CN111393626B - Secondary amino modified alkyd resin and preparation method and application thereof - Google Patents
Secondary amino modified alkyd resin and preparation method and application thereof Download PDFInfo
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- 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
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/918—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Abstract
The invention relates to secondary amino modified alkyd resin and a preparation method and application thereof. The preparation raw materials of the resin comprise an alkyd polyester polyol prepolymer and 3,3 '-dimethyl-4, 4' -diamino-dicyclohexyl methane, wherein the molar ratio of the alkyd polyester polyol prepolymer to the 3,3 '-dimethyl-4, 4' -diamino-dicyclohexyl methane is 2.5: 1-4.5: 1; the structural general formula of the alkyd polyester polyol prepolymer is shown as a formula (1), wherein R 1 、R 2 And R 3 Independently selected from substituted or unsubstituted alkyl with 1-30 carbon atoms. The secondary amino modified alkyd resin obtained by the invention has the characteristics of high solid content and low viscosity, is used for preparing polyurethane coating, has construction VOC below 300g/L, has great advantages in the aspect of environmental protection, has hardness and dryness meeting the application requirements in the field of PU wood paint, and has wide application prospect.
Description
Technical Field
The invention relates to the field of coatings, in particular to secondary amino modified alkyd resin and a preparation method and application thereof.
Background
PU coating, PE coating and NC coating are the most widely applied oily wood lacquer coating at the present stage. The PU coating is also called as a bi-component polyurethane coating, has excellent hardness, adhesive force, chemical resistance, decoration and wear resistance, and accounts for the largest proportion in wood lacquer. The PU coating mainly comprises hydroxyl-containing resin (such as alkyd resin and acrylic resin) and polyurethane resin. When the paint is prepared, the two resins are separately packaged, when in use, the two resins are mixed together, stirred evenly and sprayed on wood to be constructed, and a coating film with decorative and protective properties is formed through the gradual addition polymerization reaction of hydroxyl (-OH) groups and-NCO (isocyanate) groups in the matrix resin. The PU coating is prepared from the following components in percentage by weight: main paint: curing agent: diluent 1: 0.5: 0.3-1.0, the solid content of the main paint is 50-70%, and the solid content of the curing agent is about 30-50%, so that the total solid content during construction is about 40-50%.
The furniture coating needs lower construction viscosity, the coating contains more organic solvents, Volatile Organic Compounds (VOC) are about 500 g/L-600 g/L, and the solvents are finally volatilized into the atmosphere to cause serious pollution. With the increasing environmental protection requirements of the country, additional taxes (coatings with VOC emission higher than 420 g/L) have been adopted, so that the improvement of the solid content during the PU coating construction and the reduction of the VOC emission are of great significance.
Chinese patent 201710917693.4 discloses a 90% high solid content alkyd resin and a preparation method thereof, the alkyd resin is prepared from vegetable oil fatty acid, organic acid anhydride, polyhydric alcohol, oligomer polyhydric alcohol, benzoic acid and dodecanol through polycondensation, and has the advantages of high solid content (more than or equal to 90%), low viscosity, low VOC, strong adhesive force, water resistance, high drying speed and the like, but the hardness of a paint film is not enough.
Chinese patent 201710219931.4 discloses an environment-friendly alkyd resin with high solid content and its preparation method, wherein the alkyd resin is mainly prepared from soya-oleic acid, dimer acid, phthalic anhydride, pentaerythritol and diethylene glycol, and the alkyd resin has the advantages of benzene-free, low toxicity, low cost, high solid content and the like, and is applied to industrial air-drying white paint systems.
Chinese patent 201280063350.1 discloses a hydroxyamino polymer, the invention of which relates to a process for the preparation of a hydroxyamino polymer, said process comprising the steps of a) reacting a starter compound having at least one zerewitinoff-active H-atom with an unsaturated cyclic carboxylic acid anhydride and at least one alkylene oxide compound for obtaining a prepolymer having hydroxyl groups. b) Addition of primary amines and/or ammonia to the double bonds of the hydroxyl-bearing prepolymer obtained according to step a) for obtaining a hydroxylamino polymer, wherein the ratio of added amino groups to hydroxyl groups in the hydroxylamino polymer is at least 0.6. The product prepared by the invention is used for stopping bleeding in medicine.
Disclosure of Invention
Based on the above, there is a need to provide a secondary amine modified alkyd resin with high solid content and low viscosity, which is used for preparing a two-component polyurethane coating, reduces the usage amount of a solvent, reduces the emission of VOC, and still meets the requirements of a conventional PU wood coating system on hardness and dryness.
The technical scheme is as follows:
a secondary amine modified alkyd resin is prepared from the following raw materials:
an alkyd polyester polyol prepolymer and 3,3 '-dimethyl-4, 4' -diamino-dicyclohexylmethane;
the molar ratio of the alkyd polyester polyol prepolymer to the 3,3 '-dimethyl-4, 4' -diamino-dicyclohexylmethane is 2.5: 1-4.5: 1;
the structural general formula of the alkyd polyester polyol prepolymer is shown as formula (1):
wherein R is 1 、R 2 And R 3 Independently selected from substituted or unsubstituted alkyl with 1-30 carbon atoms.
In one embodiment, the molar ratio of the alkyd polyester polyol prepolymer to the 3,3 '-dimethyl-4, 4' -diamino-dicyclohexylmethane is 2.5:1 to 4: 1.
In one embodiment, the molar ratio of the alkyd polyester polyol prepolymer to the 3,3 '-dimethyl-4, 4' -diamino-dicyclohexylmethane is 2.5:1 to 3: 1.
In one embodiment, the alkyd polyester polyol prepolymer is prepared from the following raw materials in parts by weight:
20-30 parts of lauric acid, 5-10 parts of ethylene glycol, 20-35 parts of phthalic anhydride, 4-8 parts of benzoic acid, 2-10 parts of maleic anhydride, 4-12 parts of trimethylolpropane, 10-20 parts of pentaerythritol and 0.1-20 parts of an auxiliary agent.
In one embodiment, the alkyd polyester polyol prepolymer is prepared from the following raw materials in parts by weight:
22-26 parts of lauric acid, 6-8 parts of ethylene glycol, 25-30 parts of phthalic anhydride, 4-5 parts of benzoic acid, 4-8 parts of maleic anhydride, 5-10 parts of trimethylolpropane, 12-15 parts of pentaerythritol and 1-10 parts of an auxiliary agent.
In one embodiment, the alkyd polyester polyol prepolymer has a general structural formula as shown in formula (2):
r, R 'and R' are partial residues of ethylene glycol, pentaerythritol, trimethylolmethane and carboxyl groups after reaction.
In one embodiment, the auxiliary agent is selected from at least one of a color reducing agent, a thinning solvent, and a water-carrying agent.
In one embodiment, the color reducing agent is selected from at least one of hypophosphorous acid and triphenyl phosphite.
In one embodiment, the letdown solvent is selected from at least one of xylene and butyl acetate.
In one embodiment, the water-carrying agent is selected from at least one of xylene and toluene.
In one embodiment, the method for preparing the alkyd polyester polyol prepolymer comprises the following steps:
mixing the lauric acid, the ethylene glycol, the phthalic anhydride, the benzoic acid, the maleic anhydride, the trimethylolpropane, the pentaerythritol and part of the auxiliary agent, reacting for 3-5 h at the temperature of 152-156 ℃, heating to 210-220 ℃ for continuous reaction, esterifying, cooling to below 180 ℃ when the acid value of the system is less than or equal to 15mgKOH/g, and then adding the rest of the auxiliary agent into the system.
The invention also provides a preparation method of the secondary amine modified alkyd resin, which comprises the following steps:
mixing the alkyd polyester polyol prepolymer with 3,3 '-dimethyl-4, 4' -diamino-dicyclohexyl methane, reacting for 3-10 h at 110-130 ℃, and standing for 20-30 days.
In one embodiment, the preparation method of the secondary amine modified alkyd resin comprises the following steps:
dropwise adding 3,3 '-dimethyl-4, 4' -diamino-dicyclohexyl methane into the alkyd polyester polyol prepolymer at the temperature of 50-100 ℃, wherein the dropwise adding time is 1-3 h; after the dropwise addition is finished, the reaction is carried out for 3 to 10 hours at the temperature of between 110 and 130 ℃, and then the mixture is placed for 20 to 30 days.
The invention also provides application of the secondary amine modified alkyd resin in preparation of a two-component polyurethane coating.
The invention principle and the beneficial effects of the invention are as follows:
the preparation raw materials of the secondary amine modified alkyd resin provided by the invention comprise: the alkyd polyester polyol prepolymer and the 3,3 '-dimethyl-4, 4' -diamino-dicyclohexyl methane are mixed according to a molar ratio of 2.5:1 to 4.5: 1. The molecular structure of the alkyd polyester polyol prepolymer is a polyester polyol structure with a certain amount of double bonds on a main chain and long carbon chain ester groups on a side chain.
The inventors of the present invention found through a great deal of creative work: unsaturated double bonds in the structure of the alkyd polyester polyol prepolymer react with 3,3 '-dimethyl-4, 4' -diamino-dicyclohexylmethane, secondary amino groups are introduced into side chains, the content of active groups is increased, the secondary amino group modified resin is applied to a two-component polyurethane coating, the secondary amino groups and the active hydroxyl groups can react with-NCO groups, the reaction activity of the modified resin is improved, and the drying speed and the hardness of a paint film in a film forming process under a high solid content construction state can be effectively guaranteed. The alkyd polyester polyol prepolymer reacts with 3,3 '-dimethyl-4, 4' -diamino-dicyclohexyl methane to generate secondary amino modified alkyd resin with the advantages of high solid content and low viscosity, and when the alkyd polyester polyol prepolymer is used for preparing a two-component polyurethane coating, the consumption of a solvent can be reduced, the discharge of VOC is reduced, the discharge amount of VOC is less than 300g/L, and the alkyd polyester polyol prepolymer completely conforms to the concept of environment-friendly production; meanwhile, the hardness and the dryness of the paint film still meet the requirements of the conventional PU wood coating system, and all performance indexes meet the national standard, so that the paint film has a wide application prospect.
In addition, unsaturated double bonds in the structure of the alkyd polyester polyol prepolymer react with 3,3 '-dimethyl-4, 4' -diamino-dicyclohexylmethane, secondary amino groups are introduced into side chains, the content of active groups is increased, and when the secondary amino group modified resin is applied to a double-component polyurethane coating, the secondary amino groups and the active hydroxyl groups can react with-NCO groups, so that the reactivity of the modified resin is improved, particularly the reactivity in a low-temperature environment is improved, and a paint film can still have good drying speed and hardness in the low-temperature environment. The long-chain branch in the structure of the alkyd polyester polyol prepolymer can enhance the compatibility of the modified resin with other systems, and when the alkyd polyester polyol prepolymer is applied to the field of bi-component wood paint, the alkyd polyester polyol prepolymer is sprayed on a solid wood or pressed density wood board substrate to show an excellent leveling effect.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
A secondary amine modified alkyd resin is prepared from the following raw materials:
an alkyd polyester polyol prepolymer and 3,3 '-dimethyl-4, 4' -diamino-dicyclohexylmethane;
the molar ratio of the alkyd polyester polyol prepolymer to the 3,3 '-dimethyl-4, 4' -diamino-dicyclohexylmethane is 2.5: 1-4.5: 1;
the structural general formula of the alkyd polyester polyol prepolymer is shown as formula (1):
wherein R is 1 、R 2 And R 3 Independently selected from substituted or unsubstituted alkyl with 1-30 carbon atoms.
The preparation raw materials of the secondary amine modified alkyd resin provided by the invention comprise: the alkyd polyester polyol prepolymer and the 3,3 '-dimethyl-4, 4' -diamino-dicyclohexyl methane are mixed according to a molar ratio of 2.5:1 to 4.5: 1. The molecular structure of the alkyd polyester polyol prepolymer is a polyester polyol structure with a certain amount of double bonds on a main chain and long carbon chain ester groups on side chains.
The inventors of the present invention found through a great deal of creative work: unsaturated double bonds in the structure of the alkyd polyester polyol prepolymer react with 3,3 '-dimethyl-4, 4' -diamino-dicyclohexylmethane, secondary amino groups are introduced into side chains, the content of active groups is increased, the secondary amino group modified resin is applied to a two-component polyurethane coating, the secondary amino groups and the active hydroxyl groups can react with-NCO groups, the reaction activity of the modified resin is improved, and the drying speed and the hardness of a paint film in a film forming process under a high solid content construction state can be effectively guaranteed. The alkyd polyester polyol prepolymer reacts with 3,3 '-dimethyl-4, 4' -diamino-dicyclohexyl methane to generate secondary amino modified alkyd resin with the advantages of high solid content and low viscosity, and when the alkyd polyester polyol prepolymer is used for preparing a two-component polyurethane coating, the consumption of a solvent can be reduced, the discharge of VOC is reduced, the discharge amount of VOC is less than 300g/L, and the alkyd polyester polyol prepolymer completely conforms to the concept of environment-friendly production; meanwhile, the hardness and the dryness of the paint film still meet the requirements of the conventional PU wood coating system, and all performance indexes meet the national standard, so that the paint film has a wide application prospect.
In addition, unsaturated double bonds in the structure of the alkyd polyester polyol prepolymer react with 3,3 '-dimethyl-4, 4' -diamino-dicyclohexylmethane, secondary amino groups are introduced into side chains, the content of active groups is increased, and when the secondary amino group modified resin is applied to a double-component polyurethane coating, the secondary amino groups and the active hydroxyl groups can react with-NCO groups, so that the reactivity of the modified resin is improved, particularly the reactivity in a low-temperature environment is improved, and a paint film can still have good drying speed and hardness in the low-temperature environment. The long-chain branch in the structure of the alkyd polyester polyol prepolymer can enhance the compatibility of the modified resin with other systems, and when the alkyd polyester polyol prepolymer is applied to the field of bi-component wood paint, the alkyd polyester polyol prepolymer is sprayed on a solid wood or pressed density wood board substrate to show an excellent leveling effect.
In the invention, the molar ratio of the alkyd polyester polyol prepolymer to the 3,3 '-dimethyl-4, 4' -diamino-dicyclohexylmethane is 2.5: 1-4.5: 1; preferably, the molar ratio of the alkyd polyester polyol prepolymer to the 3,3 '-dimethyl-4, 4' -diamino-dicyclohexylmethane is 2.5: 1-4: 1; more preferably, the molar ratio of the alkyd polyester polyol prepolymer to the 3,3 '-dimethyl-4, 4' -diamino-dicyclohexylmethane is 2.5:1 to 3: 1; it is understood that the molar ratio of alkyd polyester polyol prepolymer to 3,3 '-dimethyl-4, 4' -diamino-dicyclohexylmethane can be set to, but is not limited to, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1, 3.0:1, 4.2:1, and 4.5: 1.
In the present invention, R 1 、R 2 And R 3 Independently selected from substituted or unsubstituted alkyl with 1-30 carbon atoms. Preferably, R 1 、R 2 And R 3 Independently selected from substituted or unsubstituted alkyl with 2-20 carbon atoms.
In one embodiment, the alkyd polyester polyol prepolymer is prepared from the following raw materials in parts by weight:
20-30 parts of lauric acid, 5-10 parts of ethylene glycol, 20-35 parts of phthalic anhydride, 4-8 parts of benzoic acid, 2-10 parts of maleic anhydride, 4-12 parts of trimethylolpropane, 10-20 parts of pentaerythritol and 0.1-20 parts of an auxiliary agent.
By reasonably optimizing the formula of the alkyd polyester polyol prepolymer and grafting a carbon chain ester group with the chain length of 12 carbon atoms on the side end, the compatibility of the alkyd polyester polyol prepolymer with other systems can be enhanced.
In one preferred embodiment, the alkyd polyester polyol prepolymer of the invention is prepared from the following raw materials in parts by weight:
22-26 parts of lauric acid, 6-8 parts of ethylene glycol, 25-30 parts of phthalic anhydride, 4-5 parts of benzoic acid, 4-8 parts of maleic anhydride, 5-10 parts of trimethylolpropane, 12-15 parts of pentaerythritol and 1-10 parts of an auxiliary agent.
In one embodiment, the alkyd polyester polyol prepolymer has a general structural formula as shown in formula (2):
r, R 'and R' are partial residues of ethylene glycol, pentaerythritol, trimethylolmethane and carboxyl groups after reaction.
The reaction of the alkyd polyester polyol prepolymer with 3,3 '-dimethyl-4, 4' -diamino-dicyclohexylmethane is shown below:
in one embodiment, the auxiliary agent is selected from at least one of a color reducing agent, a thinning solvent, and a water-carrying agent.
In one embodiment, the color reducing agent is selected from at least one of hypophosphorous acid and triphenyl phosphite.
In one embodiment, the letdown solvent is selected from at least one of xylene and butyl acetate.
In one embodiment, the water-carrying agent is selected from at least one of xylene and toluene.
In one embodiment, the method for preparing the alkyd polyester polyol prepolymer comprises the following steps:
mixing the lauric acid, the ethylene glycol, the phthalic anhydride, the benzoic acid, the maleic anhydride, the trimethylolpropane, the pentaerythritol and part of the auxiliary agent, reacting for 3-5 h at the temperature of 152-156 ℃, heating to 210-220 ℃ for continuous reaction, cooling to below 180 ℃ when the acid value of the system is less than or equal to 15mgKOH/g, and then adding the rest of the auxiliary agent into the system.
In one preferred embodiment, the preparation method of the alkyd polyester polyol prepolymer comprises the following steps:
mixing the lauric acid, the ethylene glycol, the phthalic anhydride, the benzoic acid, the maleic anhydride, the trimethylolpropane, the pentaerythritol, the color reducing agent and the water carrying agent, reacting for 3 to 5 hours at the temperature of 152 to 156 ℃, heating to 210 to 220 ℃ for continuous reaction, cooling to below 180 ℃ when the acid value of the system is less than or equal to 15mgKOH/g, and adding a diluting solvent into the system.
The invention also provides a preparation method of the secondary amino modified alkyd resin, which comprises the following steps:
mixing the alkyd polyester polyol prepolymer with 3,3 '-dimethyl-4, 4' -diamino-dicyclohexyl methane, reacting for 3-10 h at 120-130 ℃, and standing for 20-30 days.
In a more preferable embodiment, the alkyd polyester polyol prepolymer and 3,3 '-dimethyl-4, 4' -diamino-dicyclohexylmethane are mixed, reacted for 4 to 8 hours at the temperature of 120 to 130 ℃, cooled to normal temperature when the amine value is less than or equal to 20mgKOH/g, and then placed for 20 to 30 days.
In one preferable embodiment, the preparation method of the secondary amine modified alkyd resin comprises the following steps:
dropwise adding 3,3 '-dimethyl-4, 4' -diamino-dicyclohexyl methane into the alkyd polyester polyol prepolymer at the temperature of 50-100 ℃, wherein the dropwise adding time is 1-3 h; after the dropwise addition, the mixture reacts for 3 to 10 hours at the temperature of between 110 and 130 ℃, and then is placed for 20 to 30 days.
The invention also provides application of the secondary amine modified alkyd resin in preparation of a two-component polyurethane coating.
The following are specific examples.
Example 1
The embodiment provides a secondary amine modified alkyd resin and a preparation method thereof.
(1) Preparation of alkyd polyester polyol prepolymer 1
Mixing 24.55 parts of lauric acid, 7.78 parts of ethylene glycol, 28.44 parts of phthalic anhydride, 4.49 parts of benzoic acid, 4.49 parts of maleic anhydride, 5.99 parts of trimethylolpropane, 14.97 parts of pentaerythritol, 0.12 part of hypophosphorous acid and 3.84 parts of dimethylbenzene, introducing nitrogen, heating to 152-156 ℃, refluxing the dimethylbenzene for reaction for 4 hours, slowly heating to 215 ℃, cooling to below 180 ℃ when the acid value is esterified to be less than or equal to 15mgKOH/g, diluting to 90.1% of solid solution by using 5.33 parts of butyl acetate to obtain an alkyd polyester polyol prepolymer 1, and packaging for later use, wherein the performance results are shown in Table 1.
(2) Preparation of Secondary Amino-modified alkyd resin A
Under the condition of introducing nitrogen at 50 ℃, 232 parts of 3,3 '-dimethyl-4, 4' -diamino-dicyclohexylmethane is dripped into 5467.5 parts of alkyd polyester polyol prepolymer 1, the molar ratio of the two is 2.7:1, the equivalent ratio is 0.68:1, the dripping time is 2 hours, after the dripping is finished, the temperature is slowly raised to 120 ℃, the reaction is carried out for 6 hours, when the amine value is less than or equal to 20mgKOH/g, the temperature is reduced to normal temperature, the secondary amine modified alkyd resin A is placed for 30 days, after the free primary amine is basically reacted, the performance result is shown in table 2.
(3) Preparation of polyurethane coating A
Mixing the secondary amine modified alkyd resin A and TDI (toluene diisocyanate) tri-hydroxy prepolymer prepared by Jia Bao Li company according to the proportion of NCO: OH ═ 1: 1, preparing a light varnish, and then adding butyl acetate: xylene ═ 1: the diluent of 1 was diluted to a sprayable state (12-14S/coat-4 cups) to give polyurethane coating a, which was sprayed on 30CM by 20CM veneers, tested for dryness, and the VOC content at the time of spraying was calculated, the results are shown in table 3.
Example 2
The embodiment provides a secondary amine modified alkyd resin and a preparation method thereof.
(1) Preparation of alkyd polyester polyol prepolymer 2
Mixing 22 parts of lauric acid, 7 parts of ethylene glycol, 27 parts of phthalic anhydride, 4 parts of benzoic acid, 4 parts of maleic anhydride, 5 parts of trimethylolpropane, 14 parts of pentaerythritol, 0.05 part of hypophosphorous acid and 3 parts of dimethylbenzene, introducing nitrogen, heating to 152-156 ℃, refluxing the dimethylbenzene for reaction for 4 hours, slowly heating to 215 ℃, cooling to below 180 ℃ when esterification is carried out until the acid value is less than or equal to 15mgKOH/g, diluting with 4 parts of butyl acetate to obtain a solution with 90.1% of solid content to obtain an alkyd polyester polyol prepolymer 2, and packaging for later use, wherein the performance results are shown in table 1.
(2) Preparation of Secondary amino modified alkyd resin B
Under the condition of introducing nitrogen at 50 ℃, 232 parts of 3,3 '-dimethyl-4, 4' -diamino-dicyclohexylmethane is dripped into 6100 parts of alkyd polyester polyol prepolymer 2, the molar ratio of the two is 4:1, the dripping time is 3 hours, after the dripping is finished, the temperature is slowly raised to 110 ℃, the reaction is carried out for 8 hours, when the amine value is less than or equal to 20mgKOH/g, the temperature is reduced to normal temperature, the secondary amine group modified alkyd resin B is obtained after the free primary amine is basically reacted, and the performance result is shown in table 2.
(3) Preparation of polyurethane coating B
And (3) mixing the secondary amine modified alkyd resin B with TDI (toluene diisocyanate) tri-hydroxyl prepolymer prepared by Jia Bao Li company at the ratio of NCO: OH 1: 1, preparing a light varnish, and then adding butyl acetate: xylene ═ 1: the diluent of 1 was diluted to a sprayable state (12-14S/coat-4 cups) to give polyurethane coating B, which was sprayed on 30CM by 20CM veneers, tested for dryness, and the VOC content at the time of spraying was calculated, the results are shown in table 3.
Example 3
The embodiment provides a secondary amine modified alkyd resin and a preparation method thereof.
(1) Preparation of alkyd polyester polyol prepolymer 3
26 parts of lauric acid, 8 parts of ethylene glycol, 29 parts of phthalic anhydride, 5 parts of benzoic acid, 5 parts of maleic anhydride, 6 parts of trimethylolpropane, 15 parts of pentaerythritol, 0.15 part of hypophosphorous acid and 5 parts of dimethylbenzene are mixed, nitrogen is introduced, the temperature is raised to 152-156 ℃, the dimethylbenzene is refluxed for reaction for 4 hours, then the temperature is slowly raised to 215 ℃, the temperature is lowered to below 180 ℃ when the esterification is carried out until the acid value is less than or equal to 15mgKOH/g, 5 parts of butyl acetate is diluted into 90.1 percent of solid solution, the alkyd polyester polyol prepolymer 3 is obtained and packaged for standby use, and the performance results are shown in table 1.
(2) Preparation of Secondary amino modified alkyd resin C
Under the condition of 50 ℃ and nitrogen gas introduction, 232 parts of 3,3 '-dimethyl-4, 4' -diamino-dicyclohexyl methane (mole number: 1, equivalent number: 2.5) is added into 6312.5 parts of alkyd polyester polyol prepolymer 4 (mole number: 2.5, equivalent number: 2.5) in a dropwise manner, the mole ratio of the 3,3 '-dimethyl-4, 4' -diamino-dicyclohexyl methane is 2.5:1, the equivalent ratio is 1.6:1, the dropwise adding time is 3 hours, the temperature is slowly increased to 110 ℃, the reaction is carried out for 8 hours, when the amine value is less than or equal to 20mgKOH/g, the temperature is reduced to normal temperature, the mixture is placed for 30 days, when the free reaction is basically finished, the secondary amine modified alkyd resin C is obtained, and the performance results are shown in table 2.
(3) Preparation of polyurethane coating C
Mixing the secondary amine modified alkyd resin C and TDI (toluene diisocyanate) tri-hydroxy prepolymer manufactured by Jia Bao Li company according to the proportion of NCO: OH ═ 1: 1, preparing a light varnish, and then adding butyl acetate: xylene ═ 1: the diluent of 1 was diluted to a sprayable state (12-14S/coat-4 cups) to give polyurethane coating C, which was sprayed on 30CM by 20CM veneers, tested for dryness, and the VOC content of the spray was calculated and the results are shown in table 3.
Comparative example 1
The present comparative example provides an alkyd polyester polyol prepolymer and a method of making the same.
(1) Preparation of alkyd polyester polyol prepolymer 1
The same as in example 1.
(2) Preparation of polyurethane coating D
Mixing alkyd polyester polyol prepolymer 1 with TDI (toluene diisocyanate) tri-hydroxy prepolymer prepared by Jia Bao Li company, wherein the ratio of NCO: OH ═ 1: 1, preparing a light varnish, and then adding butyl acetate: xylene ═ 1: the diluent of 1 was diluted to a sprayable state (12-14S/coat-4 cups) to give polyurethane coating D, which was sprayed on 30CM by 20CM veneers, tested for dryness, and the VOC content of the spray was calculated and the results are shown in table 3.
Comparative example 2
This comparative example provides an alkyd resin with a solids content of 90% and was prepared according to the second example of the specification of patent CN 201710917693.4.
(1) Preparation of 90% solids alkyd E
Adding 25.0 parts of soybean oil, 18.0 parts of phthalic anhydride, 12.0 parts of adipic acid, 3.5 parts of maleic anhydride, 12 parts of glycerol, 4.2 parts of trimethylolpropane, 6.0 parts of neopentyl glycol and 4005.2 parts of polyether glycol into a reaction kettle in sequence according to the weight percentage, starting to heat, introducing nitrogen after materials in the kettle are completely melted, starting to stir and heat to 120 ℃, adding 0.6 part of organic tin catalyst, then heating to 165-180 ℃, adding 5.0 parts of benzoic acid and 3 parts of reflux dimethylbenzene, carrying out heat preservation reaction for 2-3 hours, removing 3.6 parts of water brought out by reflux reaction, and conveying the cooled reflux solvent to the top of a packing tower by a circulating pump:
when the amount of the separated water is small, adding 2.5 parts of dodecanol, heating to 190 ℃ for reaction for 1 hour, heating to 200 ℃ for heat preservation reaction for 1 hour, and then heating to 210 ℃ for heat preservation reaction for 2-3 hours:
sampling, stopping adding nitrogen after the sample is qualified, cooling to below 150 ℃, adding 6.6 parts of solvent (butyl acetate), diluting, stirring for 20 minutes, filtering and packaging to obtain 90% solid alkyd resin E, wherein the performance results are shown in tables 1 and 2.
(2) Preparation of polyurethane coating E
Mixing 90% solid alkyd resin and TDI trihydroxy prepolymer prepared by Jia Bao Li company, and reacting the mixture with NCO: OH ═ 1: 1, preparing a light varnish, and then adding butyl acetate: xylene ═ 1: the diluent of 1 was diluted to a sprayable state (12-14S/coat-4 cups) to give polyurethane coating E, which was sprayed on 30CM by 20CM veneers, tested for dryness, and the VOC content at the time of spraying was calculated, the results are shown in table 3.
Experimental example 1
The properties of the alkyd polyester polyol prepolymers or alkyd resins of examples 1-3 and comparative examples 1-2 were tested, and the test standards or methods were as follows:
solid parts (%): GB/T2793;
acid value (mgKOH/g): GB/T2895;
viscosity (mPa. S/25 ℃ C.): GB/T2794; botiffei DV-1 rotational viscometer;
hydroxyl value (mgKOH/g): GB/12008;
molar equivalent: calculated by theory.
The test results are shown in table 1:
TABLE 1
Experimental example 2
The properties of the secondary amine modified alkyd resins or alkyd resins of examples 1-3 and comparative examples 1-2 were tested using the following test standards or methods:
solid parts (%): GB/T2793;
color number (Fe-Co): GB/T1722
Acid value (mgKOH/g): GB/T2895;
viscosity (mPa. S/25 ℃ C.): GB/T2794; botiffei DV-1 rotational viscometer;
hydroxyl value (mgKOH/g): GB/12008;
amine value (mgKOH/g): JIS K7237-.
The test results are shown in table 2:
TABLE 2
Experimental example 3
The paint film performance in examples 1 to 3 and comparative examples 1 to 2 was tested.
1-3 and comparative examples 1-2 of secondary amino modified alkyd resin or alkyd resin and TDI trihydroxy prepolymer L-75 (traditionally named as curing agent, 75% solid) manufactured by Jia Baoli corporation, wherein the molar ratio of NCO: OH ═ 1: 1, preparing a light varnish, and then adding butyl acetate: xylene ═ 1: the diluted water of 1 is diluted to be in a spraying state (12-14S/coating-4 cups), sprayed on a 30 CM-20 CM veneer, and tested for dryness, hardness and VOC content in a construction state, wherein the test environmental temperature is 25 +/-2 ℃, and the humidity is 50 +/-10%.
The evaluation method is as follows:
(1) the paint film dryness test is carried out according to the GB 1728 paint film and putty drying time measuring method standard.
(2) Paint film hardness test the test is carried out according to the GB 6739 color paint and varnish pencil method for determining the paint film hardness standard.
(3) The adhesion test was carried out according to the standard of the marking test for paint films of GB/T9286 paints and varnishes.
(4) VOC was measured according to the standard for determining the Volatile Organic Compound (VOC) content of coatings containing reactive diluents in GB/T34682.
The test results are shown in table 3:
TABLE 3
| Item | Watch (min) | Nut stem (h) | VOC g/L | Hardness of |
| Example 1 | 15.0 | 1.0 | 230 | H |
| Example 2 | 18.0 | 1.5 | 220 | H |
| Example 3 | 20.0 | 2.5 | 280 | 2H |
| Comparative example 1 | 120 | 20 | 270 | 2B |
| Comparative example 2 | 180 | 28 | 350 | B |
As can be seen from Table 3, when the secondary amino modified alkyd resin disclosed in the embodiments 1-3 of the invention is used for preparing a polyurethane coating, the construction VOC can be less than 300g/L, the secondary amino modified alkyd resin has great advantages in environmental protection, the hardness and dryness of the secondary amino modified alkyd resin also meet the application requirements in the field of PU wood paint, and the product disclosed by the invention completely meets the toxic and harmful substance limit standard of GB18581 interior decoration and finishing materials and the GB/T23997 interior decoration and finishing polyurethane coating standard, and is particularly suitable for application and popularization in the coating and coating of wood furniture.
According to the comparison example 1, if the alkyd polyester polyol prepolymer is directly used for preparing polyurethane coating without secondary amine group modification and applied to PU double-component coating, a single hydroxyl (-OH) active group reacts with polyurethane curing agent-NCO, the period time of a stereo macromolecule obtained by reaction is prolonged, so that the drying is slow, the molecular motion is restricted in the later reaction stage, the molecular weight of a paint film cannot be better expanded, and the paint film hardness is insufficient; in comparison with comparative example 2, it can be seen that if the alkyd resin is modified with soybean oil, the drying speed of the reaction between the low molecular weight alkyd resin and the polyurethane curing agent and the final crosslinking molecular weight cannot be improved, the drying speed of the paint is slow, and the hardness of the paint film is insufficient.
The results shown in tables 1-3 are fully demonstrated that according to the technical scheme of the invention, the alkyd resin with high solid content, low viscosity and high activity can be obtained, and when the alkyd resin is used for preparing a two-component polyurethane coating, the drying speed and hardness of a paint film in a film forming process can be effectively ensured under a high solid content construction state, the using amount of a solvent can be reduced, the discharge of VOC (volatile organic compounds) is reduced, and the alkyd resin has a wide application prospect.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (11)
1. A secondary amino modified alkyd resin is characterized in that the preparation raw materials comprise:
an alkyd polyester polyol prepolymer and 3,3 '-dimethyl-4, 4' -diamino-dicyclohexylmethane;
the molar ratio of the alkyd polyester polyol prepolymer to the 3,3 '-dimethyl-4, 4' -diamino-dicyclohexylmethane is 2.5: 1-4.5: 1;
the alkyd polyester polyol prepolymer is prepared from the following raw materials in parts by weight: 20-30 parts of lauric acid, 5-10 parts of ethylene glycol, 20-35 parts of phthalic anhydride, 4-8 parts of benzoic acid, 2-10 parts of maleic anhydride, 4-12 parts of trimethylolpropane, 10-20 parts of pentaerythritol and 0.1-20 parts of an auxiliary agent;
the preparation method of the alkyd polyester polyol prepolymer comprises the following steps: mixing the lauric acid, the ethylene glycol, the phthalic anhydride, the benzoic acid, the maleic anhydride, the trimethylolpropane, the pentaerythritol and part of the auxiliary agent, reacting for 3-5 h at 152-156 ℃, heating to 210-220 ℃ for continuous reaction, cooling to below 180 ℃ when the acid value of the system is less than or equal to 15mgKOH/g, and then adding the rest of the auxiliary agent into the system.
2. The secondary amino-modified alkyd resin of claim 1, wherein the molar ratio of the alkyd polyester polyol prepolymer to the 3,3 '-dimethyl-4, 4' -diamino-dicyclohexylmethane is 2.5:1 to 4: 1.
3. The secondary amino-modified alkyd resin of claim 1, wherein the molar ratio of the alkyd polyester polyol prepolymer to the 3,3 '-dimethyl-4, 4' -diamino-dicyclohexylmethane is 2.5:1 to 3: 1.
4. The secondary amine modified alkyd resin of claim 1, wherein the alkyd polyester polyol prepolymer is prepared from the following raw materials in parts by weight:
22-26 parts of lauric acid, 6-8 parts of ethylene glycol, 25-30 parts of phthalic anhydride, 4-5 parts of benzoic acid, 4-8 parts of maleic anhydride, 5-10 parts of trimethylolpropane, 12-15 parts of pentaerythritol and 1-10 parts of an auxiliary agent.
5. The secondary amine-modified alkyd resin of claim 4, wherein the adjuvant is selected from at least one of a color reducing agent, a let-down solvent, and a water-carrying agent.
6. The secondary amino-modified alkyd resin of claim 5, wherein the color-reducing agent is selected from at least one of hypophosphorous acid and triphenyl phosphite.
7. The secondary amine-modified alkyd resin of claim 5, wherein the let-down solvent is selected from at least one of xylene and butyl acetate.
8. The secondary amine-modified alkyd resin of claim 5, wherein the water-carrying agent is selected from at least one of xylene and toluene.
9. The method for producing a secondary amino-modified alkyd resin according to any of claims 1 to 8, comprising the steps of:
mixing the alkyd polyester polyol prepolymer with 3,3 '-dimethyl-4, 4' -diamino-dicyclohexyl methane, reacting for 3-10 h at 110-130 ℃, and standing for 20-30 days.
10. The method of preparing a secondary amine-modified alkyd resin according to claim 9, comprising the steps of:
dropwise adding 3,3 '-dimethyl-4, 4' -diamino-dicyclohexyl methane into the alkyd polyester polyol prepolymer at the temperature of 50-100 ℃, wherein the dropwise adding time is 1-3 h; after the dropwise addition is finished, reacting for 3-10 h at the temperature of 110-130 ℃, and standing for 20-30 days.
11. Use of a secondary amine modified alkyd resin according to any of claims 1 to 8 in the preparation of a two-component polyurethane coating.
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