CN112812305A - Fluorine modified PAE resin, preparation method thereof and coating composition - Google Patents
Fluorine modified PAE resin, preparation method thereof and coating composition Download PDFInfo
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- CN112812305A CN112812305A CN202011628223.4A CN202011628223A CN112812305A CN 112812305 A CN112812305 A CN 112812305A CN 202011628223 A CN202011628223 A CN 202011628223A CN 112812305 A CN112812305 A CN 112812305A
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- fluorine
- pae resin
- polycaprolactone
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- modified pae
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- 229920005989 resin Polymers 0.000 title claims abstract description 79
- 239000011347 resin Substances 0.000 title claims abstract description 79
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 30
- 239000011737 fluorine Substances 0.000 title claims abstract description 30
- 239000008199 coating composition Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 40
- -1 maleic acid ester Chemical class 0.000 claims abstract description 37
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 33
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 33
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 150000004985 diamines Chemical class 0.000 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920002545 silicone oil Polymers 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 13
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011976 maleic acid Substances 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- RILLZYSZSDGYGV-UHFFFAOYSA-N 2-(propan-2-ylamino)ethanol Chemical class CC(C)NCCO RILLZYSZSDGYGV-UHFFFAOYSA-N 0.000 claims description 49
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 31
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 19
- 229920000570 polyether Polymers 0.000 claims description 19
- 150000001412 amines Chemical class 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 239000012948 isocyanate Substances 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 claims description 5
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 4
- 238000005576 amination reaction Methods 0.000 claims description 3
- 150000002009 diols Chemical class 0.000 claims description 3
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 238000005336 cracking Methods 0.000 abstract description 3
- 230000018044 dehydration Effects 0.000 abstract 1
- 238000006297 dehydration reaction Methods 0.000 abstract 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 12
- 150000002221 fluorine Chemical class 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000007259 addition reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- JVILOEQYWFMSBF-UHFFFAOYSA-N 2-(propan-2-ylamino)ethanol;hydrochloride Polymers [Cl-].CC(C)[NH2+]CCO JVILOEQYWFMSBF-UHFFFAOYSA-N 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920000608 Polyaspartic Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001153 fluoro group Polymers F* 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 125000005009 perfluoropropyl group Chemical group FC(C(C(F)(F)F)(F)F)(F)* 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- ZLYYJUJDFKGVKB-OWOJBTEDSA-N (e)-but-2-enedioyl dichloride Chemical compound ClC(=O)\C=C\C(Cl)=O ZLYYJUJDFKGVKB-OWOJBTEDSA-N 0.000 description 1
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical group O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000012615 aggregate Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229920013822 aminosilicone Polymers 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/325—Polymers modified by chemical after-treatment with inorganic compounds containing nitrogen
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a fluorine modified PAE resin and a preparation method and a coating composition thereof, wherein any one or more of polyetheramine, amino-terminated silicone oil and polycaprolactone diamine is added into a reaction vessel, a solvent is added for reflux dehydration, and the solvent is separated; and then dripping the mixture of fluorine-containing maleic acid ester and acrylonitrile under the condition of introducing nitrogen, and preserving heat after the dripping is finished to obtain the fluorine modified PAE resin. The resin and the floor coating composition prepared from the resin have the characteristics of safety, comfort, silence, wear resistance and no solvent, the elasticity and the strength of the floor are improved, and the floor is less prone to cracking.
Description
Technical Field
The invention relates to the field of polymers and high molecular coatings, in particular to a fluorine modified PAE resin, a preparation method thereof and a coating composition.
Background
A large amount of wear-resistant powder is generally added to the existing organic super wear-resistant terrace, so that the terrace is high in rigidity, easy to crack and poor in foot feeling and comfort. Since the inorganic filler is added in a large amount to resist stains, the chemical resistance is poor. The filler is separated out and easy to raise dust after long-term use. The weather resistance is poor.
Chinese patent CN109096132A (application date 2018, 9 and 6) discloses a fluorine-containing polyaspartic ester resin and a synthesis method thereof, wherein a double-curing coating composition based on polyaspartic ester, polyisocyanate and an acrylate-containing compound is prepared by synthesizing trifluoroacetate PAE resin by utilizing trifluoroethanol, butenedioyl chloride and aliphatic hydrocarbyl diamine, and fluorine-containing groups are introduced into the resin, so that the weather resistance of a product is improved, specifically, the surface tension is reduced, the water contact angle is improved, and the hydrophobicity, the surface stain resistance and the ice covering resistance of the material are enhanced. However, the product still has the problems of higher rigidity, insufficient elasticity, easy cracking and the like of the coating when in use, and the average elongation at break is not more than 250%.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a fluorine modified PAE resin with wear resistance, ageing resistance, light loss resistance, high elasticity and high temperature resistance; it is still another object of the present invention to provide a process for preparing the aforementioned fluorine-modified PAE resin; the invention also aims to provide a super wear-resistant elastic floor coating composition compounded by the fluorine modified PAE resin.
The technical scheme is as follows: for the aforementioned fluorine-modified PAE resin, as shown in formula (I):
wherein R is selected from the group consisting of perfluoro substituted C1-C4 saturated hydrocarbon groups, and as a preferred embodiment of the present invention R is selected from the group consisting of perfluoro C1-C3 alkyl groups; most preferably, R is perfluoromethyl or perfluoroethyl.
X is selected from one or more of polysiloxane, polyether and polycaprolactone, which are respectively from amino-terminated silicone oil, polyether amine and polycaprolactone diamine. Wherein the polyether amine is a series of substances of Hensman D230-D1500; the average molecular weight of the amino-terminated silicone oil is between 220 and 2000; the average molecular weight of the polycaprolactone diamine is between 200 and 2000.
As a preferred embodiment, the amino-terminated silicone oil may be 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane, or a polymer of 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane and octamethylcyclotetrasiloxane (D4) (average molecular weight: 200-.
As a preferred embodiment, the polyetheramine is selected from any one of the products including, but not limited to, the U.S. Hounsfield series D230-D1500.
As a preferable embodiment, the polycaprolactone diamine is a polymer obtained by alcoholysis reaction of polycaprolactone diamine, and has an average molecular weight of 200-2000.
The preparation method of the fluorine modified PAE resin comprises the following steps:
(1) adding any one or more of polyetheramine, amino-terminated silicone oil and polycaprolactone diamine into a reaction container, adding a solvent, refluxing and dehydrating, and separating the solvent;
(2) and (3) dropwise adding a mixture of fluorine-containing maleic acid ester and acrylonitrile under the condition of introducing nitrogen, and preserving heat after the dropwise adding is finished to obtain the modified PAE resin, wherein the modified PAE resin is represented by the formula (I).
Wherein R is selected from perfluoro-substituted C1-C4 saturated hydrocarbon group, and X is selected from polysiloxane group, polyether group and polycaprolactone group. The fluorine-containing maleic acid ester is selected from any one of perfluorodimethyl maleate, perfluorodiethyl maleate, perfluorodipropyl maleate and perfluorodibutyl maleate.
Wherein, the solvent in the step (1) is selected from any one or combination of more of toluene, xylene and petroleum ether.
The ratio of the total amount of the polyether amine, the amino-terminated silicone oil and the polycaprolactone diamine to the total amount of the mixture of the fluorine-containing maleic acid ester and the acrylonitrile is 1 (2-2.5). The molar ratio of the vinyl-containing substance is properly excessive in view of the loss of the polymerization of the vinyl moiety, and it is sufficient to convert the primary amine into the secondary amine. As a most preferred embodiment of the present invention, the aforementioned ratio is preferably 1: 2.1.
Furthermore, the molar ratio of the fluorine-containing maleic acid ester to the acrylonitrile is 10 (0.5-2). The addition of a proper amount of acrylonitrile monomer resin is wear-resistant and increases the impact strength, but the resin strength decreases with the increase of the acrylonitrile amount after the addition of a certain amount. As the best mode of the invention, the adding ratio of the two is 10: 0.8.
The fluorine modified PAE resin, especially the fluorine modified PAE resin obtained by the preparation method, can be used for compounding a wear-resistant floor coating composition with obviously improved elasticity coefficient. The fluorine modified PAE resin coating composition comprises a component A and a component B which are compounded before use,
the component A comprises:
at least one modified PAE resin, wherein the modified PAE resin is a mixture of at least one modified PAE resin,
at least one leveling agent;
and B component:
an isocyanate curing agent;
wherein the modified PAE resin is shown as the formula (I). And R is selected from perfluoro-substituted C1-C4 saturated alkyl, and mainly comes from components such as perfluorodimethyl maleate, perfluorodiethyl maleate, perfluorodipropyl maleate, perfluorodibutyl maleate and the like added in the preparation method; x is selected from polysiloxane, polyether and polycaprolactone group, and is mainly from amino-terminated silicone oil, polyether amine and polycaprolactone diamine added in the preparation method.
The leveling agent is selected from any one or combination of BYK-066, BYK-333 and BYK-354.
The isocyanate curing agent is selected from the group consisting of, but not limited to, TDI (toluene diisocyanate) derivatives (TDI-TMP) or trimers thereof, HDI (hexamethylene diisocyanate) derivatives (HDI-TDI, HDI-TMP) or trimers thereof. Preferably, the isocyanate curing agent is HDI trimer.
On the basis of the formula, the component A can also be added with ingredients such as wear-resistant powder, titanium dioxide, aggregate, fumed silica, color paste and the like. The abrasion resistant powder is typically silica and is typically added in an amount not exceeding 35 wt% of the fluorine modified PAE resin. The addition amount of the aggregate and the color paste is not more than 10 percent of the total mass of the component A.
Preferably, the mixing ratio of the A component to the B component is 2: 1.
As a preferable embodiment of the present invention, the fluorine-modified PAE resin coating composition comprises, by mass:
the component A comprises the following components in percentage by mass:
and B component:
100% of isocyanate curing agent;
the mixing ratio of the component A to the component B is 2 (1-1.5).
Has the advantages that: the invention is based on the mixture of fluorine-containing maleate and acrylonitrile and any one of polyether amine, amino-terminated silicone oil and polycaprolactone diamine, and has the advantages of no solvent and mild reaction. Compared with the existing fluorine-containing PAE resin, the obtained organic silicon modified/polyether amine modified/polycaprolactone modified fluorine-containing PAE resin has higher elongation at break, and is particularly reflected in elasticity and silence. The PAE resin is used for preparing the floor coating, has the characteristics of safety, elasticity, silence, wear resistance and no solvent, improves the elasticity and the strength, and is less prone to cracking.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1 Silicone modified fluorine containing PAE resin
An organic silicon modified fluorine-containing PAE resin is shown as a formula (I):
r is perfluoroethyl, and X is derived from 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane (also known as "amino-bis-head").
The preparation method comprises the following steps:
(1) adding an amino double-end socket into a flask with a water separator, adding 20 wt% of dimethylbenzene, heating and refluxing to dewater, and then vacuumizing to 0.6MPa to separate out a dimethylbenzene solvent;
(2) cooling to 40-60 ℃, and dropwise adding a mixture of perfluorodiethyl maleate and acrylonitrile under the condition of introducing nitrogen, wherein the molar ratio of the amino double-end socket to the mixture of perfluorodiethyl maleate and acrylonitrile is 1:2.1, and the molar ratio of perfluorodiethyl maleate to acrylonitrile is 10: 0.8. Gradually heating to 60-65 ℃ when the dropwise addition reaction is finished, and then maintaining the temperature for 30 hours to obtain the organic silicon modified fluorine-containing PAE resin which is yellow slightly transparent liquid.
Example 2 Silicone modified fluorine containing PAE resin
A silicone-modified fluorine-containing PAE resin, the same as general formula (I) of example 1, R being perfluoropropyl, except that: x is derived from amino-terminated silicone oil with molecular weight of 400 (1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane reacts with octamethylcyclotetrasiloxane D4 to obtain amino-terminated silicone oil polymer with average molecular weight of 400).
The preparation method comprises the following steps:
(1) adding amino-terminated silicone oil into a flask provided with a water separator, adding 20 wt% of dimethylbenzene, heating and refluxing to dewater, and then vacuumizing to 0.6MPa to separate out a dimethylbenzene solvent;
(2) cooling to 40-60 ℃, and dropwise adding a mixture of perfluorodipropyl maleate and acrylonitrile under the condition of introducing nitrogen, wherein the molar ratio of the amino silicone oil with the molecular weight of 400 to the mixture of the perfluorodipropyl maleate and the acrylonitrile is 1:2, and the molar ratio of the perfluorodipropyl maleate and the acrylonitrile is 10: 0.6. Gradually heating to 60-65 ℃ when the dropwise addition reaction is finished, and then maintaining the temperature for 30 hours to obtain the organic silicon modified fluorine-containing PAE resin which is yellow slightly transparent liquid.
Example 3 Polyetheramine modified fluorine containing PAE resin
A polyetheramine modified fluorine-containing PAE resin, the same as general formula (I) of example 1, R being perfluoroethyl, except that: x is from polyetheramine (D400, hensmei, usa).
The preparation method comprises the following steps:
(1) adding D400 into a flask with a water separator, adding 20 wt% of dimethylbenzene, heating and refluxing to dewater, and then vacuumizing to 0.6MPa to separate out a dimethylbenzene solvent;
(2) cooling to 40-60 ℃, and dropwise adding a mixture of perfluorodipropyl maleate and acrylonitrile under the condition of introducing nitrogen, wherein the molar ratio of D400 to the mixture of perfluorodipropyl maleate and acrylonitrile is 1:2.1, and the molar ratio of perfluorodipropyl maleate to acrylonitrile is 10: 0.9. Gradually heating to 60-65 ℃ when the dropwise addition reaction is finished, and then maintaining the temperature for 30 hours to obtain the polyether amine modified fluorine-containing PAE resin. The resin is white slightly transparent liquid.
Example 4 Polyetheramine modified fluorine containing PAE resin
A polyetheramine modified fluorine-containing PAE resin, the same as general formula (I) of example 1, R being perfluoropropyl, except that: x is derived from polyetheramine (D230, Hounsfield, USA).
The preparation method comprises the following steps:
(1) adding D230 into a flask with a water separator, adding 20 wt% of dimethylbenzene, heating and refluxing to dewater, and then vacuumizing to 0.6MPa to separate out a dimethylbenzene solvent;
(2) and (3) cooling to 40-60 ℃, and dropwise adding a mixture of the perfluorodiethyl maleate and the acrylonitrile under the condition of introducing nitrogen, wherein the molar ratio of the D230 to the mixture of the perfluorodiethyl maleate and the acrylonitrile is 1:2.3, and the molar ratio of the perfluorodiethyl maleate to the acrylonitrile is 10: 1. Gradually heating to 60-65 ℃ when the dropwise addition reaction is finished, and then maintaining the temperature for 30 hours to obtain the polyether amine modified fluorine-containing PAE resin. The resin is white slightly transparent liquid.
Example 5 polycaprolactone-modified fluorinated PAE resin
A polycaprolactone-modified fluorine-containing PAE resin, which is the same as the general formula (I) in example 1, wherein R is a perfluoroethyl group, and is different from the following components in that: x is derived from a molecular weight 500 polycaprolactone diamine (average molecular weight 500 polycaprolactone diol (PCL205 Shenzhen Shenhuawei) catalyzed amination product).
(1) Adding polycaprolactone diamine into a flask with a water separator, adding 20 wt% of xylene, heating and refluxing until the mixture is dehydrated, and then vacuumizing to 0.6MPa to separate out a xylene solvent;
(2) cooling to 40-60 ℃, and dropwise adding a mixture of perfluorodiethyl maleate and acrylonitrile under the condition of introducing nitrogen, wherein the molar ratio of polycaprolactone diamine to the mixture of perfluorodiethyl maleate and acrylonitrile is 1:2.1, and the molar ratio of perfluorodiethyl maleate to acrylonitrile is 10: 1. Gradually heating to 60-65 ℃ when the dropwise addition reaction is finished, and then maintaining the temperature for 30 hours to obtain the polycaprolactone modified PAE resin. The resin was an amber liquid.
Example 6 polycaprolactone-modified fluorinated PAE resin
A polycaprolactone-modified fluorine-containing PAE resin, which is the same as the general formula (I) in example 1, wherein R is a perfluoromethyl group, and is different from the following components in that: x is derived from polycaprolactone diamine with the molecular weight of 1000 (the catalytic amination product of polycaprolactone diol with the average molecular weight of 500 (PCL210 Shenzhen Shenhuawei industry)).
(1) Adding polycaprolactone diamine into a flask with a water separator, adding 20 wt% of xylene, heating and refluxing until the mixture is dehydrated, and then vacuumizing to 0.6MPa to separate out a xylene solvent;
(2) cooling to 40-60 ℃, and dropwise adding a mixture of perfluorodimethyl maleate and acrylonitrile under the condition of introducing nitrogen, wherein the molar ratio of polycaprolactone diamine to the mixture of perfluorodimethyl maleate and acrylonitrile is 1:2.4, and the molar ratio of perfluorodimethyl maleate to acrylonitrile is 10: 0.6. Gradually heating to 60-65 ℃ when the dropwise addition reaction is finished, and then maintaining the temperature for 30 hours to obtain the polycaprolactone modified PAE resin. The resin was an amber liquid.
Example 7A hybrid modified PAE resin coating composition
A mixed modified PAE resin coating composition comprises a component A and a component B:
the component A comprises the following components in percentage by mass:
and B component:
HI 100100% basf
Before use, the mixing ratio of the component A to the component B is 10 (6-9), and the optimal ratio of 10 to 7 is selected.
Example 8A polycaprolactone-modified PAE resin coating composition
A polycaprolactone-modified PAE resin coating composition comprises a component A and a component B:
the component A comprises the following components in percentage by mass:
the component B is as follows:
HI 100100% basf
The mixing ratio of the component A and the component B is 2 (1-1.5), and the optimal ratio is 2: 1.
Example 9A Silicone-modified PAE resin coating composition
A mixed modified PAE resin coating composition comprises a component A and a component B:
the component A comprises the following components in percentage by mass:
and B component:
HI 100100% basf
Before use, the mixing ratio of the component A to the component B is 10 (7-10), and the optimal ratio of 10 to 8 is selected.
Example 10A polyetheramine-modified PAE resin coating composition
A polycaprolactone-modified PAE resin coating composition comprises a component A and a component B:
the component A comprises the following components in percentage by mass:
the component B is as follows:
HI 100100% basf
The mixing ratio of the component A and the component B is 10 (5-8), and the optimal ratio of 10:6 is selected.
Comparative example 1
The component A comprises the following components in percentage by mass:
the component B is as follows:
HI 100100% basf
The mixing ratio of the component A to the component B is 10: 7.
Comparative example 2
The component A comprises the following components in percentage by mass:
the component B is as follows:
HI 100100% basf
The mixing ratio of the component A to the component B is 10: 7.
Wherein the patent resin in the component A is synthesized according to the resin disclosed in the example 3 of Chinese patent CN109096132A (2018, 9, 6).
Test examples
This comparative example was tested using the modified PAE resin coating compositions of examples 7-10, and the coating compositions of comparative example 1 and comparative example 2 as controls; comparative example 3 a commercially available polyurethane wear resistant floor finish and curing agent (dexin DXF-WRP) was used. The following 10 indexes are detected according to a method of national standard of the terrace industry GB/T22374-2018. The detection method is a rolling coating method, the thickness of a rolling coating paint film is 60-100um, and detection is carried out after condensation for 48 hours.
TABLE 1 comparison of PAE resin coating composition Performance test
As can be seen from the above table, the resin coating compositions compounded based on the three types of modified fluorine-containing PAE resins of examples 1-5 all have flat, smooth and continuous appearance without bubbles, the surface drying time is within 30 minutes, and the actual drying time is 17 hours. And the elongation at break of more than 350 percent is ensured, which is obviously higher than that of the existing product. The elasticity of the product is improved, and meanwhile, the wear resistance is not obviously influenced, so that the product has more application scenes and longer service life.
Claims (10)
1. A fluorine modified PAE resin, represented by formula (I):
wherein, R is selected from perfluoro-substituted C1-C4 saturated hydrocarbon group, and X is selected from one or more of polysiloxane group, polyether group and polycaprolactone group.
2. The fluorine-modified PAE resin according to claim 1, wherein: r is perfluoromethyl or perfluoroethyl.
3. A fluorine modified PAE resin according to claim 1 or 2, characterized in that: the polysiloxane group, polyether group and polycaprolactone group are respectively from amino-terminated silicone oil, polyether amine and polycaprolactone diamine, wherein:
the polyether amine has an average molecular weight of 200-2000,
the average molecular weight of the amino-terminated silicone oil is 220-2000,
the average molecular weight of the polycaprolactone diamine is 200-2000.
4. The preparation method of the fluorine modified PAE resin is characterized by comprising the following steps:
(1) adding any one or more of polyether amine, amino-terminated silicone oil and polycaprolactone diamine into a reaction container, adding a solvent, refluxing and dehydrating, and then separating the solvent in vacuum;
(2) and (2) dropwise adding a mixture of fluorine-containing maleic acid ester and acrylonitrile under the condition of introducing nitrogen, and keeping the temperature after the dropwise adding end point to obtain fluorine modified PAE resin, wherein the formula (I) is as follows:
wherein R is selected from perfluoro-substituted C1-C4 saturated hydrocarbon group, and X is polysiloxane group, polyether group and polycaprolactone group; the fluorine-containing maleic acid ester is selected from any one of perfluorodimethyl maleate, perfluorodiethyl maleate, perfluorodipropyl maleate and perfluorodibutyl maleate.
5. The method of preparing a fluorine-modified PAE resin according to claim 4, wherein:
the molecular weight of the polyetheramine is 200-2000,
the molecular weight of the amino-terminated silicone oil is 220-2000,
the molecular weight of the polycaprolactone diamine is 200-2000.
6. The method of preparing a fluorine-modified PAE resin according to claim 5, wherein:
the polyether amine is selected from any one of U.S. Hensmei D230-D1500 series;
the amino-terminated silicone oil is selected from any one of 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane and octamethylcyclotetrasiloxane polymer;
the polycaprolactone diamine is a polymer obtained by amination reaction of polycaprolactone diol.
7. The process for the preparation of a fluorine modified PAE resin according to any one of claims 4 to 6, wherein: the ratio of the total amount of the polyether amine, the amino-terminated silicone oil and the polycaprolactone diamine to the total amount of the mixture of the fluorine-containing maleic acid ester and the acrylonitrile is 1 (2-2.5).
8. The method of preparing a fluorine-modified PAE resin according to claim 7, wherein: the molar ratio of the fluorine-containing maleic acid ester to the acrylonitrile is 10 (0.5-2).
9. A fluorine-modified PAE resin coating composition characterized by: the composition comprises a component A and a component B which are compounded before use,
the component A contains:
at least one modified PAE resin according to claim 1,
at least one leveling agent;
the component B comprises:
an isocyanate curing agent.
10. The fluorine-modified PAE resin coating composition of claim 9, wherein:
the component A comprises the following components in percentage by mass:
and B component:
100% of isocyanate curing agent;
the mixing ratio of the component A to the component B is 2 (1-1.5).
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