CN113045748B - Modified hollow glass microsphere, cast nylon 6 composition containing modified hollow glass microsphere and preparation method thereof - Google Patents
Modified hollow glass microsphere, cast nylon 6 composition containing modified hollow glass microsphere and preparation method thereof Download PDFInfo
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- CN113045748B CN113045748B CN201911384084.2A CN201911384084A CN113045748B CN 113045748 B CN113045748 B CN 113045748B CN 201911384084 A CN201911384084 A CN 201911384084A CN 113045748 B CN113045748 B CN 113045748B
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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
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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
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/28—Glass
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
Abstract
The invention discloses a modified hollow glass microsphere, a cast nylon 6 composition containing the modified hollow glass microsphere and a preparation method thereof. The preparation method of the modified hollow glass microsphere comprises the following steps: putting the glass microspheres into a reaction kettle, adding ammonia water, carrying out primary stirring at normal pressure and normal temperature, closing the reaction kettle, pressurizing to 0.2-0.3MPA, carrying out secondary stirring at normal temperature, opening the reaction kettle, and sequentially carrying out filtering, washing and drying to obtain the modified hollow glass microspheres. The invention carries out surface modification treatment on the glass microsphere, so that a great amount of hydroxyl groups are enriched on the surface of the glass microsphere. The special glass microspheres are added into nylon, so that the strength and the impact property of the cast nylon 6 composition can be obviously improved. The cast nylon 6 composition product prepared by the invention has the characteristics of low density, light weight, excellent mechanical property and the like.
Description
Technical Field
The invention belongs to the field of polymer composite materials, and particularly relates to a modified hollow glass microsphere, a cast nylon 6 composition containing the modified hollow glass microsphere and a preparation method thereof.
Background
The hollow glass microsphere is a hollow glass sphere with tiny size, and belongs to an inorganic non-metallic material. The typical particle size range is 10-180 microns, the bulk density is 0.1-0.25 g/cubic centimeter, and the material has the advantages of light weight, low heat conduction, sound insulation, high dispersion, good electrical insulation and thermal stability and the like, and is a novel light material which is developed in 2008 and has wide application and excellent performance. The color is pure white. Can be widely used in any product with requirements on appearance color.
The hollow glass microsphere has light specific weight and large volume, the density is about one tenth of the density of the particles of the traditional filler, the basic weight of the product can be greatly reduced after the hollow glass microsphere is filled, more resin for production is replaced and saved, and the product cost is reduced. With an organically modified (oleophilic) surface. The hollow glass microspheres are tiny round spheres, and have better fluidity in liquid resin than flaky, acicular or irregular fillers, so the filling performance is excellent. More importantly, the small microspheres are isotropic, so that the defect of inconsistent shrinkage of different parts caused by orientation is avoided, the dimensional stability of the product is ensured, and the product cannot warp.
The hollow glass microsphere has sound and heat insulating property because of the inside of the thin gas, and is an excellent filler for various heat insulating and sound isolating products. The insulating properties of the hollow glass microspheres may also be used to protect the product from thermal shock caused by alternating between rapid heating and quenching conditions. The high specific resistance and the low water absorption rate can be widely used for processing and producing cable insulating materials.
The glass microsphere particles of the spheres determine the minimum specific surface area and low oil absorption rate, the using amount of resin can be greatly reduced in the using process, the viscosity can not be greatly increased even under the premise of high adding amount, the production operation condition is greatly improved, and the production efficiency can be improved by 10-20%.
In the prior art, when the glass microspheres are applied to a cast nylon 6 (caprolactam) composition, the density of the composition can be reduced, and the strength and the impact resistance of the composition can be improved. The glass microspheres and the cast nylon 6 have poor interface bonding capacity and poor compatibility, and commonly used coupling agents KH550 and KH570 are added to improve the interface bonding capacity, however, the coupling agents have limited strength and impact resistance in the microsphere-filled caprolactam composition, and further application of the microsphere-filled caprolactam composition is limited.
Disclosure of Invention
The invention aims to provide a modified hollow glass microsphere, a cast nylon 6 composition containing the modified hollow glass microsphere and a preparation method thereof, and aims to solve the problems in the prior art.
The purpose of the invention is realized by the following technical scheme:
a modified hollow glass microsphere is prepared by the following method: putting the glass microspheres into a reaction kettle, adding ammonia water, carrying out primary stirring at normal pressure and normal temperature, closing the reaction kettle, pressurizing to 0.2-0.3MPA, carrying out secondary stirring at normal temperature, opening the reaction kettle, and sequentially carrying out filtering, washing and drying to obtain the modified hollow glass microspheres.
In a further scheme, the weight ratio of the glass microspheres to ammonia water is 1; the mass concentration of the ammonia water is 25-28%.
In a further scheme, the glass microspheres are of hollow structures, and the wall thickness is 0.08-0.25 g/cm 3 The grain size is 10-150 microns.
In a further scheme, the stirring speed of the primary stirring is 100-150 revolutions per minute, and the stirring time is 5-10 minutes; the stirring speed of the secondary stirring is 60-100 r/min, and the stirring time is 10-20 min.
The invention also aims to provide a casting nylon 6 composition containing the modified hollow glass microspheres, which is prepared from the following components in parts by weight:
in a further embodiment, the activator is toluene diisocyanate.
The third object of the present invention is to provide the above-mentioned method for preparing a cast nylon 6 composition, comprising the steps of: adding caprolactam and modified hollow glass microspheres into a reaction kettle according to the proportion, heating to 100-120 ℃, closing the kettle, removing water under negative pressure for 5-10min, and stirring at the speed of 60-100 revolutions per minute; and opening the kettle, adding the sodium hydroxide, the activating agent, the antioxidant 1098 and the antioxidant 168 according to the proportion, uniformly stirring, casting into a mold, heating the mold to 170-190 ℃, and maintaining the curing time for 20-30 minutes to prepare the cast nylon 6 composition.
Compared with the prior art, the invention has the beneficial effects that:
(1) The method utilizes ammonia water to carry out surface modification treatment on the glass microspheres under the pressurizing condition, wherein the pressurizing condition is that the ammonia gas dissolved in the ammonia water has certain volatility, and the volatilization of the ammonia gas can be reduced under the pressurizing condition, so that the ammonia gas in the ammonia water is kept in a certain concentration range, the action of the ammonia water on the glass microspheres is ensured, and the purpose of full reaction is achieved. According to the invention, the surface of the glass microsphere is enriched with a large amount of hydroxyl groups by carrying out surface modification treatment on the glass microsphere, and when the glass microsphere containing the hydroxyl groups is added into nylon, the hydroxyl groups participate in polymerization, so that the glass microsphere and the nylon 6 are bonded by macromolecular chains, and the strength and the impact property of the cast nylon 6 composition are obviously improved.
(2) Because the modified hollow glass microspheres are used, the prepared cast nylon 6 composition product has the characteristics of low density, light weight, excellent mechanical property and the like.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The types and suppliers of the reagents used in this example were as follows:
caprolactam is purchased from basf, germany, technical grade;
sodium hydroxide was purchased from corridor, peng color, fine chemical, ltd, and analytically pure;
the ammonia water has a concentration of 25-28%, is purchased from Tianjin Kemi European chemical reagent Co., ltd, and is analytically pure;
glass microspheres were purchased from 3M company, USA under the brand IM30K;
the activator is toluene diisocyanate, commercially available.
The reagents are provided only for illustrating the sources and components of the reagents used in the experiments of the present invention, so as to be fully disclosed, and do not indicate that the present invention cannot be realized by using other reagents of the same type or other reagents supplied by other suppliers.
Example 1
Preparing modified hollow glass microspheres: 100 parts by weight of glass microspheres are placed in a reaction kettle, 500 parts by weight of ammonia water is added, and the mixture is stirred for 8 minutes at normal pressure and temperature, wherein the stirring speed is 120 r/min. And (3) closing the kettle, pressurizing to 0.25MPA, stirring at the speed of 80 rpm, stirring at normal temperature for 15 minutes, opening the kettle, and sequentially filtering, washing and drying to obtain the modified hollow glass microspheres.
Preparation of cast nylon 6 composition: putting 100 parts of caprolactam and 5 parts of modified hollow glass microspheres into a reaction kettle, heating to 100 ℃, closing the kettle, removing water under negative pressure for 10min, and stirring at 100 revolutions per minute; and opening the kettle, adding 0.5 part of sodium hydroxide, 0.5 part of activating agent, 1 part of antioxidant 1098 and 1 part of antioxidant 168, uniformly stirring, casting into a mold, heating the mold to 170 ℃, and maintaining the curing time for 30 minutes to prepare the cast nylon 6 composition.
Example 2
The preparation method of the modified hollow glass microspheres is the same as that of example 1;
preparation of cast nylon 6 composition: putting 100 parts of caprolactam and 15 parts of modified hollow glass microspheres into a reaction kettle, heating to 120 ℃, closing the kettle, removing water under negative pressure for 5min, and stirring at 60 revolutions per minute; and opening the kettle, adding 1 part of sodium hydroxide, 1 part of activating agent, 1.5 parts of antioxidant 1098 and 1.5 parts of antioxidant 168, uniformly stirring, casting into a mold, heating the mold to 190 ℃, and maintaining the curing time for 30 minutes to prepare the cast nylon 6 composition.
Example 3
The preparation method of the modified hollow glass microspheres is the same as that of example 1;
preparation of cast nylon 6 composition: putting 100 parts of caprolactam and 8 parts of modified hollow glass microspheres into a reaction kettle, heating to 100 ℃, closing the kettle, removing water under negative pressure for 5min, and stirring at 60 revolutions per minute; and opening the kettle, adding 0.6 part of sodium hydroxide, 0.6 part of activating agent, 1.5 parts of antioxidant 1098 and 1.5 parts of antioxidant 168, uniformly stirring, casting into a mold, heating the mold to 180 ℃, and maintaining the curing time for 25 minutes to prepare the cast nylon 6 composition.
Example 4
The preparation method of the modified hollow glass microspheres is the same as that of example 1;
preparation of cast nylon 6 composition: putting 100 parts of caprolactam and 12 parts of modified hollow glass microspheres into a reaction kettle, heating to 120 ℃, closing the kettle, removing water under negative pressure for 10min, and stirring at 100 revolutions per minute; and opening the kettle, adding 0.7 part of sodium hydroxide, 0.7 part of activating agent, 1.5 parts of antioxidant 1098 and 1.5 parts of antioxidant 168, uniformly stirring, casting into a mold, heating the mold to 190 ℃, and maintaining the curing time for 30 minutes to prepare the cast nylon 6 composition.
Example 5
Preparation method of modified hollow glass microspheres is the same as example 1
Preparation of cast nylon 6 composition: putting 100 parts of caprolactam and 10 parts of modified hollow glass microspheres into a reaction kettle, heating to 110 ℃, closing the kettle, removing water under negative pressure for 8min, and stirring at 80 r/min; and opening the kettle, adding 0.8 part of sodium hydroxide, 0.7 part of activating agent, 1 part of antioxidant 1098 and 1 part of antioxidant 168, uniformly stirring, casting into a mold, heating the mold to 180 ℃, and maintaining the curing time for 25 minutes to prepare the cast nylon 6 composition.
Comparative example 1
In comparison with example 5. The processing method of the modified glass microspheres comprises the following steps: 100 parts of glass microspheres and 1 part of KH550 are put into a mixer and mixed uniformly. Other technical parameters are the same.
Comparative example 2
In comparison with example 5. The processing method of the modified glass microspheres comprises the following steps: 100 parts of glass microspheres and 1 part of KH570 are put into a mixer to be uniformly mixed. Other technical parameters are the same.
Comparative example 3
In comparison with example 5.
The modified hollow glass microsphere of the comparative example is prepared by the following preparation process:
100 parts by weight of commercially available glass microspheres are placed in a reaction kettle, 500 parts by weight of ammonia water is added, and the mixture is stirred for 8 minutes at normal pressure and temperature, wherein the stirring speed is 120 revolutions per minute. And opening the kettle, filtering, washing with water, and drying to obtain the modified hollow glass microspheres.
Placing 100 parts of caprolactam and 10 parts of modified hollow glass microspheres into a reaction kettle, heating to 110 ℃, closing the kettle, removing water under negative pressure for 8min, and stirring at 80 revolutions per minute; and opening the kettle, adding 0.8 part of sodium hydroxide, 0.7 part of activating agent, 1 part of antioxidant 1098 and 1 part of antioxidant 168, uniformly stirring, casting into a mold, heating the mold to 180 ℃, and maintaining the curing time for 25 minutes to prepare the cast nylon 6 composition.
Comparative example 4
In comparison with example 5.
The modified hollow glass microsphere of the comparative example is prepared by the following preparation process:
100 parts by weight of commercially available glass microspheres were placed in a reaction vessel, 500 parts by weight of an aqueous solution of sodium hydroxide (5 g/100 g) was added thereto, and the mixture was stirred at normal pressure and temperature for 8 minutes at a stirring speed of 120 rpm. And opening the kettle, filtering, washing with water, and drying to obtain the modified hollow glass microspheres.
Preparation of cast nylon 6 composition: putting 100 parts of caprolactam, 0.8 part of sodium hydroxide and 10 parts of modified hollow glass microspheres into a reaction kettle, heating to 110 ℃, closing the kettle, removing water under negative pressure for 8min, and stirring at 80 revolutions per minute; and opening the kettle, adding 0.7 part of activating agent, 1 part of antioxidant 1098 and 1 part of antioxidant 168, uniformly stirring, casting into a mold, heating the mold to 180 ℃, and maintaining the curing time for 25 minutes to prepare the cast nylon 6 composition.
Comparative example 5
In comparison with example 5.
The modified hollow glass microsphere of the comparative example is prepared by the following preparation process:
100 parts by weight of commercially available glass microspheres are placed in a reaction kettle, 500 parts by weight of ammonia water is added, and the mixture is stirred for 8 minutes at normal pressure and temperature, wherein the stirring speed is 120 revolutions per minute. The mixture is pressurized to 0.25MPA, stirred for 15 minutes at normal temperature and the stirring speed is 80 r/min. And opening the kettle, filtering, washing and drying to obtain the modified hollow glass microspheres.
Putting 100 parts of caprolactam, 0.8 part of sodium hydroxide and 10 parts of modified hollow glass microspheres into a reaction kettle, heating to 110 ℃, closing the kettle, removing water under negative pressure for 8min, and stirring at 80 revolutions per minute; and opening the kettle, adding 0.7 part of activating agent, 1 part of antioxidant 1098 and 1 part of antioxidant 168, uniformly stirring, casting into a mold, heating the mold to 180 ℃, and maintaining the curing time for 25 minutes. A cast nylon 6 composition was prepared.
The mechanical property test method comprises the following steps:
the mechanical property test method adopts ASTM standard injection molding. The spline dimensions (length × width × thickness) are: tensile bars (dumbbell type) 170mm by 13mm by 3.2mm; notched impact bars, 127mm by 13mm by 3.2mm, V-notches, with a notch depth of 1/5.
Tensile strength: the tensile rate was 5mm/min as measured by ASTM D638.
Impact strength of the simply supported beam notch: testing according to ASTM D6110-2018.
The performance test results are shown in table 1:
TABLE 1 Performance test results
Compared with the comparative examples 1 and 2, the ammonia water modified glass microsphere in the invention has better treatment effect than that of coupling agents KH550 and KH570 commonly used in the market by adopting ammonia water to modify the glass microsphere in the embodiment 5, greatly enhances the interfacial bonding capacity between caprolactam and the glass microsphere, and can obviously improve the mechanical property of the cast nylon 6 composition.
As can be seen by comparing example 5 with comparative example 3, it is very important to treat hollow glass microspheres with 0.2-0.3MPA under pressure, this step is eliminated, the hydroxylation rate on the surfaces of the hollow glass microspheres is very low, and the improvement of the tensile strength and impact strength of the nylon 6 cast nylon composition is limited. The reason may be that ammonia has certain volatility, and the volatilization rate of ammonia can be reduced under the pressurizing condition, so that ammonia in ammonia water is kept in a certain concentration range, and the surface treatment effect of ammonia water on glass beads is ensured.
As can be seen by comparing example 5 with comparative example 4, a common sodium hydroxide solution cannot be used when handling glass beads. The sodium hydroxide solution can corrode the surface of the glass beads, damage the glass beads and lead to sphere breakage. Affecting the properties of the final cast nylon composition.
As can be seen by comparing example 5 with comparative example 5, sodium hydroxide could not be mixed with the glass beads for a long time with the caprolactam being dewatered. The surface of the glass beads is slightly corroded, and the performance of the final cast nylon composition is affected.
The embodiments described above are intended to facilitate one of ordinary skill in the art in understanding and using the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (6)
1. A casting nylon 6 composition containing modified hollow glass microspheres is characterized in that: the composition is prepared from the following components in parts by weight:
100 parts of caprolactam, namely preparing a mixture of caprolactam,
0.5 to 1 portion of sodium hydroxide,
0.5-1 part of an activating agent,
5-15 parts of modified hollow glass microspheres,
1098-2 parts of an antioxidant agent,
1-2 parts of an antioxidant 168;
the modified hollow glass microsphere is prepared by the following method: putting the glass microspheres into a reaction kettle, adding ammonia water, carrying out primary stirring at normal pressure and normal temperature, closing the kettle, pressurizing to 0.2-0.3MPa, carrying out secondary stirring at normal temperature, opening the kettle, and sequentially carrying out filtering, washing and drying to obtain the modified hollow glass microspheres.
2. The cast nylon 6 composition containing modified hollow glass microspheres of claim 1, wherein: the weight ratio of the glass microspheres to ammonia water is 1; the mass concentration of the ammonia water is 25-28%.
3. The cast nylon 6 composition containing modified hollow glass microspheres of claim 1, wherein: the glass microspheres are of hollow structures, and the wall thickness is 0.08-0.25 g/cm 3 The grain diameter is 10-150 microns.
4. The cast nylon 6 composition containing modified hollow glass microspheres of claim 1, wherein: the stirring speed of the primary stirring is 100-150 rpm, and the stirring time is 5-10 minutes; the stirring speed of the secondary stirring is 60-100 r/min, and the stirring time is 10-20 min.
5. The cast nylon 6 composition containing modified hollow glass microspheres of claim 1, wherein: the activating agent is toluene diisocyanate.
6. The method of preparing a cast nylon 6 composition containing modified hollow glass microspheres of any one of claims 1 to 5, wherein: the method comprises the following steps: adding caprolactam and modified hollow glass microspheres into a reaction kettle according to the proportion, heating to 100-120 ℃, closing the kettle, removing water under negative pressure for 5-10min, and stirring at the speed of 60-100 revolutions per minute; and opening the kettle, adding the sodium hydroxide, the activating agent, the antioxidant 1098 and the antioxidant 168 according to the proportion, uniformly stirring, casting into a mold, heating the mold to 170-190 ℃, and maintaining the curing time for 20-30 minutes to prepare the cast nylon 6 composition.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081927A (en) * | 2007-07-05 | 2007-12-05 | 吉林大学 | Glass micro-bead filling modified mould nylon plate and preparation method thereof |
| CN101293755A (en) * | 2008-06-25 | 2008-10-29 | 陈建华 | Surface modification method for hollow glass tiny bead and uses thereof |
| CN109957236A (en) * | 2019-04-03 | 2019-07-02 | 河南城建学院 | Activeness and quietness wearable lightweight cast nylon composite material and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2660268B1 (en) * | 2010-12-28 | 2019-08-07 | Shanghai Genius Advanced Material (Group) Co. Ltd | Nano particle/polyamide composite material, preparation method therefor, and use thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081927A (en) * | 2007-07-05 | 2007-12-05 | 吉林大学 | Glass micro-bead filling modified mould nylon plate and preparation method thereof |
| CN101293755A (en) * | 2008-06-25 | 2008-10-29 | 陈建华 | Surface modification method for hollow glass tiny bead and uses thereof |
| CN109957236A (en) * | 2019-04-03 | 2019-07-02 | 河南城建学院 | Activeness and quietness wearable lightweight cast nylon composite material and preparation method |
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