CN110066497A - A kind of low smell, it is low distribute, high abrasion polyethylene terephthalate composition and preparation method thereof - Google Patents
A kind of low smell, it is low distribute, high abrasion polyethylene terephthalate composition and preparation method thereof Download PDFInfo
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Abstract
The present invention disclose a kind of low smell, it is low distribute, high abrasion polyethylene terephthalate composition and preparation method thereof, the composition is made by weight of following components: 54-90 parts of polyethylene terephthalate, 1-5 parts of polybutylene terephthalate (PBT), 0-5 parts of maleic anhydride, 5-45 parts of glass fibre, 1-5 parts of odor adsorption master batch, 0.1-0.5 parts of molybdenum disilicide, 0.2-1.0 parts of lubricant, 0.1-1 parts of antioxidant.The present invention carries out impregnation to glass fibre with polypyromellitimide dispersion liquid, greatly improve dispersibility of the glass fibre in polyethylene terephthalate matrix, and composition obtained is made to have significant raising in terms of wear-resisting property, maintain excellent mechanical property；The small molecule content in composition is reduced using odor adsorption master batch, total volatile organism TVOC is significantly reduced；While guarantee composition low odor characteristics, every physical and mechanical property, the moulding processability of material are unaffected.
Description
Technical field
The present invention relates to technical field of polymer materials, specifically a kind of low smell, it is low distribute, the poly- terephthaldehyde of high abrasion
Sour glycol ester composition and preparation method thereof.
Background technique
Polyethylene terephthalate (PET) is exchanged by dimethyl terephthalate (DMT) with glycol ester or to benzene two
Formic acid and ethylene glycol esterification first synthesize bishydroxyethyl terephthalate, then carry out polycondensation reaction again and are made.It is full that it belongs to crystal type
And polyester, it is milky or light yellow, highly crystalline polymer, smooth surface is glossy, is a kind of tree common in life
Rouge.
Polyethylene terephthalate has excellent physical mechanical property in wider temperature range, is used for a long time
For temperature up to 120 DEG C, electrical insulating property is excellent, or even under high-temperature high-frequency, electrical property is still preferable, but corona resistance is poor, resists
Creep properties, fatigue durability and dimensional stability are all fine.
Although polyethylene terephthalate has many excellent performances, wanted in some pairs of smells, wear-resisting properties
Higher field is asked, the application of polyethylene terephthalate will receive very big limitation.Therefore it needs to further decrease it
Smell, coefficient of friction and wear rate, this just needs to realize by the modification of polyethylene terephthalate.
Summary of the invention
The purpose of the present invention is to provide a kind of low smell, it is low distribute, high abrasion polyethylene terephthalate combination
Object and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of low smell, it is low distribute, high abrasion polyethylene terephthalate composition, by weight by following components
It is prepared:
Further scheme, the melt index of the polyethylene terephthalate are 25-28g/10min；Gather to benzene two
The melt index of formic acid butanediol ester is 28-30g/10min.
The glass fibre is the modified glass-fiber after polypyromellitimide dispersion liquid impregnation.
The polypyromellitimide dispersion liquid refers to that average grain diameter is 0.1-0.2 μm of polypyromellitimide tree
Rouge suspends the colloidal solution that is formed in water, and the viscosity of the colloidal solution is 0.05Pas, concentration 60wt%；It is described poly-
The number-average molecular weight of equal diimides is 50,000, elongation at break 3-10%.
The odor adsorption master batch is made of the component of following parts by weight: 100 parts of high density polyethylene (HDPE), hydrophobicity diatomite
5 parts, 10 parts of hydrophobic active charcoal, 5 parts of needle-shaped zeolite molecular sieve, 10 parts of zinc ricinate, 5 parts of nano silica, stearic acid
1 part of calcium, 5 parts of melamine.
The high density polyethylene (HDPE) crystallinity 85%, number-average molecular weight are 250,000.
The lubricant is the mixing of one or more of silicone powder, white oil, silicone oil, paraffin, stearic acid, zinc stearate
Object.
The antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant
And the mixture of (2, the 4- di-tert-butyl-phenyl) ester of phosphorous acid three (irgasfos 168) 1010).
It is another object of the present invention to provide a kind of preparation method of polyethylene terephthalate composition, packets
Include the following steps:
(1) by after glass fibre cleaning, drying, be immersed in polypyromellitimide dispersion liquid, take out drying and
It baked and banked up with earth in 200 DEG C of temperature, be sintered to obtain modified glass-fiber；
(2) by 100 parts of high density polyethylene (HDPE), 5 parts of hydrophobicity diatomite, 10 parts of hydrophobic active charcoal, needle-shaped zeolite molecules
Sieve 5 parts, 10 parts of zinc ricinate, 5 parts of nano silica, 1 part of calcium stearate, 5 parts of melamine be uniformly mixed, then double
Extruding pelletization in screw extruder obtains odor adsorption master batch；
(3) by 54-90 parts of polyethylene terephthalate, 1-5 parts of polybutylene terephthalate (PBT), maleic anhydride 0-
5 parts, 1-5 parts of odor adsorption master batch, 0.1-0.5 parts of molybdenum disilicide, 0.2-1.0 parts of lubricant and 0.1-1 parts of antioxidant are added
It is stirred in high-speed mixer, adds twin-screw extrude after mixing；It again will be through (1) treated modified glass fibre
Dimension 5-45 part from the glass fiber opening of extruder be added, be granulated after melting extrusion, be made low smell, it is low distribute, high abrasion gather pair
Ethylene terephthalate composition.
Further scheme, area's temperature of double screw extruder is 180-190 DEG C, two area's temperature in the step (2), (3)
Degree is 180-190 DEG C, three area's temperature are 190-200 DEG C, four area's temperature are 210-220 DEG C, five area's temperature are 230-300 DEG C, six
Area's temperature is 245-300 DEG C；Twin-screw engine speed is 500rpm.
Beneficial effects of the present invention:
1, the present invention carries out impregnation to glass fibre with extraordinary polypyromellitimide dispersion liquid, greatly improves
Dispersibility of the glass in polyethylene terephthalate matrix, and make polyethylene terephthalate obtained resistance to
Mill aspect of performance has significant raising, and maintains excellent mechanical property；
The present invention selects number-average molecular weight to impregnate glass for the polypyromellitimide of 50,000, elongation at break 3-10%
Glass fiber, to can solve the fiber impregnation inefficient occurred during glass fiber impregnated, not exclusively, fiber dipping occurs
The technical problems such as disconnected fibre.
2, it is 25-28g/10min, poly terephthalic acid that the present invention, which selects the melt index of polyethylene terephthalate,
The melt index of butanediol ester is 28-30g/10min, and poly- pair can be wherein adjusted after the addition of polybutylene terephthalate (PBT)
The mobility of ethylene terephthalate melt guarantees that in process polyethylene terephthalate plasticizing uniformly, is melted
It is smooth to melt mixing.
3, the molybdenum disilicide dosage in the present invention is 0.1-0.5 parts, is avoided largely using combination caused by molybdenum disilicide
Physical performance degradation；Molybdenum disilicide plays very important synergistic effect to composition wear-resisting property.
4, odor adsorption master batch of the present invention use crystallinity 85%, number-average molecular weight be 250,000 high density polyethylene (HDPE) as
Matrix can improve the compatibility of itself and glass fibre, polyethylene terephthalate when in use, ensure that master batch in group
Close the dispersibility in objects system.
5, the present invention reduces the small molecule content in composition using extraordinary odor adsorption master batch, keeps general volatile organic
Object TVOC is significantly reduced；And while guarantee composition low odor characteristics, the molding of every physical and mechanical property, material
Processing performance is unaffected.
6, area's temperature of the double screw extruder in the present invention is 180-190 DEG C, two area's temperature are 180-190 DEG C, three
Area's temperature is 190-200 DEG C, four area's temperature are 210-220 DEG C, five area's temperature are 230-300 DEG C, six area's temperature are 245-300
℃；Twin-screw engine speed is 500rpm, and this processing temperature, engine speed are able to solve in process, and appearance adds
It is blocked at material, feeding is unsaturated, and plasticizing is uneven, the technical problems such as overflow.
Specific embodiment
Present invention is further described in detail combined with specific embodiments below.
Glass fibre and odor adsorption master batch are prepared by following method in following embodiments:
Modified glass-fiber: will be immersed in polypyromellitimide dispersion liquid after glass fibre cleaning, drying, take out
It dries and is baked and banked up with earth at a temperature of 200 DEG C, is sintered to obtain polypyromellitimide modified glass-fiber；Wherein gather equal benzene tetramethyl
Acid imide dispersion liquid is that the polypyromellitimide resin that average grain diameter is 0.1-0.2 μm is suspended in the glue formed in liquid water
Liquid solution, the viscosity of the colloidal solution is 0.05Pas, concentration 60wt%.Polypyromellitimide number-average molecular weight
It is 50,000, elongation at break 3-10%.
The preparation of odor adsorption master batch: 100 parts of high density polyethylene (HDPE), 5 parts of hydrophobicity diatomite, hydrophobic active charcoal 10
Part, 5 parts of needle-shaped zeolite molecular sieve, 10 parts of zinc ricinate, 5 parts of nano silica, 1 part of calcium stearate, 5 parts of melamine,
Carry out uniformly mixed, then extruding pelletization obtains odor adsorption master batch in double screw extruder.
High density polyethylene (HDPE) crystallinity 85%, number-average molecular weight are 250,000.
Polyethylene terephthalate melt index is 25-28g/10min；Polybutylene terephthalate (PBT) melting refers to
Number is 28-30g/10min.
Embodiment 1
By 70 parts of polyethylene terephthalates, 1 part of polybutylene terephthalate (PBT), 1 part of maleic anhydride, 3 parts of gas
Taste adsorbs master batch, 0.5 part of molybdenum disilicide, 1 part of silicone powder, 0.5 part of antioxidant 1010,0.5 part of irgasfos 168, and high-speed stirring is added
Mix in machine, high-speed stirred, mix to uniformly after add twin-screw extrude, by 30 parts of polypyromellitimide modified glass
Fiber is added from glass fiber opening, is granulated after melting extrusion, be made low smell, it is low distribute, high abrasion polyethylene terephthalate
Ester composition.
One area's temperature of the double screw extruder is 180 DEG C, two area's temperature are 180 DEG C, three area's temperature are 190 DEG C, four
Area's temperature is 210 DEG C, five area's temperature are 230 DEG C, six area's temperature are 245 DEG C；Twin-screw engine speed is 500rpm.
Embodiment 2
By 54 parts of polyethylene terephthalates, 2 parts of polybutylene terephthalate (PBT)s, 2 parts of maleic anhydrides, 1 part of gas
Taste adsorbs master batch, 0.2 part of molybdenum disilicide, 0.2 part of paraffin, 0.1 part of antioxidant 1010,0.1 part of irgasfos 168, and high-speed stirring is added
Mix in machine, high-speed stirred, mix to uniformly after add twin-screw extrude, by 30 parts of polypyromellitimide modified glass
Fiber is added from glass fiber opening, is granulated after melting extrusion, be made low smell, it is low distribute, high abrasion polyethylene terephthalate
Ester composition.
One area's temperature of the double screw extruder is 190 DEG C, two area's temperature are 190 DEG C, three area's temperature are 200 DEG C, four
Area's temperature is 220 DEG C, five area's temperature are 300 DEG C, six area's temperature are 300 DEG C；Twin-screw engine speed is 500rpm.
Embodiment 3
By 90 parts of polyethylene terephthalates, 5 parts of polybutylene terephthalate (PBT)s, 5 parts of maleic anhydrides, 5 parts of gas
Taste adsorbs master batch, 0.1 part of molybdenum disilicide, 0.5 part of stearic acid, 0.2 part of antioxidant 1010,0.3 part of irgasfos 168, and high speed is added
In blender, high-speed stirred is mixed to adding twin-screw extrude after uniformly, by the modified glass of 20 parts of polypyromellitimide
Glass fiber is added from glass fiber opening, is granulated after melting extrusion, be made low smell, it is low distribute, high abrasion poly terephthalic acid second two
Ester composition.
One area's temperature of the double screw extruder is 180 DEG C, two area's temperature are 180 DEG C, three area's temperature are 190 DEG C, four
Area's temperature is 210 DEG C, five area's temperature are 230 DEG C, six area's temperature are 245 DEG C；Twin-screw engine speed is 500rpm.
Comparative example 1
Add common activated carbon of sorbent, common anti-wear agent molybdenum disulfide.
By 70 parts of polyethylene terephthalates, 3 parts of active carbons, 5 parts of molybdenum disulfide, 1 part of silicone powder, 0.5 part of antioxygen
1010,0.5 parts of irgasfos 168s of agent are added in high-speed mixer, high-speed stirred, mix to uniformly rear and double screw extruder is added
In, 30 parts of glass fibres are added from glass fiber opening, are granulated after melting extrusion.
One area's temperature of the double screw extruder is 180 DEG C, two area's temperature are 180 DEG C, three area's temperature are 190 DEG C, four
Area's temperature is 210 DEG C, five area's temperature are 230 DEG C, six area's temperature are 245 DEG C；Twin-screw engine speed is 500rpm.
To polyethylene terephthalate composition prepared by above-described embodiment 1-3 and comparative example 1, its power is detected respectively
Learn performance, oder levels, TVOC and wear-resisting property.Wherein mechanical property is detected using ASTM standard, oder levels, TVOC
It is detected using GMW standard, wear-resisting property is measured according to standard GB/T5478-2008, and physical data see the table below 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | |
| Tensile strength MPa | 145 | 177 | 161 | 80 |
| Notch impact strength KJ/m2 | 37 | 33 | 40 | 6 |
| Wearability (750g, 1000r) | 0.08 | 0.08 | 0.10 | 0.51 |
| TVOC ugC/g | 34 | 34 | 35 | 163 |
| Oder levels | 8 grades | 8 grades | 8 grades | 5 grades |
As can be seen from Table 1, due to being added to odor adsorption master batch in 1-3 of the embodiment of the present invention, compared to comparison
Active carbon in example 1, hence it is evident that the smell and emission characteristics for improving material make the composition TVOC of preparation lower than 40ugC/g.In addition,
The abrasion index of products of the present invention is extremely low, presents excellent wear-resisting property.This is because the present invention utilizes dipping
The glass fibre of processing significantly improves glass in the dispersibility of polyethylene terephthalate matrix, has composition resistance to
The advantages of grinding agent additive amount is few, wear-resisting protrusion, mechanical property significantly improves.
Embodiment 4
By 90 parts of polyethylene terephthalates, 5 parts of polybutylene terephthalate (PBT)s, 5 parts of maleic anhydrides, 5 parts of gas
Taste adsorbs master batch, 0.1 part of molybdenum disilicide, 0.5 part of stearic acid, 0.2 part of antioxidant 1010,0.3 part of irgasfos 168, and high speed is added
In blender, high-speed stirred is mixed to adding twin-screw extrude after uniformly, by the modified glass of 5 parts of polypyromellitimide
Glass fiber is added from glass fiber opening, is granulated after melting extrusion, be made low smell, it is low distribute, high abrasion poly terephthalic acid second two
Ester composition.
One area's temperature of the double screw extruder is 180 DEG C, two area's temperature are 180 DEG C, three area's temperature are 190 DEG C, four
Area's temperature is 210 DEG C, five area's temperature are 230 DEG C, six area's temperature are 245 DEG C；Twin-screw engine speed is 500rpm.
Embodiment 5
By 90 parts of polyethylene terephthalates, 5 parts of polybutylene terephthalate (PBT)s, 5 parts of maleic anhydrides, 5 parts of gas
Taste adsorbs master batch, 0.1 part of molybdenum disilicide, 0.5 part of stearic acid, 0.2 part of antioxidant 1010,0.3 part of irgasfos 168, and high speed is added
In blender, high-speed stirred is mixed to adding twin-screw extrude after uniformly, by the modified glass of 45 parts of polypyromellitimide
Glass fiber is added from glass fiber opening, is granulated after melting extrusion, be made low smell, it is low distribute, high abrasion poly terephthalic acid second two
Ester composition.
One area's temperature of the double screw extruder is 180 DEG C, two area's temperature are 180 DEG C, three area's temperature are 190 DEG C, four
Area's temperature is 210 DEG C, five area's temperature are 230 DEG C, six area's temperature are 245 DEG C；Twin-screw engine speed is 500rpm.
This hair can be understood and applied the above description of the embodiments is intended to facilitate those skilled in the art
It is bright.Person skilled in the art obviously easily can make various modifications to case study on implementation, and described herein one
As principle be applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to implementation cases here
Example, those skilled in the art's announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be
Within protection scope of the present invention.
Claims (10)
1. a kind of low smell, it is low distribute, high abrasion polyethylene terephthalate composition, it is characterised in that: by following groups
Divide and be prepared by weight:
54-90 parts of polyethylene terephthalate
1-5 parts of polybutylene terephthalate (PBT)
0-5 parts of maleic anhydride
5-45 parts of glass fibre
1-5 parts of odor adsorption master batch
0.1-0.5 parts of molybdenum disilicide
0.2-1.0 parts of lubricant
0.1-1 parts of antioxidant.
2. low smell according to claim 1, it is low distribute, high abrasion polyethylene terephthalate composition, it is special
Sign is: the melt index of the polyethylene terephthalate is 25-28g/10min；Polybutylene terephthalate (PBT)
Melt index be 28-30g/10min.
3. low smell according to claim 1, it is low distribute, high abrasion polyethylene terephthalate composition, it is special
Sign is: the glass fibre is the modified glass-fiber after polypyromellitimide dispersion liquid impregnation.
4. low smell according to claim 3, it is low distribute, high abrasion polyethylene terephthalate composition, it is special
Sign is: the polypyromellitimide dispersion liquid refers to that average grain diameter is 0.1-0.2 μm of polypyromellitimide tree
Rouge suspends the colloidal solution that is formed in water, and the viscosity of the colloidal solution is 0.05Pas, concentration 60wt%；It is described poly- equal
The number-average molecular weight of diimides is 50,000, elongation at break 3-10%.
5. low smell according to claim 1, it is low distribute, high abrasion polyethylene terephthalate composition, it is special
Sign is: the odor adsorption master batch is made of the component of following parts by weight: 100 parts of high density polyethylene (HDPE), hydrophobicity diatomite 5
Part, 10 parts of hydrophobic active charcoal, 5 parts of needle-shaped zeolite molecular sieve, 10 parts of zinc ricinate, 5 parts of nano silica, calcium stearate
1 part, 5 parts of melamine.
6. low smell according to claim 1, it is low distribute, high abrasion polyethylene terephthalate composition, it is special
Sign is: the high density polyethylene (HDPE) crystallinity 85%, and number-average molecular weight is 250,000.
7. low smell according to claim 1, it is low distribute, high abrasion polyethylene terephthalate composition, it is special
Sign is: the lubricant is the mixing of one or more of silicone powder, white oil, silicone oil, paraffin, stearic acid, zinc stearate
Object.
8. low smell according to claim 1, it is low distribute, high abrasion polyethylene terephthalate composition, it is special
Sign is: the antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant
And the mixture of (2, the 4- di-tert-butyl-phenyl) ester of phosphorous acid three (irgasfos 168) 1010).
9. low smell as described in claim 1, it is low distribute, the preparation side of high abrasion polyethylene terephthalate composition
Method, it is characterised in that: include the following steps:
(1) it by after glass fibre cleaning, drying, is immersed in polypyromellitimide dispersion liquid, takes out drying and at 200 DEG C
It baked and banked up with earth in temperature, be sintered to obtain modified glass-fiber；
(2) by 100 parts of high density polyethylene (HDPE), 5 parts of hydrophobicity diatomite, 10 parts of hydrophobic active charcoal, needle-shaped zeolite molecular sieve 5
Part, 10 parts of zinc ricinate, 5 parts of nano silica, 1 part of calcium stearate, 5 parts of melamine be uniformly mixed, then in double spiral shells
Extruding pelletization in bar extruder obtains odor adsorption master batch；
(3) by 54-90 parts of polyethylene terephthalate, 1-5 parts of polybutylene terephthalate (PBT), 0-5 parts of maleic anhydride,
High speed is added in 1-5 parts of odor adsorption master batch, 0.1-0.5 parts of molybdenum disilicide, 0.2-1.0 parts of lubricant and 0.1-1 parts of antioxidant
It is stirred in blender, adds twin-screw extrude after mixing；It again will be through (1) treated modified glass-fiber 5-
45 parts are added from the glass fiber opening of extruder, are granulated after melting extrusion, be made low smell, it is low distribute, high abrasion it is poly- to benzene two
Formic acid glycol ester composition.
10. low smell according to claim 9, it is low distribute, the system of high abrasion polyethylene terephthalate composition
Preparation Method, it is characterised in that: area's temperature of double screw extruder is 180-190 DEG C, two area's temperature in the step (2), (3)
For 180-190 DEG C, three area's temperature be 190-200 DEG C, four area's temperature are 210-220 DEG C, five area's temperature are 230-300 DEG C, 6th area
Temperature is 245-300 DEG C；Twin-screw engine speed is 500rpm.
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| CN111269548A (en) * | 2020-03-26 | 2020-06-12 | 深圳远致富海智能产业有限公司 | Heat-resistant low-temperature-resistant wear-resistant composition and preparation method thereof |
| CN111647971A (en) * | 2020-05-18 | 2020-09-11 | 中山尚洋科技股份有限公司 | Cosmetic brush hair and preparation method thereof |
| CN114957934A (en) * | 2022-06-27 | 2022-08-30 | 扬州君禾薄膜科技有限公司 | Antibacterial antistatic polyester chip and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111269548A (en) * | 2020-03-26 | 2020-06-12 | 深圳远致富海智能产业有限公司 | Heat-resistant low-temperature-resistant wear-resistant composition and preparation method thereof |
| CN111269548B (en) * | 2020-03-26 | 2022-05-24 | 深圳市汇进智能产业有限公司 | Heat-resistant low-temperature-resistant wear-resistant composition and preparation method thereof |
| CN111647971A (en) * | 2020-05-18 | 2020-09-11 | 中山尚洋科技股份有限公司 | Cosmetic brush hair and preparation method thereof |
| CN114957934A (en) * | 2022-06-27 | 2022-08-30 | 扬州君禾薄膜科技有限公司 | Antibacterial antistatic polyester chip and preparation method thereof |
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Application publication date: 20190730 |