CN102887972B - Ternary polymerization polytetrafluoroethylene resin, and preparation method and concentrated dispersion liquid thereof - Google Patents
Ternary polymerization polytetrafluoroethylene resin, and preparation method and concentrated dispersion liquid thereof Download PDFInfo
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Abstract
The invention relates to a ternary polymerization polytetrafluoroethylene resin which is formed by copolymerizing tetrafluoroethylene, fluorine-containing olefin and perfluor (alkyl vinyl ether) and also relates to a preparation method and concentrated dispersion liquid of the ternary polymerization polytetrafluoroethylene resin. On the basis that the original characteristics of the polytetrafluoroethylene resin are kept, the provided ternary polymerization polytetrafluoroethylene resin can be processed to form products with various specifications and shapes through melting, so that the application range of the polytetrafluoroethylene resin is widened; the provided concentrated dispersion liquid of the polytetrafluoroethylene can fully cover the surface of a base material during film coating, and the light-transmitting performance and the glossiness of the coated film are improved; and by the provided preparation method, the production cost is reduced, environment pollution is reduced, the reaction conditions are mild, and high safety can be achieved.
Description
Technical field
The present invention relates to TFE copolymer field, the teflon resin, its preparation method that is specifically related to a kind of terpolymer with and concentrated dispersion liquid.
Background technology
Teflon resin is the engineering plastics with Good All-around Property, according to its polymerization technique difference, be divided into suspending resin and dispersion resin, but which kind of teflon resin all greatly can not carry out melt-processed because of its melt viscosity, and this has limited the Application Areas of teflon resin.
Polytetrafluoroethylene aqueous dispersion can be by spraying, impregnating method, at fabric, the surfaces such as metal form has chemical stability, viscosity not, weathering resistance, waterproof and oilproof, the film that the transparency is superior, can be widely used in from household application to industrial goods and even aerospace articles for use, as electric cooker inwall, the non-sticky of electric iron bottom is filmed, storage vessel on food technology, housing decoration, the not viscosity application of wrapping mechanism etc., various rubber, the non-sticky application of mould for plastics inwall, paper industry, the cylinder of textile industry, the non-sticky application of duplicating machine cylinder, non-sticky application of automobile component and computer component etc.
The fluoro-containing coating that the ptfe emulsion of take is base-material, because the atomic radius of fluorine atom is little, electronegativity is large, polarizability is little, length of covalent bond that fluorine atom and carbon atom form is extremely short, bond energy is very big, makes it thermostability, weathering resistance, erosion resistance and non-stick property that macro property shows as height.But because it does not flow under melt temperature, be insoluble to most organic solvents, with base material poor adhesion, after application, need high temperature sintering, be difficult to obtain free of pinholes and film, thereby limited its Application Areas.For a long time, the research and development person of tetrafluoroethylene is for these problems, and a large amount of research has been carried out in the aspects such as the polymerization technique of Paratetrafluoroethylene, formula, synthetic technology, blend, application techniques, and has obtained gratifying achievements.Particularly fluorochemical monomer copolymerization is succeeded in developing, and for synthesized high-performance, multi-functional tetrafluoro coating have been opened up new approach, and tetrafluoro coating one is jumped and rank among the row of universal lacquer.Widened greatly the Application Areas of fluoro-containing coating.
CN1151994A discloses a kind of preparation method of tetrafluoroethylene terpolymer, is mainly as resin extruded processing, adopts TFE/HFP/PEVE terpolymer, and polymerization pressure is high, reaches 4.2MPa, and resulting polymers resin has good warp resistance performance.
CN1754894 discloses a kind of preparation method of modified Teflon aqueous dispersions, mainly by modified monomer modification, improve the film forming properties of aqueous dispersions, in polymerization process, by pressure change, adjust particle structure, in invention, emphasize the modifying function of modified monomer, in particle, modified monomer content seldom, is 0.1 ~ 1.0wt% of PTFE.Aqueous dispersions is with respect to the concentrated dispersion liquid of PTFE, still very strict to the conditional request of the course of processing, needs high temperature sintering moulding, and therefore the processing characteristics as water-borne coatings does not improve.
Summary of the invention
For overcoming the restriction in the defect of existing teflon resin in performance and application, the object of this invention is to provide a kind of terpolymer teflon resin.
Another object of the present invention is to provide a kind of preparation method of terpolymer teflon resin.
Another object of the present invention is to provide the concentrated dispersion liquid of a kind of terpolymer tetrafluoroethylene.
Terpolymer teflon resin provided by the invention, is formed by tetrafluoroethylene, Fluorine containing olefine and perfluor (alkyl vinyl ether) copolymerization; Wherein, the mass percent of Fluorine containing olefine is 2.0～4.5%, and the mass percent of perfluor (alkyl vinyl ether) is 2.0～4.5%.
Described perfluor (alkyl vinyl ether) (PAVE) be perfluor (methylvinylether) (PMVE), perfluor (ethyl vinyl ether) (PEVE) or perfluor (propyl vinyl ether) (PPVE).
Described Fluorine containing olefine is vinylidene, trifluoro-ethylene, trifluorochloroethylene, five fluorine propylene or R 1216s.
The present invention has adopted PAVE as comonomer, molecular end has alkene ether structure, there is good copolymerizable with fluoroolefin (comprising tetrafluoroethylene and fluoroolefin comonomer), in molecule, oxyalkyl unit composition ether chain has good wetting ability, therefore the dispersion stability forming is good, but oxyalkyl repeating unit is too much, can cause smear weathering resistance and the water tolerance of polytetrafluoroethylene aqueous dispersion to decline, therefore, the appropriate PAVE that adds in multipolymer, both guarantee weathering resistance and the water tolerance of filming, and can guarantee again the stability of aqueous dispersions.Preferred perfluor (alkyl vinyl ether) is PPVE, compares, on the one hand with PMVE, PEVE, PPVE molecular chain is longer, more can reduce the degree of crystallinity of multipolymer, on the other hand, under identical reaction conditions, the solubleness of PPVE in water medium is larger, more be conducive to it and participate in copolyreaction, and PPVE reactivity ratio is lower than TFE, reaction process milder, temperature is more easily controlled, and the repeatability of technique is better.
The preparation method of terpolymer teflon resin provided by the invention is: in water medium, the monomer of tetrafluoroethylene, Fluorine containing olefine and perfluor (alkyl vinyl ether) is carried out to copolyreaction and form described teflon resin; Wherein, the temperature of reaction of described copolyreaction is 50～80 ℃, and reaction pressure is 1.0～2.0MPa.
Preferably, described preparation method comprises the following steps:
(1) in reactor, add water, ealkaline buffer and dispersion agent, stir;
(2) adding tetrafluoroethylene monomer to make the pressure in described reactor is 0.01～0.1MPa, and then adds fluorinated olefin monomers, perfluor (alkyl vinyl ether) monomer, chain-transfer agent and initiator;
(3) reactor is warming up to 50～80 ℃, adds tetrafluoroethylene monomer to make pressure in described reactor rise to 1.0～2.0MPa and start polyreaction;
(4) keep the pressure in described reactor constant until reaction finishes, cohesion, is dried, and obtains described teflon resin;
Wherein, the solid content that reaction finishes in rear described water medium is 20～35% by mass percentage.
In above-mentioned preparation method, polymerization temperature and polymerization pressure affect the solubleness of each monomer in reaction medium, thereby have affected the performance of polymkeric substance.Polymerization temperature in above-mentioned preparation method and polymerization pressure are set, can reduce resulting teflon resin fusing point, improve the performance of teflon resin.
Described ealkaline buffer is volatile salt, and the consumption in every 100 weight parts water media is 0.1～0.5 weight part, preferred 0.1～0.3 weight part.Described ealkaline buffer can be converted into more stable amino-complex by most of carboxyl end group, stops the corrosion of issuable HF to reactor in polymerization process.
Described chain-transfer agent is methylene dichloride or methyl alcohol, and the consumption in every 100 weight parts water media is 0.1～1.0 weight part, preferred 0.1～0.5 weight part.Described chain-transfer agent can avoid molecular weight distribution to broaden, and reduces the chain termination reaction producing because of comonomer perfluor (alkyl vinyl ether) rearrangement.
Described dispersion agent is ammonium perfluorocaprylate, and the consumption in every 100 weight parts water media is 0.1～0.5 weight part, preferably 0.1～0.3 weight part.
Described initiator is inorganic peroxysulfate, and the consumption in every 100 weight parts water media is 0.01～0.05 weight part.Described inorganic peroxysulfate is ammonium persulphate, Sodium Persulfate or Potassium Persulphate.
The molecular weight of terpolymer teflon resin provided by the invention is 1.0 * 10
5～3.0 * 10
6between, fusing point is 300～320 ℃, melting index 0.2～50g/10min(372 ℃, 5kg load).
The concentrated dispersion liquid of terpolymer tetrafluoroethylene provided by the invention is the concentrated dispersion liquid of water-based of teflon resin described in above technical scheme any one, wherein, the particle diameter of described teflon resin is 0.18～0.24 μ m, and mass percent concentration is 50～60%.
Above-mentioned concentrated dispersion liquid also comprises that mass percentage concentration is the pH value conditioning agent that 5～10% nonionogenic tenside and mass percentage concentration are 0.1～0.3%.
Described nonionogenic tenside is polyethenoxy ether class tensio-active agent, as alkylphenol polyoxyethylene or alkyl polyoxyethylene ether; Described pH value conditioning agent is supercarbonate, as saleratus, sodium bicarbonate or bicarbonate of ammonia.
Concentrated dispersion liquid provided by the invention can be used separately, also can blending concentrate in dispersion liquid in other tetrafluoroethylene, for spraying or dipping base material, for base material provides non-sticky, films.Concentrated dispersion liquid provided by the invention, because having greatly, improves the more traditional tetrafluoroethylene of its meltbility, in sintering process, flow more abundant, also can blending concentrate in dispersion liquid in common tetrafluoroethylene, in sintering, melt-flow is filled up the rejected region of filming, therefore can give the brighter and cleaner surface of filming, the glossiness of filming can be largely increased.
The present invention has the following advantages:
(1) in terpolymer teflon resin provided by the invention, comonomer add the fusing point that has reduced multipolymer, make the resin obtaining can carry out melt-processed, retaining on the basis of the characteristics such as teflon resin high-low temperature resistant, corrosion-resistant, chemical-resistant resistance, non-viscosity, the goods that can melt-processed become all size and shape, the scope of application that has improved teflon resin, has expanded Application Areas.
(2) the concentrated dispersion liquid of tetrafluoroethylene provided by the invention in use can suitably reduce sintering temperature, and under lower sintering temperature, polymkeric substance can melt-flow, and therefore, while filming, covering substrates is surperficial completely.Meanwhile, adding of comonomer, has changed the structure of tetrafluoroethylene molecular chain, at tetrafluoroethylene, has in rule segment and has introduced different side chains, has reduced polymer crystallization degree, thereby improves the transparency and the glossiness of filming.
(3) preparation method provided by the invention has abandoned the organic solvent that may threaten to environment, and adopt, carries out terpolymer in water medium, has saved production cost, has reduced environmental pollution; In polymerization process, can remain under lower pressure and carry out, reaction conditions is gentle, and the security of whole polymerization process is improved greatly.In a word, preparation method of the present invention makes the preparation process of polytetrafluoroethyl-ne alkene copolymer more be easy to realize, and is applicable to scale operation.
Embodiment
Following examples are used for illustrating the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
To band, stir and temperature adjustment chuck, inner capacities is in the stainless steel autoclave of 5L, add 2.8kg deionized water, 5g volatile salt, 5g ammonium perfluorocaprylate (be made into mass percent concentration be 50% the aqueous solution), with 70rpm, stir, with nitrogen replacement 3 times, and replace 2 times with tetrafluoroethylene monomer, it is qualified analyzing oxygen level below 30ppm, being pressed into tetrafluoroethylene monomer makes still internal pressure reach 0.05MPa, be pressed into 50gHFP gas, use metering outfit to be pressed into 40gPPVE, 10g methyl alcohol and 0.4g ammonium persulphate, reactor is warming up to 70 ℃, be pressed into tetrafluoroethylene monomer to still internal pressure and reach 1.6MPa.Along with reaction is carried out, use tetrafluoroethylene monomer to maintain still internal pressure constant, temperature rising, when the tetrafluoroethylene monomer consuming in reaction reaches 1.6kg, finish reaction, when reaction finishes, temperature of reaction system is about 77 ℃, stop stirring and supplying with tetrafluoroethylene monomer, reclaim still internal pressure to normal pressure, obtain terpolymer PTFE polymer fluid, wherein the solid content of resin is approximately 30%, average primary particle diameter is 0.24um, and the content of comonomer in resin is approximately 4 (wt) %.
Polymer fluid is diluted to solid content and is about 10%, and intense mechanical stirs cohesion, and fine powder is 160 ℃ of oven dry, and test melting point resin is 310 ℃, and melting index is 12.4g/10min(372 ℃, 5kg load).
Get 1000g polymer fluid, add 60g emulsifying agent and 1.8g bicarbonate of ammonia, standing 65 ℃ of left and right, obtain that solid content is about 55%, emulsifier content is about 6% dispersion concentrated solution, survey glossiness, testing tool is vancometer, adopts 60 ° of input angle tests, and glossiness (luminous reflectance factor) is 27.4-30.4.
Embodiment 2
With embodiment 1 identical process, only PPVE consumption is adjusted to 50g, reaction end temp is 79 ℃, gained melting point resin is 304 ℃, melting index is 20.4g/10min(372 ℃, 5kg load).
With the concentrated dispersion liquid of embodiment 1 identical process preparation, glossiness is 29.3-32.8.
Embodiment 3
With embodiment 1 identical process, only PPVE consumption is adjusted to 30g, reaction end temp is about 78 ℃, and gained melting point resin is 313 ℃, melting index is 9.3g/10min(372 ℃, 5kg load).
With the concentrated dispersion liquid of embodiment 1 identical process preparation, glossiness is 27.1-29.8.
Embodiment 4
With embodiment 1 identical process, starting temperature is adjusted into 65 ℃, HFP consumption is adjusted to 60g, and when reaction finishes, temperature is about 75 ℃, and gained melting point resin is 306 ℃, melting index is 18.5g/10min(372 ℃, 5kg load).
With the concentrated dispersion liquid of embodiment 1 identical process preparation, glossiness is 28.3-31.6.
Embodiment 5
With embodiment 1 identical process, reacting initial temperature is adjusted into 72 ℃, HFP consumption is adjusted to 40g, and end temp is about 79 ℃, and gained melting point resin is 312 ℃, melting index is 11.3g/10min(372 ℃, 5kg load).
With the concentrated dispersion liquid of embodiment 1 identical process preparation, glossiness is 27.6-30.7.
Embodiment 6
With embodiment 1 identical process, reacting initial temperature is adjusted into 63 ℃, methanol usage is adjusted to 20g, and end temp is about 75 ℃, and gained melting point resin is 303 ℃, melting index is 45.0g/10min(372 ℃, 5kg load).
With the concentrated dispersion liquid of embodiment 1 identical process preparation, glossiness is 28.7-31.8.
Embodiment 7
With embodiment 1 identical process, reacting initial temperature is adjusted into 70 ℃, methanol usage is adjusted to 5g, and end temp is about 78 ℃, and gained melting point resin is 313 ℃, melting index is 7.8g/10min(372 ℃, 5kg load).
With the concentrated dispersion liquid of embodiment 1 identical process preparation, glossiness is 27.3-30.2.
Embodiment 8
With embodiment 1 identical process, starting temperature is adjusted to 55 ℃, end temp is about 65 ℃, and gained melting point resin is 309 ℃, melting index is 28.6g/10min(372 ℃, 5kg load).
With the concentrated dispersion liquid of embodiment 1 identical process preparation, glossiness is 29.5-32.9.
Embodiment 9
With embodiment 1 identical process, starting temperature is adjusted into 70 ℃, the pressure in reaction process is adjusted to 1.0MPa, end temp is about 80 ℃, and gained melting point resin is 315 ℃, melting index is 0.4g/10min(372 ℃, 5kg load).
With the concentrated dispersion liquid of embodiment 1 identical process preparation, glossiness is 26.5-29.2.
Comparative example 1
To band, stir and temperature adjustment chuck, inner capacities is in the stainless steel autoclave of 5L, add 2.8kg deionized water, 1g succinic acid, 5g ammonium perfluorocaprylate (be made into mass percent concentration be 50% the aqueous solution), with 70rpm, stir, with nitrogen replacement 3 times, and replace 2 times with tetrafluoroethylene monomer, it is qualified analyzing oxygen level below 30ppm, being pressed into tetrafluoroethylene monomer makes still internal pressure reach 0.05MPa, add 80gHFP, use metering outfit to be pressed into 0.4g ammonium persulphate, reactor is warming up to 80 ℃, be pressed into tetrafluoroethylene monomer to still internal pressure and reach 2.5MPa.Along with reaction is carried out, use tetrafluoroethylene monomer to maintain still internal pressure constant, when the tetrafluoroethylene monomer consuming in reaction reaches 1.8kg, finish reaction, stop stirring and supplying with tetrafluoroethylene monomer, reclaim still internal pressure to normal pressure, obtain PTFE aqueous dispersions, wherein the solid content of resin is approximately 35%, and average primary particle diameter is 0.24um, and melting point resin is 327 ℃.
Get 1000g polymer fluid, add 60g emulsifying agent and 1.8g bicarbonate of ammonia, standing 65 ℃ of left and right, obtain that solid content is about 55%, emulsifier content is about 6% dispersion concentrated solution, survey glossiness and be 9.8-12.6(testing method and testing tool with embodiment 1).
Comparative example 2
To band, stir and temperature adjustment chuck, inner capacities is in the stainless steel autoclave of 5L, add 2.8kg deionized water, 1g succinic acid, 5g ammonium perfluorocaprylate (be made into mass percent concentration be 50% the aqueous solution), with 70rpm, stir, with nitrogen replacement 3 times, and replace 2 times with tetrafluoroethylene monomer, it is qualified analyzing oxygen level below 30ppm, being pressed into tetrafluoroethylene monomer makes still internal pressure reach 0.05MPa, add 100gPPVE, use metering outfit to be pressed into 0.4g ammonium persulphate, reactor is warming up to 80 ℃, be pressed into tetrafluoroethylene monomer to still internal pressure and reach 2.5MPa.Along with reaction is carried out, use tetrafluoroethylene monomer to maintain still internal pressure constant, when the tetrafluoroethylene monomer consuming in reaction reaches 1.8kg, finish reaction, stop stirring and supplying with tetrafluoroethylene monomer, reclaim still internal pressure to normal pressure, obtain PTFE aqueous dispersions, wherein the solid content of resin is approximately 34%, and average primary particle diameter is 0.24um, and melting point resin is 326 ℃.
Get 1000g polymer fluid, add 60g emulsifying agent and 1.8g bicarbonate of ammonia, standing 65 ℃ of left and right, obtain that solid content is about 55%, emulsifier content is about 6% dispersion concentrated solution, survey glossiness and be 10.2-13.1(testing method and testing tool with embodiment 1).
Comparative example 3
With embodiment 1 identical process, do not add HFP, and the consumption of PPVE is adjusted to 90g, reaction end temp is 78 ℃, gained melting point resin is 318 ℃, melting index is 18.9g/10min(372 ℃, 5kg load).
With the concentrated dispersion liquid of embodiment 1 identical process preparation, glossiness is 11.4-13.8.
Comparative example 4
With embodiment 1 identical process, do not add PPVE, and the consumption of HFP is adjusted to 90g, reaction end temp is 80 ℃, gained melting point resin is 299 ℃, melting index is 19.7g/10min(372 ℃, 5kg load).
With the concentrated dispersion liquid of embodiment 1 identical process preparation, glossiness is 9.6-12.1.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements, all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (8)
1. a terpolymer teflon resin, is characterized in that, by tetrafluoroethylene, Fluorine containing olefine and perfluor (alkyl vinyl ether) copolymerization, is formed; Wherein, the mass percent of Fluorine containing olefine is 2.0～4.5%, and the mass percent of perfluor (alkyl vinyl ether) is 2.0～4.5%;
Described perfluor (alkyl vinyl ether) is perfluor (methylvinylether), perfluor (ethyl vinyl ether) or perfluor (propyl vinyl ether);
Described Fluorine containing olefine is vinylidene, trifluoro-ethylene, trifluorochloroethylene, five fluorine propylene or R 1216s.
2. the preparation method of teflon resin described in claim 1, is characterized in that, in water medium, the monomer of tetrafluoroethylene, Fluorine containing olefine and perfluor (alkyl vinyl ether) is carried out to copolyreaction and form described teflon resin; Wherein, the temperature of reaction of described copolyreaction is 50～80 ℃, and reaction pressure is 1.0～2.0MPa;
Described preparation method comprises the following steps:
(1) in reactor, add water, ealkaline buffer and dispersion agent, stir;
(2) adding tetrafluoroethylene monomer to make the pressure in described reactor is 0.01～0.1MPa, and then adds fluorinated olefin monomers, perfluor (alkyl vinyl ether) monomer, chain-transfer agent and initiator;
(3) reactor is warming up to 50～80 ℃, adds tetrafluoroethylene monomer to make pressure in described reactor rise to 1.0～2.0MPa and start polyreaction;
(4) keep the pressure in described reactor constant until reaction finishes, cohesion, is dried, and obtains described teflon resin;
Wherein, the solid content that reaction finishes in rear described water medium is 20～35% by mass percentage.
3. preparation method according to claim 2, is characterized in that, described ealkaline buffer is volatile salt, and the consumption in every 100 weight parts water media is 0.1～0.5 weight part.
4. preparation method according to claim 2, is characterized in that, described chain-transfer agent is methylene dichloride or methyl alcohol, and the consumption in every 100 weight parts water media is 0.1～1.0 weight part.
5. preparation method according to claim 4, is characterized in that, described chain-transfer agent is methylene dichloride or methyl alcohol, and the consumption in every 100 weight parts water media is 0.1～0.5 weight part.
6. preparation method according to claim 2, is characterized in that, described dispersion agent is ammonium perfluorocaprylate, and the consumption in every 100 weight parts water media is 0.1～0.5 weight part.
7. preparation method according to claim 2, is characterized in that, described initiator is inorganic peroxysulfate, and the consumption in every 100 weight parts water media is 0.01～0.05 weight part.
8. a terpolymer tetrafluoroethylene concentrates dispersion liquid, it is characterized in that, described concentrated dispersion liquid is the concentrated dispersion liquid of the water-based of teflon resin described in claim 1, wherein, the particle diameter of described teflon resin is 0.18～0.24 μ m, and mass percent concentration is 50～60%.
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| CN104311717B (en) * | 2014-11-17 | 2016-05-25 | 中昊晨光化工研究院有限公司 | A kind of preparation method and products therefrom that squeezes effective polytetrafluoroethyldispersion dispersion resin |
| CN111171209A (en) * | 2018-11-12 | 2020-05-19 | 中昊晨光化工研究院有限公司 | Fluororesin and preparation method thereof |
| CN114292358B (en) * | 2021-12-31 | 2023-05-02 | 金华永和氟化工有限公司 | Fusible polytetrafluoroethylene resin and preparation method thereof |
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| CN102086243A (en) * | 2010-12-01 | 2011-06-08 | 中昊晨光化工研究院 | Method for preparing high-gloss PTFE (Polytetrafluoroethylene) dispersion concentrated solution |
| CN102532388A (en) * | 2011-12-31 | 2012-07-04 | 中昊晨光化工研究院 | Method for preparing ethylene-tetrafluoroethylene copolymers |
| CN102675781A (en) * | 2012-05-07 | 2012-09-19 | 中昊晨光化工研究院 | Condensed polytetrafluoroethylene aqueous dispersion, preparation method and application thereof |
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| CN102086243A (en) * | 2010-12-01 | 2011-06-08 | 中昊晨光化工研究院 | Method for preparing high-gloss PTFE (Polytetrafluoroethylene) dispersion concentrated solution |
| CN102532388A (en) * | 2011-12-31 | 2012-07-04 | 中昊晨光化工研究院 | Method for preparing ethylene-tetrafluoroethylene copolymers |
| CN102675781A (en) * | 2012-05-07 | 2012-09-19 | 中昊晨光化工研究院 | Condensed polytetrafluoroethylene aqueous dispersion, preparation method and application thereof |
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