CN106589717B - A kind of method that mechanochemistry prepares poly- phenol amine-ptfe composite - Google Patents
A kind of method that mechanochemistry prepares poly- phenol amine-ptfe composite Download PDFInfo
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- CN106589717B CN106589717B CN201611079832.2A CN201611079832A CN106589717B CN 106589717 B CN106589717 B CN 106589717B CN 201611079832 A CN201611079832 A CN 201611079832A CN 106589717 B CN106589717 B CN 106589717B
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- ptfe
- phenol
- amine
- polytetrafluoroethylene
- mechanochemistry
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
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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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The present invention provides a kind of methods that mechanochemical reaction prepares poly- phenol amine-ptfe composite.Method and step is as follows: (1) phenol of certain mol proportion and amine being added in pure water or the water of certain pH value, stir, be uniformly mixed；(2) the phenol amine aqueous solution is transferred to mortar, and suitable polytetrafluoroethylene (PTFE) is added；(3) blend is ground in mortar, be ground to polytetrafluoroethylene (PTFE) becomes dark brown completely, and no longer floats on liquid level；(4) after the reaction was completed, it is washed respectively with water and dehydrated alcohol, is freeze-dried to constant weight, obtains poly- phenol amine-ptfe composite.Preparation method of the present invention is easy, and preparation time is short, and preparation cost is low, and post-processing is simple；The hydrophily of polytetrafluoroethylene (PTFE) is significantly improved, being more widely applied for polytetrafluoroethylene (PTFE) is made.
Description
Technical field
The present invention relates to a kind of methods that mechanochemistry polymerization prepares poly- phenol amine-ptfe composite.
Background technique
Low consumption, low-carbon, environmental protection, sustainable development are the call and the national following selection of relationship of current era.So
And wear phenomenon, a kind of generally existing natural phenomena caused by rubbing, as condemned MAT'L the main reason for, generally deposit
Great riches is being caused to lose.Therefore, tribology, the destruction that reduces fretting wear, material is reduced or avoided are studied, is both
The energy saving and most effective means of material, and be the inevitable choice in accordance with era development.
Polytetrafluoroethylene (PTFE) is a kind of important high molecular material, has extremely excellent performance, such as high lubrication
Property, chemical stability, against weather etc., be widely used in the industrial departments such as aerospace, machinery, building, have become existing
Many key technologies are solved in generation science and technology and improve the indispensable material of production technology level.However, its own surface
Can be extremely low, surface wettability is very poor, so that its terrifically hydrophobic, oleophobic, hardly possible limits its potential in conjunction with other materials
It plays, also limits application of its micro-nano powder as high-performance lubricating additive.
For the surface inertness for solving the problems, such as PTFE, scientific worker modifies to increase its surface by various means
Add its wetability and the compatibility with other materials.Current method mainly has: sodium-naphthalene chemistry of complex etching processing method, height
Energy via radiation grafting modification method, the modified method of laser emission, ion implantation modification and plasma modification method etc..Although these methods are all
The preferable modified ptfe of energy, still, it is extensive to limit these methods for expensive drug, complicated process and special instrument
Using.
Polytetrafluoroethylene (PTFE) is modified with mechanochemical reaction, so far it has not been found that similar report.
Summary of the invention
For overcome the problems, such as the shortcomings of the prior art and, the purpose of the present invention is to provide a kind of preparation of mechanochemistry is poly-
Phenol amine-ptfe composite method, the preparation time is short, preparation process is environmentally protective, it is simple and easy etc. excellent to prepare
Point is polymerization that is a kind of mild, easy to operate and realizing industrialized production.
To achieve the purpose of the present invention, the following technical schemes are provided:
A kind of method that mechanochemistry prepares poly- phenol amine-ptfe composite, it is characterised in that following steps:
(1) phenol of certain mol proportion and amine are added in pure water or the water of certain pH value, are stirred, is uniformly mixed；
(2) the phenol amine aqueous solution is transferred to mortar, and suitable polytetrafluoroethylene (PTFE) is added；
(3) blend is ground in mortar, be ground to polytetrafluoroethylene (PTFE) becomes dark brown completely, and no longer floats on
On liquid level；
(4) after the reaction was completed, it is washed respectively with water and dehydrated alcohol, is freeze-dried to constant weight, obtains poly- phenol amine-polytetrafluoro
Ethylene composite material.
Preparation method of the present invention is easy, and preparation time is short, and preparation cost is low, and post-processing is simple；Significantly improve polytetrafluoro
The hydrophily of ethylene makes being more widely applied for polytetrafluoroethylene (PTFE).
Further, phenol is at least one of catechol, hydroquinone, pyrogallol in the step.
Further, amine is that diethylenetriamine, triethylene tetramine, tetraethylenepentamine or structural formula are in the step
NH2(CH2)nNH2At least one of fatty amine (n represents 2 to 12 integer).
Further, the molar ratio of phenol and amine is 0.8 ~ 1.2: 1 in the step.
Further, the mass ratio of polytetrafluoroethylene (PTFE) and phenol is 1: 0.02 ~ 1 in the step.
Further, certain pH value is pH=7.0 ~ 9.9 in the step.
Further, milling time is 1 ~ 4 hour in the step.
The invention proposes a kind of brand-new schemes for preparing modified Teflon, i.e., pass through mechanochemistry using phenol and amine
The method of polymerization is modified.Mechanochemistry polymerization compare common electrochemistry and chemical polymerization, have preparation time it is short, preparation
The advantages that process is environmentally protective, preparation method is simple, process flow is simple and polymerization efficiency is higher, machinery polymerization pass through outer
The mechanical force added enables and polymerize faster under other reaction conditions in the very slow poly- phenol amine of ptfe surface polymerization
In ptfe surface.To enable polytetrafluoroethylene (PTFE) to be dispersed in water, preferably it is applied to solid friction field.
Compared with other technologies, the invention has the following advantages:
(1) the preparation low raw-material cost of the poly- phenol amine-ptfe composite through the invention, convenient for pushing away
Wide to use, the polytetrafluoroethylene (PTFE) after modification has hydrophily, can be applied in wider solid friction system.
(2) preparation process of the present invention is simple, and preparation process is environmentally protective, is suitble to scale industrial production.
Specific embodiment
Technical solution of the present invention is further elaborated combined with specific embodiments below, these embodiments are intended merely to explain
It states technical solution of the present invention and the limitation to the claims in the present invention content cannot be considered as.Raw materials used in embodiment is normal
It is conventional method that rule commercial products device therefor, which is conventional equipment test method,.
Embodiment 1
Catechol and triethylene tetramine are added in pure water, its molar ratio 0.9: 1 is made, is stirred, is uniformly mixed；So
The phenol amine aqueous solution is transferred to mortar afterwards, and polytetrafluoroethylene (PTFE) is added, makes its mass ratio 10: 1 with catechol, grinding 2
After hour, is separated, is washed, dried, can be prepared by poly- phenol amine-ptfe composite.
Embodiment 2
Hydroquinone and hexamethylene diamine are added in the water of pH value 8.0, its molar ratio 1: 1 is made, is stirred, is uniformly mixed；
Then the phenol amine aqueous solution is transferred to mortar, and polytetrafluoroethylene (PTFE) is added, make its mass ratio 5: 1 with catechol, grinding 3
After hour, is separated, is washed, dried, can be prepared by poly- phenol amine-ptfe composite.
Embodiment 3
(1) 0.035 catechol and 0,037g1,6- hexamethylene diamine are added to the mortar containing 5mL pH for 8.5 buffers
In, it stirs evenly as far as possible.
(2) 0.420g polytetrafluoroethylene (PTFE) is added.
(3) blend is ground to 4 h in the agate mortar, be ground to polytetrafluoroethylene (PTFE) becomes dark brown completely, and not
It floats on buffer again；
(4) after the reaction was completed, it is washed respectively with water and dehydrated alcohol, until pH value of solution is neutrality, it is dry to constant weight, gathered
Phenol amine-ptfe composite.
Embodiment 4
(1) 0.070g catechol and 0,074g1,6- hexamethylene diamine are added to the mortar containing 5mL pH for 9.0 buffers
In, it stirs evenly as far as possible.
(2) 0.420g polytetrafluoroethylene (PTFE) is added.
(3) blend is ground to 3 h in the agate mortar, be ground to polytetrafluoroethylene (PTFE) becomes dark brown completely, and not
It floats on buffer again；
(4) after the reaction was completed, it is washed respectively with water and dehydrated alcohol, until pH value of solution is neutrality, it is dry to constant weight, gathered
Phenol amine-ptfe composite.
Claims (6)
1. a kind of method for preparing poly- phenol amine-ptfe composite with mechanochemistry polymerization；Method and step is as follows:
The phenol of certain mol proportion and amine are added in pure water or the water of certain pH value, are uniformly mixed；After be transferred to mortar, be added appropriate
Polytetrafluoroethylene (PTFE), ground, be ground to polytetrafluoroethylene (PTFE) becomes dark brown completely, and no longer floats on liquid level；It washes
Drying is washed, poly- phenol amine-ptfe composite is obtained；
The milling time is 1~4 hour.
2. a kind of side for preparing poly- phenol amine-ptfe composite with mechanochemistry polymerization as described in claim 1
Method, it is characterised in that the phenol is at least one of catechol, hydroquinone, pyrogallol；The polytetrafluoroethyl-ne
Alkene is micron order.
3. a kind of side for preparing poly- phenol amine-ptfe composite with mechanochemistry polymerization as described in claim 1
Method, it is characterised in that the amine is that diethylenetriamine, triethylene tetramine, tetraethylenepentamine or structural formula are NH2(CH2)nNH2
At least one of fatty amine, n represents 2 to 12 integer.
4. a kind of side for preparing poly- phenol amine-ptfe composite with mechanochemistry polymerization as described in claim 1
Method, it is characterised in that the molar ratio of the phenol and amine is 0.8~1.2:1.
5. a kind of side for preparing poly- phenol amine-ptfe composite with mechanochemistry polymerization as described in claim 1
Method, it is characterised in that the mass ratio of the polytetrafluoroethylene (PTFE) and phenol is 1:0.02~1.
6. a kind of side for preparing poly- phenol amine-ptfe composite with mechanochemistry polymerization as described in claim 1
Method, it is characterised in that the certain pH value is pH=7.0~9.9.
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| CN201611079832.2A CN106589717B (en) | 2016-11-30 | 2016-11-30 | A kind of method that mechanochemistry prepares poly- phenol amine-ptfe composite |
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| CN201611079832.2A CN106589717B (en) | 2016-11-30 | 2016-11-30 | A kind of method that mechanochemistry prepares poly- phenol amine-ptfe composite |
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| CN106589717B true CN106589717B (en) | 2018-12-21 |
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| KR20200099819A (en) * | 2019-02-15 | 2020-08-25 | 성균관대학교산학협력단 | Modified polytetrafluoroethylene, method for preparing the same, ion exchange membranes using the same and method for preparing ion exchange membranes using the same |
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| CN104262664A (en) * | 2014-09-10 | 2015-01-07 | 齐鲁工业大学 | Preparation method of poly(phenol-amine) superhydrophilic particulates |
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