CN103739800A - Film forming matter for phenolic resin paint and preparation method of film forming matter - Google Patents
Film forming matter for phenolic resin paint and preparation method of film forming matter Download PDFInfo
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- CN103739800A CN103739800A CN201410016050.9A CN201410016050A CN103739800A CN 103739800 A CN103739800 A CN 103739800A CN 201410016050 A CN201410016050 A CN 201410016050A CN 103739800 A CN103739800 A CN 103739800A
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Abstract
The invention relates to a film forming matter for phenolic resin paint. The film forming matter comprises the following raw materials in percentage by mass: 4.0-6.0% of styrene, 3.0-5.0% of butyl acrylate, 8.0-10.0% of glycidyl methacrylate, 3.0-5.0% of hexafluorobutyl acrylate, 0.04-0.06% of initiator, 0.02-0.05% of 1-docosanethiol, 9.0-12.0% of rosin, 6.0-8.0% of phenol, 2.0-3.0% of paraformaldehyde, 0.03-0.05% of H accelerant, 8.0-10.0% of linoleic acid, 10.0-12.0% of soya oil acid and the balance of 100#-2 solvent. The film forming matter for the phenolic resin paint, disclosed by the invention, has the characteristics of rapid dryness, good water resistance, chemical resistance, stain resistance and weather resistance, high hardness, controllability in reaction speed and reaction endpoint and low cost.
Description
Technical field
The present invention relates to a kind of phenolic resin coating film forming matter and preparation method thereof, belong to phenolic resin paint technical field.
Background technology
Phenolic resin coating is one of kind that in coatings industry, production history is the longest, the polymkeric substance that it mainly obtains through refining take resol or modified phenolic resins and dry vegetable oil (tung oil, flax wet goods), as film forming matter, coordinates the modulation such as various face, filler, metallic soap drier, solvent to form.In today, although various synthetic resin paints are widely used, but phenolic resin paint is still with features such as higher cost performance and fabulous application properties, in occupation of larger Coating Market share, according to relevant authoritative department statistics, the phenolic resin paint output of the above paint of China's scale manufacturing concern production in 2012 reaches more than 300,000 tons, the output value surpasses 3,000,000,000, be one of maximum at present paint kind, by industries such as building, traffic, machinery, hardware & tools, wood furnitures, adopted in a large number.
At present, along with the fast development of the various high-performance synthetic resin paints such as epoxy coating, polyurethane coating, acrylic coating, phenolic resin coating will obtain synchronized development, just must improve the quality and performance of its product, especially at aspects such as rate of drying, water-fast, resistant to chemical media, hardness, be improved raising; Improve the quality and performance of phenolic resin coating, the crucial performance improving film-forming resin.Relevant resol and the coating such as current disclosed Chinese patent CN101899136A, CN101712739A, CN102372983A, great majority are performances that the performance by improving film forming matter is improved coating.And domestic paint manufacturers is when producing phenolic resin coating and use film forming matter, generally adopt the production technique of heat refining method, be about to resol or rosin modified phenolic resin and dry vegetable oil etc. and carry out refining under 280～310 ℃ of conditions, make to occur between each component a series of very complicated chemical reactions, as reactions such as polymerization, oxygenolysis, transesterify, saponification, generate the high molecular polymer being cross-linked with each other together.But this is tempered technique and has more drawback, the period that is mainly manifested in reaction end is extremely short, conventionally at 2-10 minute, and the control of terminal is maked decision in the short period of time by rule of thumb by tempering operator, the quality of film forming matter is subject to the impact of human factor very large, as be less than reaction end and react with regard to premature termination, in film forming matter, can contain the inadequate rosin modified phenolic resin of more reaction, plant wet goods composition, make film forming matter inside have heterogeneous phenomenon, show as film forming matter outward appearance poor definition, therefore the phenolic resin coating of preparing with it will produce paint film and be clamminess, water tolerance, dryness, the quality problems such as difference of hardness.As arrived reaction end and there is no timely termination reaction, will cause film forming matter viscosity too high, painting need be added solvent, and will there is gelling when serious in the paint stability in storage variation of making, cause product rejection.
Summary of the invention
The object of this invention is to provide one, to have dryness fast, and water tolerance, chemical proofing, contamination resistance, weather resisteant is good, hardness is high, and speed of response and reaction end controlled, film forming matter and preparation method thereof for phenolic resin coating that cost is low.
The present invention is that the technical scheme achieving the above object is: a kind of phenolic resin coating film forming matter, is characterized in that: its raw material is comprised of the component of following mass percent, comprises
Wherein: described glycidyl methacrylate is the acrylate monomer that contains epoxy-functional.
Wherein: described initiator is peroxide initiator.
The polymerization degree n of described paraformaldehyde is 8～12.
The preparation method of film forming matter for phenolic resin coating of the present invention, is characterized in that: carry out according to the following steps, its raw material all by mass percentage,
1., the vinylformic acid hexafluoro butyl ester of 4.0～6.0% vinylbenzene, 3.0～5.0% butyl acrylate, 8.0～10.0% glycidyl methacrylate and 3.0～5.0% and 0.02～0.03% initiator are added to the high-order dropwise adding tank with stirrer, throwing is started stirrer after finishing, by even, stand-by abundant the prepolymer in high-order dropwise adding tank dispersed with stirring;
2., get with the 100#-2 solvent of prepolymer equal mass and add reactor, when starting stirrer on reactor to 100#-2 stirring solvent and being heated to 90 ± 2 ℃, be incubated, the prepolymer average rate in header tank is dropped in reactor, time for adding is controlled at 2 ± 0.05 hours, dropping finishes rear insulation reaction 1 ± 0.05 hour, disposable adding in reactor after 100#-2 dissolution with solvents by remaining initiator by 5 times of its quality, continue insulation reaction 2 ± 0.05 hours, while again feed liquid being heated to 115 ± 2 ℃, insulation reaction 2 ± 0.05 hours, at interval of 15 ± 0.2 minute feed liquid reactor in carried out to viscosity measurements thereafter, when the viscosity of sludge in reactor reaches 500～1000mPas/25 ℃ of scope, 0.02～0.05% n-dodecyl mercaptan is added in reactor, be incubated cooling after 30 ± 5 minutes and finish reaction, make fluorine-containing cinnamic acrylic ester polymkeric substance,
3., 9.0～12.0% rosin is added in another reactor, and be incubated that to rosin, by solid, all to be melted be liquid while being heated to 130～150 ℃, after starting stirrer and being stirred to evenly, add 6.0～8.0% phenol and stir after temperature be down to 80～90 ℃, add 2.0～3.0% paraformaldehyde and 0.03～0.05% H promotor, 4～6 hours post-heating of insulation reaction heat up, and steam gradually except moisture content in reactor by the heat-up rate of 10 ℃/h, while being again warming up to 130 ± 2 ℃, be incubated, and sampling detects intermediate fusing point, when intermediate fusing point reaches 60～80 ℃ of scopes, be cooled to below 80 ℃, linolenic acid 8.0～10.0% and 10.0～12.0% behenic acid and the fluorine-containing cinnamic acrylic ester polymkeric substance making add in reactor, while being heated to while stirring 150 ± 2 ℃, with 5 ℃ ± 0.5/h, slowly heat up, steadily carry out esterification polyreaction, and regularly except de-esterifying water, wherein the temperature of material in reactor is the highest must not exceed 190 ℃, esterification polyreaction is carried out 4 ± 0.05 hours, sampling detects the outward appearance of resin, acid number and viscosity, when resin outward appearance presents transparent limpid, acid number≤8 and viscosity are when 1500～3000mPas/25 ℃ of scope, termination reaction, resin is cooled to 150 ℃ below also with remaining 100#-2 solvent latting drown, after filtration, discharging makes phenolic resin coating film forming matter.
Phenolic resin coating of the present invention adopts distinctive formula system with film forming matter, because glycidyl methacrylate is the acrylate functional monomer that contains epoxy-functional, with epoxide group, there is higher reactive behavior, can with contain carboxyl, amido, the chemical substance of the functional groups such as isocyanato is carried out polyreaction, when glycidyl methacrylate and vinylbenzene, butyl acrylate and the polymerization of vinylformic acid hexafluoro butyl ester form fluorine-containing cinnamic acrylic ester polymkeric substance, make film forming matter there is good hardness, strengthen water-fast and chemical proofing and good snappiness and resistance to tanning by the sun property, and the contained hexafluoro butyl ester of fluorine-containing cinnamic acrylic ester polymer lateral chain group, giving the surface that polymkeric substance is lower can, have and improve the water-fast of film forming matter, anti-stain characteristic, the effects such as weather resisteant effect.The present invention plays the effect of Molecular regulator amount in acroleic acid polymerization by n-dodecyl mercaptan, speed of response and reaction end are controlled, the molecular weight that can effectively control polymkeric substance increases, and controls the molecular size range of polymkeric substance, can improve phenolic resin coating film forming matter yield rate.
Phenolic resin coating of the present invention with film forming matter take fluorine-containing styrene-propene acid polymer as main chain, with rosin modified phenolic resin, behenic acid, linolenic acid is side chain, the high molecular polymer of complete, there is speed of response and reaction end is controlled, polymer molecular structure is regular, narrow molecular weight distribution, the fluorin radical that contains some amount due to side chain, surperficial feature that can be lower, efficiently solve original phenolic resin coating with containing the more rosin modified phenolic resin fully not reacting in film forming matter, plant wet goods composition and inner occur heterogeneous disadvantage, in the dryness that improves phenolic resin coating, water tolerance, chemical proofing, weather resisteant, contamination resistance, in the performance basis such as hardness, can effectively avoid tempering some mass defects that phenolic resin coating film forming matter brings because terminal control is improper.
Phenolic resin coating of the present invention uses film forming matter in whole preparation process, due to double-bond polymerization reaction not occurring, therefore do not consume the unsaturated double-bond in vegetable oil acid, solving former heat refining method has two key copolyreaction to occur in preparation process, need the problem of the unsaturated double-bond that consumes some amount, therefore, although adopt linolenic acid and behenic acid combination in formula system of the present invention, but the dryness of film forming matter is still fine, adopt pure oleum lini phenolic resin coating processed film forming matter to there is certain cost advantage.
Embodiment
Phenolic resin coating film forming matter of the present invention, its raw material is comprised of the component of following mass percent, comprises 4.0～6.0% vinylbenzene, 3.0～5.0% butyl acrylate, 8.0～10.0% glycidyl methacrylate, 3.0～5.0% vinylformic acid hexafluoro butyl ester, 0.04～0.06% initiator, 0.02～0.05% n-dodecyl mercaptan, 9.0～12.0% rosin, 6.0～8.0% phenol, 2.0～3.0% paraformaldehyde, 0.03～0.05% H promotor, 8.0～10.0% linolenic acid, the 100#-2 solvent of 10.0～12.0% behenic acid and surplus, wherein, glycidyl methacrylate of the present invention is the acrylate monomer that contains epoxy-functional, this acrylate monomer with epoxide group, there is higher reactive behavior, therefore can with contain carboxyl, the chemical substance of the functional group such as amido and isocyanato is carried out polyreaction, and the present invention adopts Hubei Longma chemical company limited to manufacture the technical grade glycidyl methacrylate of producing.
The present invention is improved film forming matter hardness at phenolic resin coating with playing in film forming matter, is strengthened the effects such as water-fast, chemical proofing, as the general industry level vinylbenzene that adopts changzhou Xin Chemical Co., Ltd. to produce by vinylbenzene.
The present invention improves film forming matter snappiness and resistance to effect of tanning by the sun at phenolic resin coating with playing in film forming matter by butyl acrylate, as the general industry level butyl acrylate that can adopt Dongfang Chemical Plant, Beijing, The East Chemical Plant,Beijing to produce.
The present invention selects vinylformic acid hexafluoro butyl ester; because its fluorine content is high; and the contained hexafluoro butyl ester of the side chain group in film forming matter for phenolic resin coating; can there is " shielding protection " effect to high polymer main chain and inside; give the lower surface of polymkeric substance can, water-fast, the anti-stain characteristic, the weather resisteant effect that improve phenolic resin coating film forming matter.The general industry level vinylformic acid hexafluoro butyl ester that the present invention can adopt Harbin Xue Jiafu chemistry of silicones company limited to manufacture.
Initiator of the present invention is peroxide initiator, is applicable to high solid low viscosity propylene acid resin synthetic, Trigonox42 or Trigonox42S or the Trigonox21S etc. that can adopt Tianjin Akzo Nobel's superoxide company limited to provide.
The present invention plays the effect of Molecular regulator amount by n-dodecyl mercaptan in acroleic acid polymerization reaction, and the molecular weight that therefore can effectively control polymkeric substance increases, and reaches the object of the molecular size range of controlling polymkeric substance, the steady quality of film forming matter.The general industry level n-dodecyl mercaptan that the present invention can select Guangzhou He Shi wall chemical materials company limited to manufacture
Its acid number >=166mgHOH/g of the rosin that the present invention selects, because rosin is a kind of unsaturated acid, contains conjugated double bond, therefore can occur 1 with phenol formaldehyde resin of the present invention, 4 addition reactions, therefore can improve oil soluble, the hardness of phenolic resin coating film forming matter, the general industry level rosin that the present invention can adopt Youxi County, Fujian Province Heng Yuan Chemical Co., Ltd. to manufacture.
The present invention has hyperergy, polyfunctionality feature by phenol, and as the chief component of resol of the present invention, as the general industry level phenol that adopts Beijing Yanshan Petrochemical company limited to manufacture.
Its polymerization degree n of paraformaldehyde of the present invention is 8～12, the present invention utilizes paraformaldehyde have hyperergy feature and phenol polycondensation and form resol, and both can reduce in the mill the energy consumption of dehydration, and can greatly reduce again wastewater treatment capacity, there is good manufacturability.The general industry level paraformaldehyde that the present invention can adopt Shanghai solvent factory to manufacture.
H promotor of the present invention can promote the condensation reaction of phenol and formaldehyde, and generation molecular chain two ends exist the resol of methylol.The general industry level H promotor that can adopt Jinan Kang Sheng Chemical Co., Ltd. to manufacture.
The linolenic acid that the present invention selects belongs to dryness oleic acid, therefore contain more unsaturated double-bond, has normal temperature Quick Oxidation film forming properties in air, therefore can give phenolic resin coating film forming matter and have the fast feature of dryness.The general industry level linolenic acid that can adopt Anhui Rui Fen get grease deep processing company limited to manufacture.
The behenic acid that the present invention selects belongs to semi-drying oleic acid, and the unsaturated double-bond that it contains some amount has normal temperature oxidation film forming properties in air, the general industry level behenic acid that can adopt Nanjing born grease company limited to manufacture.
The 100#-2 solvent that the present invention selects is industrial raw material, has good solvency power, and moderate rate of volatilization is the good solvent of manufacturing natural oil lipid paint, as the 100#-2 solvent that adopts Hua Lun chemical plant, Yangzhou, Jiangsu to manufacture.
Phenolic resin coating of the present invention is used its concrete raw material of film forming matter by mass percentage, in Table 1,
Table 1
The preparation method of film forming matter for phenolic resin coating of the present invention, carries out according to the following steps, and its raw material is all by shown in table 1,
1., the initiator of vinylbenzene, butyl acrylate, glycidyl methacrylate and vinylformic acid hexafluoro butyl ester and 0.02～0.03% is added to the high-order dropwise adding tank with stirrer, throwing is started stirrer after finishing, by even, stand-by abundant the prepolymer in high-order dropwise adding tank dispersed with stirring;
2., get with the 100#-2 solvent of prepolymer equal mass and add reactor, when starting stirrer on reactor to 100#-2 stirring solvent and being heated to 90 ± 2 ℃, be incubated, the prepolymer average rate in header tank is dropped in reactor, time for adding is controlled at 2 ± 0.05 hours, dropping finishes rear insulation reaction 1 ± 0.05 hour, disposable adding in reactor after 100#-2 dissolution with solvents by remaining initiator by 5 times of its quality, continue insulation reaction 2 ± 0.05 hours, while again feed liquid being heated to 115 ± 2 ℃, insulation reaction 2 ± 0.05 hours, at interval of 15 ± 0.2 minute feed liquid reactor in carried out to viscosity measurements thereafter, when the viscosity of sludge in reactor reaches 500～1000mPas/25 ℃ of scope, n-dodecyl mercaptan is added in reactor, be incubated cooling after 30 ± 5 minutes and finish reaction, make fluorine-containing cinnamic acrylic ester polymkeric substance,
3., rosin is added in another reactor, and be incubated that to rosin, by solid, all to be melted be liquid while being heated to 130～150 ℃, after starting stirrer and being stirred to evenly, add phenol and stir after temperature be down to 80～90 ℃, add paraformaldehyde and H promotor, 4～6 hours post-heating of insulation reaction heat up, and steam gradually except moisture content in reactor by the speed of 10 ℃/h, while being again warming up to 130 ± 2 ℃, be incubated, and sampling detects intermediate fusing point, when intermediate fusing point reaches 60～80 ℃ of scopes, be cooled to below 80 ℃, linolenic acid and behenic acid are added in reactor with the fluorine-containing cinnamic acrylic ester polymkeric substance making, while being heated to while stirring 150 ± 2 ℃, with 5 ℃ ± 0.5/h, slowly heat up, steadily carry out esterification polyreaction, and regularly except de-esterifying water, wherein the temperature of material in reactor is the highest must not exceed 190 ℃, esterification polyreaction is carried out 4 ± 0.05 hours, sampling detects the outward appearance of resin, acid number and viscosity, when resin outward appearance presents transparent limpid, acid number≤8 and viscosity are when 1500～3000mPas/25 ℃ of scope, termination reaction, resin is cooled to 150 ℃ below also with remaining 100#-2 solvent latting drown, after filtration, discharging makes phenolic resin coating film forming matter.
Adopt urea formaldehyde paint film forming matter of the present invention to prepare F01-1 phenolic varnish, by GB/T25253-2010 < < phenolic resin paint > > standard, carry out Performance Detection.Be shown in Table 2, its over-all properties has had very large lifting, meets or exceeds the technical requirements of GB/T25253-2010 < < phenolic resin paint > > standard completely.
Table 2
| Test item | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| At condition in container | Be uniform state | Be uniform state | Be uniform state | Be uniform state | Be uniform state | Be uniform state | Be uniform state |
| Former paint color/number | 12 | 11 | 12 | 11 | 11 | 12 | 11 |
| Elution time (ISO6 cup)/s | 68 | 63 | 72 | 75 | 71 | 65 | 68 |
| Non-volatile content/% | 46.8 | 47.2 | 46.8 | 48.0 | 47.0 | 46.5 | 47.5 |
| Skinning (48h) | Not skinning | Not skinning | Not skinning | Not skinning | Not skinning | Not skinning | Not skinning |
| Application property | Brush accessible | Brush accessible | Brush accessible | Brush accessible | Brush accessible | Brush accessible | Brush accessible |
| Paint film appearance | Smooth | Smooth | Smooth | Smooth | Smooth | Smooth | Smooth |
| Surface drying/hour | 4.0 | 3.5 | 4.0 | 4.5 | 3.5 | 4.0 | 3.5 |
| Do solid work/hour | 13.0 | 15 | 14.5 | 14.5 | 13.5 | 14.0 | 14.5 |
| Hardness | 0.41 | 0.38 | 0.36 | 0.39 | 0.39 | 0.40 | 0.37 |
| Sticking power/level | 1 | 2 | 1 | 1 | 2 | 1 | 1 |
| Snappiness/mm | 2 | 2 | 1 | 2 | 2 | 2 | 1 |
| Gloss (60 °)/unit value | 87 | 86 | 88 | 86 | 87 | 85 | 87 |
| Water tolerance/8h | Without abnormal | Without abnormal | Without abnormal | Without abnormal | Without abnormal | Without abnormal | Without abnormal |
Claims (4)
1. a phenolic resin coating film forming matter, is characterized in that: its raw material is comprised of the component of following mass percent, comprises
Wherein: described glycidyl methacrylate is the acrylate monomer that contains epoxy-functional.
2. phenolic resin coating film forming matter according to claim 1, is characterized in that: described initiator is peroxide initiator.
3. phenolic resin coating film forming matter according to claim 1, is characterized in that: the polymerization degree n of described paraformaldehyde is 8～12.
4. the preparation method with film forming matter according to phenolic resin coating described in claim 1, is characterized in that: carry out according to the following steps, its raw material all by mass percentage,
1., the vinylformic acid hexafluoro butyl ester of 4.0～6.0% vinylbenzene, 3.0～5.0% butyl acrylate, 8.0～10.0% glycidyl methacrylate and 3.0～5.0% and 0.02～0.03% initiator are added to the high-order dropwise adding tank with stirrer, throwing is started stirrer after finishing, by even, stand-by abundant the prepolymer in high-order dropwise adding tank dispersed with stirring;
2., get with the 100#-2 solvent of prepolymer equal mass and add reactor, when starting stirrer on reactor to 100#-2 stirring solvent and being heated to 90 ± 2 ℃, be incubated, the prepolymer average rate in header tank is dropped in reactor, time for adding is controlled at 2 ± 0.05 hours, dropping finishes rear insulation reaction 1 ± 0.05 hour, disposable adding in reactor after 100#-2 dissolution with solvents by remaining initiator by 5 times of its quality, continue insulation reaction 2 ± 0.05 hours, while again feed liquid being heated to 115 ± 2 ℃, insulation reaction 2 ± 0.05 hours, at interval of 15 ± 0.2 minute feed liquid reactor in carried out to viscosity measurements thereafter, when the viscosity of sludge in reactor reaches 500～1000mPas/25 ℃ of scope, 0.02～0.05% n-dodecyl mercaptan is added in reactor, be incubated cooling after 30 ± 5 minutes and finish reaction, make fluorine-containing cinnamic acrylic ester polymkeric substance,
3., 9.0～12.0% rosin is added in another reactor, and be incubated that to rosin, by solid, all to be melted be liquid while being heated to 130～150 ℃, after starting stirrer and being stirred to evenly, add 6.0～8.0% phenol and stir after temperature be down to 80～90 ℃, add 2.0～3.0% paraformaldehyde and 0.03～0.05% H promotor, 4～6 hours post-heating of insulation reaction heat up, and steam gradually except moisture content in reactor by the heat-up rate of 10 ℃/h, while being again warming up to 130 ± 2 ℃, be incubated, and sampling detects intermediate fusing point, when intermediate fusing point reaches 60～80 ℃ of scopes, be cooled to below 80 ℃, linolenic acid 8.0～10.0% and 10.0～12.0% behenic acid and the fluorine-containing cinnamic acrylic ester polymkeric substance making add in reactor, while being heated to while stirring 150 ± 2 ℃, with 5 ℃ ± 0.5/h, slowly heat up, steadily carry out esterification polyreaction, and regularly except de-esterifying water, wherein material in reactor temperature is the highest must not exceed 190 ℃, esterification polyreaction is carried out 4 ± 0.05 hours, sampling detects the outward appearance of resin, acid number and viscosity, when resin outward appearance presents transparent limpid, acid number≤8 and viscosity are when 1500～3000mPas/25 ℃ of scope, termination reaction, resin is cooled to 150 ℃ below also with remaining 100#-2 solvent latting drown, after filtration, discharging makes phenolic resin coating film forming matter.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102358815A (en) * | 2011-07-25 | 2012-02-22 | 上海电动工具研究所 | One-component self-drying acrylic acid grafted epoxy ester aqueous dispersion coating and its preparation method |
| CN103102446A (en) * | 2013-03-01 | 2013-05-15 | 湖北乾兴化工有限公司 | Hydroxylated acrylic resin for automobile refinishing varnish and preparation method of hydroxylated acrylic resin |
| WO2013092541A1 (en) * | 2011-12-21 | 2013-06-27 | Akzo Nobel Coatings International B.V. | Solvent-based coating compositions |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102358815A (en) * | 2011-07-25 | 2012-02-22 | 上海电动工具研究所 | One-component self-drying acrylic acid grafted epoxy ester aqueous dispersion coating and its preparation method |
| WO2013092541A1 (en) * | 2011-12-21 | 2013-06-27 | Akzo Nobel Coatings International B.V. | Solvent-based coating compositions |
| CN103102446A (en) * | 2013-03-01 | 2013-05-15 | 湖北乾兴化工有限公司 | Hydroxylated acrylic resin for automobile refinishing varnish and preparation method of hydroxylated acrylic resin |
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