CN104829840A - Preparation method of caprolactam-cyclotetrasiloxane co-polymer and powder thereof - Google Patents
Preparation method of caprolactam-cyclotetrasiloxane co-polymer and powder thereof Download PDFInfo
- Publication number
- CN104829840A CN104829840A CN201510007179.8A CN201510007179A CN104829840A CN 104829840 A CN104829840 A CN 104829840A CN 201510007179 A CN201510007179 A CN 201510007179A CN 104829840 A CN104829840 A CN 104829840A
- Authority
- CN
- China
- Prior art keywords
- hexanolactam
- cyclotetrasiloxane
- powder
- preparation
- multipolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Silicon Polymers (AREA)
Abstract
The invention relates to the field of high-molecular materials and provides a preparation method of a caprolactam-cyclotetrasiloxane co-polymer and a powder thereof for solving a problem of a high industrial cost of nylon 12 in the field of 3D printing in the prior art. The relative mechanical performances of the co-polymer are described as follows: tensile strength: 25-60 MPa, elongation at break: 15-150%, and water absorption: 2.5-0.4%. The particle size of the powder is 10-80 [mu]m. The powder of the co-polymer is excellent in thermodynamic performances, size stability performances and transparence performances and the like, is low in production and use cost, is homogeneous in particle size and can be applied in the field of 3D printing (with laser sintering).
Description
Technical field
The present invention relates to polymeric material field, relate in particular to one and be applicable to 3D printing hexanolactam-cyclotetrasiloxane (D4) multipolymer in (laser sintering technology SLS) field and the preparation method of powder thereof.
Background technology
3D prints also known as increasing material manufacture (Additive Manufacturing, AM), and belong to the one of Rapid Prototyping technique, it is the technology directly manufacturing almost arbitrary shape 3D solid based on a kind of digital model file.3D prints and uses powdery metal or plastics etc. can jointing material, carrys out constructed object, i.e. " layer appearance method " by the mode of successively stacking accumulation.In 3D printing field, plastics are conventional printed materials, and wherein nylon is most important a kind of printed material.
Nylon is also one of the engineering plastics of most widespread use the earliest, can be prepared, also can synthesize with omega-amino acid or cyclic lactam by diamine and diprotic acid.According to the difference containing carbonatoms in diamine and diprotic acid or amino acid, multiple different polymeric amide can be obtained, as PA6, PA66, PA11, PA12, PA46, PA610, PA1010 and a lot of kind such as semi-aromatic nylon (PA6T) and extraordinary nylon.The intramolecular amide group of nylon 6 can form good hydrogen bond structure, and Intermolecular Forces makes it have greatly the advantages such as intensity is high, good toughness, wear resistance are good.But amide group in nylon 6 molecule simultaneously also easily and water molecules formation hydrogen bond make it have stronger water-absorbent, cause product poor dimensional stability in use; And crystallization velocity and degree of crystallinity higher, in SLS laser sintered (3D prints field) process, there will be the problem such as warpage, deformation retract, thus make its also cannot be applied to separately at present 3D print field.Application at present in 3D printing field, nylon 12 because its water-intake rate is low, good stability of the dimension and occupy about 95% share, but the industrial cost of nylon 12 is higher, is unfavorable for the popularization of SLS technology.
Application number is that the Chinese patent of CN201410182754.3 discloses a kind of polypropylene heterophasic copolymer resin and its preparation method and application that can be used for the high rubber content that 3D prints, and this disclosure of the invention is a kind of can be used for polypropylene heterophasic copolymer resin of the high rubber content that 3D prints and its preparation method and application.But compared with polypropylene material, the fusing point of nylon is high, heat-resistant stability good, intensity is high, wear resistance is good, good stability of the dimension.
Summary of the invention
For solving the problem that the industrial cost of nylon 12 is higher in 3D printing field at present, the present invention proposes the preparation method of a kind of hexanolactam-cyclotetrasiloxane multipolymer and powder thereof, produce without any hazardous and noxious substances such as waste gas waste water in preparation whole process, reaction required time is short, transformation efficiency is high, molecular weight stabilizers, and cost is low.
The present invention is achieved by the following technical solutions: the preparation method of a kind of hexanolactam-cyclotetrasiloxane multipolymer and powder thereof is following steps:
(1) hexanolactam is heated to molten state at reduced pressure conditions;
At reduced pressure, hexanolactam heating 130 ~ 140 DEG C is become molten state, and the moisture in constantly backflow removing monomer.
As preferably, the vacuum tightness of decompression is less than or equal to 0.1Mpa, keeps return velocity at 30/min ~ 50 droplet/min.
(2) add catalyzer and obtain active anion monomer;
Temperature is risen to 135 ~ 150 DEG C, add catalyzer and obtain active anion monomer, described catalyzer is selected from one or more in NaOH, KOH, sodium caprolactam(ate), hexanolactam potassium, sodium ethylate, sodium methylate etc., the mol ratio of catalyzer and hexanolactam is 0.001 ~ 0.015: 1, be preferably 0.003 ~ 0.01: 1, be more preferably 0.007 ~ 0.01: 1.
As preferably, this process will prevent air from entering reaction system, oxide anion monomer.
(3) under anhydrous and oxygen-free condition, add activator, add cyclotetrasiloxane after stirring again and obtain prepolymer, then polyreaction in mould prepolymer being cast to preheating, obtain hexanolactam-cyclotetrasiloxane multipolymer;
As preferably, the water produced in first reduced-pressure backflow 10 ~ 30min removing step (2), then under anhydrous and oxygen-free condition, add activator stir 2 ~ 0.5min, the temperature adding activator is 135 ~ 150 DEG C., add cyclotetrasiloxane after stirring again and obtain prepolymer, cast in after stirring in the mould of preheating in advance, the preheating temperature of casting die is 150 ~ 170 DEG C.Polyreaction at 140 ~ 170 DEG C is also incubated 20 ~ 60min and obtains hexanolactam-cyclotetrasiloxane multipolymer.
The mol ratio of cyclotetrasiloxane and hexanolactam is 0.005 ~ 0.10: 1, is preferably 0.02 ~ 0.08: 1, is more preferably 0.04 ~ 0.07: 1.
Described activator is selected from toluene 2; one or more in 4-vulcabond (TDI), hexamethylene diisocyanate (HMDI), cyclohexyl carboxyamide base hexanolactam (CCC), benzoyl caprolactam (PCC), hexamethylene diisocyanate (HDI), '-diphenylmethane diisocyanate (MDI), diphenyl carbonate; the mol ratio of activator and hexanolactam is 0.0005 ~ 0.0040: 1; be preferably 0.0015 ~ 0.0030: 1, be more preferably 0.0020 ~ 0.0025: 1.
As preferably, stir after adding activator, churning time thereupon cyclotetrasiloxane ratio increase and reduce, preferred churning time is 1min.After adding cyclotetrasiloxane, the reaction times is less than or equal to 1min.
As preferably, in the process of above-mentioned reduced-pressure backflow, vacuum tightness is less than or equal to 0.1MPa, the speed of evacuation of vacuum pump will be controlled simultaneously, keep return velocity at 30/min ~ 50 droplet/min, after adding catalyzer, because temperature of reaction raises to some extent, the speed of evacuation suitably should be reduced to ensure that return velocity is stablized.
(4) hexanolactam-cyclotetrasiloxane multipolymer prepared by step (3) is joined in the container that formic acid is housed dissolve;
As preferably, the usage quantity of formic acid is the amount making solute dissolves, and makes it under magnetic stirring to dissolve completely.
(5) solution that step (4) obtains is poured into be equipped with in the container of precipitation agent, be stirred to till precipitation no longer separates out;
Described precipitation agent is selected from the miscible solvent with formic acid, precipitation agent be preferably selected from distilled water, ethanol, acetone, tetrahydrofuran (THF), benzene, toluene, glycerine, ethyl acetate, ether one or more, as preferably, the usage quantity of precipitation agent and the volume ratio of formic acid are 2 ~ 6: 1.
(6) product step (5) obtained through pulverize at low temperature or grinding, obtains hexanolactam-cyclotetrasiloxane copolymer powder by the solid drying that obtains after filtration under diminished pressure.
As preferably, the product with precipitation that step (5) obtains dries the 105 DEG C of vacuum-dryings of rear elder generation by the solid obtained after filtration under diminished pressure, then pulverize at low temperature or grinding sieve, low temperature range is-170 DEG C ~-40 DEG C, and the hexanolactam obtained-cyclotetrasiloxane copolymer powder particle diameter is 10 ~ 80 microns.
As preferably, filter the filtrate obtained and carry out separation re-using through methods such as extraction, underpressure distillation again.
The present invention considers hexanolactam and the cyclotetrasiloxane similarity in configuration aspects, hexanolactam-cyclotetrasiloxane multipolymer has been prepared by the mode of anionic copolymerization, described copolymer powder passes through the method for solution precipitating and pulverize at low temperature, by multipolymer through stirring and dissolving in formic acid, slowly pour into afterwards in precipitation agent, and rapid stirring makes it Precipitation, after again pulverize at low temperature screening.The method reaction required time of anionic copolymerization is short, and transformation efficiency high molecular is stablized, and produces in preparation whole process without any hazardous and noxious substances such as waste gas waste water.
Hexanolactam of the present invention-cyclotetrasiloxane multipolymer and the application of powder in 3D printing field thereof.The invention provides the preparation method of a kind of partial properties and the close multipolymer of nylon 120 points and powder thereof, the multipolymer obtained and powder tensile strength thereof are 25 ~ 60Mpa, elongation at break is 15% ~ 150%, powder diameter is 10 ~ 80 microns, transparency and pure nylon 12 is basically identical and cost is lower, can use as the substitute of nylon 12 to a certain extent.
Compared with prior art, the invention has the beneficial effects as follows:
(1) the method applied in the present invention, resultant velocity is fast and nontoxic, safety non-pollution, meets the requirement of Green Chemistry;
(2) product of the present invention's synthesis can use as the substitute of nylon 12, and cost is lower simultaneously, is only 1/5th of nylon 12 cost.
Embodiment
Below by embodiment, the present invention is described in further detail.
Embodiment 1
Under the condition of vacuum tightness 0.1Mpa, 1mol hexanolactam is heated to 130 DEG C and becomes molten state, and the moisture in constantly backflow removing monomer.Temperature is risen to 135 DEG C, add 0.002mol catalyst n aOH, obtain active anion monomer, this process will prevent air from entering reaction system, oxide anion monomer, then reduced-pressure backflow 30min removes the water that catalyzed reaction produces, return velocity is 30/min, then adds 0.0015mol activator TDI stirring 2min, then adds the cyclotetrasiloxane monomer of 0.005mol, cast in after stirring in the mould of preheating in advance, the preheating temperature of mould is 170 DEG C.Polyreaction at 170 DEG C is also incubated 60min and obtains hexanolactam-cyclotetrasiloxane multipolymer.Afterwards above-mentioned hexanolactam-cyclotetrasiloxane multipolymer is placed in the beaker that formic acid is housed, makes it under magnetic stirring to dissolve completely; Above-mentioned solution is slowly poured into and is equipped with in the beaker of ethanol, and constantly stir until precipitation is separated out completely, till no longer increasing.The above-mentioned product with precipitation is dried the 105 DEG C of vacuum-dryings of rear elder generation by the solid obtained after filtration under diminished pressure, obtains through-40 DEG C of pulverizing hexanolactam-cyclotetrasiloxane copolymer powder that particle diameter is 20 microns more afterwards.
Filter the filtrate obtained and carry out separation re-using through methods such as extraction, underpressure distillation again.
Through Mechanics Performance Testing, the tensile strength of the hexanolactam that embodiment 1 obtains-cyclotetrasiloxane multipolymer and powder thereof is 25MPa, and elongation at break is 55%.
Embodiment 2
Under the condition of vacuum tightness 0.05Mpa, 1mol hexanolactam is heated to 134 DEG C and becomes molten state, and the moisture in constantly backflow removing monomer.Temperature is risen to 138 DEG C, add 0.004mol catalyzer KOH, obtain active anion monomer, this process will prevent air from entering reaction system, oxide anion monomer, then reduced-pressure backflow 25min removes the water that catalyzed reaction produces, return velocity is 34/min, then adds activator 0.002mol activator HMDI stirring 1.5min, then adds cyclotetrasiloxane 0.015mol, cast in after stirring in the mould of preheating in advance, the preheating temperature of mould is 166 DEG C.Polyreaction at 166 DEG C is also incubated 40min and obtains hexanolactam-cyclotetrasiloxane multipolymer.Afterwards above-mentioned hexanolactam-cyclotetrasiloxane multipolymer is placed in the beaker that formic acid is housed, makes it under magnetic stirring to dissolve completely; Above-mentioned solution is slowly poured into and is equipped with in the beaker of acetone, and constantly stir until precipitation is separated out completely, till no longer increasing.Dry rear elder generation 105 DEG C vacuum-dryings with the product after precipitation by the solid obtained after filtration under diminished pressure by above-mentioned, obtain through-100 DEG C of grindings hexanolactam-cyclotetrasiloxane copolymer powder that particle diameter is 35 microns more afterwards.
Filter the filtrate obtained and carry out separation re-using through methods such as extraction, underpressure distillation again.
Through Mechanics Performance Testing, the tensile strength of the hexanolactam that embodiment 2 obtains-cyclotetrasiloxane multipolymer and powder thereof is 32MPa, and elongation at break is 65%.
Embodiment 3
Under the condition of vacuum tightness 0.01Mpa, 1mol hexanolactam is heated to 136 DEG C and becomes molten state, and the moisture in constantly backflow removing monomer.Temperature is risen to 140 DEG C, add catalyzer 0.008mol hexanolactam potassium, obtain active anion monomer, this process will prevent air from entering reaction system, oxide anion monomer.Then reduced-pressure backflow 20min removes the water that catalyzed reaction produces, return velocity is 38/min, add 0.0027mol activator PCC again and stir 1.0min, add cyclotetrasiloxane 0.03mol again, cast in the mould of preheating in advance after stirring, the preheating temperature of mould is 160 DEG C, and polyreaction at 160 DEG C is also incubated 30min, obtains hexanolactam-cyclotetrasiloxane multipolymer.Afterwards above-mentioned hexanolactam-cyclotetrasiloxane multipolymer is placed in the beaker that formic acid is housed, makes it under magnetic stirring to dissolve completely; Above-mentioned solution is slowly poured into and is equipped with in the beaker of tetrahydrofuran (THF), and constantly stir until precipitation is separated out completely.The above-mentioned product with precipitation is dried the 105 DEG C of vacuum-dryings of rear elder generation by the solid obtained after filtration under diminished pressure, obtains through-170 DEG C of pulverizing hexanolactam-cyclotetrasiloxane copolymer powder that particle diameter is 50 microns more afterwards.
Filter the filtrate obtained and carry out separation re-using through methods such as extraction, underpressure distillation again.
Through Mechanics Performance Testing, the tensile strength of the hexanolactam that embodiment 3 obtains-cyclotetrasiloxane multipolymer and powder thereof is 41MPa, and elongation at break is 105%.
Embodiment 4
Under the condition of vacuum tightness 0.02Mpa, 1mol hexanolactam is heated to 138 DEG C and becomes molten state, and the moisture in constantly backflow removing monomer.Temperature is risen to 145 DEG C, add catalyzer 0.01mol sodium methylate, obtain active anion monomer, this process will prevent air from entering reaction system, oxide anion monomer.Then reduced-pressure backflow 20min removes the water that catalyzed reaction produces, return velocity is 44/min, then adds 0.0031mol activator HDI stirring 0.8min, then adds cyclotetrasiloxane 0.06mol, cast in the mould of preheating in advance evenly, the preheating temperature of mould is 155 DEG C.Polyreaction at 155 DEG C is also incubated 30min, obtains hexanolactam-cyclotetrasiloxane multipolymer.Afterwards above-mentioned hexanolactam-cyclotetrasiloxane multipolymer is placed in the beaker that formic acid is housed, makes it under magnetic stirring to dissolve completely; Above-mentioned solution is slowly poured in the beaker of toluene, and constantly stirs until precipitation is separated out completely, till no longer increasing.The above-mentioned product with precipitation is dried the 105 DEG C of vacuum-dryings of rear elder generation by the solid obtained after filtration under diminished pressure, obtains through-120 DEG C of pulverizing hexanolactam-cyclotetrasiloxane copolymer powder that particle diameter is 55 microns more afterwards.
Filter the filtrate obtained and carry out separation re-using through methods such as extraction, underpressure distillation again.
Through Mechanics Performance Testing, the tensile strength of the hexanolactam that embodiment 4 obtains-cyclotetrasiloxane multipolymer and powder thereof is 48MPa, and elongation at break is 85%.
Embodiment 5
Under the condition of vacuum tightness 0.001Mpa, 1mol hexanolactam is heated to 140 DEG C and becomes molten state, and the moisture in constantly backflow removing monomer.Temperature is risen to 150 DEG C, add catalyzer 0.01mol sodium ethylate and 0.002mol sodium caprolactam(ate), obtain active anion monomer, this process will prevent air from entering reaction system, oxide anion monomer.Then reduced-pressure backflow 15min removes the water that catalyzed reaction produces, return velocity is 49/min, the diphenyl carbonate adding activator 0.0035molOCC and 0.0005mol again stirs 0.6min, then cyclotetrasiloxane 0.09mol is added, cast in the mould of preheating in advance evenly, the preheating temperature of mould is 155 DEG C.At 155 DEG C, polymerization insulation 25min obtains hexanolactam-cyclotetrasiloxane multipolymer.Afterwards above-mentioned hexanolactam-cyclotetrasiloxane multipolymer is placed in the beaker that formic acid is housed, makes it under magnetic stirring to dissolve completely; Above-mentioned solution is slowly poured in the beaker that distilled water and ethyl acetate are housed, and constantly stirs until precipitation is separated out completely.The above-mentioned product with precipitation is dried the 105 DEG C of vacuum-dryings of rear elder generation by the solid obtained after filtration under diminished pressure, obtains through-170 DEG C of pulverizing hexanolactam-cyclotetrasiloxane copolymer powder that particle diameter is 85 microns more afterwards.
Filter the filtrate obtained and carry out separation re-using through methods such as extraction, underpressure distillation again.
Through Mechanics Performance Testing, the tensile strength of the hexanolactam that embodiment 5 obtains-cyclotetrasiloxane multipolymer and powder thereof is 38MPa, and elongation at break is 56%.
Above preferred embodiment, just for instruction and explanation of content of the present invention, does not form the restriction to content of the present invention.Although contriver enumerates in more detail to invention has been, but, the content that those skilled in the art discloses according to summary of the invention part and embodiment, various amendment can be made or/and it is obvious for supplementing or adopting similar mode to substitute to described specific embodiment, and technique effect of the present invention can be realized, therefore, repeat no longer one by one herein.The term occurred in the present invention, for the elaboration of technical solution of the present invention and understanding, is not construed as limiting the invention.
Claims (10)
1. a preparation method for hexanolactam-cyclotetrasiloxane multipolymer and powder thereof, is characterized in that, described preparation method is following steps:
(1) hexanolactam is heated to molten state at reduced pressure conditions;
(2) add catalyzer and obtain active anion monomer;
(3) under anhydrous and oxygen-free condition, add activator, add cyclotetrasiloxane after stirring again and obtain prepolymer, then polyreaction in mould prepolymer being cast to preheating, obtain hexanolactam-cyclotetrasiloxane multipolymer;
(4) hexanolactam-cyclotetrasiloxane multipolymer prepared by step (3) is joined in the container that formic acid is housed dissolve;
(5) solution that step (4) obtains is poured into be equipped with in the container of precipitation agent, be stirred to precipitation and no longer separate out; (6) product step (5) obtained through pulverize at low temperature or grinding, obtains hexanolactam-cyclotetrasiloxane copolymer powder by the solid drying that obtains after filtration under diminished pressure.
2. the preparation method of a kind of hexanolactam-cyclotetrasiloxane multipolymer according to claim 1 and powder thereof, is characterized in that, under the condition of decompression in step (1), the melt temperature of hexanolactam is 130 ~ 140 DEG C.
3. the preparation method of a kind of hexanolactam-cyclotetrasiloxane multipolymer according to claim 1 and powder thereof, it is characterized in that, described catalyzer is selected from one or more in NaOH, KOH, sodium caprolactam(ate), hexanolactam potassium, sodium ethylate, sodium methylate etc., and the mol ratio of catalyzer and hexanolactam is 0.001 ~ 0.015: 1.
4. a kind of hexanolactam-laurolactam multipolymer according to claim 1 or 3 and the preparation method of powder thereof, is characterized in that, in step (2), the interpolation temperature of catalyzer is 135 ~ 150 DEG C.
5. the preparation method of a kind of hexanolactam-cyclotetrasiloxane multipolymer according to claim 1 and powder thereof; it is characterized in that; described activator is selected from toluene 2; one or more in 4-vulcabond, hexamethylene diisocyanate, cyclohexyl carboxyamide base hexanolactam, benzoyl caprolactam, hexamethylene diisocyanate, '-diphenylmethane diisocyanate, diphenyl carbonate; the mol ratio of activator and hexanolactam is 0.0005 ~ 0.0040: 1, and the mol ratio of hexanolactam and cyclotetrasiloxane is 1: 0.005 ~ 0.1mol.
6. the preparation method of a kind of hexanolactam-cyclotetrasiloxane multipolymer and powder thereof according to claim 1 or 5, it is characterized in that, the temperature adding activator in step (3) is 135 ~ 150 DEG C., after adding cyclotetrasiloxane the reaction times be less than or equal to 1min after be cast in the grinding tool of preheating, the preheating temperature of casting die is 150 ~ 170 DEG C, polyreaction is 140 ~ 170 DEG C, polyreaction soaking time 20 ~ 60min.
7. the preparation method of a kind of hexanolactam-cyclotetrasiloxane multipolymer according to claim 1 and powder thereof, it is characterized in that, described precipitation agent is selected from one or more in distilled water, ethanol, acetone, tetrahydrofuran (THF), benzene, toluene, glycerine, ethyl acetate, ether.
8. the preparation method of a kind of hexanolactam-cyclotetrasiloxane multipolymer according to claim 1 and powder thereof, it is characterized in that, step (6) low temperature range is-170 DEG C ~-40 DEG C, and the hexanolactam obtained-cyclotetrasiloxane copolymer powder particle diameter is 10 ~ 80 microns.
9. the preparation method of a kind of hexanolactam-cyclotetrasiloxane multipolymer according to claim 1 and 2 and powder thereof, it is characterized in that, the vacuum tightness reduced pressure in preparation method's process is less than or equal to 0.1Mpa.
10. hexanolactam as claimed in claim 1-cyclotetrasiloxane multipolymer and the application of powder in 3D printing field thereof.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510007179.8A CN104829840A (en) | 2015-01-08 | 2015-01-08 | Preparation method of caprolactam-cyclotetrasiloxane co-polymer and powder thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510007179.8A CN104829840A (en) | 2015-01-08 | 2015-01-08 | Preparation method of caprolactam-cyclotetrasiloxane co-polymer and powder thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN104829840A true CN104829840A (en) | 2015-08-12 |
Family
ID=53808062
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510007179.8A Pending CN104829840A (en) | 2015-01-08 | 2015-01-08 | Preparation method of caprolactam-cyclotetrasiloxane co-polymer and powder thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN104829840A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017044735A1 (en) * | 2015-09-10 | 2017-03-16 | Dow Corning Corporation | 3d printing method utilizing thermoplastic silicone composition |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102391502A (en) * | 2011-09-22 | 2012-03-28 | 淮阴工学院 | Preparation method of cast nylon/silicon oil/potassium titanate crystal whisker composite material |
CN102977592A (en) * | 2012-12-04 | 2013-03-20 | 合肥杰事杰新材料股份有限公司 | POSS/PA6 (polyhedral oligomeric silsesquioxane/polycaprolactam) composite material and preparation method thereof |
-
2015
- 2015-01-08 CN CN201510007179.8A patent/CN104829840A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102391502A (en) * | 2011-09-22 | 2012-03-28 | 淮阴工学院 | Preparation method of cast nylon/silicon oil/potassium titanate crystal whisker composite material |
CN102977592A (en) * | 2012-12-04 | 2013-03-20 | 合肥杰事杰新材料股份有限公司 | POSS/PA6 (polyhedral oligomeric silsesquioxane/polycaprolactam) composite material and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
冯建荣 王有槐: "己内酰胺与环硅氧烷阴离子开环共聚研究", 《高分子学报》 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017044735A1 (en) * | 2015-09-10 | 2017-03-16 | Dow Corning Corporation | 3d printing method utilizing thermoplastic silicone composition |
CN108137925A (en) * | 2015-09-10 | 2018-06-08 | 美国陶氏有机硅公司 | Use the 3D printing processes of thermoplastic silicone composition |
CN108137925B (en) * | 2015-09-10 | 2022-02-25 | 美国陶氏有机硅公司 | 3D printing method using thermoplastic silicone composition |
US11286389B2 (en) | 2015-09-10 | 2022-03-29 | Dow Silicones Corporation | 3D printing method utilizing thermoplastic silicone composition |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Ageyeva et al. | Polymers and related composites via anionic ring-opening polymerization of lactams: Recent developments and future trends | |
CN102532526B (en) | Continuous polymerization production process of high-viscosity polyamide 6 | |
CN107108906B (en) | Polyamide microparticles | |
KR101408574B1 (en) | Method for preparing nylon microspheres and nylon microspheres prepared thereby | |
CN101768266B (en) | Method for preparing semi-aromatic nylon | |
RU2423399C2 (en) | Method of obtaining thermoplastic polymer based particles and powder obtained using said method | |
CN104830053A (en) | Caprolactam-laurolactam co-polymer modified by glass fiber and preparation method of powder thereof | |
CN103180367A (en) | Polyarylene sulfide production method and polyarylene sulfide | |
CN104086983A (en) | Graphene/nylon composite material as well as preparation method and application of graphene/nylon composite material | |
CN105026461A (en) | Preparation of polyamides by hydrolytic polymerization, postpolymerization and subsequent extraction | |
Sibikin et al. | Toward industrial use of anionically activated lactam polymers: Past, present and future | |
CN101357996B (en) | Multi-microporous epoxy thermosetting resin, preparation method and application thereof | |
CN103100263A (en) | Preparation method of graphite modified reinforced polypropylene composite filter plate | |
CN101228208A (en) | Process for preparing a block copolymer from polyimides and use of the block copolymer for producing powders and mouldings | |
CN103547568A (en) | Resin-transfer-moldable terminal-modified imide oligomer using 2-phenyl-4,4'-diaminodiphenyl ether and having excellent moldability, mixture thereof, varnish containing same, and cured resin thereof and fiber-reinforced cured resin thereof made by re | |
CN104829840A (en) | Preparation method of caprolactam-cyclotetrasiloxane co-polymer and powder thereof | |
CN104193989A (en) | Preparation method of bio-based polyamide copolymer elastomer | |
CN104098772A (en) | Novel polyamide-imide preparation method | |
CN109824897A (en) | A kind of polyamidoimide and preparation method thereof | |
CN105542166B (en) | A kind of alternative laser sintering and moulding polyimide powder and preparation method thereof | |
CN102212185B (en) | Method for preparing high-melting-point polylactic acid composite material | |
CN111808259A (en) | 3D printing silicone rubber and preparation method and application thereof | |
CN105860058A (en) | PA6/PA66 binary copolymer material and preparation method thereof | |
CN101367997B (en) | Process for producing epoxy resin MC nylon composite material | |
CN111499890B (en) | Hollow micro powder of polyaryletherketone polymer and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
EXSB | Decision made by sipo to initiate substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150812 |