CN110229328A - A kind of preparation method and application of nylon powder - Google Patents
A kind of preparation method and application of nylon powder Download PDFInfo
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- CN110229328A CN110229328A CN201910490117.5A CN201910490117A CN110229328A CN 110229328 A CN110229328 A CN 110229328A CN 201910490117 A CN201910490117 A CN 201910490117A CN 110229328 A CN110229328 A CN 110229328A
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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
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
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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
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
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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
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- Polymers & Plastics (AREA)
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- Life Sciences & Earth Sciences (AREA)
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Abstract
The present invention relates to a kind of preparation method and applications of nylon powder, it is uniformly mixed by hexamethylene diamine, decamethylene diamine, adipic acid, decanedioic acid, dodecanedioic acid and caprolactam by different mass fraction proportions, it adds additive and carries out the obtained nylon resin of polymerization reaction, then nylon powder is made through machinery powder or chemical powdering, the nylon coated buckle as made from this product has dyeing kinetics controllable, and color is gorgeous, and color fastness is high, the advantages that at low cost, can be widely applied to underwear nylon coated buckle industry.
Description
Technical field
The invention belongs to nylon material technical field, in particular to a kind of preparation method and application of nylon powder.
Background technique
Underwear is buckled with encapsulated, using nylon coated, has nontoxic, antirust, salt spray resistance, coating gorgeous, easy dyeing, color fastness
The features such as high, is widely applied in the encapsulated field of buckleing of underwear.At present mainly based on external nylon 11, also there is nylon 1010 in the country
It is applied to the field, but high expensive with the nylon powder of Nylon 1012 preparation, is unfavorable for promoting.
Summary of the invention
The technical issues of solution: the application is mainly to propose a kind of preparation method and application of nylon powder, is solved existing
High expensive present in technology is unfavorable for the technical problems such as popularization, is easy to get with raw material, at low cost, function admirable, convenient for system
Standby feature.
Technical solution:
A kind of preparation method of nylon powder, includes the following steps:
Step 1: weighing hexamethylene diamine, decamethylene diamine, adipic acid, decanedioic acid, dodecanedioic acid and caprolactam raw material, the raw material
Specific weighing mode is to weigh hexamethylene diamine by mass fraction proportion: decanedioic acid: caprolactam=(29 ~ 32): (51 ~ 58): (10 ~
Or hexamethylene diamine 20): dodecanedioic acid: caprolactam=(24 ~ 30): (56 ~ 65): (5 ~ 15) or hexamethylene diamine: decanedioic acid: adipic acid=
(37 ~ 38): (48 ~ 57): (6 ~ 14) or hexamethylene diamine: dodecanedioic acid: adipic acid=(34 ~ 36): (53 ~ 63): (3 ~ 11) or oneself two
Amine: decamethylene diamine: decanedioic acid=(26 ~ 33): (4 ~ 14): (60 ~ 63) or hexamethylene diamine: decamethylene diamine: dodecanedioic acid=(23 ~ 30): (4 ~
13): (64 ~ 66) or decamethylene diamine: decanedioic acid: caprolactam=(4 ~ 14): (6 ~ 16): (70 ~ 90) or decamethylene diamine: dodecanedioic acid:
Caprolactam=(2 ~ 10): (3 ~ 11): (75 ~ 95)；
Step 2: the additive of adding raw materials gross mass 2.1-7.5% in the feed, is uniformly mixed to obtain mixture；
Step 3: mixture is put into autoclave, seal, nitrogen displacement air in kettle is discharged, inflated with nitrogen to 0.05-
0.2MPa, heating, when material temperature rises to 200 DEG C, pressure starts heat-insulation pressure keeping, time 2 h when reaching 1.2MPa；
Step 4: then uniformly letting out pressure to normal pressure in 2 hours, and keep the temperature 2 hours under normal pressure；
Step 5: being filled with nitrogen to 0.2MPa, outlet valve is opened, material, which is infused, takes the lead, cold rinse bank, pelleter pelletizing, through vacuum
Drying is to get nylon resin；
Step 6: nylon powder is made by machinery powder or chemical powdering in nylon resin.
As a preferred technical solution of the present invention: additive is antioxidant, brightener, at surface in the second step
Manage agent and molecular weight regulator.
As a preferred technical solution of the present invention: the antioxidant is compound antioxidant, is by mass fraction proportion
Phosphorous acid: antioxidant 1098: irgasfos 168=(1 ~ 5): (5 ~ 10): (5 ~ 10), additional amount are the 1 ~ 3% of mixture total mass.
As a preferred technical solution of the present invention: the brightener is compounding brightener, is by mass fraction proportion
Polyether-modified water-soluble silicon oil: styrax: calcium stearate=(0.1 ~ 0.5): (1 ~ 5): (1 ~ 5), additional amount are the total matter of mixture
The 0.5 ~ 2% of amount.
As a preferred technical solution of the present invention: the surface treating agent is the one of anionic surfactant
Kind or several compounds, the anionic surfactant such as neopelex, additional amount are the total matter of mixture
The 0.5 ~ 2% of amount.
As a preferred technical solution of the present invention: the molecular weight regulator is adipic acid, and additional amount is mixture
The 0.1 ~ 0.5% of gross mass.
As a preferred technical solution of the present invention: mixing velocity is 1000-2000r/min in the second step, is mixed
The conjunction time is 2-5min, and pressure release speed is 0.02-0.12MPa/min in the 4th step, is dried under vacuum to moisture content < in the 5th step
0.5%。
As a preferred technical solution of the present invention: mechanical milling step is that nylon resin is added in the 6th step
The titanium dioxide of the antioxidant 1010 of 1% mass ratio and 10% mass ratio, it is modified through extruder, by deep cooling crush after drying, powder is sieved,
Nylon powder is made.
As a preferred technical solution of the present invention: chemical powdering step is to put into nylon resin in the 6th step
Autoclave is added the antioxidant 1010 of 1% mass ratio and the titanium dioxide of 10% mass ratio, 96% ethyl alcohol, the ethyl alcohol is added
Weight is 3-4 times of nylon resin weight, and through 170-180 DEG C of high-temperature digestion, cooling is precipitated, and is centrifugated, drying, sieves powder, system
Obtain nylon powder.
In addition, the present invention also provides the nylon powders that the preparation method of the nylon powder is prepared to prepare nylon
The encapsulated application buckled.
The utility model has the advantages that the preparation method and application of herein described nylon powder uses above technical scheme and the prior art
It compares, has following technical effect that
1, whole production domesticization of synthetic nylon resin raw material have been showed, not only the performance of nylon resin than originally gets a promotion, and also drops
Low production cost, it is ensured that raw material it is in liberal supply.
2, it is easy to get with raw material, at low cost, function admirable is convenient for the characteristics of preparing.
3,172 ~ 190 DEG C of product fusing point, melt index (230 DEG C, 2.16kg): 40-56 grams/10 minutes, (shore was hard for hardness
Degree): 68-70, toughness: batten doubling is continuous.
4, coating color: color is gorgeous, no white point, without color spot, and coating gloss is high, surface slip.
5, outdoor sunshine 30 days of encapsulated button, color is without substantially changeing.
6, tensile strength 55-75MPa, bending strength 75-95MPa, notch impact strength 45-55J/m, wearability and acidproof
Caustic corrosion performance is good, and wearability coefficient of friction is high lower than 0.2, PV value, and Taber Abrasion 1-3mg/1000 times is surveyed by DIN53754
Abrasion loss 1-3mg, self-lubrication is good and salt spray resistance, oil resistant, resistance to -60 DEG C of low temperature.
Specific embodiment
Below with reference to embodiment, the present invention will be further described.
Embodiment 1
A kind of preparation method of nylon powder, includes the following steps:
Step 1: 87 kilograms of hexamethylene diamine are weighed by mass fraction proportion, and 153 kilograms of decanedioic acid, 60 kilograms of caprolactam, antioxygen
4.5 kilograms of agent, 1.5 kilograms of brightener, 1 kilogram of neopelex, 600 grams of adipic acid, the antioxidant is by phosphorous acid
500 grams, antioxidant 1098 be that 2 kilograms and irgasfos 168 are 2 kilograms and compound, the brightener by 500 grams of calcium stearate,
500 grams and 500 grams of styrax of polyether-modified water-soluble silicon oil compound；
Step 2: being uniformly mixed to obtain mixture, mixing velocity 1000-2000r/min, incorporation time 2-5min；
Step 3: mixture is put into autoclave, seal, nitrogen displacement air in kettle is discharged, inflated with nitrogen is extremely
0.2MPa, heating, when material temperature rises to 200 DEG C, pressure starts heat-insulation pressure keeping, time 2 h when reaching 1.2MPa；
Step 4: then uniformly letting out pressure in 2 hours to normal pressure, pressure release speed is 0.1MPa/min, and is protected under normal pressure
Temperature 2 hours；
Step 5: being filled with nitrogen to 0.2MPa, outlet valve is opened, material, which is infused, takes the lead, cold rinse bank, pelleter pelletizing, through vacuum
Drying is to moisture content < 0.5% to get nylon resin.
Nylon resin product index is as follows:
Fusing point: 175 ~ 185 DEG C
Melt index (230 DEG C, 2.16kg): 50 grams/10 minutes
Hardness (shore hardness): 70
Toughness: batten doubling is continuous.
Step 6: nylon resin to be added to the antioxidant 1010 of 1% mass ratio and the titanium dioxide of 10% mass ratio, through extruder
It is modified, by deep cooling crush after drying, powder is sieved, nylon powder is made；
Step 7: nylon powder is prepared nylon coated buckle, encapsulated button embryo is prepared first, and vibration is entered after then heating embryo
Moving plate, by powder on embryo, the heated band heating of embryo after upper powder, press polish obtains nylon coated buckle, the acidity for being 1% in concentration
In dyestuff, dyed 20 minutes in 80 DEG C, then through washing to obtain the final product.
Testing result is as follows:
Coating color: color is gorgeous, no white point, without color spot, and coating gloss is high, surface slip；Encapsulated button outdoor sunshine 30 days,
Color is without substantially changeing.
Embodiment 2
A kind of preparation method of nylon powder, includes the following steps:
Step 1: 90 kilograms of hexamethylene diamine are weighed by mass fraction proportion, and 180 kilograms of dodecanedioic acid, 30 kilograms of caprolactam,
3.5 kilograms of antioxidant, 2 kilograms of brightener, 0.5 kilogram of neopelex, 800 grams of adipic acid, the antioxidant is by Asia
500 grams of phosphoric acid, 1,098 2 kilograms of antioxidant and 1 kilogram of irgasfos 168 compound, and the brightener is by calcium stearate 500
Gram, 1000 grams of polyether-modified water-soluble silicon oil and 500 grams of styrax compound；
Step 2: being uniformly mixed to obtain mixture, mixing velocity 1000-2000r/min, incorporation time 2-5min；
Step 3: mixture is put into autoclave, seal, nitrogen displacement air in kettle is discharged, inflated with nitrogen is extremely
0.2MPa, heating, when material temperature rises to 200 DEG C, pressure starts heat-insulation pressure keeping, time 2 h when reaching 1.2MPa；
Step 4: then uniformly letting out pressure in 2 hours to normal pressure, pressure release speed is 0.1MPa/min, and is protected under normal pressure
Temperature 2 hours；
Step 5: being filled with nitrogen to 0.2MPa, outlet valve is opened, material, which is infused, takes the lead, cold rinse bank, pelleter pelletizing, through vacuum
Drying is to moisture content < 0.5% to get nylon resin.
Nylon resin product index is as follows:
Fusing point: 1780 ~ 190 DEG C
Melt index (230 DEG C, 2.16kg): 40 grams/10 minutes
Hardness (shore hardness): 68
Toughness: batten doubling is continuous.
Step 6: nylon resin is put into autoclave, the antioxidant 1010 and 10% mass ratio of 1% mass ratio is added
, it is put into 96% ethyl alcohol, the ethyl alcohol weight is 3-4 times of nylon resin weight, through 170-180 DEG C of high-temperature digestion, cooling analysis
Out, it is centrifugated, powder is sieved in drying, and nylon powder is made；
Step 7: nylon powder is prepared nylon coated buckle, encapsulated button embryo is prepared first, and vibration is entered after then heating embryo
Moving plate, by powder on embryo, the heated band heating of embryo after upper powder, press polish obtains nylon coated buckle, the acidity for being 2% in concentration
In dyestuff, dyed 20 minutes in 70 DEG C, then through washing to obtain the final product.
Testing result is as follows:
Coating color: color is gorgeous, no white point, without color spot, and coating gloss is high, surface slip；Encapsulated button outdoor sunshine 30 days,
Color is without substantially changeing.
Embodiment 3
A kind of preparation method of nylon powder, includes the following steps:
Step 1: 114 kilograms of hexamethylene diamine are weighed by mass fraction proportion, and 144 kilograms of decanedioic acid, 42 kilograms of adipic acid, antioxygen
3 kilograms of agent, 1.5 kilograms of brightener, 1.5 kilograms of neopelex, 500 grams of adipic acid, the antioxidant is by phosphorous acid
500 grams, 1,098 2 kilograms of antioxidant and 0.5 kilogram of irgasfos 168 compound, the brightener by 500 grams of calcium stearate,
500 grams and 500 grams of styrax of polyether-modified water-soluble silicon oil compound；
Step 2: being uniformly mixed to obtain mixture, mixing velocity 1000-2000r/min, incorporation time 2-5min；
Step 3: mixture is put into autoclave, seal, nitrogen displacement air in kettle is discharged, inflated with nitrogen is extremely
0.2MPa, heating, when material temperature rises to 200 DEG C, pressure starts heat-insulation pressure keeping, time 2 h when reaching 1.2MPa；
Step 4: then uniformly letting out pressure in 2 hours to normal pressure, pressure release speed is 0.1MPa/min, and is protected under normal pressure
Temperature 2 hours；
Step 5: being filled with nitrogen to 0.2MPa, outlet valve is opened, material, which is infused, takes the lead, cold rinse bank, pelleter pelletizing, cold rinse bank
For cooling down material, brittle state is cooled to by soft tough state, is convenient for blank, it is big to control resin particle for pelleter revolving speed speed
It is small, it is vacuum dried to moisture content < 0.5% to get nylon resin.
Nylon resin product index is as follows:
Fusing point: 172 ~ 182 DEG C
Melt index (230 DEG C, 2.16kg): 56 grams/10 minutes
Hardness (shore hardness): 70
Toughness: batten doubling is continuous.
Step 6: nylon resin to be added to the antioxidant 1010 of 1% mass ratio and the titanium dioxide of 10% mass ratio, through extruder
It is modified, by deep cooling crush after drying, powder is sieved, nylon powder is made；
Step 7: nylon powder is prepared encapsulated button embryo, vibrating disk is entered after then heating embryo, by powder on embryo, on
The heated band heating of embryo after powder, press polish obtains nylon coated buckle, in dense 5% acid dyes, dyes 30 points in 60 DEG C
Clock, then through washing to obtain the final product.
Testing result is as follows:
Coating color: color is gorgeous, no white point, without color spot, and coating gloss is high, surface slip；Encapsulated button outdoor sunshine 30 days,
Color is without substantially changeing.
The important indicator of nylon coated buckle is the dyeing in acid dyes, and nylon coated buckle surface color is equal after dyeing
It is even, cannot there are white point and color spot, therefore, the adjustment of dyeing is particularly important.
The resin fast for dyeing kinetics, the acid dyes aqueous solution of Yao Caiyong low concentration, concentration are controlled 0.5% ~ 1.5%
Between, dyeing temperature controls between 60 ~ 70 DEG C, and dyeing time was controlled at 20 ~ 30 minutes, just can ensure that coating surface dyeing is equal
Uniform color fastness, and it is easy to control the dyeing depth degree of nylon coated buckle.
The resin slow for dyeing kinetics, the acid dyes aqueous solution of Yao Caiyong high concentration, concentration control 1.5% ~ 5% it
Between, dyeing temperature controls between 70 ~ 90 DEG C, and dyeing time was controlled at 20 ~ 30 minutes, just can ensure that coating surface even dyeing
And color fastness.
Above-described embodiment is the part material proportion listed in this patent, be will not enumerate herein.Without departing substantially from
In the case where the application spirit and essence, to modification made by the application method, step or condition and replaces, belong to the application
Range.
Claims (10)
1. a kind of preparation method of nylon powder, it is characterised in that include the following steps:
Step 1: weighing hexamethylene diamine, decamethylene diamine, adipic acid, decanedioic acid, dodecanedioic acid and caprolactam raw material, the raw material
Specific weighing mode is to weigh hexamethylene diamine by mass fraction proportion: decanedioic acid: caprolactam=(29 ~ 32): (51 ~ 58): (10 ~
Or hexamethylene diamine 20): dodecanedioic acid: caprolactam=(24 ~ 30): (56 ~ 65): (5 ~ 15) or hexamethylene diamine: decanedioic acid: adipic acid=
(37 ~ 38): (48 ~ 57): (6 ~ 14) or hexamethylene diamine: dodecanedioic acid: adipic acid=(34 ~ 36): (53 ~ 63): (3 ~ 11) or oneself two
Amine: decamethylene diamine: decanedioic acid=(26 ~ 33): (4 ~ 14): (60 ~ 63) or hexamethylene diamine: decamethylene diamine: dodecanedioic acid=(23 ~ 30): (4 ~
13): (64 ~ 66) or decamethylene diamine: decanedioic acid: caprolactam=(4 ~ 14): (6 ~ 16): (70 ~ 90) or decamethylene diamine: dodecanedioic acid:
Caprolactam=(2 ~ 10): (3 ~ 11): (75 ~ 95)；
Step 2: the additive of adding raw materials gross mass 2.1-7.5% in the feed, is uniformly mixed to obtain mixture；
Step 3: mixture is put into autoclave, seal, nitrogen displacement air in kettle is discharged, inflated with nitrogen to 0.05-
0.2MPa, heating, when material temperature rises to 200 DEG C, pressure starts heat-insulation pressure keeping, time 2 h when reaching 1.2MPa；
Step 4: then uniformly letting out pressure to normal pressure in 2 hours, and keep the temperature 2 hours under normal pressure；
Step 5: being filled with nitrogen to 0.2MPa, outlet valve is opened, material, which is infused, takes the lead, cold rinse bank, pelleter pelletizing, through vacuum
Drying is to get nylon resin；
Step 6: nylon powder is made by machinery powder or chemical powdering in nylon resin.
2. the preparation method of nylon powder according to claim 1, it is characterised in that: additive is antioxygen in the second step
Agent, brightener, surface treating agent and molecular weight regulator.
3. the preparation method of nylon powder according to claim 2, it is characterised in that: the antioxidant is compound antioxidant,
Be phosphorous acid by mass fraction proportion: antioxidant 1098: irgasfos 168=(1 ~ 5): (5 ~ 10): (5 ~ 10), additional amount are mixed
Close the 1 ~ 3% of material gross mass.
4. the preparation method of nylon powder according to claim 2, it is characterised in that: the brightener is compounding brightener,
Be polyether-modified water-soluble silicon oil by mass fraction proportion: styrax: calcium stearate=(0.1 ~ 0.5): (1 ~ 5): (1 ~ 5) adds
Enter 0.5 ~ 2% that amount is mixture total mass.
5. the preparation method of nylon powder according to claim 2, it is characterised in that: the surface treating agent is anion
One or more of compounds of type surfactant, the anionic surfactant such as neopelex, add
Enter 0.5 ~ 2% that amount is mixture total mass.
6. the preparation method of nylon powder according to claim 2, it is characterised in that: the molecular weight regulator for oneself two
Acid, additional amount are the 0.1 ~ 0.5% of mixture total mass.
7. stating the preparation method of nylon powder according to claim 1, it is characterised in that: mixing velocity is in the second step
1000-2000r/min, incorporation time 2-5min, pressure release speed is 0.02-0.12MPa/min in the 4th step, true in the 5th step
Sky is dry to moisture content < 0.5%.
8. the preparation method of nylon powder according to claim 1, it is characterised in that: mechanical milling step in the 6th step
It is modified through extruder for nylon resin to be added to the antioxidant 1010 of 1% mass ratio and the titanium dioxide of 10% mass ratio, it is passed through after drying
Deep cooling crush is crossed, powder is sieved, nylon powder is made.
9. the preparation method of nylon powder according to claim 1, it is characterised in that: chemical powdering step in the 6th step
For nylon resin is put into autoclave, the antioxidant 1010 of 1% mass ratio and the titanium dioxide of 10% mass ratio is added, is added
96% ethyl alcohol, the ethyl alcohol weight are 3-4 times of nylon resin weight, and through 170-180 DEG C of high-temperature digestion, cooling is precipitated, centrifugation
Powder is sieved in separation, drying, and nylon powder is made.
10. the nylon powder that a kind of preparation method of nylon powder described in claim 1 is prepared is preparing nylon coated buckle
On application.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910490117.5A CN110229328A (en) | 2019-06-06 | 2019-06-06 | A kind of preparation method and application of nylon powder |
| LU102280A LU102280B1 (en) | 2019-06-06 | 2020-06-02 | Method for producing nylon powder and its use |
| PCT/CN2020/094029 WO2020244523A1 (en) | 2019-06-06 | 2020-06-02 | Method for preparing nylon powder and use thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910490117.5A CN110229328A (en) | 2019-06-06 | 2019-06-06 | A kind of preparation method and application of nylon powder |
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| CN110229328A true CN110229328A (en) | 2019-09-13 |
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|---|---|
| CN (1) | CN110229328A (en) |
| LU (1) | LU102280B1 (en) |
| WO (1) | WO2020244523A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110724378A (en) * | 2019-09-17 | 2020-01-24 | 南京工程学院 | 3D laser printing material and preparation method thereof |
| WO2020244523A1 (en) * | 2019-06-06 | 2020-12-10 | 南京工程学院 | Method for preparing nylon powder and use thereof |
| CN112827606A (en) * | 2021-01-04 | 2021-05-25 | 惠州鸿为新材料科技有限公司 | Preparation method of novel long carbon chain nylon powder |
| CN113105858A (en) * | 2021-04-12 | 2021-07-13 | 惠州鸿为新材料科技有限公司 | Nylon glue for preventing screw from loosening |
| CN113501977A (en) * | 2021-08-05 | 2021-10-15 | 惠州鸿为新材料科技有限公司 | Preparation method of low-cost high-performance nylon powder |
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- 2020-06-02 LU LU102280A patent/LU102280B1/en active IP Right Grant
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| CN109824887A (en) * | 2019-01-31 | 2019-05-31 | 珠海派锐尔新材料有限公司 | A kind of preparation method of nylon-type microsphere powder |
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| LU102280B1 (en) | 2020-12-14 |
| WO2020244523A1 (en) | 2020-12-10 |
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Application publication date: 20190913 |