CN109721728A - A kind of polyamide 6/fluorescein composite material and preparation method - Google Patents
A kind of polyamide 6/fluorescein composite material and preparation method Download PDFInfo
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- CN109721728A CN109721728A CN201811606363.4A CN201811606363A CN109721728A CN 109721728 A CN109721728 A CN 109721728A CN 201811606363 A CN201811606363 A CN 201811606363A CN 109721728 A CN109721728 A CN 109721728A
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- fluorescein
- polyamide
- composite material
- adipic acid
- caprolactams
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Abstract
The application belongs to the polymer composites technical field in material science, and in particular to a kind of polyamide 6/fluorescein composite material and preparation method patent application matters.The material is prepared using situ aggregation method, using fluorescein as filler in preparation process, using adipic acid as catalyst.When preparation, system is risen to 190 ~ 210 DEG C first, heating melting back flow reaction；After reaction, vapor is discharged, so that system temperature is increased to 210 ~ 230 DEG C, system is then made to be gradually heated to 260 DEG C；It finally vacuumizes and is gradually decreased to -0.08MPa.Polymer composites provided herein are used by the addition of fluorescein, polymer material performance have on the one hand been greatly improved, on the other hand, due to the addition of fluorescent material, the application range of polymerizing polyamide material has been widened, therefore there is preferable practical value and promote and apply meaning.
Description
Technical field
The application belongs to the polymer composites technical field in material science, and in particular to a kind of polyamide 6/fluorescence
Plain composite material and preparation method patent application matters.
Background technique
Polymer composites are one of current material scientific domain research hotspots, since this kind of material has organic and nothing
The characteristics of machine material, and more new excellent properties be can produce out by interaction between the two, therefore be to explore height
One performance, multifunctional composite important channel.
In the prior art, there are many preparation methods of polymer composites, wherein there are four types of more common: melting is altogether
Mixed method, sol-gel method, intercalation polymeric method and situ aggregation method.And due to suitable material and to polymer composites
Difference can be required, therefore different preparation methods respectively there are advantage and disadvantage, and foundation is needed to want the specific performance of polymer composites
It asks, different raw material property features suitably select and determine most suitable preparation method.
Polyamide 6 is commonly called as nylon (Nylon) 6, is one of most important engineering plastics, and yield is in five big general engineerings
It ranks first in plastics, because it is with excellent performance, such as intensity is high, flame retardant property is strong, rigid and wear-resisting property is good, is easy to add
Work etc., and it is widely used in the fields such as automobile, machinery, electronic apparatus, communication apparatus, instrument and meter, building.With modern section
The development of technology and practical application, demand of the people to polyamide 6 become higher, especially to its intensity, heat resistance, cold-resistant
Property etc..These inherent defects such as " dimensional stability are poor, and water absorption rate is higher " of polyamide 6 become the weight for limiting its application
Want factor.In order to improve the mechanical performance of polyamide 6, it is often necessary to inorganic filler or organic filler is added as modifying agent,
To improve the comprehensive performance of polyamide 6.In the prior art, based on different performance requirement, also have more using this technical thought as base
The technological improvement of plinth progress simultaneously achieves preferable technical effect.But in general, due to the difference of technical performance demand, for
New material design, the new capability improvement carried out based on polyamide 6 still has the necessity further explored.
Summary of the invention
The application is designed to provide a kind of polyamide 6/fluorescein composite material, to allow to meet an urgent need in safety
(such as mark of security against fire facility equipment, the mark of buoyant apparatus, emergency evacuation mark, emergency guidance lighting), traffic fortune
Defeated (such as traffic sign) field plays certain effect.
Details are as follows for the technical solution that the application is taken.
A kind of polyamide 6/fluorescein composite material, the material are prepared using situ aggregation method, in preparation process with
Fluorescein is filler, and using acid as catalyst, specific preparation process is as described below:
(1) epsilon-caprolactams, water (specifically for example, by using distilled water), acid catalyst, fluorescein are added in reaction vessel, it is close
Envelope, makes system rise to 190 ~ 210 DEG C from room temperature, 2 ~ 4 h of back flow reaction sufficiently reacts after heating melting；
In reaction process, to react fully, magnetic agitation mode can be aided with and be stirred, to react fully；
The acid catalyst, using inorganic acid or organic acid, specifically for example, by using adipic acid, acetic acid, sulfuric acid, phosphoric acid, ammonia
Base caproic acid etc.；
For using adipic acid as catalyst, in terms of mass volume ratio example, each specific dosage of material is epsilon-caprolactams: water: oneself
Diacid: the fluorescein=50 ~ mL:1 ~ 2 of 100 g:1 ~ 3 g:0.1-1.5g；
Specific dosage is for example are as follows: epsilon-caprolactams: water: adipic acid: fluorescein=100 g:2 mL:1 g:0.1-1.5g；
(2) to after reaction, discharge vapor in step (1), then system temperature is made to be increased to 210 ~ 230 in 0.5 ~ 1h
DEG C, so that system is gradually heated to 260 DEG C in 1.5 ~ 2h, (it should be noted that heating rate is unsuitable too fast, temperature is increased
The too fast stabilization for being unfavorable for product quality), as polyamide 6/fluorescein composite material；To ensure end product quality, preferably
Operation is should be, and is kept this temperature (260 DEG C), is vacuumized and be gradually decreased to -0.08Mpa, be then vented again；
Last shape of product, type cast molding while hot as needed.
When specific cast molding, it can be cast into tensile strength of the dumbbell shape sample for test material, or be cast into " V "
Font notched sample is used for the impact strength of test material.
The polyamide 6/fluorescein composite material is applied in fluorescence instruction product, such as anti-in meeting an urgent need safely
The mark of safety devices equipment, the mark of buoyant apparatus, emergency evacuation mark, emergency guidance lighting, or it is used for communications and transportation
In traffic mark etc..
In the application, by the way that polymer and fluorescein are compounded to form new polymer composites, it can not only embody
The excellent properties such as the light of polymer, good toughness, intensity height also impart the new characteristic of polymer.Utilize x-ray diffractometer
(XRD) after the instrument and equipments such as/thermogravimetric analyzer (TGA) characterize prepared composite material, test and analysis result table
Bright: with the addition of fluorescein filler, the crystalline structure of polyamide 6 matrix tends to γ crystal form；And with adding for fluorescein
Enter, the performance parameters such as slight, impact flexibility of stretching of polymer composites are also significantly enhanced, and show preferable property
It can improvement effect；And due in polymer fluorescein still there is fluorescent characteristic, can relatively be used on it is safe emergency (such as fire-fighting pacify
Mark, the mark of buoyant apparatus, emergency evacuation mark, emergency guidance lighting of full facility equipment etc.), communications and transportation (such as traffic
Mark) etc. need field of fluorescence and play a role.
In general, polymer composites provided herein pass through fluorescence although preparation method is more conventional
The addition of element uses, and polymer material performance has on the one hand been greatly improved, and on the other hand, due to the addition of fluorescent material, widens
The application range of polymerizing polyamide material, therefore there is preferable practical value and promote and apply meaning.
Detailed description of the invention
Fig. 1 is polyamide 6 and polyamide 6/image of the fluorescein composite material under ultraviolet light, A(left figure in figure) be
Polyamide 6/fluorescein composite material, B(right figure) it is polyamide 6；
Fig. 2 is polyamide 6 and polyamide 6/fluorescein composite material XRD spectrum；
Fig. 3 is polyamide 6 and polyamide 6/fluorescein composite material thermogravimetric curve；
Fig. 4 is polyamide 6 and polyamide 6/fluorescein composite material tensile strength and impact flexibility.
Specific embodiment
Explanation is further explained to the application below with reference to embodiment.Before introducing specific embodiment, with regard to following realities
Situations such as applying part experimental material, laboratory apparatus in example is briefly introduced and is described as follows.
Experimental material:
Epsilon-caprolactams (CP, chemistry are pure), BASF AG produces (Chinese Zhengzhou),
Adipic acid (AR is analyzed pure), sends Buddhist nun's chemical reagent factory (Chinese Zhengzhou),
Fluorescein (AR), Shanghai Jing Chun biochemical technology limited liability company (Chinese Shanghai)；
Key instrument:
X-ray diffraction analyzer (X-PertPro), Dutch Philips Co., Ltd,
Thermogravimetric analyzer (TGA), Shanghai You Ke instrument and meter Co., Ltd,
Microcomputer controlled electro minor universal testing machine (WDW-10D), Shijin Group Co., Ltd., Jinan,
Pendulum impact test (ZBC-1400-2), Shenzhen Sans Material Detection Co., Ltd.
Embodiment
Polyamide 6 provided by the present embodiment/fluorescein composite material, the material are prepared using situ aggregation method,
Using fluorescein as filler in preparation process, using adipic acid as catalyst, specific preparation process is as described below:
(1) by 100 g of epsilon-caprolactams, 2 mL of distilled water, 1.0 g of adipic acid, fluorescein (fluorescein dosage be respectively 0.1g,
0.3g, 0.5g, 0.7g, 0.9g) it is added in three-necked flask, heated melting magnetic agitation makes system rise to 190 DEG C from room temperature,
Back flow reaction 3h；
(2) to after reaction, after discharging vapor, make system temperature be increased to 230 DEG C in 0.5h, then in step (1)
System is set to be gradually heated to 260 DEG C in 1.5；
This temperature is kept, vacuumizes and is gradually decreased to -0.08MPa, emptying is cast into dumbbell specimens for testing material respectively while hot
The tensile strength of material, and it is cast into impact strength of " V " the font notched sample for test material.
It should be noted that " dumbbell " the shape sample, " V " font notched sample, with reference to national standard GB/T 1040-1992
It requires in GB/T 1040-1993, is no longer described in detail.
Comparative example
As a comparison case, preparation method and the same above-described embodiment of material amounts, difference, which is only that, does not add fluorescein；Equally, divide
It has not cast dumbbell shape sample and " V " font notched sample.
Material characterization and performance measurement are carried out respectively to sample prepared by above-described embodiment, comparative example.It should be noted that
It is 24 hours dry in 80 DEG C of baking ovens before all samples test, to eliminate influence of the moisture to material property.Concrete outcome
It is described below.
(1) material characterization
(1) fluorescent characteristic
Whether inventor still there is fluorescent characteristic to carry out fluorescein in polyamide 6 under ultraviolet light/fluorescein composite material
Detection determines, as a result as shown in Figure 1 (Fig. 1 is section Example testing of materials result).
It will be seen from figure 1 that polyamide 6/fluorescein composite material still has fluorescein under the irradiation of ultraviolet light
Fluorescent characteristic, and fluorescence uniformity, this is the result shows that the preparation method of the application can be such that fluorescein is uniformly dispersed
In basis material, and do not have to destroy fluorescein original structure during synthetic composite material, so that composite material
Still with the fluorescent characteristic of fluorescein.
(2) X-ray diffraction analysis
Using X-ray diffractometer respectively to polyamide 6 (comparative example) and polyamide 6/fluorescein composite material (fluorescence cellulose content
0.5% material) existence in polyamide 6 matrix of crystalline structure and fluorescein be measured.Test parameter are as follows:
30 mA of electric current, voltage are 40 kV, and 2 °/min of scanning speed, scanning range is 5 ° -85 °, 0.03 ° of sweep spacing.
XRD spectrum is as shown in Figure 2.Analysis can be seen that the addition due to fluorescein, so that polyamide 6 not only has α brilliant
Type structure also has γ crystal form.Specifically, in addition to the α feature for occurring 20.1 ° and 24.1 ° is spread out on the XRD curve of polyamide 6
Peak is penetrated, there are also the γ diffraction maximums at 22.2 °；And the composite material of fluorescein is added compared with pure polyamide 6, alpha-crystal form spreads out
Peak decrease is penetrated, i.e., fluorescein has promoted polyamide 6 crystalline texture to tend to γ crystal form.Think: after fluorescein is added, so that
Agglomeration is difficult to avoid that, in turn results in the retard motion of polyamide 6 molecule, it is intended to generate γ crystal form.
(3) thermogravimetic analysis (TGA)
Determine polyamide 6 (comparative example) and polyamide 6/(fluorescein contains fluorescein composite material respectively using thermogravimetric analyzer
Measure 0.5% material) thermogravimetric curve.When test: temperature range is 20 DEG C ~ 700 DEG C, and heating rate is 20 DEG C/min.
Thermogravimetric curve is as shown in Figure 3.Analysis is as can be seen that polyamide 6/fluorescein composite material and pure polyamide 6
Thermal decomposition process is similar, and more slow lower than 400 DEG C of decomposition rates, higher than 430 DEG C decomposition rates start to accelerate, but due to fluorescence
The addition of element, the thermal decomposition temperature of composite material is still raised.Specifically, the thermal decomposition temperature of polyamide 6 is
415 DEG C, after fluorescein is added, thermal decomposition temperature is 432 DEG C.In general, the thermal decomposition temperature degree of cross-linking of composite material
There is close relationship, thermal decomposition temperature increases with the raising of the degree of cross linking in any case.Therefore, fluorescein is added
Afterwards, by the polymerization reaction of fluorescein and the amino of polyamide, the molecular chain structure of polyamide is changed, to make its thermal decomposition
Temperature increases.
(2) Mechanics Performance Testing
With reference to corresponding GB standard (GB/T 1040-1992 and GB/T 1040-1993), respectively to polyamide 6 and polyamide 6/
Fluorescein composite material tensile strength is measured with impact flexibility, as a result as shown in Figure 4.
Analysis can be seen that the increase with fluorescein additional amount, and the mechanical property presentation of composite material first increases drops afterwards
Low trend.When fluorescence cellulose content is 0.5%, the tensile strength of system is maximum, reaches 43.26MPa, improves than pure polyamide 6
38.9%；The maximum impact intensity of same composite material also appears in 0.5%, reaches 15.36MPa, improves than pure polyamide 6
49.3%。
According to the analysis, the variation of the tensile strength for system, when fluorescence cellulose content is 0.5%, fluorescein is in polyamide
Disperse in 6 systems relatively uniform；When its content is more than 0.5%, the viscosity of system increases, so that the dispersion difficulty of fluorescein becomes
Greatly, fluorescein has been likely to occur the phenomenon that moiety aggregation, results in the reduction of the tensile strength of composite material.And for system
The reason of impact flexibility changes: when fluorescence cellulose content is 0.5%, fluorescein is uniformly dispersed in polyamide 6 matrix, improves
The plastic deformation of compound system is capable of the impact stress of dispersion, absorbs more impact energys, so that the impact of composite material
Intensity greatly enhances.
In conclusion it has been recognised by the inventors that will not be broken when preparing polyamide 6/fluorescein composite material using situ aggregation method
The structure of bad fluorescein, and assign polyamide 6 good fluorescence property, but when fluorescein additive amount is no more than 0.5%, can make
Fluorescein is more evenly dispersed in basis material, and composite material tensile strength, thermal decomposition temperature, maximum impact can be made strong
Some column physicochemical properties such as degree, which obtain preferable degree, to be improved.And the fluorescent characteristic based on these performance improvements and new material, it can incite somebody to action
In terms of polyamide 6/fluorescein composite material and its product are met an urgent need for safety, mark, lifesaving such as security against fire facility equipment
The mark of equipment, emergency evacuation mark, meet an urgent need guidance lighting and military installations cove lighting；In traffic and transport field for handing over
Logical mark；In terms of building decoration, it can be used for decorating, beautify indoor and outdoor surroundings, electric energy is saved in easy improving eyesight；It can also be used in instrument
The instruction of instruments and meters disk and common consumer product decoration, therefore with good application prospect.
Claims (6)
1. a kind of polyamide 6/fluorescein composite material, which is characterized in that the material is prepared using situ aggregation method, preparation
In the process using fluorescein as filler, using adipic acid as catalyst, which is made by the steps acquisition:
(1) epsilon-caprolactams, water, adipic acid, fluorescein being added in reaction vessel, sealing makes system rise to 190 ~ 210 DEG C,
2 ~ 4 h of back flow reaction after heating melting；
In terms of mass volume ratio example, each specific dosage of material is epsilon-caprolactams: water: adipic acid: fluorescein=50 ~ 100 g:1 ~
3 mL:1 ~ 2 g:0.1 ~ 1.5g；
(2) to after reaction, discharge vapor in step (1), then system temperature is made to be increased to 210 ~ 230 in 0.5 ~ 1h
DEG C, so that system is gradually heated to 260 DEG C in 1.5 ~ 2h；
This temperature is kept, vacuumizes and is gradually decreased to -0.08MPa.
2. polyamide 6 as described in claim 1/fluorescein composite material, which is characterized in that in step (1), each material is specifically used
Amount is epsilon-caprolactams: water: adipic acid: fluorescein=100 g:2 mL:1 g:0.1 ~ 1.5g.
3. polyamide 6 as claimed in claim 2/fluorescein composite material, which is characterized in that in step (1), each material is specifically used
Amount is epsilon-caprolactams: water: adipic acid: fluorescein=100 g:2 mL:1 g:0.1 ~ 0.9g.
4. polyamide 6 as claimed in claim 3/fluorescein composite material, which is characterized in that in step (1), each material is specifically used
Amount is epsilon-caprolactams: water: adipic acid: fluorescein=100 g:2 mL:1 g:0.3g；
It or is epsilon-caprolactams: water: adipic acid: fluorescein=100 g:2 mL:1 g:0.5g；
It or is epsilon-caprolactams: water: adipic acid: fluorescein=100 g:2 mL:1 g:0.7g.
5. the preparation method of any one of the claim 1 ~ 4 polyamide 6/fluorescein composite material, which is characterized in that including such as
Lower step:
(1) epsilon-caprolactams, water, adipic acid, fluorescein being added in reaction vessel, sealing makes system rise to 190 ~ 210 DEG C,
2 ~ 4 h of back flow reaction after heating melting；
(2) to after reaction, discharge vapor in step (1), then system temperature is made to be increased to 210 ~ 230 in 0.5 ~ 1h
DEG C, so that system is gradually heated to 260 DEG C in 1.5 ~ 2h；
This temperature is kept, vacuumizes and is gradually decreased to -0.08MPa.
6. any one of the claim 1 ~ 4 polyamide 6/fluorescein composite material is applied in fluorescence instruction product.
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| CN201811606363.4A CN109721728B (en) | 2018-12-27 | 2018-12-27 | Polyamide 6/fluorescein composite material and preparation method thereof |
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| CN201811606363.4A CN109721728B (en) | 2018-12-27 | 2018-12-27 | Polyamide 6/fluorescein composite material and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111410790A (en) * | 2020-04-29 | 2020-07-14 | 广东圆融新材料有限公司 | Humidity-sensitive fluorescent modified polypropylene material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1488790A (en) * | 2003-08-07 | 2004-04-14 | 东华大学 | Long-persistence/mminous polyamide fiber and preparing method thereof |
| US20070290174A1 (en) * | 2004-09-30 | 2007-12-20 | Arnold Stephen C | Lactam polymer derivatives |
| CN102690438A (en) * | 2012-06-14 | 2012-09-26 | 东华大学 | Polymer-based fluorescent functional composite material and fusing process method thereof |
-
2018
- 2018-12-27 CN CN201811606363.4A patent/CN109721728B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1488790A (en) * | 2003-08-07 | 2004-04-14 | 东华大学 | Long-persistence/mminous polyamide fiber and preparing method thereof |
| US20070290174A1 (en) * | 2004-09-30 | 2007-12-20 | Arnold Stephen C | Lactam polymer derivatives |
| CN102690438A (en) * | 2012-06-14 | 2012-09-26 | 东华大学 | Polymer-based fluorescent functional composite material and fusing process method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111410790A (en) * | 2020-04-29 | 2020-07-14 | 广东圆融新材料有限公司 | Humidity-sensitive fluorescent modified polypropylene material and preparation method thereof |
| CN111410790B (en) * | 2020-04-29 | 2022-10-25 | 广东圆融新材料有限公司 | Humidity-sensitive fluorescent modified polypropylene material and preparation method thereof |
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| CN109721728B (en) | 2021-09-07 |
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