CN1445278A - Super malleable nylon and its preparing method - Google Patents
Super malleable nylon and its preparing method Download PDFInfo
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- CN1445278A CN1445278A CN 03116291 CN03116291A CN1445278A CN 1445278 A CN1445278 A CN 1445278A CN 03116291 CN03116291 CN 03116291 CN 03116291 A CN03116291 A CN 03116291A CN 1445278 A CN1445278 A CN 1445278A
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- nylon
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- maleic anhydride
- anhydride graft
- toughened
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Abstract
A super-toughness nylon is prepared from nylon, maleic acid anhydride grafted polyolefin elastomer and peroxide as cross-linking agent through pugging in dual-screw extruder for shearing while cross-linking. Its advantages are simple process and high impact resistance.
Description
Technical field:
The present invention relates to the method that a kind of polymer blending prepares super-toughened nylon, particularly a kind of method for preparing super-toughened nylon by dynamic vulcanization maleic anhydride graft polyolefin elastomer.
Background technology:
So-called dynamic vulcanization promptly makes the vulcanization of rubber in the process of rubber and thermoplastic molten blend.1962, A.M.Gessler at first proposes to prepare thermoplastic elastomer (US Patent 3 with dynamic vulcanization process, 037,954), after after the W.K.Fisher systematic study of U.S. Uniroyal company, the said firm succeeded in developing dynamic vulcanization EPT rubber/thermoplastic elastomer (US Patent 3,758,643) in 1972.The beginning of the eighties, A.Y.Coran proposed the dynamic full vulcanization technology on the basis of summing up forefathers, by the development research of U.S. Monsanto company, make the dynamic full vulcanization EPT rubber/thermoplastic elastomer, formally realized suitability for industrialized production with trade(brand)name Santoprene in nineteen eighty-two.Have machine-shaping conveniently owing to adopt dynamic vulcanization technology to produce thermoplastic elastomer, waste material can reuse, the production efficiency height, and the characteristics such as low and high comprehensive performance that consume energy, thereby cause people's extensive studies interest.
Dynamic vulcanization technology normally prepares the novel method of novel thermoplastic elastomer.And the report that is applied to functionalised polyolefin material toughening modifying nylon does not see that as yet bibliographical information is arranged.And traditional functionalised polyolefin material that passes through is by many with the report of the preparation tenacity increased nylon of the non-dynamic vulcanization melt blending of nylon.
Domestic patent CN90106778, CN91101624, CN97100554, CN97108021, CN99109924 and foreign patent DE19502819, EP0377511, EP0400964, EP0455507, EP0469693, US6303691, US6444754, modern plastics processed and applied 1,998 10 (3): 8, modern plastics processed and applied 2,001 13 (4): 8, China's plastics 2,001 15 (6): 39, China's plastics 1,999 13 (9): 30, China's plastics 2,001 15 (12): 21 grades are adds expanding material with polyolefine material tenacity increased nylon or direct report with functionalised polyolefin material tenacity increased nylon aspect, and the expanding material that it adopted is the polyethylene of maleic anhydride graft, polypropylene, or ABS, SBS, SEBS, EPDM, EPR, polyolefine materials such as POE.The expanding material that the present invention adopts also is the POE of maleic anhydride graft, but the present invention is all not adopt dynamic vulcanization technology to carry out crosslinked mutually to elastomerics in these reports with these report differences.
Summary of the invention:
The polyolefin elastomer that the invention provides a kind of dynamic vulcanization nylon/maleic anhydride graft prepares super-toughened nylon material and preparation method thereof.Super-toughened nylon of the present invention comprises following component: the polyolefin elastomer of nylon, maleic anhydride graft and peroxide cross-linking agent, wherein the consumption of nylon is the 90-70 weight part, the polyolefin elastomer consumption of maleic anhydride graft is the 10-30 weight part, and the peroxide cross-linking system consumption is the 0.05-2.5 weight part.
Nylon of the present invention is nylon 6, nylon 66.
The polyolefin elastomer of maleic anhydride graft of the present invention is the ethylene-octene copolymer (POE-g-MAH) of maleic anhydride graft, and percentage of grafting is 0.02-1.5%.For example percentage of grafting is 0.7%, and the trade mark is the CMG9802 that rises of day, and it adopts the Dupont Engage8150 of company type POE scorification grafted maleic anhydride.Also can adopt the POE of other trades mark to adopt the method for fusion-grafting maleic anhydride to prepare the ethylene-octene copolymer of the maleic anhydride graft that this institute uses.
Peroxide cross-linking agent of the present invention is 2,5-dimethyl-2,5 pair (tert-butyl peroxy base) hexane.(be called for short: two 2,5)
The preparation method of super-toughened nylon of the present invention is as follows: under 220-240 ℃ temperature, in twin screw extruder, add the nylon of said ratio, the ethylene-octene copolymer and the peroxide cross-linking agent of maleic anhydride graft, in melt blending with the ethylene-octene copolymer dynamic vulcanization of maleic anhydride graft.
It is simple to adopt this method to prepare the super-toughened nylon complete processing, the super-toughened nylon good processability of preparation, and suitability is strong.After adopting dynamic vulcanization technology, the functionalised polyolefin material granule of complete cure evenly spreads to nylon external phase.Compare with non-dynamic vulcanization functionalised polyolefin material tenacity increased nylon technology, adopt dynamic vulcanization process to use the breach cantilever stroke intensity of the super-toughened nylon of 20 parts of polyolefin elastomer preparations, near the breach cantilever stroke intensity of the super-toughened nylon that adopts 30 parts of polyolefine material preparations of non-dynamic vulcanization process, can reduce the production cost of producing super-toughened nylon material.
Embodiment:
Following embodiment further specifies of the present invention, rather than limits the scope of the invention.
The preparation of embodiment 1-7 nylon/maleic anhydride grafted ethene-octene super-toughened nylon
Press the prescription in the table 1, under 235 ℃ temperature, in twin screw extruder, add following composition: the ethylene-octene elastomerics of nylon 6, maleic anhydride graft, wherein the consumption of nylon 6 is the 90-70 weight part, the ethylene-octene copolymer consumption of maleic anhydride graft is the 10-30 weight part, 2,5-dimethyl-2,5 pair (tert-butyl peroxy base) hexane consumption is 0.15 weight part.Prepare batten by standard size.Sample 1 is unmodified pure nylon, and sample 2-4 is for adopting traditional way, and the super-toughened nylon of different amounts functionalised polyolefin modification, sample 5-7 prepare the super-toughened nylon of different amounts functionalised polyolefin for the employing dynamic vulcanization process.
Sample is pressed respectively: ASTM D638-93/89, ASTM D256-97, ASTM D648, ASTM D790 test stretching, impact, thermal distortion, flexural strength.
Table 1
Prescription/weight part 1234567
PA6 100 90 80 70 90 80 70
POE-g-MAH 10 20 30 10 20 30
Two 2,5 0.15 0.15 0.15
Mechanical property
Tensile strength (MPa) 57.0 57.0 45.8 45.2 47.3 43.2 42.8
Tensile yield (%) 258.2 258.2 264.0 275 187 190.7 285 notched Izod impact strength Izod (J/M) 39 39 693 923 88 879 1077
Flexural strength (MPa) 76.8 76.8 53.0 36.6 63.3 46.5 42.3
Modulus in flexure (MPa) 1,750 1,750 1,191 906.4 1,455 1,030 944
The preparation of embodiment 8-11 nylon/maleic anhydride grafted ethene-octene super-toughened nylon
Example 8-11 is for adopting the prescription of different vulcanizing agent consumptions and increase vulcanization aid, press the prescription in the table 2, under 235 ℃ temperature, in twin screw extruder, add following composition: the ethylene-octene elastomerics and 2 of nylon 6, maleic anhydride graft, 5-dimethyl-2,5 pair (tert-butyl peroxy base) hexane.
Prepare batten by standard size.Sample is pressed respectively: ASTM D638-93/89, ASTM D256-97, ASTM D648, ASTM D790 test stretching, impact, thermal distortion, flexural strength.
Table 2
Proportioning/weight part 89 10 11
PA6 80 80 80 80
POE-g-MAH 20 20 20 20
Two 2,50 0.15 0.2 0.25
Mechanical property
Tensile strength (MPa) 45.8 43.2 54.7 51.31
Tensile yield (%) 264.0 190.7 310.7 376.6 notched Izod impact strength Izod (J/M) 693 879 990 482
Flexural strength (MPa) 53.0 46.5 47.2 53.48
Modulus in flexure (MPa) 1,191 1,030 1,070 1207
Claims (5)
1. super-toughened nylon, it is characterized in that this super-toughened nylon comprises following component: the polyolefin elastomer of nylon, maleic anhydride graft and peroxide cross-linking agent, wherein the consumption of nylon is the 90-70 weight part, the polyolefin elastomer consumption of maleic anhydride graft is the 10-30 weight part, and the peroxide cross-linking system consumption is the 0.05-2.5 weight part.
2. a kind of super-toughened nylon according to claim 1 is characterized in that the nylon that is adopted is nylon 6, also can be nylon 66.
3. a kind of super-toughened nylon according to claim 1 is characterized in that the polyolefin elastomer of the maleic anhydride graft that adopted is the ethylene-octene copolymer of maleic anhydride graft, and percentage of grafting is 0.02-1.5%.
4. a kind of super-toughened nylon according to claim 1 is characterized in that the peroxide cross-linking agent that adopts is 2,5-dimethyl-2,5 pair (tert-butyl peroxy base) hexane.
5. the preparation method of a super-toughened nylon is characterized in that: when adopting the polyolefin elastomer tenacity increased nylon of maleic anhydride graft, elastomerics is adopted mutually the method for dynamic vulcanization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031162916A CN100484999C (en) | 2003-04-10 | 2003-04-10 | Super malleable nylon and its preparing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031162916A CN100484999C (en) | 2003-04-10 | 2003-04-10 | Super malleable nylon and its preparing method |
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| Publication Number | Publication Date |
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| CN1445278A true CN1445278A (en) | 2003-10-01 |
| CN100484999C CN100484999C (en) | 2009-05-06 |
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| CNB031162916A Expired - Fee Related CN100484999C (en) | 2003-04-10 | 2003-04-10 | Super malleable nylon and its preparing method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100465232C (en) * | 2006-04-17 | 2009-03-04 | 华东理工大学 | Nylon 66 nano composite material and preparation method thereof |
| CN1786074B (en) * | 2004-12-07 | 2010-05-05 | 马自达汽车股份有限公司 | Thermoplastic resin composition, molded product therefrom and outside plate part for vehicle using the molded product |
| CN101235196B (en) * | 2008-01-14 | 2010-09-29 | 北京兴润达塑胶技术有限公司 | Toughening agent for polyamide and toughened polyamide by the same |
| CN103571184A (en) * | 2012-07-31 | 2014-02-12 | 金发科技股份有限公司 | Nylon 6 molding composition, and preparation method and application thereof |
| CN103951969A (en) * | 2014-04-02 | 2014-07-30 | 合肥杰事杰新材料股份有限公司 | Polyamide toughening material and preparation method thereof |
| CN105778487A (en) * | 2016-05-11 | 2016-07-20 | 合肥工业大学 | High-toughness and high-strength PA6/EPDM-g-MAH alloy and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5371141A (en) * | 1985-07-31 | 1994-12-06 | Shell Oil Company | High impact resistant blends of thermoplastic polyamides and modified block copolymers |
| ATE138959T1 (en) * | 1990-08-02 | 1996-06-15 | Buna Sow Leuna Olefinverb Gmbh | IMPACT-RESISTANT POLYAMIDE MOLDING COMPOUNDS |
| IT1274469B (en) * | 1995-05-11 | 1997-07-17 | Spherilene Spa | DYNAMICALLY VULCANIZABLE POLYOLEFINIC COMPOSITIONS |
| CN1290594A (en) * | 1999-06-24 | 2001-04-11 | 中国科学院长春应用化学研究所 | Method for preparing polyamide polynropylene alloy |
| CN1148415C (en) * | 2001-08-30 | 2004-05-05 | 上海交通大学 | Prepn. method for superductile nylon/ABS alloy |
-
2003
- 2003-04-10 CN CNB031162916A patent/CN100484999C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1786074B (en) * | 2004-12-07 | 2010-05-05 | 马自达汽车股份有限公司 | Thermoplastic resin composition, molded product therefrom and outside plate part for vehicle using the molded product |
| CN100465232C (en) * | 2006-04-17 | 2009-03-04 | 华东理工大学 | Nylon 66 nano composite material and preparation method thereof |
| CN101235196B (en) * | 2008-01-14 | 2010-09-29 | 北京兴润达塑胶技术有限公司 | Toughening agent for polyamide and toughened polyamide by the same |
| CN103571184A (en) * | 2012-07-31 | 2014-02-12 | 金发科技股份有限公司 | Nylon 6 molding composition, and preparation method and application thereof |
| CN103571184B (en) * | 2012-07-31 | 2017-04-19 | 金发科技股份有限公司 | Nylon 6 molding composition, and preparation method and application thereof |
| CN103951969A (en) * | 2014-04-02 | 2014-07-30 | 合肥杰事杰新材料股份有限公司 | Polyamide toughening material and preparation method thereof |
| CN105778487A (en) * | 2016-05-11 | 2016-07-20 | 合肥工业大学 | High-toughness and high-strength PA6/EPDM-g-MAH alloy and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN100484999C (en) | 2009-05-06 |
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Assignee: Ningbo Jinhai Plastic Mould Co., Ltd. Assignor: Shanghai Jiao Tong University Contract record no.: 2012990000286 Denomination of invention: Super malleable nylon and its preparing method Granted publication date: 20090506 License type: Exclusive License Open date: 20031001 Record date: 20120502 |
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