CN102942783B - Composite material of polyamide (PA)6/recycled polyethylene glycol terephthalate (PET) bottle slices and preparation method thereof - Google Patents
Composite material of polyamide (PA)6/recycled polyethylene glycol terephthalate (PET) bottle slices and preparation method thereof Download PDFInfo
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- CN102942783B CN102942783B CN201210493421.3A CN201210493421A CN102942783B CN 102942783 B CN102942783 B CN 102942783B CN 201210493421 A CN201210493421 A CN 201210493421A CN 102942783 B CN102942783 B CN 102942783B
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Abstract
The invention relates to a composite material of polyamide (PA)6/polyethylene glycol terephthalate (PET), in particular to the composite material of the PA6/recycled PET bottle slices and a preparation method thereof. The composite material comprises the components, by weight: 40-60 parts of the PA6, 10-30 parts of the recycled PET bottle slices, 25-35 parts of non-alkali glass fibers, 1-10 parts of compatilizer, 0.1-1 part of antioxygen and 0.1-1 part of lubricant. By means of the composite material of the PA6/recycled PET bottle slices, the application range of the recycled PET bottle slices is expanded, and cost of the PA6 composite material is reduced. In addition, the composite material is environment-friendly, low in carbon, capable of being widely applied to preparation of mechanical parts and the like and good in mechanical property, and the tensile strength of the composite material can reach 150MPa. The preparation method of the composite material of the PA6/recycled PET bottle slices is simple in compound process and processing process, and the composite material of the PA6/recycled PET bottle slices can be easily prepared.
Description
Technical field
The present invention relates to the matrix material of a kind of PA6/PET, specifically, relate to matrix material of a kind of PA6/ recycled PET bottles sheet and preparation method thereof.
Background technology
Polyethylene terephthalate (PET), not only, because the good and cheap price of the over-all propertieies such as its chemistry, physical properties is except being widely used in fiber applications, in beverage bottle, its usage quantity is also quite large.Along with the widespread use of PET in edible liquid soft packaging field, brought the recovery problem of a large amount of waste and old beverage bottles.Along with PET consumption increases gradually, the amount that PET bottle reclaims also increases gradually.According to statistics, the average recovery utilization rate of PET bottle is 20.4%, the high country of recovery utilization rate as Switzerland, Germany and Japanese philosophy be 100%, 49% and 46%, and China is only 1.7%.The PET bottle sheet major part reclaiming is " degradation utilizes ", is used for producing low-grade fiber, film and non-edible packing bottle etc.; And " upgrading utilize " only accounts for 8.4% left and right as high performance engineering plastics.The bottle sheet of recycled PET is mainly used in the spinning of the staple fibre of some low-grade polyester (PET).So, for the bottle sheet of recycled PET, need to further expand field and the product of its application, improve its added value of product.
Nylon 6 is widely used in mechanical component due to the performance of the excellences such as it has higher intensity, good wear resistance, the preparation of electrical component, but because its price is higher, limited it in the more application of wide spectrum.The PET bottle sheet that adds recovery in nylon 6 material, has not only reduced the cost of matrix material, and has further expanded the purposes of the PET reclaiming.Consider the poor problem of consistency of the two, in the preparation process of matrix material, conventionally add a certain amount of compatilizer, but effect is often unsatisfactory.
The present invention has adopted the multipolymer of a kind of special PET-PA6 as compatilizer, nylon 6 is had to good consistency, again PET is had to good consistency, be suitable as the compatilizer of this matrix material, effectively improved the performance of PA6/ recycled PET matrix material.
Summary of the invention
Primary goal of the invention of the present invention has been to propose a kind of matrix material of PA6/ recycled PET bottles sheet.
The second goal of the invention of the present invention is to propose the preparation method of this matrix material.
In order to realize object of the present invention, the technical scheme of employing is:
The matrix material that the present invention relates to a kind of PA6/ recycled PET bottles sheet, it consists of: nylon 6 40～60 weight parts, recycled PET bottles sheet 10～30 weight parts, alkali-free glass fiber 25～35 weight parts, compatilizer 1～10 weight part, oxidation inhibitor 0.1～1 weight part and lubricant 0.1～1 weight part; Be preferably: nylon 6 42～55 weight parts, recycled PET bottles sheet 10～25 weight parts, alkali free glass fibre 25～30 weight parts, compatilizer 1～5 weight part, oxidation inhibitor 0.1～0.5 weight part and lubricant 0.1～0.5 weight part; More preferably: nylon 6 42～48 weight parts, recycled PET bottles sheet 20～25 weight parts, alkali free glass fibre 25～30 weight parts, compatilizer 1.5～2.5 weight parts, oxidation inhibitor 0.1～0.25 weight part and lubricant 0.1～0.25 weight part.
The first optimal technical scheme of the present invention is, the solution solvent viscosity ratio of described nylon 6 is 2.5～2.7, preferably 2.6～2.7.
The second optimal technical scheme of the present invention is that described alkali free glass fibre is long fibre or short fiber, preferably short fiber; The diameter of described short fiber is 10～15 microns, preferably 12～14 microns, and more preferably 13 microns.
The 3rd optimal technical scheme of the present invention is, described compatilizer is PET-PA6 multipolymer, the content 10%～15% of nylon Unit 6 in multipolymer wherein, and the sequence of its molecular chain is distributed as:
N, the scope of n` is: 1<n<176,1<n`<88; M, the value of m` is greater than 1, is less than the ratio of the relative molecular weight of the relative molecular-weight average of acidic dyeable polyester and ethylene glycol terephthalate monomer.
This compatilizer adopts the synthetic acidic dyeable polyester of patent ZL2007101788799, and its preparation method is:
(1) ratio that is 1:2.2 by dimethyl terephthalate (DMT) (DMT) and ethylene glycol in the ratio of amount of substance joins in reactor, at 170 ℃～260 ℃, carries out transesterification reaction, and the reaction times is 20～60 minutes; Or the ratio that is 1:2.2 in the ratio of amount of substance by terephthalic acid (PTA) and ethylene glycol joins in reactor, carry out esterification at 250～260 ℃, the reaction times is 20～60 minutes;
(2) after transesterification reaction or esterification, 0.03% polycondensation catalyst that interpolation mass percent is total reactant quality, polycondensation catalyst is for containing antimony type oxide, simultaneously, adding mass ratio is that 5%～20% polyamide polymer of total reactant quality carries out copolyreaction, polymeric amide is nylon 6 and/or nylon 66, when temperature reaches 180～250 ℃, pumping high vacuum, keeps vacuum tightness between 30～70Pa, continues to be warmed up to 260～265 ℃, reaction 2-4 hour, intrinsic viscosity reaches 0.72～0.78, and acidic dyeable polyester fibre section is prepared in discharging.
The 4th optimal technical scheme of the present invention is, described for the intrinsic viscosity of recycled PET bottles sheet is 0.48～0.58dl/g, preferably 0.50～0.58dl/g.
The 5th optimal technical scheme of the present invention is that described oxidation inhibitor is antioxidant 1010 or oxidation inhibitor 1098.
The 6th optimal technical scheme of the present invention is that described lubricant is selected from least one in ethylene bis stearamide, calcium stearate, polyoxyethylene wax or Zinic stearas.
The preparation method who the invention still further relates to a kind of matrix material of PA6/ recycled PET bottles sheet, the method comprises the following steps:
(1) recycled PET bottles sheet and nylon 6 are dried;
(2) even with compatilizer, oxidation inhibitor and mix lubricant in proportion;
(3) the main spout by twin screw extruder adds in twin screw extruder, when melt extruding, from side drawing-in device, be metered into alkali-free glass fiber and melt extrude, extruded material, after cooling, air-dry, pelletizing, being dried, obtains white PA6/ recycled PET bottles sheet matrix material.
The first optimal technical scheme of preparation method of the present invention is, in step (1), described dry be to be dried in vacuum drying oven; And be further preferably divided into two stages and be dried, wherein the first stage is dry 3～5h, preferably 3.5～4.5h under the condition of 75～80 ℃ of temperature; Subordinate phase is dry 7～10h, preferably 8～9h under the condition of 135～145 ℃ of temperature.
The second optimal technical scheme of preparation method of the present invention is that, in step (2), described mixing time is to mix 10～15 minutes.
Preparation method's of the present invention the 3rd optimal technical scheme is, the Temperature Setting scope of described twin screw extruder is 250～270 ℃, and screw speed is 200～500rpm, and vacuum tightness is-0.6～1.0Kgf/cm
2.
Preparation method's of the present invention the 4th optimal technical scheme is that the temperature in described twin screw extruder Ge district is:
One district's temperature: 210～225 ℃,
Two district's temperature: 240～250 ℃,
Three district's temperature: 255～264 ℃,
Four district's temperature: 265～269 ℃,
Five district's temperature: 270～275 ℃,
Six district's temperature: 270～275 ℃,
Seven district's temperature: 263～268 ℃.
Below technical scheme of the present invention is made further explanation.
The present invention proposes a kind of PA6/ recycled PET bottles sheet matrix material, not only realized the high value added utilization again of recycled PET bottles sheet, and expanded the recycle scope of recycled PET bottles sheet material, reduced the cost of nylon 6 composite material simultaneously, further expanded its Application Areas, this advanced composite material can be widely used in component of machine, electronic apparatus component, the preparation of sports equipment component.It consists of: nylon 6 40～60 weight parts, recycled PET bottles sheet 10～30 weight parts, alkali-free glass fiber 25～35 weight parts, compatilizer 1～10 weight part, oxidation inhibitor 0.1～1 weight part and lubricant 0.1～1 weight part; Be preferably: nylon 6 42～55 weight parts, recycled PET bottles sheet 10～25 weight parts, alkali free glass fibre 25～30 weight parts, compatilizer 1～5 weight part, oxidation inhibitor 0.1～0.5 weight part and lubricant 0.1～0.5 weight part; More preferably: nylon 6 42～48 weight parts, recycled PET bottles sheet 20～25 weight parts, alkali free glass fibre 25～30 weight parts, compatilizer 1.5～2.5 weight parts, oxidation inhibitor 0.1～0.25 weight part and lubricant 0.1～0.25 weight part.
Wherein, the solution solvent viscosity ratio of nylon 6 is 2.5～2.7, preferably 2.6～2.7.The intrinsic viscosity of recycled PET bottles sheet is 0.48～0.58dl/g, preferably 0.50～0.58dl/g.Alkali free glass fibre is long fibre or short fiber, preferably short fiber; The diameter of short fiber is less, and the performance of material is better, and in the present invention, the diameter of short fiber is 10～15 microns, and preferably 12～14 microns, more preferably 13 microns.The diameter of short fiber has larger impact to the dispersiveness of matrix material and mechanical property, and in the present invention, selecting diameter is not only good dispersity of the prepared matrix material of the short fiber of 10～15 microns, and its good mechanical performance.
Described oxidation inhibitor is antioxidant 1010 or oxidation inhibitor 1098, thereby guarantees processing characteristics and the appearance requirement of matrix material, adapts to different service requirementss.Described lubricant is selected from least one in ethylene bis stearamide, calcium stearate, polyoxyethylene wax or Zinic stearas, and further preferred ethylene bis stearamide.
Compatilizer in this research invention adopts the synthetic acidic dyeable polyester of patent ZL2007101788799, thereby has solved the compatible problem of nylon 6 with PET, and has further increased the performance of matrix material.Both the structural unit that had contained PET in this copolymer molecule structure, the structural unit that contains again nylon 6, therefore compatible with PET, compatible with nylon 6 again, be a kind of non-response type compatilizer, in nylon 6 and PET system, play and reduce both interfacial tensions, increase interfacial thickness, make System forming there is the evenly Thermodynamically stable phase structure of micron-scale phase separation architectural feature of macroscopic view, make matrix material keep good mechanical property.
Matrix material of the present invention is a kind of novel low-carbon environment-friendly matrix material, can be widely used in component of machine, electronic apparatus component, the preparation of sports equipment component.Its tensile strength reaches 150～160MPa, and flexural strength can reach 240～250MPa, little with intensity (tensile strength reaches 150MPa, and flexural strength can the reach 240MPa) difference of pure glass glass fiber reinforced nylon 6.If do not added the PA6/ recycled PET bottles sheet matrix material tensile strength of the similar formula of compatilizer, drop to 120MPa, flexural strength drops to 210MPa, and material surface does not have the incompatible appearance of layering and peeling.
The invention still further relates to a kind of that nylon 6, recycled PET bottles sheet and certain proportion compatilizer, oxidation inhibitor, mix lubricant is evenly, then added alkali-free glass fiber, by twin screw extruder, a kind of method of PA6/ recycled PET bottles sheet is prepared in blend.The method compound process and the course of processing are simple, are easy to processing preparation.The white PA6/ recycled PET bottles sheet matrix material of preparing by the method, the cost of material is low, low-carbon (LC), environmental protection, mechanical property is good, and application surface is extensive.
Compared with prior art, tool of the present invention has the following advantages:
(1) PA6/ recycled PET bottles sheet matrix material provided by the present invention, has not only expanded the range of application of recycled PET bottles sheet, and has reduced the cost of nylon 6 composite material, and matrix material environmental protection, low-carbon (LC), can be widely used in the preparations such as component of machine.
(2) PA6/ recycled PET bottles sheet matrix material provided by the present invention, mechanical property is good, and tensile strength reaches 150MPa, elongation at break 2.5%, flexural strength can reach 240MPa, and notched Izod impact strength can reach 11.5KJ/m
2, little with the mechanical property difference of pure glass fiber reinforced nylon 6 matrix material.
(3) PA6/ recycled PET bottles sheet composite material and preparation method thereof provided by the present invention, compound process and the course of processing are simple, are easy to processing preparation.
The specific embodiment of the present invention only limits to further explain and explanation the present invention, not to Composition of contents restriction of the present invention.
Embodiment
Embodiment 1
A PA6/ recycled PET bottles sheet matrix material, its composition is as shown in table 1:
Table 1: unit (kg)
| Nylon 6 | Recycled PET bottles sheet | Alkali free glass fibre | Compatilizer | Oxidation inhibitor | Lubricant |
| 42 | 15 | 25 | 5 | 0.25 | 0.35 |
Wherein, the solution solvent viscosity ratio of nylon 6 is 2.5;
The intrinsic viscosity of recycled PET bottles sheet is 0.48dl/g;
Alkali free glass fibre is for long fine;
Compatilizer is PET-PA6 multipolymer, be to adopt the synthetic acidic dyeable polyester of patent ZL2007101788799, the content 10%～15% of nylon Unit 6 in multipolymer wherein, and the sequence of its molecular chain is distributed as:
N, the scope of n` is: 1<n<176,1<n`<88; M, the value of m` is greater than 1, is less than the ratio of the relative molecular weight of the relative molecular-weight average of acidic dyeable polyester and ethylene glycol terephthalate monomer;
Oxidation inhibitor is antioxidant 1010;
Lubricant is calcium stearate.
Embodiment 2:
A PA6/ recycled PET bottles sheet matrix material, its composition is as shown in table 2:
Table 2: unit (kg)
| Nylon 6 | Recycled PET bottles sheet | Alkali free glass fibre | Compatilizer | Oxidation inhibitor | Lubricant |
| 45 | 20 | 25 | 1.5 | 0.1 | 0.1 |
Wherein, the solution solvent viscosity ratio of nylon 6 is 2.6;
The intrinsic viscosity of recycled PET bottles sheet is 0.58dl/g;
Alkali free glass fibre is short fiber, and the diameter of short fiber is 13 microns;
Compatilizer is PET-PA6 multipolymer, be to adopt the synthetic acidic dyeable polyester of patent ZL2007101788799, the content 10%～15% of nylon Unit 6 in multipolymer wherein, and the sequence of its molecular chain is distributed as:
N, the scope of n` is: 1<n<176,1<n`<88; M, the value of m` is greater than 1, is less than the ratio of the relative molecular weight of the relative molecular-weight average of acidic dyeable polyester and ethylene glycol terephthalate monomer;
Oxidation inhibitor is oxidation inhibitor 1098;
Lubricant is polyoxyethylene wax.
Embodiment 3:
A PA6/ recycled PET bottles sheet matrix material, its composition is as shown in table 3:
Table 3: unit (kg)
| Nylon 6 | Recycled PET bottles sheet | Alkali free glass fibre | Compatilizer | Oxidation inhibitor | Lubricant |
| 48 | 25 | 30 | 4 | 0.2 | 0.15 |
Wherein, the solution solvent viscosity ratio of nylon 6 is 2.7;
The intrinsic viscosity of recycled PET bottles sheet is 0.50dl/g;
Alkali free glass fibre is short fiber, and the diameter of short fiber is 10 microns;
Compatilizer is PET-PA6 multipolymer, be to adopt the synthetic acidic dyeable polyester of patent ZL2007101788799, the content 10%～15% of nylon Unit 6 in multipolymer wherein, and the sequence of its molecular chain is distributed as:
N, the scope of n` is: 1<n<176,1<n`<88; M, the value of m` is greater than 1, is less than the ratio of the relative molecular weight of the relative molecular-weight average of acidic dyeable polyester and ethylene glycol terephthalate monomer;
Oxidation inhibitor is antioxidant 1010;
Lubricant is Zinic stearas.
Embodiment 4:
A PA6/ recycled PET bottles sheet matrix material, its composition is as shown in table 4:
Table 4: unit (kg)
| Nylon 6 | Recycled PET bottles sheet | Alkali free glass fibre | Compatilizer | Oxidation inhibitor | Lubricant |
| 55 | 28 | 30 | 2.5 | 0.25 | 0.25 |
Wherein, the solution solvent viscosity ratio of nylon 6 is 2.6;
The intrinsic viscosity of recycled PET bottles sheet is 0.55dl/g;
Alkali free glass fibre is short fiber, and the diameter of short fiber is 15 microns;
Compatilizer is PET-PA6 multipolymer, be to adopt the synthetic acidic dyeable polyester of patent ZL2007101788799, the content 10%～15% of nylon Unit 6 in multipolymer wherein, and the sequence of its molecular chain is distributed as:
N, the scope of n` is: 1<n<176,1<n`<88; M, the value of m` is greater than 1, is less than the ratio of the relative molecular weight of the relative molecular-weight average of acidic dyeable polyester and ethylene glycol terephthalate monomer;
Oxidation inhibitor is oxidation inhibitor 1098;
Lubricant is Zinic stearas.
Embodiment 5:
A PA6/ recycled PET bottles sheet matrix material, its composition is as shown in table 5:
Table 5: unit (kg)
| Nylon 6 | Recycled PET bottles sheet | Alkali free glass fibre | Compatilizer | Oxidation inhibitor | Lubricant |
| 40 | 10 | 25 | 1 | 0.15 | 0.15 |
Wherein, the solution solvent viscosity ratio of nylon 6 is 2.65;
The intrinsic viscosity of recycled PET bottles sheet is 0.52dl/g;
Alkali free glass fibre is short fiber, and the diameter of short fiber is 14 microns;
Compatilizer is PET-PA6 multipolymer, be to adopt the synthetic acidic dyeable polyester of patent ZL2007101788799, the content 10%～15% of nylon Unit 6 in multipolymer wherein, and the sequence of its molecular chain is distributed as:
N, the scope of n` is: 1<n<176,1<n`<88; M, the value of m` is greater than 1, is less than the ratio of the relative molecular weight of the relative molecular-weight average of acidic dyeable polyester and ethylene glycol terephthalate monomer;
Described oxidation inhibitor is oxidation inhibitor 1098;
Lubricant is the mixture of calcium stearate and Zinic stearas, and its weight ratio is 2:1.
Embodiment 6:
A PA6/ recycled PET bottles sheet matrix material, its composition is as shown in table 6:
Table 6: unit (kg)
| Nylon 6 | Recycled PET bottles sheet | Alkali free glass fibre | Compatilizer | Oxidation inhibitor | Lubricant |
| 60 | 30 | 35 | 10 | 0.5 | 0.5 |
Wherein, the solution solvent viscosity ratio of nylon 6 is 2.7;
The intrinsic viscosity of recycled PET bottles sheet is 0.57dl/g;
Alkali free glass fibre short fiber, the diameter of short fiber is 15 microns;
Compatilizer is PET-PA6 multipolymer, be to adopt the synthetic acidic dyeable polyester of patent ZL2007101788799, the content 10%～15% of nylon Unit 6 in multipolymer wherein, and the sequence of its molecular chain is distributed as:
N, the scope of n` is: 1<n<176,1<n`<88; M, the value of m` is greater than 1, is less than the ratio of the relative molecular weight of the relative molecular-weight average of acidic dyeable polyester and ethylene glycol terephthalate monomer;
Described oxidation inhibitor is oxidation inhibitor 1098;
Lubricant is the mixture in calcium stearate, polyoxyethylene wax, Zinic stearas, and its weight ratio is 2:1:1.
Embodiment 7
The preparation method of the PA6/ recycled PET bottles sheet matrix material of embodiment 1 ~ 3 formula is:
1. recycled PET bottles sheet and nylon 6 are dried; Described dry be to be dried in vacuum drying oven, be divided into two stages to be dried, the first stage is dry 3h under the condition of 80 ℃ of temperature; Subordinate phase is dry 7h under the condition of 145 ℃ of temperature;
2. even with compatilizer, oxidation inhibitor and mix lubricant in proportion, mixing time is to mix 10 minutes;
3. the main spout by twin screw extruder adds in twin screw extruder, when melt extruding, from side drawing-in device, be metered into alkali-free glass fiber and melt extrude, extruded material, after cooling, air-dry, pelletizing, being dried, obtains white PA6/ recycled PET bottles sheet matrix material; The temperature in described twin screw extruder Ge district is:
One district's temperature: 220 ℃,
Two district's temperature: 245 ℃,
Three district's temperature: 260 ℃,
Four district's temperature: 265 ℃,
Five district's temperature: 270 ℃,
Six district's temperature: 270 ℃,
Seven district's temperature: 265 ℃;
Screw speed is 500rpm, and vacuum tightness is-0.6Kgf/cm
2.
The physicals of the alloy material preparing is:
Table 7:
| Tensile strength (MPa) | Elongation at break (%) | Flexural strength (MPa) | Notched Izod impact strength (KJ/m 2) | |
| Embodiment 1 | 151 | 2.5 | 245 | 11.5 |
| Embodiment 2 | 152 | 2.6 | 248 | 11.6 |
| Embodiment 3 | 155 | 2.5 | 250 | 11.5 |
Embodiment 8
The preparation method of the PA6/ recycled PET bottles sheet matrix material of embodiment 4 ~ 6 formulas is:
1. recycled PET bottles sheet and nylon 6 are dried; Described dry be to be dried in vacuum drying oven, be divided into two stages to be dried, the first stage is dry 5h under the condition of 75 ℃ of temperature; Subordinate phase is dry 10h under the condition of 135 ℃ of temperature;
2. even with compatilizer, oxidation inhibitor and mix lubricant in proportion, mixing time is to mix 15 minutes;
3. the main spout by twin screw extruder adds in twin screw extruder, when melt extruding, from side drawing-in device, be metered into alkali-free glass fiber and melt extrude, extruded material, after cooling, air-dry, pelletizing, being dried, obtains white PA6/ recycled PET bottles sheet matrix material;
One district's temperature: 220 ℃,
Two district's temperature: 245 ℃,
Three district's temperature: 260 ℃,
Four district's temperature: 265 ℃,
Five district's temperature: 270 ℃,
Six district's temperature: 270 ℃,
Seven district's temperature: 265 ℃;
Screw speed is 500rpm, and vacuum tightness is 1.0Kgf/cm
2.
The physicals of the alloy material preparing is:
Table 8:
| Tensile strength (MPa) | Elongation at break (%) | Flexural strength (MPa) | Notched Izod impact strength (KJ/m 2) | |
| Embodiment 4 | 153 | 2.7 | 245 | 11.6 |
| Embodiment 5 | 154 | 2.6 | 248 | 11.5 |
| Embodiment 6 | 156 | 2.5 | 247 | 11.5 |
| Embodiment 7 | 155 | 2.5 | 247 | 11.6 |
Embodiment 9
1. the Nylon 6 48wt% that is 2.6 by solution solvent viscosity ratio, recycled PET bottles sheet 20wt%, be dried; Described dry be to be dried in vacuum drying oven, be divided into two stages to be dried, the first stage is dry 4.5h under the condition of 80 ℃ of temperature; Subordinate phase is dry 9h under the condition of 145 ℃ of temperature;
2. by said mixture and compatilizer 1.5wt%, antioxidant 1010 0.25wt%, Lubricate EBS 0.25wt% mixes, and mixing time is to mix 15 minutes;
Compatilizer is PET-PA6 multipolymer, be to adopt the synthetic acidic dyeable polyester of patent ZL2007101788799, the content 10%～15% of nylon Unit 6 in multipolymer wherein, and the sequence of its molecular chain is distributed as:
N, the scope of n` is: 1<n<176,1<n`<88; M, the value of m` is greater than 1, is less than the ratio of the relative molecular weight of the relative molecular-weight average of acidic dyeable polyester and ethylene glycol terephthalate monomer;
3. the main spout by twin screw extruder adds in twin screw extruder, when melt extruding, from side drawing-in device, being metered into diameter is that 13 microns of alkali-free glass fiber staple fibre 30wt% melt extrude, extruded material, after cooling, air-dry, pelletizing, being dried, obtains white PA6/ recycled PET bottles sheet matrix material; The temperature in described twin screw extruder Ge district is:
One district's temperature: 220 ℃,
Two district's temperature: 245 ℃,
Three district's temperature: 260 ℃,
Four district's temperature: 265 ℃,
Five district's temperature: 270 ℃,
Six district's temperature: 270 ℃,
Seven district's temperature: 265 ℃;
Screw speed is 400rpm, and vacuum tightness is-0.6Kgf/cm
2.
Matrix material injection moulding can be 40 ℃ of moulding in die temperature, and the tensile strength of formed material reaches 152Mpa, and flexural strength reaches 245Mpa, elongation at break 2.6%, notched Izod impact strength 11.7KJ/m
2, surface luster, without peeling, without demixing phenomenon.
Embodiment 10
1. the Nylon 6 42% that is 2.6 by solution solvent viscosity ratio, recycled PET bottles sheet: 25%, row is dry; Described dry be very
In empty baking oven, be dried, be divided into two stages to be dried, the first stage is dry 3.5h under the condition of 80 ℃ of temperature; Subordinate phase is dry 8h under the condition of 145 ℃ of temperature;
2. said mixture is mixed to mixing time 15 minutes with compatilizer 2.5%, antioxidant 1010 0.25%, Lubricate EBS 0.25%;
Compatilizer is PET-PA6 multipolymer, be to adopt the synthetic acidic dyeable polyester of patent ZL2007101788799, the content 10%～15% of nylon Unit 6 in multipolymer wherein, and the sequence of its molecular chain is distributed as:
N, the scope of n` is: 1<n<176,1<n`<88; M, the value of m` is greater than 1, is less than the ratio of the relative molecular weight of the relative molecular-weight average of acidic dyeable polyester and ethylene glycol terephthalate monomer;
3. the main spout by twin screw extruder adds in twin screw extruder, when melt extruding, from side drawing-in device, being metered into diameter is that 13 microns of alkali-free glass fiber staple fibre 30wt% melt extrude, extruded material, after cooling, air-dry, pelletizing, being dried, obtains white PA6/ recycled PET bottles sheet matrix material; The temperature in described twin screw extruder Ge district is:
One district's temperature: 220 ℃,
Two district's temperature: 245 ℃,
Three district's temperature: 260 ℃,
Four district's temperature: 265 ℃,
Five district's temperature: 270 ℃,
Six district's temperature: 270 ℃,
Seven district's temperature: 265 ℃;
Screw speed is 400rpm, and vacuum tightness is-0.6Kgf/cm
2.
Matrix material injection moulding can be in 40 ℃ of moulding of die temperature, and the tensile strength of formed material reaches 150Mpa, and flexural strength reaches 242Mpa, elongation at break 2.5%, notched Izod impact strength 11.5KJ/m
2, surface luster, without peeling, without demixing phenomenon.
Claims (20)
1. the matrix material of a PA6/ recycled PET bottles sheet, it is characterized in that the consisting of of described matrix material: nylon 6 40～60 weight parts, recycled PET bottles sheet 10～30 weight parts, alkali-free glass fiber 25～35 weight parts, compatilizer 1～10 weight part, oxidation inhibitor 0.1～1 weight part and lubricant 0.1～1 weight part; Described compatilizer is PET-PA6 multipolymer and/or PET-PA66 multipolymer, wherein the mass content 10%～15% of nylon 6 and/or nylon Unit 66 in multipolymer; The sequence of its molecular chain is distributed as:
N, the scope of n` is: 1<n<176,1<n`<88; M, the value of m` is greater than 1, is less than the ratio of the relative molecular weight of PET-PA6 multipolymer and/or the relative molecular-weight average of PET-PA66 multipolymer and ethylene glycol terephthalate monomer.
2. the matrix material of PA6/ recycled PET bottles sheet according to claim 1, it is characterized in that the consisting of of described matrix material: nylon 6 42～55 weight parts, recycled PET bottles sheet 10～25 weight parts, alkali free glass fibre 25～30 weight parts, compatilizer 1～5 weight part, oxidation inhibitor 0.1～0.5 weight part and lubricant 0.1～0.5 weight part.
3. the matrix material of PA6/ recycled PET bottles sheet according to claim 1, it is characterized in that the consisting of of described matrix material: nylon 6 42～48 weight parts, recycled PET bottles sheet 20～25 weight parts, alkali free glass fibre 25～30 weight parts, compatilizer 1.5～2.5 weight parts, oxidation inhibitor 0.1～0.25 weight part and lubricant 0.1～0.25 weight part.
4. the matrix material of PA6/ recycled PET bottles sheet according to claim 1, is characterized in that, the solution solvent viscosity ratio of described nylon 6 is 2.5～2.7.
5. the matrix material of PA6/ recycled PET bottles sheet according to claim 4, is characterized in that, the solution solvent viscosity ratio of described nylon 6 is 2.6～2.7.
6. the matrix material of PA6/ recycled PET bottles sheet according to claim 1, is characterized in that, described alkali free glass fibre is long fibre or short fiber; The diameter of described short fiber is 10～15 microns.
7. the matrix material of PA6/ recycled PET bottles sheet according to claim 6, is characterized in that, described alkali free glass fibre is short fiber.
8. the matrix material of PA6/ recycled PET bottles sheet according to claim 6, is characterized in that, the diameter of described short fiber is 12～14 microns.
9. the matrix material of PA6/ recycled PET bottles sheet according to claim 8, is characterized in that, the diameter of described short fiber is 13 microns.
10. the matrix material of PA6/ recycled PET bottles sheet according to claim 1, is characterized in that, the intrinsic viscosity of described recycled PET bottles sheet is 0.48～0.58dl/g.
The matrix material of 11. PA6/ recycled PET bottles sheets according to claim 10, is characterized in that, the intrinsic viscosity of described recycled PET bottles sheet is 0.50～0.58dl/g.
The matrix material of 12. PA6/ recycled PET bottles sheets according to claim 1, is characterized in that, described oxidation inhibitor is antioxidant 1010 or oxidation inhibitor 1098.
The matrix material of 13. PA6/ recycled PET bottles sheets according to claim 1, is characterized in that, described lubricant is selected from least one in ethylene bis stearamide, calcium stearate, polyoxyethylene wax or Zinic stearas.
The preparation method of the matrix material of 14. 1 kinds of PA6/ recycled PET bottles sheets as claimed in claim 1, is characterized in that, said method comprising the steps of:
(1) recycled PET bottles sheet and nylon 6 are dried;
(2) even with compatilizer, oxidation inhibitor and mix lubricant in proportion;
(3) the main spout by twin screw extruder adds in twin screw extruder, when melt extruding, from side drawing-in device, be metered into alkali-free glass fiber and melt extrude, extruded material, after cooling, air-dry, pelletizing, being dried, obtains white PA6/ recycled PET bottles sheet matrix material.
The preparation method of the matrix material of 15. PA6/ recycled PET bottles sheets according to claim 14, is characterized in that, in step (1), described dry be to be dried in vacuum drying oven.
The preparation method of the matrix material of 16. PA6/ recycled PET bottles sheets according to claim 15, it is characterized in that, in step (1), described be dryly divided into two stages and carry out, wherein the first stage is dry 3～5h under the condition of 75～80 ℃ of temperature; Subordinate phase is dry 7～10h under the condition of 135～145 ℃ of temperature.
The preparation method of the matrix material of 17. PA6/ recycled PET bottles sheets according to claim 16, is characterized in that, time of drying first stage 3.5～4.5h; Subordinate phase 8～9h time of drying.
The preparation method of the matrix material of 18. PA6/ recycled PET bottles sheets according to claim 14, is characterized in that, in step (2), described mixing time is to mix 10～15 minutes.
The preparation method of the matrix material of 19. PA6/ recycled PET bottles sheets according to claim 14, it is characterized in that, the Temperature Setting scope of described twin screw extruder is 250～270 ℃, and screw speed is 200～500rpm, and vacuum tightness is-0.6～1.0Kgf/cm
2.
The preparation method of the matrix material of 20. PA6/ recycled PET bottles sheets according to claim 14, is characterized in that, the temperature in described twin screw extruder Ge district is:
One district's temperature: 210～225 ℃,
Two district's temperature: 240～250 ℃,
Three district's temperature: 255～264 ℃,
Four district's temperature: 265～269 ℃,
Five district's temperature: 270～275 ℃,
Six district's temperature: 270～275 ℃,
Seven district's temperature: 263～268 ℃.
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| CN105017764A (en) * | 2014-04-24 | 2015-11-04 | 上海奇彩塑胶原料有限公司 | Composite material of halogen-free flame-retardant reinforced PA66/recycled PET bottle-grade chips and preparation method thereof |
| CN110845711B (en) * | 2019-07-19 | 2021-10-29 | 江建明 | Control method and application of PET average sequence length in PET-PA6 |
| CN111154255A (en) * | 2019-12-23 | 2020-05-15 | 会通新材料股份有限公司 | Glass fiber reinforced PA6 material with low water absorption and stable size and preparation method thereof |
| CN114231023B (en) * | 2021-12-27 | 2023-10-31 | 中广核俊尔(浙江)新材料有限公司 | Low-cost, low-water-absorption and easy-molding PA/PET alloy material and preparation method thereof |
| CN114687006B (en) * | 2022-04-12 | 2023-02-14 | 雅香丽化妆用品（深圳）有限公司 | Quick-drying filament yarn, preparation method thereof and toothbrush |
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| CN1749314A (en) * | 2005-10-09 | 2006-03-22 | 华东理工大学 | PA/PET high molecule alloy material |
| CN101717562A (en) * | 2009-11-27 | 2010-06-02 | 北京航空航天大学 | Transparent high-barrier polyethylene glycol terephthalate composite material product |
| CN102229738A (en) * | 2011-05-17 | 2011-11-02 | 威海联桥新材料科技股份有限公司 | High glow-wire flame retardant reinforced PET/PA (polyethylene terephthalate/polyamide) alloy material and production method thereof |
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| CN1749314A (en) * | 2005-10-09 | 2006-03-22 | 华东理工大学 | PA/PET high molecule alloy material |
| CN101717562A (en) * | 2009-11-27 | 2010-06-02 | 北京航空航天大学 | Transparent high-barrier polyethylene glycol terephthalate composite material product |
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