CN103936904B - Dispersion - Google Patents
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- CN103936904B CN103936904B CN201410193870.5A CN201410193870A CN103936904B CN 103936904 B CN103936904 B CN 103936904B CN 201410193870 A CN201410193870 A CN 201410193870A CN 103936904 B CN103936904 B CN 103936904B
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Abstract
The invention discloses a dispersion which is a water-based dispersion solution composed of a fluorine-containing polymer free of perfluoro-octanoic acid or perfluoro-octylsulfonic acid and a polyfluothane oxy ether acid salt water solution used as an emulsifier, wherein the polyfluothane oxy ether acid is a halogen-terminated or hydrogen-terminated polyfluothane oxy ether acid emulsifier. The technical scheme mainly relates to the following three improvements: (1) the polyfluothane oxy ether acid or salt thereof selected instead of PFOA/PFOS as the fluorine-containing emulsifier can be effectively used in aqueous emulsion polymerization reaction of fluorinated monomers; (2) the prepared fluorine-containing polymer is free of perfluoro-octanoic acid or perfluoro-octylsulfonic acid, and thus, satisfies the environmental requirement; and (3) the fluorine-containing polymer conforms to the cost accounting, can greatly enhance the single-kettle yield of the equipment on the premise of not increasing the production equipment and personnel, and meanwhile, can enhance the polymerization time, polymerization yield and other production indexes.
Description
Technical field
The present invention is a kind of dispersion and in particular to preparing fluoropolymer and emulsifying agent group during fluoropolymer
The compounding substances becoming, belong to the synthesis field of fluoropolymer.
Background technology
Fluoropolymer is the general name of the alkanes polymer that part hydrogen atom is replaced by fluorine atoms, and is also that a class is more special
Different macromolecular material, can carry out polyreaction under certain condition by one or more fluorochemical monomer and form, high in its structure
The fluorine carbon key of bond energy and fluorine atom to the shielding action of strand so as to have a series of excellent characteristics, such as: excellent is resistance to
Chemical corrosivity, dielectric properties, against weather, non-stick, excellent frictional behaviour etc., certainly, due to its excellent performance, contain
It is indispensable that fluoropolymer has become the multiple fields such as modern science and technology, national defence, electric, chemical industry, medicine and mechanical industry
One of material.
In the polymerization process of fluoropolymer, it usually needs add a certain amount of fluorine-containing emulsifier, in the field, I
Know that perfluorooctane sulfonate (pfos) or its salt can be but just beautiful early in calendar year 2001 as the fluorine-containing emulsifier in polyreaction
Environmental Protection Administration of state (epa) proposes disabling decree, for this reason, 3m company also specially have developed perfluoro butyl sulfonic acid (pfbs) c4f9so3h
To replace pfos, the fluorocarbon chain of pfbs is short, no substantially persistency biological accumulation, in the short time, body can be discharged with human metabolism
Outward, and it mediates thing nonhazardouss, its commodity proves safeguard functions and environmentally friendly through a large amount of tests, by epa and the world its
His environmental protection mechanism is ratified.But show according to latest data, existing the most frequently used fluorine-containing emulsifier is perfluoro caprylic acid and its salt, with it
The reaching its maturity of market, its safety and environmental-protecting performance have also suffered to query, and 2006, epa promulgated restriction decree, and this decree is recognized
Generate the chemicals of pfoa for perfluorooctanoic acid (pfoa) and some decomposable asymmetric choice net due to the stability of its height and to be difficult to degrade
Characteristic it is most likely that the major disease such as cause cancer, for this reason, domestic and international Ge great manufacturing enterprise be just devoted to studying a kind of new
Compound, to substitute this kind of fluorine-containing emulsifier with high stability feature, improves fluoropolymer and uses process in each field
In safety coefficient, particularly medicine wait with the industry field of direct body contact in, its security performance is even more important.
Disclosed as having that fluorine-containing emulsifier in polymerization process uses: PFPE (cn101218264b), ring-type
The fluorine-containing emulsifier (cn101745338a) of fluorochemical (cn102089335a), replacement perfluoro caprylic acid and its esters, formula
xcf2cf2(o)mcf2cf2ocf2The fluorine-containing emulsifier (cn101287766, cn101291987) that cooa represents, above-mentioned fluorine-containing emulsifying
The all alternative pfoa/ pfos of agent is used for the emulsion polymerization of fluorinated monomer, and the water-based emulsion of its fluoropolymer is all not
Show fluorine-containing octanoic acid or its salt adverse effect.
From above-mentioned patent documentation disclosure we also with knowable to, existing disclosed fluorine-containing emulsifier is all effective
Although solving the Toxicological Characterization of fluorine-containing emulsifier, but be all not directed to the products such as yield and the granularity of fluoropolymer
Feature, taking above-mentioned patent of invention cn101218264b as a example, in this patent documentation, give polymerization time, particle mean size,
The particle specific gravity of ssg(fluoropolymer), the correction data of solids content, in addition to polymerization time, remainder data all no obvious ripples
Dynamic, although it follows that the existing fluorine-containing emulsifier being related to without perfluoro caprylic acid solve pfoa/ pfos high stability and
The harm that difficult degradation spy may cause to human body, but any substantial improvement is not made to whole production efficiency, based on existing
There is being growing more intense of the market competition, we must find a kind of new fluorine-containing emulsifier, not only the making of alternative pfoa/ pfos
With meanwhile, also long-term, effective economic benefit can be obtained from properties of product.
Content of the invention
It is an object of the invention to provide a kind of dispersion, this dispersion is by without perfluoro caprylic acid or perfluorooctane sulfonate
Fluoropolymer and as emulsifying agent poly- polyfluoroalkoxy ether acid salt aqueous solution aqueous liquid dispersion, due to
Poly- polyfluoroalkoxy ether acid as emulsifying agent does not produce stable carbon 8 in the environment, is not belonging to the straight chain that carbon atom is more than 8 yet
Perfluorocarbon saturated hydrocarbons homologue, simultaneously as the introducing of ehter bond, more makes its degradation property increase, is difficult to be enriched with the environment, because
This, there is not bioconcentration and other toxicity in this aqueous liquid dispersion, be suitably widely popularized use.
The present invention is achieved through the following technical solutions: a kind of dispersion, including following components: without perfluoro caprylic acid or perfluor
The fluoropolymer of pungent sulfonic acid and as emulsifying agent poly- polyfluoroalkoxy ether acid salt aqueous solution, the aqueous dispersion being mixed into
Liquid, described poly- polyfluoroalkoxy ether acid is selected from following combinations of one or more:
Meet the poly- polyfluoroalkoxy ether acid of following formula ():
(),
Meet the poly- polyfluoroalkoxy ether acid of following formula ():
(),
Meet the poly- polyfluoroalkoxy ether acid of following formula ():
(),
Wherein:
T:、、、、；
X:h, cl, br, i；
R:h, cl, br, i；
Y:so3H and its salt, cooh and its salt, ch2ch2Cooh and its salt, ch2ch2so3H and its salt,
cooch2ch2Cooh and its salt, cooch2ch2so3H and its salt,And its salt；And its salt；
The value of n is: 0～4
The value of m is: 1～20
The value of p is: 0～4
The value of q is: 0～1
From the general structure of above-mentioned poly- polyfluoroalkoxy ether acid, poly- polyfluoroalkoxy ether acid and its esters are in the environment
Do not produce stable carbon 8, be not belonging to the straight chain perfluorocarbon saturated hydrocarbons homologue that carbon atom is more than 8 yet, simultaneously as the drawing of ehter bond
Enter, so that its degradation property is increased, therefore, will not persistently be present in environment it is difficult to form biological savings property, thus to human body
Damage.
Further, described poly- polyfluoroalkoxy ether acid is the poly- polyfluoroalkoxy ether acid breast with halogen or hydrogen for the end group
Agent.
In the present invention, substituted during existing fluoropolymer manufactures using most using poly- polyfluoroalkoxy ether acid emulsifying agent
Pfoa/ pfos is effective, shows: the performance indications of described poly- polyfluoroalkoxy ether acid emulsifying agent include:
Acid number (in terms of naoh): < 150mg/g；
Cross oxygen value: < 1.5 g/100g；
Boiling point: < 260 DEG C；
Surface tension: < 40mn/m；
Critical micelle concentration (cmc): < 5%.
Optimize, the performance indications of described poly- polyfluoroalkoxy ether acid emulsifying agent further include:
Acid number (in terms of naoh): < 100mg/g；
Cross oxygen value: < 0.5g/100g；
Boiling point: < 160 DEG C；
Surface tension: < 20mn/m；
Critical micelle concentration (cmc): < 1.5 %.
In the present invention, the aqueous solution of the described salt of the poly- polyfluoroalkoxy ether acid as emulsifying agent is water-soluble in alkalescence
At the uniform velocity Deca poly- polyfluoroalkoxy ether acid in liquid, Deca while stirring and be obtained, prepared poly- polyfluoroalkoxy ether acid
The ph value of the aqueous solution of salt is 7～9, and poly- polyfluoroalkoxy ether acid is (0.1～20) with the weight proportion of water: 100.
Wherein, described alkaline aqueous solution includes ammonia, sodium hydrate aqueous solution, potassium hydroxide aqueous solution, magnesium hydroxide
The mixing of one or more of aqueous solution, triethanolamine aqueous solution.
Optimize, the preparation temperature of the described aqueous solution of salt of poly- polyfluoroalkoxy ether acid is 25～50 DEG C, Deca speed
Spending for 0.1～10ml/s, mixing speed is 20～200rpm.The described fluoropolymer without perfluoro caprylic acid or perfluorooctane sulfonate
In solid-state.
The weight proportion of the described fluoropolymer without perfluoro caprylic acid or perfluorooctane sulfonate and water is: (3～7): 10.
Described dispersion does not contain perfluoro caprylic acid or perfluorooctane sulfonate.
The present invention compared with prior art, has advantages below and a beneficial effect:
(1) present invention is using poly- polyfluoroalkoxy ether acid and its salt as the emulsifying in fluoropolymer aqueous emulsion polymerization
Agent, can effectively replace existing fluorine-containing emulsifier such as: pfoa/ pfos etc., environmental friendliness, this poly- polyfluoroalkoxy ether acid and
Its salt will not produce stable carbon 8 in the environment, is also not belonging to the homologue that carbon atom is more than 8 straight chain perfluorocarbon saturated hydrocarbons,
Simultaneously as the introducing of ehter bond, so that its degradation property is increased, be difficult to be enriched with the environment, be suitably widely popularized use.
(2) present invention is used as emulsifying agent by poly- polyfluoroalkoxy ether acid and its salt, is entered by one or more fluorinated monomer
Row aqueous emulsion polymerization, prepared fluoropolymer does not contain perfluoro caprylic acid or perfluorooctane sulfonate, meets environmental requirement, there is not biology
Accumulative and other toxicity, can be widely applied to the safety coefficients such as kitchen tools, medicine and require in higher field.
(3) in the present invention, the solid of the fluorinated monomer aqueous emulsion being produced with this kind of poly- polyfluoroalkoxy ether acid and its salt
Content height (calculated by mass), do not increase manufacturing facilities and personnel in the case of equipment output per single reactor can be greatly improved, for example:
With the solids content (calculated by mass) of this kind of poly- polyfluoroalkoxy ether acid and its fluorinated monomer aqueous emulsion of salt preparation, Ke Yida
To 35%～60%, it is the solid of the fluorinated monomer aqueous emulsion typically being produced as surfactant using perfluoroalkyl acid and its salt
2～3 times of content.
(4) enforcement of the present invention applies also for the aqueous emulsion polymerization of fluorinated monomer using traditional fluorinated emulsifying agent
Equipment, effectively raises the cost benefit of this polyreaction, great market value.
(5) in the present invention, needed for the fluorinated monomer aqueous emulsion being produced with this kind of poly- polyfluoroalkoxy ether acid and its salt
Production time is short, and the production capacity of process units can be greatly improved, and reduces production cost, for example: using perfluoroalkyl acid and its
Salt produces Kynoar as emulsifying agent, and generally 8～10 hours one-pot reaction time, such as using this kind of poly- polyfluoroalkoxy
, as the surfactant producing Kynoar, its one-pot reaction time can foreshorten to 4～6 hours for ether acid acid and its salt.
(6) in the present invention, nano level fluorinated monomer water and milk can be produced with this kind of poly- polyfluoroalkoxy ether acid and its salt
Liquid, emulsion is in light blue transparence.
(7) in the present invention, the fluorinated monomer of super high molecular weight can be produced with this kind of poly- polyfluoroalkoxy ether acid and its salt
Aqueous emulsion and sub-material, the relative number-average molecular weight of general fluorinated monomer polymer is more than 10*106.
Specific embodiment
Below the goal of the invention of the present invention, technical scheme and beneficial effect are described in further detail.
It is noted that described further below is all exemplary it is intended to provide further to the required present invention
Bright, unless otherwise stated, all technology used herein and scientific terminology have the common skill with the technical field of the invention
The identical meanings that art personnel are generally understood that.
U.S. Environmental Protection Agency (EPA) (epa) has revealed that pfoa/ pfos and its salt has that degradability is poor, be easy to enrichment etc. in environment
Characteristic, all can cause toxic hazard to environment and human body, but due to its special performance, pfoa/ pfos is often used for producing
Indispensable processing aid during high-effect fluoropolymer, these dynamical fluoropolymers are also widely used
In the people's livelihood articles for use such as science and technology of aviation, transport, electron trade and kitchen tools, long-term use is it is most likely that cause cancer etc. is great
Disease.Existing published patent documentation cn101218264b, cn102089335a, cn101745338a, cn101287766,
Cn101291987 has disclosed the harm of above-mentioned pfoa/ pfos, and wishes that finding one kind can substitute pfoa/ pfos, and conduct
The fluorine-containing emulsifier that surfactant during aqueous emulsion polymerization uses, these fluorine-containing emulsifiers such as: PFPE, ring-type contain fluorination
The fluorine-containing emulsifier of compound, replacement perfluoro caprylic acid and its esters, formula xcf2cf2(o)mcf2cf2ocf2The fluorine-containing breast that cooa represents
Agent can be used to the aqueous emulsion polymerization of fluorinated monomer, also show the biology lower than pfoa/ pfos and its salt
Accumulation and environmental degradability, but further it is intended that finding a kind of more efficient implementation it may be assumed that can not only substitute
The fluorine-containing emulsifier that pfoa/ pfos uses as surfactant during aqueous emulsion polymerization, simultaneously moreover it is possible to improve polymerization time,
The production targets such as polymerization yield rate, thus meet cost-benefit accounting.For this reason, present invention is disclosed a kind of dispersion, its technology
Scheme has related generally to the improvement of three below aspect:
(1) select poly- polyfluoroalkoxy ether acid and its salt to substitute pfoa/ pfos as fluorine-containing emulsifier, can effectively answer
Aqueous emulsion polymerization for fluorinated monomer；
(2) fluoropolymer being obtained does not contain perfluoro caprylic acid or perfluorooctane sulfonate, meets environmental requirement；
(3) meet cost accounting, do not increase manufacturing facilities and personnel in the case of can be greatly improved equipment one-pot produce
Amount, simultaneously moreover it is possible to improve the production targets such as polymerization time, polymerization yield rate.
In the present invention, involved dispersion is by the fluoropolymer without perfluoro caprylic acid or perfluorooctane sulfonate and work
For the aqueous solution of the salt of the poly- polyfluoroalkoxy ether acid of emulsifying agent, the aqueous liquid dispersion being mixed into, can be summarized in terms of two:
First, in said components, the fluoropolymer without perfluoro caprylic acid or perfluorooctane sulfonate is by one or more
Fluorinated monomer obtains in the case that poly- polyfluoroalkoxy ether acid is as emulsifying agent after liquid phase polymerization；
Second, the aqueous solution as the salt of the poly- polyfluoroalkoxy ether acid of emulsifying agent is at the uniform velocity Deca in alkaline aqueous solution
Poly- polyfluoroalkoxy ether acid, Deca while stirring and be obtained, rate of addition and mixing speed distinguish 0.1～10ml/s, 20
～200rpm, prepares temperature at 25～50 DEG C, the ph value of the prepared aqueous solution of salt of poly- polyfluoroalkoxy ether acid is 7～9, gathers
Polyfluoroalkoxy ether acid is (0.1～20) with the weight proportion of water: 100, alkaline aqueous solution then can choose ammonia, sodium hydroxide water
The mixing of one or more of solution, potassium hydroxide aqueous solution, magnesium hydroxide aqueous solution, triethanolamine aqueous solution.
The following is and technical solution of the present invention is further described:
First, from the preparation process of the fluoropolymer without perfluoro caprylic acid or perfluorooctane sulfonate, it is known that poly- many
Fluoroalkyloxy ether acid is selected from the combination of following one or more:
Meet the poly- polyfluoroalkoxy ether acid of following formula ():
(),
Meet the poly- polyfluoroalkoxy ether acid of following formula ():
(),
Meet the poly- polyfluoroalkoxy ether acid of following formula ():
(),
Wherein:
T:、、、、；
X:h, cl, br, i；
R:h, cl, br, i；
Y:so3H and its salt, cooh and its salt, ch2ch2Cooh and its salt, ch2ch2so3H and its salt,
cooch2ch2Cooh and its salt, cooch2ch2so3H and its salt,And its salt；And its salt；
The value of n is: 0～4
The value of m is: 1～20
The value of p is: 0～4
The value of q is: 0～1
From the general structure of above-mentioned poly- polyfluoroalkoxy ether acid, poly- polyfluoroalkoxy ether acid emulsifying agent can be end group
With the poly- polyfluoroalkoxy ether acid emulsifying agent of halogen or hydrogen, for example: with vinylidene, oxygen, tetrafluoroethene and hexafluoropropene
Mix by a certain percentage, under 500w ultra-vioket radiation, keep system temperature at 65 DEG C, anti-by photooxidation free poly tone
Should, the poly- polyfluoroalkoxy ether acid with hydrogen for the end group can be obtained.Structural formula is as follows:
Wherein, the value of n is: 0～4；The value of m is: 1～20；The value of p is: 0～4；The value of q is: 0～1.
Again for example: mixed with certain proportion with bromotrifluoroethylene, oxygen, tetrafluoroethene and hexafluoropropene, in 500w ultraviolet
Under light irradiation, keep system temperature at 65 DEG C, reacted by photooxidation free poly tone, end group can be obtained poly- many with bromine
Fluoroalkyloxy ether acid emulsifying agent.Structural formula is as follows:
Wherein, the value of n is: 0～4；The value of m is: 1～20；The value of p is: 0～4；The value of q is: 0～1.
It is pointed out that in the structural formula with halogen or the poly- polyfluoroalkoxy ether acid emulsifying agent of hydrogen for the end group, when
When the halogen of end group upper band is all f, i.e. PFPE, for commercial production, be can not realize large-scale production it is necessary to
The monomer adding carried halogen on end group not to be f in preparation process, as chain-transferring agent, just enables industrialized production, raw
Production. art is relatively numerous and diverse, therefore, the poly- polyfluoroalkoxy ether acid emulsifying agent with halogen or hydrogen for the end group according to the present invention
Do not include PFPE emulsifying agent.
In practical application, because above-mentioned poly- polyfluoroalkoxy ether acid and its esters will not produce stable carbon in the environment
8, also it is not belonging to the homologue that carbon atom is more than 8 straight chain perfluorocarbon saturated hydrocarbons, simultaneously as the introducing of ehter bond, so that it is dropped
Solution performance increase, therefore, thus poly- polyfluoroalkoxy ether acid as fluorine-containing emulsifier be used for fluorinated monomer aqueous emulsion polymerization and
During prepared fluoropolymer, this fluoropolymer does not contain perfluoro caprylic acid or perfluorooctane sulfonate, will not persistently be present in environment,
Also the biological savings property of difficult to form, can be widely applied to the safety coefficients such as kitchen tools, medicine and requires in higher people's livelihood articles for use, will not
Human body is damaged.
On this basis, we are measured to the performance indications of the above-mentioned poly- polyfluoroalkoxy ether acid emulsifying agent enumerated,
As shown in table 1:
Table 1
Secondly, it is known that the above-mentioned liquid-phase polymerization being related to is a kind of preparation method of conventional fluoropolymer,
In the present invention, this liquid phase polymerization refers to aqueous emulsion polymerization, and the aqueous emulsion polymerization in its polymerization process mainly has fluorination single
Body, initiator, water, four elements of emulsifying agent it is known that, we have found a kind of new fluorine-containing emulsifier (that is: gather
Polyfluoroalkoxy ether acid emulsifying agent) substituting pfoa/ pfos, and the fluoropolymer being obtained can be solid-state, and it is pungent not contain perfluor
Acid or perfluorooctane sulfonate, certainly, dispersion according to the present invention does not exactly contain containing of perfluoro caprylic acid or perfluorooctane sulfonate by this yet
Fluoropolymer and as emulsifying agent poly- polyfluoroalkoxy ether acid salt aqueous solution aqueous liquid dispersion, therefore,
Prepared dispersion does not contain perfluoro caprylic acid or perfluorooctane sulfonate yet, wherein, gathers without perfluoro caprylic acid or the fluorine-containing of perfluorooctane sulfonate
The weight proportion of compound and water is (3～7): 10.In actual mechanical process, as the poly- polyfluoroalkoxy ether acid of emulsifying agent
The aqueous solution of salt is at the uniform velocity Deca poly- polyfluoroalkoxy ether acid in alkaline aqueous solution, Deca while stirring and be obtained, droplet
Acceleration and mixing speed 0.1～10ml/s, 20～200rpm respectively, prepares temperature at 25～50 DEG C, prepared poly- many halothane
The ph value of the aqueous solution of the salt of epoxide ether acid is 7～9, and poly- polyfluoroalkoxy ether acid is (0.1～20) with the weight proportion of water:
100, alkaline aqueous solution then can choose ammonia, sodium hydrate aqueous solution, potassium hydroxide aqueous solution, magnesium hydroxide aqueous solution, three second
The mixing of one or more of aqueous alkanolamine.
During preparing fluoropolymer and dispersion, to better implement the present invention, we also need to fluorine-containing list
Body, proportioning of initiator, poly- polyfluoroalkoxy ether acid emulsifying agent and water etc. are selected, indispensable.In invention, initiator
Selection mainly have two classes: inorganic peroxide (as persulfate etc.), organic peroxide (alkyl peroxide etc.)；In fluorine
Change in the selection course of monomer it has been found that the selection of fluorinated monomer may include following several situation:
(1) press physical state divide, fluorinated monomer can be gaseous fluorinated monomer (such as: tetrafluoroethene, CTFE,
Vinylidene, hexafluoropropene etc.) or liquid fluorinated monomers (such as: perfluoropropylvinylether, perfluoro methyl vinyl ether etc.)
The combination of the fluorinated monomer of two classes or gaseous state and liquid is (such as: the mixing of tetrafluoroethene and perfluoropropylvinylether
The mixture of thing, vinylidene and perfluoro methyl vinyl ether)；
(2) press structural formula to divide, fluorinated monomer can include the fluorochemical monomer with halogen or hydrogen for the end group (such as: trifluoro chlorine
Ethylene, vinylidene etc.) it is also possible to include perfluorinated monomer (such as: tetrafluoroethene, perfluoropropylvinylether etc.).
From above-mentioned situation, fluorinated monomer according to the present invention can be tetrafluoroethene, CTFE, hexafluoro third
Alkene, vinylidene, hexafluoropropylene oxide, perfluoroalkyl vinyl ether class, one or more of fluorothene etc., in practical application
When, the difference of the fluoropolymer due to producing, corresponding, the suitable fluorinated monomer of selection carries out homopolymerization or copolymerization also has accordingly
Standard, these are all disclosed in prior art, but the present invention desirably finds out and is applied to these homopolymerizations or copolymerization is anti-
The proportioning of the poly- polyfluoroalkoxy ether acid emulsifying agent answered and water so that under conditions of initiator exists, these homopolymerizations or copolymerization
Reaction all can embody the features such as polymerization time is fast, polymerization yield rate is high, meanwhile, prepared fluoropolymer do not contain perfluoro caprylic acid or
Perfluorooctane sulfonate.For this reason, the present invention is defined, limit the poly- polyfluoro alcoxyl of its use to the aqueous emulsion polymerization of fluorinated monomer
Base ether acid (using as emulsifying agent) is (0.1～20) with the weight proportion of water in this aqueous emulsion polymerization: 100, optimization,
Its weight proportion is (0.1～0.9): 100.
Below with four exemplary embodiments to enumerate explanation according to the present invention without perfluoro caprylic acid or perfluorooctane sulfonate
Fluoropolymer and its specific embodiment of aqueous liquid dispersion (dispersion), certainly, protection scope of the present invention is not limited to
In following examples.
Embodiment 1:
Politef is produced through aqueous emulsion polymerization by gaseous fluorinated monomer tetrafluoroethene, in this aqueous emulsion polymerization
Add the bromo- poly- polyfluoroalkoxy ether acid of 1- as fluorine-containing emulsifier, specific implementation step is as follows:
A: prepare the aqueous solution of the salt of the bromo- poly- polyfluoroalkoxy carboxylic ether acid of 1-: add 700ml in 2000ml glass beaker
Deionized water and the ammonia of 100ml 25%, then pass through liquid glass droplet funnel slow at the uniform velocity Deca 200g in deionized water
The bromo- poly- polyfluoroalkanoic acids of 1-, are stirred while Deca, and mixing speed is 80 rpm, then, obtains poly- polyfluoro alcoxyl
Base ether acid ammonia spirit is standby, and wherein, the bromo- poly- polyfluoroalkoxy carboxylic ether acid ammonium of 1- is 20:100 with the weight proportion of water；
B: polymerization prepares: enters line replacement deoxygenation with nitrogen to polymerization autoclave, makes this polymerization autoclave be evacuated to oxygen in kettle
Content≤25ppm；
C: polymerization process:
A: feed intake: in the 100l rustless steel polymerization autoclave have baffle plate add 55kg deionized water, 972g paraffin with
And the bromo- poly- polyfluoroalkoxy carboxylic ether acid ammonia spirit of 1- of 962.5g20%；
B: prepare initiator: 6.0g Ammonium persulfate. is dissolved in 1l warm water (about 75 DEG C), obtains 0.6% Ammonium persulfate.
Aqueous solution；
C: initiation reaction: with tetrafluoroethene, polymerization autoclave is pressurizeed, stir and be warming up to 73 DEG C, stirring
Speed is 200rpm；With tetrafluoroethene, polymerization autoclave is boosted again, until polymeric kettle in pressure reach 1.865mpa,
When temperature is 73 DEG C, add, with dosing pump, the initiator prepared in step b into polymeric kettle；
D: when the pressure of polymerization autoclave is down to 1.756mpa (generally in 5 minutes), adds tetrafluoroethene again, make
Pressure in polymerization autoclave is maintained at 1.865mpa, temperature is 73 DEG C, carries out polyreaction；
E: when tetrafluoroethene addition reaches 27kg, make polyreaction stop, total response time is 160min.
D: obtain aqueous dispersion of polytetrafluoroethyland: after polyreaction stops, by tetrafluoro unreacted in polymerization autoclave
Ethylene enters recovery system, the aqueous polytetrafluoroethyldispersion emulsion obtained by cooling, and removes upper strata paraffin.
After measured, the solid component concentration of the aqueous polytetrafluoroethyldispersion emulsion being obtained by said method is about 49.09%, institute
The amount of the bromo- poly- polyfluoroalkoxy carboxylic ether acid ammonia of 1- using is that the weight ratio of water in 192.5g, with aqueous emulsion polymerization is
0.35:100.
Comparative example 1:
Politef is produced through aqueous emulsion polymerization by gaseous fluorinated monomer tetrafluoroethene, in this aqueous emulsion polymerization
Add perfluorooctanoic acid as fluorine-containing emulsifier, implementation step is same as Example 1.
The aqueous dispersion of polytetrafluoroethyland that we obtain to the method is measured, as follows: politef water
Property emulsion solid component concentration be about 32.6%, the amount of the perfluorooctanoic acid being used is in 275g, with aqueous emulsion polymerization
The weight of water is than for 0.5:100.
Above-described embodiment 1 and comparative example 1 are counted, obtain following data, as shown in table 2:
Table 2
Embodiment 2:
Polytrifluorochloroethylene is produced through aqueous emulsion polymerization by gaseous fluorinated monomer CTFE, gathers in this aqueous emulsion
Add the bromo- poly- polyfluoroalkoxy carboxylic ether acid of 1- as fluorine-containing emulsifier in conjunction, specific implementation step is as follows:
A: prepare the aqueous solution of the salt of the bromo- poly- polyfluoroalkoxy carboxylic ether acid of 1-: add in 5000ml glass beaker
2800ml deionized water and the ammonia of 400ml 25%, then pass through liquid glass droplet funnel slow at the uniform velocity Deca in deionized water
The bromo- poly- polyfluoroalkanoic acids of 1- of 800g, are stirred while Deca, and mixing speed is 80 rpm, then, obtain poly- many
Fluoroalkyloxy ether acid ammonia spirit is standby, and wherein, the bromo- poly- polyfluoroalkoxy carboxylic ether acid ammonia of 1- is 20 with the weight proportion of water:
100；
B: polymerization prepares: enters line replacement deoxygenation with nitrogen to polymerization autoclave, makes this polymerization autoclave be evacuated to polymeric kettle
Interior oxygen content≤20ppm；
C: polymerization process:
A: feed intake: add 75kg deionized water, 160g sodium carbonate in the 100l rustless steel polymerization autoclave have baffle plate
And the bromo- poly- polyfluoroalkoxy carboxylic ether acid ammonia spirit of 1- of 962.5g 20%；
B: prepare initiator: 8.0g Ammonium persulfate. is dissolved in 1l warm water (about 75 DEG C), obtains 0.8% Ammonium persulfate.
Aqueous solution；
C: initiation reaction: with CTFE, polymerization autoclave is pressurizeed, stir and be warming up to 50 DEG C, stir
Mixing speed is 500rpm；With CTFE, polymerization autoclave is boosted again, until pressure reaches in polymeric kettle
When 2.52mpa, temperature are 50 DEG C, with dosing pump, add the initiator prepared in step b into polymeric kettle；
D: in course of reaction, continue to add CTFE monomer into reactor, to keep reactor pressure to maintain
2.52mpa, when CTFE addition reaches 35kg, makes polyreaction stop, total response time is 300min.
D: obtain polytrifluorochloroethylene aqueous liquid dispersion: after polyreaction stops, by polymerization autoclave unreacted three
Fluorine vinyl chloride enters recovery system, the polytrifluorochloroethylene water-based emulsion obtained by cooling.
After measured, the solid component concentration of the aqueous polytetrafluoroethyldispersion emulsion being obtained by said method is about 43.38%, institute
The amount of the bromo- poly- polyfluoroalkoxy carboxylic ether acid ammonia of 1- using is that the weight ratio of water in 487.5g, with aqueous emulsion polymerization is
0.65:100.
Embodiment 3:
Vinylidene CTFE is produced through aqueous emulsion polymerization by vinylidene, CTFE, in this aqueous emulsion
Add the chloro- poly- polyfluoroalkoxy ether-P-TOLUENE SULFO ACID 99's ammonium of 1- as fluorine-containing emulsifier in polymerization, specific implementation step is as follows:
A: prepare the aqueous solution of the salt of the chloro- poly- polyfluoroalkoxy ether-P-TOLUENE SULFO ACID 99 of 1-: add in 2000ml glass beaker
700ml deionized water and the ammonia of 100ml 25%, then pass through liquid glass droplet funnel slow at the uniform velocity Deca in deionized water
The chloro- poly- polyfluoroalkoxy ether-P-TOLUENE SULFO ACID 99 of 1- of 200g, is stirred while Deca, and mixing speed is 80 rpm, so
Afterwards, obtain poly- polyfluoroalkoxy ether acid aqueous ammonium, wherein, the weight of the chloro- poly- polyfluoroalkoxy ether-P-TOLUENE SULFO ACID 99's ammonium of 1- and water
Proportioning is 20:100；
B: polymerization prepares: enters line replacement deoxygenation with nitrogen to polymerization autoclave, makes this polymerization autoclave be evacuated to polymeric kettle
Interior oxygen content≤25ppm；
C: polymerization process:
A: feed intake: in the 100l rustless steel polymerization autoclave have baffle plate add 64kg deionized water, 800g paraffin with
And the aqueous solution of the chloro- poly- polyfluoroalkoxy ether-P-TOLUENE SULFO ACID 99's ammonium of 1- of 2240g 20%；
B: prepare initiator: 32g Ammonium persulfate. is dissolved in 1l warm water (about 75 DEG C), obtains 3.2% Ammonium persulfate. water
Solution, then, adds 80 grams of diethyl malonate in 3.2% ammonium persulfate aqueous solution, obtains compounding mixing and causes
Agent；
C: initiation reaction: using the mix monomer of the vinylidene of 95mol% and the CTFE of 5mol%, high pressure is gathered
Close kettle to be boosted, stir and be warming up to 60 DEG C, mixing speed is 200rpm.Then with mix monomer, reactor is continued
Of continuing rising be depressed into 2.5mpa, maintain autoclave temp at 6060 DEG C, with dosing pump, will be molten for the mixed initiator being configured in step b
Liquid squeezes into reactor；
D: when the mix monomer addition of vinylidene, CTFE reaches 37kg, make polyreaction stop, adding up to
Response time is 320min.
D: obtain the aqueous liquid dispersion of vinylidene chlorotrifluoroethylene: after polyreaction stops, just high pressure
In polymeric kettle, the mix monomer of the CTFE of the vinylidene of unreacted 95mol% and 5mol%, enters recovery system, cold
The water-based emulsion of obtained vinylidene chlorotrifluoroethylene, removes the paraffin on upper strata.
After measured, the solid constituent of the water-based emulsion of vinylidene chlorotrifluoroethylene being obtained by said method
Concentration is about 46.88%, and the amount of the chloro- poly- polyfluoroalkoxy ether-P-TOLUENE SULFO ACID 99's ammonium of the 1- being used is 448g, with aqueous emulsion polymerization
In system, the weight of water is than for 0.7:100.
Embodiment 4:
Vinylidene hexafluoropropene tetrafluoro is produced through aqueous emulsion polymerization by vinylidene, hexafluoropropene, tetrafluoroethene
Ethylene, adds the chloro- poly- polyfluoroalkoxy ether-P-TOLUENE SULFO ACID 99's ammonium of 1- as fluorine-containing emulsifier in this aqueous emulsion polymerization, specifically real
Apply step as follows:
A: prepare the aqueous solution of the salt of the chloro- poly- polyfluoroalkoxy ether-P-TOLUENE SULFO ACID 99 of 1-: add in 5000ml glass beaker
2800ml deionized water and the ammonia of 400ml 25%, then pass through liquid glass droplet funnel slow at the uniform velocity Deca in deionized water
The chloro- poly- polyfluoroalkoxy ether-P-TOLUENE SULFO ACID 99 of 1- of 800g, is stirred while Deca, and mixing speed is 80 rpm, so
Afterwards, obtain poly- polyfluoroalkoxy ether acid aqueous ammonium, wherein, the weight of the chloro- poly- polyfluoroalkoxy ether-P-TOLUENE SULFO ACID 99's ammonium of 1- and water
Proportioning is 20:100.
B: polymerization prepares: enters line replacement deoxygenation with nitrogen to polymerization autoclave, makes this polymerization autoclave be evacuated to polymeric kettle
Interior oxygen content≤20ppm.
C: polymerization process:
A: feed intake: add 60kg deionized water, 80gph regulator in the 100l rustless steel polymerization autoclave have baffle plate
The aqueous solution of the chloro- poly- polyfluoroalkoxy ether-P-TOLUENE SULFO ACID 99's ammonium of 1- of (disodium hydrogen phosphate) and 750g 20%；
B: prepare initiator: 12.5g Ammonium persulfate. is dissolved in 1l warm water (about 75 DEG C), obtains 1.25% persulfuric acid
Aqueous ammonium；
The tetrafluoroethene mixing of the vinylidene of c: initiation reaction: 45mol%, the hexafluoropropene of 50mol% and 5mol% is single
Body, boosts to polymerization autoclave, stirs and is warming up to 120 DEG C, and mixing speed is 200rpm, then single with mixing
Body continues to boost to 3.5mpa to reactor, maintains autoclave temp at 120 DEG C, with dosing pump, mixed by configured in step b
Close initiator solution and squeeze into reactor, start to react；
D: when mix monomer inventory reaches 16.8kg, keep reaction temperature to be 120 DEG C, mixing speed 200rpm, use
Dosing pump, adds 10ml diethyl oxalate into autoclave；
E: when the mixing addition of vinylidene, hexafluoropropene and tetrafluoroethene reaches 24kg, make polyreaction stop.
Total response time is 260min.
D: obtain the aqueous liquid dispersion of vinylidene hexafluoropropene TFE copolymer: after polyreaction stops,
The tetrafluoroethene of the vinylidene of use 45mol% unreacted in polymerization autoclave, the hexafluoropropene of 50mol% and 5mol% is mixed
Close monomer and enter recovery system, the water-based emulsion of the vinylidene hexafluoropropene TFE copolymer obtained by cooling.
After measured, the water-based emulsion of vinylidene hexafluoropropene TFE copolymer being obtained by said method
Solid component concentration is about 37%, and the amount of the chloro- poly- polyfluoroalkoxy ether-P-TOLUENE SULFO ACID 99's ammonium of the 1- being used is 448g, with aqueous emulsion
In polymerization system, the weight of water is than for 0.25:100.
The method recorded according to jis-k5663, the aqueous liquid dispersion that we obtain to aforementioned four embodiment and comparative example 1
Dispersion stabilization be determined, obtain following data, as shown in table 3:
Table 3
Wherein, the method for testing of mechanical stability is, aqueous liquid dispersion 100g is stirred in 5000rpm even phase disperser
5min, measures its coagulation amount (unit: ppm) after placing 1d；The method of testing of high-temperature stability is that aqueous liquid dispersion is at 50 DEG C
After placing 60d, visually to determine whether precipitum.
In actual industrial production, above-mentioned four kinds of fluoropolymers (politef, the polytrifluorochloroethylene, partially being related to
Fluorothene CTFE, vinylidene hexafluoropropene tetrafluoroethene) it is respectively provided with wide application prospect, such as: oil
Chemical industry, electric, building coating or the numerous areas such as dipping, automobile decoration, appliance shell, medical science, quasiconductor, fiber cloth,
Now be directed to patent documentation cn101218264b(documents 1), cn102089335a(documents 2), cn101745338a(pair
Than file 3), cn101287766(documents 4), cn101291987(documents 5) involved by fluorine-containing emulsifier, with reality
Apply as a example preparing the specific embodiment of politef and its dispersion in example 1, prepare politef and its dispersion respectively
Body, its preparation time is as shown in table 4 with product index:
Table 4
According to above-mentioned data analysiss, according to the present invention by poly- polyfluoroalkoxy ether acid (the bromo- poly- polyfluoroalkoxy of 1-
Carboxylic ether acid ammonium) as emulsifying agent, during preparing fluoropolymer (politef) and its aqueous liquid dispersion, with contrast
File 1～5 is compared, and all has a clear superiority on primary ion particle diameter, the solids content of aqueous liquid dispersion, percentage elongation,
The polymerization time of fluoropolymer, the particle specific gravity of ssg(fluoropolymer), the effect that draws high intensity aspect also ideal,
Suitably it is widely popularized use.
The above, be only presently preferred embodiments of the present invention, and not the present invention is done with any pro forma restriction, every according to
Any simple modification above example made according to the technical spirit of the present invention, equivalent variations, each fall within the protection of the present invention
Within the scope of.
Claims (6)
1. a kind of dispersion it is characterised in that: include following components: without the fluoropolymer of perfluoro caprylic acid or perfluorooctane sulfonate
With the aqueous solution of the salt of the poly- polyfluoroalkoxy ether acid as emulsifying agent, the aqueous liquid dispersion being mixed into, described dispersion is not
Containing perfluoro caprylic acid or perfluorooctane sulfonate,
Fluoropolymer without perfluoro caprylic acid or perfluorooctane sulfonate is in poly- polyfluoroalkoxy by one or more fluorinated monomer
Ether acid obtains after liquid phase polymerization as in the case of emulsifying agent, and described poly- polyfluoroalkoxy ether acid is selected from following one kind or several
The combination planted:
Meet the poly- polyfluoroalkoxy ether acid of following formula ():
(),
Meet the poly- polyfluoroalkoxy ether acid of following formula ():
(),
Wherein:
T:、、、；
X:h, br；
R:h, br, i；
Y:so3H and its salt, cooh and its salt, ch2ch2Cooh and its salt, ch2ch2so3H and its salt,
cooch2ch2Cooh and its salt, cooch2ch2so3H and its salt,And its salt；And its salt；
The value of n is: 0～4；
The value of m is: 1～20；
The value of p is: 0～4；
The value of q is: 0～1,
The aqueous solution of the described salt of the poly- polyfluoroalkoxy ether acid as emulsifying agent is that at the uniform velocity Deca is gathered in alkaline aqueous solution
Polyfluoroalkoxy ether acid, Deca while stirring and be obtained, the ph of the prepared aqueous solution of salt of poly- polyfluoroalkoxy ether acid
It is worth for 7～9, poly- polyfluoroalkoxy ether acid is (0.1～20) with the weight proportion of water: 100；Described without perfluoro caprylic acid or complete
The weight proportion of the fluoropolymer of the pungent sulfonic acid of fluorine and water is (3～7): 10.
2. a kind of dispersion according to claim 1 it is characterised in that: the performance indications of described poly- polyfluoroalkoxy ether acid
Including:
In terms of naoh, acid number: < 150 mg/g；
Cross oxygen value: < 1.5 g/100g；
Boiling point: < 260 DEG C；
Surface tension: < 40mn/m；
Critical micelle concentration (cmc): < 5%.
3. a kind of dispersion according to claim 2 it is characterised in that: the performance indications of described poly- polyfluoroalkoxy ether acid
Including:
In terms of naoh, acid number: < 100mg/g；
Cross oxygen value: < 0.5g/100g；
Boiling point: < 160 DEG C；
Surface tension: < 20mn/m；
Critical micelle concentration (cmc): < 1.5 %.
4. a kind of dispersion according to claim 1 it is characterised in that: described alkaline aqueous solution includes ammonia, hydrogen-oxygen
Change the mixing of one or more of sodium water solution, potassium hydroxide aqueous solution, magnesium hydroxide aqueous solution, triethanolamine aqueous solution.
5. a kind of dispersion according to claim 1 it is characterised in that: the water of the described salt of poly- polyfluoroalkoxy ether acid
The preparation temperature of solution is 25～50 DEG C, rate of addition is 0.1～10ml/s, mixing speed is 20～200rpm.
6. a kind of dispersion according to claim 1 it is characterised in that: described without perfluoro caprylic acid or perfluorooctane sulfonate
Fluoropolymer is in solid-state.
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| ITMI20012744A1 (en) * | 2001-12-21 | 2003-06-21 | Ausimont Spa | POLYMERIZATION PROCESS OF SULPHONIC MONOMERS |
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