CN111548462A - Organic fluorine-silicon copolymer and synthesis and application methods thereof - Google Patents
Organic fluorine-silicon copolymer and synthesis and application methods thereof Download PDFInfo
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- CN111548462A CN111548462A CN202010417164.XA CN202010417164A CN111548462A CN 111548462 A CN111548462 A CN 111548462A CN 202010417164 A CN202010417164 A CN 202010417164A CN 111548462 A CN111548462 A CN 111548462A
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 26
- 238000003786 synthesis reaction Methods 0.000 title abstract description 9
- 230000015572 biosynthetic process Effects 0.000 title abstract description 8
- 238000000034 method Methods 0.000 title abstract description 8
- -1 fluoroalkyl acrylate Chemical compound 0.000 claims abstract description 37
- 238000000576 coating method Methods 0.000 claims abstract description 31
- 239000011248 coating agent Substances 0.000 claims abstract description 29
- 239000003999 initiator Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 15
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000077 silane Inorganic materials 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000004094 surface-active agent Substances 0.000 claims abstract description 5
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- 239000011347 resin Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 238000001308 synthesis method Methods 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 150000002432 hydroperoxides Chemical class 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 6
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 abstract 1
- 239000002861 polymer material Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000004342 Benzoyl peroxide Substances 0.000 description 11
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 11
- 235000019400 benzoyl peroxide Nutrition 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000003075 superhydrophobic effect Effects 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- JTXUAHIMULPXKY-UHFFFAOYSA-N 3-trihydroxysilylpropan-1-amine Chemical compound NCCC[Si](O)(O)O JTXUAHIMULPXKY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 1
- 102100040411 Tripeptidyl-peptidase 2 Human genes 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 108010039189 tripeptidyl-peptidase 2 Proteins 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/122—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to saturated polysiloxanes containing hydrolysable groups, e.g. alkoxy-, thio-, hydroxy-
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C09D187/005—Block or graft polymers not provided for in groups C09D101/00 - C09D185/04
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a synthesis and application method of an organic fluorine-silicon copolymer, which is characterized by comprising the following raw materials in parts by mass: 5-30 parts of fluoroalkyl acrylate, 1-5 parts of hydroxyl-terminated silane, 0.2-1 part of initiator and 30-100 parts of solvent, and carrying out polymerization reaction to form the F-Si copolymer. It can be used as coating surface active agent directly added into coating, or as intermediate to be mixed and copolymerized with other monomer or polymer to synthesize new type polymer material.
Description
Technical Field
The invention relates to a new organic fluorine-silicon copolymer material, which belongs to the technical field of fine chemical engineering and application thereof, and the product is mainly used as a super-hydrophobic additive of a low-surface-energy coating and added into a coating component, so that the surface energy of the coating can be effectively reduced, and the effects of non-wetting, anti-scaling and corrosion prevention are achieved.
Background
The 'West-east gas transportation' project of petroleum and natural gas in China starts in 2002-2012 and has a total length of more than 15000 kilometers. At the moment, the domestic oil and gas pipeline engineering does not realize the importance of drag reduction in the coating, and is only limited to the technical aspects of pipeline corrosion and coating protection. Therefore, the epoxy resin powder coating is adopted for the internal coating protection of the pipeline in the 'West-east gas transportation' project. The coating has the defects that the coating needs to be sintered at high temperature, and the energy consumption is large; the surface smoothness is insufficient, dirt is easy to retain, and the oil and gas conveying resistance is increased; the corrosion resistance is poor, and the economic life is relatively short. The disadvantages of such conventional coatings are related to the properties of the substrate material and are difficult to overcome with conventional coating techniques.
In order to overcome the defects of the traditional anticorrosive coating, the invention tries to prepare a super-hydrophobic surface active additive through chemical synthesis to reduce the surface tension of the coating and reduce the surface energy of the coating so as to achieve the aims of internal drag reduction, anti-scaling and anticorrosion.
Disclosure of Invention
The invention provides an organic fluorine-silicon copolymer and a preparation method thereof, which can be used as a surface active auxiliary agent to improve the hydrophobicity and the corrosion resistance of a coating.
The organic fluorine-silicon copolymer (F-Si copolymer) provided by the invention is composed of the following raw materials in parts by mass: 5-30 parts of fluoroalkyl acrylate, 1-5 parts of hydroxyl-terminated silane, 0.2-1 part of initiator and 30-110 parts of solvent.
Further, the fluoroalkyl acrylate is perfluoroalkyl acrylate.
Further, the perfluoroalkyl acrylate has the following structural formula:
fluoroalkyl acrylates of the general formula perfluoroalkylethyl methacrylate
X is (C)1-C8) Alkyl, (C)1-C8) Alkenyl or (C)4-C8) A cycloalkyl group;
R1is- (CF)2)nCF3Wherein n is less than or equal to 6.
Further, the initiator is selected from one or more of acyl peroxides, hydroperoxides, dialkyl peroxides, ester peroxides and ketone peroxides.
Further, the hydroxyl-terminated silane is hydroxyl-terminated polysiloxane.
Further, the solvent is selected from one or more of toluene, xylene and butyl acetate.
Further, the IR spectrum of the organic fluorine-silicon copolymer is 1700-1750 cm-1、1100～1300cm-1All have characteristic peaks.
The invention also discloses a preparation method of the organic fluorine-silicon copolymer, which comprises the following synthetic steps:
step 1: heating a solvent to 80-100 ℃, adding part of fluoroalkyl acrylate and part of initiator, and stirring and reacting for 1-4 hours at 100-120 ℃;
step 2: and (3) adding the rest raw materials into the solution obtained in the step (1), and reacting for 3-5 h at 120-150 ℃.
Further, the method comprises the following steps:
step 1: taking solvent in N2Heating to 80-100 ℃ under protection, adding 1/2 fluoroalkyl acrylate and 1/2 initiator, and stirring to react for 1-4 h at 100-120 ℃;
step 2: and (3) dropwise adding hydroxyl-terminated silane, the residual fluoroalkyl acrylate and an initiator into the solution obtained in the step (1) at a constant temperature, and reacting for 3-5 h at 120-150 ℃.
Further, the step 2 specifically includes: and (2) dropwise adding hydroxyl-terminated silane and residual fluoroalkyl acrylate into the solution obtained in the step (1) at a constant temperature, reacting for 3-5 h at 120-150 ℃, adding an initiator, and reacting for 3-5 h at 120-150 ℃.
The invention also discloses F-Si/F4The novel prepolymer is synthesized by blending and copolymerizing the organic fluorine-silicon copolymer prepared by the synthesis method and tetrafluoroethylene resin.
The invention also discloses a low surface energy drag reduction coating which is prepared by mixing the organic fluorine-silicon copolymer prepared by the synthesis method with a coating surfactant and the coating.
Compared with the prior art, the invention utilizes the fluoroalkyl acrylate and the hydroxyl-terminated silane to carry out polymerization reaction to form the F-Si copolymer which can be matched with other resins to form a prepolymer or used as a fluorosilicone surfactant to be added into the coating, thereby effectively improving the hydrophobicity and the corrosion resistance of the coating.
Drawings
FIG. 1 is a characteristic IR spectrum of an F-Si interpolymer of example 1 of the present invention;
FIG. 2 shows different F-Si/F ratios in example 2 of the present invention4Adding the prepared hydrophobic coating effect;
FIG. 3 shows the effect of hydrophobic coatings prepared with different amounts of TFSMA added in example 3 of the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
In example 1 of the present invention, the fluoroalkyl acrylate was perfluoroalkylethyl methacrylate (i.e., X is ethyl and R is R)1is-CF3) (ii) a The hydroxyl-terminated silane is WS62M organosilicon; the initiator is acyl peroxide, in particular benzoyl peroxide; the solvent is mixed solution of xylene and butyl acetate, and is shown in Table-1.
TABLE-1 synthetic F-Si interpolymer formulation
Different processes are adopted to optimize the schemes of the embodiments 2-5 of the invention.
Example 2
Taking 750g of solvent, heating to 80 ℃ under stirring, adding 100g of perfluoroalkyl ethyl methacrylate, 3g of benzoyl peroxide, heating to 100 ℃ for reaction for 2h → dripping 100g of residual perfluoroalkyl ethyl methacrylate and 45g of WS62M organic silicon → reaction for 4h → dripping 2g of residual benzoyl peroxide, heating to 120 ℃ for reaction for 2.5h, and discharging to obtain the F-Si copolymer solution.
Example 3
Taking 750g of solvent, heating to 100 ℃ under stirring, adding 100g of perfluoroalkyl ethyl methacrylate, 3g of benzoyl peroxide, heating to 110 ℃ for reaction for 2h → dripping 100g of residual perfluoroalkyl ethyl methacrylate and 45g of WS62M organic silicon → reaction for 4h → dripping 2g of residual benzoyl peroxide, heating to 120 ℃ for reaction for 2.5h, and discharging to obtain the F-Si copolymer solution.
Example 4
Taking 750g of solvent, heating to 110 ℃ under stirring, adding 100g of perfluoroalkyl ethyl methacrylate, 3g of benzoyl peroxide, heating to 120 ℃ for reaction for 2h → dripping 100g of residual perfluoroalkyl ethyl methacrylate and 45g of WS62M organic silicon → reaction for 4h → dripping 2g of residual benzoyl peroxide, heating to 130 ℃ for reaction for 2.5h, and discharging to obtain the F-Si copolymer solution.
Example 5
Taking 750g of solvent, heating to 120 ℃ under stirring, adding 100g of perfluoroalkyl ethyl methacrylate, 3g of benzoyl peroxide, heating to 130 ℃ for reaction for 2h → dripping 100g of residual perfluoroalkyl ethyl methacrylate and 45g of WS62M organic silicon, reacting for 4h → dripping 2g of residual benzoyl peroxide, heating to 140 ℃ for reaction for 2.5h, and gelling.
As determined by comparison of the synthesis processes of the above embodiments 2 to 5, the increase of the synthesis temperature not only increases the decomposition rate of the initiator and accelerates the polymerization reaction rate, but also correspondingly increases the chain transfer rate of the solvent along with the increase of the temperature. Thus, increasing the temperature reduces the molecular weight of the polymer, while decreasing the temperature and increasing the reaction time increases the molecular weight, but the resin synthesis temperature should be matched to the half-life of the initiator, and benzoyl peroxide dissociates rapidly at a higher temperature of 130 ℃ into the highly reactive benzene radical and CO2The highly reactive benzene radical is an effective hydrogen abstracting agent at temperatures above 130 ℃, resulting in considerable branching, increasing the C-F-Si branching of the polymer, giving it a lower surface free energy. The experimental results show that polymer branching increases with increasing synthesis process temperature. However, when the temperature is 140 ℃ or higher, the synthesis experiment fails. This is because the initiator benzoyl peroxide loses its effectiveness at too high a temperature.
Example 6
The invention utilizes fluoroalkyl acrylate and hydroxyl-terminated silane to carry out polymerization reaction to form F-Si copolymer which can be matched with other resins to form prepolymer. For example, a copolymer of F-Si and a tetrafluoroethylene/vinyl copolymer resin (abbreviated as F)4Resin) is mixed according to the mass ratio of 20-50: 50-80 (wt), then stirred and heated in a reaction kettle for 60-80 ℃/30-60 min → heated to 100-120 ℃/1-4 h for discharging, and the organic fluorine silicon prepolymer (F-Si/F) is prepared4). The prepolymer forms more graft or block structures, so that the hydrophobicity of the prepolymer is enhanced, and the water contact angle is increased. Adopts TH-100HDI trimer curing agent and F-Si/F4After the prepolymers are blended according to the mass parts of 1: 9, 1: 6 and 1: 3 respectively, the water contact angle of the prepared coating film is measured, and the measurement result is shown in figure 1: 1: 9(a) theta is more than or equal to 150 degrees, which indicates that F is in the coating film-Si/F4The higher the prepolymer content, the larger the contact angle.
Example 7
The F-Si copolymer can also be directly added into the organic titanium polymer coating as surface activity, and the combined formula is as follows:
group A) according to the mass portion, 15-20 portions of TPP-II hydroxyl organic titanium polymer, 5-10 portions of YNP-40 poly-phenol-oxygen resin solution, 5-10 portions of 2404 phenolic resin solution, 5-10 portions of D607 solvent-free elastic saturated polyester, 3-8 portions of HTLN-15 hydroxyl-terminated liquid nitrile rubber, 3-10 portions of F-Si copolymer (used as a surfactant), 0.5-1.0 portion of FR-0516 wetting dispersant, 0.3-1.0 portion of BYK-052 defoamer, 0.2-1.0 portion of BYK-306 rheological agent, 0.5-1.0 portion of SD-1 organic bentonite, 0.5-1.0 portion of F118 anti-settling agent, 10-15 portions of PZ20 zinc phosphate antirust pigment, 5-10 portions of superfine mica powder, 5-10 portions of 3-aminopropyl trihydroxysilane and 5-10 portions of oxazolidine active diluent. Group B) 10-20 parts of TH-100HDI trimer isocyanate curing agent, and can be directly subpackaged.
The application ratio of the two-component paint is respectively 3: 1(a), 6: 1(B) and 9: 1 (c). Drying conditions are as follows: surface drying is carried out at 25 ℃/2-4 h, and solid drying is carried out at 25 ℃/24 h. The coating films of tests (a), (b) and (c) were subjected to a contact angle test, and the test results are shown in FIG. 2: when the mass part of the F-Si copolymer added into the coating is more than or equal to 10 percent, the contact angle reaches the maximum value (theta is more than 120 degrees), and the hydrophobic property of a paint film can be effectively improved.
Finally, it should be noted that the above-mentioned embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above-mentioned embodiments, it should be understood by those skilled in the art that the modifications and equivalents of the specific embodiments of the present invention can be made by those skilled in the art after reading the present specification, but these modifications and variations do not depart from the scope of the claims of the present application.
Claims (11)
1. The organic fluorine-silicon copolymer is characterized by comprising the following raw materials in parts by mass: 5-30 parts of fluoroalkyl acrylate, 1-5 parts of hydroxyl-terminated silane, 0.2-1 part of initiator and 30-100 parts of solvent.
2. The F-Si interpolymer of claim 1, wherein the fluoroalkyl acrylate is a perfluoroalkyl acrylate having the chemical formula:
3. the organofluorosilicone interpolymer of claim 1, wherein the hydroxyl terminated silane is a hydroxyl terminated polysiloxane having the formula:
4. the organofluorosilicone copolymer according to claims 1 to 3, which is prepared by the following synthetic route:
5. the organofluorosilicone interpolymer of claim 1, wherein the initiator is selected from one or more of acyl peroxides, hydroperoxides, dialkyl peroxides, ester peroxides, and ketone peroxides.
6. The organofluorosilicone interpolymer of claim 1, wherein the solvent is selected from one or more of toluene, xylene, and butyl acetate.
7. The organofluorosilicone interpolymer of claim 4, comprising the following steps:
step 1: heating a solvent to 80-100 ℃, adding part of fluoroalkyl acrylate and part of initiator, and stirring and reacting for 1-4 hours at 100-120 ℃;
step 2: and (3) adding the rest raw materials into the solution obtained in the step (1), and reacting for 3-5 h at 120-150 ℃.
8. The organofluorosilicone copolymer according to claim 7, wherein the preparation method comprises the following steps:
step 1: taking solvent in N2Heating to 80-100 ℃ under protection, adding 1/2 fluoroalkyl acrylate and 1/2 initiator, and stirring to react for 1-4 h at 100-120 ℃;
step 2: and (3) dropwise adding hydroxyl-terminated silane, the residual fluoroalkyl acrylate and an initiator into the solution obtained in the step (1) at a constant temperature, and reacting for 3-5 h at 120-150 ℃.
9. The organofluorosilicone interpolymer according to claim 8, wherein step 2 specifically comprises: and (2) dropwise adding hydroxyl-terminated silane and residual fluoroalkyl acrylate into the solution obtained in the step (1) at a constant temperature, reacting for 3-5 h at 120-130 ℃, adding an initiator, and reacting for 3-5 h at 120-130 ℃.
10. F-Si/F4Novel prepolymer, characterized by being synthesized by blending and copolymerizing the organofluorosilicone copolymer prepared by the synthesis method according to claims 4 to 9 with tetrafluoroethylene-based resin.
11. A drag reducing coating with low surface energy, which is prepared by mixing the organofluorosilicone copolymer prepared by the synthesis method of claims 4-9 with a coating surfactant.
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| CN112691607A (en) * | 2020-12-26 | 2021-04-23 | 张家港邦力材料科技有限公司 | Gemini type fluorine-containing surfactant and preparation method and application thereof |
| CN116656203A (en) * | 2023-08-02 | 2023-08-29 | 江西永通科技股份有限公司 | Coating composition with mildew-proof and antibacterial properties and preparation method thereof |
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| CN116656203A (en) * | 2023-08-02 | 2023-08-29 | 江西永通科技股份有限公司 | Coating composition with mildew-proof and antibacterial properties and preparation method thereof |
| CN116656203B (en) * | 2023-08-02 | 2023-10-27 | 江西永通科技股份有限公司 | Coating composition with mildew-proof and antibacterial properties and preparation method thereof |
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