CN109251410A - Low warp glass fiber reinforced polypropylene compound material and preparation method thereof - Google Patents
Low warp glass fiber reinforced polypropylene compound material and preparation method thereof Download PDFInfo
- Publication number
- CN109251410A CN109251410A CN201810922704.2A CN201810922704A CN109251410A CN 109251410 A CN109251410 A CN 109251410A CN 201810922704 A CN201810922704 A CN 201810922704A CN 109251410 A CN109251410 A CN 109251410A
- Authority
- CN
- China
- Prior art keywords
- reinforced polypropylene
- glass
- fiber reinforced
- glass fiber
- polypropylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229920001155 polypropylene Polymers 0.000 title claims abstract description 56
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 55
- -1 polypropylene Polymers 0.000 title claims abstract description 55
- 239000003365 glass fiber Substances 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 28
- 150000001875 compounds Chemical class 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 16
- 239000011152 fibreglass Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000004005 microsphere Substances 0.000 claims abstract description 5
- 239000011521 glass Substances 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 6
- 238000005453 pelletization Methods 0.000 claims description 6
- 239000011236 particulate material Substances 0.000 claims description 5
- 230000003078 antioxidant Effects 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N Maleic anhydride Chemical group 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- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Chemical compound 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- 210000002356 Skeleton Anatomy 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group 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C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000001965 increased Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/22—Expandable microspheres, e.g. Expancel®
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
Abstract
The invention belongs to technical field of polymer composite materials, more particularly to low warp glass fiber reinforced polypropylene compound material and preparation method thereof, it is prepared by following raw material according to mass percent proportion: fiber glass reinforced polypropylene modified particles material 95.0-99.9%, microspheres 0.1-5.0%, total 100%, after mixing, it is molded according to conventional Shooting Technique condition.Low warp glass fiber reinforced polypropylene compound material provided by the invention and preparation method thereof can effectively improve the warpage issues of moulding while keeping the basic performance indices of glass fiber reinforced polypropylene composite material.
Description
Technical field
The invention belongs to technical field of polymer composite materials, and in particular to low warp glass fiber reinforced polypropylene compound material
And preparation method thereof.
Background technique
Polypropylene (PP) material has good processing performance and relatively high cost performance.But virgin pp material stiffness
It is relatively low, impact resistance is poor.Therefore for some applications for thering is high-rigidity high impact to require, such as automobile instrument framework,
Skylight skeleton, tail-gate plate, it is often necessary to glass be added as reinforcing filler.Short glass fiber length generally as reinforcing filler is 1-
4 millimeters long, roving glass fiber length is 8-15 millimeters, and diameter is 10-20 microns, and draw ratio is more than 100.And other common increasings
The typical aspect ratio of strong filler such as talcum powder and calcium carbonate is respectively 20 and 1 or so, and usual partial size is 7 microns.Therefore,
Enhance the draw ratio of glass much higher than other common Non-fibrous reinforcing fillers.The so high draw ratio of glass usually makes to be enhanced
Macromolecule base-material stronger molecular chain orientation is generated in injection moulding process, cause be orientated internal stress.In addition, fiberglass reinforced is poly-
The coefficient of heat conduction of propylene is only higher than virgin pp, not as good as the one third of talc powder filled polypropylene.This is easy to lead
It causes to shrink uneven when cooling and shaping and generate cooling internal stress.Therefore the presence of both internal stress often makes fiberglass reinforced
Polypropylene moulding generates warpage.
Summary of the invention
In view of the above technical problems, the object of the present invention is to provide a kind of low warp glass fiber reinforced polypropylene compound materials
Formula and preparation method.Particularly as being to add a small amount of expanded by heating microballoon in the injection molding of fiber glass reinforced polypropylene modified particles, so
The low warpage moulding that warpage is obviously improved can be obtained by by conventional Shooting Technique and equipment afterwards.
It is realized especially by following technical scheme
Low warp glass fiber reinforced polypropylene compound material is prepared by following raw material according to mass percent proportion: glass
Fiber reinforced polypropylene modified particles material 95.0-99.9%, microspheres 0.1-5.0% add up to 100%.
Wherein, the fiber glass reinforced polypropylene modified particles material, including following raw material are matched according to mass fraction and are prepared
Gained: 35~90 parts of polypropylene, 10~65 parts of glass fibre, 0.1-10 parts of compatilizer, antioxidant and ultraviolet absorber 0.1~
0.8 part, 0.1~0.5 part of lubricant.
Further, the polypropylene is homopolypropylene or copolymer polypropylene.
The glass fibre is short glass fiber, long glass fibres or glass fibre master batch.
The compatilizer is maleic anhydride grafts or coupling agent.
It further include other auxiliary agents, as fire retardant can add in right amount according to products application.
The preparation method of low warp glass fiber reinforced polypropylene compound material, comprising the following steps:
Step 1: preparing fiber glass reinforced polypropylene material;
Short glass fiber reinforced polypropylene: using short glass fiber as raw material, lead to after all raw materials are sufficiently mixed in proportion
Extruder extruding pelletization is crossed, short fiber reinforced polypropylene modified particles are made;
Long glass fiber-reinforced polypropylene: using long glass fibres as raw material, the raw material in addition to glass fibre is abundant in proportion
It is compound by cable cladding process or infusion process and continuous long glass fibres after mixing, it is poly- that long fiber reinforced is made after pelletizing
Propylene modified particles;
Step 2: fiber glass reinforced polypropylene modified particles material and microspheres are mixed;
Step 3: being molded according to conventional Shooting Technique condition.
The injection temperature of short glass fiber reinforced polypropylene material is 210 degree or so, the injection molding of long glass fiber-reinforced polypropylene materials
Temperature is 220-250 degree or so.
Low warp glass fiber reinforced polypropylene compound material provided by the invention and preparation method thereof is keeping fiberglass reinforced poly-
While the basic performance indices of acrylic composite, the warpage issues of moulding can be effectively improved.
Specific embodiment
It is described in conjunction with the embodiments the specific technical solution of the present invention.
Expanded by heating microballoon is that inside has escaping gas solvent, the microballoon of heat in the exterior plastic housing structure.Microballoon is heated
Volume can acutely expand 80-100 times afterwards.Present invention employs the thermoplasticity provided by Xi Neng chemical science and technology (Shanghai) Co., Ltd.
Expandable microspheres.
Following percentage is all mass percent.
Embodiment 1: low warpage long glass fiber-reinforced polypropylene is prepared
40% long glass fiber-reinforced polypropylene includes preparing gained by following raw material: melt the polypropylene referred to 100 or so:
54.5%;Maleic anhydride inoculated polypropylene: 5%;Glass: 40%;Antioxidant 1010: 0.25%;Irgasfos 168: 0.25%;
Above-mentioned raw materials obtain long glass fiber reinforced particle by melt impregnation extruding pelletization.Extruder temperature is set in 170
Between~220 DEG C, dipping die head temperature is set as 280 degree.
In long glass fiber reinforced particulate material addition 1% expanded by heating microballoon, it is dry-mixed uniformly after, under 230 degree injection molding grow
Rectangular big plate B.
As a comparison, then long glass fiber reinforced particulate material is molded to the big plate A of rectangle directly under 230 degree.
Embodiment 2: low warpage short glass fiber reinforced polypropylene is prepared
40% short glass fiber reinforced polypropylene includes following raw material components: melt refer to 20 or so polypropylene: 85.5%;Malaysia
Anhydride-grafted polypropylene: 4%;Glass: 20%;Antioxidant 1010: 0.25%;Irgasfos 168: 0.25%;
Above-mentioned raw materials, which obtain short glass fiber by double-screw extruding pelletizing, enhances particle.Extruder temperature is set in 170~220
Between DEG C.
This short glass fiber enhancing particulate material in addition 1% expanded by heating microballoon, it is dry-mixed uniformly after, also 210 degree bets
Mould the big plate D of rectangle.
As a comparison, above-mentioned short glass fiber enhancing particulate material is directly molded the big plate C of rectangle under 210 degree.
Resulting product warpage appraisal procedure:
Firstly, the big plate of injection molding rectangle (356X100X3.2mm).Then, it 24 hours after injection molding is completed, will grow
The rectangular big plate tow sides of injection molding are successively horizontally arranged, and record is detached from the most apex angle of horizontal plane at a distance from horizontal plane.Record
The average value of at least 5 pieces slab warpings.Testing result is shown in Table 2.
Table 1: it is molded big plate ingredient
A | B | C | D | |
40% long glass fiber-reinforced polypropylene | 100% | 99% | ||
20% short glass fiber reinforced polypropylene | 100% | 99% | ||
Expanded by heating microballoon | 1% | 1% |
Table 2: it is molded big plate performance
Warpage degree (millimeter) | Density (g/cm3) | Charpy Impact (KJ/cm2) | |
A | 2.3 | 1.22 | 71 |
B | 0.7 | 1.21 | 69 |
C | 1.8 | 1.22 | 13 |
D | 0.5 | 1.21 | 13 |
The warpage of moulding is significantly improved by the expanded by heating microballoon of the visible addition 1% of table 2, simultaneously other are basic
Physical property such as density and impact property is uninfluenced.
Claims (6)
1. low warp glass fiber reinforced polypropylene compound material, which is characterized in that matched including following raw material according to mass percent
Be prepared: fiber glass reinforced polypropylene modified particles material 95.0-99.9%, microspheres 0.1-5.0% add up to 100%.
2. low warp glass fiber reinforced polypropylene compound material according to claim 1, which is characterized in that the glass increases
Strong polypropylene modification particulate material, including following raw material match obtained by preparation according to mass fraction: 35~90 parts of polypropylene, glass fibers
10~65 parts of dimension, 0.1-10 parts of compatilizer, antioxidant and 0.1~0.8 part of ultraviolet absorber, 0.1~0.5 part of lubricant.
3. low warp glass fiber reinforced polypropylene compound material according to claim 2, which is characterized in that the polypropylene
For homopolypropylene or copolymer polypropylene.
4. low warp glass fiber reinforced polypropylene compound material according to claim 2, which is characterized in that the glass fibers
Dimension is short glass fiber, long glass fibres or glass fibre master batch.
5. low warp glass fiber reinforced polypropylene compound material according to claim 2, which is characterized in that described is compatible
Agent is maleic anhydride grafts or coupling agent.
6. according to claim 1 to the preparation method of low warp glass fiber reinforced polypropylene compound material described in 5, feature exists
In, comprising the following steps:
Step 1: preparing fiber glass reinforced polypropylene modified particles material;
Short glass fiber reinforced polypropylene: using short glass fiber as raw material, by squeezing after all raw materials are sufficiently mixed in proportion
Short fiber reinforced polypropylene modified particles are made in machine extruding pelletization out;
Long glass fiber-reinforced polypropylene: using long glass fibres as raw material, the raw material in addition to glass fibre is sufficiently mixed in proportion
It is compound by cable cladding process or infusion process and continuous long glass fibres after good, long fiber reinforced polypropylene is made after pelletizing
Modified particles;
Step 2: fiber glass reinforced polypropylene modified particles material and microspheres are mixed;
Step 3: being molded according to conventional Shooting Technique condition;
The injection temperature of short fiber reinforced polypropylene modified particles is 210 degree, the injection temperature of long fiber reinforced polypropylene modification particle
For 220-250 degree.
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