CN103073714A - Preparation method of cast nylon/ montmorillonite nanocomposite material - Google Patents
Preparation method of cast nylon/ montmorillonite nanocomposite material Download PDFInfo
- Publication number
- CN103073714A CN103073714A CN2013100164755A CN201310016475A CN103073714A CN 103073714 A CN103073714 A CN 103073714A CN 2013100164755 A CN2013100164755 A CN 2013100164755A CN 201310016475 A CN201310016475 A CN 201310016475A CN 103073714 A CN103073714 A CN 103073714A
- Authority
- CN
- China
- Prior art keywords
- monomer
- nylon
- preparation
- polynite
- montmorillonite
- 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.)
- Granted
Links
Landscapes
- Polyamides (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a preparation method of a cast nylon/ montmorillonite nanocomposite material. The preparation method of the cast nylon/ montmorillonite nanocomposite material comprises the following steps: firstly, adding montmorillonoid, water and an aprotic polar solvent into a first reaction kettle with 40-60% of hexanolactam counted by the total mass, heating to 70-85DEG C, stirring for 0.5-2h, and vacuumizing the reaction kettle for 15-60min till the reaction kettle is in a vacuum state; secondly, adding isocyanate, reacting for 15-30min, heating to 130-140DEG C, and further vacuumizing; at the same time, adding 60-40% of hexanolactam monomer into a second reaction kettle, heating till the monomer begins melting, beginning vacuumizing, adding a catalyst after all the monomer is melted, heating to 130-140DEG C, and further vacuumizing for 10-15min; and finally, mixing materials in the first reaction kettle and the second reaction kettle, casting the mixture into a 150-170DEG C mould, polymerizing and moulding, reacting for 10-30min, and naturally cooling.
Description
Technical field
The present invention relates to a kind of preparation method of nylon composite materials, specifically relate to a kind of preparation method of nylon monomer-cast nylon/Nano composite material of montmorillonite.Belong to the nylon composite materials preparing technical field.
Background technology
Japan's Toyota's technology and laboratory, centre of development at first were used for Nylon 6 preparation nylon 6/ Nano composite material of montmorillonite to polynite in 1985, its realization industrialization were used for automobile, the fields such as electronics and food product pack in 1989.Preparation polymkeric substance Nano composite material of montmorillonite, key are the modification of polynite and the dispersity in polymeric matrix and the nanometer laminated structure that whether reaches intercalation or peel off.Because the face face of polynite self is piled up crystal reunion attitude and wetting ability, make it be difficult to well be scattered in the hydrophobic polymeric matrix.So at first to carry out polynite organically-modified, thereby obtain having with polymkeric substance the organo montmorillonite of consistency.The most frequently used organic modifiers is long chain alkyl ammonium salt normally, and quaternary ammonium salt cationic is used for improving the consistency of polynite and specific resin.The modifier molecules structure, for example the chain length of alkyl chain, chain number and unsaturation attitude all are the key factors that determines polynite consistency, dispersity and extent of exfoliation in matrix material.Although quaternary ammonium salt is like a bomb for the preparation of nano composite polymer-montmorillonoid material, their common shortcoming is poor heat stability.The thermostability of organo montmorillonite is very crucial, because the moulding of most matrix materials all is under twin screw melting mixing or monomer in situ polymerization high temperature polynite to be scattered in the matrix.The hot stage possibility certain time that experiences in the composite material shaping process, if the machine-shaping temperature is higher than the thermostability of organo montmorillonite, the degraded that will produce organic modifiers reduces polynite and polymer interface consistency.The low disadvantageous effect of thermostability of bringing for eliminating quaternary ammonium salt-modified MMT, some research miaow pyridine salt and phosphoric acid salt modified montmorillonoid.Although the hot initial decomposition temperature of the polynite of miaow pyridine salt and phosphoric acid salt modification has improved 100 ℃ than ammonium salt class, because miaow pyridine salt and phosphatic contaminative and expensive price have been limited to its application.
Therefore select suitable organic modifiers and technique that polynite is not only reached in matrix and peel off, and with matrix good chemical bonding to be arranged be an of great value target.Jieshijie Novel Materials Co., Ltd, Shanghai has developed a kind of peel montmorillonite/casting nylon nano-composite material, the patent No. 200510111374.1.The said firm utilizes the water inorganic polynite of expanding to allow caprolactam monomer enter interlayer, adds catalyzer and initiator casting reaction moulding again.Although made matrix material is polynite to be peeled off attitude and be scattered in the matrix, inorganic polynite and matrix do not form chemical bonding, thereby have affected the further raising of its mechanical property.Therefore not only to make polynite be the nano level of peeling off and be scattered in the system, the more important thing is to make itself and matrix form chemical bonding.But existing technical scheme all can't be accomplished this point, so still need existing imvite modified method is improved.
Summary of the invention
Purpose of the present invention mainly is to exist polynite and matrix not to form chemical bonding for existing Nylon/montmorillonite Nanocomposites preparation, polynite is peels off attitude and is scattered in deficiency in the matrix, proposes a kind of preparation method that can make polynite and matrix form a kind of nylon monomer-cast nylon/Nano composite material of montmorillonite of chemical bonding.
For achieving the above object, the present invention has taked following manufacture method: a kind of preparation method of nylon monomer-cast nylon/Nano composite material of montmorillonite, and take MC nylon technique as the basis, its preparation technology is:
At first polynite, water and aprotic polar solvent are added and be equipped with in the first reactor of 40%-60% caprolactam monomer total mass, be warming up to 70～85 ℃ and stir 0.5～2h, reactor is vacuumized 15～60 min, make reactor be in vacuum state, then add isocyanate reaction 15～30min, be warming up to again 130～140 ℃ and continue to vacuumize; Simultaneously the caprolactam monomer total mass of other 60%-40% is added in the second reactor in addition, be heated to monomer and dissolve and just begin to vacuumize, monomer all adds catalyzer after the fusing, and is warming up to 130～140 ℃, continues to vacuumize 10～15min; At last the first reactor and the second reactor material are mixed, pour into 150～170 ℃ of in-site polymerization moulding, reaction 10～30min, naturally cooling; Wherein,
The content of described polar organic solvent is 10～200% of caprolactam monomer total mass;
The ion exchange capacity that described isocyanic ester add-on has in the adding polynite by 0.2%～0.4% and institute of caprolactam monomer total mass one to twice with;
Described polynite consumption is 0.01～10% of caprolactam monomer total mass;
Described catalyzer add-on is 0.2%～5% of caprolactam monomer total mass;
The vacuum tightness of described evacuation process is 99000～99997Pa;
The consumption of described water is 10～50 times of polynites.
Further, described polynite is one or more any mixing in sublimed original polynite, sodium-based montmorillonite and the calcium-base montmorillonite.
Further, described catalyzer is one or more any mixing among sodium caprolactam(ate), hexanolactam magnesium bromide, NaOH, KOH, Na2CO3, NaH, the LiH;
Further, described isocyanic ester is one or more any mixing among MDI, TDI, HDI, NDI, PAPI, HTDI, HMDI, TMXDI and the IPDI.
Further, described aprotic polar solvent is one or more any mixing in dimethyl formamide, N,N-DIMETHYLACETAMIDE, pyridine, acetone, tetrahydrofuran (THF), pyrrolidone, toluene and the hexanaphthene.
Further, described water is one or both any mixing in deionized water or the distilled water.
Adopt the advantage after the above-mentioned manufacture method to be, the present invention adopts organic modification montmonrillonite, owing to contain the cationic water compounds such as Li, Na, Rb, Cs, Ca with the electronegativity of balance crystalline between cheating engaging layer, these ions are not suitable for a little less than tetrahedron causes the interlayer bonding force very, and water and polar monomer can enter interlayer enlarges interlamellar spacing.So the present invention utilizes water and polar organic solvent that swelling is carried out in polynite, introduce again hexanolactam and isocyanic ester, hexanolactam is further enlarged the cheating engaging layer spacing, and isocyanic ester can generate with the reaction of the unnecessary water of interlayer and replaces urea and again enlarge the cheating engaging layer spacing.Isocyanic ester can also with montmorillonite layer surface hydroxyl reaction, thereby make polynite surface grafting isocyanic ester and organise, and unnecessary isocyanate groups can cause caprolactam polymerization.On nylon monomer-cast nylon technique basis, single stage method of the present invention prepares nano composite material, and technique is simple, and energy consumption is low, and polynite is cheap, and product properties is excellent.
Embodiment
Below in conjunction with specific examples, the invention will be further described.
Embodiment 1
5g polynite and 100g water are added in the A still 400g hexanolactam, and 70～85 ℃ are stirred 2h, vacuumize 15～60 min under 99340Pa vacuum tightness, then add 4gMDI reaction 15～30min and are warming up to 130～140 ℃ and continue to vacuumize; Simultaneously the 600g caprolactam monomer is heated in addition monomer and dissolves and just begin to vacuumize 15～30min in the B still, vacuum tightness is 99340Pa, adds 30gNaOH and also is warming up to 130～140 ℃, continues to vacuumize 10～15min; Mix at last A still and B still and pour into 150～170 ℃ of in-site polymerization moulding, reaction 10～30min, naturally cooling.
Embodiment 2
10g polynite and 300g water are added in the A still 500g hexanolactam, and 70～85 ℃ are stirred 2h, vacuumize 15～60 min under 99340Pa vacuum tightness, then add 6gMDI reaction 15～30min and are warming up to 130～140 ℃ and continue to vacuumize; Simultaneously the 500g caprolactam monomer is heated in addition monomer and dissolves and just begin to vacuumize 15～30min in the B still, vacuum tightness is 99340Pa, adds 30gNaOH and also is warming up to 130～140 ℃, continues to vacuumize 10～15min; Mix at last A still and B still and pour into 150～170 ℃ of in-site polymerization moulding, reaction 10～30min, naturally cooling.
Embodiment 3
50g polynite, 1000g water and 500gDMAC are added in the A still 600g hexanolactam, and 70～85 ℃ are stirred 2h, vacuumize 15～60 min under 99340Pa vacuum tightness, then add 15gMDI reaction 15～30min and are warming up to 130～140 ℃ and continue to vacuumize; Simultaneously the 400g caprolactam monomer is heated in addition monomer and dissolves and just begin to vacuumize 15～30min in the B still, vacuum tightness is 99340Pa, adds 30gNaOH and also is warming up to 130～140 ℃, continues to vacuumize 10～15min; Mix at last A still and B still and pour into 150～170 ℃ of in-site polymerization moulding, reaction 10～30min, naturally cooling.
Embodiment 4
100g polynite, 2000g water and 500gDMAC are added in the A still 500g hexanolactam, and 70～85 ℃ are stirred 2h, vacuumize 15～60 min under 99340Pa vacuum tightness, then add 25gMDI reaction 15～30min and are warming up to 130～140 ℃ and continue to vacuumize; Simultaneously the 500g caprolactam monomer is heated in addition monomer and dissolves and just begin to vacuumize 15～30min in the B still, vacuum tightness is 99340Pa, adds 30gNaOH and also is warming up to 130～140 ℃, continues to vacuumize 10～15min; Mix at last A still and B still and pour into 150～170 ℃ of in-site polymerization moulding, reaction 10～30min, naturally cooling.
Embodiment 5
10g polynite, 100g water and 500gDMAC are added in the A still 500g hexanolactam, and 70～85 ℃ are stirred 2h, vacuumize 15～60 min under 99340Pa vacuum tightness, then add 15gTDI reaction 15～30min and are warming up to 130～140 ℃ and continue to vacuumize; Simultaneously the 500g caprolactam monomer is heated in addition monomer and dissolves and just begin to vacuumize 15～30min in the B still, vacuum tightness is 99340Pa, adds 10gNaOH and also is warming up to 130～140 ℃, continues to vacuumize 10～15min; Mix at last A still and B still and pour into 150～170 ℃ of in-site polymerization moulding, reaction 10～30min, naturally cooling.
Embodiment 6
10g polynite, 100g water and 500gDMF are added in the A still 500g hexanolactam, and 70～85 ℃ are stirred 2h, vacuumize 15～60 min under 99340Pa vacuum tightness, then add 15gHDI reaction 15～30min and are warming up to 130～140 ℃ and continue to vacuumize; Simultaneously the 500g caprolactam monomer is heated in addition monomer and dissolves and just begin to vacuumize 15～30min in the B still, vacuum tightness is 99340Pa, adds the 40g sodium caprolactam(ate) and also is warming up to 130～140 ℃, continues to vacuumize 10～15min; Mix at last A still and B still and pour into 150～170 ℃ of in-site polymerization moulding, reaction 10～30min, naturally cooling.
Embodiment 7
10g polynite, 100g water and 500gDMF are added in the A still 450g hexanolactam, and 70～85 ℃ are stirred 2h, vacuumize 15～60 min under 99340Pa vacuum tightness, then add 15gIPDI reaction 15～30min and are warming up to 130～140 ℃ and continue to vacuumize; Simultaneously the 550g caprolactam monomer is heated in addition monomer and dissolves and just begin to vacuumize 15～30min in the B still, vacuum tightness is 99340Pa, adds 50g hexanolactam magnesium bromide and also is warming up to 130～140 ℃, continues to vacuumize 10～15min; Mix at last A still and B still and pour into 150～170 ℃ of in-site polymerization moulding, reaction 10～30min, naturally cooling.
Description by above-described embodiment can be found out the preparation method who the present invention relates to a kind of nylon monomer-cast nylon/Nano composite material of montmorillonite, and take MC nylon technique as the basis, its preparation technology is:
At first polynite, water and aprotic polar solvent are added and be equipped with in the first reactor of 40%-60% caprolactam monomer total mass, be warming up to 70～85 ℃ and stir 0.5～2h, reactor is vacuumized 15～60 min, make reactor be in vacuum state, then add isocyanate reaction 15～30min, be warming up to again 130～140 ℃ and continue to vacuumize; Simultaneously the caprolactam monomer total mass of other 60%-40% is added in the second reactor in addition, be heated to monomer and dissolve and just begin to vacuumize, monomer all adds catalyzer after the fusing, and is warming up to 130～140 ℃, continues to vacuumize 10～15min; At last the first reactor and the second reactor material are mixed, pour into 150～170 ℃ of in-site polymerization moulding, reaction 10～30min, naturally cooling; Wherein,
The content of described polar organic solvent is 10～200% of caprolactam monomer total mass;
The ion exchange capacity that described isocyanic ester add-on has in the adding polynite by 0.2%～0.4% and institute of caprolactam monomer total mass one to twice with;
Described polynite consumption is 0.01～10% of caprolactam monomer total mass;
Described catalyzer add-on is 0.2%～5% of caprolactam monomer total mass;
The vacuum tightness of described evacuation process is 99000～99997Pa;
The consumption of described water is 10～50 times of polynites.
Further, described polynite is one or more any mixing in sublimed original polynite, sodium-based montmorillonite and the calcium-base montmorillonite.
Further, described catalyzer is one or more any mixing among sodium caprolactam(ate), hexanolactam magnesium bromide, NaOH, KOH, Na2CO3, NaH, the LiH;
Further, described isocyanic ester is one or more any mixing among MDI, TDI, HDI, NDI, PAPI, HTDI, HMDI, TMXDI and the IPDI.
Further, described aprotic polar solvent is one or more any mixing in dimethyl formamide, N,N-DIMETHYLACETAMIDE, pyridine, acetone, tetrahydrofuran (THF), pyrrolidone, toluene and the hexanaphthene.
Further, described water is one or both any mixing in deionized water or the distilled water.
Adopt the advantage after the above-mentioned manufacture method to be, the present invention adopts organic modification montmonrillonite, owing to contain the cationic water compounds such as Li, Na, Rb, Cs, Ca with the electronegativity of balance crystalline between cheating engaging layer, these ions are not suitable for a little less than tetrahedron causes the interlayer bonding force very, and water and polar monomer can enter interlayer enlarges interlamellar spacing.So the present invention utilizes water and polar organic solvent that swelling is carried out in polynite, introduce again hexanolactam and isocyanic ester, hexanolactam is further enlarged the cheating engaging layer spacing, and isocyanic ester can generate with the reaction of the unnecessary water of interlayer and replaces urea and again enlarge the cheating engaging layer spacing.Isocyanic ester can also with montmorillonite layer surface hydroxyl reaction, thereby make polynite surface grafting isocyanic ester and organise, and unnecessary isocyanate groups can cause caprolactam polymerization.On nylon monomer-cast nylon technique basis, single stage method of the present invention prepares nano composite material, and technique is simple, and energy consumption is low, and polynite is cheap, and product properties is excellent.
Although the present invention describes with reference to specific embodiment, but this description and not meaning that is construed as limiting the present invention, describe with reference to the present invention, other variations of the disclosed embodiments, if all can expect for those skilled in the art, so such variation should belong within this claim limited range and the spirit.
Claims (6)
1. the preparation method of a nylon monomer-cast nylon/Nano composite material of montmorillonite take MC nylon technique as the basis, is characterized in that its preparation technology is:
At first polynite, water and aprotic polar solvent are added and be equipped with in the first reactor of 40%-60% caprolactam monomer total mass, be warming up to 70～85 ℃ and stir 0.5～2h, reactor is vacuumized 15～60 min, make reactor be in vacuum state, then add isocyanate reaction 15～30min, be warming up to again 130～140 ℃ and continue to vacuumize; Simultaneously the caprolactam monomer total mass of other 60%-40% is added in the second reactor in addition, be heated to monomer and dissolve and just begin to vacuumize, monomer all adds catalyzer after the fusing, and is warming up to 130～140 ℃, continues to vacuumize 10～15min; At last the first reactor and the second reactor material are mixed, pour into 150～170 ℃ of in-site polymerization moulding, reaction 10～30min, naturally cooling; Wherein,
The content of described polar organic solvent is 10～200% of caprolactam monomer total mass;
The ion exchange capacity that described isocyanic ester add-on has in the adding polynite by 0.2%～0.4% and institute of caprolactam monomer total mass one to twice with;
Described polynite consumption is 0.01～10% of caprolactam monomer total mass;
Described catalyzer add-on is 0.2%～5% of caprolactam monomer total mass;
The vacuum tightness of described evacuation process is 99000～99997Pa;
The consumption of described water is 10～50 times of polynites.
2. the preparation method of described a kind of nylon monomer-cast nylon/Nano composite material of montmorillonite according to claim 1 is characterized in that, described polynite is one or more any mixing in sublimed original polynite, sodium-based montmorillonite and the calcium-base montmorillonite.
3. the preparation method of described a kind of nylon monomer-cast nylon/Nano composite material of montmorillonite according to claim 1, it is characterized in that described catalyzer is one or more any mixing among sodium caprolactam(ate), hexanolactam magnesium bromide, NaOH, KOH, Na2CO3, NaH, the LiH.
4. the preparation method of described a kind of nylon monomer-cast nylon/Nano composite material of montmorillonite according to claim 1, it is characterized in that described isocyanic ester is one or more any mixing among MDI, TDI, HDI, NDI, PAPI, HTDI, HMDI, TMXDI and the IPDI.
5. the preparation method of described a kind of nylon monomer-cast nylon/Nano composite material of montmorillonite according to claim 1, it is characterized in that described aprotic polar solvent is one or more any mixing in dimethyl formamide, N,N-DIMETHYLACETAMIDE, pyridine, acetone, tetrahydrofuran (THF), pyrrolidone, toluene and the hexanaphthene.
6. the preparation method of described a kind of nylon monomer-cast nylon/Nano composite material of montmorillonite according to claim 1 is characterized in that described water is one or both any mixing in deionized water or the distilled water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310016475.5A CN103073714B (en) | 2013-01-17 | 2013-01-17 | A kind of preparation method of nylon monomer-cast nylon/Nano composite material of montmorillonite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310016475.5A CN103073714B (en) | 2013-01-17 | 2013-01-17 | A kind of preparation method of nylon monomer-cast nylon/Nano composite material of montmorillonite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103073714A true CN103073714A (en) | 2013-05-01 |
| CN103073714B CN103073714B (en) | 2015-08-12 |
Family
ID=48150427
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310016475.5A Active CN103073714B (en) | 2013-01-17 | 2013-01-17 | A kind of preparation method of nylon monomer-cast nylon/Nano composite material of montmorillonite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103073714B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613922A (en) * | 2013-11-29 | 2014-03-05 | 江门市奇德工程塑料科技有限公司 | High-barrier nano PA6 composite material and preparation method thereof |
| CN106496546A (en) * | 2016-10-13 | 2017-03-15 | 扬州赛尔达尼龙制造有限公司 | A kind of imvite modified MC nylon lining board of grinder and its manufacture method |
| CN106977916A (en) * | 2017-04-28 | 2017-07-25 | 湖南工业大学 | A kind of nano composite materials of MCPA6/MIL 101 and its preparation method and application |
| CN112175160A (en) * | 2020-10-14 | 2021-01-05 | 安徽宏翔农业机械有限公司 | Preparation method of high-strength clean agricultural ground roller adhesive |
| CN117186388A (en) * | 2023-08-01 | 2023-12-08 | 中山海明中科新材料有限公司 | Nylon composite material and preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109852049B (en) * | 2019-01-14 | 2020-12-22 | 湖南工业大学 | Cast nylon/polymer microsphere composite material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1796458A (en) * | 2004-12-28 | 2006-07-05 | 上海杰事杰新材料股份有限公司 | Method for toughening and reinforcing nylon by using new type organic montmorillonite |
| CN1982373A (en) * | 2005-12-12 | 2007-06-20 | 上海杰事杰新材料股份有限公司 | Production of peel montmorillonite/casting nylon nano-composite material |
| CN101735448A (en) * | 2008-11-18 | 2010-06-16 | 熊长宏 | Method for preparing polyamide-6 nano composite material |
-
2013
- 2013-01-17 CN CN201310016475.5A patent/CN103073714B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1796458A (en) * | 2004-12-28 | 2006-07-05 | 上海杰事杰新材料股份有限公司 | Method for toughening and reinforcing nylon by using new type organic montmorillonite |
| CN1982373A (en) * | 2005-12-12 | 2007-06-20 | 上海杰事杰新材料股份有限公司 | Production of peel montmorillonite/casting nylon nano-composite material |
| CN101735448A (en) * | 2008-11-18 | 2010-06-16 | 熊长宏 | Method for preparing polyamide-6 nano composite material |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613922A (en) * | 2013-11-29 | 2014-03-05 | 江门市奇德工程塑料科技有限公司 | High-barrier nano PA6 composite material and preparation method thereof |
| CN106496546A (en) * | 2016-10-13 | 2017-03-15 | 扬州赛尔达尼龙制造有限公司 | A kind of imvite modified MC nylon lining board of grinder and its manufacture method |
| CN106977916A (en) * | 2017-04-28 | 2017-07-25 | 湖南工业大学 | A kind of nano composite materials of MCPA6/MIL 101 and its preparation method and application |
| CN106977916B (en) * | 2017-04-28 | 2019-09-24 | 湖南工业大学 | A kind of MCPA6/MIL-101 nanocomposite and its preparation method and application |
| CN112175160A (en) * | 2020-10-14 | 2021-01-05 | 安徽宏翔农业机械有限公司 | Preparation method of high-strength clean agricultural ground roller adhesive |
| CN117186388A (en) * | 2023-08-01 | 2023-12-08 | 中山海明中科新材料有限公司 | Nylon composite material and preparation method and application thereof |
| CN117186388B (en) * | 2023-08-01 | 2024-04-19 | 中山海明中科新材料有限公司 | Nylon composite material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103073714B (en) | 2015-08-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103073714B (en) | A kind of preparation method of nylon monomer-cast nylon/Nano composite material of montmorillonite | |
| CN107417867B (en) | Preparation method of graphene oxide modified composite phase change microcapsule | |
| CN104241621B (en) | The silica-based composite negative pole material of a kind of lithium ion battery | |
| CN102201275B (en) | Lithium salt and graphene composite material as well as preparation method and application thereof | |
| CN102173403B (en) | Preparation method of micro-nano lithium ferric phosphate (LiFePO4) positive electrode material of lithium-ion battery | |
| CN103172852B (en) | A kind of preparation method of organo montmorillonite/casting nylon nano-composite material | |
| He et al. | PEG-based polyurethane/Paraffin@ SiO2/Boron nitride phase change composite with efficient thermal conductive pathways and superior mechanical property | |
| CN103627021A (en) | Preparation method of polymethacrylimide foam | |
| CN102516774A (en) | Preparation method of modified silicon resin matrix and application of the modified silicon resin matrix | |
| CN105129857A (en) | Flower-shaped tungsten oxide nanometer material and preparing method thereof | |
| CN114621721B (en) | Polyurethane pouring sealant for low-density heat-insulating power battery | |
| CN101857702A (en) | High-performance PVC (polyvinyl chloride) paste resin/micro-nano SiO2 composite material and preparation technology thereof | |
| CN114752129A (en) | HDPE-based heat-conducting composite material and preparation method and application thereof | |
| CN110204788A (en) | A kind of preparation method of alginate/hydrotalcite flame retardant composite material | |
| CN109554164B (en) | Composite phase-change material and preparation method thereof | |
| CN100489031C (en) | Super branched polyamine/montmorillonite/graphite nano composite material and preparation thereof | |
| CN104650581A (en) | Preparation method of graphene/polyamide dielectric composite material | |
| CN106380585A (en) | Preparation method of antistatic copolyester | |
| JP6367960B2 (en) | Apparatus and method for continuous production of particulate polyamide resin | |
| CN106531462A (en) | Polypyrrole carbon electrode material with added lithium iron phosphate and graphene composite material | |
| CN112038110B (en) | Ultra-high strength thermoreversible hydrogel electrolyte and preparation method thereof | |
| CN106356522A (en) | Low-temperature microwave synthesis method of Li3VO4 hollow nanocube with electrochemical stability for efficiently storing lithium | |
| CN103435312B (en) | A kind of preparation method of light wall brick | |
| CN102153744B (en) | Preparation method of halloysite nanotube reinforced flame-retardant anionic polymerization nylon | |
| CN101786857A (en) | Graphite gluing product and manufacture method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |