CN107189533B - Anti-cracking additive, preparation method of anti-cracking additive and unsaturated polyester coating - Google Patents
Anti-cracking additive, preparation method of anti-cracking additive and unsaturated polyester coating Download PDFInfo
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- CN107189533B CN107189533B CN201710368538.1A CN201710368538A CN107189533B CN 107189533 B CN107189533 B CN 107189533B CN 201710368538 A CN201710368538 A CN 201710368538A CN 107189533 B CN107189533 B CN 107189533B
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- 238000005336 cracking Methods 0.000 title claims abstract description 93
- 239000000654 additive Substances 0.000 title claims abstract description 66
- 230000000996 additive effect Effects 0.000 title claims abstract description 64
- 238000000576 coating method Methods 0.000 title claims abstract description 35
- 239000011248 coating agent Substances 0.000 title claims abstract description 33
- 229920006305 unsaturated polyester Polymers 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 66
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 14
- 229920000570 polyether Polymers 0.000 claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 12
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 11
- 230000018044 dehydration Effects 0.000 claims abstract description 11
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000006482 condensation reaction Methods 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 28
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 20
- -1 polyoxyethylene Polymers 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 12
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 12
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 12
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 10
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 8
- 229920001451 polypropylene glycol Polymers 0.000 claims description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 7
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 7
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 6
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 5
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 4
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 claims description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 4
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 4
- LDMRLRNXHLPZJN-UHFFFAOYSA-N 3-propoxypropan-1-ol Chemical compound CCCOCCCO LDMRLRNXHLPZJN-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 4
- 239000001530 fumaric acid Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- 229960004063 propylene glycol Drugs 0.000 claims description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 239000003973 paint Substances 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 238000010790 dilution Methods 0.000 description 6
- 239000012895 dilution Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical group C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920006337 unsaturated polyester resin Polymers 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000011094 fiberboard Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007376 cm-medium Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940117969 neopentyl glycol Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005507 spraying Methods 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/329—Phosphorus containing acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention relates to the field of chemical synthesis, and provides a cracking-resistant additive, a preparation method of the cracking-resistant additive and an unsaturated polyester coating. The raw materials of the additive comprise, by weight, 5.4-30 parts of unsaturated dibasic acid, 0.6-10 parts of dihydric alcohol, 40-55 parts of polyether glycol, 0.1-0.2 part of antioxidant and 18.7-20.4 parts of solvent, and the coating has excellent anti-cracking performance. The additive can effectively improve the cracking performance of a paint film and has great market application potential; a method of preparing a crack resistant additive comprising: mixing unsaturated dibasic acid, dihydric alcohol, polyether glycol and an antioxidant, introducing inert gas, heating, performing dehydration condensation reaction, cooling, and adding a solvent, wherein the preparation method is simple and easy to implement and has strong operability; the unsaturated polyester coating comprises 1-5 wt% of the anti-cracking additive.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a cracking-resistant additive, a preparation method of the cracking-resistant additive and an unsaturated polyester coating.
Background
In the cross-linking and curing process of the traditional unsaturated polyester resin, excessive low-activity free radicals can be formed due to the existence of oxygen, so that the growth of polymer molecular chains is influenced, and the surface of a coating film is sticky. In the prior art, in order to improve the drying property of a paint film in air, a dicyclopentadiene structure is usually introduced for solving the problem, but the introduction of the dicyclopentadiene structure can simultaneously increase the resin brittleness, so that the traditional dicyclopentadiene modified unsaturated polyesters have the common defect, have different degrees of cracking risks when preparing unsaturated polyester coatings, and are particularly prominent when the temperature is low in winter or the paint film is thick.
Therefore, the invention of a crack resistant additive capable of solving the above problems is a problem to be solved.
Disclosure of Invention
In view of the above-mentioned deficiencies in the prior art, a first object of the present invention is to provide a crack-resistant additive which is effective in improving the cracking performance of paint films and has a great market application potential.
The second purpose of the invention is to provide a preparation method of the anti-cracking additive, which is simple and easy to implement and has strong operability.
A third object of the present invention is to provide an unsaturated polyester coating having excellent crack resistance.
In order to achieve the above object, the preferred solution adopted by the present invention is:
the anti-cracking additive comprises, by weight, 5.4-30 parts of unsaturated dibasic acid, 0.6-10 parts of dihydric alcohol, 40-55 parts of polyether glycol, 0.1-0.2 part of antioxidant and 18.7-20.4 parts of solvent.
Further, in the preferred embodiment of the invention, the unsaturated dibasic acid is 20-30 parts, the dihydric alcohol is 2-10 parts, the polyether glycol is 50-55 parts, the antioxidant is 0.15-0.2 part and the solvent is 19-20.4 parts by weight.
Further, in a preferred embodiment of the present invention, the unsaturated dicarboxylic acid includes at least one of maleic anhydride, maleic acid, fumaric acid, itaconic acid, and unsaturated dicarboxylic acid.
Further, in a preferred embodiment of the present invention, the diol includes at least one of neopentyl glycol, 1, 2-propanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, diethylene glycol, dipropylene glycol, 2, 4-trimethyl-1, 3-pentanediol, and 1, 4-butanediol.
Further, in a preferred embodiment of the present invention, the polyether glycol includes at least one of a polyoxyethylene glycol, a polyoxypropylene glycol, a polyoxyethylene-oxypropylene copolyol, and a polytetrahydrofuran ether glycol.
Further, in the preferred embodiment of the present invention, the molecular weight of the polyoxyethylene glycol is 400-8000, the molecular weight of the polyoxypropylene glycol is 400-8000, the molecular weight of the polyoxyethylene-oxypropylene copolymer glycol is 400-8000, and the molecular weight of the polytetrahydrofuran ether glycol is 250-3000.
Further, in a preferred embodiment of the present invention, the antioxidant comprises at least one of hypophosphorous acid and triphenyl phosphite.
Further, in a preferred embodiment of the present invention, the solvent includes at least one of propylene glycol methyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether.
The preparation method of the anti-cracking additive comprises the following steps: mixing unsaturated dibasic acid, dihydric alcohol, polyether glycol and antioxidant, introducing inert gas, heating to 200-210 ℃ for dehydration condensation reaction, stopping the reaction when the reaction degree reaches 95%, cooling to 100 ℃, and adding a solvent.
An unsaturated polyester coating comprises 1-5% of the anti-cracking additive by mass.
The anti-cracking additive, the preparation method of the anti-cracking additive and the unsaturated polyester coating provided by the invention have the beneficial effects that:
(1) unsaturated dibasic acid, dihydric alcohol, polyether glycol and an antioxidant which are raw materials of the anti-cracking additive provided by the invention are subjected to heating dehydration condensation reaction to obtain unsaturated linear polyester containing a large number of flexible polyether chain segments (-R-O-R-);
(2) in the process of forming a film by a coating, unsaturated double bonds contained in the flexible linear unsaturated polyester of the anti-cracking additive participate in the free radical chain growth reaction of unsaturated polyester resin and styrene, and a flexible chain segment is introduced into a paint film to play a role of flexible bridging, so that the brittleness of the paint film is improved, and the effect of preventing cracking can be achieved;
(3) the proportioning range of the raw materials of the anti-cracking additive provided by the invention is obtained through creative tests of an inventor, and the anti-cracking additive prepared in the proportioning range can better improve the anti-cracking performance of the coating;
(5) in the preparation method of the anti-cracking additive, the inventor obtains the anti-cracking additive through creative tests, the dehydration condensation reaction is carried out at the temperature of 200-210 ℃, the reaction is stopped when the reaction reaches 95 percent, and the anti-cracking additive with the best anti-cracking performance can be prepared when the temperature is reduced to 100 ℃;
(6) the unsaturated polyester coating provided by the invention has a good anti-cracking effect due to the addition of the anti-cracking additive provided by the invention;
(7) the unsaturated polyester coating provided by the invention is added with the anti-cracking additive with the mass fraction of 1% -5%, and the anti-cracking effect of the unsaturated polyester coating is better within the addition range.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The anti-cracking additive comprises the following raw materials in parts by weight: 5.4 parts of maleic anhydride, 0.6 part of 1, 4-butanediol, 40 parts of polyoxyethylene glycol with the molecular weight of 400, 0.1 part of hypophosphorous acid and 18.7 parts of propylene glycol monobutyl ether.
A preparation method of the anti-cracking additive comprises the following steps:
5.4 parts of maleic anhydride, 0.6 part of 1, 4-butanediol, 40 parts of polyoxyethylene glycol with the molecular weight of 400 and 0.1 part of hypophosphorous acid are added into a reaction kettle, nitrogen is introduced, the temperature is increased to 200-plus-210 ℃ for dehydration condensation, the reaction is stopped when the reaction degree reaches 95 percent, the temperature is reduced to 100 ℃, and 18.7 parts of propylene glycol monobutyl ether is added for dilution to obtain the anti-cracking additive.
Example 2
The anti-cracking additive comprises, by weight, 18.3 parts of maleic acid, 3.7 parts of fumaric acid, 0.7 part of 1, 2-propylene glycol, 0.7 part of diethylene glycol, 2.1 parts of dipropylene glycol, 8 parts of polyoxyethylene-oxypropylene copolyol with the molecular weight of 1000, 30 parts of polyoxypropylene glycol with the molecular weight of 2000, 25 parts of polyoxypropylene glycol with the molecular weight of 4000, 0.18 part of triphenyl phosphite, 10.4 parts of propylene glycol monomethyl ether, 4 parts of propylene glycol methyl ether acetate and 5 parts of propylene glycol monoethyl ether.
A preparation method of the anti-cracking additive comprises the following steps:
adding 18.3 parts of maleic acid, 3.7 parts of fumaric acid, 0.7 part of 1, 2-propylene glycol, 0.7 part of diethylene glycol, 2.1 parts of dipropylene glycol, 8 parts of polyoxyethylene-propylene oxide copolymerized glycol with the molecular weight of 1000, 30 parts of polyoxypropylene glycol with the molecular weight of 2000, 25 parts of polyoxypropylene glycol with the molecular weight of 4000 and 0.18 part of triphenyl phosphite into a reaction kettle, introducing nitrogen, heating to 200 ℃ and 210 ℃ for dehydration condensation, stopping the reaction after the reaction degree reaches 95%, cooling to 100 ℃, adding 10.4 parts of propylene glycol monomethyl ether, 4 parts of propylene glycol methyl ether acetate and 5 parts of propylene glycol monoethyl ether for dilution to obtain the anti-cracking additive.
Example 3
The anti-cracking additive comprises the following raw materials in parts by weight: 20 parts of maleic anhydride, 10 parts of itaconic acid, 2 parts of 1, 3-propylene glycol, 3 parts of 2-methyl-1, 3-propylene glycol, 5 parts of 2,2, 4-trimethyl-1, 3-pentanediol, 55 parts of polytetrahydrofuran ether glycol with the molecular weight of 1000, 0.1 part of hypophosphorous acid, 0.1 part of triphenyl phosphite, 10 parts of propylene glycol monopropyl ether and 10.4 parts of propylene glycol methyl ether acetate.
A preparation method of the anti-cracking additive comprises the following steps:
adding 20 parts of maleic anhydride, 10 parts of itaconic acid, 2 parts of 1, 3-propylene glycol, 3 parts of 2-methyl-1, 3-propylene glycol, 5 parts of 2,2, 4-trimethyl-1, 3-pentanediol, 55 parts of polytetrahydrofuran ether glycol with the molecular weight of 1000, 0.1 part of hypophosphorous acid and 0.1 part of triphenyl phosphite into a reaction kettle, introducing nitrogen, heating to 200 plus materials, dehydrating and condensing at 210 ℃, stopping the reaction when the reaction degree reaches 95%, cooling to 100 ℃, adding 10 parts of propylene glycol monopropyl ether and 10.4 parts of propylene glycol methyl ether acetate for dilution to obtain the anti-cracking additive.
Example 4
The anti-cracking additive comprises the following raw materials in parts by weight: 20 parts of maleic anhydride, 2 parts of 1, 4-butanediol, 50 parts of polyoxyethylene glycol with the molecular weight of 400, 0.15 part of hypophosphorous acid and 19 parts of propylene glycol monobutyl ether.
A preparation method of the anti-cracking additive comprises the following steps:
adding 20 parts of maleic anhydride, 2 parts of 1, 4-butanediol, 50 parts of polyoxyethylene glycol with molecular weight of 400 and 0.15 part of hypophosphorous acid into a reaction kettle, introducing nitrogen, heating to 200-210 ℃ for dehydration condensation, stopping the reaction when the reaction degree reaches 95%, cooling to 100 ℃, and adding 19 parts of propylene glycol monobutyl ether for dilution to obtain the anti-cracking additive.
Comparative example 1
The anti-cracking additive comprises the following raw materials in parts by weight: 50 parts of maleic anhydride, 30 parts of 1, 4-butanediol, 20 parts of polyoxyethylene glycol with the molecular weight of 400, 0.5 part of hypophosphorous acid and 16 parts of propylene glycol monobutyl ether.
A preparation method of the anti-cracking additive comprises the following steps:
adding 30 parts of maleic anhydride, 20 parts of 1, 4-butanediol, 20 parts of polyoxyethylene glycol with molecular weight of 400 and 0.5 part of hypophosphorous acid into a reaction kettle, introducing nitrogen, heating to 200-210 ℃ for dehydration condensation, stopping the reaction when the reaction degree reaches 95%, cooling to 100 ℃, and adding 16 parts of propylene glycol monobutyl ether for dilution to obtain the anti-cracking additive.
Comparative example 2
The anti-cracking additive comprises the following raw materials in parts by weight: 20 parts of maleic anhydride, 2 parts of 1, 4-butanediol, 50 parts of polyoxyethylene glycol with the molecular weight of 400, 0.15 part of hypophosphorous acid and 19 parts of propylene glycol monobutyl ether.
A preparation method of the anti-cracking additive comprises the following steps:
adding 20 parts of maleic anhydride, 2 parts of 1, 4-butanediol, 50 parts of polyoxyethylene glycol with molecular weight of 400 and 0.15 part of hypophosphorous acid into a reaction kettle, introducing nitrogen, heating to 230 ℃ for dehydration condensation, stopping reaction when the reaction degree reaches 90%, cooling to 60 ℃, and adding 19 parts of propylene glycol monobutyl ether for dilution to obtain the anti-cracking additive.
Experimental example 1
The anti-cracking additives provided in examples 1 to 4, the anti-cracking additives provided in comparative examples 1 to 2, the anti-cracking additive provided in example 4, and the commercially available anti-cracking additive were set as experimental groups 1 to 9, respectively.
The raw materials of the unsaturated polyester coating are shown in the following table 1:
table 1 raw material parameter table for unsaturated polyester coatings provided in experimental groups 1-9
The paint preparation process comprises the following steps: the raw material components in the experimental groups 1-9 are mixed according to the proportion shown in the table 1, and are respectively added into a high-speed dispersion machine at 1500rpm for dispersion for 30 minutes to prepare the unsaturated polyester coating.
Experimental example 2
(1) The unsaturated polyester coating prepared from the experimental groups 1-9 is prepared into the paint liquid of the experimental groups 1-9 according to the following construction ratio: 200g of unsaturated polyester coating; 60g of a diluent (methyl acetate: toluene: 70%: 30%); 3g of cobalt iso-octoate (6% metallic cobalt content); methyl ethyl ketone peroxide 3.2g (10% active oxygen content).
(2) Spraying two-component alkyd polyurethane sealing primer once on a 20 cm-30 cm medium-density fiberboard, standing for 30 minutes, and longitudinally forming two grooves on the fiberboard, wherein the depth of each groove is 0.5cm, and the length of each groove is 20 cm. Fixing a surrounding edge with the height of 1cm on the periphery of the sample plate by using a craft adhesive tape to prevent the unsaturated polyester coating from overflowing; the prepared paint liquids of the experimental groups 1 to 9 are all respectively sprayed on the sample plate and are thickly coated. And after the paint is sprayed and naturally aired for 24 hours, the test of the cracking performance of the cold-hot cycle is started.
(3) Primary cold and hot circulation: keeping the temperature at 60 ℃ for 11 hours; the temperature was held at-25 ℃ for 11 hours. The test results are shown in table 2:
TABLE 2 comparative test results for crack resistance at typical addition levels
| Sample plate number | Number of cycles | Degree of cracking |
| Experimental group 1 | 2 | Very slight cracking |
| Experimental group 2 | 2 | Without cracking |
| Experimental group 3 | 2 | Very slight cracking |
| Experimental group 4 | 2 | Without cracking |
| Experimental group 5 | 2 | Slight cracking |
| Experimental group 6 | 2 | Slight cracking |
| Experimental group 7 | 2 | Slight cracking |
| Experimental group 8 | 2 | Slight crack |
| Experimental group 9 | 2 | Cracking of |
As can be seen from Table 2, after 2 cycles, the cracking degree of the experimental groups 1-9 is lower than that of the experimental group 9, and the results show that the anti-cracking effect of the anti-cracking additive prepared according to the component formula provided by the invention as the component of the unsaturated polyester coating is better than that of the anti-cracking agent commercially available as the component of the unsaturated polyester coating, and the anti-cracking effect of the paint prepared by the anti-cracking additive is better than that of the paint prepared by using the anti-cracking agent as the component of the unsaturated polyester coating, so that the unsaturated linear polyester containing a large amount of flexible polyether segments (-R-O-R-) can be obtained by heating, dehydrating and condensing the unsaturated dibasic acid, the dihydric alcohol, the polyether diol and the antioxidant which are used as the raw materials of the anti-cracking additive provided by the invention, and the unsaturated double bonds contained in the flexible linear unsaturated polyester of the anti-cracking additive provided by the invention participate in the free radical chain extension reaction of the unsaturated polyester resin and styrene in the film forming process of the coating, the flexible chain segment is introduced into the paint film to play a role of flexible bridging, so that the brittleness of the paint film is improved, and the effect of preventing cracking can be achieved.
The cracking resistance degree of the experimental groups 1-4 is better than that of the experimental group 5, and the result shows that the proportioning range of the raw materials of the cracking resistance additive provided by the invention is obtained through creative tests of the inventor, and the cracking resistance of the coating can be better improved by the prepared cracking resistance additive in the proportioning range.
The cracking resistance degree of the experimental group 2 and the experimental group 4 is better than that of the experimental group 1 and the experimental group 2, and the result shows that the proportion range of the raw materials of the cracking resistance additive provided by the invention is as follows: 20-30 parts of unsaturated dibasic acid, 2-10 parts of dihydric alcohol, 50-55 parts of polyether glycol, 0.15-0.2 part of antioxidant and 19-20.4 parts of solvent, so that the best anti-cracking effect can be obtained.
The anti-cracking effect of the experimental group 4 is better than that of the experimental group 6, and the result shows that the inventor obtains through creative tests that the dehydration condensation reaction is carried out at the temperature of 200-210 ℃, the reaction is stopped when the reaction reaches 95%, and the anti-cracking additive with the best anti-cracking performance can be prepared when the temperature is reduced to 100 ℃.
The anti-cracking effect of the experimental group 4 is better than that of the experimental groups 7 and 8, and the result shows that the anti-cracking additive provided by the invention with the mass fraction of 1-5% is added, and the anti-cracking effect of the unsaturated polyester coating is the best within the addition range.
In conclusion, the cracking-resistant additive prepared by the formula and the component proportion range provided by the embodiment of the invention is added into the unsaturated polyester coating, so that the problem that the traditional dicyclopentadiene modified unsaturated polyester resin is easy to crack in application can be solved; the preparation method of the anti-cracking additive provided by the invention is simple in steps and strong in operability; the unsaturated polyester coating provided by the invention has excellent cracking resistance due to the adoption of the cracking resistance additive provided by the embodiment of the invention.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. 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.
Claims (5)
1. An unsaturated polyester coating is characterized in that: comprises 1 to 5 mass percent of anti-cracking additive; the raw materials of the additive comprise, by weight, 20-30 parts of unsaturated dibasic acid, 2-10 parts of dihydric alcohol, 50-55 parts of polyether glycol, 0.15-0.2 part of antioxidant and 19-20.4 parts of solvent;
the polyether glycol comprises at least one of polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene-oxypropylene copolymer glycol and polytetrahydrofuran ether glycol;
the molecular weight of the polyoxyethylene glycol is 400-8000, the molecular weight of the polyoxypropylene glycol is 400-8000, the molecular weight of the polyoxyethylene-oxypropylene copolymer glycol is 400-8000, and the molecular weight of the polytetrahydrofuran ether glycol is 250-3000;
the preparation method of the additive comprises the following steps: mixing the unsaturated dibasic acid, the dihydric alcohol, the polyether glycol and the antioxidant, introducing inert gas, heating to 200-210 ℃ for dehydration condensation reaction, stopping the reaction when the reaction degree reaches 95%, cooling to 100 ℃, and adding the solvent.
2. The unsaturated polyester coating of claim 1, wherein: the unsaturated dibasic acid comprises at least one of maleic anhydride, maleic acid, fumaric acid and itaconic acid.
3. The unsaturated polyester coating of claim 1, wherein: the dihydric alcohol comprises at least one of neopentyl glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 2-methyl-1, 3-propylene glycol, diethylene glycol, dipropylene glycol, 2, 4-trimethyl-1, 3-pentanediol and 1, 4-butanediol.
4. The unsaturated polyester coating of claim 1, wherein: the antioxidant comprises at least one of hypophosphorous acid and triphenyl phosphite.
5. The unsaturated polyester coating of claim 1, wherein: the solvent comprises at least one of propylene glycol methyl ether acetate, propylene glycol methyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether.
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| CN101555315A (en) * | 2009-05-18 | 2009-10-14 | 上海新天和树脂有限公司 | Modified unsaturated polyester resin of polyethylene glycol, preparation method and application of glass steel grating |
| CN103724604A (en) * | 2013-12-10 | 2014-04-16 | 浙江天和树脂有限公司 | Preparation method of air-drying unsaturated polyester resin |
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| CN101555315A (en) * | 2009-05-18 | 2009-10-14 | 上海新天和树脂有限公司 | Modified unsaturated polyester resin of polyethylene glycol, preparation method and application of glass steel grating |
| CN103724604A (en) * | 2013-12-10 | 2014-04-16 | 浙江天和树脂有限公司 | Preparation method of air-drying unsaturated polyester resin |
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| Title |
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| "聚醚二元醇不饱和聚酯树脂及其柔性固化体系";杨群等;《热固性树脂》;20070130;第22卷(第1期);第9-12页 * |
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