CN104804397B - Polycarbafil resin with low warpage and preparation method thereof - Google Patents
Polycarbafil resin with low warpage and preparation method thereof Download PDFInfo
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- CN104804397B CN104804397B CN201510210664.5A CN201510210664A CN104804397B CN 104804397 B CN104804397 B CN 104804397B CN 201510210664 A CN201510210664 A CN 201510210664A CN 104804397 B CN104804397 B CN 104804397B
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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
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- 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
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- 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
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention discloses a kind of polycarbafil resin with low warpage and preparation method thereof；Described resin includes the following each component of parts by weight part: Merlon 49～68 parts, glass fibre 30～50 parts, epoxy resin 0.5～2 parts, processing aid 0.1～2 parts.One aspect of the present invention uses the glass fibre ground, and fibre protogrowth degree is 50～200um, and low length fiber is not susceptible to orientation；On the other hand, adding a certain amount of thermosetting epoxy resin, epoxy end reacts with resin and fiber respectively, is conducive to fiber machine-direction oriented in resin flowing, two aspects, has slackened horizontal, longitudinal fiber orientation difference, has significantly improved angularity.
Description
Technical field
The invention belongs to macromolecule modified technical field, be specifically related to a kind of polycarbafil resin with low warpage
And preparation method thereof, it is widely used in the consumer electronics field such as mobile phone, camera.
Background technology
PC is amorphism engineering plastics, have excellent impact strength, thermally-stabilised, glossiness, suppression bacteria characteristic,
Flame-retarding characteristic and resistance tocrocking.Glass fiber-reinforced polycarbonate improves mechanical property and the rigidity of Merlon, and line expands system
Number greatly reduces, and dimensional stability is greatly improved, and molding shrinkage significantly reduces, and overcomes Merlon simultaneously and is weak to answer
Power cracking and the defect of fatigue strength.For substituting the load part in the die casting such as aluminum, zinc field and the goods that dimensional requirement is high.
Can be widely used in the industrial products such as machinery, instrument, electric, telecommunication, such as, manufacturing electric power tool shell, electronics calculating
Machine part, airplane parts, the spaceman helmet, attachments of a bicycle and other rigidity, dimensionally stable, impact resistance are had higher
The parts required.
But, owing to glass fiber-reinforced polycarbonate resin is during melt-flow, glass fibre (GF) all can be along stream
Dynamic direction is orientated, thus causes horizontal stroke, longitudinal contraction difference, causes product buckling deformation.If product generation warpage
Deformation, then the position such as buckle, screw hole changes, and affects final assembly, affects the appearance tactile impression of product simultaneously.
Just improve the angularity aspect of glass fiber-reinforced polycarbonate resin, the employing mentioned such as publication number CN101704997A
Glass fibre and mineral-filled compounding solution, reason is that the orientation of mineral is the most inconspicuous, but the meta-alkali of mineral own
Property easily causes the defect of product surface white macula；The method using flat GF in publication number CN102719071A, compares circle
Shape GF, improves the orientation of fiber, but warpage improves not notable and article surface is floating fine unchanged.
Summary of the invention
It is an object of the invention to the deficiency overcoming above-mentioned prior art to exist, it is provided that a kind of enhancing with low warpage gathers
Carbonate resin and preparation method thereof.What one aspect of the present invention was selected is the glass fibre ground, and fibre protogrowth degree is
50～200um, low length fiber is not susceptible to orientation；On the other hand, a certain amount of thermosetting epoxy resin, ring are added
Oxygen end reacts with resin and fiber respectively, is conducive to fiber machine-direction oriented in resin flowing, and two aspects act on jointly,
Slacken horizontal, longitudinal fiber orientation difference, improve angularity.
It is an object of the invention to be achieved through the following technical solutions:
The present invention relates to a kind of polycarbafil resin with low warpage, including the following each component of parts by weight part:
Preferably, described Merlon be weight average molecular weight be 18000～25000 aliphatic or fragrance adoption
Carbonic ester.
Preferably, described Merlon is phosgenation or the bisphenol A polycarbonate of ester-interchange method production.
Preferably, described glass fibre is milled glass fibre, and primary a length of 50～200um are a diameter of
10～13um.Described milled glass fibre processes through silane coupling agent or water retting surface.
Preferably, described epoxy resin be epoxide equivalent be the thermosetting epoxy resin of 1500～2000e/eq.
Preferably, described processing aid selected from antioxidant, interior lubrication and releasing agent, antistatic additive, stabilizer,
In dyestuff and pigment at least one.
The invention still further relates to the preparation method of a kind of polycarbafil resin with low warpage according to the present invention, institute
The method of stating comprises the steps:
A, weigh described each component according to parts by weight；
B, described Merlon, epoxy resin and processing aid are mixed in moderate-speed mixers 10～30min；
C, throwing in double screw extruder by step B gained compound, described glass fibre side is fed, and squeezes through melted
Go out, pelletize, obtain described glass fiber-reinforced polycarbonate resin composition.
Preferably, described double screw extruder includes that ten temperature controlled region, the temperature in described temperature control 1～2 district are
200～280 DEG C, the temperature in temperature control 3～4 district is 200～280 DEG C, and the temperature in temperature control 5～6 district is 200～280 DEG C,
The temperature in temperature control 7～8 district is 200～280 DEG C, and the temperature in temperature control 9～10 district is 200～280 DEG C.
Preferably, described double screw extruder has at two evacuation, be wherein positioned at one material conveying section end,
Position between the starting end of melt zone；At another, vaccum-pumping equipment is positioned at metering section.
Compared with prior art, there is advantages that the primary length of milled glass fibre that the present invention uses
Low, and be distributed in resin and be orientated without obvious direction, thus the product warpage aspect after injection is improved notable, and product
Appearance is excellent, without defects such as white patches on surface, floating fibres, substantially increases the yield of goods.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail.Following example will assist in those skilled in the art and enter
One step understands the present invention, but limits the present invention the most in any form.It should be pointed out that, the ordinary skill people to this area
For Yuan, without departing from the inventive concept of the premise, it is also possible to make certain adjustments and improvements.These broadly fall into this
Bright protection domain.
In following example, the selected PC trade mark is that PC-300-15, LG-Dow produce, and weight average molecular weight is 23000.
Grinding glass 1, the trade mark 510, Zhejiang megalith produces, primary a length of 3mm, a diameter of 10um, surface silicon
Alkanes coupling agent treatment.
Grinding glass 2, the trade mark 7980, the bright Sheng of the U.S. produces, and primary a length of 200um, a diameter of 10um, surface is used
Distilled water class coupling agent treatment.
Flat glass 3 trade mark, 3PA-830, Japan spins production in day east, primary a length of 3mm, and sheet footpath ratio is for 4:1, table
Face silane coupling agent processes.
Epoxy resin 1, trade mark NPES-907, South Asia produces, and epoxide equivalent is 1500～1800e/eq.
Epoxy resin 2, trade mark E20, commercially available, epoxide equivalent is 500～600e/eq.
Embodiment 1
The present embodiment relates to a kind of glass fiber-reinforced polycarbonate resin with low warpage and preparation method thereof；Contained each group
Divide and consumption be as shown in table 1, be prepared as follows:
By each component by weight: PC-300-15 is 68,510 to be 30, and NPES-907 is 2.Through melt temperature
Extrude for the double screw extruder of 200-280 DEG C, pelletize.The most each district temperature is: the temperature in double screw extruder 1-2 district
For 200-280 DEG C, the temperature in 3-4 district is 200-280 DEG C, and the temperature in 5-6 district is 200-280 DEG C, temperature control 7-8 district
Temperature is 200-280 DEG C, and the temperature in temperature control 9-10 district is 200-280 DEG C.
Embodiment 2
The present embodiment relates to a kind of glass fiber-reinforced polycarbonate resin with low warpage and preparation method thereof；Contained each group
Divide and consumption be as shown in table 1, be prepared as follows:
By each component by weight: PC-300-15 is 68,7980 to be 30, and NPES-907 is 2.Through melt temperature
Extrude for the double screw extruder of 200-280 DEG C, pelletize.The most each district temperature is: the temperature in double screw extruder 1-2 district
For 200-280 DEG C, the temperature in 3-4 district is 200-280 DEG C, and the temperature in 5-6 district is 200-280 DEG C, temperature control 7-8 district
Temperature is 200-280 DEG C, and the temperature in temperature control 9-10 district is 200-280 DEG C.
Embodiment 3
The present embodiment relates to a kind of glass fiber-reinforced polycarbonate resin with low warpage and preparation method thereof；Contained each group
Divide and consumption be as shown in table 1, be prepared as follows:
By each component by weight: PC-300-15 is 49,7980 to be 50, and NPES-907 is 0.5.Through melted temperature
The double screw extruder extrusion that degree is 200-280 DEG C, pelletize.The most each district temperature is: the temperature in double screw extruder 1-2 district
Degree is for 200-280 DEG C, and the temperature in 3-4 district is 200-280 DEG C, and the temperature in 5-6 district is 200-280 DEG C, temperature control 7-8 district
Temperature be 200-280 DEG C, the temperature in temperature control 9-10 district is 200-280 DEG C.
Embodiment 4
The present embodiment relates to a kind of glass fiber-reinforced polycarbonate resin with low warpage and preparation method thereof；Contained each group
Divide and consumption be as shown in table 1, be prepared as follows:
By each component by weight: PC-300-15 is 59,7980 to be 40, and NPES-907 is 1.Through melt temperature
Extrude for the double screw extruder of 200-280 DEG C, pelletize.The most each district temperature is: the temperature in double screw extruder 1-2 district
For 200-280 DEG C, the temperature in 3-4 district is 200-280 DEG C, and the temperature in 5-6 district is 200-280 DEG C, temperature control 7-8 district
Temperature is 200-280 DEG C, and the temperature in temperature control 9-10 district is 200-280 DEG C.
Meanwhile, increasing by two comparative examples, six formula are molded into mobile phone shell product, injection temperature is 315 DEG C, test
Result such as table 1 below:
Table 1
From the experimental result of table 1 it can be seen that for glass fiber-reinforced polycarbonate resin, grind GF and general GF phase
Ratio, the former has a clear superiority at angularity aspect.Finding, GF content is the highest simultaneously, and warpage performance is the poorest, and reason is probably
GF difference horizontal, machine-direction oriented is the biggest.By comparative example it can be seen that grind GF and have in terms of warpage substantially than flat GF
Advantage, the epoxy resin of high epoxide equivalent just can have more preferable warpage to show.
Above the specific embodiment of the present invention is described.It is to be appreciated that the invention is not limited in above-mentioned spy
Determining embodiment, those skilled in the art can make various deformation or amendment within the scope of the claims, this not shadow
Ring the flesh and blood of the present invention.
Claims (7)
1. a polycarbafil resin with low warpage, it is characterised in that include the following each component of parts by weight part:
Described glass fibre is milled glass fibre, primary a length of 50～200 μm, a diameter of 10～13 μm；
Described epoxy resin be epoxide equivalent be the thermosetting epoxy resin of 1500～2000g/eq.
The polycarbafil resin with low warpage the most according to claim 1, it is characterised in that described Merlon be weight average molecular weight be aliphatic or the aromatic copolycarbonate of 18000～25000.
The polycarbafil resin with low warpage the most according to claim 1, it is characterised in that described Merlon is phosgenation or the bisphenol A polycarbonate of ester-interchange method production.
The polycarbafil resin with low warpage the most according to claim 1, it is characterised in that described processing aid is selected from antioxidant, interior lubrication and releasing agent, antistatic additive, stabilizer, dyestuff and pigment at least one.
5. the preparation method according to the polycarbafil resin with low warpage according to any one of Claims 1 to 4, it is characterised in that described method comprises the steps:
A, weigh described each component according to parts by weight；
B, described Merlon, epoxy resin and processing aid are mixed in moderate-speed mixers 10～30min；
C, throwing in double screw extruder by step B gained compound, described glass fibre side is fed, through melt extruding, and pelletize, obtain described glass fiber-reinforced polycarbonate resin composition.
The preparation method of the polycarbafil resin with low warpage the most according to claim 5, it is characterized in that, described double screw extruder includes ten temperature controlled region, the temperature in described temperature control 1～2 district is 200～280 DEG C, the temperature in temperature control 3～4 district is 200～280 DEG C, the temperature in temperature control 5～6 district is 200～280 DEG C, and the temperature in temperature control 7～8 district is 200～280 DEG C, and the temperature in temperature control 9～10 district is 200～280 DEG C.
The preparation method of the polycarbafil resin with low warpage the most according to claim 5, it is characterised in that described double screw extruder has at two evacuation, is wherein positioned at the starting end of the end of material conveying section, melt zone at one；At another, vaccum-pumping equipment is positioned at metering section.
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| CN104804397B true CN104804397B (en) | 2016-11-30 |
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| CN105131549B (en) * | 2015-08-28 | 2016-11-09 | 金发科技股份有限公司 | A kind of polycarbonate compositions and preparation method thereof |
| KR102087405B1 (en) * | 2016-01-14 | 2020-03-10 | 주식회사 엘지화학 | Reinforced polycarbonate resin and article made thherefrom |
| CN106317827A (en) * | 2016-08-24 | 2017-01-11 | 王鹏 | PC alloy material and preparing method and application thereof |
| CN110591322B (en) * | 2019-08-30 | 2024-03-22 | 金发科技股份有限公司 | Glass fiber reinforced polycarbonate composite material and preparation method and application thereof |
| CN112852055A (en) * | 2021-01-06 | 2021-05-28 | 珠海格力新材料有限公司 | Filling modified PP material and preparation method thereof |
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| EP2810989B1 (en) * | 2012-01-31 | 2019-07-31 | Mitsubishi Engineering-Plastics Corporation | Polycarbonate resin composition |
| KR101381044B1 (en) * | 2012-02-03 | 2014-04-17 | 주식회사 엘지화학 | Non―halogen flame retardant and high rigidity polycarbonate resin composition |
| JP5579909B2 (en) * | 2012-09-14 | 2014-08-27 | 三菱エンジニアリングプラスチックス株式会社 | Resin composition for laser direct structuring, resin molded product, and method for producing resin molded product with plating layer |
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Inventor after: Yang Chunhua Inventor after: Ding Bupeng Inventor after: Li Qiang Inventor after: Luo Minghua Inventor after: Xin Minqi Inventor before: Yang Chunhua Inventor before: Li Qiang Inventor before: Luo Minghua Inventor before: Xin Minqi |
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