CN106947077A - A kind of ultra-toughness MC nylon materials and preparation method thereof - Google Patents
A kind of ultra-toughness MC nylon materials and preparation method thereof Download PDFInfo
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- CN106947077A CN106947077A CN201710182935.XA CN201710182935A CN106947077A CN 106947077 A CN106947077 A CN 106947077A CN 201710182935 A CN201710182935 A CN 201710182935A CN 106947077 A CN106947077 A CN 106947077A
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- toughness
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- caprolactam
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
Abstract
The present invention proposes a kind of ultra-toughness MC nylon materials, and composition of raw materials composition includes by weight：100 parts of caprolactam；0.1~0.35 part of base catalyst；0.75~1 part of activating agent；0~0.15 part of modified manometer silicon dioxide.The modified manometer silicon dioxide that the present invention is used is by specially treated, the Amino End Group dendritic macromole used, end is with multiple amino and macromolecular center is hydrolyzable alkoxyl silicone ester group, under certain condition, dendritic macromole is evenly distributed on silica particle surface, passes through Covalent bonding together；Dendritic macromole functionalized SiO 2 has the dispersiveness and high surface energy of height, and being dispersed in realizes the coordination plasticizing effect of island effect and network blackboard in caprolactam, significantly improve the mechanical property of material.
Description
Technical field
The present invention relates to a kind of ultra-toughness MC nylon materials and preparation method thereof.
Background technology
Monomer moulding casting nylon is also known as MC nylon, is engineering plastic of the caprolactam as obtained by prepared by anionic polymerization
Material, its better mechanical property, intensity is 1.5 times of general nylon, and because MC nylon products have, lightweight, intensity is high, moisten certainly
The multifrequency nature such as sliding, wear-resisting, anti-corrosion, insulation, therefore it is mainly used in replacing metal to make bearing, bearing shell, the friction pair such as gear
Part.It is poor that non-modified MC nylon has low-temperature flexibility in actual applications, it is difficult in large-scale Aero-Space, electricity
The field extensive uses such as son, transport, automobile fitting part, therefore research high tenacity MC nylon products are current mains direction of studying.
A large amount of reports existing at present carry out toughening modifying to MC nylon, and Chinese patent CN103509336A discloses MC nylon
Composite and preparation method thereof, is modified using PA bat wools to MC nylon, and toughness has obtained certain raising；In
State's number of patent application 200710173608.4 discloses a kind of cast in situ nylon carbon nanotube composite materials and its preparation
Method, carries out polymerisation using CNT and caprolactam, substantially increases the intensity of material, but the cost of material is but
Increase considerably and toughness does not have greatly improved.
The content of the invention
The present invention proposes a kind of ultra-toughness MC nylon materials and preparation method thereof, and the silica Jing Guo specially treated is made
It is added to for toughener in caprolactam and carries out in-situ polymerization, improves the mechanical property and heat resistance of MC nylon with this.
The technical proposal of the invention is realized in this way：
A kind of ultra-toughness MC nylon materials, composition of raw materials composition includes by weight：
Preferably, at least one of the base catalyst in potassium hydroxide, NaOH, metallic sodium.
Preferably, the activating agent is selected from '-diphenylmethane diisocyanate, triphenylmethane triisocyanate, toluene diisocyanate
Any of acid esters, dicyclohexyl methyl hydride diisocyanate, hexamethylene diisocyanate.
Preferably, the modified manometer silicon dioxide is reacted by dendritic macromole silicon dioxide granule, used
Hydrolyzable alkoxyl silicone ester group is carried centered on Amino End Group dendritic macromole, is combined by covalent bond with silica.
A kind of preparation method of ultra-toughness MC nylon materials, comprises the following steps：
(1) caprolactams of 100 parts by weight is added in conical flask, is placed in oil bath pan and is warming up to 90 DEG C of heating and makes oneself
Lactams is melted, and after adding 0~0.15 part by weight modified nano silicon after caprolactam melting, stirring is allowed to be completely dissolved in
Among caprolactam melt；
(2) system obtained by step (1) is warming up to 120 DEG C, dehydration is vacuumized under the conditions of magnetic agitation, air pocket occurs
When release vacuum；
(3) 0.1~0.35 parts by weight base catalyst is added in the system of step (2), is vacuumized, while temperature rises to
140 DEG C, continue magnetic agitation and be dehydrated to there is air pocket, persistently vacuumize 10 minutes, release vacuum；
(4) system obtained by step (3) is added 0.75~1 parts by weight of activated dose while stirring, obtains treating aggressiveness system, pour
Into the mould preheated in advance in 180 DEG C of baking ovens, continue to heat after 2 hours, be cooled to room temperature, obtain ultra-toughness MC nylon materials
Material.
What the present invention was produced has the beneficial effect that：(1) modified manometer silicon dioxide that the present invention is used is by specially treated
, the Amino End Group dendritic macromole used, end is with multiple amino and macromolecular center is hydrolyzable alkoxy estersil
Group, under certain condition, dendritic macromole are evenly distributed on silica particle surface, pass through Covalent bonding together；(2) set
Dendritic macromolecules functionalized SiO 2 has the dispersiveness and high surface energy of height, and being dispersed in caprolactam realizes
The coordination plasticizing effect of island effect and network blackboard, significantly improves the mechanical property of material.
Embodiment
It is clearly and completely described below in conjunction with embodiment of the present invention technical scheme, it is clear that described
Embodiment be only a part of embodiment of the invention, rather than whole embodiment.Based on the embodiment in the present invention, ability
The every other embodiment that domain those of ordinary skill is obtained under the premise of creative work is not made, belongs to guarantor of the present invention
The scope of shield.
Embodiment 1
Caprolactam that will be 100 parts is added in conical flask, is placed in oil bath pan and is warming up to 90 DEG C of heating and makes caprolactam
Melting.System is warming up to 120 DEG C, dehydration is vacuumized under the conditions of magnetic agitation, occurs releasing vacuum during air pocket；Continue to stir
Mix 0.35 part of NaOH of addition to vacuumize, while system is warming up to 140 DEG C, continues stirring dehydration and air pocket occur, persistently take out
Vacuum 10 minutes, releases vacuum；Continue to stir, add 0.75 part of toluene di-isocyanate(TDI), obtain prepolymerization system, be cast in advance
In the mould preheated in 180 DEG C of baking ovens, continue to heat after 2 hours, be cooled to room temperature, obtain MC nylon materials, test knot
Fruit is shown in Table 1.
Embodiment 2
Caprolactam that will be 100 parts is added in conical flask, is placed in oil bath pan and is warming up to 90 DEG C of heating and makes caprolactam
Melting, after adding 0.05 part of modified manometer silicon dioxide after caprolactam melting, stirring is allowed to be completely dissolved in caprolactam melt
It is central.System is warming up to 120 DEG C, dehydration is vacuumized under the conditions of magnetic agitation, occurs releasing vacuum during air pocket；Continue to stir
Mix 0.35 part of NaOH of addition to vacuumize, while system is warming up to 140 DEG C, continues stirring dehydration and air pocket occur, persistently take out
Vacuum 10 minutes, releases vacuum；Continue to stir, add 0.75 part of toluene di-isocyanate(TDI), obtain prepolymerization system, be cast in advance
In the mould preheated in 180 DEG C of baking ovens, continue to heat after 2 hours, be cooled to room temperature, obtain MC nylon materials, test knot
Fruit is shown in Table 1.
Embodiment 3
Caprolactam that will be 100 parts is added in conical flask, is placed in oil bath pan and is warming up to 90 DEG C of heating and makes caprolactam
Melting, after adding 0.1 part of modified manometer silicon dioxide after caprolactam melting, stirring is allowed to be completely dissolved in caprolactam melt and worked as
In.System is warming up to 120 DEG C, dehydration is vacuumized under the conditions of magnetic agitation, occurs releasing vacuum during air pocket；Continue to stir
Add 0.35 part of NaOH to vacuumize, while system is warming up to 140 DEG C, continues stirring dehydration and air pocket occur, persistently take out true
It is empty 10 minutes, release vacuum；Continue to stir, add 0.75 part of toluene di-isocyanate(TDI), obtain prepolymerization system, be cast to and exist in advance
In the mould preheated in 180 DEG C of baking ovens, continue to heat after 2 hours, be cooled to room temperature, obtain MC nylon materials, test result
It is shown in Table 1.
Embodiment 4
Caprolactam that will be 100 parts is added in conical flask, is placed in oil bath pan and is warming up to 90 DEG C of heating and makes caprolactam
Melting, after adding 0.15 part of modified manometer silicon dioxide after caprolactam melting, stirring is allowed to be completely dissolved in caprolactam melt
It is central.System is warming up to 120 DEG C, dehydration is vacuumized under the conditions of magnetic agitation, occurs releasing vacuum during air pocket；Continue to stir
Mix 0.35 part of NaOH of addition to vacuumize, while system is warming up to 140 DEG C, continues stirring dehydration and air pocket occur, persistently take out
Vacuum 10 minutes, releases vacuum；Continue to stir, add 0.75 part of toluene di-isocyanate(TDI), obtain prepolymerization system, be cast in advance
In the mould preheated in 180 DEG C of baking ovens, continue to heat after 2 hours, be cooled to room temperature, obtain MC nylon materials, test knot
Fruit is shown in Table 1.
Comparative example 1
Caprolactam that will be 100 parts is added in conical flask, is placed in oil bath pan and is warming up to 90 DEG C of heating and makes caprolactam
Melting, after adding 0.1 part of modified manometer silicon dioxide after caprolactam melting, stirring is allowed to be completely dissolved in caprolactam melt and worked as
In.System is warming up to 120 DEG C, dehydration is vacuumized under the conditions of magnetic agitation, occurs releasing vacuum during air pocket；Continue to stir
Add 0.1 part of NaOH to vacuumize, while system is warming up to 140 DEG C, continues stirring dehydration and air pocket occur, persistently vacuumize
10 minutes, release vacuum；Continue to stir, add 0.75 part of toluene di-isocyanate(TDI), obtain prepolymerization system, be cast to and exist in advance
In the mould preheated in 180 DEG C of baking ovens, continue to heat after 2 hours, be cooled to room temperature, obtain MC nylon materials, test result
It is shown in Table 1.
Comparative example 2
Caprolactam that will be 100 parts is added in conical flask, is placed in oil bath pan and is warming up to 90 DEG C of heating and makes caprolactam
Melting, after adding 0.1 part of modified manometer silicon dioxide after caprolactam melting, stirring is allowed to be completely dissolved in caprolactam melt and worked as
In.System is warming up to 120 DEG C, dehydration is vacuumized under the conditions of magnetic agitation, occurs releasing vacuum during air pocket；Continue to stir
Add 0.35 part of NaOH to vacuumize, while system is warming up to 140 DEG C, continues stirring dehydration and air pocket occur, persistently take out true
It is empty 10 minutes, release vacuum；Continue to stir, add 1 part of toluene di-isocyanate(TDI), obtain prepolymerization system, be cast in advance 180
In the mould preheated in DEG C baking oven, continue to heat after 2 hours, be cooled to room temperature, obtain MC nylon materials, test result is shown in Table 1.
The MC nylon material performance tests of table 1
It can be seen that by above performance test：When modified manometer silicon dioxide content be 0.1 part, base catalyst be 0.35
When part, activating agent are 0.75 part, the performance of MC nylon materials is optimal.Compared with the MC nylon without modified manometer silicon dioxide,
The tensile strength of material improves 29.29%, and elastic modelling quantity improves 34.33%, and bending strength improves 78.95%, especially
It is that impact strength improves the most substantially, improves 453.17%；In addition, add modified manometer silicon dioxide after material it is thermally-stabilised
Performance is also improved
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, all essences in the present invention
God is with principle, and any modifications, equivalent substitutions and improvements made etc. should be included within the scope of the present invention.
Claims (5)
1. a kind of ultra-toughness MC nylon materials, it is characterised in that composition of raw materials composition includes by weight：
2. a kind of ultra-toughness MC nylon materials as claimed in claim 1 and preparation method thereof, it is characterised in that the base catalyst
At least one in potassium hydroxide, NaOH, metallic sodium.
3. a kind of ultra-toughness MC nylon materials as claimed in claim 1 and preparation method thereof, it is characterised in that the activating agent choosing
From '-diphenylmethane diisocyanate, triphenylmethane triisocyanate, toluene di-isocyanate(TDI), the isocyanic acid of dicyclohexyl methyl hydride two
Any of ester, hexamethylene diisocyanate.
4. a kind of ultra-toughness MC nylon materials as claimed in claim 1 and preparation method thereof, it is characterised in that the modified Nano
Silica is reacted by dendritic macromole silicon dioxide granule, is carried centered on used Amino End Group dendritic macromole
Hydrolyzable alkoxyl silicone ester group, is combined by covalent bond with silica.
5. a kind of preparation method of ultra-toughness MC nylon materials, it is characterised in that comprise the following steps：
(1) caprolactam of 100 parts by weight is added in conical flask, being placed in oil bath pan to be warming up to 90 DEG C and heat makes acyl in oneself
Amine is melted, and after adding 0~0.15 part by weight modified nano silicon after caprolactam melting, stirring is allowed to be completely dissolved in oneself
Among acid amides melt；
(2) system obtained by step (1) is warming up to 120 DEG C, dehydration is vacuumized under the conditions of magnetic agitation, occurs solving during air pocket
Except vacuum；
(3) 0.1~0.35 parts by weight base catalyst is added in the system of step (2), is vacuumized, while temperature rises to 140 DEG C,
Continue magnetic agitation to be dehydrated to there is air pocket, persistently vacuumize 10 minutes, release vacuum；
(4) system obtained by step (3) is added 0.75~1 parts by weight of activated dose while stirring, obtains treating aggressiveness system, be poured into thing
In the mould first preheated in 180 DEG C of baking ovens, continue to heat after 2 hours, be cooled to room temperature, obtain ultra-toughness MC nylon materials.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710182935.XA CN106947077A (en) | 2017-03-24 | 2017-03-24 | A kind of ultra-toughness MC nylon materials and preparation method thereof |
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| CN201710182935.XA CN106947077A (en) | 2017-03-24 | 2017-03-24 | A kind of ultra-toughness MC nylon materials and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111961337A (en) * | 2020-08-13 | 2020-11-20 | 扬州尼尔工程塑料有限公司 | MC nylon/SiC @ SiO2Method for preparing composite material |
| CN115627037A (en) * | 2022-11-11 | 2023-01-20 | 湖北格林斯柏体育产业(集团)有限公司 | Preparation process of seamless semi-prefabricated court material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111961337A (en) * | 2020-08-13 | 2020-11-20 | 扬州尼尔工程塑料有限公司 | MC nylon/SiC @ SiO2Method for preparing composite material |
| CN115627037A (en) * | 2022-11-11 | 2023-01-20 | 湖北格林斯柏体育产业(集团)有限公司 | Preparation process of seamless semi-prefabricated court material |
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Application publication date: 20170714 |