CN117343430A - Glass fiber reinforced thermoplastic composite particles - Google Patents
Glass fiber reinforced thermoplastic composite particles Download PDFInfo
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- CN117343430A CN117343430A CN202311286184.8A CN202311286184A CN117343430A CN 117343430 A CN117343430 A CN 117343430A CN 202311286184 A CN202311286184 A CN 202311286184A CN 117343430 A CN117343430 A CN 117343430A
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- glass fiber
- fiber reinforced
- thermoplastic composite
- reinforced thermoplastic
- reinforced plastic
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 82
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 27
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 27
- 239000011246 composite particle Substances 0.000 title claims abstract description 21
- 239000011152 fibreglass Substances 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 19
- 239000004743 Polypropylene Substances 0.000 claims description 23
- 229920001155 polypropylene Polymers 0.000 claims description 23
- -1 polypropylene Polymers 0.000 claims description 20
- 239000007822 coupling agent Substances 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000012745 toughening agent Substances 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 239000011256 inorganic filler Substances 0.000 claims description 7
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 7
- 239000004611 light stabiliser Substances 0.000 claims description 7
- 229920000459 Nitrile rubber Polymers 0.000 claims description 5
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- 244000043261 Hevea brasiliensis Species 0.000 claims description 3
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 229920001903 high density polyethylene Polymers 0.000 claims description 3
- 239000004700 high-density polyethylene Substances 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- 229920003049 isoprene rubber Polymers 0.000 claims description 3
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 3
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 3
- 229920001684 low density polyethylene Polymers 0.000 claims description 3
- 239000004702 low-density polyethylene Substances 0.000 claims description 3
- 229920003052 natural elastomer Polymers 0.000 claims description 3
- 229920001194 natural rubber Polymers 0.000 claims description 3
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 12
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 238000004064 recycling Methods 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 6
- 239000000945 filler Substances 0.000 abstract description 6
- 229920001577 copolymer Polymers 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 20
- 238000012216 screening Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000004381 surface treatment Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000012763 reinforcing filler Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000006136 alcoholysis reaction Methods 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000002025 wood fiber Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229940057995 liquid paraffin Drugs 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/14—Copolymers of propene
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Abstract
The glass fiber reinforced thermoplastic composite particle comprises the following components: thermoplastic base material, glass fiber reinforced plastic powder and toughening copolymer; the short glass fiber provides an anti-deformation effect, adopts glass fiber reinforced plastic powder filler to reduce water absorption, increases structural strength and rigidity, and increases surface toughness by toughening the copolymer; the building template made of the thermoplastic composite material has high rigidity and toughness, light weight, small deformation, high thermal deformation temperature, long weather resistance and long application of the building template; meanwhile, the recycled materials, namely glass fiber and glass fiber reinforced plastic powder, are used as proportioning components, so that the method is energy-saving and environment-friendly, the recycling and further utilization of the wind power blade are realized, and the ecological recycling and ecological application can be realized.
Description
Technical Field
The invention belongs to the technical field of polymer composite materials, and particularly relates to glass fiber reinforced thermoplastic composite particles.
Background
The polypropylene (PP) material has good processability and relatively high cost performance. But the pure polypropylene material has lower rigidity and poor impact resistance. For applications where high rigidity and high impact resistance are required, such as building form applications, which are subjected to a large number of external impacts, the product needs to have sufficient strength and toughness. The current improvement of the rigidity of polypropylene materials often requires the addition of glass fibers as reinforcing fillers. The glass fiber used as reinforcing filler has a length of 8-15 mm, a diameter of about 10-20 μm and an aspect ratio of over 100. While typical aspect ratios of other commonly used reinforcing fillers such as talc and calcium carbonate are about 20 and 1, respectively, and typically have particle sizes of about 7 microns. Therefore, the length-diameter ratio of the reinforced glass fiber is far higher than that of other common non-fibrous reinforcing fillers. The length-diameter ratio of the glass fiber often enables the reinforced polymer base material to generate stronger molecular chain orientation in the injection molding process, so that orientation internal stress is caused, and the final injection molding product is easy to generate buckling deformation. In addition, the inorganic fillers such as talcum powder, calcium carbonate and the like have water absorption, so that the product absorbs more water when being applied in a humid environment. And the overall demand of the building template is large, and the cost control of the production raw materials is also a problem to be solved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a thermoplastic composite material with high strength, high toughness and high dimensional stability.
The aim of the invention can be achieved by the following technical scheme:
the glass fiber reinforced thermoplastic composite particles are characterized by comprising the following components in parts by weight:
the thermoplastic substrate can be one or more of high-density polyethylene, low-density polyethylene, linear low-density polyethylene and polypropylene.
The glass fiber is short glass fiber and is glass fiber reinforced plastic from waste blades, cabin covers and air guide covers of the wind driven generator.
The glass fiber reinforced plastic composite material also comprises inorganic filler, wherein the inorganic filler is glass fiber reinforced plastic powder, and the weight part of the inorganic filler is 11-15.
The glass fiber reinforced plastic powder is from glass fiber reinforced plastic in waste blades, engine room covers and air guide covers of the wind driven generator.
Also comprises 5 to 10 parts by weight of toughening agent. The toughening agent is one or a mixture of a plurality of thermoplastic elastomer, styrene-butadiene rubber, nitrile rubber, butadiene rubber, isoprene rubber, natural rubber, chloroprene rubber, dynamic cross-linked rubber and thermoplastic polyurethane;
the dispersing agent is maleic anhydride grafted polypropylene, the density is 0.89-0.91 g/cm < 3 >, and the grafting rate is 1-4%.
The coupling agent is one or a mixture of more of isocyanate, aluminate, titanate and silane coupling agent.
Other auxiliaries include:
0.1 to 0.5 of antioxidant;
0.2 to 0.5 percent of light stabilizer.
The application of glass fiber reinforced thermoplastic composite particles comprises melting, extrusion molding, vacuum cooling and shaping, primary traction, heating and stress relief, secondary traction and cutting to obtain building templates meeting requirements.
Compared with the prior art, the glass fiber reinforced thermoplastic composite particles produced by the invention have the advantages that the short glass fibers provide an anti-deformation effect, the glass fiber reinforced plastic powder filler is adopted to reduce the water absorption, the structural strength and the rigidity are increased, the toughening copolymer is adopted to improve the surface toughness, and the building template made of the thermoplastic composite material has high rigidity and toughness, light weight, small deformation and high heat deformation temperature, and meanwhile, has long-term weather resistance, and can ensure long-term application of the building template. Meanwhile, the recycled materials are used as proportioning components, so that the method is energy-saving and environment-friendly, the recycling and further utilization of the wind power blades are realized, and the ecological recycling and ecological application can be realized.
Drawings
FIG. 1 is a flow chart of a preparation process.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Examples 1 to 4:
a process for preparing glass fiber reinforced thermoplastic composite particles.
(1) Feeding and mixing materials
A. And (5) carrying out surface treatment on the short glass fiber.
Mode one:
the glass fiber adopted is dried and cleaned. Pouring the short glass fiber into a high-speed mixer, stirring at high speed, and adding a coupling agent for surface treatment when the temperature of the material rises to 100 ℃. And cooling the treated short glass fiber and packaging for later use.
Wherein, the silane coupling agent and industrial alcohol are mixed for 20 to 30 minutes at room temperature according to the volume ratio of 1 to 5:5 to 10, and the silane coupling agent after alcoholysis is obtained; the silane coupling agent is gamma-aminopropyl triethoxysilane;
mixing the alcoholysis silane coupling agent with the short glass fiber, and stirring to obtain a surface-treated short glass fiber; the weight ratio of the silane coupling agent after alcoholysis to the short glass fiber is 1-5:95-99, the stirring time is 10-30 min, the rotating speed is 1300-2000 rpm/min, and the adopted equipment is a high-speed stirrer;
the solvent is isopropanol or ethanol.
Mode two:
the short glass fiber is obtained by recycling and processing the old materials, and if the short glass fiber obtained after original screening is doped with more dust, the surface cleaning treatment is needed. And (3) carrying out water treatment on the short glass fibers obtained after screening, soaking and cleaning the short glass fibers through water tank equipment, wherein a filter screen is arranged in the water tank equipment and is used for placing the short glass fibers to be cleaned, so that the short glass fibers are prevented from losing during soaking and cleaning. And filtering the short glass fiber with the surface cleaned, standing for 1-2 hours, and reducing the water content of the short glass fiber to be qualified. The modified surface treatment can be performed.
Mixing titanate coupling agent and liquid paraffin according to the volume ratio of 1-5:5 at room temperature for 20-30 min to obtain diluted titanate coupling agent; the titanate coupling agent is a chelate phosphate titanium coupling agent quaternary ammonium salt; the titanate coupling agent TC-WT is purchased from Tianchen chemical auxiliary agent oil plants in Tianchang city.
The chemical formula is。
Mixing the diluted titanate coupling agent with the water treatment short glass fiber, and stirring to obtain a modified surface treatment short glass fiber; the weight ratio of the diluted titanate coupling agent to the short glass fiber is 1-3:97-99, the stirring time is 10-20 min, the rotating speed is 1300-2000 rpm/min, and the adopted equipment is a high-speed stirrer;
the solvent can be liquid paraffin (i.e. white oil), solvent oil, or water.
The short glass fiber after the modified surface treatment is easier to be uniformly dispersed in the base material, and provides good coupling effect between the inorganic short glass fiber and a polymer system. The length of the short glass fiber is less than 2mm, the short glass fiber is uniformly dispersed in the base material, the directivity is avoided, the problem of anisotropy easily generated by adding the glass fiber into a polymer product is better overcome, and the excellent coupling combination is beneficial to improving the structural strength of the product.
B. The substrate components are mixed in proportion.
The base material polypropylene (PP) and a plurality of auxiliary agents are respectively weighed and poured into a high-speed mixer for stirring.
a. Firstly, the base material polypropylene is poured into a high-speed mixer with the rotating speed of 900 revolutions per minute to be stirred for standby.
b. And pouring the various auxiliary agents into a high-speed mixer with the rotating speed of 900 revolutions per minute for mixing at one time until the friction heat generated by mixing raises the temperature of the materials to 80 ℃ for discharging, and then sending the mixed materials into a cooling stirrer for stirring and cooling to the ambient temperature (0-40 ℃).
c. Drying the mixed material; in the drying treatment, the time is 1.5-3 h, and the temperature is 60-100 ℃.
C. Mixing materials.
And respectively placing the short glass fiber and polypropylene mixture subjected to surface treatment into a storage barrel. The produced 50% short glass fiber reinforced polypropylene particles can be conveyed into a hopper of a mixer by a feeding machine according to the proportion of 50:50 by a surface treatment short glass fiber and polypropylene mixture, and conveyed to an extruder by a conveyor after being uniformly stirred by the mixer. The content of the short glass fiber can be adjusted according to the characteristic requirement of the product.
(2) Extrusion
And (3) uniformly stirring by a mixer, extruding and granulating the mixture in an extruder by a melt impregnation method to obtain glass fiber reinforced polypropylene particles. The extruder temperature was set between 100 and 200℃and the impregnation die temperature was set at 200 ℃.
The extrusion process is a purely physical melt change process. The materials are conveyed to the extruder barrel and then are electrically heated, the materials gradually become a plastic state when advancing in the barrel and are pressed and compacted, and under the action of the rotation and the pressure of the screw, the materials are pushed to the machine head and pass through the die in the machine head, so that the materials are formed into required plastic strips.
In the granulation treatment, the temperatures of all areas of the screw extruder are as follows in sequence: the first heating zone temperature t1=100 to 120 ℃, the second heating zone temperature t2=130 to 140 ℃, the third heating zone temperature t3=150 to 160 ℃, the fourth heating zone temperature t4=160 to 170 ℃, the fifth heating zone temperature t5=170 to 180 ℃, the sixth heating zone temperature t6=180 to 190 ℃, the seventh heating zone temperature t7=190 to 200 ℃, the eighth heating zone temperature t8=190 to 200 ℃, the ninth heating zone temperature t9=190 to 200 ℃, and the extrusion die temperature=180 to 205 ℃. The rotating speed of the screw is 140-200 rpm/min; the equipment used was a ZSK-25WLE twin-screw extruder, available from WP, germany
(3) Cooling
The temperature of the plastic strip extruded by the extruder is reduced to about 70 ℃ by a circulating cooling water tank. The water in the cooling tank is recycled.
(4) Water blowing
And drying the moisture carried on the surface of the plastic strip at the tail end of the cooling water tank by using an electric hair dryer, and enabling the blown water to enter the circulating cooling water tank for recycling.
(5) Dicing
And cutting the cooled and molded plastic strip semi-finished product into a granular finished product with the grain diameter of 4mm by adopting a rotary blade. The short glass fibers in the finished particle product are uniformly dispersed, so that the problem of anisotropy is avoided, and the structural strength of the product is improved.
(6) Sieving, drying
And (3) feeding the finished glass fiber reinforced polypropylene particles after dicing into a granulator, screening out particles with the particle size meeting the requirements, conveying the particles to a storage bin, and collecting and recycling unqualified particles.
Drying the glass fiber reinforced polypropylene particles to obtain dried particles; in the drying treatment, the time is 24-48 h, and the temperature is 60-100 ℃.
Weighing materials according to the components and proportions provided in Table 1;
the material properties of the products were tested according to GB standard and the test results are shown in Table 2.
The following materials were used in the examples:
the polypropylene is K8003 produced by medium petrochemical industry. KH-550 (γ -aminopropyl triethoxysilane) produced by the south kyo dado photofabrication headquarters; an antioxidant 1010; an antioxidant 168; light stabilizer 3346 and light stabilizer 3853S.
The dispersing agent and the toughening agent are all commercially available chemicals. The dispersant is maleic anhydride grafted polypropylene with density of 0.89-0.91 g/cm3 and grafting rate of 1-4%. The toughening agent is nitrile rubber.
Table 1 the components and proportions of examples 1-4 (all examples below are in weight percent)
In the examples 1, 2 and 4, short glass fibers (< 2 mm) are used as raw materials, all the raw materials are fully mixed according to a certain proportion, and then extruded and granulated by an extruder to prepare the short fiber reinforced polypropylene modified particles;
in comparative example 3, long glass fibers (< 8 mm) were used as raw materials, and after the raw materials other than glass fibers were thoroughly mixed in proportion during the production, the long fiber-reinforced polypropylene modified particles were produced by compounding the long glass fibers with continuous long glass fibers by a cable coating method or an impregnation method and granulating the resultant.
TABLE 2 Properties (GB) of examples 1-4
| Component (A) | Example 1 | Example 2 | Comparative example 3 | Comparative example 4 |
| PP | 40 | 25 | 40 | 25 |
| Glass fiber (Length) | 30(<2mm) | 45(<2mm) | 30(<8mm) | 45(<2mm) |
| Filler (component) | 12 (glass fiber reinforced plastic powder) | 12 (glass fiber reinforced plastic powder) | 12 (glass fiber reinforced plastic powder) | 12 (calcium carbonate) |
| Dispersing agent | 11 | 11 | 11 | 11 |
| Tensile Strength | 98 | 115 | 102 | 105 |
| Flexural Strength | 214 | 248 | 220 | 226 |
| Flexural modulus | 6850 | 7420 | 7340 | 6980 |
| Impact Strength | 45.2 | 57.1 | 50.2 | 49.4 |
As can be seen from the table, with the increase of the glass fiber content, the tensile strength, the bending resistance and the impact strength of the product can be increased. There was no particular difference in the product strength characteristics of long glass fibers (< 8 mm) and short glass fibers (< 2 mm) at the same glass fiber content. In addition, the glass fiber reinforced plastic powder is used as the filler, and compared with the conventional calcium carbonate filler, the strength characteristics of the product are improved.
The product warpage evaluation method comprises the following steps:
rectangular large plates (300 mm long by 100mm wide by 3mm high) were injection molded using the pellets of example 1 and comparative example 3. Then, 24 hours after injection molding is completed, the front and back sides of the rectangular injection molding large plate are horizontally placed, and the distance between the top angle which is separated from the horizontal plane most and the horizontal plane is recorded. An average of warpage of at least 5 boards was recorded as a detection result.
The short glass fiber (2 mm) can obviously improve the buckling deformation of the injection molding flat plate, and the strength performance of the product is close.
Product water absorption evaluation method:
using pellets of example 2 and comparative example 4, sheet test pieces having a thickness of 5mm were produced. Polishing the surface of the sheet test piece by a sander, placing the sheet test piece in a constant-temperature water tank (the water temperature is set to be 23 ℃), taking out the surface after soaking for a certain time, wiping the surface, measuring the mass change before and after soaking, and calculating the water absorption rate of the sheet test piece as a detection result according to the change compared with the original mass.
| Component (A) | Example 2 | Comparative example 4 |
| PP | 25 | 25 |
| Glass fiber (Length) | 45(<2mm) | 45(<2mm) |
| Filler (component) | 12 (glass fiber reinforced plastic powder) | 12 (calcium carbonate) |
| Dispersing agent | 11 | 11 |
| Tensile Strength | 115 | 105 |
| Flexural Strength | 248 | 226 |
| Flexural modulus | 7420 | 6980 |
| Impact Strength | 57.1 | 49.4 |
| Water absorption (%) | 3 | 6 |
The obvious improvement of the glass fiber reinforced plastic powder reduces the water absorption of the product and improves the strength of the product.
Example 5
Weighing 50 parts by weight of copolymerized polypropylene with a melt index of 2-5 g/10min, 35 parts by weight of short glass fiber, 4 parts by weight of glass fiber reinforced plastic powder, 6 parts by weight of toughener nitrile rubber, 4 parts by weight of dispersant maleic anhydride grafted polypropylene, 0.4 part by weight of coupling agent KH550, 0.1 part by weight of antioxidant 1010, 0.1 part by weight of antioxidant 168, light stabilizer 3346 and light stabilizer 3853S, and mixing the components according to a weight ratio of 3:4 to obtain a light stabilizer of 0.4;
uniformly mixing in a high-speed mixer, and mixing in the high-speed mixer for 5 minutes;
and extruding by a double-screw extruder to obtain the short fiber reinforced polypropylene modified composite particles. The extruder temperature was set between 100 and 200℃and the impregnation die temperature was set at 200 ℃.
The building template is manufactured by extruding and molding short fiber reinforced polypropylene modified composite particles through the processes of melting thermoplastic composite materials, extruding and molding products, vacuum cooling and shaping, primary traction, heating and stress relief, secondary traction, cutting, stacking, packaging and the like.
In the above embodiments, the thermoplastic substrate may be one or more of high density polyethylene, low density polyethylene, linear low density polyethylene, polypropylene.
The toughening agent is thermoplastic elastomer, which can be one or a mixture of several of styrene-butadiene rubber, nitrile rubber, butadiene rubber, isoprene rubber, natural rubber, chloroprene rubber, dynamic cross-linked rubber and thermoplastic polyurethane.
The coupling agent can be one or more of isocyanate, aluminate, titanate and silane coupling agent.
In order to reduce the processing cost of the product, the recovered materials are absorbed, and the glass fiber reinforced plastic powder/the short glass fiber are all from the wind power blade recovery process.
(1) Pretreatment material for wind power blade
The retired wind power blade is dismembered into blocks of 0.8m-1m by a special blade cutting tool. The dismembering procedure can be completed on site in a wind farm;
(2) Coarse crushing of wind power blade
Because of the high hardness, high toughness and heavy weight of the blade material, it is very difficult to process the blade material, and no more sophisticated processing modes and equipment exist at present to process the blade material into a material of not more than 5 cm.
The coarse crushing process adopts a special crusher for glass fiber reinforced plastic to crush the blocks after the dismembering, and the blocks can be crushed into glass fiber reinforced plastic scraps with the grain size of 2cm-5 cm.
(3) Wind power blade primary screening
The proportion of PVC, bassal wood and glass fiber reinforced plastic in the wind power blade is 5%, 5% and 90%, respectively, and three substances of PVC, bassal wood and glass fiber reinforced plastic can be separated from the wind power blade after coarse crushing.
And separating by adopting a first screening machine according to the specific gravity difference of the three substance components, and feeding the coarse crushed glass fiber reinforced plastic scraps into the first screening machine to separate PVC, bassal wood and glass fiber reinforced plastic.
(4) Fine crushing of glass fibre reinforced plastic
The glass fiber reinforced plastic particles after the first-stage screening can be conveyed to a fine crusher by a conveyor to be crushed again, and finally crushed into 1cm particle materials,
(5) Two-stage screening
The proportions of glass fiber and glass fiber reinforced plastic particles in the glass fiber reinforced plastic are respectively 50% and 50%, and according to the proportion difference of components, the glass fiber reinforced plastic particles and the glass fiber reinforced plastic particles are separated by adopting a screening machine, and fine crushed glass fiber reinforced plastic fragments enter a second screening machine to separate the glass fiber and the glass fiber reinforced plastic. After the glass fiber is separated from the resin component by the coarse crushing and fine crushing processes, the length of the glass fiber is shorter (less than 2 mm), and the glass fiber is used as a short glass fiber for processing building templates.
(6) Glass fiber reinforced plastic granule grinding powder
And conveying the glass fiber reinforced plastic particles (1 cm) obtained after fine crushing and secondary screening to a grinder for grinding by using a superfine pulverizer, crushing and screening, and grinding the materials into glass fiber reinforced plastic (resin) powder with the particle size of 0.15 mm. The glass fiber reinforced plastic powder is used for processing building templates.
Finally, it should be noted that: the foregoing is merely illustrative of the present invention and is not to be construed as limiting thereof, and although the present invention has been described in detail, it will be apparent to those skilled in the art that modifications may be made to the foregoing embodiments, or equivalents may be substituted for elements thereof. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The glass fiber reinforced thermoplastic composite particles are characterized by comprising the following components in parts by weight:
2. the glass fiber reinforced thermoplastic composite particles according to claim 1, wherein the thermoplastic substrate is one or more of high density polyethylene, low density polyethylene, linear low density polyethylene, and polypropylene.
3. The glass fiber reinforced thermoplastic composite particle of claim 1, wherein the glass fiber is short glass fiber, and is glass fiber reinforced plastic from waste blades, engine room covers and fairings of wind driven generators.
4. The glass fiber reinforced thermoplastic composite particle according to claim 1, further comprising an inorganic filler, wherein the inorganic filler is glass fiber reinforced plastic powder, and the weight part of the inorganic filler is 11-15.
5. The glass fiber reinforced thermoplastic composite particle of claim 4, wherein the glass fiber reinforced plastic powder is from glass fiber reinforced plastic in waste blades, cabin covers and fairings of wind driven generators.
6. The glass fiber reinforced thermoplastic composite particle according to claim 1, further comprising 5 to 10 parts by weight of a toughening agent.
7. The glass fiber reinforced thermoplastic composite particles according to claim 6, wherein the toughening agent is a thermoplastic elastomer, which can be one or a mixture of several of styrene-butadiene rubber, nitrile rubber, butadiene rubber, isoprene rubber, natural rubber, chloroprene rubber, dynamic cross-linked rubber and thermoplastic polyurethane;
the dispersing agent is maleic anhydride grafted polypropylene.
8. The glass fiber reinforced thermoplastic composite particle according to claim 1, wherein the coupling agent is one or a mixture of more of isocyanate, aluminate, titanate and silane coupling agent.
9. The glass fiber reinforced thermoplastic composite particle of claim 1, wherein the other adjuvants comprise:
0.1 to 0.5 of antioxidant;
0.2 to 0.5 percent of light stabilizer.
10. The use of the glass fiber reinforced thermoplastic composite particles according to claim 1, wherein the glass fiber reinforced thermoplastic composite particles are melted, extruded, vacuum cooled to set, first pulled, heated to remove stress, second pulled, and cut to form a building template meeting the requirements.
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