CN103214830B - Preparation method of high-strength and high-toughness polyamide/polyester alloy - Google Patents
Preparation method of high-strength and high-toughness polyamide/polyester alloy Download PDFInfo
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- CN103214830B CN103214830B CN201310153464.1A CN201310153464A CN103214830B CN 103214830 B CN103214830 B CN 103214830B CN 201310153464 A CN201310153464 A CN 201310153464A CN 103214830 B CN103214830 B CN 103214830B
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Abstract
The invention discloses a preparation method of a high-strength and high-toughness polyamide/polyester alloy. The preparation method comprises the following steps of: processing PET (polyethylene Terephthalate) through sodium benzoate to obtain a high terminal carboxyl group PET; processing polyamide through polyolefin grafted maleic anhydride to obtain carboxyl-terminated polyamide; reacting a bifunctional epoxide with the terminal carboxyl group PET and the carboxyl-terminated polyamide to obtain a copolymer of the PET and the polyamide; and carrying out capacity increasing and chain extension on the PET and the polyamide, thus obtaining the high-strength and high-toughness polyamide/polyester alloy. According to the preparation method of the high-strength and high-toughness polyamide/polyester alloy, the polyolefin grafted maleic anhydride is adopted, an anhydride group and the terminal amino group are reacted and grafted at a molten state, and the resulting product which is the terminal carboxyl group has high output, and the toughness of the product is greatly improved due to an introduced graft; the bifunctional epoxide is adopted, thus the copolymer material gains high toughness of modified polyamide, and also gains the mechanical strength which is increased along with the raise of molecular weight; and the preparation method has the advantages that the adopted raw components are wide in resource and low in price, and the industrialization is easily realized accordingly.
Description
Technical field
The present invention relates to a kind of preparation method of high-intensity high-tenacity polyamide/polyester alloy, belong to technical field of polymer materials.
Background technology
Polymeric amide PA6 and polyester PET, as important engineering plastics, have obvious relative merits separately.PA6 due to the height regularity of its structure, high crystalline and excellent comprehensive mechanical property, and is widely used in machinery, automobile and other industries.But there is poor dimensional stability, high-hydroscopicity, the shortcoming such as expensive.PET structure height is symmetrical, and weathering resistance, dimensional stability better have good film-forming properties and cheap.But the most engineering plastics because of its second-order transition temperature higher, under usual processing mould temperature, crystallization velocity is slow, and shaping cycle is long, surface irregularity, is easily out of shape, and injection moulding plastic is fragility, be difficult to be applied to the shortcomings such as large-scale mechanical part, limit its widespread use.
The report probing into PA6/PET matrix material is in recent years many, wherein mostly inquire into be compound system be spun to film properties, as document " preparation of PA6/PET hollow tangerine lobe type bicomponent spunbond ultra-fine fibre ", author Zhao Yixia etc. utilizes tubular drafting to prepare 16 lobe PA6/PET(40/60) hollow tangerine lobe type two-pack ultra-fine fibre goods, by to water content, DSC, drying process and melt-spinning technology analysis, the cross section structure indicating PA6/PET tangerine lobe type two-pack ultra-fine fibre goods is by the impact of melt pressure and spinning temperature.
Patent CN1749314A reports a kind of preparation method of PA/PET high molecule alloy material, after PET, PA and SEBS vacuum-drying, mix in high-speed mixer, add MDI chainextender, oxidation inhibitor (DPN/DLTP) continues mixing and drop into twin screw extruder reactive extrursion after 10 minutes.Mix to extrude in twin screw extruder with glass fibre after patent CN102850781A reports and PET, nylon, oxidation inhibitor, fire retardant, lubricant is dry mixed in super mixer and prepare matrix material.The impact property of patent CN1749314A interalloy reaches 60kJ/m2, and tensile strength is 56MPa, and flexural strength is 63 MPa, although improve impact property preferably, but tensile strength and flexural strength deficiency, limit its Application Areas, such as engine case lid.In patent CN102850781A, the impact property of matrix material is 10kJ/m
2, flexural strength is 102MPa, and tensile strength is 99 MPa, but impact property is lower, and owing to adding glass, causes the material surface prepared coarse and water absorbability large, can not be applied to precision mechanical part very well.This patent product material smooth surface and strength high toughness is large.
Summary of the invention
The object of the present invention is to provide a kind of preparation method with the polyamide/polyester alloy of high tenacity high mechanical strength.
The preparation method of high-intensity high-tenacity polyamide/polyester alloy of the present invention, comprises the steps:
1) by PET and Sodium Benzoate in mass ratio 100:1-3 drop into high-speed mixer, extruded by twin screw extruder after mixing, obtain the PET of end carboxyl;
2) by polymeric amide and Polyolefin Grafted Maleic Anhydride in mass ratio 100:5-20 drop into high-speed mixer, extruded by twin screw extruder after mixing, obtain the polymeric amide of end carboxyl;
3) extrude after the polymeric amide of the PET of end carboxyl, end carboxyl, bifunctional epoxy compound and the additive in mass ratio mixing of 25-40:60-75:0.5-1:5-10 input high-speed mixer through twin screw extruder, obtain high-intensity high-tenacity polyamide/polyester alloy.
PET limiting viscosity described in step 1) is preferably 0.6 ~ 1.0dl/g.
Extruder temperature described in step 1) is 190 DEG C ~ 270 DEG C, screw speed 200 ~ 400r/min.
Step 2) described in polymeric amide be preferably PA6 or PA66 or PA1010.
Step 2) described in Polyolefin Grafted Maleic Anhydride be preferably PP-g-MAH or PE-g-MAH or POE-g-MAH.
Step 2) described extruder temperature is 160 DEG C ~ 240 DEG C, screw speed is 200 ~ 400r/min.
Bifunctional epoxy compound described in step 3) is BDDE or 1,6-hexanediol diglycidyl ether.
Additive described in step 3) is talcum powder or graphite or molybdenumdisulphide.
Extruder temperature described in step 3) is 160 DEG C ~ 270 DEG C, and screw speed is 200 ~ 400r/min.
The present invention's innovative point compared with prior art and improvement effect as follows: (1) the present invention uses Sodium Benzoate can improve PET content of carboxyl end group, and can be used as PET crystallization nucleating agent; (2) the present invention uses Polyolefin Grafted Maleic Anhydride, in the molten state, anhydride group and Amino End Group reactive grafting, the introducing of strong polar group makes both consistencies improve, products therefrom content of carboxyl end group is high, and the grafts of introducing also improves the toughness of product greatly.(3) the present invention uses bifunctional epoxy compound, the multipolymer of PET and polymeric amide is formed with the polymeric amide of high tenacity end carboxyl and the polyester original position of end carboxyl, increase-volume is carried out to PET and polymeric amide, and chain extension is carried out to PET, polymeric amide, molecular weight increases, form random long-chain copolymeric structure, make the higher toughness that this copolymer material has modified polyamide simultaneously and the physical strength increased with molecular weight increases, meanwhile, the present invention's each feed composition wide material sources low price used, be easy to industrialization.
Embodiment
Below in conjunction with specific embodiment, further description is carried out to flesh and blood of the present invention.If no special instructions, described number is mass parts.
embodiment 1
100 parts of PET and 1 part of Sodium Benzoate put into and drop into twin screw extruder after high-speed mixer 75 DEG C mixes 5min and extrude, obtain the PET of end carboxyl, extruder temperature is 190 DEG C ~ 270 DEG C, screw speed 200 ~ 400r/min.100 parts of PA6,10 parts of PP-g-MAH are added high-speed mixer mixing, and mixture is dropped into the PA6 of the high tenacity end carboxyl that twin screw extruder is extruded, extruder temperature is 160 DEG C ~ 240 DEG C, screw speed 200 ~ 400r/min.Get the PET of PA6 and the 40 part end carboxyl of above-mentioned 60 parts of high tenacity end carboxyl, 0.5 part 1,4-butanediol diglycidyl ether and 5 parts of graphite add the high mixed 10min of high-speed mixer 75 DEG C heating, mixture is dropped into twin screw extruder extruding pelletization, extruder temperature is 160 DEG C ~ 270 DEG C, and screw speed is 200 ~ 400r/min.Tensile strength 81 MPa of gained polyamide/polyester alloy, flexural strength 101 MPa, simply supported beam notched Izod impact strength 25 kJ/m
2.
embodiment 2
100 parts of PET and 1 part of Sodium Benzoate put into and drop into twin screw extruder after high-speed mixer 75 DEG C mixes 5min and extrude, obtain the PET of end carboxyl, extruder temperature is 240 ~ 270 DEG C, screw speed 200 ~ 400r/min.100 parts of PA6,5 parts of PP-g-MAH are added high-speed mixer mixing, and mixture is dropped into the PA6 of the high tenacity end carboxyl that twin screw extruder is extruded, extruder temperature is 160 DEG C ~ 240 DEG C, and screw speed is 200 ~ 400r/min.Get the PET of PA6 and the 40 part end carboxyl of above-mentioned 60 parts of high tenacity end carboxyl, 0.5 part 1,6-hexanediol diglycidyl ether and 5 parts of talcum powder add the high mixed 10min of high-speed mixer 75 DEG C heating, mixture is dropped into twin screw extruder extruding pelletization, extruder temperature is 160 DEG C ~ 270 DEG C, and screw speed is 200 ~ 400r/min.Tensile strength 85 MPa of gained polyamide/polyester alloy, flexural strength 108 MPa, simply supported beam notched Izod impact strength 31 kJ/m
2.
embodiment 3
100 parts of PET and 3 parts of Sodium Benzoates put into and drop into twin screw extruder after high-speed mixer 75 DEG C mixes 5min and extrude, obtain the PET of end carboxyl, extruder temperature is 240 ~ 270 DEG C, screw speed 200 ~ 400r/min.100 parts of PA66,10 parts of PE-g-MAH are added high-speed mixer mixing, mixture is dropped into twin screw extruder and extrude to obtain the PA66 of high tenacity end carboxyl, extruder temperature is 160 DEG C ~ 240 DEG C, and screw speed is 200 ~ 400r/min.Get the PET of above-mentioned 70 parts of modified Pa 6s 6 and 30 parts of end carboxyl, 0.5 part 1,4-butanediol diglycidyl ether and 7.5 parts of talcum powder add the high mixed 10min of high-speed mixer 75 DEG C heating, mixture is dropped into twin screw extruder extruding pelletization, extruder temperature is 160 DEG C ~ 270 DEG C, and screw speed is 200 ~ 400r/min.The tensile strength 80MPa of gained polyamide/polyester alloy, flexural strength 97 MPa, simply supported beam notched Izod impact strength 24 kJ/m
2.
embodiment 4
100 parts of PET and 1 part of Sodium Benzoate put into and drop into twin screw extruder after high-speed mixer 75 DEG C mixes 5min and extrude, obtain the PET of end carboxyl, extruder temperature is 240 ~ 270 DEG C, screw speed 200 ~ 400r/min.100 parts of PA66,5 parts of PE-g-MAH are added high-speed mixer mixing, and mixture is dropped into the PA66 of the high tenacity end carboxyl that twin screw extruder is extruded, extruder temperature is 160 DEG C ~ 240 DEG C, and screw speed is 200 ~ 400r/min.Get the PET of PA66 and the 40 part end carboxyl of above-mentioned 60 parts of high tenacity end carboxyl, 0.5 part 1,6-hexanediol diglycidyl ether and 5 parts of talcum powder add the high mixed 10min of high-speed mixer 75 DEG C heating, mixture is dropped into twin screw extruder extruding pelletization, extruder temperature is 160 DEG C ~ 270 DEG C, and screw speed is 200 ~ 400r/min.Tensile strength 87 MPa of gained polyamide/polyester alloy, flexural strength 112 MPa, simply supported beam notched Izod impact strength 34 kJ/m
2.
embodiment 5
100 parts of PET and 1 part of Sodium Benzoate put into and drop into twin screw extruder after high-speed mixer 75 DEG C mixes 5min and extrude, obtain the PET of end carboxyl, extruder temperature is 240 ~ 270 DEG C, screw speed 200 ~ 400r/min.100 parts of PA1010,10 parts of POE-g-MAH are added high-speed mixer mixing, and mixture is dropped into the PA1010 that twin screw extruder obtains high tenacity end carboxyl, extruder temperature is 160 DEG C ~ 240 DEG C, and screw speed is 200 ~ 400r/min.Get the PET of PA1010 and the 25 part end carboxyl of above-mentioned 75 parts of high tenacity end carboxyl, 0.5 part 1,4-butanediol diglycidyl ether and 5 parts of molybdenumdisulphide add the high mixed 10min of high-speed mixer 75 DEG C heating, mixture is dropped into twin screw extruder extruding pelletization, extruder temperature is 160 DEG C ~ 270 DEG C, and screw speed is 200 ~ 400r/min.The tensile strength 82MPa of gained polyamide/polyester alloy, flexural strength 93 MPa, simply supported beam notched Izod impact strength 40 kJ/m
2.
embodiment 6
100 parts of PET and 1 part of Sodium Benzoate put into and drop into twin screw extruder after high-speed mixer 75 DEG C mixes 5min and extrude, obtain the PET of end carboxyl, extruder temperature is 240 ~ 270 DEG C, screw speed 200 ~ 400r/min.100 parts of PA1010,5 parts of POE-g-MAH are added high-speed mixer mixing, and mixture is dropped into the PA1010 that twin screw extruder obtains high tenacity end carboxyl, extruder temperature is 160 DEG C ~ 240 DEG C, and screw speed is 200 ~ 400r/min.Get the PET of PA1010 and the 40 part end carboxyl of above-mentioned 60 parts of high tenacity end carboxyl, 0.5 part 1,6-hexanediol diglycidyl ether and 5 parts of molybdenumdisulphide add the high mixed 10min of high-speed mixer 75 DEG C heating, mixture is dropped into twin screw extruder extruding pelletization, extruder temperature is 160 DEG C ~ 270 DEG C, and screw speed is 200 ~ 400r/min.Tensile strength 85 MPa of gained polyamide/polyester alloy, flexural strength 104 MPa, simply supported beam notched Izod impact strength 28 kJ/m
2.
embodiment 7
100 parts of PET and 1 part of Sodium Benzoate put into and drop into twin screw extruder after high-speed mixer 75 DEG C mixes 5min and extrude, obtain the PET of end carboxyl, extruder temperature is 240 ~ 270 DEG C, screw speed 200 ~ 400r/min.100 parts of PA1010,20 parts of PE-g-MAH are added high-speed mixer mixing, and mixture is dropped into the PA1010 that twin screw extruder obtains high tenacity end carboxyl, extruder temperature is 160 DEG C ~ 240 DEG C, and screw speed is 200 ~ 400r/min.Get the PET of PA1010 and the 40 part end carboxyl of above-mentioned 60 parts of high tenacity end carboxyl, 1 part 1,6-hexanediol diglycidyl ether and 10 parts of molybdenumdisulphide add the high mixed 10min of high-speed mixer 75 DEG C heating, mixture is dropped into twin screw extruder extruding pelletization, extruder temperature is 160 DEG C ~ 270 DEG C, and screw speed is 200 ~ 400r/min.Tensile strength 83 MPa of gained polyamide/polyester alloy, flexural strength 97 MPa, simply supported beam notched Izod impact strength 38 kJ/m
2.
Claims (8)
1. a preparation method for high-intensity high-tenacity polyamide/polyester alloy, is characterized in that, comprises the steps:
1) by PET and Sodium Benzoate in mass ratio 100:1-3 drop into high-speed mixer, extruded by twin screw extruder after mixing, obtain the PET of end carboxyl;
2) by polymeric amide and Polyolefin Grafted Maleic Anhydride in mass ratio 100:5-20 drop into high-speed mixer, extruded by twin screw extruder after mixing, obtain the polymeric amide of end carboxyl;
3) extrude after the polymeric amide of the PET of end carboxyl, end carboxyl, bifunctional epoxy compound and the additive in mass ratio mixing of 25-40:60-75:0.5-1:5-10 input high-speed mixer through twin screw extruder, obtain high-intensity high-tenacity polyamide/polyester alloy; Described bifunctional epoxy compound is BDDE or 1,6-hexanediol diglycidyl ether.
2. the preparation method of polyamide/polyester alloy according to claim 1, it is characterized in that, the PET limiting viscosity described in step 1) is 0.6 ~ 1.0dl/g.
3. the preparation method of polyamide/polyester alloy according to claim 1, it is characterized in that, extruder temperature described in step 1) is 190 DEG C ~ 270 DEG C, screw speed 200 ~ 400r/min.
4. the preparation method of polyamide/polyester alloy according to claim 1, is characterized in that, step 2) described in polymeric amide be PA6 or PA66 or PA1010.
5. the preparation method of polyamide/polyester alloy according to claim 1, is characterized in that, step 2) described in Polyolefin Grafted Maleic Anhydride be PP-g-MAH or PE-g-MAH or POE-g-MAH.
6. the preparation method of polyamide/polyester alloy according to claim 1, is characterized in that, step 2) described extruder temperature is 160 DEG C ~ 240 DEG C, screw speed is 200 ~ 400r/min.
7. the preparation method of polyamide/polyester alloy according to claim 1, is characterized in that, the additive described in step 3) is talcum powder or graphite or molybdenumdisulphide.
8. the preparation method of polyamide/polyester alloy according to claim 1, it is characterized in that, extruder temperature described in step 3) is 160 DEG C ~ 270 DEG C, and screw speed is 200 ~ 400r/min.
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| CN103740100B (en) * | 2014-01-14 | 2016-02-17 | 中广核三角洲（苏州）新材料研发有限公司 | Nylon cable sheath material of a kind of polyester chain extension and preparation method thereof |
| CN105504801B (en) * | 2015-12-14 | 2018-09-21 | 中广核三角洲（江苏）塑化有限公司 | A kind of high intensity lower shrinkage nylon material and preparation method thereof for 3D printing |
| CN106751806A (en) * | 2016-12-29 | 2017-05-31 | 上海普利特复合材料股份有限公司 | A kind of reactive compatibilizer prepares the alloy material for reclaiming carpet PA66 resins and recycled PET |
| CN108948688A (en) * | 2018-08-22 | 2018-12-07 | 中广核俊尔（上海）新材料有限公司 | A kind of fiber glass reinforced PBT/PET material |
| CN115181416B (en) * | 2022-07-15 | 2023-12-22 | 华润化学材料科技股份有限公司 | Polyamide engineering plastic and preparation method and application thereof |
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| JPH11217499A (en) * | 1997-04-25 | 1999-08-10 | Toray Ind Inc | Flame-retardant resin composition and molded article thereof |
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| CN100494272C (en) * | 2005-12-30 | 2009-06-03 | 上海杰事杰新材料股份有限公司 | Polyester composite material and method for preparing same |
| CN100448930C (en) * | 2006-08-03 | 2009-01-07 | 上海交通大学 | Process of preparing engineering plastics with recovered polyethylene terephthalate |
| JP5551379B2 (en) * | 2009-03-31 | 2014-07-16 | 帝人株式会社 | Thermoplastic materials for automotive fuel parts |
| WO2010146143A1 (en) * | 2009-06-19 | 2010-12-23 | Rhodia Operations | Composition of a blend of polyamide and polyester resins |
| FR2952063B1 (en) * | 2009-10-30 | 2012-10-12 | Seb Sa | THERMOPLASTIC POLYMER MATERIAL BASED ON PET AND METHOD OF MANUFACTURING SUCH ARTICLE |
| CN102850781B (en) * | 2011-06-29 | 2016-09-07 | 合肥杰事杰新材料股份有限公司 | A kind of PET/PA6 alloy material and preparation method thereof |
| CN102702695B (en) * | 2012-06-15 | 2013-10-23 | 昆山聚威工程塑料有限公司 | Heat conducting polyamide (PA)/polybutylene terephthalate (PBT) alloy |
| CN103013097A (en) * | 2012-11-22 | 2013-04-03 | 上海普利特复合材料股份有限公司 | Ultra high-toughness glass fiber reinforcement nylon 6 composite material and preparation method thereof |
| CN103044869B (en) * | 2013-01-25 | 2015-08-19 | 本松工程塑料（杭州）有限公司 | Fire-retardant enhancing pet material of high crystallization rate and preparation method thereof |
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| JPH11217499A (en) * | 1997-04-25 | 1999-08-10 | Toray Ind Inc | Flame-retardant resin composition and molded article thereof |
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