CN1279115C - Co-fixing polyethylene terephthalate in high tenacity and preparation method - Google Patents
Co-fixing polyethylene terephthalate in high tenacity and preparation method Download PDFInfo
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- CN1279115C CN1279115C CN 200410017174 CN200410017174A CN1279115C CN 1279115 C CN1279115 C CN 1279115C CN 200410017174 CN200410017174 CN 200410017174 CN 200410017174 A CN200410017174 A CN 200410017174A CN 1279115 C CN1279115 C CN 1279115C
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Abstract
The present invention provides a cross blend object of polyethylene glycol terephthalate (PET) with high toughness and a preparation method. The cross blend object of the PET with high toughness is composed of the PET, an elastic body containing an epoxy base group and a crosslinking agent containing nitrogen. The components are added in a double-screw extruder under processing temperature of 250 to 300 DEG C; the components are shorn and mixed, and simultaneously, the crosslinking agent and the epoxy base group generate a ring opening reaction so as to realize the crosslinking of the elastic body with the epoxy base group; the crosslinking elastic body is dispersed in a PET continuous phase so as to effectively improve the shock resistance of the PET. The preparation method provided by the present invention has the advantage of simple processing technology; the cross blend object with high toughness has favorable toughness and keeps certain rigidity simultaneously.
Description
Technical field:
The present invention relates to a kind of high tenacity polyethylene terephthalate (PET) blend and preparation method thereof, particularly a kind of method that adopts dynamic vulcanization technology to prepare high tenacity PET blend.
Background technology:
PET has high strength, high rigidity, good thermotolerance, chemical proofing and electrical insulation capability, thereby is widely used in fiber, film and beverage bottle field.Yet also there are some latent defects in the PET of non-modified, and problems such as when it is used as engineering plastics, toughness deficiency, crystallization rate are slow, the back poor dimensional stability of being heated just seem very outstanding.
In order to improve the toughness of PET, the co-mixing system to PET/ functionalized elastomeric body has carried out big quantity research both at home and abroad.Plastics 1,998 27 (2): 33～36, polymer material science and engineering 1,994 5 (9): 81～86, China's plastics 2,001 15 (5): 39～41, Chinese patent CN98102049.6 has reported respectively with ethylene-methyl methacrylate glycidyl ester copolymer (E-GMA) and ethylene-propylene acetoacetic ester-glycidyl methacrylate copolymer (E-EA-GMA), low density polyethylene (LDPE) (LDPE-g-MAH) with maleic anhydride graft, metallocene catalysed polyethylene (mPE-GMA) with glycidyl methacrylate graft, (POE-MAH) is toughness reinforcing to PET with maleic anhydride grafted ethene-octene copolymer.These functionalized elastomeric addings can make the shock resistance of PET increase, but also can make the rigidity of PET simultaneously, and heat-resisting and solvent resistance descends.
Static vulcanization technology and dynamic vulcanization technology are disclosed in USP 3037954 this piece documents, dynamic vulcanization technology is meant that vulcanizable elastomerics is dispersed in the resinoid thermoplastic polymer, and makes the elastomerics sulfuration in continuously stirring with when shearing blend polymer.Dynamic vulcanization normally prepares the method for novel thermoplastic elastomer, and the report that is applied to functionalized elastic body toughening engineering plastics is comparatively rare, reported the method for preparing super-toughened nylon with dynamic vulcanization technology among the patent CN03116291.6 at home, its linking agent that adopts is 2,5-dimethyl-2,5 pair (tert-butyl peroxy base) hexane.
Summary of the invention:
The objective of the invention is to keep other performances of PET as far as possible, obtain a kind of high tenacity PET blend with better over-all properties for significantly improving the PET flexible simultaneously.
High tenacity PET blend of the present invention is made up of PET, the elastomerics that has epoxide group and nitrogenous linking agent, wherein the consumption of PET accounts for the 50wt%～95wt% of blend, the elastomeric consumption that has epoxide group accounts for the 5wt%～50wt% of blend, and the consumption of nitrogenous linking agent accounts for the elastomeric 0.3wt%～2wt% that has epoxide group.
The limiting viscosity of PET of the present invention is 0.5～1.0dl/g.
The elastomerics that has epoxide group of the present invention is the polyolefin elastomer of ethylene-propylene acetoacetic ester-glycidyl methacrylate copolymer, ethylene-propylene acid butyl ester-glycidyl methacrylate copolymer or glycidyl methacrylate graft, as glycidyl methacrylate graft polyethylene, glycidyl methacrylate graft ethylene-octene copolymer etc.
Nitrogenous linking agent of the present invention be Dicyanodiamide, glyoxal ethyline, 2-ethyl-4 Methylimidazole, adipic dihydrazide, m-phthalic acid two hydrazides, the last of the ten Heavenly stems hydrazine etc.
High tenacity PET blend preparation method of the present invention is as follows: join in the twin screw extruder simultaneously after PET, the elastomerics that has epoxide group and nitrogenous linking agent are mixed, wherein the consumption of PET accounts for the 50wt%～95wt% of blend, the elastomeric consumption that has epoxide group accounts for the 5wt%～50wt% of blend, the consumption of nitrogenous linking agent accounts for the elastomeric 0.3wt%～2wt% that has epoxide group, more than the consumption of the three kinds of compositions per-cent summation that accounts for blend be 100wt%; Under the driving screw rotating speed of 250～300 ℃ processing temperatures and 300～500rpm, carry out extruding pelletization, obtain high tenacity PET blend.
The present invention has adopted the technology of dynamic vulcanization, its sulfidation is by in the course of processing, nitrogenous linking agent and epoxide group generation ring-opening reaction, make have an epoxide group elastomer crosslinked realize that crosslinked elastomerics is evenly dispersed in the PET external phase under the shearing action of forcing machine.
Present method complete processing is simple, and the high tenacity PET blend notched Izod impact strength at room temperature that makes can reach 616J/m.Compare with the material of dynamic vulcanization not, when reaching identical notched Izod impact strength, the elastomerics consumption of the material behind the dynamic vulcanization obviously reduces, and makes it also keep certain rigid when obtaining excellent toughness.
Embodiment:
Following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1～5: adopting limiting viscosity is the PET of 0.6dl/g, (E.I.Du Pont Company produces with ethylene-propylene acid butyl ester-glycidyl methacrylate copolymer, commodity are called PTW) be elastomerics, with 2-ethyl-4 Methylimidazole (EMI-2,4) be linking agent, after each component mixed by the prescription in the table 1, under the driving screw rotating speed of 255～260 ℃ processing temperatures and 400rpm, use the twin screw extruder extruding pelletization, obtain high tenacity PET blend.
The particle of extruding the high tenacity PET blend that obtains in vacuum drying oven 105 ℃ down after dry 12 hours on injection moulding machine the injection standard sample.Sample respectively according to DIN-EN-ISO527, ISO179 and ISO178 standard stretch, the test of impact and bending property.
The prescription of the different dosage of crosslinking agent of table 1 and mechanical property
| Prescription | Comparative Examples | 1 | 2 | 3 | 4 | 5 |
| PET(wt％) PTW(wt％) *EMI-2,4 (wt%) mechanical property hot strength (MPa) elongation at break (%) notched Izod impact strength (J/m) bending strength (MPa) bending modulus (MPa) | 80 20 33.8 662.0 354 50.2 1431 | 80 20 0.5 35.7 587.0 407 50.8 1431 | 80 20 1 37.2 608.0 429 52.7 1471 | 80 20 1.5 38.3 582.5 417 52.9 1473 | 80 20 2 39.8 408.1 363 55.5 1552 | 80 20 3 35.6 358.8 58 51.5 1443 |
*Annotate: EMI-2 in the table, 4 consumptions are the weight percent that accounts for PTW
When adding 0.5%～2%EMI-2,4 o'clock, the tensile yield of material descended to some extent as can be seen from Table 1, and tensile strength, notched Izod impact strength, flexural strength and modulus in flexure all obviously increase.Also can see simultaneously, work as EMI-2,4 consumptions reach at 3% o'clock, and the various aspects of performance of material all declines to a great extent, and this is owing to over cure and excessive EMI-2, and 4 promote what the PET degraded caused
Embodiment 6～8: adopting limiting viscosity is the PET of 0.6dl/g, (E.I.Du Pont Company produces with ethylene-propylene acid butyl ester-glycidyl methacrylate copolymer, commodity are called PTW) be elastomerics, with 2-ethyl-4 Methylimidazole (EMI-2,4) be linking agent, after each component mixed by the prescription in the table 2, under the driving screw rotating speed of 255～260 ℃ processing temperatures and 400rpm, use the twin screw extruder extruding pelletization, obtain high tenacity PET blend.
The particle of extruding the high tenacity PET blend that obtains in vacuum drying oven 105 ℃ down after dry 12 hours on injection moulding machine the injection standard sample.Sample respectively according to DIN-EN-ISO527, ISO179 and ISO178 standard stretch, the test of impact and bending property.
Different elastomerics consumptions of table 2 and employing and the prescription and the mechanical property that do not adopt dynamic vulcanization
| Prescription | Comparative Examples | Comparative Examples | Comparative Examples | 6 | 7 | 8 |
| PET(wt％) PTW(wt％) *EMI-2,4 (wt%) mechanical property hot strength (MPa) elongation at break (%) notched Izod impact strength (J/m) bending strength (MPa) bending modulus (MPa) | 95 5 51.84 105.2 19 71.2 2127 | 85 15 39.17 624.0 157 58.3 1616 | 70 30 27.26 427.2 534 34.4 963 | 95 5 1 53.09 92.2 37 82.2 2251 | 85 15 1 44.51 591.5 223 65.3 1832 | 70 30 1 29.60 579.5 616 42.4 1225 |
*Annotate: EMI-2 in the table, 4 consumptions are the weight percent that accounts for PTW
Under identical PTW consumption, the tensile yield of having carried out the material of dynamic vulcanization has decline slightly than the material that does not carry out dynamic vulcanization as can be seen from Table 2, and tensile strength, notched Izod impact strength, flexural strength and modulus in flexure then all obviously increase.The high tenacity PET that this explanation adopts preparation method of the present invention to obtain has good comprehensive performances, has also kept certain rigid when obtaining excellent toughness.
Claims (4)
1. the preparation method of a high tenacity polyethylene terephthalate blend, it is characterized in that polyethylene terephthalate, have and join in the twin screw extruder simultaneously after the elastomerics of epoxide group and nitrogenous linking agent mix, wherein the consumption of polyethylene terephthalate accounts for the 50wt%～95wt% of blend, the elastomeric consumption that has epoxide group accounts for the 5wt%～50wt% of blend, the consumption of nitrogenous linking agent accounts for the elastomeric 0.3wt%～2wt% that has epoxide group, more than the consumption of the three kinds of compositions per-cent summation that accounts for blend be 100wt%; Extruding pelletization under the driving screw rotating speed of 250～300 ℃ processing temperatures and 300～500rpm obtains the polyethylene terephthalate blend of high tenacity.
2. the preparation method of a kind of high tenacity polyethylene terephthalate blend according to claim 1 is characterized in that the limiting viscosity of the polyethylene terephthalate that adopted is 0.5～1.0dl/g.
3. the preparation method of a kind of high tenacity polyethylene terephthalate blend according to claim 1 is characterized in that the elastomerics that has epoxide group that is adopted is the polyolefin elastomer of ethylene-propylene acetoacetic ester-glycidyl methacrylate copolymer, ethylene-propylene acid butyl ester-glycidyl methacrylate copolymer or glycidyl methacrylate graft.
4. the preparation method of a kind of high tenacity polyethylene terephthalate blend according to claim 1, it is characterized in that the nitrogenous linking agent that is adopted be Dicyanodiamide, glyoxal ethyline, 2-ethyl-4 Methylimidazole, adipic dihydrazide, m-phthalic acid two hydrazides or the last of the ten Heavenly stems hydrazine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410017174 CN1279115C (en) | 2004-03-25 | 2004-03-25 | Co-fixing polyethylene terephthalate in high tenacity and preparation method |
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| CN 200410017174 CN1279115C (en) | 2004-03-25 | 2004-03-25 | Co-fixing polyethylene terephthalate in high tenacity and preparation method |
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| CN1563185A CN1563185A (en) | 2005-01-12 |
| CN1279115C true CN1279115C (en) | 2006-10-11 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100425652C (en) * | 2005-12-13 | 2008-10-15 | 苏州市凯米克新材料有限公司 | High-performance reinforced fire-retardant polyster engineering plastic |
| CN108396402B (en) * | 2018-03-15 | 2020-12-15 | 江苏垶恒复合材料有限公司 | High-toughness polyester staple fiber and preparation method thereof |
| CN109910401A (en) * | 2019-03-13 | 2019-06-21 | 苏州新颖新材料科技股份有限公司 | A kind of high-performance acoustic noise reduction film coated plate |
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