CN106810859A - A kind of functional agglomerate for improving nylon resin heat resistance - Google Patents
A kind of functional agglomerate for improving nylon resin heat resistance Download PDFInfo
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- CN106810859A CN106810859A CN201611097358.6A CN201611097358A CN106810859A CN 106810859 A CN106810859 A CN 106810859A CN 201611097358 A CN201611097358 A CN 201611097358A CN 106810859 A CN106810859 A CN 106810859A
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/03—Polymer mixtures characterised by other features containing three 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
The present invention relates to feature masterbatch field, a kind of functional agglomerate for improving nylon resin heat resistance is specifically disclosed, be prepared from by the component of following weight portion：100~120 parts of vector resin, 15~25 parts of nanometer grade silica powder, 15~25 parts of powdered plant tanning agent, 8~10 parts of nanoscale Fluorspar Powder, 5~7 parts of toughener, 5~7 parts of heat stabilizer, 0.8~1.2 part of coupling agent, 0.8~1.2 part of dispersant, 0.8~1.0 part of antioxidant, wherein vector resin is polyhexamethylene adipamide, the wherein preferred lignin fibre of toughener, the preferred nanoscale graphite alkene of heat stabilizer, the preferred silane coupler of coupling agent, the preferred OPE of dispersant.Functional agglomerate of the invention limits nylon resin segment random motion by being internally formed hydrogen bond in nylon resin, improves nylon resin heat resistance, while warpage defect is avoided, and nylon resin toughness, ageing resistance are strong, and resin quality is uniform.
Description
Technical field
The present invention relates to feature masterbatch field, and in particular to a kind of functional agglomerate of raising nylon resin heat resistance.
Background technology
Nylon resin is polyhexamethylene adipamide resin, and with preferable fatigue strength and rigidity, coefficient of friction is low, wear-resisting
Property is good, applies in auto parts and components, electric power and field of electronic devices.But with automotive small, electronic electric equipment high-performance
Change, plant equipment lightweight progress faster, the performance requirement to nylon resin are higher, and especially nylon is existed as structural material
Heat resistance aspect proposes requirement very high.When temperature is more than 80 DEG C, the internal molecular motion unit in nylon resin（Chain
Section）Random warm-up movement causes intermolecular spacing to increase more than intermolecular cohesive action, nylon resin is shown poor heat resistance
Phenomenon.It is in the prior art to add glass fibre to improve heat resistance, the resistance to ag(e)ing of nylon resin in nylon resin.But glass
Fiber meeting streamwise orientation in injection moulding process, causes mechanical property and shrinkage factor to strengthen in the orientation direction, causes system
Product deform warpage.Chinese patent CN103254623A, a kind of antiwear heat resisting star nylon of patent name, date of publication in August, 2013
21, disclose one kind and be added with glass fibre, heat stabilizer, copper acetate, silicone oil, polycaprolactone, carbon fiber, thermosetting resin
Nylon resin, with the on-deformable advantage of high temperature.But glass fibre makes nylon products there is the latent defect of deformation warpage.
Master batch be by the modified chemical auxiliary agent uniform load of super quantity in the vector resin obtained from granular aggregation.With
Directly modified chemical auxiliary agent is added in product to compare：The dispersion effect of master batch makes well the performance of product uniform, the carrier of master batch
The compatibility of resin and product resin makes well the performance of the product of addition master batch lift effect more preferably, master batch using safety,
It is full-featured.
The content of the invention
The heat resistance of nylon resin is improved for addition glass fibre in the prior art and there is the potential scarce of product warpage
Risk is fallen into, it is an object of the invention to provide a kind of functional agglomerate added in nylon resin, by functional agglomerate
Composite parts improves the heat resistance of nylon resin, can meet automotive small, the high performance of electronic electric equipment, machine
The light-weighted application requirement of tool equipment, while avoiding the occurrence of warping phenomenon.
The present invention provides following technical scheme：
A kind of functional agglomerate for improving nylon resin heat resistance, is prepared from by the component of following weight portion：Vector resin 100~
120 parts, 15~25 parts of nanometer grade silica powder, 15~25 parts of powdered plant tanning agent, 8~10 parts of nanoscale Fluorspar Powder, toughness reinforcing
5~7 parts of agent, 5~7 parts of heat stabilizer, 0.8~1.2 part of coupling agent, 0.8~1.2 part of dispersant, 0.8~1.0 part of antioxidant, its
Middle vector resin is polyhexamethylene adipamide.
Functional agglomerate of the invention is using polyhexamethylene adipamide resin as vector resin and the compatibility of nylon resin
It is good, can make that functional agglomerate is dispersed to be added in nylon resin, functional agglomerate is improved the effect of heat resistance of nylon resin
Fruit is more preferably.There are three kinds of nanometer grade silica powder, powdered plant tanning agent and nanoscale Fluorspar Powder in functional agglomerate of the invention
Composite parts, dispersed filling in nylon resin is added to as the component of functional agglomerate.Wherein nanometer grade silica powder
Surface have substantial amounts of silicone hydroxyl, hydrogen bond, nanoscale firefly can be formed with the hydrogen atom in the acid amides in nylon resin or hydroxyl
Fluorine in stone flour also because with stronger electronegativity with nylon resin in acid amides in hydrogen atom or hydroxyl form hydrogen bond, powder
Tannin in shape vegetable tanning agent contain more phenolic hydroxyl group also with nylon resin in acid amides in hydrogen atom or hydroxyl formed hydrogen
Key, this in three composition hydrogen bond is formed by different mechanism and nylon resin internal structure, cooperatively form in nylon resin
The restriction of segment warm-up movement, so as to improve the heat resistance of nylon resin.Silica and Fluorspar Powder can improve Buddhist nun simultaneously
The intensity of imperial resin, strengthens the heat resistance of nylon resin.Toughener can improve bending and the tensile strength of nylon resin, and heat is steady
Determine agent assisted recombination composition and improve heat-resisting effect, coupling agent improves the surface-active between nylon resin and composite parts, dispersant
Each component is set to be uniformly dispersed, so as to cooperate with the effect of composite parts.
Used as a modification of the present invention, toughener is lignin fibre.Lignin fibre can strengthen nylon resin
Good toughness tensile strength, it is ensured that the physical property of nylon resin is basicly stable, the heat resistance effect of master batch of strengthening function.
Used as a modification of the present invention, heat stabilizer is nanoscale graphite alkene.The network structure of nanoscale graphite alkene exists
Nylon resin is internally formed articulamentum, can improve the heat endurance of nylon resin, prevents thermal deformation, master batch of strengthening function it is heat-resisting
Effect.
Used as a modification of the present invention, the coupling agent is silane coupler.Silane coupler improves Fluorspar Powder, two
Surface-active between silica and nylon resin, promotes the formation of hydrogen bond, improves the effect of functional agglomerate.
Used as a modification of the present invention, the dispersant is OPE.In OPE functional agglomerate
Each composition be uniformly dispersed after being added in nylon resin, it is ensured that the uniformity of nylon resin quality.
Used as a modification of the present invention, the component of the antioxidant is calculated as with weight part ratio：BHT：Citric acid=1:1.2
~1.5.BHT can effectively improve the resistance to ag(e)ing of nylon resin, the heat-resisting effect of master batch of strengthening function with the combination of citric acid.
A kind of preparation method of the functional agglomerate for improving nylon resin heat resistance, comprises the following steps：
（1）Each material component of weight portion is put into mixing and blending machine and is mixed 45~60 minutes in 50~60 DEG C of stirrings, stirring
The r/min of speed 250~300；
（2）By in mixed material input double screw extruder, the mixing speed for keeping double screw extruder is 180~220 r/
Min, the temperature range that each section of double screw extruder is 155~200 DEG C, after fully melting is combined, extrudes granulating；
（3）By step（2）The screen cloth sieving of the mesh of mesh~+20 of gained particle process -15.
Raw material is stirred in mixing and blending machine high speed first, improves the consistency of performance of functional agglomerate.By double
Screw extruder melts compound extruded into graininess.The particle diameter of functional agglomerate of the invention can pass through the sieve of -15 mesh of mesh~+20
Net, addition can both ensure dispersed in nylon resin, and the melting dispersion effect of the excessive influence functional agglomerate of particle diameter is avoided again
Really.
As a modification of the present invention, step（2）The temperature control of each section of middle double screw extruder is respectively：One section
155~160 DEG C, two sections 160~170 DEG C, three sections 170~180 DEG C, four sections 180~190 DEG C, five sections 190~195 DEG C, six sections
195~200 DEG C, seven sections 190~195 DEG C, die head temperature is 190~195 DEG C.By the behaviour for setting each section of double screw extruder
It is gradually increasing as temperature, heat-resisting, anti-oxidant, the thermally-stabilised and lubrication dispersing characteristic of each component in abundant release function master batch,
The stable and uniform for improving functional agglomerate performance is consistent.
As a modification of the present invention, step is being carried out（3）By step before screening（2）140~155 DEG C of gained particle
Aeration-drying obtains dry particle in 2~4 hours.So can be uniform with promotion functions master batch surface texture, it is easy to long-term storage.
Beneficial effects of the present invention are as follows：
Be supported in vector resin for nanometer grade silica powder, Fluorspar Powder and vegetable tanning agent by functional agglomerate of the invention, passes through
The random motion of the segment of hydrogen bond limitation nylon resin is internally formed in nylon resin, the heat resistance of nylon resin is improved, together
When avoid the warpage defect that glass fibre causes, and strengthen the toughness of nylon resin, ageing resistance, resin quality is equal
It is even.
Specific embodiment
Specific embodiment of the invention is described further below：
Embodiment 1：
A kind of functional agglomerate for improving nylon resin heat resistance, is prepared from by the component of following weight portion：Vector resin 100
G, the g of nanometer grade silica powder 15, the g of powdered plant tanning agent 15, the g of nanoscale Fluorspar Powder 8, the g of toughener 5, heat stabilizer 5
G, the g of coupling agent 0.8, the g of dispersant 0.8, the g of antioxidant 0.8, wherein vector resin are polyhexamethylene adipamide, and toughener is wood
Quality fiber, heat stabilizer is Graphene, and coupling agent is preferably silane coupler, and dispersant is preferably OPE, is resisted
Oxygen agent is preferably BHT and citric acid in combination, and weight part ratio is：BHT：Citric acid=1:1.2~1.5.
The preparation method for improving the functional agglomerate of nylon resin heat resistance is comprised the following steps：
（1）Each material component of weight portion is put into mixing and blending machine and is mixed 45 minutes in 50 DEG C of stirrings, mixing speed 250
r/min；
（2）By in mixed material input double screw extruder, the mixing speed for keeping double screw extruder is 180 r/min, double
The temperature range that each section of screw extruder is 155~200 DEG C, after fully melting is combined, extrudes granulating；
（3）By step（2）The screen cloth sieving of the mesh of mesh~+20 of gained particle process -15.
To obtain performance uniformly and showing preferable master batch, step（2）The temperature control of each section of middle double screw extruder point
It is not：One section 155~160 DEG C, two sections 160~170 DEG C, three sections 170~180 DEG C, four sections 180~190 DEG C, five section 190~
195 DEG C, six sections 195~200 DEG C, seven sections 190~195 DEG C, die head temperature is 190~195 DEG C.
To improve the uniformity coefficient on functional agglomerate surface, by step（2）The aeration-drying 4 hours of 140 DEG C of gained particle must be done
Dry particle, then passes through step again（3）Screening.
The particle for passing through -15 eye mesh screens of mesh~+20 is the functional agglomerate of the raising nylon resin heat resistance to be obtained.
Embodiment 2：
A kind of functional agglomerate for improving nylon resin heat resistance, is prepared from by the component of following weight portion：Vector resin 110
G, the g of nanometer grade silica powder 20, the g of powdered plant tanning agent 20, the g of nanoscale Fluorspar Powder 9, the g of toughener 6, heat stabilizer 6
G, the g of coupling agent 1.0, the g of dispersant 1.0, the g of antioxidant 0.9, wherein vector resin are polyhexamethylene adipamide, and toughener is wood
Quality fiber, heat stabilizer is Graphene, and coupling agent is preferably silane coupler, and dispersant is preferably OPE, is resisted
Oxygen agent is preferably BHT and citric acid in combination, and weight part ratio is：BHT：Citric acid=1:1.2~1.5.
The preparation method for improving the functional agglomerate of nylon resin heat resistance is comprised the following steps：
（1）Each material component of weight portion is put into mixing and blending machine and is mixed 50 minutes in 55 DEG C of stirrings, mixing speed 270
r/min；
（2）By in mixed material input double screw extruder, the mixing speed for keeping double screw extruder is 200 r/min, double
The temperature range that each section of screw extruder is 155~200 DEG C, after fully melting is combined, extrudes granulating；
（3）By step（2）The screen cloth sieving of the mesh of mesh~+20 of gained particle process -15.
To obtain performance uniformly and showing preferable master batch, step（2）The temperature control of each section of middle double screw extruder point
It is not：One section 155~160 DEG C, two sections 160~170 DEG C, three sections 170~180 DEG C, four sections 180~190 DEG C, five section 190~
195 DEG C, six sections 195~200 DEG C, seven sections 190~195 DEG C, die head temperature is 190~195 DEG C.
To improve the uniformity coefficient on functional agglomerate surface, by step（2）The aeration-drying 3 hours of 150 DEG C of gained particle must be done
Dry particle, then passes through step again（3）Screening.
The particle for passing through -15 eye mesh screens of mesh~+20 is the functional agglomerate of the raising nylon resin heat resistance to be obtained.
Embodiment 3：
A kind of functional agglomerate for improving nylon resin heat resistance, is prepared from by the component of following weight portion：Vector resin 120
G, the g of nanometer grade silica powder 25, the g of powdered plant tanning agent 25, the g of nanoscale Fluorspar Powder 10, the g of toughener 7, heat stabilizer 7
G, the g of coupling agent 1.2, the g of dispersant 1.2, the g of antioxidant 1.0, wherein vector resin are polyhexamethylene adipamide, and toughener is wood
Quality fiber, heat stabilizer is Graphene, and coupling agent is preferably silane coupler, and dispersant is preferably OPE, is resisted
Oxygen agent is preferably BHT and citric acid in combination, and weight part ratio is：BHT：Citric acid=1:1.2~1.5.
The preparation method for improving the functional agglomerate of nylon resin heat resistance is comprised the following steps：
（1）Each material component of weight portion is put into mixing and blending machine and is mixed 60 minutes in 60 DEG C of stirrings, mixing speed 300
r/min；
（2）By in mixed material input double screw extruder, the mixing speed for keeping double screw extruder is 220 r/min, double
The temperature range that each section of screw extruder is 155~200 DEG C, after fully melting is combined, extrudes granulating；
（3）By step（2）The screen cloth sieving of the mesh of mesh~+20 of gained particle process -15.
To obtain performance uniformly and showing preferable master batch, step（2）The temperature control of each section of middle double screw extruder point
It is not：One section 155~160 DEG C, two sections 160~170 DEG C, three sections 170~180 DEG C, four sections 180~190 DEG C, five section 190~
195 DEG C, six sections 195~200 DEG C, seven sections 190~195 DEG C, die head temperature is 190~195 DEG C.
To improve the uniformity coefficient on functional agglomerate surface, by step（2）The aeration-drying 2 hours of 155 DEG C of gained particle must be done
Dry particle, then passes through step again（3）Screening.
The particle for passing through -15 eye mesh screens of mesh~+20 is the functional agglomerate of the raising nylon resin heat resistance to be obtained.
Commercially available general nylon resin（Comparative example 1）With the nylon of the functional agglomerate for being added with embodiments of the invention 1,2,3
Resin（Respectively test specimens 1, test specimens 2, test specimens 3）Performance data contrast it is as shown in table 1：
The performance comparison data of table 1
| Test event | Testing standard | Comparative example 1 | Test specimens 1 | Test specimens 2 | Test specimens 3 |
| Heat distortion temperature | ASTM D648 | 87.5 ℃ | 99.2 ℃ | 103.4 ℃ | 108.1 ℃ |
| Tensile strength | ASTM D638 | 89 MPa | 97 MPa | 103 MPa | 109 MPa |
| Izod notched impact strength | GB/T 1843-2008 |
Functional agglomerate of the invention can significantly improve the heat resistance of nylon resin, it is to avoid produce warpage defect, and enhance Buddhist nun
The toughness of imperial resin, ageing resistance.
Claims (9)
1. it is a kind of improve nylon resin heat resistance functional agglomerate, it is characterised in that be prepared from by the component of following weight portion：
100~120 parts of vector resin, 15~25 parts of nanometer grade silica powder, 15~25 parts of powdered plant tanning agent, nanoscale Fluorspar Powder
8~10 parts, 5~7 parts of toughener, 5~7 parts of heat stabilizer, 0.8~1.2 part of coupling agent, 0.8~1.2 part of dispersant, antioxidant
0.8~1.0 part, wherein vector resin is polyhexamethylene adipamide.
2. a kind of functional agglomerate for improving nylon resin heat resistance according to claim 1, its feature exists, and toughener is wood
Quality fiber.
3. it is according to claim 1 it is a kind of improve nylon resin heat resistance functional agglomerate, it is characterised in that heat stabilizer
It is nanoscale graphite alkene.
4. it is according to claim 1 it is a kind of improve nylon resin heat resistance functional agglomerate, it is characterised in that the coupling
Agent is silane coupler.
5. it is according to claim 1 it is a kind of improve nylon resin heat resistance functional agglomerate, it is characterised in that the dispersion
Agent is OPE.
6. it is according to claim 1 it is a kind of improve nylon resin heat resistance functional agglomerate, it is characterised in that the antioxygen
The component of agent is calculated as with weight part ratio：BHT：Citric acid=1:1.2~1.5.
7. it is a kind of as described in claim 1 to 6 is any raising nylon resin heat resistance functional agglomerate preparation method, including
Following steps：
（1）Each material component of weight portion is put into mixing and blending machine and is mixed 45~60 minutes in 50~60 DEG C of stirrings, stirring
The r/min of speed 250~300；
（2）By in mixed material input double screw extruder, the mixing speed for keeping double screw extruder is 180~220 r/
Min, the temperature range that each section of double screw extruder is 155~200 DEG C, after fully melting is combined, extrudes granulating；
（3）By step（2）The screen cloth sieving of the mesh of mesh~+20 of gained particle process -15.
8. the preparation method of a kind of functional agglomerate for improving nylon resin heat resistance according to claim 7, its feature exists
In step（2）The temperature control of each section of middle double screw extruder is respectively：One section 155~160 DEG C, two sections 160~170 DEG C,
Three sections 170~180 DEG C, four sections 180~190 DEG C, five sections 190~195 DEG C, six sections 195~200 DEG C, seven sections 190~195 DEG C,
Die head temperature is 190~195 DEG C.
9. the preparation method of a kind of functional agglomerate for improving nylon resin heat resistance according to claim 7, its feature exists
In carrying out step（3）By step before screening（2）The aeration-drying 2~4 hours of 140~155 DEG C of gained particle obtains dry
Grain.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611097358.6A CN106810859A (en) | 2016-12-02 | 2016-12-02 | A kind of functional agglomerate for improving nylon resin heat resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611097358.6A CN106810859A (en) | 2016-12-02 | 2016-12-02 | A kind of functional agglomerate for improving nylon resin heat resistance |
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| Publication Number | Publication Date |
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| CN106810859A true CN106810859A (en) | 2017-06-09 |
Family
ID=59106013
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| CN201611097358.6A Pending CN106810859A (en) | 2016-12-02 | 2016-12-02 | A kind of functional agglomerate for improving nylon resin heat resistance |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111574826A (en) * | 2020-04-27 | 2020-08-25 | 浙江巨化新材料研究院有限公司 | Polytetrafluoroethylene master batch for nylon modification and preparation method thereof |
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| JP2006199748A (en) * | 2005-01-18 | 2006-08-03 | Asahi Kasei Chemicals Corp | Method for producing resin composition |
| CN103772966A (en) * | 2013-12-24 | 2014-05-07 | 贵州蓝图新材料有限公司 | Micro-silica fume reinforced nylon material and preparation method thereof |
| CN105504795A (en) * | 2015-12-30 | 2016-04-20 | 天津金发新材料有限公司 | Heat-resistant and hydrolysis-resistant reinforced nylon composite material and preparation method thereof |
| CN105566898A (en) * | 2016-02-04 | 2016-05-11 | 广东奇德新材料股份有限公司 | Nano nylon 6 composite material |
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2016
- 2016-12-02 CN CN201611097358.6A patent/CN106810859A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006199748A (en) * | 2005-01-18 | 2006-08-03 | Asahi Kasei Chemicals Corp | Method for producing resin composition |
| CN103772966A (en) * | 2013-12-24 | 2014-05-07 | 贵州蓝图新材料有限公司 | Micro-silica fume reinforced nylon material and preparation method thereof |
| CN105504795A (en) * | 2015-12-30 | 2016-04-20 | 天津金发新材料有限公司 | Heat-resistant and hydrolysis-resistant reinforced nylon composite material and preparation method thereof |
| CN105566898A (en) * | 2016-02-04 | 2016-05-11 | 广东奇德新材料股份有限公司 | Nano nylon 6 composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111574826A (en) * | 2020-04-27 | 2020-08-25 | 浙江巨化新材料研究院有限公司 | Polytetrafluoroethylene master batch for nylon modification and preparation method thereof |
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