CN116023750B - Glass fiber reinforced AS composition and preparation method thereof - Google Patents
Glass fiber reinforced AS composition and preparation method thereof Download PDFInfo
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- CN116023750B CN116023750B CN202211718058.0A CN202211718058A CN116023750B CN 116023750 B CN116023750 B CN 116023750B CN 202211718058 A CN202211718058 A CN 202211718058A CN 116023750 B CN116023750 B CN 116023750B
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- 239000003607 modifier Substances 0.000 claims abstract description 8
- 239000003822 epoxy resin Substances 0.000 claims description 18
- 229920000647 polyepoxide Polymers 0.000 claims description 18
- 239000004593 Epoxy Substances 0.000 claims description 14
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 9
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 6
- 239000012760 heat stabilizer Substances 0.000 claims description 6
- 239000004611 light stabiliser Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims 1
- 239000000049 pigment Substances 0.000 claims 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 30
- 229920001893 acrylonitrile styrene Polymers 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 4
- 238000005336 cracking Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- 239000004229 Alkannin Substances 0.000 description 1
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000004172 quinoline yellow Substances 0.000 description 1
- 239000002151 riboflavin Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004149 tartrazine Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a glass fiber reinforced AS composition and a preparation method thereof. The AS composition comprises the following components in parts by weight: 56-90 parts of AS resin; 10-30 parts of glass fiber; 1-10 parts of interface modifier. The AS composition has small transverse and longitudinal strength deviation, good mechanical properties and good processability.
Description
Technical Field
The invention belongs to the technical field of modified plastics, and particularly relates to a glass fiber reinforced AS composition and a preparation method thereof.
Background
The acrylonitrile-styrene (AS) resin is one kind of thermoplastic plastic prepared with Styrene (ST) and Acrylonitrile (AN) AS material and through copolymerization. AS resin has excellent performance, excellent dimensional stability, electrical property, wear resistance, chemical resistance and dyeing property, and is an important engineering plastic with good molding and machining. The high strength and high modulus of the reinforced modified AS resin are improved, so that the modified AS resin is particularly suitable for products such AS air conditioner fan blades and the like which need high dynamic stability.
However, with the development of industry, the requirements for materials are continuously increasing. Taking a tap in certain air conditioning industry as an example, the new requirement of dynamic stability is 10000 revolutions/min, and no crack or cracking phenomenon exists after 5 minutes. The main reason for the cracking of the fan blade is that the glass fiber can be oriented in the flowing process of the melt, so that the transverse and longitudinal strength deviation of the workpiece is larger.
Disclosure of Invention
The invention aims to solve the technical problem of providing a glass fiber reinforced AS composition and a preparation method thereof, so AS to overcome the defects of larger transverse and longitudinal strength deviation and poor mechanical property of the AS composition in the prior art.
The invention provides a glass fiber reinforced AS composition, which comprises the following components in parts by weight:
56-90 parts of AS resin;
10-30 parts of glass fiber;
1-10 parts of interface modifier;
the interface modifier is hyperbranched epoxy resin;
the epoxy equivalent of the hyperbranched epoxy resin is 350-450g/mol. The method for testing the epoxy equivalent is a quaternary ammonium bromide direct titration method.
Preferably, the AS composition comprises the following components in parts by weight:
60-80 parts of AS resin;
15-25 parts of glass fiber;
2-8 parts of interface modifier.
Preferably, the AS resin is a copolymer of acrylonitrile and styrene, and the weight fraction of the acrylonitrile is 20-30%.
Preferably, the glass fibers are long glass fibers and/or chopped glass fibers.
Preferably, the glass fibers are alkali-free glass fibers.
Preferably, the glass fibers have an average diameter of 8-20 μm.
More preferably, the glass fibers have an average diameter of 10 to 13 μm.
Preferably, the viscosity of the hyperbranched epoxy resin is 500-700cp. The viscosity is tested in accordance with GB 12007.4-1989.
Preferably, the hyperbranched epoxy resin end group is an epoxy group, and the skeleton of the hyperbranched epoxy resin is an aromatic polyester polyether hyperbranched polymer.
Preferably, the AS composition further comprises 0-3 parts of other auxiliary agents.
Preferably, the other auxiliary agents comprise one or more of heat stabilizer, light stabilizer and processing aid; the processing aid comprises one or more of esters, metal soaps (Cast and Znst) and amides (erucamide).
Preferably, the weight portion of the heat stabilizer is 0.1-1 portion.
Preferably, the heat stabilizer comprises one or more of phenols, phosphites, thioesters and stearic acid.
Preferably, the light stabilizer is 0.1 to 1 part by weight.
Preferably, the light stabilizer comprises a hindered amine and/or an ultraviolet absorber.
Preferably, the processing aid is 0.1-2 parts by weight.
The invention also provides a preparation method of the glass fiber reinforced AS composition, which comprises the following steps:
mixing the other components except the glass fiber, adding the obtained premix into a double-screw extruder from a main feeding port, adding the glass fiber into a side feeding port, carrying out melt extrusion, granulating and drying to obtain the AS composition.
Preferably, the mixing time is 1-3min.
Preferably, the processing conditions of the melt extrusion are: the temperature of the first area is 180-210 ℃, the temperature of the second area is 190-220 ℃, the temperature of the third area is 190-230 ℃, the temperature of the fourth area is 190-240 ℃, the temperature of the fifth area is 190-240 ℃, the temperature of the sixth area is 190-240 ℃, the temperature of the seventh area is 190-240 ℃, the temperature of the eighth area is 190-240 ℃, the temperature of the ninth area is 190-240 ℃ and the rotating speed of the host is 250-600 revolutions per minute.
Preferably, the twin screw extruder has an aspect ratio of (36-48): 1.
The invention also provides application of the glass fiber reinforced AS composition in household appliances, such AS axial flow, through flow, centrifugal fan blades and the like in air conditioners.
The epoxy group of the hyperbranched epoxy resin is polar, and the compatibility of the cyano group in the acrylonitrile in the AS resin which is the polar group is excellent. The ring structure of the hyperbranched epoxy resin can lock the glass fiber, limit the movement of the glass fiber and reduce the orientation degree of the glass fiber in the forming process. The higher the epoxy equivalent, the weaker the binding force with AS resin and the capability of locking glass fiber, the larger the glass fiber orientation degree, the larger the transverse and longitudinal strength deviation, and the worse the mechanical property; after the epoxy equivalent is reduced to a certain content, the physical properties of the composite material can reach a higher level, the epoxy equivalent is reduced again, the physical properties of the composite material are improved limitedly, but the combination with AS resin is stronger, the lower the melt flow rate of the composite material is, and the more difficult the molding processability is.
Advantageous effects
The invention adopts hyperbranched epoxy resin with specific epoxy equivalent, can reduce the transverse and longitudinal strength deviation, improve the mechanical property and simultaneously ensure the processability.
The AS composition of the invention has the bending strength of more than or equal to 160MPa and the cantilever beam impact strength (notch) of more than or equal to 6.4kJ/m 2 The MFR is 6.5-20g/10min, and the ratio of transverse and longitudinal tensile strength is less than or equal to 1.5.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
Reagent source:
AS resin 1: acrylonitrile weight fraction 24.5%, SAN NF2200, ningbo Co., ltd; AS resin 2: the weight fraction of acrylonitrile is 30.6%, SAN 350, daqing petrochemical company
AS resin 3: the acrylonitrile weight fraction is 19.3%, SAN 310N TR, jinhu petrochemical Co Ltd;
glass fiber 1: chopped fibers having an average diameter of 13 μm, E6CR13-4.5-534A, china boulder Co., ltd; glass fiber 2: chopped fibers having an average diameter of 10 μm, E6CR10-4.5-534A, china boulder Co., ltd; hyperbranched epoxy resin 1: the epoxy equivalent is 400g/mol, the viscosity is 700cp, E102, suzhou sea Bode resin technology Co., ltd;
hyperbranched epoxy resin 2: the epoxy equivalent is 450g/mol, the viscosity is 500cp, E103, and the Suzhou sea Bode resin technology Co., ltd;
hyperbranched epoxy resin 3: the epoxy equivalent is 312g/mol, the viscosity is 550cp, E101, and the Suzhou sea Bode resin technology Co., ltd;
hyperbranched epoxy resin 4: the epoxy equivalent is 526g/mol, the viscosity is 350cp, E104, suzhou sea Bode resin technology Co., ltd;
styrene-maleic anhydride grafts: SMA 700, jiaxing Hua Wen chemical Co., ltd;
other auxiliaries:
heat stabilizer: calcium stearate, commercially available;
light stabilizers: benzotriazole, commercially available;
processing aid: EBS, commercially available;
unless otherwise specified, some of the components (e.g., heat stabilizer, light stabilizer, processing aid) in the examples and comparative examples of the present invention are the same commercially available products.
The preparation method of the AS composition comprises the following steps: mixing the components except glass fiber in a high-speed mixer for 1-3min according to the mixture ratio of table 1 and table 2; uniformly mixing to obtain a premix; placing the premix into a main feeding port of a double-screw extruder, adding glass fibers from a side feeding port, carrying out melt extrusion, granulating and drying to obtain the glass fiber reinforced plastic composite material, wherein the processing conditions of the melt extrusion are as follows: 180-210 ℃ in the first area, 190-220 ℃ in the second area, 190-230 ℃ in the third area, 190-240 ℃ in the fourth area, 190-240 ℃ in the fifth area, 190-240 ℃ in the sixth area, 190-240 ℃ in the seventh area, 190-240 ℃ in the eighth area, 190-240 ℃ in the ninth area, and 250-600 revolutions per minute of the host machine; the aspect ratio of the twin screw extruder was 40:1.
Performance test:
(1) Flexural strength: testing according to ISO 178-2019, wherein the testing temperature is 23+/-2 ℃ and the humidity is 50+/-5%;
(2) Cantilever impact strength (notch): testing according to ISO 180-2019, wherein the testing temperature is 23+ -2deg.C, the humidity is 50+ -5%, and the notch is A-type;
(3) MFR: ISO 1133-1-2011, test conditions of 220 ℃ and 10kg. The method comprises the steps of carrying out a first treatment on the surface of the
(4) Ratio of transverse to longitudinal tensile strength: injection molding 200 x 3mm square panels molded from one end, bars were cut from the transverse and longitudinal directions of the flow direction, respectively, tested for tensile strength (ISO 527-2019, test temperature 23±2 ℃, humidity 50±5%) and the ratio of the transverse and longitudinal tensile strengths was calculated.
Table 1 example formulation (parts by weight)
Table 2 comparative example ratio (parts by weight)
As is clear from tables 1 to 2, the hyperbranched epoxy resin of comparative example 1 has an epoxy equivalent lower than the range of the present invention, and the ratio of the flexural strength, the Izod impact strength, and the transverse-longitudinal tensile strength is almost the same as that of example 1, but the MFR of comparative example 1 is lower, and the molding processability is difficult. The hyperbranched epoxy resin of comparative example 2 has an epoxy equivalent exceeding the range of the present invention, and the ratio of flexural strength, izod impact strength, and transverse-longitudinal tensile strength is significantly inferior to that of example 1. Comparative example 3 used a conventional interface modifier whose ratio of flexural strength, cantilever impact strength, and transverse-longitudinal tensile strength was significantly inferior to that of example 1, which merely improved the surface adhesion of the resin and glass fibers, and could not limit the displacement of the glass fibers, and especially in the high-speed injection molding process, the orientation of the glass fibers was extremely severe, resulting in easy weld line cracking of the product. Comparative example 4, without the addition of hyperbranched epoxy resin, had significantly inferior flexural strength, izod impact strength, and transverse-longitudinal tensile strength to example 1. Therefore, the hyperbranched epoxy resin with specific epoxy equivalent is adopted, so that the transverse and longitudinal strength deviation can be reduced, the mechanical property is improved, and the processability is ensured.
Claims (10)
1. The glass fiber reinforced AS composition is characterized by comprising the following components in parts by weight:
56-90 parts of AS resin;
10-30 parts of glass fiber;
1-10 parts of interface modifier;
the interface modifier is hyperbranched epoxy resin;
the epoxy equivalent of the hyperbranched epoxy resin is 350-450g/mol.
2. The AS composition according to claim 1, wherein the AS composition comprises the following components in parts by weight:
60-80 parts of AS resin;
15-25 parts of glass fiber;
2-8 parts of interface modifier.
3. The AS composition of claim 1, wherein the AS resin comprises 20% to 30% acrylonitrile by weight.
4. The AS composition according to claim 1, wherein the glass fibers are long glass fibers and/or chopped glass fibers.
5. The AS composition according to claim 1, wherein the glass fibers have an average diameter of 8-20 μm.
6. The AS composition according to claim 1, wherein the AS composition further comprises 0-3 parts of other adjuvants.
7. The AS composition according to claim 6, wherein the other auxiliary agents comprise one or more of a heat stabilizer, a light stabilizer, a processing aid, a toner, a pigment; the processing aid comprises one or more of esters, metal soaps and amides.
8. A process for the preparation of an AS composition AS claimed in any one of claims 1 to 7, comprising:
mixing the other components except the glass fiber, adding the obtained premix into a double-screw extruder from a main feeding port, adding the glass fiber into a side feeding port, carrying out melt extrusion, granulating and drying to obtain the AS composition.
9. The method of claim 8, wherein the melt extrusion processing conditions are: 180-210 ℃ in the first area, 190-220 ℃ in the second area, 190-230 ℃ in the third area, 190-240 ℃ in the fourth area, 190-240 ℃ in the fifth area, 190-240 ℃ in the sixth area, 190-240 ℃ in the seventh area, 190-240 ℃ in the eighth area, 190-240 ℃ in the ninth area, and 250-600 revolutions per minute of the host machine; the length-diameter ratio of the twin-screw extruder is (36-48): 1.
10. Use of an AS composition AS claimed in any one of claims 1 to 7 in a household appliance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211718058.0A CN116023750B (en) | 2022-12-29 | 2022-12-29 | Glass fiber reinforced AS composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211718058.0A CN116023750B (en) | 2022-12-29 | 2022-12-29 | Glass fiber reinforced AS composition and preparation method thereof |
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| Publication Number | Publication Date |
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| CN116023750A CN116023750A (en) | 2023-04-28 |
| CN116023750B true CN116023750B (en) | 2024-02-23 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0733484A (en) * | 1993-07-21 | 1995-02-03 | Asahi Fiber Glass Co Ltd | Sizing agent for glass fiber and glass fiber for reinforcing |
| JPH07228756A (en) * | 1994-02-17 | 1995-08-29 | Asahi Fiber Glass Co Ltd | Glass fiber binder, reinforcing glass fiber using same, and glass fiber-reinforced resin material |
| CN101555341A (en) * | 2009-05-25 | 2009-10-14 | 国家复合改性聚合物材料工程技术研究中心 | High-strength fiber glass reinforced ABS composite material and preparation method thereof |
| CN114163746A (en) * | 2021-11-11 | 2022-03-11 | 天津金发新材料有限公司 | Glass fiber reinforced AS composition and application thereof |
| CN115466416A (en) * | 2022-08-26 | 2022-12-13 | 上海金山锦湖日丽塑料有限公司 | Impact-resistant improved glass fiber reinforced PC/ABS alloy material and preparation method thereof |
-
2022
- 2022-12-29 CN CN202211718058.0A patent/CN116023750B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0733484A (en) * | 1993-07-21 | 1995-02-03 | Asahi Fiber Glass Co Ltd | Sizing agent for glass fiber and glass fiber for reinforcing |
| JPH07228756A (en) * | 1994-02-17 | 1995-08-29 | Asahi Fiber Glass Co Ltd | Glass fiber binder, reinforcing glass fiber using same, and glass fiber-reinforced resin material |
| CN101555341A (en) * | 2009-05-25 | 2009-10-14 | 国家复合改性聚合物材料工程技术研究中心 | High-strength fiber glass reinforced ABS composite material and preparation method thereof |
| CN114163746A (en) * | 2021-11-11 | 2022-03-11 | 天津金发新材料有限公司 | Glass fiber reinforced AS composition and application thereof |
| CN115466416A (en) * | 2022-08-26 | 2022-12-13 | 上海金山锦湖日丽塑料有限公司 | Impact-resistant improved glass fiber reinforced PC/ABS alloy material and preparation method thereof |
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