, the ultrashort glass 45 that length is 150 μm
Part, 10 parts of compatilizer maleic anhydride inoculated polypropylene, coupling agent γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane 2.5
Part, 0.5 part of ester of heat stabilizer epoxy tetrahydrophthalic acid, [the β-(3,5- di-tert-butyl-hydroxy phenyl) third of antioxidant four
Acid] 0.1 part of pentaerythritol ester, double 0.15 part of the octadecyls of antioxidant thio-2 acid, lubricant pentaerythritol stearate
It 0.25 part, is placed in high-speed mixer and disperses 30 minutes；
(2) by the raw material after dispersion by after melting, plasticizing, extrusion, traction, being made for fast rapid-result in extruder
The wear-resistant polyolefin composite material of type.
Composite material is configured to test bars through fusion stacking molding mode.Composite property is shown in Table one.
Case of comparative examples 1
(1) it is equipped with raw material in the following proportions: 100 parts of polyvinyl resin matrix, 0.1 part of heat stabilizer epoxy stearate,
0.02 part of pentaerythritol ester of antioxidant four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid], [the tertiary fourth of 2.4- bis- of antioxidant three
Base phenyl] 0.03 part of phosphite ester, 0.05 part of lubricant ethylidine bis-stearamides are placed in high-speed mixer and disperse 10 minutes；
(2) by the raw material after dispersion by after melting, plasticizing, extrusion, traction, being made for fast rapid-result in extruder
The wear-resistant polyolefin composite material of type.
Composite material is configured to test bars through fusion stacking molding mode.Polythene material performance is shown in Table one.
Case of comparative examples 2
(1) it is equipped with raw material in the following proportions: 100 parts of acrylic resin copolymer matrix, heat stabilizer epoxy tetrahydro neighbour benzene two
0.1 part of formic acid esters, 0.02 part of pentaerythritol ester of antioxidant four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid], antioxidant
Thio-2 acid double 0.03 part of octadecyls, are placed in high-speed mixer dispersion 10 by 0.05 part of lubricant pentaerythritol stearate
Minute；
(2) by the raw material after dispersion by after melting, plasticizing, extrusion, traction, being made for fast rapid-result in extruder
The wear-resistant polyolefin composite material of type.
Composite material is configured to test bars through fusion stacking molding mode.Polypropylene material performance is shown in Table one.
Table one:
Wear-resistant polyolefin composite material prepared by the present invention for fusion stacking rapid shaping has high-intensitive, high heat resistance
And the features such as high abrasion, while further increasing the shaping speed of product.It is by data in table one it is found that prepared by the present invention super
Short glass fiber modified poly ethylene composite material tensile strength is up to 27, and (case of comparative examples 1) improves 50.0% more before modified；Thermal change
Shape temperature is up to 52 DEG C, improves 40.5% more before modified；Taber Abrasion is 58mg/1000 times minimum, reduces more before modified
30.1%；Shaping speed is most 35cm fastly3/ h, improves 52.2% more before modified.Ultrashort glass modified copolymer prepared by the present invention
PP composite material tensile strength is up to 32, and (case of comparative examples 2) improves 52.4% more before modified；Heat distortion temperature is up to
97 DEG C, 29.3% is improved more before modified；Taber Abrasion is 44mg/1000 times minimum, reduces by 38.9% more before modified；Shaping speed
It is most fastly 41cm3/ h, improves 57.7% more before modified.Furthermore production equipment according to the present invention and process for producing composite material
Simply, can directly using and be extended to fusion stacking rapid shaping field, and prepare the component that there is certain wearability to require.
This hair can be understood and applied the above description of the embodiments is intended to facilitate those skilled in the art
It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to implementations here
Example, those skilled in the art's announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be
Within protection scope of the present invention.
Claims (9)
1. a kind of wear-resistant polyolefin composite material for rapid shaping, which is characterized in that contain comprising following components and parts by weight
Amount:
100 parts of resin matrix,
5~45 parts of ultrashort glass,
2~10 parts of compatilizer,
0.5~2.5 part of coupling agent,
0.1~0.5 part of heat stabilizer,
0.05~0.25 part of antioxidant,
0.05~0.25 part of lubricant.
2. a kind of wear-resistant polyolefin composite material for rapid shaping as described in claim 1, which is characterized in that described
Resin matrix is polyethylene or copolymer polypropylene.
3. a kind of wear-resistant polyolefin composite material for rapid shaping as described in claim 1, which is characterized in that described
Ultrashort Length of Glass Fiber is 10~150 μm.
4. a kind of wear-resistant polyolefin composite material for rapid shaping as described in claim 1, which is characterized in that described
Compatilizer is maleic anhydride grafted polyethylene or maleic anhydride inoculated polypropylene.
5. a kind of wear-resistant polyolefin composite material for rapid shaping as described in claim 1, which is characterized in that described
Coupling agent is gamma-aminopropyl-triethoxy-silane or γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy silicane.
6. a kind of wear-resistant polyolefin composite material for rapid shaping as described in claim 1, which is characterized in that described
Heat stabilizer is epoxy stearate or epoxy tetrahydrophthalic acid ester.
7. a kind of wear-resistant polyolefin composite material for rapid shaping as described in claim 1, which is characterized in that described
Antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, three [2.4- di-tert-butyl-phenyls] Asia
Phosphate or the double octadecyls of thio-2 acid.
8. a kind of wear-resistant polyolefin composite material for rapid shaping as described in claim 1, which is characterized in that described
Lubricant is ethylidine bis-stearamides or pentaerythritol stearate.
9. a kind of preparation method of wear-resistant polyolefin composite material for rapid shaping as described in claim 1 ~ 8 is any,
It is characterized in that comprising the steps of:
(1) by 100 parts of resin matrix, 5~45 parts of ultrashort glass, 2~10 parts of compatilizer, 0.5~2.5 part of coupling agent, thermostabilization
0.1~0.5 part of agent, 0.05~0.25 part of antioxidant and 0.05~0.25 part of lubricant are uniformly mixed, and are placed in high-speed mixer
Dispersion 10~30 minutes；
(2) by the raw material after dispersion by after melting, plasticizing, extrusion, traction, being made for rapid shaping in extruder
Wear-resistant polyolefin composite material.
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Application publication date: 20190104 |