CN102181100B - Glass fiber reinforced co-polypropylene composite material and preparation method of the Glass fiber reinforced co-polypropylene composite material - Google Patents
Glass fiber reinforced co-polypropylene composite material and preparation method of the Glass fiber reinforced co-polypropylene composite material Download PDFInfo
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- CN102181100B CN102181100B CN201110065557XA CN201110065557A CN102181100B CN 102181100 B CN102181100 B CN 102181100B CN 201110065557X A CN201110065557X A CN 201110065557XA CN 201110065557 A CN201110065557 A CN 201110065557A CN 102181100 B CN102181100 B CN 102181100B
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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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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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
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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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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- 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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- 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
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92923—Calibration, after-treatment or cooling zone
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Abstract
The invention discloses a glass fiber reinforced co-polypropylene composite material and a preparation method of the glass fiber reinforced co-polypropylene composite material. The preparation method includes the steps as follows: uniformly mixing co-polypropylene, polypropylene grafted with maleic anhydride, homopolymerized polypropylene organic peroxide initiator, and antioxidant in proportion; adding the mixture in a double-screw extruder and simultaneously adding glass fiber strand roving; and conducting melt extrusion for granulation at the temperature of 170-220 DEG C, thus obtaining the glass fiber reinforced co-polypropylene composite material, wherein the melt index of the obtained composite material is 18-35g/10min, the tensile strength is 49-89 Mpa, the breaking elongation is 9-35%, the Young modulus is 2.3-5.3GPa and the notch impact strength is 10-33kJ/m2. The glass fiber reinforced co-polypropylene composite material provided by the invention has not only outstanding strength, modulus, and impact resisting and heat resisting properties, but also excellent processing flow property, and can injection-mold and form thin-wall products with attractive appearance and complex shape; and the glass fiber reinforced co-polypropylene composite material has the characteristics of being light in weight and cheap in cost can substitute for engineering plastics such as expensive ABS (Acrylonitrile Butadiene Styrene) and nylon.
Description
Technical field
The invention belongs to fiber glass reinforced polypropylene (PP/GF) matrix material and preparing technical field thereof, be specifically related to the good glass of a kind of HS, high-modulus, H.T. and processing characteristics and strengthen COPP matrix material and preparation method thereof.
Background technology
Pp material is abundant, and synthesis technique is simple, and is cheap, and the resin over-all properties is good, and purposes is a kind of crucial general-purpose plastics very extensively.But polypropylene low temperature poor toughness, notch sensitivity are strong, and mechanical property is not high, has limited its application (Wang Duoren, synthetic resins and engineering plastics production technology, Beijing, China Light Industry Press, 2001,8) on the functional structure parts yet.
Though glass-reinforced polypropylene has greatly improved tensile strength, modulus and the thermotolerance of material, and cost performance is apparently higher than general engineering plastics, thereby obtained to use widely at aerospace, boats and ships and automotive field.But adopt because of the matrix resin of traditional fiber glass reinforced polypropylene is general be HOPP (Liu's study, Zhuan Hui, Cheng Yongfeng, the performance study of roving glass fiber REINFORCED PET engineering plastics. plastics industry, 2006,34 (12): 26-28; Thomasset J, Carreau P J, Sanschagrin B, et al.Rheologlealproperties of long glass fiberfilled polypropylene.JNon-Newtonian Fluid Mech, 2005,125:25-34; Wang Hongzeng, Li Rongxun, Liu Baocheng. the development of RPP motor car engine fan modifying material, plastics science and technology, 2005 (6): 32-35; Zhang Ning, Li Zhongheng, Tao Yu, long glass fiber-reinforced polypropylene composite study, plastics industry, 2006,34 (12): 29-32; Deng), thereby make prepared fiber glass reinforced polypropylene material still have certain performance deficiency:
1) because of employed HOPP self notched Izod impact strength is low, is merely～5kJ/m
2Though, add glass after shock strength increase, the toughness of material especially notched Izod impact strength and elongation at break to improve ten minutes limited, still can not satisfy the request for utilization of some functional structure parts.
2) because the fiber glass reinforced polypropylene melt viscosity is big, when especially glass fiber content is higher, thereby mobile relatively poor, be difficult for injection moulding.
3) because the consistency of glass that adds and HOPP is relatively poor, thereby in prepared fiber glass reinforced polypropylene goods, often there is glass to float on product surface, causes " floating fine phenomenon ", have a strong impact on products appearance.
To these performance deficiencies that traditional fiber glass reinforced polypropylene material exists, Chinese scholars has been carried out a large amount of research, tries hard to find out the terms of settlement that overcomes these defectives.But terms of settlement of regrettably looking for or employing add toughner (like SEBS, TPU etc.), or adopt external lubricant (Vestolen PP 7052 is cured, stearate etc.) to improve toughness, processing characteristics or products appearance (Lian Rong Ping, the Xu Mingzhi of material; Li Qiang, Huang Rui, glass fiber reinforced polypropylene composite material performance study; Plastics science and technology, 2008,36 (8): 40-44 etc.; Tjong SC, Xu SA, Li RK; Et al.MechanicalBehavior and Fracture Toughness Evaluation of Maleic AnhydideCompatibilized Short GlassFiber/SBS/Polypropylene Hybrid Composites.Composites Science andTechnology, 2002,62:831～840); But the toughner that adds costs an arm and a leg, and cost is higher; Though and the external lubricant that adds can improve the flowability of material to a certain extent, it is not good with the matrix resin consistency, has the lubricant migration, causes product surface to whiten, and influences problems such as outward appearance.
Summary of the invention
The objective of the invention is to prior art deficiency, provide the good glass of a kind of HS, high-modulus, H.T. and processing characteristics to strengthen the COPP matrix material.
Another purpose of the present invention provides the above-mentioned glass of preparation and strengthens the COPP composite process.
Glass provided by the invention strengthens the COPP matrix material, it is characterized in that the contained component of this matrix material counts by weight:
50～80 parts of COPPs
10～40 parts of spun glass assembled rovings
5～10 parts of polypropylene grafted maleic anhydrides
2～10 parts of HOPPs
0.01～0.1 part of organic peroxide evocating agent
0.05～0.3 part in oxidation inhibitor,
And the melting index of this matrix material (200 ℃, load 2.26Kg) is 18～35g/10min, and tensile strength is 49～89MPa, and elongation at break is 9～35%, and Young's modulus is 2.3～5.3GPa, and notched Izod impact strength is 10～33kJ/m
2
COPP described in this matrix material is atactic copolymerized polypropene or block copolymerization polypropylene, and its socle girder notched Izod impact strength>=50kJ/m
2, melting index is 0.3～5g/10min; Described spun glass assembled roving handles through silane coupling agent for the surface and filament diameter is the long yarn of 6～17 μ m; Described HOPP melting index is 2～10g/10min.
The percentage of grafting of the polypropylene grafted maleic anhydride described in this matrix material is 0.5～1.0%; Described organic peroxide evocating agent is Di Cumyl Peroxide 99 or Lucidol.
Oxidation inhibitor described in this matrix material is at least a in antioxidant 1010, the oxidation inhibitor 168.
The above-mentioned glass of preparation provided by the invention strengthens the method for co-polypropylene matrix material; It is characterized in that this method is after directly 50～80 parts of COPPs, 5～10 parts of polypropylene grafted maleic anhydrides, 2～10 parts of HOPPs, 0.01～0.1 part of organic peroxide evocating agent and 0.05～0.3 part of oxidation inhibitor being mixed; Add in the twin screw extruder; Simultaneously 10～40 parts of spun glass assembled rovings are added inlet from the glass of twin screw extruder and add, and get final product at 170-220 ℃ of extruding pelletization.
COPP described in this method is atactic copolymerized polypropene or block copolymerization polypropylene, and its socle girder notched Izod impact strength>=50kJ/m
2, melting index is 0.3～5g/10min; Described spun glass assembled roving handles through silane coupling agent for the surface and filament diameter is the long yarn of 6～17 μ m; Described HOPP melting index is 2～10g/10min.
The percentage of grafting of the polypropylene grafted maleic anhydride described in this method is 0.5～1.0%; Described organic peroxide evocating agent is Di Cumyl Peroxide 99 or Lucidol.
Oxidation inhibitor described in this method is at least a in antioxidant 1010, the oxidation inhibitor 168.
The present invention compared with prior art has the following advantages:
1, because matrices of composite material provided by the invention adopts is the multipolymer of COPP (PPR) for ethene and propylene; It has higher tensile yield strength and shock resistance for HOPP, especially its notched Izod impact strength can be up to 80kJ/m
2, on this basis, strengthen through glass again, just can prepare and not only have good rigidity but also have excellent in toughness, especially notched Izod impact strength has solved the problem of PP/GF poor toughness in the prior art far above traditional fiber glass reinforced polypropylene based composites.
2, because the organic peroxide evocating agent that contains in the matrix material provided by the invention can interrupt the molecular chain of polypropylene segment in the course of processing; Widen polyacrylic MWD; Thereby can reduce the viscosity of material; Significantly improve the processing fluidity that glass strengthens COPP, be suitable for injection processing especially, especially prepare thin-gage goods.
3, because the organic peroxide evocating agent that contains in the matrix material provided by the invention can interrupt the molecular chain of polypropylene segment in the course of processing; Make that polyacrylic MWD broadens in the material; And because of the less Vestolen PP 7052 flowability of molecular weight wherein is superior to bigger Vestolen PP 7052 of molecular weight and glass inorganic materials; In the shearing of the course of processing, be easy to be distributed in product surface, thereby can the glass that float on the surface be hidden, basically eliminate " floating fine " phenomenon of prior art.
4, the MWD owing to the COPP that contains in the matrix material provided by the invention broadens; Low-molecular-weight Vestolen PP 7052 increases, and the existing good consistency of low-molecular-weight Vestolen PP 7052 and matrix, can improve the flowability of material again; Thereby do not need to add again lubricant; Also just avoided adding the surface transport that lubricant brings, caused the product surface whiting, influenced problems such as outward appearance.
5, because the proportion of prepared glass fiber reinforced polypropylene composite material raw materials cost of the present invention and prepared goods is all low than engineering plastics (ABS, PA, POM etc.); And performance but near in addition surpass ABS (seeing table) and nylon; Thereby its cost performance is high, alternative part engineering plastics.
6, the inventive method technology is simple, and tooling cost is low, is easy to realize industriallization.
Embodiment
Through embodiment the present invention is carried out concrete description below; It is important to point out that present embodiment only is used for the present invention is further specified; Can not be interpreted as the restriction to protection domain of the present invention, the person skilled in the art in this field makes some nonessential improvement according to the content of foregoing invention and adjustment still belongs to protection scope of the present invention.
In addition, what be worth explanation is, below the melting index of material of each embodiment preparation be to test down at 200 ℃, load 2.26Kg; Tensile strength, elongation at break and Young's modulus are by GB/T 1040-92 standard testing; Notched Izod impact strength is by GB/T 1843-94 standard testing.
Embodiment 1
With 50 parts of socle girder notched Izod impact strength is 50kJ/m
2, melting index is the block copolymerization polypropylene of 5g/10min; 10 parts of percentage of grafting are 0.5% polypropylene grafted maleic anhydride; 2 parts of melting index are the HOPP of 2g/10min; 0.01 part Di Cumyl Peroxide 99,0.1 part of antioxidant 1010 is mixed together evenly, and the material that mixes is added the twin screw extruder from charging opening; Add 40 parts of surfaces simultaneously from glass ingress, the barrel wall of screw rod melt zone top and handle and filament diameter is the spun glass assembled roving of 6 μ m, and under 170～220 ℃, melt extrude granulation and can obtain high performance glass and strengthen the block copolymerization polypropylene matrix material through silane coupling agent.Through test, the melting index of this material (200 ℃, load 2.26Kg) is 35g/10min, and tensile strength is 89MPa, and elongation at break is 9%, and Young's modulus is 5.3GPa, and notched Izod impact strength is 10kJ/m
2
Embodiment 2
With 80 parts of socle girder notched Izod impact strength is 80kJ/m
2, melting index is the atactic copolymerized polypropene of 0.3g/10min; 5 parts of percentage of grafting are 1% polypropylene grafted maleic anhydride; 5 parts of melting index are the HOPP of 10g/10min; 0.1 part Lucidol, 0.05 part of oxidation inhibitor 168 is mixed together evenly, and the material that mixes is added the twin screw extruder from charging opening; Add 10 parts of surfaces simultaneously from glass ingress, the barrel wall of screw rod melt zone top and handle and filament diameter is the spun glass assembled roving of 17 μ m, and under 170～220 ℃, melt extrude granulation and can obtain high performance glass and strengthen the block copolymerization polypropylene matrix material through silane coupling agent.Through test, the melting index of this material (200 ℃, load 2.26Kg) is 21g/10min, and tensile strength is 49MPa, and elongation at break is 35%, and Young's modulus is 2.3GPa, and notched Izod impact strength is 33kJ/m
2
Embodiment 3
With 60 parts of socle girder notched Izod impact strength is 60kJ/m
2, melting index is the atactic copolymerized polypropene of 3g/10min; 7 parts of percentage of grafting are 0.8% polypropylene grafted maleic anhydride; 8 parts of melting index are the HOPP of 8g/10min; 0.05 part Lucidol; 0.1 part oxidation inhibitor 168 by 1: 1 mixed is mixed together evenly with antioxidant 1010; The material that mixes from charging opening adds twin screw extruder, is added 20 parts of surfaces simultaneously and handles and filament diameter is the spun glass assembled roving of 10 μ m through silane coupling agent from the glass ingress, barrel wall top of screw rod melt zone, and under 170～220 ℃, melt extrude granulation and can obtain high performance glass and strengthen the block copolymerization polypropylene matrix material.Through test, the melting index of this material (200 ℃, load 2.26Kg) is 18g/10min, and tensile strength is 63MPa, and elongation at break is 22%, and Young's modulus is 3.5GPa, and notched Izod impact strength is 24kJ/m
2
Embodiment 4
With 70 parts of socle girder notched Izod impact strength is 70kJ/m
2, melting index is the block copolymerization polypropylene of 2g/10min; 6 parts of percentage of grafting are 0.7% polypropylene grafted maleic anhydride; 10 parts of melting index are the HOPP of 5g/10min; 0.06 part Lucidol; 0.3 part oxidation inhibitor 168 by 2: 1 mixed is mixed together evenly with antioxidant 1010; The material that mixes from charging opening adds twin screw extruder, is added 30 parts of surfaces simultaneously and handles and filament diameter is the spun glass assembled roving of 15 μ m through silane coupling agent from the glass ingress, barrel wall top of screw rod melt zone, and under 170～220 ℃, melt extrude granulation and can obtain high performance glass and strengthen the block copolymerization polypropylene matrix material.Through test, the melting index of this material (200 ℃, load 2.26Kg) is 28g/10min, and tensile strength is 77MPa, and elongation at break is 18%, and Young's modulus is 4.0GPa, and notched Izod impact strength is 20kJ/m
2
Embodiment 5
With 50 parts of socle girder notched Izod impact strength is 90kJ/m
2, melting index is the block copolymerization polypropylene of 0.3g/10min; 7 parts of percentage of grafting are 0.9% polypropylene grafted maleic anhydride; 5 parts of melting index are the HOPP of 8g/10min; 0.08 part Di Cumyl Peroxide 99; 0.2 part oxidation inhibitor 168 by 1: 2 mixed is mixed together evenly with antioxidant 1010; The material that mixes from charging opening adds twin screw extruder, is added 10 parts of surfaces simultaneously and handles and filament diameter is the spun glass assembled roving of 9 μ m through silane coupling agent from the glass ingress, barrel wall top of screw rod melt zone, and under 170～220 ℃, melt extrude granulation and can obtain high performance glass and strengthen the block copolymerization polypropylene matrix material.Through test, the melting index of this material (200 ℃, load 2.26Kg) is 21g/10min, and tensile strength is 52MPa, and elongation at break is 18%, and Young's modulus is 2.8GPa, and notched Izod impact strength is 23kJ/m
2
Prepared glass fibre reinforced composite material and the ABS performance comparison of table the present invention
Claims (6)
1. a glass strengthens the COPP matrix material, it is characterized in that the contained component of this matrix material counts by weight:
And the melting index of this matrix material is 18 ~ 35g/10min under the load 2.26Kg at 200 ℃, and tensile strength is 49 ~ 89MPa, and elongation at break is 9 ~ 35%, and Young's modulus is 2.3 ~ 5.3GPa, and notched Izod impact strength is 10 ~ 33kJ/m
2, wherein said COPP is atactic copolymerized polypropene or block copolymerization polypropylene, and its socle girder breach Chong Ji Qiang Du ≧ 50kJ/m
2, melting index is 0.3 ~ 5g/10min; Described spun glass assembled roving handles through silane coupling agent for the surface and filament diameter is the long yarn of 6 ~ 17 μ m; Described HOPP melting index is 2 ~ 10 g/10min.
2. glass according to claim 1 strengthens the COPP matrix material, and the percentage of grafting that it is characterized in that the polypropylene grafted maleic anhydride described in this matrix material is 0.5 ~ 1.0%; Described organic peroxide evocating agent is Di Cumyl Peroxide 99 or Lucidol.
3. glass according to claim 1 and 2 strengthens the COPP matrix material, it is characterized in that the oxidation inhibitor described in this matrix material is at least a in antioxidant 1010, the oxidation inhibitor 168.
4. one kind prepares the method that the described glass of claim 1 strengthens the co-polypropylene matrix material; It is characterized in that this method be directly with 50 ~ 80 parts of COPPs, 5 ~ 10 parts of polypropylene grafted maleic anhydrides, 2 ~ 10 parts of HOPPs, 0.01 ~ 0.1 part of organic peroxide evocating agent and 0.05 ~ 0.3 part of oxidation inhibitor by after mixing; Add in the twin screw extruder; Simultaneously 10 ~ 40 parts of spun glass assembled rovings being added inlet from the glass of twin screw extruder adds; And get final product at 170-220 ℃ of extruding pelletization, wherein said COPP is atactic copolymerized polypropene or block copolymerization polypropylene, and its socle girder breach Chong Ji Qiang Du ≧ 50kJ/m
2, melting index is 0.3 ~ 5g/10min; Described spun glass assembled roving handles through silane coupling agent for the surface and filament diameter is the long yarn of 6 ~ 17 μ m; Described HOPP melting index is 2 ~ 10 g/10min.
5. the method for preparing glass enhancing COPP matrix material according to claim 4, the percentage of grafting that it is characterized in that the polypropylene grafted maleic anhydride described in this method is 0.5 ~ 1.0%; Described organic peroxide evocating agent is Di Cumyl Peroxide 99 or Lucidol.
6. describedly prepare the methods that glass strengthens the COPP matrix material according to claim 4 or 5, it is characterized in that the oxidation inhibitor described in this method is at least a in antioxidant 1010, the oxidation inhibitor 168.
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| CN1315465A (en) * | 2000-03-30 | 2001-10-03 | 上海杰事杰新材料股份有限公司 | Glass-fibre reinforced warp-resistant polypropylene with low shrinkage ratio |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105273316A (en) * | 2015-10-21 | 2016-01-27 | 惠州市昌亿科技股份有限公司 | Long glass fibers with few revealed slight glass fibers and PP (polypropylene) composite material containing long glass fibers and having high impact resistance |
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| CN102181100A (en) | 2011-09-14 |
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