CN102199280A - Fluoro-polyester resin and preparation method and application thereof - Google Patents
Fluoro-polyester resin and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a fluoro-polyester resin and a preparation method and application thereof. The preparation method for the fluoro-polyester resin comprises the following steps of: reacting alkyl diol, cyclic anhydride, a fluorine-free mono-epoxy compound and a fluoro-containing mono-epoxy compound, diluting a reaction product by using acetone, adding into distilled water with stirring, and separating out a sediment to obtain the fluoro-polyester resin. The fluoro-polyester resin, a curing agent, a filer and an aid in a certain ratio are prepared into a hydrophobic polyester powder coating. The coating film has a large contact angle with water, and has high hydrophobicity. The fluoro-polyester resin is prepared from cyclic anhydride; and because water is not generated in the reaction process and vacuum dehydration is not needed, the requirement on a polyester synthesizing device is reduced and cost is saved.
Description
Technical field
The present invention relates to polymer arts, be specifically related to a kind of fluorine-containing vibrin and its production and application.
Background technology
Polyester powder coating has photostabilization preferably, good to substrate sticking power, do not need to add priming paint, the starting material source is abundant, and do not contain organic solvent, so polyester powder coating is widely used in the application of industry and household appliances shell, chemical industry equipment, food-processing apparatus, component of machine, automobile damping spring, shelf, traffic route equipment, safety barrier etc.Polyester powder coating has been applied to the application of outdoor architecture (as the aluminium alloy window frame), air conditioner housing, park and beach facility, bicycle frame and other outdoor use metallic article abroad.
But the hydrophobic performance of normal polyester powder coating is not ideal enough, films to be vulnerable to the influence of water.Water at first is the infiltration and the diffusion of water to the polyester powder coating destructive process of filming, and diffuses into the hydrolysis of ester group that the water of filming makes vibrin then, thereby the performance of coating is reduced, and influences the Corrosion Protection and the working life of coating.In addition, that the normal polyester powder coating is filmed is acidproof, alkaline-resisting, chemical solvent resistance is relatively poor.
Many scholars propose to pass through to introduce components such as organosilicon, fluorine with preparation hydrophobic coating or coating, and have obtained certain achievement.Publication number is the preparation method who discloses a kind of epoxy resin super-hydrophobic coat in the Chinese patent application of CN101575478A: add C in Resins, epoxy
8-C
22Alkyl trichlorosilane, C
8-C
22Components such as alkyltrialkoxysilaneand prepare and have filming of super-hydrophobic and automatically cleaning ability.Publication number is to disclose a kind of furfuryl-alcohol-resin-based super hydrophobic coating and preparation method thereof in the Chinese patent application of CN101643622A: add polytetrafluoroethylene powder in furfuryl alcohol resin, that this coating has is super-hydrophobic, automatically cleaning, premium properties such as antifouling.But the polytetrafluoroethylene powder add-on is bigger, has organic solvent in the coating simultaneously.
By in polymkeric substance, introducing fluorine atom, mainly concentrate in solvent based coating and the water-borne coatings at present thereby improve coating hydrophobicity research aspect.(F.Montefusco such as F.Montefusco, et al.New difunctional fluoro-epoxide monomers:synthesis, hotopolymerization and haracterization[J] .Polymer.2004,45:4663-4668.) to adopt the perfluor hexylene glycol be feedstock production Resins, epoxy, and be dissolved in and obtain the solvent type fluoric epoxy coating in the propylene carbonate, the introducing of finding fluorine can obviously improve the hydrophobic nature of filming, and increases the contact angle of filming with water.(Zhang Rentao such as Zhang Rentao, water-based silicon fluoride paint and study from layered effect. New Building Materials .2002, (6): 19～21) with fluorine silicon resin and non-fluoro-resin blending and modifying, the utilization gradient prepares the water-based silicon fluoride paint from the principle of stratification, has improved water-fast, the resistant of water-borne coating, performance such as weather-proof, ageing-resistant.
Yet, in powder coating, use chemical process fluorine to be introduced in the matrix resin of powder coating, the research of realization coating hydrophobic function aspect is seldom.Therefore, the fluorine-containing vibrin of development of new to improve hydrophobic, the oleophobic property of polyester powder coating, will have important significance for theories and using value with the matrix resin as powder coating.
Summary of the invention
The invention provides a kind of fluorine-containing vibrin of hydrophobic performance excellence.
The present invention also provides a kind of preparation method of fluorine-containing vibrin, and this method is simple to operate, is convenient to use.
A kind of preparation method of fluorine-containing vibrin may further comprise the steps:
Alkyl diol, cyclic acid anhydride, not fluorine-containing monocycle oxycompound and fluorine-containing monocycle oxycompound are reacted, and reaction product under agitation joins in the distilled water precipitation after with acetone diluted and separates out, and obtains fluorine-containing vibrin.
The reaction principle of described reaction is as follows:
Alkyl diol in the raw material is a starting raw material, and alkyl diol carries out alcoholysis reaction with the part cyclic acid anhydride earlier, obtains the product of alcoholysis reaction; The product of alcoholysis reaction can carry out ring-opening reaction with not fluorine-containing monocycle oxycompound and fluorine-containing monocycle oxycompound, obtains the product of ring-opening reaction; The product of ring-opening reaction can be successively carries out alcoholysis reaction, carries out ring-opening reaction with not fluorine-containing monocycle oxycompound and fluorine-containing monocycle oxycompound with cyclic acid anhydride, and repeats alcoholysis reaction and ring-opening reaction, obtains final reaction product.Can recently control the composition of each structural unit in the fluorine-containing vibrin to be synthesized according to feeding intake of raw material.
The compound that the optional usefulness of described cyclic acid anhydride has the cyclic acid anhydride structure, as selecting Tetra hydro Phthalic anhydride, dihydro Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, Succinic anhydried, 2 for use, 3-dibromosuccinic anhydride, octadecyl Succinic anhydried, dioctyl Succinic anhydried, 3-methoxyl group-1,2,3,6-Tetra Hydro Phthalic Anhydride, 3-tert.-butoxy-1,2,3, a kind of in 6-Tetra Hydro Phthalic Anhydride, poly sebacic polyanhydride, the poly-Tetra hydro Phthalic anhydride.
The optional spent glycol of described alkyl diol, 1,3 butylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, 1,8-ethohexadiol, 1,9-nonanediol, decamethylene-glycol, 1, a kind of in numerous aliphatic dihydroxy alcohols such as 12-dodecanediol.
Described not fluorine-containing monocycle oxycompound can be selected epoxy chloropropane, oxyethane, propylene oxide, butylene oxide ring, epoxy hexane, epoxy soybean oil, epoxy dodecane, epoxy bromopropane, butyl ethylene oxide, epoxypinane, 1 for use, 2-octylene oxide, 3, a kind of in the 4-epoxy tetrahydrofuran (THF) etc.
The preferred tetrafluoro propyl glycidyl ether of described fluorine-containing monocycle oxycompound, for in the presence of NaOH, epoxy chloropropane and C3-Fluoroalcohol react the tetrafluoro propyl glycidyl ether that makes under the catalysis of tetraethyl-amine bromide, can adopt from great waves etc. (from great waves, Xue Wei etc. fluorine-containing glycidyl ether synthetic and characterizing. macromolecule engineering and material symposial .2006, P80～81.) the synthetic method preparation that proposes: epoxy chloropropane is being catalyzer with the tetraethylammonium bromide, under the condition that NaOH exists with C3-Fluoroalcohol in toluene solution, 60 ℃～80 ℃ (preferred 65 ℃～75 ℃) reaction 4h～6h obtains product.With product rectifying, the cut of collecting 135 ℃～145 ℃ obtains the C3-Fluoroalcohol glycidyl ether.The NaOH that adds in the reaction process can react with the HCl that reaction produces, and then promotes the synthetic of tetrafluoro propyl glycidyl ether.The mass ratio of described sodium hydroxide and C3-Fluoroalcohol (mol ratio) be preferably 0.30～0.36: 1 (1～1.2: 1), more preferably 0.31～0.33: 1 (1.05～1.08: 1).The mass ratio of described epoxy chloropropane and C3-Fluoroalcohol (mol ratio) be preferably 2.8～5.6: 1 (4～8: 1), more preferably 3.8～4.5: 1 (5.5～6.5: 1).
The reaction that the present invention prepares fluorine-containing vibrin and tetrafluoro propyl glycidyl ether all is preferably in catalyzer and solvent and carries out under existing.
The preferred quaternary ammonium salt of described catalyzer, contain in the organic compound of tertiary amine one or both; Described quaternary ammonium salt can be selected one or more in tetraethylammonium bromide, Tetrabutyl amonium bromide, benzyl trimethyl ammonium chloride, phenyl tri-tert ammonium sulfate, phenyl trimethylammonium boric acid ammonium, the phenylbenzene dioctyl ammonium chloride etc. for use; The described organic compound that contains tertiary amine can be selected two (dimethylaminophenyl) methane, xylidine, phenyl dimethyl amine, N, one or more in N-3,5-dimethylphenyl amine, di-tert-butyl-phenyl amine, octadecyl dimethyl amine, tri-tert amine, ethyl dipropylamine, the triethylamine etc. for use.The qualification that described catalyst consumption is not strict can be adjusted according to reaction needed.
Described solvent can be selected dimethyl formamide for use, one or more in N,N-DIMETHYLACETAMIDE, the dimethyl decyl amide etc.The qualification that the consumption of described solvent is not strict, high reaction rate is fast more more for concentration of reactants in the common solvent.
Reaction conditions among the preparation method of described fluorine-containing vibrin is preferably: react 0.8h～1.2h down in 100 ℃～110 ℃ in nitrogen atmosphere.
With Tetra hydro Phthalic anhydride, 1, the reaction in 100 ℃ under the catalysis of tetraethyl-amine bromide of 4-butyleneglycol, epoxy chloropropane and tetrafluoro propyl glycidyl ether is an example, and the reaction for preparing fluorine-containing vibrin is as follows:
M, n represent the mole number of epoxy group(ing) in monocycle oxycompound not fluorine-containing in the product and the fluorine-containing monocycle oxycompound respectively
Wherein, the mol ratio of Tetra hydro Phthalic anhydride and monocycle oxycompound (mixture of not fluorine-containing epoxy chloropropane and tetrafluoro propyl glycidyl ether) is preferably 1.0: 1～1.2: 1, for guaranteeing that end group is carboxyl entirely, and more preferably 1.08～1.12: 1; In the monocycle oxycompound, the quality percentage composition of tetrafluoro propyl glycidyl ether is preferably 5%～36%; Tetraethylammonium bromide shared quality hundred content in total reactant are preferably 0.4%～1.2%.
The general structure of the fluorine-containing vibrin of preparation method's preparation of described fluorine-containing vibrin is as follows:
Wherein, R
1In expression aliphatic alkyl, aromatic series alkyl, haloalkyl, the alcoxyl substituted alkyl any one, R
2In expression alkyl, cycloalkyl, the haloalkyl any one, R
3The expression alkyl, R
4Expression tetrafluoro propyl group, m and n represent the mole number of epoxy group(ing) in monocycle oxycompound structural unit not fluorine-containing in the product and the fluorine-containing monocycle oxycompound structural unit.Can adopt existing method to adjust the value of m and n as required.
Described fluorine-containing vibrin can be used for preparing the hydrophobic polyester powder coating.
Described hydrophobic polyester powder coating, form by the raw material of following quality percentage composition:
When described fluorine-containing vibrin was used to prepare the hydrophobic polyester powder coating, the quality percentage composition of fluorine was preferably 0.68%～5.44% in the fluorine-containing vibrin.
Because carbon-the fluorine bond bond distance is short, bond energy is big, make that it is heated, luminous energy is difficult to fracture as the time spent, make fluorine-containing vibrin demonstrate excellent weathering resistance, weather resistance and chemical resistance; Polarizability because of carbon-fluorine bond is little again, makes fluorine-containing vibrin obtain electrical specifications such as high electric insulation, low-k.What is more important, very little fluorine atom radius and lower carbon-fluorine bond polarizability acting in conjunction, make fluorine-containing vibrin intramolecule structure tight, therefore fluorine-containing vibrin demonstrates low surface tension and special surface property such as low frictional properties and hydrophobicity.
The present invention adopts fluorine-containing vibrin as filmogen, because the lower surface free energy of fluorine component when together solidifying with other component, can tangible surface enrichment phenomenon occur owing to the difference of surface free energy.A large amount of fluorine-containing groupses is enriched in the film coated surface after the curing, make film coated surface fluorine content be higher than inside far away, and the hydrophobic and oil repellent performance of filming is mainly determined by surface properties, so only need introduce the hydrophobicity that the small amount of fluorine element can improve film coated surface, help overcoming the expensive shortcoming of fluorochemical monomer.
Described solidifying agent can be selected a kind of in hydroxyalkyl amide class (HAA) solidifying agent, the triglycidyl isocyanurate class solidifying agent for use.
The further preferred N of described hydroxyalkyl amide class (HAA) solidifying agent, N, N, N-four [beta-hydroxyethyl] adipamide (XL-522), tetramethoxy methyne glycoluril (PL1174), N, N, N, a kind of in N-four [β-hydroxypropyl] adipamide (QM1260).
The further preferred triglycidyl isocyanurate (TGIC) of described triglycidyl isocyanurate class solidifying agent.
Will L388 far away), lime carbonate is (as sky, Guangzhou Gansu Province trade Co., Ltd: will L300 far away), talcum powder is (as Hangzhou minister standing grain trade Co., Ltd: 600 order talcum powder), silicon-dioxide is (as Guangzhou Hua Lisen trade Co., Ltd: aerosil R972), in kaolin, mica powder, silica powder etc. one or more described mineral filler can select for use barium sulfate (as sky, Guangzhou Gansu Province trade Co., Ltd:.
Described auxiliary agent can be selected this area auxiliary agent commonly used for use, one or more in preferred flow agent, defoamer, the optical brightener.
The South Sea 588), the modified polypropene acid butyl ester is (as Ningbo Zhihua Chemistry Co., Ltd.: PV99), organic silicon modified by polyether is (as the new silicon industry of Dongguan City Materials Co., Ltd: a kind of SR306) etc. described flow agent can select for use butyl polyacrylate (as the South Sea, Ningbo chemistry company limited:.
St-yrax), the polymeric amide micro mist wax is (as sky, Guangzhou Gansu Province trade Co., Ltd: a kind of AW91) etc. described defoamer can be selected 2-hydroxyl-1 for use, and 2-phenylbenzene ethyl ketone is (as Ningbo Zhihua Chemistry Co., Ltd.:.
Described optical brightener selects for use the multipolymer of butyl acrylate and methyl methacrylate (as the two new-type chemical plant of water of Jiangmen city Xinhui District: XSL701), esters of acrylic acid is (as the sharp coating apparatus in Wuxi ten thousand company limited: BZJ-931, sky, Guangzhou company limited of jade for asking rain trade Co., Ltd: a kind of TL701) etc.
The preparation method of described hydrophobic polyester powder coating may further comprise the steps:
Fluorine-containing vibrin, solidifying agent, mineral filler and auxiliary agent are mixed in high-speed mixer by described proportioning, melt extrude through twin screw extruder again, be pressed into thin slice then, obtain the hydrophobic polyester powder coating through pulverizing with after sieving.
The particle diameter of described hydrophobic polyester powder coating is preferably 20 μ m～60 μ m.
The described temperature range that melt extrudes is preferably 90 ℃～130 ℃.
Described hydrophobic polyester powder coating can be sprayed on to form after substrate surface solidifies and film, and is easy to use.Described base material is a kind of in glass, plastics, the metallic substance etc.
Described solidification value is preferably 160 ℃～180 ℃, is preferably 15min～20min set time.
Compared with prior art, the present invention has following advantage:
1. the preparation of the fluorine-containing vibrin of the present invention adopts cyclic acid anhydride as raw material, owing to do not generate water in the reaction process, does not need vacuum hydro-extraction, so reduced the requirement to the polyester synthesizer, has saved cost.
2. the present invention introduces the surface free energy that fluorine element reduction powder coating is filmed in polyester powder coating, realizes hydrophobic purpose, and the surface enrichment of fluorine-containing groups turns usefulness into and can obviously reduce the consumption of fluorochemical monomer simultaneously, thereby reduces cost.
3. the contact angle of filming to water of the hydrophobic fluorine-containing polyester powder coating of the present invention can reach 116 °, film to the contact angle of water far above the conventional polyester powder coating, and physical and mechanical propertiess such as the sticking power of filming, shock-resistance, hardness change little, chemical mediator-resitant properties such as acidproof, the water-fast and anti-solvent of filming in addition obviously improve, and workability remains unchanged simultaneously.
4. the Production Flow Chart of hydrophobic polyester powder coating of the present invention and production unit and traditional product are basic identical, and achievement is applied easily.
Description of drawings
Fig. 1 is the infrared spectrum of the tetrafluoro propyl glycidyl ether of the embodiment of the invention 1 preparation;
Fig. 2 is the infrared spectrum of the fluorine-containing vibrin of the embodiment of the invention 1 preparation;
Fig. 3 is filming to the contact angle of water and the n-Hexadecane change curve with fluorine content behind the hydrophobic polyester powder coating solidification of Comparative Examples 1 of the present invention, embodiment 1～5 preparation;
The contact angle curve over time of filming behind the hydrophobic polyester powder coating solidification of Fig. 4 for the embodiment of the invention 3 preparation in different solvents.
Embodiment
Comparative Examples 1
The prescription of synthesizing polyester resin
Prescription by above-mentioned synthesizing polyester resin adds 0.36g (4.0 * 10 in the there-necked flask that agitator, backflow cold flow pipe, import and export of nitrogen are housed of cleaning
-3Mol) 1,4-butyleneglycol, 16.28g (1.1 * 10
-1Mol) Tetra hydro Phthalic anhydride, 0.21g (1.0 * 10
-3Mol) tetraethylammonium bromide, 9.25g (1.0 * 10
-1Mol) epoxy chloropropane and 4mL solvent dimethyl formamide, logical nitrogen reacts 1h down for 100 ℃ in oil bath.Product with acetone diluted after, under agitation join product precipitation separated out, obtain light solid, dry 10h under 100 ℃, 10kPa condition pulverizes and obtains faint yellow solid.
The polyester powder coating prescription
Prescription by above-mentioned polyester powder coating, join various raw materials in the high-speed stirring mixer in proportion, carry out pre-mixing with 800 rev/mins of (rotor/min) high-speed stirring 5min, in twin screw extruder, under 90～130 ℃ of conditions, melt extrude again and obtain work in-process through premixed material, screw speed is 400rotor/min, temperature is 90 ℃, work in-process are transported in the automatic cooling tabletting machine are pressed into thin slice, for guaranteeing that material cools off fully, feeding temperature is 120 ℃, drop temperature is 30 ℃, and compressing tablet thickness is 4mm.To carry out fine powder in the air classifying mill (ACM) broken through sending into after the coarse reduction for thin slice, captures pulverized work in-process by cyclonic separator, obtaining the polyester powder coating finished product that particle diameter is 20～60 μ m after removing impurity and coarse meal through sieve apparatus again.The processing parameter of ACM is main mill rotating speed 2400rotor/min, classifier rotating speed 1200rotor/min, and classifier spacing 60 μ m, cyclonic separator increases substreams (blast 0.3MPa).
Embodiment 1
The prescription of synthetic tetrafluoro propyl glycidyl ether
| Composition | Quality/g (mole/mol) |
| Epoxy chloropropane | 55.5(6.0×10 -1) |
| C3-Fluoroalcohol | 13.20(1.0×10 -1) |
| Tetraethylammonium bromide | 0.105(5.0×10 -4) |
| Sodium hydroxide | 4.2(1.05×10 -1) |
Prescription by above-mentioned synthetic tetrafluoro propyl glycidyl ether adds epoxy chloropropane (55.5g/6.0 * 10 in four-hole boiling flask
-1Mol) with C3-Fluoroalcohol (HCF
2CF
2CH
2OH) (13.20g/1.0 * 10
-1Mol), with 0.105g (5.0 * 10
-4Mol) tetraethylammonium bromide is a catalyzer, and adds 10mL toluene as solvent, and heating is also stirred, be warmed up to 70 ℃ after, divides five times, equivalent to add sodium hydroxide and be total to 4.2g (1.05 * 10
-1Mol), reaction 5h then with products therefrom rectifying, collects 135 ℃～145 ℃ cut.The cut of collecting is carried out the infrared spectrum analysis, the result as shown in Figure 1, the cut that shows collection is the tetrafluoro propyl glycidyl ether.
The prescription of synthetic fluorine-containing vibrin
Prescription by above-mentioned synthesizing polyester resin adds 0.36g (4.0 * 10 in the there-necked flask that agitator, backflow cold flow pipe, import and export of nitrogen are housed of cleaning
-3Mol) 1,4-butyleneglycol, 16.28g (1.1 * 10
-1Mol) Tetra hydro Phthalic anhydride, 0.21g (1.0 * 10
-3Mol) tetraethylammonium bromide, 9.0g (9.733 * 10
-2Mol) epoxy chloropropane, 0.5g (2.674 * 10
-3Mol) tetrafluoro propyl glycidyl ether and 4mL solvent dimethyl formamide, logical nitrogen reacts 1h down for 100 ℃ in oil bath.Product with acetone diluted after, under agitation join product precipitation separated out, obtain light solid, dry 10h under 100 ℃, 10kPa condition pulverizes and obtains faint yellow solid.The faint yellow solid that obtains is carried out the infrared spectrum analysis, and the result shows that the faint yellow solid that obtains is fluorine-containing vibrin as shown in Figure 2.
Fluorine-containing polyester powder coating prescription
Prescription by above-mentioned fluorine-containing polyester powder coating, join various raw materials in the high-speed stirring mixer in proportion, carry out pre-mixing with 800 rev/mins of (rotor/min) high-speed stirring 5min, in twin screw extruder, under 90～130 ℃ of conditions, melt extrude again and obtain work in-process through premixed material, screw speed is 400rotor/min, temperature is 90 ℃, work in-process are transported in the automatic cooling tabletting machine are pressed into thin slice, for guaranteeing that material cools off fully, feeding temperature is 120 ℃, drop temperature is 30 ℃, and compressing tablet thickness is 4mm.To carry out fine powder in the air classifying mill (ACM) broken through sending into after the coarse reduction for thin slice, captures pulverized work in-process by cyclonic separator, obtaining the fluorine-containing polyester powder coating finished product that particle diameter is 20 μ m～60 μ m after removing impurity and coarse meal through sieve apparatus again.The processing parameter of ACM is main mill rotating speed 2400rotor/min, classifier rotating speed 1200rotor/min, and classifier spacing 60 μ m, cyclonic separator increases substreams (blast 0.3MPa).
Embodiment 2
Except in synthetic fluorine-containing vibrin prescription, using 1.0g (5.347 * 10
-3Mol) synthetic tetrafluoro propyl glycidyl ether and 8.756g (9.653 * 10 among the embodiment 1
-2Mol) epoxy chloropropane replaces 0.5g (2.674 * 10 among the embodiment 1
-3Mol) tetrafluoro propyl glycidyl ether and 9.0g (9.733 * 10
-2Mol) outside the epoxy chloropropane, all the other conditions are identical with embodiment 1, make fluorine-containing vibrin and hydrophobic fluorine-containing polyester powder coating finished product.
Embodiment 3
Except in synthetic fluorine-containing vibrin prescription, using 2.0g (1.070 * 10
-2Mol) synthetic tetrafluoro propyl glycidyl ether and 8.260g (8.930 * 10 among the embodiment 1
-2Mol) epoxy chloropropane replaces 0.5g (2.674 * 10 among the embodiment 1
-3Mol) tetrafluoro propyl glycidyl ether and 9.0g (9.733 * 10
-2Mol) outside the epoxy chloropropane, all the other conditions are identical with embodiment 1, make fluorine-containing vibrin and hydrophobic fluorine-containing polyester powder coating finished product.
Embodiment 4
Except in synthetic fluorine-containing vibrin prescription, using 3.0g (1.604 * 10
-2Mol) synthetic tetrafluoro propyl glycidyl ether and 7.764g (8.396 * 10 among the embodiment 1
-2Mol) epoxy chloropropane replaces 0.5g (2.674 * 10 among the embodiment 1
-3Mol) tetrafluoro propyl glycidyl ether and 9.0g (9.733 * 10
-2Mol) outside the epoxy chloropropane, all the other conditions are identical with embodiment 1, make fluorine-containing vibrin and hydrophobic fluorine-containing polyester powder coating finished product.
Embodiment 5
Except in synthetic fluorine-containing vibrin prescription, using 4.0g (2.139 * 10
-2Mol) synthetic tetrafluoro propyl glycidyl ether and 7.271g (7.861 * 10 among the embodiment 1
-2Mol) epoxy chloropropane replaces 0.5g (2.674 * 10 among the embodiment 1
-3Mol) tetrafluoro propyl glycidyl ether and 9.0g (9.733 * 10
-2Mol) outside the epoxy chloropropane, all the other conditions are identical with embodiment 1, make fluorine-containing vibrin and hydrophobic fluorine-containing polyester powder coating finished product.
Embodiment 6
Except in synthetic fluorine-containing vibrin prescription, with 0.120g (1.0 * 10
-3Mol) xylidine replaces 0.21g (1.0 * 10
-3Mol) tetraethylammonium bromide is as outside the catalyzer, and all the other conditions are identical with embodiment 1, makes fluorine-containing vibrin and hydrophobic fluorine-containing polyester powder coating finished product.
Embodiment 7
Except in synthetic fluorine-containing vibrin prescription, with 6.0 * 10
-2G (5.0 * 10
-4Mol) xylidine and 0.1g (5.0 * 10
-4Mol) mixture of tetraethylammonium bromide replaces 0.21g (1.0 * 10
-3Mol) tetraethylammonium bromide is as outside the catalyzer, and all the other conditions are identical with embodiment 1, makes fluorine-containing vibrin and hydrophobic fluorine-containing polyester powder coating finished product.
Embodiment 8
The quality percentage composition such as following table of each component, all the other conditions are identical with embodiment 3, make hydrophobic fluorine-containing polyester powder coating finished product in hydrophobic polyester powder coating prescription.
Embodiment 9
The quality percentage composition such as following table of each component, all the other conditions are identical with embodiment 3, make fluorine-containing hydrophobic polyester powder coating finished product in hydrophobic polyester powder coating prescription.
Embodiment 10
The quality percentage composition such as following table of each component, all the other conditions are identical with embodiment 3, make hydrophobic fluorine-containing polyester powder coating finished product in hydrophobic polyester powder coating prescription.
Embodiment 11
Except replace the N of 4% quality percentage composition among the embodiment 3 in the hydrophobic fluorine-containing polyester powder coating prescription with the triglycidyl isocyanurate (TGIC) of 3% quality percentage composition, N, N, outside N-four [beta-hydroxyethyl] adipamide, all the other conditions are identical with embodiment 3, make hydrophobic fluorine-containing polyester powder coating finished product.
Embodiment 12
Except replace the N of 4% quality percentage composition among the embodiment 3 in the hydrophobic fluorine-containing polyester powder coating prescription with the tetramethoxy methyne glycoluril PL1174 of 12% quality percentage composition, N, N, outside N-four [beta-hydroxyethyl] adipamide, all the other conditions are identical with embodiment 3, make hydrophobic fluorine-containing polyester powder coating finished product.
Embodiment 13
In hydrophobic fluorine-containing polyester powder coating prescription, use process white (sky, Guangzhou Gansu Province trade Co., Ltd: will L388 far away) the lime carbonate among the replacement embodiment 3 of equal in quality percentage composition, all the other conditions are identical with embodiment 3, make hydrophobic fluorine-containing polyester powder coating finished product.
Embodiment 14
In hydrophobic fluorine-containing polyester powder coating prescription, use talcum powder (the Hangzhou minister standing grain trade Co., Ltd: 600 order talcum powder) the lime carbonate among the replacement embodiment 3 of equal in quality percentage composition, all the other conditions are identical with embodiment 3, make hydrophobic fluorine-containing polyester powder coating finished product.
Embodiment 15
With the lime carbonate among the precipitated silica replacement embodiment 3 of equal in quality percentage composition, all the other conditions are identical with embodiment 3, make hydrophobic fluorine-containing polyester powder coating finished product in hydrophobic fluorine-containing polyester powder coating prescription.
Embodiment 16
In hydrophobic fluorine-containing polyester powder coating prescription, use modified polypropene acid butyl ester (Ningbo Zhihua Chemistry Co., Ltd.: PV99) the butyl polyacrylate among the replacement embodiment 3 of equal in quality percentage composition, all the other conditions are identical with embodiment 3, make hydrophobic fluorine-containing polyester powder coating finished product.
Embodiment 17
Except polymeric amide micro mist wax (sky, the Guangzhou Gansu Province trade Co., Ltd: AW91) the 2-hydroxyl-1 among the replacement embodiment 3 that uses the equal in quality percentage composition in the hydrophobic fluorine-containing polyester powder coating prescription, outside the 2-phenylbenzene ethyl ketone, all the other conditions are identical with embodiment 3, make hydrophobic fluorine-containing polyester powder coating finished product.
Embodiment 18
In hydrophobic fluorine-containing polyester powder coating prescription with the acrylics of equal in quality percentage composition (the sharp coating apparatus in Wuxi ten thousand company limited: BZJ-931) replace the multipolymer of butyl acrylate among the embodiment 3 and methyl methacrylate, all the other conditions are identical with embodiment 3, make hydrophobic fluorine-containing polyester powder coating finished product.
Embodiment 19
The multipolymer with butyl acrylate among the acrylics replacement embodiment 3 of equal in quality percentage composition and methyl methacrylate in hydrophobic fluorine-containing polyester powder coating prescription, all the other conditions are identical with embodiment 3, make hydrophobic fluorine-containing polyester powder coating finished product.
Respectively molecular weight, the second-order transition temperature of the vibrin of Comparative Examples 1 and embodiment 1～7 preparation are characterized with GPC, DSC, utilize Brookfield DV-II type rotational viscosimeter (Brookfield Engineering Laboratories.Inc) to measure the melt viscosity of fluorine-containing vibrin in the time of 200 ℃ simultaneously, use No. 5 rotor, rotating speed is 100rpm.The result is as shown in table 1.
The performance of the vibrin for preparing among each embodiment of table 1
| Prescription | Molecular weight (Mn) | T g(℃) | Melt viscosity (mPa.s) |
| Comparative Examples 1 | 5100 | 39.5 | 3214 |
| Embodiment 1 | 5080 | 39.8 | 3276 |
| Embodiment 2 | 5000 | 40.1 | 3297 |
| Embodiment 3 | 5180 | 40.9 | 3315 |
| Embodiment 4 | 5200 | 41.2 | 3330 |
| Embodiment 5 | 4950 | 42.1 | 3361 |
| Embodiment 6 | 5046 | 39.6 | 3265 |
| Embodiment 7 | 5120 | 39.9 | 3285 |
The result of table 1 shows, the introducing of fluorine is little to the influence of vibrin molecular weight, but the second-order transition temperature of resin is improved, and increase along with fluorine content, the second-order transition temperature of resin raises gradually, meanwhile, the melt viscosity of resin also slowly raises along with the increase of fluorine content.The kind of catalyzer is little to influences such as the molecular weight of the fluorine-containing vibrin of synthetic, second-order transition temperatures.
In the various embodiments of the present invention in the fluorine-containing vibrin of synthetic the concrete grammar of fluorine element assay be: the fluorine-containing vibrin of known quality and excessive anhydrous Na
2CO
3Mix, be heated to 800 ℃ in retort furnace, continue 8h, the refrigerative burning residue is water-soluble, and is extremely alkaline with liquefied ammonia regulator solution pH.Solution is heated to boiling back 15min, and cooling then adds CaCl
2, chlorine is replaced by fluorine, finally forms CaF
2Precipitation is filtered and is obtained solid CaF
2Product C aF
2Burn 4h at 750 ℃, weigh after the cooling (residue) revises CaF
2After the solubleness in the aqueous solution, can pass through CaF
2Amount calculate the content (CaF of F in the solution
2Solubleness in water is 16mg/L).Among each embodiment in the fluorine-containing vibrin of synthetic the fluorine element content results see Table 2, the result of table 2 shows being incorporated in the vibrin of fluorine success, and measurement result is close with theoretical value.
The contact angle test selects for use the contact angle measurement measurement to film to the contact angle of water, n-Hexadecane, and table 2 has been listed and filmed to the contact angle of water, n-Hexadecane and the result of fluorine relation with contents.
The fluorine content and the fluorine-containing polyester powder coating of the fluorine-containing vibrin of each embodiment preparation of table 2 are filmed to the contact angle of water, n-Hexadecane
Annotate: the fluorine content in the table 2 is fluorine shared mass percent in fluorine-containing vibrin
Filming to the contact angle of water and the n-Hexadecane change curve with fluorine content after solidifying according to the fluorine-containing polyester powder coating of Comparative Examples 1 and embodiment 1～5 preparation seen Fig. 3; Can find that contact angle increases with the increase of fluorine content earlier, when fluorine content increased to 3.88%, contact angle reached 116 ° of maximum values, filmed to the contact angle of water far above the conventional polyester powder coating, continuing increases fluorine content, and obvious change no longer takes place contact angle.The introducing of fluorine simultaneously can increase the contact angle of filming to oil, and contact angle increases with the increase of fluorine content earlier, and when fluorine content increased to 3.88%, contact angle reached maximum value (86 °), continues to increase fluorine content, and contact angle changes little.The result shows that the adding of fluorine can obviously increase the hydrophobic oleophobic performance of filming.
Filming after the hydrophobic fluorine-containing polyester powder coating curing of embodiment 3 preparations placed polar solvent CHCl respectively
3With non-polar solvent CCl
4In, measure and to film contact angle over time, in the different solvents contact angle over time curve see Fig. 4.As can be seen from Figure 4, no matter be at polar solvent or in non-polar solvent, prolongation is in time filmed little to the contact angle variation of solvent.
Behind the hydrophobic polyester powder coating solidification of various embodiments of the present invention preparation, mechanical property of filming and Comparative Examples 1 result compare content measurement:
Gloss is pressed the regulation of GB/T9754, tests with 60 ° of angles.
Sticking power is undertaken by the GB/T9286-1998 regulation.
Hardness is undertaken by the ISO15184:1998 regulation, and pencil is Chinese board 101 drawing pencils.
Shock resistance is undertaken by the GB/T1732-1993 regulation.Model is filmed and is carried out shock test on the anvil that lies in knocker up during square impact, and model is filmed and carried out shock test on the anvil that lies in knocker down during recoil.
Alkali resistance is undertaken by first method (infusion method) among the GB/T9274-1988.Model is immersed in 5% (mass percent) sodium hydroxide solution to specific time, take out model, visual observation is immediately filmed after washing lightly with flowing water.As have in three models two occur bubbling, ftracture, peel off, the ill phenomenons of filming such as dry linting, obviously variable color, obvious loss of gloss, then be chosen as " no abnormal ".As the ill phenomenon of filming more than occurring is described by GB/T1766-1995.
Acid resistance is undertaken by first method (infusion method) among the GB/T9274-1988.Model is immersed in 3% (mass percent) hydrochloric acid soln to specific time, take out model, visual observation is immediately filmed after washing lightly with flowing water.As have in three models two occur bubbling, ftracture, peel off, the ill phenomenons of filming such as dry linting, obviously variable color, obvious loss of gloss, then be chosen as " no abnormal ".As the ill phenomenon of filming more than occurring is described by GB/T1766-1995.
Resistance to boiling water is undertaken by the regulation of second method among the GB/T1733-1993.Model immersed in the boiling water to the time of deciding through consultation, take out, visual observation is immediately filmed wash out the foreign matter that is bonded at film coated surface with flowing water after, as have in three models two occur bubbling, ftracture, peel off, the ill phenomenons of filming such as dry linting, obviously variable color, obvious loss of gloss, then be chosen as " no abnormal ".As the ill phenomenon of filming more than occurring is described by GB/T1766-1995
The fluorine-containing performance with not fluorine-containing polyester powder coating coating of table 3 compares
| Project | Comparative Examples 1 | Embodiment 3 |
| Outward appearance | Surfacing | Surfacing |
| Shock resistance/kgcm | 35 | 40 |
| Sticking power/level | 1 | 1 |
| Gloss (on average)/% | 85 | 86 |
| Pencil hardness/H | 1 | 2 |
Annotate: it is not fluorine-containing to film in the Comparative Examples 1, and filming of embodiment 3 is fluorine-containing.
Table 3 has been listed before and after the introducing fluorine, and the mechanical property of filming changes.The result shows that the introducing of fluorine has improved the impact resistance of filming, and has increased the hardness of filming, and obvious reduction does not take place along with the adding of fluorine for sticking power, gloss simultaneously.
After table 4 is listed the fluorine-containing polyester powder coating curing of each embodiment preparation, the variation of mechanical property and resistance to acids and bases.
The film performance of the different fluorine-containing polyester powder coatings of forming of table 4 relatively
Annotate: during 1. embodiment 8,3,9,10 arranges, the add-on of fluorine-containing vibrin reduces successively, the add-on of mineral filler increases successively, the result shows: along with the reduction of fluorine-containing vibrin add-on, coating film gloss reduces, and is loss of adhesion, and shock resistance raises earlier and afterwards reduces, hardness increases gradually, and the anti-boiling water of filming, resistance to acids and bases change little.
2. during embodiment 1,2,3,4,5 arranges, the fluorine content of fluorine-containing vibrin increases gradually, film performance shows: the adding of fluorine can obviously improve anti-boiling water, the resistance to acids and bases of filming, and along with the increase of fluorine content, anti-boiling water, the resistance to acids and bases of filming improve gradually simultaneously.
3. during embodiment 3,11,12,13,14,15,16,17,18,19 arranges, change certain composition in the powder coating prescription,, find that these components are little to the performance impact of filming as solidifying agent, filler etc.
Claims (9)
1. the preparation method of a fluorine-containing vibrin is characterized in that, may further comprise the steps:
Alkyl diol, cyclic acid anhydride, not fluorine-containing monocycle oxycompound and fluorine-containing monocycle oxycompound are reacted, and reaction product under agitation joins in the distilled water precipitation after with acetone diluted and separates out, and obtains fluorine-containing vibrin.
2. the preparation method of fluorine-containing vibrin according to claim 1, it is characterized in that, described cyclic acid anhydride is Tetra hydro Phthalic anhydride, dihydro Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, Succinic anhydried, 2,3-dibromosuccinic anhydride, octadecyl Succinic anhydried, dioctyl Succinic anhydried, 3-methoxyl group-1,2,3,6-Tetra Hydro Phthalic Anhydride, 3-tert.-butoxy-1,2,3, a kind of in 6-Tetra Hydro Phthalic Anhydride, poly sebacic polyanhydride, the poly-Tetra hydro Phthalic anhydride;
Described alkyl diol is ethylene glycol, 1,3 butylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, 1,8-ethohexadiol, 1,9-nonanediol, decamethylene-glycol, 1, a kind of in the 12-dodecanediol;
Described not fluorine-containing monocycle oxycompound is epoxy chloropropane, oxyethane, propylene oxide, butylene oxide ring, epoxy hexane, epoxy soybean oil, epoxy dodecane, epoxy bromopropane, butyl ethylene oxide, epoxypinane, 1,2-octylene oxide, 3, a kind of in the 4-epoxy tetrahydrofuran (THF);
Described fluorine-containing monocycle oxycompound is the tetrafluoro propyl glycidyl ether.
3. the preparation method of fluorine-containing vibrin according to claim 1 is characterized in that, described being reflected under catalyzer and the solvent existence carried out.
4. the preparation method of fluorine-containing vibrin according to claim 1 is characterized in that, described catalyzer is quaternary ammonium salt, contain in the organic compound of tertiary amine one or both;
Described solvent is one or more in dimethyl formamide, N,N-DIMETHYLACETAMIDE, the dimethyl decyl amide.
5. according to the preparation method of claim 1 or 3 described fluorine-containing vibrin, it is characterized in that described reaction conditions is: in nitrogen atmosphere, react 0.8h～1.2h down in 100 ℃～110 ℃.
6. according to the fluorine-containing vibrin of the preparation method of each described fluorine-containing vibrin of claim 1～5 preparation.
7. the application of fluorine-containing vibrin according to claim 6 in preparation hydrophobic polyester powder coating.
8. application according to claim 7 is characterized in that, the quality percentage composition of fluorine is 0.68%～5.44% in the described fluorine-containing vibrin.
9. application according to claim 7 is characterized in that, described hydrophobic polyester powder coating is made up of the raw material of following quality percentage composition:
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Application publication date: 20110928 |