CN109575527A - A kind of polyethylene terephthalate composition and preparation method thereof - Google Patents
A kind of polyethylene terephthalate composition and preparation method thereof Download PDFInfo
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- CN109575527A CN109575527A CN201710915549.7A CN201710915549A CN109575527A CN 109575527 A CN109575527 A CN 109575527A CN 201710915549 A CN201710915549 A CN 201710915549A CN 109575527 A CN109575527 A CN 109575527A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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Abstract
The present invention provides a kind of polyethylene terephthalate composition and preparation method thereof, is prepared by weight by following components: polyethylene terephthalate, polybutylene terephthalate (PBT), ethylene-octene copolymer grafted maleic anhydride, polyaminobismaleimide modified glass-fiber, odor adsorption master batch, silicon nitride, lubricant, antioxidant.The present invention carries out impregnation to glass fibre with polyaminobismaleimide dispersion liquid, greatly glass is improved in the dispersibility of polyethylene terephthalate matrix, and polyethylene terephthalate obtained is set to have significant raising in terms of wear-resisting property, and maintain excellent mechanical property；The small molecule content in composition is reduced using odor adsorption master batch, significantly reduces total volatile organism TVOC；And 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 macromolecules, and in particular to a kind of polyethylene terephthalate composition and its system
Preparation Method.
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 object of the present invention is to provide a kind of low smell, the polyethylene terephthalate composition of high abrasion and its systems
Preparation Method.
In order to achieve the object of the present invention, technical scheme is as follows:
A kind of polyethylene terephthalate composition, is prepared by weight by following components:
Further scheme, the melting means of the polyethylene terephthalate are 25-28g/10min；Poly terephthalic acid
The melting means of butanediol ester is 28-30g/10min.
The polyaminobismaleimide modified glass-fiber is changed through polyaminobismaleimide dispersion liquid dipping
Property treated glass fibre.
The polyaminobismaleimide dispersion liquid refers to that average grain diameter is 0.1-0.2 μm of poly- amino bismaleimide
Polyimide resin suspends the colloidal solution that is formed in water, and the viscosity of the colloidal solution is 0.05Pas, concentration 60wt%；Institute
The number-average molecular weight for stating polyaminobismaleimide 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 one or more of silicone powder, white oil, silicone oil, paraffin, stearic acid, zinc stearate
Mixture.
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) 1098).
Another goal of the invention of the invention is to provide a kind of preparation method of polyethylene terephthalate composition,
It includes the following steps:
(1) it by after glass fibre cleaning, drying, is immersed in polyaminobismaleimide dispersion liquid, takes out after drying again
It is baked in 200 DEG C of temperature, is then sintered to obtain polyaminobismaleimide 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, carry out it is uniformly mixed, so
Extruding pelletization obtains odor adsorption master batch in double screw extruder afterwards；
(3) polyethylene terephthalate, polybutylene terephthalate (PBT), ethylene-octene copolymer are grafted horse
Come acid anhydrides, odor adsorption master batch, silicon nitride, lubricant and antioxidant to pour into high-speed mixer and be stirred, after mixing
It adds twin-screw extrude；It again will be through (1) treated polyaminobismaleimide modified glass-fiber from extruder
Glass fiber opening is added, and is granulated after melting extrusion, the polyethylene terephthalate composition of low smell, high abrasion is made.
Area's temperature of double screw extruder is 180-190 DEG C in the step (2), (3), two area's temperature are 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, six area's temperature are 245-
300℃；Twin-screw engine speed is 500rpm.
Beneficial effects of the present invention:
1, the present invention carries out impregnation to glass fibre with extraordinary polyaminobismaleimide dispersion liquid, greatly changes
It has been apt to glass in the dispersibility of polyethylene terephthalate matrix, and polyethylene terephthalate obtained is made to exist
There is significant raising in terms of wear-resisting property, and maintains excellent mechanical property；
The present invention selects number-average molecular weight to soak for the polyaminobismaleimide of 50,000, elongation at break 3%-10%
Stain glass fibre, to can solve the fiber impregnation inefficient occurred during glass fiber impregnated, dipping is incomplete, fiber
There are the technical problems such as disconnected fibre.
2, the melting means of polyethylene terephthalate is the melting means of 25-28g/10min, polybutylene terephthalate (PBT)
For 28-30g/10min, it is molten that polyethylene terephthalate can be wherein adjusted after the addition of polybutylene terephthalate (PBT)
The mobility of body guarantees that in process uniformly, melting mixing is smooth for polyethylene terephthalate plasticizing.
3, the silicon nitride dosage in the present invention is 0.1-0.5 parts, avoids largely to use and combines physical property caused by silicon nitride
It can degradation；Silicon nitride 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 fiber, polyethylene terephthalate when in use, ensure that master batch in composition
Dispersibility in system.
5, the small molecule content in composition is reduced using extraordinary odor adsorption master batch, makes total volatile organism TVOC
It significantly reduces；And while guarantee composition low odor characteristics, the molding processibility of every physical and mechanical property, material
It can be 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
The following describes the present invention further through the description of specific embodiments, glass fibre in following embodiments
It is prepared by following method with odor adsorption master batch:
The impregnation of glass fibre: polyaminobismaleimide dispersion liquid will be immersed in after glass fibre cleaning, drying
In, it is baked at a temperature of 200 DEG C again after taking out drying, is finally sintered to obtain polyaminobismaleimide modified glass fibre
Dimension；Wherein polyaminobismaleimide dispersion liquid is the polyaminobismaleimide resin that average grain diameter is 0.1-0.2 μm
It is suspended in the colloidal solution formed in liquid water, the viscosity of the colloidal solution is 0.05Pas, concentration 60wt%.
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.
Polyaminobismaleimide number-average molecular weight is 50,000, elongation at break 3%-10%.
High density polyethylene (HDPE) crystallinity 85%, number-average molecular weight are 250,000.
Polyethylene terephthalate melting means is 25-28g/10min, polybutylene terephthalate (PBT) melting means is 28-
30g/10min。
Embodiment 1
By 70 parts of polyethylene terephthalate, 1 part of polybutylene terephthalate (PBT), ethylene-octene copolymer is connect
1 part of maleic anhydride of branch, 3 parts, 0.5 part silicon nitride of odor adsorption master batch, 1 part of silicone powder, 0.5 part of antioxidant, 1098,0.5 parts of antioxygens
Agent 168 is poured into high-speed mixer, high-speed stirred, mix to uniformly after add twin-screw extrude, by poly- amino span come
30 parts of imide-modified glass fibre is added from glass fiber opening, is granulated after melting extrusion, be made low smell, it is low distribute, high abrasion
Polyethylene terephthalate 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 terephthalate, 2 parts of polybutylene terephthalate (PBT), ethylene-octene copolymer is connect
2 parts of maleic anhydride of branch, 1 part, 0.2 part silicon nitride of odor adsorption master batch, 0.2 part of silicone powder, 0.1 part 1098,0.1 parts of antioxidant it is anti-
Oxygen agent 168 is poured into high-speed mixer, high-speed stirred, mix to uniformly after add twin-screw extrude, by poly- amino span
Carry out 30 parts of imide-modified glass fibre to be added from glass fiber opening, be granulated after melting extrusion, low smell is made, low distribute, is high resistance to
Grind polyethylene terephthalate 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 terephthalate, 5 parts of polybutylene terephthalate (PBT), 5 parts of odor adsorption master batch,
0.1 part of silicon nitride, 0.5 part of silicone powder, 0.2 part of antioxidant, 1098,0.3 parts of irgasfos 168s pour into high-speed mixer, high-speed stirring
It mixes, mixes to adding twin-screw extrude after uniformly, by 20 parts of polyaminobismaleimide modified glass-fiber from glass
Mouthful be added, be granulated after melting extrusion, be made low smell, it is low distribute, high abrasion polyethylene terephthalate 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 4
By 90 parts of polyethylene terephthalate, 5 parts of polybutylene terephthalate (PBT), ethylene-octene copolymer is connect
5 parts of maleic anhydride of branch, 5 parts, 0.1 part silicon nitride of odor adsorption master batch, 0.5 part of silicone powder, 0.1 part of antioxidant 1098 pour into high speed
In blender, high-speed stirred, mix to uniformly after add twin-screw extrude, by polyaminobismaleimide modified glass
5 parts of 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 terephthalate, 5 parts of polybutylene terephthalate (PBT), ethylene-octene copolymer is connect
5 parts of maleic anhydride of branch, 5 parts, 0.1 part silicon nitride of odor adsorption master batch, 0.5 part of silicone powder, 0.2 part 1098,0.3 parts of antioxidant it is anti-
Oxygen agent 168 is poured into high-speed mixer, high-speed stirred, mix to uniformly after add twin-screw extrude, by poly- amino span
Carry out 45 parts of imide-modified glass fibre to be added from glass fiber opening, be granulated after melting extrusion, low smell is made, low distribute, is high resistance to
Grind polyethylene terephthalate 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 terephthalate, 3 parts, 5 parts molybdenum disulfide of active carbon, 1 part of silicone powder, 0.5 part of antioxygen
1098,0.5 parts of irgasfos 168s of agent pour into high-speed mixer, high-speed stirred, mix to uniformly rear and double screw extruder is added
In, 300 parts of glass fibre are added from glass fiber opening, is 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.
1 performance data of table
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | |
| Tensile strength MPa | 147 | 176 | 159 | 80 |
| Notch impact strength KJ/m2 | 35 | 36 | 41 | 6 |
| Wearability (750g, 1000r) | 0.10 | 0.11 | 0.12 | 0.51 |
| TVOC ugC/g | 38 | 37 | 37 | 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 TVOC of the composition of preparation lower than 40ugC/g.Separately
Outside, the abrasion index of products of the present invention is extremely low, presents excellent wear-resisting property.This is because the present invention utilizes leaching
The glass fibre of stain processing significantly improves glass in the dispersibility of polyethylene terephthalate matrix, has composition
The advantages of anti-wear agent additive amount is few, wear-resisting protrusion, mechanical property significantly improves.
Above-mentioned each specific embodiment is that the invention will be further described, but this is not a limitation of the present invention, ability
Field technique personnel basic thought according to the present invention, can make various modifications or improvements, but without departing from of the invention
Basic thought is all within the scope of the present invention.
Claims (10)
1. a kind of polyethylene terephthalate composition, it is characterised in that: be prepared by weight by following components:
54-90 parts of polyethylene terephthalate,
1-5 parts of polybutylene terephthalate (PBT),
0-5 parts of ethylene-octene copolymer grafted maleic anhydride,
5-45 parts of polyaminobismaleimide modified glass-fiber,
1-5 parts of odor adsorption master batch,
0.1-0.5 parts of silicon nitride,
0.2-1.0 parts of lubricant,
0.1-1 parts of antioxidant.
2. a kind of polyethylene terephthalate composition according to claim 1, it is characterised in that: described poly- to benzene
The melting means of naphthalate is 25-28g/10min；The melting means of polybutylene terephthalate (PBT) is 28-30g/10min.
3. a kind of polyethylene terephthalate composition according to claim 1, it is characterised in that: the poly- amino
Bi-maleimide modified glass fibre is the glass fibre after polyaminobismaleimide dispersion liquid impregnates modification.
4. a kind of polyethylene terephthalate composition according to claim 3, it is characterised in that: the poly- amino
The polyaminobismaleimide resin that bismaleimide dispersion liquid refers to that average grain diameter is 0.1-0.2 μm suspends in water
The colloidal solution of formation, the viscosity of the colloidal solution is 0.05Pas, concentration 60wt%；The poly- amino bismaleimide
The number-average molecular weight of amine is 50,000, elongation at break 3%-10%.
5. a kind of polyethylene terephthalate composition according to claim 1, it is characterised in that: the smell is inhaled
Attached master batch is made of the component of following parts by weight: 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.
6. a kind of polyethylene terephthalate composition according to claim 5, it is characterised in that: described is highly dense
Polyethylene crystallinity 85% is spent, number-average molecular weight is 250,000.
7. a kind of polyethylene terephthalate composition according to claim 1, it is characterised in that: the lubrication
Agent is the mixtures of silicone powder, the one or more of white oil, silicone oil, paraffin, stearic acid, zinc stearate.
8. a kind of polyethylene terephthalate composition according to claim 1, it is characterised in that: the antioxygen
Agent is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and phosphorous acid three (2,4- di-tert-butyl-phenyl)
The mixture of ester.
9. preparing a kind of described in any item methods of polyethylene terephthalate composition of claim 1 ~ 8, feature
It is: includes the following steps:
(1) it by after glass fibre cleaning, drying, is immersed in polyaminobismaleimide dispersion liquid, exists again after taking out drying
It is baked in 200 DEG C of temperature, is then sintered to obtain polyaminobismaleimide 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, carry out uniformly mixed, then exist
Extruding pelletization obtains odor adsorption master batch in double screw extruder；
(3) by polyethylene terephthalate, polybutylene terephthalate (PBT), ethylene-octene copolymer grafted maleic
Acid anhydride, odor adsorption master batch, silicon nitride, lubricant and antioxidant are poured into high-speed mixer and are stirred, and are added after mixing
In double screw extruder；It again will be through (1) treated polyaminobismaleimide modified glass-fiber from the glass of extruder
Mouth is added, and is granulated after melting extrusion, the polyethylene terephthalate composition of low smell, high abrasion is made.
10. preparation method according to claim 9, it is characterised in that: double screw extruder in the step (2), (3)
One area's temperature is 180-190 DEG C, two area's temperature are 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 be 230-300 DEG C, six area's temperature are 245-300 DEG C；Twin-screw engine speed is 500rpm.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241874A (en) * | 2010-09-20 | 2011-11-16 | 深圳市科聚新材料有限公司 | Flame-retardant masterbatch modified polybutylene terephthalate material and preparation method thereof |
| CN104693696A (en) * | 2013-12-05 | 2015-06-10 | 上海杰事杰新材料(集团)股份有限公司 | Modified polybutylene telephthalate material and preparation method thereof |
| CN106479170A (en) * | 2015-08-27 | 2017-03-08 | 合肥杰事杰新材料股份有限公司 | A kind of low abnormal smells from the patient, low distribute, high abrasion-proof and high temperature resistant nylon and preparation method thereof |
-
2017
- 2017-09-29 CN CN201710915549.7A patent/CN109575527A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241874A (en) * | 2010-09-20 | 2011-11-16 | 深圳市科聚新材料有限公司 | Flame-retardant masterbatch modified polybutylene terephthalate material and preparation method thereof |
| CN104693696A (en) * | 2013-12-05 | 2015-06-10 | 上海杰事杰新材料(集团)股份有限公司 | Modified polybutylene telephthalate material and preparation method thereof |
| CN106479170A (en) * | 2015-08-27 | 2017-03-08 | 合肥杰事杰新材料股份有限公司 | A kind of low abnormal smells from the patient, low distribute, high abrasion-proof and high temperature resistant nylon and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 左继成等: "《高分子材料成型加工基本原理及工艺》", 31 January 2017, 北京理工大学出版社 * |
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Application publication date: 20190405 |