CN103073714B - A kind of preparation method of nylon monomer-cast nylon/Nano composite material of montmorillonite - Google Patents
A kind of preparation method of nylon monomer-cast nylon/Nano composite material of montmorillonite Download PDFInfo
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Abstract
The invention provides a kind of preparation method of nylon monomer-cast nylon/Nano composite material of montmorillonite, first polynite, water and aprotic polar solvent are added in the first reactor that 40%-60% hexanolactam total mass is housed, be warming up to 70 ~ 85 DEG C and stir 0.5 ~ 2h, 15 ~ 60min is vacuumized to reactor, reactor is made to be in vacuum state, then add isocyanate reaction 15 ~ 30min, then be warming up to 130 ~ 140 DEG C and continue to vacuumize; The caprolactam monomer of other 60%-40% is added in the second reactor in addition simultaneously, be heated to monomer and dissolve and just start to vacuumize, add catalyzer after monomer all melts, and be warming up to 130 ~ 140 DEG C, continue to vacuumize 10 ~ 15min; Finally the first reactor and the second reactor material are mixed, pour into 150 ~ 170 DEG C of in-site polymerizations shaping, reaction 10 ~ 30min, 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 nylon composite materials preparing technical field.
Background technology
First Japan's Toyota's technology and laboratory, centre of development were used for polynite to prepare nylon 6/ Nano composite material of montmorillonite in Nylon 6 in 1985, within 1989, were realized industrialization, for automobile, and the field such as electronics and food product pack.Prepare polymkeric substance Nano composite material of montmorillonite, key is the modification of polynite and the dispersity in polymeric matrix and whether reaches the nanometer laminated structure of intercalation or stripping.Because crystal reunion state and wetting ability are piled up in the face, face of polynite self, it is made to be difficult to well be scattered in hydrophobic polymeric matrix.So first will carry out organically-modified to polynite, thus obtain the organo montmorillonite with polymkeric substance with consistency.The most frequently used organic modifiers normally long chain alkyl ammonium salt, quaternary ammonium salt cationic is used for improving the consistency of polynite and specific resin.Modifier molecules structure, the chain length of such as alkyl chain, chain number and unsaturation state are all the key factors determining polynite consistency, dispersity and extent of exfoliation in the composite.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 shaping of most matrix material is all make polynite be scattered in matrix under twin screw melting mixing or monomer in situ polymerization high temperature.The hot stage possibility certain time experienced in composite material shaping process, if machine-shaping temperature is higher than the thermostability of organo montmorillonite, the degraded that will produce organic modifiers makes polynite and polymer interface consistency reduce.For eliminating the low disadvantageous effect of thermostability that quaternary ammonium salt-modified MMT brings, some research miaow pyridine salt and phosphate-modified polynite.Although miaow pyridine salt and the hot initial decomposition temperature of phosphate-modified polynite improve 100 DEG C than ammonium salt class, because the price of miaow pyridine salt and phosphatic contaminative and costliness has limited to its application.
Therefore select suitable organic modifiers and technique to make polynite not only reach stripping in the base, and have good chemical bonding to be an of great value target with matrix.Jieshijie Novel Materials Co., Ltd, Shanghai have developed a kind of peel montmorillonite/casting nylon nano-composite material, the patent No. 200510111374.1.The said firm utilizes the polynite of water intumescent inorganic to allow caprolactam monomer enter interlayer, then add catalyzer and initiator casting reaction shaping.Although made matrix material makes polynite be peel off state to be scattered in matrix, inorganic polynite and matrix do not form chemical bonding, thus have impact on the further raising of its mechanical property.Therefore not only to make polynite be the nano-scale dispersion of stripping in system, the more important thing is and itself and matrix will be made to form chemical bonding.But existing technical scheme all cannot accomplish this point, so still need to improve existing imvite modified method.
Summary of the invention
Object of the present invention mainly there is polynite for existing Nylon/montmorillonite Nanocomposites preparation and matrix does not form chemical bonding, polynite is scattered in the deficiency in matrix in stripping state, propose a kind of preparation method that polynite and matrix can be made to form a kind of nylon monomer-cast nylon/Nano composite material of montmorillonite of chemical bonding.
For achieving the above object, this invention takes following manufacture method: a kind of preparation method of nylon monomer-cast nylon/Nano composite material of montmorillonite, based on MC nylon technique, its preparation technology is:
First polynite, water and aprotic polar solvent are added in the first reactor that 40%-60% caprolactam monomer total mass is housed, be warming up to 70 ~ 85 DEG C and stir 0.5 ~ 2h, 15 ~ 60 min are vacuumized to reactor, reactor is made to be in vacuum state, then add isocyanate reaction 15 ~ 30min, then be warming up to 130 ~ 140 DEG C and continue to vacuumize; The caprolactam monomer total mass of other 60%-40% is added in the second reactor in addition simultaneously, be heated to monomer and dissolve and just start to vacuumize, add catalyzer after monomer all melts, and be warming up to 130 ~ 140 DEG C, continue to vacuumize 10 ~ 15min; Finally the first reactor and the second reactor material are mixed, pour into 150 ~ 170 DEG C of in-site polymerizations shaping, reaction 10 ~ 30min, naturally cooling; Wherein,
The content of described polar organic solvent is 10 ~ 200% of caprolactam monomer total mass;
Described isocyanic ester add-on is caprolactam monomer total mass 0.2% ~ 0.4% and institute add one to the twice of the ion exchange capacity had in polynite with;
Described polynite consumption is 0.01 ~ 10% of caprolactam monomer total mass;
Described catalyst charge 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 polynite 10 ~ 50 times.
Further, described polynite is any mixing of one or more in sublimed original polynite, sodium-based montmorillonite and calcium-base montmorillonite.
Further, described catalyzer is sodium caprolactam(ate), hexanolactam magnesium bromide, one or more in NaOH, KOH, Na2CO3, NaH, LiH mix arbitrarily;
Further, described isocyanic ester is that one or more in MDI, TDI, HDI, NDI, PAPI, HTDI, HMDI, TMXDI and IPDI mix arbitrarily.
Further, described aprotic polar solvent is that one or more in dimethyl formamide, N,N-DIMETHYLACETAMIDE, pyridine, acetone, tetrahydrofuran (THF), pyrrolidone, toluene and hexanaphthene mix arbitrarily.
Further, described water is that one or both in deionized water or distilled water mix arbitrarily.
The advantage after above-mentioned manufacture method is adopted to be, the present invention adopts organic modification montmonrillonite, owing to containing the cationic water compounds such as Li, Na, Rb, Cs, Ca between cheating engaging layer with the electronegativity of balance crystalline, these ions are not suitable for tetrahedron and cause inter-layer bonding force very weak, and water and polar monomer can enter interlayer makes interlamellar spacing expand.So the present invention utilizes water and polar organic solvent to carry out swelling to polynite, introduce hexanolactam and isocyanic ester again, hexanolactam is further expanded cheating engaging layer spacing, and isocyanic ester can react and generate substituted urea and again expand cheating engaging layer spacing by the water unnecessary with interlayer.Isocyanic ester can also react with montmorillonite layer surface hydroxyl, thus makes polynite surface grafting isocyanic ester and organise, and unnecessary isocyanate groups can cause caprolactam polymerization.On nylon monomer-cast nylon Process ba-sis, 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 A still 400g hexanolactam, 70 ~ 85 DEG C are stirred 2h, vacuumize 15 ~ 60 min under 99340Pa vacuum tightness, then add 4gMDI and react 15 ~ 30min and be warming up to 130 ~ 140 DEG C and continue to vacuumize; 600g caprolactam monomer is heated in B still monomer in addition dissolve and just start to vacuumize 15 ~ 30min, vacuum tightness is 99340Pa, adds 30gNaOH and is warming up to 130 ~ 140 DEG C, continuing to vacuumize 10 ~ 15min simultaneously; Finally mixing A still and B still, to pour into 150 ~ 170 DEG C of in-site polymerizations shaping, reaction 10 ~ 30min, naturally cooling.
Embodiment 2
10g polynite and 300g water are added in A still 500g hexanolactam, 70 ~ 85 DEG C are stirred 2h, vacuumize 15 ~ 60 min under 99340Pa vacuum tightness, then add 6gMDI and react 15 ~ 30min and be warming up to 130 ~ 140 DEG C and continue to vacuumize; 500g caprolactam monomer is heated in B still monomer in addition dissolve and just start to vacuumize 15 ~ 30min, vacuum tightness is 99340Pa, adds 30gNaOH and is warming up to 130 ~ 140 DEG C, continuing to vacuumize 10 ~ 15min simultaneously; Finally mixing A still and B still, to pour into 150 ~ 170 DEG C of in-site polymerizations shaping, reaction 10 ~ 30min, naturally cooling.
Embodiment 3
50g polynite, 1000g water and 500gDMAC are added in A still 600g hexanolactam, 70 ~ 85 DEG C are stirred 2h, vacuumize 15 ~ 60 min under 99340Pa vacuum tightness, then add 15gMDI and react 15 ~ 30min and be warming up to 130 ~ 140 DEG C and continue to vacuumize; 400g caprolactam monomer is heated in B still monomer in addition dissolve and just start to vacuumize 15 ~ 30min, vacuum tightness is 99340Pa, adds 30gNaOH and is warming up to 130 ~ 140 DEG C, continuing to vacuumize 10 ~ 15min simultaneously; Finally mixing A still and B still, to pour into 150 ~ 170 DEG C of in-site polymerizations shaping, reaction 10 ~ 30min, naturally cooling.
Embodiment 4
100g polynite, 2000g water and 500gDMAC are added in A still 500g hexanolactam, 70 ~ 85 DEG C are stirred 2h, vacuumize 15 ~ 60 min under 99340Pa vacuum tightness, then add 25gMDI and react 15 ~ 30min and be warming up to 130 ~ 140 DEG C and continue to vacuumize; 500g caprolactam monomer is heated in B still monomer in addition dissolve and just start to vacuumize 15 ~ 30min, vacuum tightness is 99340Pa, adds 30gNaOH and is warming up to 130 ~ 140 DEG C, continuing to vacuumize 10 ~ 15min simultaneously; Finally mixing A still and B still, to pour into 150 ~ 170 DEG C of in-site polymerizations shaping, reaction 10 ~ 30min, naturally cooling.
Embodiment 5
10g polynite, 100g water and 500gDMAC are added in A still 500g hexanolactam, 70 ~ 85 DEG C are stirred 2h, vacuumize 15 ~ 60 min under 99340Pa vacuum tightness, then add 15gTDI and react 15 ~ 30min and be warming up to 130 ~ 140 DEG C and continue to vacuumize; 500g caprolactam monomer is heated in B still monomer in addition dissolve and just start to vacuumize 15 ~ 30min, vacuum tightness is 99340Pa, adds 10gNaOH and is warming up to 130 ~ 140 DEG C, continuing to vacuumize 10 ~ 15min simultaneously; Finally mixing A still and B still, to pour into 150 ~ 170 DEG C of in-site polymerizations shaping, reaction 10 ~ 30min, naturally cooling.
Embodiment 6
10g polynite, 100g water and 500gDMF are added in A still 500g hexanolactam, 70 ~ 85 DEG C are stirred 2h, vacuumize 15 ~ 60 min under 99340Pa vacuum tightness, then add 15gHDI and react 15 ~ 30min and be warming up to 130 ~ 140 DEG C and continue to vacuumize; 500g caprolactam monomer is heated in B still monomer in addition dissolve and just start to vacuumize 15 ~ 30min, vacuum tightness is 99340Pa, adds 40g sodium caprolactam(ate) and is warming up to 130 ~ 140 DEG C, continuing to vacuumize 10 ~ 15min simultaneously; Finally mixing A still and B still, to pour into 150 ~ 170 DEG C of in-site polymerizations shaping, reaction 10 ~ 30min, naturally cooling.
Embodiment 7
10g polynite, 100g water and 500gDMF are added in A still 450g hexanolactam, 70 ~ 85 DEG C are stirred 2h, vacuumize 15 ~ 60 min under 99340Pa vacuum tightness, then add 15gIPDI and react 15 ~ 30min and be warming up to 130 ~ 140 DEG C and continue to vacuumize; 550g caprolactam monomer is heated in B still monomer in addition dissolve and just start to vacuumize 15 ~ 30min, vacuum tightness is 99340Pa, adds 50g hexanolactam magnesium bromide and is warming up to 130 ~ 140 DEG C, continuing to vacuumize 10 ~ 15min simultaneously; Finally mixing A still and B still, to pour into 150 ~ 170 DEG C of in-site polymerizations shaping, reaction 10 ~ 30min, naturally cooling.
Can find out by the description of above-described embodiment the preparation method that the present invention relates to a kind of nylon monomer-cast nylon/Nano composite material of montmorillonite, based on MC nylon technique, its preparation technology is:
First polynite, water and aprotic polar solvent are added in the first reactor that 40%-60% caprolactam monomer total mass is housed, be warming up to 70 ~ 85 DEG C and stir 0.5 ~ 2h, 15 ~ 60 min are vacuumized to reactor, reactor is made to be in vacuum state, then add isocyanate reaction 15 ~ 30min, then be warming up to 130 ~ 140 DEG C and continue to vacuumize; The caprolactam monomer total mass of other 60%-40% is added in the second reactor in addition simultaneously, be heated to monomer and dissolve and just start to vacuumize, add catalyzer after monomer all melts, and be warming up to 130 ~ 140 DEG C, continue to vacuumize 10 ~ 15min; Finally the first reactor and the second reactor material are mixed, pour into 150 ~ 170 DEG C of in-site polymerizations shaping, reaction 10 ~ 30min, naturally cooling; Wherein,
The content of described polar organic solvent is 10 ~ 200% of caprolactam monomer total mass;
Described isocyanic ester add-on is caprolactam monomer total mass 0.2% ~ 0.4% and institute add one to the twice of the ion exchange capacity had in polynite with;
Described polynite consumption is 0.01 ~ 10% of caprolactam monomer total mass;
Described catalyst charge 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 polynite 10 ~ 50 times.
Further, described polynite is any mixing of one or more in sublimed original polynite, sodium-based montmorillonite and calcium-base montmorillonite.
Further, described catalyzer is sodium caprolactam(ate), hexanolactam magnesium bromide, one or more in NaOH, KOH, Na2CO3, NaH, LiH mix arbitrarily;
Further, described isocyanic ester is that one or more in MDI, TDI, HDI, NDI, PAPI, HTDI, HMDI, TMXDI and IPDI mix arbitrarily.
Further, described aprotic polar solvent is that one or more in dimethyl formamide, N,N-DIMETHYLACETAMIDE, pyridine, acetone, tetrahydrofuran (THF), pyrrolidone, toluene and hexanaphthene mix arbitrarily.
Further, described water is that one or both in deionized water or distilled water mix arbitrarily.
The advantage after above-mentioned manufacture method is adopted to be, the present invention adopts organic modification montmonrillonite, owing to containing the cationic water compounds such as Li, Na, Rb, Cs, Ca between cheating engaging layer with the electronegativity of balance crystalline, these ions are not suitable for tetrahedron and cause inter-layer bonding force very weak, and water and polar monomer can enter interlayer makes interlamellar spacing expand.So the present invention utilizes water and polar organic solvent to carry out swelling to polynite, introduce hexanolactam and isocyanic ester again, hexanolactam is further expanded cheating engaging layer spacing, and isocyanic ester can react and generate substituted urea and again expand cheating engaging layer spacing by the water unnecessary with interlayer.Isocyanic ester can also react with montmorillonite layer surface hydroxyl, thus makes polynite surface grafting isocyanic ester and organise, and unnecessary isocyanate groups can cause caprolactam polymerization.On nylon monomer-cast nylon Process ba-sis, 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 not meaning that is construed as limiting the present invention, describe with reference to the present invention, other changes of the disclosed embodiments, if all can expect for those skilled in the art, so such change should belong within this claim limited range and spirit.
Claims (6)
1. the preparation method of nylon monomer-cast nylon/Nano composite material of montmorillonite, based on MC nylon technique, it is characterized in that, adopt organic modification montmonrillonite, water and polar organic solvent is utilized to carry out swelling to polynite, introduce hexanolactam and isocyanic ester again, hexanolactam is further expanded cheating engaging layer spacing, and isocyanic ester can react and generate substituted urea and again expand cheating engaging layer spacing by the water unnecessary with interlayer; Utilize isocyanic ester and montmorillonite layer surface hydroxyl to react, thus make polynite surface grafting isocyanic ester and organise, and cause caprolactam polymerization by unnecessary isocyanate groups, its preparation technology is:
First polynite, water and aprotic polar solvent are added in the first reactor that 40%-60% caprolactam monomer total mass is housed, be warming up to 70 ~ 85 DEG C and stir 0.5 ~ 2h, 15 ~ 60 min are vacuumized to reactor, reactor is made to be in vacuum state, then add isocyanate reaction 15 ~ 30min, then be warming up to 130 ~ 140 DEG C and continue to vacuumize; The caprolactam monomer total mass of other 60%-40% is added in the second reactor in addition simultaneously, be heated to monomer and dissolve and just start to vacuumize, add catalyzer after monomer all melts, and be warming up to 130 ~ 140 DEG C, continue to vacuumize 10 ~ 15min; Finally the first reactor and the second reactor material are mixed, pour into 150 ~ 170 DEG C of in-site polymerizations shaping, reaction 10 ~ 30min, naturally cooling; Wherein,
The content of described polar organic solvent is 10 ~ 200% of caprolactam monomer total mass;
Described isocyanic ester add-on is caprolactam monomer total mass 0.2% ~ 0.4% and institute add one to the twice of the ion exchange capacity had in polynite with;
Described polynite consumption is 0.01 ~ 10% of caprolactam monomer total mass;
Described catalyst charge 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 polynite 10 ~ 50 times.
2. the preparation method of a kind of nylon monomer-cast nylon/Nano composite material of montmorillonite according to claim 1, it is characterized in that, described polynite is any mixing of one or more in sublimed original polynite, sodium-based montmorillonite and calcium-base montmorillonite.
3. the preparation method of a kind of nylon monomer-cast nylon/Nano composite material of montmorillonite according to claim 1, it is characterized in that, described catalyzer is sodium caprolactam(ate), hexanolactam magnesium bromide, NaOH, KOH, Na
2cO
3, one or more in NaH, LiH mix arbitrarily.
4. the preparation method of 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 that one or more in MDI, TDI, HDI, NDI, PAPI, HTDI, HMDI, TMXDI and IPDI mix arbitrarily.
5. the preparation method of 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 that one or more in dimethyl formamide, N,N-DIMETHYLACETAMIDE, pyridine, acetone, tetrahydrofuran (THF), pyrrolidone, toluene and hexanaphthene mix arbitrarily.
6. the preparation method of a kind of nylon monomer-cast nylon/Nano composite material of montmorillonite according to claim 1, is characterized in that, described water is that one or both in deionized water or distilled water mix arbitrarily.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109852049A (en) * | 2019-01-14 | 2019-06-07 | 湖南工业大学 | A kind of nylon monomer-cast nylon/polymer microballoon composite material and preparation method and application |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103613922B (en) * | 2013-11-29 | 2016-04-20 | 广东奇德新材料股份有限公司 | A kind of high-barrier nano PA6 nano 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 |
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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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109852049A (en) * | 2019-01-14 | 2019-06-07 | 湖南工业大学 | A kind of nylon monomer-cast nylon/polymer microballoon composite material and preparation method and application |
| 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 |
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