CN106832262A - With nano combined nylon material for exempting to spray optical property high and preparation method thereof - Google Patents
With nano combined nylon material for exempting to spray optical property high and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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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
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- C08K2201/003—Additives being defined by their diameter
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/011—Nanostructured additives
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Abstract
The invention discloses a kind of with nano combined nylon material for exempting to spray optical property high and preparation method thereof.The nano combined nylon material is prepared using following methods：Step one, caprolactam, water and organic acid are mixed；Step 2, it is warming up to 180 230 DEG C, reacts 1 5h；Step 3, addition modified inorganic nano silicate, are warming up to 240 280 DEG C, react 1 5h, obtain prepolymer.Step 4, polymerization that above-mentioned prepolymer depressurizes, obtain nano combined nylon material.The method that the present invention uses a step in-situ polymerization, improve the compatibility of modified inorganic nano silicate and nylon, be conducive to dispersion of the modified inorganic nano silicate in nylon matrix, purer nylon has more excellent mechanical property, hot property and exempts to spray optical property high；And the nano combined nylon material preparation process is simple, condition is preferably controlled, and is suitable to industrialized production, can be widely applied to the production of the plastic casing products such as electric power tool shell, automotive upholstery and household electrical appliance.
Description
Technical field
It is the present invention relates to a kind of nylon material and preparation method thereof more particularly to a kind of with exempting to spray receiving for optical property high
Rice composite nylon material and preparation method thereof.
Background technology
Nylon is the macromolecular compound containing amide group on main polymer chain, steady with good mechanical performance, heat
The advantages of qualitative, chemical stability, wearability and electrical insulating property, it is widely used in the row such as automobile, building, electronic apparatus, chemical industry
Industry.Compared with nylon paint component, exempt from spraying bloom nylon product be easily molded, high yield rate, product can 100% reclaim again profit
With the polluters such as poisonous and hazardous gas, dust will not be produced to environment.Exempt from spraying bloom nylon material in preparation process
Prosthetic or machine painting process, reduce operation and cost, avoid environmental pollution, and the VOC for reducing material is distributed, so
Gradually replacing paint part is used in automotive trim to exempt from spraying nylon.
Spraying bloom nylon product is exempted from preparation at present mainly two methods of polymer blending techniques and in-situ polymerization technology.
Polymer blending techniques are by polymer melt or solution and inorganic nano-particle (such as metal powder, pearl essence, ceramic powder, sulfuric acid
Barium etc.) mixing, between polymer molecular chain is entered into inorganic nano-particle using power chemistry or Thermodynamic effect, make nano-particle
Between spacing increase.Open source information CN104672898A, CN105623249A, CN100467540C etc. are a series of inorganic by adding
Bead, glass, calcium silicates improve the glossiness of polymer to blending in nylon matrix, but the method is difficult to nanoparticle
Son is dispersed in polymeric matrix, and nano-particle is higher due to surface cohesion energy density, easily reunites, and composite holds
Easily there is macroscopic view to be separated.
In-situ polymerization technology is first to enter in nano-particle or dispersion/cladding polymer monomer dispersion, monomeric small molecule
Around nano-particle, then in-situ polymerization, using liberated heat when being polymerized, overcomes the Coulomb force between nano-particle, inorganic
Particle is evenly dispersed in polymeric matrix with nanoscale.Open source information CN105542453A, CN101899153A etc. will
The inorganic nano-particles such as montmorillonite, nano silicon are aggregated in nylon matrix, but these methods cannot all be prepared exempts from spray
Apply the nylon material of bloom.So, the key technology for exempting to spray the preparation of bloom nylon product is always to use a step in building-up process
With nanoscale be dispersed in nylon matrix the inorganic nano-particle of certain size by method so that inorganic nano-particle and polymer two
Interphase interface has stronger cementation.
The content of the invention
For the drawbacks described above of prior art, one of technical problems to be solved by the invention be to provide it is a kind of have exempt from spray
Apply the preparation method of the nano combined nylon material of optical property high.
The two of the technical problems to be solved by the invention are to provide to have obtained by the above method and exempt to spray optical property high
Nano combined nylon material.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of preparation method with the nano combined nylon material for exempting to spray optical property high, comprises the steps：
Step one, caprolactam, water and organic acid are mixed；
Preferably, the quality of the caprolactam, water and organic acid is：(90-100):(0.5-8):(0.5-8)；
Preferably, the organic acid is the organic matter containing carboxyl, such as aminocaproic acid, benzoic acid, octanoic acid, adipic acid, second
One kind or its mixture in diacid and amion acetic acid；
Step 2, it is warming up to 180-230 DEG C, reacts 1-5h；
Preferably, started to warm up to 180-230 DEG C from room temperature, keeping temperature, control pressure is 0-100KPa, react 1-
5h；It is further preferred that programming rate control is in 1-20 DEG C/min；Stress control is in 20-80KPa；
Step 3, addition modified inorganic nano silicate, are warming up to 240-280 DEG C, react 1-5h, obtain prepolymer；
Preferably, the addition of modified inorganic nano silicate accounts for the 0.05-5wt% of caprolactam；
Preferably, 240-280 DEG C is warming up to, keeping temperature, control pressure is 0-100KPa, reacts 1-5h；It is further excellent
Selection of land, programming rate is controlled in 1-20 DEG C/min；Stress control is in 20-80KPa；
Step 4, polymerization that above-mentioned prepolymer depressurizes, obtain nano combined nylon material.
Reaction is filled with protective gas when being discharged after terminating.The protective gas is nitrogen or argon gas.
Preferably, the decompression polymerization in the step 4 is that pressure first is dropped into -80KPa, is reacted 0.5-2.5 hours；
Pressure is dropped into -200KPa again, is reacted 0.5-2.5 hours.
Wherein, the modified inorganic nano silicate in step 3, is prepared from using following methods：
A1, the N,N-dimethylformamide (No. CAS in 50-200ml：The silicate nano of 1-10g is added in 68-12-2)
Particle is made into suspension X；
A2,1-10g silane couplers gamma-aminopropyl-triethoxy-silane and 1-10g acid anhydrides are dispersed in 50-
In the DMF solution of 500ml, 1-5h is stirred at 20-80 DEG C, obtain solution Y；
A3, to suspension X and 1-10ml water obtained in step A1 is added in the solution Y of step A2, stir 1-5h, separate,
Washed with alcohol, obtained modified inorganic nano silicate.
The silicate nano particle is one kind or its mixture in mica, talcum and montmorillonite.It is laminated structure, piece
Thickness degree 1-5nm, 0.1-100 μm of lamella diameter.
The coupling agent is, silane coupler or titanate coupling agent.Silane coupler can select KH550, KH560,
The silane coupler of the models such as KH570, KH792, DL602, DL171.
The acid anhydrides is trihemellitic acid acid anhydride (No. CAS:552-30-7), succinic anhydride (No. CAS:108-30-5) with adjacent benzene two
Formic anhydride (No. CAS:One kind or its mixture in 85-43-8).
The alcohol is one kind or its mixture in methyl alcohol, ethanol, propyl alcohol and glycerine.Washed 3-5 times with alcohol row.
It is a kind of with the nano combined nylon material for exempting to spray optical property high present invention also offers providing, using above-mentioned side
Method is prepared.
The present invention improves the compatibility of modified inorganic nano silicate and nylon using the method for a step in-situ polymerization,
Be conducive to dispersion of the modified inorganic nano silicate in nylon matrix, purer nylon has more excellent mechanical property, hot property
With exempt to spray optical property high；And the nano combined nylon material preparation process is simple, condition is preferably controlled, and is suitable to industrial metaplasia
Produce, can be widely applied to the production of the plastic casing products such as electric power tool shell, automotive upholstery and household electrical appliance.
A kind of preparation method with the nano combined nylon material for exempting to spray optical property high of the invention, by one-step method
The nano combined nylon material of in-situ polymerization reduces operation and cost, avoids environmental pollution, and the VOC for reducing material is distributed,
With larger market popularization value.
Nano combined nylon material prepared by the present invention, melt index is：260 DEG C, be 50-100g/ under the conditions of load 5kg
10min。
Specific embodiment
Below by specific embodiment, the present invention is described in detail, but the purposes of these exemplary embodiments and
Purpose is only used for enumerating the present invention, not constitutes any type of any restriction to real protection scope of the invention, more non-to incite somebody to action
Protection scope of the present invention is confined to this.
Raw material preparation example 1
The preparation of modified inorganic nano silicate：
A1, the addition 5g silicate nano particles in the DMF of 100ml, stir, and are made into suspended
Liquid X；
A2, by 5g silane couplers gamma-aminopropyl-triethoxy-silane (i.e.：KH550 coupling agents) and 5g succinic anhydrides it is equal
It is even to be dispersed in the DMF solution of 300ml, 3h is stirred at 60 DEG C, obtain solution Y；
A3, to suspension X and 5ml water obtained in step A1 is added in the solution Y of step A2, stir 3h, separate, use ethanol
Washed, dried, obtained modified inorganic nano silicate.
The silicate nano particle is mica, is laminated structure, lamellar spacing 3nm, 50 μm of lamella diameter.
Embodiment 1
90 parts of caprolactams, 5 parts of water and 5 parts of benzoic acid are mixed；Heat up, programming rate is controlled in 10 DEG C/min,
Started to warm up to 180 DEG C from room temperature.At a temperature of 180 DEG C, 2h is reacted.
Then normal pressure is down to by excluding vapor, adds 1 part of modified inorganic nano silicate, and stirred, then risen
Temperature, programming rate is controlled in 10 DEG C/min, is warming up to 240 DEG C.At a temperature of 240 DEG C, 4h is reacted, obtain prepolymer.
Control pressure is -20KPa, and now distillate temperature is 80 DEG C, is reacted 1 hour；Control pressure is -100KPa again,
Now distillate temperature is 60 DEG C, then is reacted 1 hour.
Reaction terminate after discharging when be filled with nitrogen, you can obtain of the invention with exempting to spray the nano combined of optical property high
Nylon material.
Embodiment 2
Oneself 95 parts of caprolactams, 1 part of water and 4 parts of benzene adipic acids are mixed, regulation pH value is 7.3, heating melting；Will
Frit reaction thing is first warming up to 180 DEG C of reaction 2h, is then down to normal pressure by excluding vapor, adds 1 part of modified inorganic nanometer
Silicate simultaneously stirs, then is warming up to 240 DEG C of reaction 4h, obtains prepolymer.
Control pressure is -20KPa, is reacted 1 hour；Control pressure is -100KPa again, then is reacted 1 hour.
Reaction terminate after discharging when be filled with nitrogen, you can obtain of the invention with exempting to spray the nano combined of optical property high
Nylon material.
Embodiment 3
Oneself 95 parts of caprolactams, 1 part of water and 4 parts of benzene adipic acids are mixed, regulation pH value is 7.3, heating melting；Will
Frit reaction thing is first warming up to 200 DEG C of reaction 2h, is then down to normal pressure by excluding vapor, adds 4 parts of modified inorganic nanometers
Silicate simultaneously stirs, then is warming up to 240 DEG C of reaction 5h, obtains prepolymer.
Control pressure is -20KPa, is reacted 1 hour；Control pressure is -100KPa again, then is reacted 1 hour.
Reaction terminate after discharging when be filled with nitrogen, you can obtain of the invention with exempting to spray the nano combined of optical property high
Nylon material.
Embodiment 4
Oneself 98 parts of caprolactams, 1 part of water and 1 part of amino phenyl acetate are mixed, regulation pH value is 7.7, heating melting；
Frit reaction thing is first warming up to 200 DEG C of reaction 4h, then normal pressure is down to by excluding vapor, adds 2 parts of modified inorganics to receive
Rice silicate simultaneously stirs, then is warming up to 240 DEG C of reaction 3h, obtains prepolymer.
Control pressure is -20KPa, is reacted 1 hour；Control pressure is -100KPa again, then is reacted 1 hour.
Reaction terminate after discharging when be filled with nitrogen, you can obtain of the invention with exempting to spray the nano combined of optical property high
Nylon material.
Modified inorganic nano silicate in embodiment 1-4 is using the modified inorganic nanometer obtained by raw material preparation example 1
Silicate.
If without other special instructions, the part in embodiment 1-4 is weight portion.
The various embodiments described above products obtained therefrom is carried out into performance test, correlated performance test result is as shown in table 1 below.
The properties of product test comparison table of table 1
| Performance | Test method | Unit | Common nylon 6 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Tensile strength | ISO527 | MPa | 51 | 85 | 80 | 90 | 92 |
| Elongation at break | ISO527 | % | 23 | 6 | 8 | 3 | 5 |
| Bending strength | ISO 178 | MPa | 105 | 128 | 135 | 150 | 127 |
| Notch impact strength | ISO179-1 | 4.2 | 4.8 | 5.2 | 4.1 | 5.5 | |
| Unnotched impact strength | ISO179-1 | 31 | 46 | 42 | 55 | 50 | |
| Melt index | ISO1133 | g/10min | 64 | 79 | 82 | 72 | 94 |
| Glossiness | ISO2813 | 43 | 88 | 80 | 85 | 83 | |
| Surface | Visually observe | It is coarse | Minute surface | Minute surface | Minute surface | Minute surface |
Melt index test condition：260 DEG C of temperature, counterweight 5kg.
Preferably, in the present invention, acid anhydrides is the mixture of 40-60wt% trihemellitic acids acid anhydride and 40-60wt% succinic anhydrides；
The organic acid is aminocaproic acid (No. CAS:It is 60-32-2) 1 with benzoic acid Mass ratio：The mixture of (0.5-3).
Raw material preparation example 2
The preparation of modified inorganic nano silicate：
A1, the addition 5g silicate nano particles in the DMF of 100ml, stir, and are made into suspended
Liquid X；
It is A2,5g silane couplers gamma-aminopropyl-triethoxy-silane, 2.5g succinic anhydrides and 2.5g trihemellitic acid acid anhydrides is equal
It is even to be dispersed in the DMF solution of 300ml, 3h is stirred at 60 DEG C, obtain solution Y；
A3, to suspension X and 5ml water obtained in step A1 is added in the solution Y of step A2, stir 3h, separate, use ethanol
Washed, dried, obtained modified inorganic nano silicate.
The silicate nano particle is mica, is laminated structure, lamellar spacing 3nm, 50 μm of lamella diameter.
Embodiment 5
Method is with embodiment 1, difference：Modified inorganic nano silicate is using modified obtained by raw material preparation example 2
Inorganic nano silicate.
Raw material preparation example 3
The preparation of modified inorganic nano silicate：
A1, the addition 5g silicate nano particles in the DMF of 100ml, stir, and are made into suspended
Liquid X；
A2,5g silane couplers gamma-aminopropyl-triethoxy-silane and 5g trihemellitic acid acid anhydrides are dispersed in 300ml's
In DMF solution, 3h is stirred at 60 DEG C, obtain solution Y；
Suspension X and 5ml water obtained in step A1 is added in A3, the solution Y of step A2,3h is stirred, separated, entered with ethanol
Row washing, drying obtains modified inorganic nano silicate.
The silicate nano particle is mica, is laminated structure, lamellar spacing 3nm, 50 μm of lamella diameter.
Embodiment 6
Method is with embodiment 1, difference：Modified inorganic nano silicate is using modified obtained by raw material preparation example 3
Inorganic nano silicate.
Embodiment 7
90 parts of caprolactams, 5 parts of water and 5 parts of aminocaproic acids are mixed；Heat up, programming rate control 10 DEG C/
Min, starts to warm up to 180 DEG C from room temperature.At a temperature of 180 DEG C, 2h is reacted.
Then normal pressure is down to by excluding vapor, adds the modified inorganic nanometer silicic acid obtained by 1 part of raw material preparation example 1
Salt, and stir, then heat up, programming rate is controlled in 10 DEG C/min, is warming up to 240 DEG C.At a temperature of 240 DEG C, 4h is reacted,
Obtain prepolymer.
Control pressure is -20KPa, and now distillate temperature is 80 DEG C, is reacted 1 hour；Control pressure is -100KPa again,
Now distillate temperature is 60 DEG C, then is reacted 1 hour.
Reaction terminate after discharging when be filled with nitrogen, you can obtain of the invention with exempting to spray the nano combined of optical property high
Nylon material.
Embodiment 8
90 parts of caprolactams, 5 parts of water and 3 parts of benzoic acid, 2 parts of aminocaproic acids are mixed；Heat up, programming rate control
In 10 DEG C/min, started to warm up to 180 DEG C from room temperature.At a temperature of 180 DEG C, 2h is reacted.
Then normal pressure is down to by excluding vapor, adds the modified inorganic nanometer silicic acid obtained by 1 part of raw material preparation example 1
Salt, and stir, then heat up, programming rate is controlled in 10 DEG C/min, is warming up to 240 DEG C.At a temperature of 240 DEG C, 4h is reacted,
Obtain prepolymer.
Control pressure is -20KPa, and now distillate temperature is 80 DEG C, is reacted 1 hour；Control pressure is -100KPa again,
Now distillate temperature is 60 DEG C, then is reacted 1 hour.
Reaction terminate after discharging when be filled with nitrogen, you can obtain of the invention with exempting to spray the nano combined of optical property high
Nylon material.
Table 2：Properties of product test comparison table
| Performance | Test method | Unit | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Tensile strength | ISO527 | MPa | 92 | 84 | 87 | 91 |
| Bending strength | ISO 178 | MPa | 139 | 126 | 125 | 136 |
| Notch impact strength | ISO179-1 | 5.5 | 4.5 | 4.7 | 5.4 | |
| Unnotched impact strength | ISO179-1 | 52 | 45 | 44 | 53 | |
| Melt index | ISO1133 | g/10min | 88 | 73 | 80 | 86 |
| Glossiness | ISO2813 | 89 | 84 | 86 | 89 | |
| Surface | Visually observe | Minute surface | Minute surface | Minute surface | Minute surface |
Melt index test condition：260 DEG C of temperature, counterweight 5kg.
The present invention improves the compatibility of modified inorganic nano silicate and nylon using the method for a step in-situ polymerization,
Be conducive to dispersion of the modified inorganic nano silicate in nylon matrix, purer nylon has more excellent mechanical property, hot property
With exempt to spray optical property high；And the nano combined nylon material preparation process is simple, condition is preferably controlled, and is suitable to industrial metaplasia
Produce, can be widely applied to the production of the plastic casing products such as electric power tool shell, automotive upholstery and household electrical appliance.
Claims (10)
1. a kind of preparation method with the nano combined nylon material for exempting to spray optical property high, comprises the steps：
Step one, caprolactam, water and organic acid are mixed；
Step 2, it is warming up to 180-230 DEG C, reacts 1-5h；
Step 3, addition modified inorganic nano silicate, are warming up to 240-280 DEG C, react 1-5h, obtain prepolymer；
Step 4, polymerization that above-mentioned prepolymer depressurizes, obtain nano combined nylon material.
2. the preparation method with the nano combined nylon material for exempting to spray optical property high described in claim 1, its feature exists
In：The quality of caprolactam described in step one, water and organic acid is：(90-100):(0.5-8):(0.5-8).
3. the preparation method with the nano combined nylon material for exempting to spray optical property high described in claim 1, its feature exists
In：Organic acid described in step one is the organic matter containing carboxyl, such as aminocaproic acid, benzoic acid, octanoic acid, adipic acid, ethanedioic acid
With the one kind in amion acetic acid or its mixture.
4. the preparation method with the nano combined nylon material for exempting to spray optical property high described in claim 1, its feature exists
In：Step 2 is to be started to warm up to 180-230 DEG C from room temperature, and keeping temperature, control pressure is 0-100KPa, reacts 1-5h；Enter
Preferably, programming rate is controlled in 1-20 DEG C/min one step；Stress control is in 20-80KPa.
5. the preparation method with the nano combined nylon material for exempting to spray optical property high described in claim 1, its feature exists
In：The addition of modified inorganic nano silicate accounts for the 0.05-5wt% of caprolactam in step 3.
6. the preparation method with the nano combined nylon material for exempting to spray optical property high described in claim 1, its feature exists
In：Step 3 is to add modified inorganic nano silicate, is warming up to 240-280 DEG C, and keeping temperature, control pressure is 0-
100KPa, reacts 1-5h；It is further preferred that programming rate control is in 1-20 DEG C/min；Stress control is in 20-80KPa.
7. the preparation method with the nano combined nylon material for exempting to spray optical property high described in claim 1, its feature exists
In：Decompression polymerization in the step 4 is that pressure first is dropped into -80KPa, is reacted 0.5-2.5 hours；Pressure is declined again
To -200KPa, react 0.5-2.5 hours.
8. the preparation side with the nano combined nylon material for exempting to spray optical property high any one of claim 1-7
Method, it is characterised in that the modified inorganic nano silicate in step 3, is prepared from using following methods：
A1, in the N,N-dimethylformamide of 50-200ml add 1-10g silicate nano particle be made into suspension X；
A2,1-10g coupling agents and 1-10g acid anhydrides are dispersed in the DMF solution of 50-500ml,
20-80 DEG C of stirring 1-5h, obtains solution Y；
A3, to suspension X and 1-10ml water obtained in step A1 is added in the solution Y of step A2, stir 1-5h, separate, use alcohol
Washed, dried, obtained the modified inorganic nano silicate.
9. the preparation method with the nano combined nylon material for exempting to spray optical property high described in claim 8, its feature exists
In：Acid anhydrides described in step A2 is one kind or its mixture in trihemellitic acid acid anhydride, succinic anhydride and phthalic anhydride；The idol
Connection agent is silane coupler or titanate coupling agent.
10. a kind of with the nano combined nylon material for exempting to spray optical property high, using any one of claim 1-9 method system
It is standby and obtain.
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| CN108299820A (en) * | 2018-02-12 | 2018-07-20 | 广东新会美达锦纶股份有限公司 | One kind is exempted to spray 6 composite material of nano-nylon |
| CN108384228A (en) * | 2018-02-12 | 2018-08-10 | 广东新会美达锦纶股份有限公司 | A kind of preparation method for exempting to spray 6 composite material of nano-nylon |
| CN110540748A (en) * | 2019-10-14 | 2019-12-06 | 广东圆融新材料有限公司 | Spraying-free polyamide 11 material and preparation method thereof |
| CN110551390A (en) * | 2019-10-23 | 2019-12-10 | 广东圆融新材料有限公司 | High-toughness spraying-free polyamide 6 material and preparation method thereof |
| CN110564145A (en) * | 2019-10-12 | 2019-12-13 | 广东圆融新材料有限公司 | Spraying-free polyamide 6 material and preparation method thereof |
| CN110628211A (en) * | 2019-10-18 | 2019-12-31 | 广东圆融新材料有限公司 | Spraying-free polyamide 66/6 material and preparation method thereof |
| CN110669334A (en) * | 2019-10-25 | 2020-01-10 | 广东圆融新材料有限公司 | High-toughness spraying-free polyamide 66 material and preparation method thereof |
| CN110684191A (en) * | 2019-10-18 | 2020-01-14 | 广东圆融新材料有限公司 | Spraying-free polyamide 66 material and preparation method thereof |
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| CN111848949A (en) * | 2020-07-30 | 2020-10-30 | 吴光辉 | Reinforced nylon plate based on silicon-aluminum-based hollow microspheres and preparation process thereof |
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| CN108384228A (en) * | 2018-02-12 | 2018-08-10 | 广东新会美达锦纶股份有限公司 | A kind of preparation method for exempting to spray 6 composite material of nano-nylon |
| CN108299820A (en) * | 2018-02-12 | 2018-07-20 | 广东新会美达锦纶股份有限公司 | One kind is exempted to spray 6 composite material of nano-nylon |
| CN110564145A (en) * | 2019-10-12 | 2019-12-13 | 广东圆融新材料有限公司 | Spraying-free polyamide 6 material and preparation method thereof |
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| CN110684191A (en) * | 2019-10-18 | 2020-01-14 | 广东圆融新材料有限公司 | Spraying-free polyamide 66 material and preparation method thereof |
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| CN110551390B (en) * | 2019-10-23 | 2022-03-25 | 广东圆融新材料有限公司 | High-toughness spraying-free polyamide 6 material and preparation method thereof |
| CN110698851A (en) * | 2019-10-24 | 2020-01-17 | 广东圆融新材料有限公司 | High-toughness spraying-free polyamide 11 material and preparation method thereof |
| CN110698851B (en) * | 2019-10-24 | 2022-03-25 | 广东圆融新材料有限公司 | High-toughness spraying-free polyamide 11 material and preparation method thereof |
| CN110669334B (en) * | 2019-10-25 | 2022-03-25 | 广东圆融新材料有限公司 | High-toughness spraying-free polyamide 66 material and preparation method thereof |
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| CN110698848B (en) * | 2019-10-28 | 2022-03-25 | 广东圆融新材料有限公司 | High-toughness spray-free polyamide 66/6 material and preparation method thereof |
| CN110698848A (en) * | 2019-10-28 | 2020-01-17 | 广东圆融新材料有限公司 | High-toughness spray-free polyamide 66/6 material and preparation method thereof |
| CN111848949A (en) * | 2020-07-30 | 2020-10-30 | 吴光辉 | Reinforced nylon plate based on silicon-aluminum-based hollow microspheres and preparation process thereof |
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