CN106349559A - Long glass fiber reinforced PP (polypropylene) composite material and preparation method thereof - Google Patents
Long glass fiber reinforced PP (polypropylene) composite material and preparation method thereof Download PDFInfo
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- CN106349559A CN106349559A CN201610735672.6A CN201610735672A CN106349559A CN 106349559 A CN106349559 A CN 106349559A CN 201610735672 A CN201610735672 A CN 201610735672A CN 106349559 A CN106349559 A CN 106349559A
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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
- C08L23/12—Polypropene
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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
- C08K2201/003—Additives being defined by their diameter
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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
- C08L2201/04—Antistatic
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention provides a long glass fiber reinforced PP (polypropylene) composite material. A compatilizer is arranged particularly, so that compatibility between long glass fibers and PP can be improved effectively. According to the long glass fiber reinforced PP composite material, liquid polysulfide rubber can react with the PP, and a part of soft segment is introduced, so that the modulus of the PP is reduced, the tenacity is improved but the heat resistance is sacrificed; during curing at a room temperature, liquid butadiene-acrylonitrile rubber, as a toughening agent of the PP, has almost no toughening effect and the bonding strength is reduced; the liquid butadiene-acrylonitrile rubber is remarkable in toughening and bonding effects only in a medium-high-temperature curing system; when carboxylated-terminated liquid butadiene-acrylonitrile rubber is used for toughening the PP, the long glass fibers and the PP are compatible before curing and separating in phase after curing to form a sea-island structure, and accordingly the long glass fiber reinforced PP composite material is capable of absorbing energy and maintaining heat resistance basically.
Description
Technical field
The present invention relates to technical field of composite materials, a kind of specifically long glass fiber reinforced pp composite and preparation method thereof.
Background technology
Long glass fibres strengthens the pellet that pellet refers to one-way fiber arrangement, and its fibre length is equal with pellet length,
Generally higher than 5mm.At home, the research of roving glass fiber is still at an early stage, and roving glass fiber is generally used for improving macromolecular material
Mechanical property.Acrylic resin (pp) is a kind of broad-spectrum general-purpose plastics, is obtained by propylene monomer polymerization, acrylic resin
Advantage be that density is low, low price, and there is excellent chemical resistance, preferable mechanical performance, prominent folding
Folded property and good moulding processability.As typical crystalline materials, its fusing point is near 165 DEG C.
Long glass fiber reinforced pp material is that dimensionally stable is good with high intensity, high impact resistance, is a kind of " Qiang Erren "
Material, pp add glass fiber reinforcement after, greatly improve its mechanical performance, heat resistant type and dimensional stability.Answer actual
With in can with mould Dai Gang and replace enhancement engineering plastics, meet the fields such as small arms packing cratess, automotive field, household electrical appliances using will
Ask.But when existing roving glass fiber material is used for strengthening pp, easily occur easily producing floating fibre, dispersion effect is not good, heat stability
Difference, the range of work is narrow, the defect such as the material of mixed system does not can be uniformly dispersed.
Existing long glass fiber reinforced polypropylene material and preparation method thereof, for directly adding in polypropylene material
Glass fibre, Chinese patent 200710172918.4 discloses a kind of ultralong unit extension glass fiber reinforced polypropylene composite wood
Material, including polypropylene pp, glass fibre, composite antioxidant and other auxiliary agents, has an advantage in that, rate elongation is high and improves its thing
Rationality energy.
Chinese patent 200710172953.6 discloses a kind of glass fiber reinforced nylon 6-polypropylene alloy material,
Including nylon 6 resin, polypropylene, glass fibre, toughener, antioxidant, have an advantage in that lower cost for material and have good
Good impact property.
The defect of above prior art is that glass processing procedure is pretty troublesome, treatment fluid complicated component.Simultaneously also cannot be effective
Suppression float fibre phenomenon, obtained pp composite materials property, especially notched Izod impact hit performance and cannot meet using will
Ask.Meanwhile, the long glass fiber reinforced pp material obtained by prior art in injection, will assemble, float on surface of the work by roving glass fiber.
Content of the invention
In view of this, the present invention discloses a kind of low floating fibre, high-impact, the roving glass fiber of antistatic.
The purpose of the present invention is achieved through the following technical solutions:
A kind of long glass fiber reinforced pp composite, its raw material includes by weight:
Alkali-free roving glass fiber 10-30 part；
Pp 60-90 part；
Light stabilizer 0.1-0.5 part；
Toughener 0.5-0.9 part；
Compatilizer 2-6 part；
Antioxidant 0.3-0.8 part；
Described alkali-free continuous glass-fiber length is 6-12mm, a diameter of 11-20 μm；Its raw material of described compatilizer includes hydroxyl by weight
Ethyl cellulose 2-3 part, propylene glycol 0.1-0.5 part, Polyvinylpyrrolidone 0.01-0.07 part, potassium nitrate 3-8 part.
In the present invention, especially a kind of compatilizer is set, the compatibility of roving glass fiber and pp can be effectively improved.Polyvinylpyrrolidine
Ketone is highly soluble in water and containing halogenated hydrocarbon solvent, alcohols, amine, nitroparaffins and low-molecular-weight fatty acid etc., insoluble in acetone, second
The minority solvent such as ether, Oleum Terebinthinae, aliphatic hydrocarbon and alicyclic.Can be compatible with most inorganic acid salts, various kinds of resin.Described compatilizer energy
Enough surface adsorption abilities effectively strengthening pp, so that alkali-free roving glass fiber more uniformly disperse and pp in, make alkali-free roving glass fiber and pp
Crosslinked compound action significantly increase, effectively improve the toughness of composite.Meanwhile, Polyvinylpyrrolidone energy and liquid polysulfide
Rubber synergistic, can form one layer of smooth organic molecule film layer on pp surface, greatly enhance the antistatic property of material.
Further, described light stabilizer is 527uv；Described toughener is liquid polysulfide rubber；Described antioxidant is antioxygen
Agent 168.
Light stabilizer and toughener, antioxidant all can be selected for prior art and realizes.
Further, described long glass fiber reinforced pp composite also includes the thermoplastic stabilizer of 0.2-0.3 part by weight；Institute
State the hydrochloric acid that thermoplastic stabilizer includes the sodium sulfate of 1-3 part, 0.1-0.4 part calcium chloride and 2-3 part 3wt% concentration by weight.
Long glass fiber reinforced pp composite injection when, due to mobility, the density contrast of the low temperature, pp and roving glass fiber of mould
Different, roving glass fiber is easily separated with pp, leads to the product table edema over the face fibre roving glass fiber of molding, while impact product appearance, due to producing
The roving glass fiber on product surface is assembled and firmly crisp, frangible, and interiors of products roving glass fiber concentration is low and easy stress deformation.The therefore present invention
It is especially added with thermoplastic stabilizer, maintain roving glass fiber, pp mixed system when long glass fiber reinforced pp composite of the present invention is molded
Stability, prevents roving glass fiber and pp layering under molten condition it is ensured that the smooth in appearance of injecting products and possess good mechanical property
Energy.Above effect has sodium sulfate, calcium chloride and hydrochloric acid synergistic to produce.
Present invention simultaneously provides a kind of method preparing described long glass fiber reinforced pp composite, comprise the steps:
A. prepare compatilizer: hydroxyethyl cellulose, potassium nitrate are heated to 100 DEG C using air bath, instill propylene glycol, insulation
Polyvinylpyrrolidone is added after 30min；
B. the preparation of thermoplastic stabilizer: described sodium sulfate, calcium chloride and mixed in hydrochloric acid are heated to 50 DEG C and keep 20min；
C. press setting weight part and pp, light stabilizer, toughener, compatilizer, antioxidant, thermoplastic stabilizer are added mixed at high speed
Device mix homogeneously post-heating is cooled to 35～40 DEG C to after 80～90 DEG C, is subsequently adding the long glass of alkali-free of setting weight part
Fibre, is obtained long glass fiber reinforced pp composite through mixing, forming processes.
Above compatilizer, the preparation method of thermoplastic stabilizer, be conducive to improve compatilizer, thermoplastic stabilizer effectiveness send out
Wave.The unspecified technical characteristic of the present invention, all can be selected for prior art and realizes.
The present invention provides a kind of long glass fiber reinforced pp composite, especially arranges a kind of compatilizer, can effectively improve long glass
The fine compatibility with pp.In the presence of micro Polyvinylpyrrolidone and potassium nitrate, it is 6-12mm that length just can be greatly improved,
A diameter of 11-20 μm of roving glass fiber and the compatibility of pp material, make roving glass fiber be uniformly mixed in pp material, effectively improve institute
The mechanical property of prepared pp composite.Present invention simultaneously provides a kind of side preparing described long glass fiber reinforced pp composite
Method, design compatilizer, the preparation method of thermoplastic stabilizer, be conducive to improving compatilizer, the performance of thermoplastic stabilizer effectiveness.
Liquid polysulfide rubber can be reacted with pp, introduces a part of soft segment, reduce pp modulus, improve toughness, sacrificial
Domestic animal thermostability.LNBR as the toughener of pp, almost without toughening effect during cold curing, adhesive strength on the contrary under
Fall；Only high temperature curing system, toughness reinforcing more apparent with adhesive effect.The toughness reinforcing pp of carboxyl end of the liquid acrylonitrile-butadiene rubber, phase before solidification
Hold, split-phase after solidification, formed " island structure ", can apparatus with shock absorbing, and substantially do not reduce thermostability.
Specific embodiment
For the ease of it will be appreciated by those skilled in the art that being described in further detail to the present invention below in conjunction with embodiment:
Embodiment 1
The present embodiment provides a kind of long glass fiber reinforced pp composite, and its raw material includes by weight:
23 parts of alkali-free roving glass fiber；
88 parts of pp；
0.3 part of light stabilizer；
0.7 part of toughener；
5 parts of compatilizer；
0.6 part of antioxidant；
Described alkali-free continuous glass-fiber length is 10mm, a diameter of 14 μm；Its raw material of described compatilizer includes ethoxy by weight
2.5 parts of cellulose, 0.2 part of propylene glycol, 0.04 part of Polyvinylpyrrolidone, 5 parts of potassium nitrate.
Further, described light stabilizer is 527uv；Described toughener is liquid polysulfide rubber；Described antioxidant is anti-
Oxygen agent 168.
Further, described long glass fiber reinforced pp composite also includes 0.2 part by weight of thermoplastic stabilizer；Described
Thermoplastic stabilizer includes the hydrochloric acid of 2 parts by weight of sodium sulfate, 0.2 part of calcium chloride and 3 parts of 3wt% concentration.
The present embodiment also provides a kind of method preparing above-mentioned long glass fiber reinforced pp composite, comprises the steps:
A. prepare compatilizer: hydroxyethyl cellulose, potassium nitrate are heated to 100 DEG C using air bath, instill propylene glycol, insulation
Polyvinylpyrrolidone is added after 30min；
B. the preparation of thermoplastic stabilizer: described sodium sulfate, calcium chloride and mixed in hydrochloric acid are heated to 50 DEG C and keep 20min；
C. press setting weight part and pp, light stabilizer, toughener, compatilizer, antioxidant, thermoplastic stabilizer are added mixed at high speed
Device mix homogeneously post-heating is cooled to 35～40 DEG C to after 80～90 DEG C, is subsequently adding the long glass of alkali-free of setting weight part
Fibre, is obtained long glass fiber reinforced pp composite through mixing, forming processes.
Embodiment 2
The present embodiment provides a kind of long glass fiber reinforced pp composite, and its raw material includes by weight:
30 parts of alkali-free roving glass fiber；
60 parts of pp；
0.5 part of light stabilizer；
0.5 part of toughener；
6 parts of compatilizer；
0.3 part of antioxidant；
Described alkali-free continuous glass-fiber length is 12mm, a diameter of 11 μm；Its raw material of described compatilizer includes ethoxy by weight
3 parts of cellulose, 0.1 part of propylene glycol, 0.07 part of Polyvinylpyrrolidone, 3 parts of potassium nitrate.
Further, described light stabilizer is 527uv；Described toughener is liquid polysulfide rubber；Described antioxidant is anti-
Oxygen agent 168.
Further, described long glass fiber reinforced pp composite also includes 0.3 part by weight of thermoplastic stabilizer；Described
Thermoplastic stabilizer includes the hydrochloric acid of 1 part by weight of sodium sulfate, 0.4 part of calcium chloride and 2 parts of 3wt% concentration.
The present embodiment adopts the method for embodiment 1 to be obtained.
Embodiment 3
The present embodiment provides a kind of long glass fiber reinforced pp composite, and its raw material includes by weight:
10 parts of alkali-free roving glass fiber；
90 parts of pp；
0.1 part of light stabilizer；
0.9 part of toughener；
2 parts of compatilizer；
0.8 part of antioxidant；
Described alkali-free continuous glass-fiber length is 6mm, a diameter of 20 μm；It is fine that its raw material of described compatilizer includes ethoxy by weight
2 parts of dimension element, 0.5 part of propylene glycol, 0.01 part of Polyvinylpyrrolidone, 8 parts of potassium nitrate.
Further, described light stabilizer is 527uv；Described toughener is liquid polysulfide rubber；Described antioxidant is anti-
Oxygen agent 168.
Further, described long glass fiber reinforced pp composite also includes 0.2 part by weight of thermoplastic stabilizer；Described
Thermoplastic stabilizer includes the hydrochloric acid of 3 parts by weight of sodium sulfate, 0.1 part of calcium chloride and 3 parts of 3wt% concentration.
The present embodiment adopts the blending method of prior art, and mixing after various raw materials are mixed is obtained.
Embodiment 4
The present embodiment provides a kind of long glass fiber reinforced pp composite, and its raw material includes by weight:
14 parts of alkali-free roving glass fiber；
80 parts of pp；
0.4 part of light stabilizer；
0.6 part of toughener；
5 parts of compatilizer；
0.7 part of antioxidant；
Described alkali-free continuous glass-fiber length is 8mm, a diameter of 18 μm；It is fine that its raw material of described compatilizer includes ethoxy by weight
3 parts of dimension element, 0.1 part of propylene glycol, 0.07 part of Polyvinylpyrrolidone, 3 parts of potassium nitrate.
Further, described light stabilizer is 527uv；Described toughener is liquid polysulfide rubber；Described antioxidant is anti-
Oxygen agent 168.
The present embodiment adopts the blending method of prior art, and mixing after various raw materials are mixed is obtained.
Comparative example 1
This comparative example provides a kind of long glass fiber reinforced pp composite, and its raw material includes by weight:
23 parts of alkali-free roving glass fiber；
88 parts of pp；
0.3 part of light stabilizer；
0.7 part of toughener；
5 parts of compatilizer；
0.6 part of antioxidant；
Described alkali-free continuous glass-fiber length is 10mm, a diameter of 14 μm；Its raw material of described compatilizer includes ethoxy by weight
2.5 parts of cellulose, 0.2 part of propylene glycol, 5 parts of potassium nitrate.
Further, described light stabilizer is 527uv；Described toughener is liquid polysulfide rubber；Described antioxidant is anti-
Oxygen agent 168.
Further, described long glass fiber reinforced pp composite also includes 0.2 part by weight of thermoplastic stabilizer；Described
Thermoplastic stabilizer includes 2 parts by weight of sodium sulfate and the hydrochloric acid of 3 parts of 3wt% concentration.
Comparative example 2
The present embodiment provides a kind of long glass fiber reinforced pp composite, and its raw material includes by weight:
23 parts of alkali-free roving glass fiber；
88 parts of pp；
0.3 part of light stabilizer；
0.7 part of toughener；
5 parts of compatilizer；
0.6 part of antioxidant；
Described alkali-free continuous glass-fiber length is 10mm, a diameter of 14 μm；Its raw material of described compatilizer includes ethoxy by weight
2.5 parts of cellulose, 0.2 part of propylene glycol, 0.04 part of Polyvinylpyrrolidone.
Further, described light stabilizer is 527uv；Described toughener is liquid polysulfide rubber；Described antioxidant is anti-
Oxygen agent 168.
Further, described long glass fiber reinforced pp composite also includes 0.2 part by weight of thermoplastic stabilizer；Described
Thermoplastic stabilizer includes the hydrochloric acid of 0.2 part by weight calcium chloride and 3 parts of 3wt% concentration.
The tensile strength that the mechanical property of composite passes through to test gained judges, the impact resistance of material passes through two kinds of sides
Method characterizes, and a kind of is notch impact strength by test material and unnotched impact strength characterizes, and another kind is by material
The square plate of 150mm*150mm*3mm made by material, and square plate is passed through to support rack to live, with the ball of 0.5kg from different height oneself
Struck in square plate by falling bodies, observe how many square plates crackle highly.The floating fibre situation of composite is by surface
On the mould being processed by shot blasting, material is made square plate, by secondary former phase instrument, surface is observed.
Carry out tensile strength, impact property and surface floating fiber situation to embodiment 1-4 and comparative example 1-2 to be measured, and
With reference to gb 50611-2010 " electronic engineering antistatic design specification ", carry out antistatic test, its test result is shown in Table 1.
Table 1.
Injection test.
Long glass fiber reinforced pp composite is molded using prior art, is shaped to the side of 30cm × 30cm × 30cm
Block, observes its surface floating fiber situation.Cut out the epidermis of 30cm × 30cm × 2cm on 6 surfaces of square, and obtain one and cut
The blockage of epidermis；Test epidermis and the density rate of blockage.Density rate ρ=(ρ epidermis-ρ blockage) × 100%.Its knot
Fruit is as shown in table 2.
Table 2.
It is the wherein specific implementation of the present invention above, its description is more concrete and detailed, but can not therefore be interpreted as
Restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from this
On the premise of bright design, some deformation can also be made and improve, these obvious alternative forms belong to the present invention's
Protection domain.
Claims (4)
1. a kind of long glass fiber reinforced pp composite, its raw material includes by weight:
Alkali-free roving glass fiber 10-30 part；
Pp 60-90 part；
Light stabilizer 0.1-0.5 part；
Toughener 0.5-0.9 part；
Compatilizer 2-6 part；
Antioxidant 0.3-0.8 part；
Described alkali-free continuous glass-fiber length is 6-12mm, a diameter of 11-20 μm；Its raw material of described compatilizer includes hydroxyl by weight
Ethyl cellulose 2-3 part, propylene glycol 0.1-0.5 part, Polyvinylpyrrolidone 0.01-0.07 part, potassium nitrate 3-8 part.
2. long glass fiber reinforced pp composite according to claim 1 it is characterised in that: described light stabilizer be 527uv；
Described toughener is liquid polysulfide rubber；Described antioxidant is irgasfos 168.
3. long glass fiber reinforced pp composite according to claim 1 it is characterised in that: described long glass fiber reinforced pp be combined
Material also includes the thermoplastic stabilizer of 0.2-0.3 part by weight；Described thermoplastic stabilizer includes the sulphuric acid of 1-3 part by weight
The hydrochloric acid of sodium, 0.1-0.4 part calcium chloride and 2-3 part 3wt% concentration.
4. a kind of method preparing long glass fiber reinforced pp composite as claimed in claim 3, comprises the steps:
A. prepare compatilizer: hydroxyethyl cellulose, potassium nitrate are heated to 100 DEG C using air bath, instill propylene glycol, insulation
Polyvinylpyrrolidone is added after 30min；
B. the preparation of thermoplastic stabilizer: described sodium sulfate, calcium chloride and mixed in hydrochloric acid are heated to 50 DEG C and keep 20min；
C. press setting weight part and pp, light stabilizer, toughener, compatilizer, antioxidant, thermoplastic stabilizer are added mixed at high speed
Device mix homogeneously post-heating is cooled to 35～40 DEG C to after 80～90 DEG C, is subsequently adding the long glass of alkali-free of setting weight part
Fibre, is obtained long glass fiber reinforced pp composite through mixing, forming processes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610735672.6A CN106349559A (en) | 2016-08-28 | 2016-08-28 | Long glass fiber reinforced PP (polypropylene) composite material and preparation method thereof |
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| CN201610735672.6A CN106349559A (en) | 2016-08-28 | 2016-08-28 | Long glass fiber reinforced PP (polypropylene) composite material and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109054172A (en) * | 2018-07-01 | 2018-12-21 | 李万强 | A kind of preparation method of medical polypropylene material |
-
2016
- 2016-08-28 CN CN201610735672.6A patent/CN106349559A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109054172A (en) * | 2018-07-01 | 2018-12-21 | 李万强 | A kind of preparation method of medical polypropylene material |
| CN109054172B (en) * | 2018-07-01 | 2021-05-18 | 天台百利塑业有限公司 | Preparation method of medical polypropylene material |
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