CN101469093B - Ultralong unit extension glass fiber reinforced polypropylene composite material - Google Patents
Ultralong unit extension glass fiber reinforced polypropylene composite material Download PDFInfo
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- CN101469093B CN101469093B CN2007101729184A CN200710172918A CN101469093B CN 101469093 B CN101469093 B CN 101469093B CN 2007101729184 A CN2007101729184 A CN 2007101729184A CN 200710172918 A CN200710172918 A CN 200710172918A CN 101469093 B CN101469093 B CN 101469093B
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- polypropylene
- composite material
- fiber reinforced
- glass fiber
- ultralong
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- -1 polypropylene Polymers 0.000 title claims abstract description 57
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 50
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 50
- 239000003365 glass fiber Substances 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000004698 Polyethylene Substances 0.000 claims abstract description 8
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- 238000001125 extrusion Methods 0.000 claims abstract description 8
- 229920000573 polyethylene Polymers 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 238000005469 granulation Methods 0.000 claims abstract description 4
- 230000003179 granulation Effects 0.000 claims abstract description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 6
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- KWUZCAVKPCRJPO-UHFFFAOYSA-N n-ethyl-4-(6-methyl-1,3-benzothiazol-2-yl)aniline Chemical group C1=CC(NCC)=CC=C1C1=NC2=CC=C(C)C=C2S1 KWUZCAVKPCRJPO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000013022 venting Methods 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract 2
- 238000007334 copolymerization reaction Methods 0.000 abstract 2
- 239000000463 material Substances 0.000 description 11
- 239000011159 matrix material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 2
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 1
- 241000024287 Areas Species 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to glass fiber reinforced polypropylene composite material with the super-long elongation. The glass fiber reinforced polypropylene composite material is characterized in that the composite material comprises the following components: 10 to 50 percent of homopolymerization polypropylene, 20 to 40 percent of copolymerization polypropylene, 10 to 40 percent of polyethylene, 0.5 to 5 percent grafted polypropylene, 10 to 40 percent of glass fibers, 0.1 to 2 percent of composite antioxidant, and 0.1 to 2 percent of other additives; and a preparation method for the composite material comprises the following steps: dryly mixing the homopolymerization polypropylene, the copolymerization polypropylene, the polyethylene, the grated polypropylene, the composite antioxidant and the other additives in a high speed mixer for 3 to 5 minutes according to the proportion; and then placing the mixed raw materials in a double screw extruder, and carrying out the melted extrusion and granulation at 160 to 250 DEG C. The prepared composite material has not only the super-long elongation, but also other excellent physical mechanical properties. In addition, the composite material also has the reduced cost.
Description
Technical field
The present invention relates to a kind of making method of glass fiber reinforced polypropylene composite material, especially a kind of preparation of ultralong unit extension glass fiber reinforced polypropylene composite material belongs to the polymer composite field.
Background technology
Polypropylene material has higher rigidity and low relative density, high tensile, good stress cracking resistance and chemical proofing, therefore is widely used in fields such as automobile, household electrical appliances, medical treatment.And polypropylene material is after being strengthened by glass fibre, and its every physical and mechanical properties is able to further raising as intensity, rigidity, dimension stability and resistance toheat, is enough to the higher engineering plastics competition of cost in many Application Areass.Yet a shortcoming of glass fiber reinforced polypropylene material is exactly that its tension set is very little, generally between 2~5%, causes in use easily brittle failure of material, can not repeatedly bend.
The polypropylene that does not strengthen or the polypropylene bending performance of talc are good, tension set is high, but intensity, rigidity and thermotolerance all do not have the height of glass-reinforced polypropylene, so it is more difficult to coordinate the Performance Ratio of this two aspect, and about this research and discussion on the one hand, in the middle of relevant documents and materials still for play-by-play was targetedly arranged.
For this reason, develop the glass fiber reinforced polypropylene composite material of a kind of Gao Gang of having, heat-resisting, these requirements of high-elongation, to satisfy the actual needs of each Application Areas, just become an important topic of the industry.
Summary of the invention
Purpose of the present invention: a kind of ultralong unit extension glass fiber reinforced polypropylene composite material is provided, and introduces simultaneously the preparation method of this Gao Gang, heat-resisting, ultralong unit extension glass fiber reinforced polypropylene composite material.
This ultralong unit extension glass fiber reinforced polypropylene composite material forms by the preparation of raw material of following weight percent:
Homo-polypropylene 10~50
Co-polypropylene 20~40
Polyethylene 10~40
Graft polypropylene 0.5~5
Glass fibre 10~40
Composite antioxidant 0.1~2
Other auxiliary agents 0.1~2
A kind of ultralong unit extension glass fiber reinforced polypropylene composite material of the present invention, it is characterized in that, described homo-polypropylene relative density is 0.89~0.92, at 230 ℃, 2.16 the melt flow rate (MFR) under the kilogram load is 0.5~10g/10min, is preferably 1.0~6g/10min.
A kind of ultralong unit extension glass fiber reinforced polypropylene composite material of the present invention, it is characterized in that, described Co-polypropylene relative density is 0.89~0.92, at 230 ℃, 2.16 the melt flow rate (MFR) under the kilogram load is 0.5~30g/10min, is preferably 5~15g/10min.
A kind of ultralong unit extension glass fiber reinforced polypropylene composite material of the present invention, it is characterized in that, described polyethylene relative density is 0.92~0.96, at 190 ℃, 2.16 the melt flow rate (MFR) under the kilogram load is 0.5~25g/10min, is preferably 2~13g/10min.
A kind of ultralong unit extension glass fiber reinforced polypropylene composite material of the present invention is characterized in that, described graft polypropylene be maleic anhydride by way grafting on polypropylene of melting, percentage of grafting is 0.1~1.5%, preferred 0.3~0.9%.
A kind of ultralong unit extension glass fiber reinforced polypropylene composite material of the present invention, it is characterized in that, described glass fibre is a kind of in alkali free glass fibre, medium-alkali glass fibre, high-strength glass fibre, and its Fibre diameter is 5~24 μ m, is preferably 10~19 μ m.
A kind of ultralong unit extension glass fiber reinforced polypropylene composite material of the present invention is characterized in that, described composite antioxidant is thio-2 acid two (18) ester, the diphosphorous acid pentaerythritol stearic acid ester 2,1,3,5-three (3,5-di-t-butyl-4 hydroxyl)-triazine-2,4, the mixture of 6 (1H, 3H, 5H)-triketones, its weight percent is respectively 0.05~2,0.01~1,0.02~1, is preferably 0.1~1.2,0.05~0.9,0.1~0.95.
A kind of ultralong unit extension glass fiber reinforced polypropylene composite material of the present invention is characterized in that, described other auxiliary agents are fire retardant, color auxiliary agent or lubricant.
The concrete steps of preparation ultralong unit extension glass fiber reinforced polypropylene composite material are as follows:: claimed by weight percentage homo-polypropylene, Co-polypropylene, polyethylene, graft polypropylene, composite antioxidant, other auxiliary agents to be dry mixed 3-5 minute in super mixer; The raw material that mixes is placed in dual-screw-stem machine (glass fibre adds at venting port), through melt extruding, granulation.Temperature is respectively (from spout to extrusion die): 160~180 ℃, and 180~200 ℃, 190~220 ℃, 210~230 ℃, 220~250 ℃.Engine speed is 20~50 hertz.
The unit elongation with overlength of the obtained matrix material of the present invention, other physical and mechanical properties are also very excellent, have also reduced simultaneously cost.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail:
In embodiment and Comparative Examples composite-material formula, homo-polypropylene is to raise the F401 of sub-petrochemical industry, and Co-polypropylene is the CB5 108 of Korea S Kpic, and polyethylene is the LLDPE 7042 of Qilu Petrochemical, graft polypropylene is homemade graft polypropylene, and percentage of grafting is 0.5%; Glass fibre is alkali free glass fibre, and diameter is 13 microns, and Tongxiang, Zhejiang megalith produces; Composite antioxidant comprises thio-2 acid two (18) ester, the diphosphorous acid pentaerythritol stearic acid ester 2,1,3,5-three (3,5-di-t-butyl-4 hydroxyl)-triazine-2,4,6 (1H, 3H, 5H)-triketone, trade(brand)name is respectively Negonox DSTP, Weston 618, Irganox 3114, and I.C.I. company, Weston company, the Ciba company of being respectively produces, and ratio is 1: 2: 5.
Various starting material (except glass fibre) have been claimed by weight percentage, after being dry mixed 3~5 minutes in super mixer; The raw material that mixes is placed in dual-screw-stem machine (glass fibre adds at venting port), through melt extruding, granulation.The section particle that obtains after dry 3 hours, is used day HT1150B injection moulding machine sample preparation of sea, Ningbo in the convection oven of 100 ℃.
Measurement of Material Mechanical Performance is tested according to iso standard: the batten of test tensile strength and tension set is 170*10*4mm, is undertaken by ISO 527, and speed is 50mm/min; The batten of tested for flexural modulus is 80*10*4mm, is undertaken by ISO 178, and speed is 2mm/min; The batten of test notched Izod impact strength is 80*10*4mm, is undertaken by ISO 179, and v-notch, pendulum are 4J.
Embodiment 1~4
In matrix material, various raw-material weight percents are as shown in table 1, and the temperature of twin screw extruder is respectively (from spout to extrusion die): 170 ℃, and 190 ℃, 215 ℃, 230 ℃, 235 ℃.Engine speed is 30 hertz.
Table 1 embodiment 1-4 formula and material property table
Embodiment 5~7
In matrix material, various raw-material weight percents are as shown in table 2, and the temperature of twin screw extruder is respectively (from spout to extrusion die): 170 ℃, and 190 ℃, 215 ℃, 230 ℃, 235 ℃.Engine speed is 30 hertz.
Table 2 embodiment 5-7 formula and material property table
Embodiment 8~11
In matrix material, various raw-material weight percents are as shown in table 3, and the temperature of twin screw extruder is respectively (from spout to extrusion die): 170 ℃, and 190 ℃, 215 ℃, 230 ℃, 235 ℃.Engine speed is 30 hertz.
Table 3 embodiment 8-11 formula and material property table
Embodiment 12~14
In matrix material, various raw-material weight percents are as shown in table 4, and the temperature of twin screw extruder is respectively (from spout to extrusion die): 170 ℃, and 190 ℃, 215 ℃, 230 ℃, 235 ℃.Engine speed is 30 hertz.
Table 4 embodiment 12-14 formula and material property table
Comparative Examples 1~5
In matrix material, various raw-material weight percents are as shown in table 5, and the temperature of twin screw extruder is respectively (from spout to extrusion die): 170 ℃, and 190 ℃, 215 ℃, 230 ℃, 235 ℃.Engine speed is 30 hertz.
Table 5 Comparative Examples 1-5 formula and material property table
Claims (5)
1. ultralong unit extension glass fiber reinforced polypropylene composite material is characterized in that:
A, formed by the preparation of raw material of following weight percent:
B, described homo-polypropylene relative density are 0.89~0.92, and at 230 ℃, the melt flow rate (MFR) under 2.16 kilograms of loads is 0.5~10g/10min; Described Co-polypropylene relative density is 0.89~0.92, and at 230 ℃, the melt flow rate (MFR) under 2.16 kilograms of loads is 0.5~30g/10min;
Described polyethylene relative density is 0.92~0.96, and at 190 ℃, the melt flow rate (MFR) under 2.16 kilograms of loads is 0.5~25g/10min; Described graft polypropylene be maleic anhydride by way grafting on polypropylene of melting, percentage of grafting is 0.1~1.5%; Described glass fibre is a kind of in alkali free glass fibre, medium-alkali glass fibre, high-strength glass fibre, and its Fibre diameter is 5~24 μ m; Described composite antioxidant is thio-2 acid two (18) ester, the diphosphorous acid pentaerythritol stearic acid ester 2,1,3,5-three (3,5-di-t-butyl-4 hydroxyl)-triazine-2,4,6(1H, 3H, 5H)-mixture of triketone, its weight percent is respectively 0.05~2,0.01~1,0.02~1; Described other auxiliary agent is fire retardant, color auxiliary agent or lubricant.
2. a kind of ultralong unit extension glass fiber reinforced polypropylene composite material according to claim 1, it is characterized in that: thio-2 acid two (18) ester, diphosphorous acid pentaerythritol stearic acid ester 2 and 1,3,5-three (3,5-di-t-butyl-4 hydroxyl)-triazine-2,4,6(1H, 3H, 5H)-mixture of triketone in, three's weight percent is 0.1~1.2,0.05~0.9,0.1~0.95.
3. a kind of ultralong unit extension glass fiber reinforced polypropylene composite material according to claim 1, it is characterized in that: its preparation method is by proportional quantity, homo-polypropylene, Co-polypropylene, polyethylene, graft polypropylene, composite antioxidant and other auxiliary agent to be dry mixed 3-5 minute in super mixer; The raw material that mixes is placed in dual-screw-stem machine, melt extrudes granulation at 160~250 ℃ of temperature; Wherein, glass fibre is added by venting port.
4. a kind of ultralong unit extension glass fiber reinforced polypropylene composite material according to claim 3, it is characterized in that: its method of heating is: from spout to the extrusion die place 160~180 ℃, 180~200 ℃, 190~220 ℃, 210~230 ℃, 220~250 ℃ of five sections carry out.
5. a kind of ultralong unit extension glass fiber reinforced polypropylene composite material according to claim 3, it is characterized in that: in making, engine speed is 20~50 hertz.
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CN2007101729184A CN101469093B (en) | 2007-12-25 | 2007-12-25 | Ultralong unit extension glass fiber reinforced polypropylene composite material |
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CN2007101729184A CN101469093B (en) | 2007-12-25 | 2007-12-25 | Ultralong unit extension glass fiber reinforced polypropylene composite material |
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CN101469093B true CN101469093B (en) | 2013-06-12 |
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CN103059418B (en) * | 2013-01-28 | 2015-04-01 | 宁波康氏塑料科技有限公司 | Preparation method of reinforced and modified polypropylene |
CN103087429B (en) * | 2013-01-30 | 2015-11-18 | 上海俊尔新材料有限公司 | A kind of low-temperature impact-resistant glass fiber reinforced polypropylene composite material and Synthesis and applications thereof |
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CN104927188A (en) * | 2015-06-05 | 2015-09-23 | 广东天保新材料有限责任公司 | Glass fiber reinforced recycled PP (polypropylene)/PE (polyethylene) composite material with high elongation and preparation method of PP/PE composite material |
CN105017648A (en) * | 2015-08-07 | 2015-11-04 | 苏州云舒新材料科技有限公司 | Modified polypropylene and preparation method thereof |
CN106633388B (en) * | 2016-11-17 | 2019-07-09 | 广东道生科技股份有限公司 | A kind of red phosphorus flame-retardant reinforced polypropylene material and preparation method thereof |
CN109181104B (en) * | 2018-08-20 | 2021-03-23 | 廊坊宇诺塑料制品有限公司 | A kind of high temperature resistant glass fiber reinforced polypropylene composite material |
CN113024950B (en) * | 2021-03-15 | 2023-05-26 | 永清县铭达工贸有限公司 | Reinforced and toughened polypropylene plastic and preparation method thereof |
CN115960414B (en) * | 2022-12-30 | 2023-11-14 | 金发科技股份有限公司 | Polypropylene composite material and preparation method and application thereof |
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EP0886669A1 (en) * | 1996-03-15 | 1998-12-30 | Amoco Corporation | Stiff, strong, tough glass-filled olefin polymer |
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