CN106221082B - A kind of composite material and preparation method of Gemini surface active modified calcium carbonate filled polytetrafluoroethylene - Google Patents
A kind of composite material and preparation method of Gemini surface active modified calcium carbonate filled polytetrafluoroethylene Download PDFInfo
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- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
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Abstract
The invention discloses a kind of composite material of Gemini surface active modified calcium carbonate filled polytetrafluoroethylene, each raw material is calculated by weight as: 70~90 parts of polytetrafluoroethylsuspending suspending powder, 10~30 parts of calcium carbonate powder, 0.05~0.2 part of Gemini surface active, 0.15~0.5 part of paraffin.The present invention is by successively using Gemini surface active agent and paraffin to be modified calcium carbonate, make gained modified calcium carbonate surface in nonpolarity, has good processing fluidity, there is extraordinary compatibility with polytetrafluoroethylene (PTFE), gained composite material exhibits are made to go out excellent mechanical property and stability, and the preparation method that is related to is simple, cost of material is low, is suitble to promote and apply.
Description
Technical field
The invention belongs to field of compound material, are related to a kind of easily preparation, low cost and high performance advanced composite material (ACM), tool
Body is related to a kind of composite material and preparation method of Gemini surface active modified calcium carbonate filled polytetrafluoroethylene.
Background technique
Polytetrafluoroethylene (PTFE) (PTFE) have excellent chemical stability, radiation resistance, dielectric properties, extremely low coefficient of friction and
Self-lubrication has important answer in the national economy such as chemical industry, machinery, electronics, electric appliance, military project, space flight, environmental protection and bridge field
With.However due to the design feature of PTFE molecule, attraction is smaller between macromolecular, and ribbon crystal is easily removed by sheet, thus table
The disadvantages of being now poor mechanical property, linear expansion coefficient and big load metamorphism.Generally use micron order graphite, molybdenum disulfide, copper powder,
The inorganic particle filled modified ptfe such as glass fibre.
Inorganic filler has many advantages, such as high-modulus, easily prepares, and filling-modified macromolecule is that a kind of simple and effective improvement is high
The method of molecule performance, calcium carbonate (including coarse whiting and light calcium) have raw material is easy to get, is cheap, stability is good, color is simple,
Many advantages, such as nontoxic, and it is widely used in the fields such as plastics, rubber, papermaking, ink, building materials, wire and cable, it is a kind of frequent
It is used to the inorganic filler of filling-modified high molecular material.Relative to PTFE synthetic resin, the price of calcium carbonate is much lower, will
Calcium carbonate is added in PTFE, and the performances such as modulus and the wearability of PTFE can be improved, and can also be substantially reduced PTFE article
Price.Simultaneously compared to using the high cost filler of the inorganic particulates such as molybdenum disulfide, copper powder modified, the cost of calcium carbonate is obviously wanted
It is low many.However since calcium carbonate belongs to inorganic particle, particle surface be it is hydrophilic and oleophobic, stronger polarity is presented, with PTFE
Binding force is low between matrix, and when loading of the calcium carbonate in PTFE matrix is high, the composite material of formation is by external impacts
When, boundary defect is easily caused, material property is caused sharply to decline；Therefore, only carrying out modification appropriate to calcium carbonate could expire
Foot has mechanical strength while biggish loading without will be greatly reduced PTFE in PTFE matrix.
In general the powder surface modification of calcium carbonate selects titanate coupling agent, aluminate coupling agent mostly, and auxiliary
It is modified that surface is carried out with other dispersing agents and auxiliary agent etc..However the moulding process requirement relatively high in view of polytetrafluoroethylene (PTFE), mostly
The above-mentioned modifying agent of number is not able to satisfy low cost, the effect of high efficiency modified calcium carbonate, though and some heatproof apolar substances
It can play the effect of surface coating modification calcium carbonate, but be extremely difficult to coat completely due to too big etc. various reasons of polarity spectrum
Effect can make modified effect not reach most preferably, that is, there is the incomplete phenomenon of modification degree, therefore further explore calcium carbonate-
The modified technique of polytetrafluoroethylene (PTFE) system has important practical application meaning.
Summary of the invention
The object of the present invention is to provide a kind of the compound of Gemini surface active modified calcium carbonate filled polytetrafluoroethylene
Material is successively modified calcium carbonate using Gemini surface active agent and paraffin, makes gained modified calcium carbonate surface in non-pole
Property, have good processing fluidity, there is extraordinary compatibility with polytetrafluoroethylene (PTFE), keeps gained composite material exhibits excellent out
Different mechanical property and stability, and the preparation method being related to is simple, cost of material is low, is suitble to promote and apply.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of composite material of Gemini surface active modified calcium carbonate filled polytetrafluoroethylene, the raw material is by weight
Number is calculated as: 75~90 parts of polytetrafluoroethylsuspending suspending powder, 10~25 parts of calcium carbonate powder, Gemini surface active 0.05~
0.2 part, 0.15~0.5 part of paraffin.
Preferably, the raw material is calculated by weight as: 70~75 parts of polytetrafluoroethylsuspending suspending powder, calcium carbonate powder 25
~30 parts, 0.10~0.25 part of Gemini surface active, 0.25~0.5 part of paraffin.
In above scheme, the calcium carbonate powder is 3000 mesh powdered whitings.
In above scheme, the structural formula of the Gemini surface active is shown in Formulas I:
Preferably, the antioxidant 1010 in the raw material also containing 0.006~0.024 parts by weight.
A kind of preparation method of the composite material of above-mentioned Gemini surface active modified calcium carbonate filled polytetrafluoroethylene,
Include the following steps:
1) calcium carbonate modified: calcium carbonate is dispersed in water and dehydrated alcohol, be added Gemini surface active into
Row isothermal reaction, is then added paraffin, and heating stirring is carried out under oil bath or water bath condition, is flowed back, after cooled to room temperature
Stop stirring, takes out solution in flask, dried, obtain modified calcium carbonate powder；
2) complex sintered: gained modified calcium carbonate powder being blended with tetrafluoroethene suspension powder, is then placed in mould
Cold moudling obtains composite board in tool, wraps composite board with aluminium foil and is placed in Muffle furnace, carries out temperature-gradient method and is sintered
The composite material of the Gemini surface active modified calcium carbonate filled polytetrafluoroethylene.
In above scheme, the isothermal reaction temperature is 50~80 DEG C, and the time is 30min~60min.
In above scheme, the heating stirring temperature is 70~92 DEG C, and return time is 100~180min.
In above scheme, the drying temperature is 45~55 DEG C.
In above scheme, the multi-steps sintering technique are as follows: the first stage rises to 180 DEG C by room temperature, constant temperature 150min；Second
Stage is warming up to 270 DEG C by 180 DEG C, constant temperature 180min；Phase III is warming up to 380 DEG C by 270 DEG C, constant temperature 180min.
The principle of the present invention are as follows:
Surface portion is carried out to calcium carbonate the invention firstly uses Gemini surface active agent to be modified, and provides item for paraffin cladding
Part recycles paraffin coated caco3 to complete to be modified；Gained modified calcium carbonate is used for filled polytetrafluoroethylene, completes composite wood
The preparation of material: since paraffin is the mixture that a variety of n-alkanes form, the polar repulsion with calcium carbonate leans on merely mechanism
Power is extremely difficult to the effect of complete coated caco3；And containing there are two hydrophilic groups in the Gemini surface active that the present invention uses
With two hydrophobic groups, compared to conventional surfactant, two hydrophilic head bases are close-coupled at by spacer group in molecule
Together, the distance of the hydrophilic head that furthered base and hydrophobic tail chain promotes hydrophilic head base in the absorption of solid liquid interface, enhances alkyl
The hydrophobic effect of the interaction of interchain, alkyl chain gets a promotion；Before being modified to calcium carbonate, calcium carbonate surface has greatly
Hydroxy functional group is measured, surface is in electronegativity, is easily closed with the hydrophilic head base junction of positively charged Gemini surface active, hydrophobic group tail
Chain calcium carbonate surface outwardly, then it is closely coupled to be easy to paraffin for the hydrophobic group tail chain of calcium carbonate surface outwardly, that is, in carbonic acid
Calcium surface coats one layer of fine and close apolar layer, basically reaches the effect of the complete coated caco3 of paraffin, makes modified calcium carbonate table
Face has good processing fluidity in nonpolarity, has extraordinary compatibility with polytetrafluoroethylene (PTFE), makes gained composite material
Show excellent mechanical property and stability.
Beneficial outcomes of the invention are as follows:
1) present invention use method modified calcium carbonate at low cost, simple process, be effectively improved calcium carbonate powder particle with
Compatibility between polytetrafluoroethylene (PTFE) makes microparticle surfaces generate new physics, chemistry, mechanical property and new function, thus most
The raising material property of limits and its loading in PTFE material；
2) it is significantly mentioned through calcium carbonate-filled ptfe composite mechanical property of this method after modified
Height reduces its manufacturing cost, enriches it using channel.
Detailed description of the invention
Fig. 1 is (a) Gemini surface active modified calcium carbonate filled polytetrafluoroethylene prepared by the embodiment of the present invention 2
2000 times of scanning electron microscope (SEM) photographs of composite material and 1 gained composite material of (b) comparative example.
Fig. 2 is the composite material drawing with 1,2,3,4 gained composite material of comparative example respectively prepared by embodiment 1,2,3,4
Stretch intensity contrast curve.
Fig. 3 is that composite material prepared by embodiment 1,2,3,4 is disconnected with 1,2,3,4 gained composite material of comparative example respectively
Split the correlation curve of elongation.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but the present invention is not
It is limited only to the following examples.
Following embodiment unless specific instructions, the commercially available chemical reagent of the reagent of use or industrial products.
In following embodiment, the structural formula of the Gemini surface active of use is shown in Formulas I:
Preparation method includes the following steps:
1) synthesis step of the double monoxone hydroquinone esters of intermediate product: hydroquinone, chloracetyl chloride and triethylamine are pressed
It is that 1:3.5:4 is mixed according to molar ratio, solvent is made with anhydrous propanone and reacts 6h at 0 DEG C；It is cooling after completion of the reaction to filter, filter
Cake three times, is poured into filtrate in ice water under stirring with acetone washing, stratification, is filtered, and filter cake first uses the mixing of water and acetone
Liquid washing, is washed with water and washs twice, is recrystallized after obtained solid is dry with acetone-petroleum ether, obtains double monoxone hydroquinones
Ester brown solid；
2) synthesis step of ten amine of intermediate product N, N- diethyl: according to molar ratio being 1 by ten alkane of 1- bromo and diethylamine:
4 mixing, make solvent with dehydrated alcohol and react for 24 hours at 95 DEG C, after reaction, with Rotary Evaporators removing etoh solvent and not
The diethylamine of reaction neutralizes residue with sodium hydroxide solution；Mixed liquor is extracted with ethyl acetate three times, merges organic phase and uses
Anhydrous magnesium sulfate is dried overnight；The ethyl acetate in filtrate is removed with Rotary Evaporators after filtering, obtains pale yellow oily liquid,
It is finally evaporated under reduced pressure to obtain the N of high-purity, ten amine of N- diethyl with oil pump；
3) synthesis step of final product Gemini surface active agent: by double monoxone hydroquinone esters and N, N- diethyl ten
Amine is 1:4 mixing according to molar ratio, makees solvent with dehydrated alcohol and reacts 96h at 90 DEG C, is washed after being cooled to room temperature with petroleum ether
It washs three times, obtains brown oil, as final high-purity product.
The following are synthetic route charts:
Embodiment 1
A kind of composite material of Gemini surface active modified calcium carbonate filled polytetrafluoroethylene, preparation method include
Following steps:
1) calcium carbonate modified: 25 weight parts of calcium carbonate are dispersed in 250ml water and 75ml dehydrated alcohol blended liquid,
Progress isothermal reaction 30min at 50 DEG C of 0.10 parts by weight Gemini surface active is added, 0.15 parts by weight paraffin is then added,
It carries out being heated to 92 DEG C of stirrings, reflux 180min under oil bath or water bath condition, stops stirring after cooled to room temperature, take out
Solution in flask is dried (45 DEG C), obtains modified calcium carbonate powder；
2) complex sintered: gained modified calcium carbonate powder and 75 parts by weight tetrafluoroethene suspension powders are placed in high-speed stirred
It is blended in device (20000-30000r/min), 0.006 parts by weight antioxidant 1010 is added, then gained mixture is transferred to
In mold, cold moudling obtains composite board (being dried for standby) on vulcanizing press, wraps composite board with aluminium foil and is placed in
In Muffle furnace, carry out temperature-gradient method sintering: the first stage rises to 180 DEG C by room temperature, constant temperature 150min；Second stage is by 180 DEG C
270 DEG C are warming up to, constant temperature 180min；Phase III is warming up to 380 DEG C by 270 DEG C, constant temperature 180min.Obtain the Gemini table
The composite material of face activating agent modified calcium carbonate filled polytetrafluoroethylene (modified calcium carbonate loading accounts for 25wt%).
Embodiment 2
A kind of composite material of Gemini surface active modified calcium carbonate filled polytetrafluoroethylene, preparation method include
Following steps:
1) calcium carbonate modified: 26 weight parts of calcium carbonate are dispersed in 260ml water and 78ml dehydrated alcohol blended liquid,
Progress isothermal reaction 40min at 70 DEG C of 0.15 parts by weight Gemini surface active is added, 0.30 parts by weight paraffin is then added,
It carries out being heated to 85 DEG C of stirrings, reflux 120min under oil bath or water bath condition, stops stirring after cooled to room temperature, take out
Solution in flask is dried (50 DEG C), obtains modified calcium carbonate powder；
2) complex sintered: gained modified calcium carbonate powder and 74 parts by weight tetrafluoroethene suspension powders are placed in high-speed stirred
It is blended in device (20000-30000r/min), 0.012 parts by weight antioxidant 1010 is added, then gained mixture is transferred to
In mold, cold moudling obtains composite board (being dried for standby) on vulcanizing press, wraps composite board with aluminium foil and is placed in
In Muffle furnace, carry out temperature-gradient method sintering: the first stage rises to 180 DEG C by room temperature, constant temperature 150min；Second stage is by 180 DEG C
270 DEG C are warming up to, constant temperature 180min；Phase III is warming up to 380 DEG C by 270 DEG C, constant temperature 180min.Obtain the Gemini table
The composite material of face activating agent modified calcium carbonate filled polytetrafluoroethylene (modified calcium carbonate loading accounts for 26wt%).
Embodiment 3
A kind of composite material of Gemini surface active modified calcium carbonate filled polytetrafluoroethylene, preparation method include
Following steps:
1) calcium carbonate modified: 29 weight parts of calcium carbonate are dispersed in 290ml water and 87ml dehydrated alcohol blended liquid,
Progress isothermal reaction 50min at 75 DEG C of 0.20 parts by weight Gemini surface active is added, 0.45 parts by weight paraffin is then added,
It carries out being heated to 80 DEG C of stirrings, reflux 110min under oil bath or water bath condition, stops stirring after cooled to room temperature, take out
Solution in flask is dried (52 DEG C), obtains modified calcium carbonate powder；
2) complex sintered: gained modified calcium carbonate powder and 71 parts by weight tetrafluoroethene suspension powders are placed in high-speed stirred
It is blended in device (20000-30000r/min), 0.024 parts by weight antioxidant 1010 is added, then gained mixture is transferred to
In mold, cold moudling obtains composite board (being dried for standby) on vulcanizing press, wraps composite board with aluminium foil and is placed in
In Muffle furnace, carry out temperature-gradient method sintering: the first stage rises to 180 DEG C by room temperature, constant temperature 150min；Second stage is by 180 DEG C
270 DEG C are warming up to, constant temperature 180min；Phase III is warming up to 380 DEG C by 270 DEG C, constant temperature 180min.Obtain the Gemini table
The composite material of face activating agent modified calcium carbonate filled polytetrafluoroethylene (modified calcium carbonate loading accounts for 29wt%).
Embodiment 4
A kind of composite material of Gemini surface active modified calcium carbonate filled polytetrafluoroethylene, preparation method include
Following steps:
It is calcium carbonate modified: 30 weight parts of calcium carbonate being dispersed in 300ml water and 90ml dehydrated alcohol blended liquid, are added
Enter progress isothermal reaction 60min at 80 DEG C of 0.25 parts by weight Gemini surface active, 0.50 parts by weight paraffin is then added,
It carries out being heated to 70 DEG C of stirrings, reflux 100min under oil bath or water bath condition, stops stirring after cooled to room temperature, take out and burn
Solution in bottle, is dried (55 DEG C), obtains modified calcium carbonate powder；
It is complex sintered: gained modified calcium carbonate powder and 70 parts by weight tetrafluoroethene suspension powders are placed in high speed agitator
It is blended in (20000-30000r/min), 0.026 parts by weight antioxidant 1010 is added, then gained mixture is transferred to mould
In tool, cold moudling obtains composite board (being dried for standby) on vulcanizing press, wraps composite board with aluminium foil and is placed in horse
Not in furnace, carry out temperature-gradient method sintering: the first stage rises to 180 DEG C by room temperature, constant temperature 150min；Second stage is risen by 180 DEG C
Temperature is to 270 DEG C, constant temperature 180min；Phase III is warming up to 380 DEG C by 270 DEG C, constant temperature 180min.Obtain the surface Gemini
The composite material of activating agent modified calcium carbonate filled polytetrafluoroethylene (modified calcium carbonate loading accounts for 29wt%).
Comparative example 1~4
The preparation method of comparative example 1,2,3,4 (respectively unmodified composite material 1,2,3,4) described composite material is distinguished
Roughly the same in the preparation method of embodiment 1,2,3,4, difference does not carry out corresponding step 1) described in calcium carbonate
Modifying process.
The scanning electron microscope (SEM) photograph of 2 gained composite material of embodiment 2 and comparative example is shown in Fig. 1, it can be seen that monodispersed CaCO3?
Grain is less, exists in the form of aggregate mostly, shows non-modified CaCO3It since surface can be high, and is in strong polarity,
So the difficulties in dispersion in PTFE matrix, easily reunites, since strong polarity leads to non-modified CaCO3Surface is in
Existing hydrophilic and oleophobic property causes particle easy to fall off in the base with PTFE poor compatibility, just even more so under stress condition.
CaCO in Fig. 1 (b)3Particle is then to be dispersed in PTFE matrix, and particle is small-sized, distributed more widely, this be because
For the CaCO modified by Gemini surface active and paraffin modification3Particle surface is changed, so that its surface nature
Change, before reducing higher surface can, the reunion tendency between particle substantially reduces, and surface is presented after being modified
For nonpolarity, so that CaCO3The compatibility of particle and PTFE are obviously improved, and also increase CaCO3The interface of particle and PTFE matrix
Binding force, more unmodified CaCO3It is not easy to fall off.The CaCO in the latter can also be found out from the comparison of Fig. 1 (a), Fig. 1 (b)3Particle
Smaller, distribution is wider, also has benefited from the modifying function of Gemini surface active.
Extension test will be carried out respectively to composite material made from embodiment 1,2,3,4 and comparative example 1,2,3,4, using height
Iron detecting instrument Co., Ltd TCS-2000 tensile testing machine, 25 DEG C of test temperature, rate of extension 20mm/min, method for making sample:
The CaCO for being completed sintering with the cut-off knife for being heated to high temperature3/ PTFE composite plate is cut into dumbbell shaped standard batten, test knot
Fruit is shown in Table 2 and table 3 respectively.The result shows that: the composite wood prepared through the method for the present invention Gemini surface active modified calcium carbonate
Material, unmodified composite material under the mechanical properties such as tensile strength and elongation at break are superior in proportion.
Comparative example 5
The preparation method of composite material described in comparative example 5 is roughly the same with preparation method described in embodiment 1, and difference exists
Corresponding Gemini surface active is added without in step 1) to be modified.Mechanical experimental results show 5 institute of comparative example
The tensile strength for stating composite material is 24.33MPa, far below the 27.48MPa of composite material described in embodiment 1；5 institute of comparative example
The elongation at break for stating composite material is 352.36%, also far below 378.34% of composite material described in embodiment 1.The above knot
Fruit shows the composite material prepared through the method for the present invention Gemini surface active modified calcium carbonate, tensile strength and extension at break
The mechanical properties such as rate are superior to that the composite material of Gemini surface active modified calcium carbonate preparation is not used.
The foregoing is merely the preferred embodiment of the present invention, it is noted that comes for those of ordinary skill in the art
It says, without departing from the concept of the premise of the invention, make several modifications and variations, these belong to protection model of the invention
It encloses.
Claims (8)
1. a kind of composite material of Gemini surface active modified calcium carbonate filled polytetrafluoroethylene, which is characterized in that each original
Material is calculated by weight as: 70~75 parts of polytetrafluoroethylsuspending suspending powder, 25~30 parts of calcium carbonate powder, Gemini surface-active
0.10~0.25 part of agent, 0.25~0.5 part of paraffin；
The structural formula of the Gemini surface active is shown in Formulas I:
2. composite material according to claim 1, which is characterized in that the calcium carbonate powder is the commercially available heavy carbon of 3000 mesh
Sour calcium.
3. composite material according to claim 1, which is characterized in that also contain 0.006~0.024 weight in the raw material
The antioxidant 1010 of part.
4. the composite wood of any one of claims 1 to 3 Gemini surface active modified calcium carbonate filled polytetrafluoroethylene
The preparation method of material, which comprises the steps of:
1) calcium carbonate modified: calcium carbonate being dispersed in water and dehydrated alcohol, Gemini surface active is added and carries out perseverance
Temperature reaction, is then added paraffin, and heating stirring, reflux are carried out under oil bath or water bath condition, is stopped after cooled to room temperature
Stirring takes out solution in flask, is dried, obtain modified calcium carbonate powder；
2) complex sintered: gained modified calcium carbonate powder being blended with tetrafluoroethene suspension powder, is then placed in mold
Cold moudling obtains composite board, wraps composite board with aluminium foil and is placed in Muffle furnace, carries out temperature-gradient method and is sintered described
Gemini surface active modified calcium carbonate filled polytetrafluoroethylene composite material.
5. the preparation method according to claim 4, which is characterized in that the isothermal reaction temperature is 50~80 DEG C, the time
For 30~60min.
6. the preparation method according to claim 4, which is characterized in that the heating stirring temperature is 70~92 DEG C, reflux
Time is 100~180min.
7. the preparation method according to claim 4, which is characterized in that the drying temperature is 40~55 DEG C.
8. the preparation method according to claim 4, which is characterized in that the multi-steps sintering technique are as follows: the first stage is by room
Temperature rise is to 180 DEG C, constant temperature 150min；Second stage is warming up to 270 DEG C by 180 DEG C, constant temperature 180min；Phase III is by 270 DEG C
380 DEG C are warming up to, constant temperature 180min.
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| CN105061957B (en) * | 2015-08-21 | 2017-05-03 | 武汉工程大学 | Method for preparing modified calcium carbonate filled polytetrafluoroethylene composite |
| CN105623161A (en) * | 2016-04-01 | 2016-06-01 | 武汉工程大学 | Glass fiber/calcium carbonate/polytetrafluoroethylene three-element composite material and preparation method thereof |
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