CN106397689A - Petroleum resin modification catalyst as well as preparation method and application method - Google Patents

Petroleum resin modification catalyst as well as preparation method and application method Download PDF

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Publication number
CN106397689A
CN106397689A CN201610804670.8A CN201610804670A CN106397689A CN 106397689 A CN106397689 A CN 106397689A CN 201610804670 A CN201610804670 A CN 201610804670A CN 106397689 A CN106397689 A CN 106397689A
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petroleum resin
catalyst
modified
petropols
peroxide
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CN201610804670.8A
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Chinese (zh)
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CN106397689B (en
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邹磊
宋自旗
程霜莉
王胤晰
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东莞昶丰新材料科技有限公司
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F289/00Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/28Oxygen or compounds releasing free oxygen
    • C08F4/32Organic compounds
    • C08F4/34Per-compounds with one peroxy-radical
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/72Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D151/00Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds

Abstract

The invention relates to the field of petroleum resin processing and in particular relates to a petroleum resin modification catalyst as well as a preparation method and an application method. The petroleum resin modification catalyst is prepared from a peroxide main catalyst, an organic tin type cocatalyst and an imidazoles catalysis stabilizing agent; the catalytic efficiency is high; compared with that of single utilization of the peroxide main catalyst, the catalytic efficiency is improved by at least 50 percent; the purity of a catalysate is high and the catalysate does not need to be decompressed again for fractionating impurities; the petroleum resin modification catalyst provided by the invention is utilized and the compatibility of modified petroleum resin and nitro-lacquer is extremely high; the petroleum resin modification catalyst can be used for preparing the nitro-lacquer with high mechanical strength; in recent years, the price of maleic acid modified rosin resin is about 13500yuan/ton; however, the price of the petroleum resin modified by a modification method provided by the invention is 7000yuan/ton to 9500yuan/ton, so that the production cost is greatly reduced.

Description

A kind of petroleum resin modified catalyst and preparation method and application method
Technical field
The present invention relates to Petropols manufacture field and in particular to a kind of petroleum resin modified catalyst and preparation method and Application process.
Background technology
In prior art, nitrate paint paints as a time-honored class wood furniture and finishing, has extensive city , although its contained solid comparison of ingredients is low, solvent load ratio is larger, and its solvent is mainly with to environment close friend's relatively Based on alcohol, esters, relatively larger to environmental disruption aromatic hydrocarbons are less, are therefore widely used in the application of pure woodwork, especially exist America and Europe occupies the absolute share in household coating material market.But inventor find, in the film forming matter of nitrate paint animi resin be to Give the crucial material of lacquer painting hardness, glossiness and polishing performance, and each component due to this material demand and nitrate paint There is the goodish compatibility, therefore most of producer is all using the relatively costly but strong maleic acid modified rosin tree of the compatibility Fat.
Inventor seeking a kind of resin that can replace maleic acid modified rosin resin reduces cost always although Petropols are gained the name for petroleum derivatives because of source, and it has, and acid number is low, and compatibility is good, water-fast, resistance to ethanol and chemicals-resistant Etc. characteristic, there is to soda acid chemically stable, and have the characteristics that regulation viscosity and heat stability are good and cheap, can be extensive For multiple industry such as rubber, adhesive, coating, papermaking, ink and field, but simple Petropols cannot be with nitrate paint Middle other components are compatible well, constrain the development of the high-end nitrate paint with Petropols as raw material.
For solving the problems, such as that Petropols cannot be compatible with other components in nitrate paint, it is badly in need of a kind of modification of Petropols Method.
The patent of invention of Patent No. 201110116550.6 discloses a kind of preparation of maleic anhydride grafted petroleum resin Method, belongs to organic polymer field, for solving the problems, such as poor compatibility in wood plastic composite.Its technical scheme is:Will Petropols, maleic anhydride rising temperature for dissolving, Deca initiator between 100~200 DEG C, time for adding is 0.5~1h, drips React 0.5~4h after one-tenth, then extract remaining maleic anhydride under vacuum conditions, obtain modified petroleum resin product.This Product is used in wood plastic composite, can significantly improve dispersion in plastic substrate for the wood powder, thus improving wood plastic composite Mechanical property, obtain the wood plastic composite of excellent performance.But because using traditional initiator, catalytic effect is paid no attention to Think, or even subsequently also need to vacuum distillation to remove maleic anhydride, and the process of vacuum distillation can make modified Petropols occur Polymerization, the side reaction product of generation can reduce the compatibility of Petropols.
For this be badly in need of a kind of high catalytic efficiency, catalysis after substantially no modified monomer residual modified catalyst.
Content of the invention
The purpose of the present invention is for above-mentioned deficiency of the prior art, provides a kind of high catalytic efficiency, basic after catalysis No petroleum resin modified catalyst of modified monomer residual and preparation method thereof, and provide one kind using this catalyst to oil tree Fat is modified improving its petroleum resin modified method with nitrate paint COMPONENTS COMPATIBILITY.
The purpose of the present invention is achieved through the following technical solutions:
A kind of petroleum resin modified catalyst is steady by the catalysis of peroxide major catalyst, organic tin promoter and imidazoles Determine agent composition.Make although being used alone peroxide major catalyst and the graft modification of Petropols being served with certain catalysis With, but its consumption, greatly it is impossible to complete addition modification monomer, therefore adds organic tin promoter and dramatically enhances The catalytic effect of peroxide major catalyst, and add imidazoles catalysis stabilizer so that modified-reaction is tended towards stability, prevent from reacting Too drastic generation side reaction product or infringement health, catalytic efficiency uses peroxide major catalyst to improve at least than merely 50%.
Wherein, described peroxide major catalyst is dibenzoyl peroxide, cumyl peroxide, peroxidating first and second Ketone, cyclohexanone peroxide, peroxidating 2, at least one in 4- pentanedione, preferably cumyl peroxide;Peroxidating owner Catalyst is the class compound containing peroxy (O O), O O bond fission after being heated, and splits into two accordingly Free radical, thus multiple grafting sites are formed on Petropols chain, realize and the grafting of modified monomer.And peroxide is sponsored The selection of agent needs to consider the activity of its different temperatures, because in petroleum resin modified course of reaction, most of mistake Oxide major catalyst should be consumed, and peroxide major catalyst also can cause polyreaction in modifying process, generates Side reaction product with Petropols poor compatibility.Present inventor passes through practice contrast many times, adjusts compound ligand System, preferably goes out and is dissolved in the half-life in benzene:171℃:1min, 117 DEG C:10h, 101 DEG C:The cumyl peroxide of 100h, this mistake Oxide is not easily decomposed during petroleum resin modified, high conversion rate, and can effectively improve the percent grafting of Petropols, with Organotin compounds good.
Described organic tin promoter is lauryl mercaptan dibutyl tin, dibutyl tin laurate, two (dodecyls Sulfur) dibutyl tin, stannous octoate, at least one in dibutyltin diacetate, preferably dibutyl tin laurate;Organotin Class promoter can effectively reduce the temperature requirements of graft reaction, and peroxide major catalyst forms big point in resin backbone Sub- free radical, under the effect of organic tin promoter, promotes the graft reaction of modified monomer and resin side chain, and further , make to crosslink reaction between side chain, form cancellated modified petroleum resin, but due to being mixed into modified monomer, greatly The big compatibility improving Petropols and nitro paint ingredients.Organic tin promoter is answered with peroxide major catalyst Join pattern and greatly increase reaction efficiency and the consumption rate of peroxide and the percent grafting of final products.Because sterically hindered Impact to catalysis activity reduces with the rising of temperature, replaces the less group of steric hindrance with the larger alkyl of steric hindrance, can make Organo-tin compound has higher stability, resistant to hydrolysis and has delay catalysis activity, for example replaces two with dioctyl tin Butyl tin, can play delay catalytic action.Replace dibutyltindilaurylmercaptide osmanthus with dialkyl tin dimaleate, two mercaptan tin alkyls Acid esters, can improve hydrolytic stability.Stannum mercaptide containing big alkyl group has high stability and postpones two kinds of work(of catalysis Can, such as mercaptan dioctyl tin etc..And present inventor is in order that graft reaction high catalytic efficiency, preferably by February Dilaurylate, and using imidazoles catalysis compound stabilizer so as to catalytic effect tends towards stability.
Described imidazoles catalysis stabilizer is 2-methylimidazole, 2- mercapto benzimidazole, 2-ethyl-4-methylimidazole, At least one in 2- phenylimidazole, preferably 2-methylimidazole.Imidazoles catalysis stabilizer has been widely used as in asphalt mixtures modified by epoxy resin The firming agent of fat, but their mechanisms of action during curing reaction but understand seldom.In the present invention, using imidazoles Catalysis stabilizer can act on peroxide major catalyst and organic tin co-catalyst system, makes catalytic reaction excessively not sharp Strong, the generation of suppression side reaction, ensure that peroxide major catalyst is sufficiently consumed in process of grafting.
Wherein, described peroxide major catalyst, organic tin promoter and imidazoles are catalyzed the weight ratio of stabilizer Example is 10:10-5:10-1, preferably part by weight are 1:1:1.Limit the compound proportion of catalyst system and catalyzing further, strengthen them Synergism, reduces cost, improve production efficiency.
Present invention also offers the preparation method of this kind of petroleum resin modified catalyst:By peroxide major catalyst, have Machine stannum class promoter and imidazoles catalysis stabilizer physical agitation mixing, are obtained the described petroleum resin modified catalysis of one kind Agent.
Present invention also offers the application process of this kind of petroleum resin modified catalyst, comprise the steps:
(1)Choose Petropols and melt so as to heat up;
(2)Sequentially add modified monomer toward in the Petropols of melting and petroleum resin modified catalyst carries out graft modification, obtain To corresponding modified resin.
Wherein, described modified monomer be maleic anhydride, at least one in fumaric acid monomer and acrylic monomerss, described change Property monomer consumption be Petropols 1wt%-15wt% it is preferable that be 5wt%.The application is entered using multiple modified monomers Row graft modification, in actual mechanical process, need to give different graft reaction temperature according to the property of monomer(Less than modification The boiling point of monomer), when such as using acrylic monomerss, graft reaction temperature need to be controlled to be 130-150 DEG C.And the application passes through limit Determine the ratio of modified monomer and Petropols it is ensured that the percent grafting of reaction, and due to using compounding catalyst system and catalyzing, follow-up locate Reason can not adopt vacuum fractionation to remove unreacted modified monomer, and in other words, the consumption rate of modified monomer is high, wherein to add Enter the peroxide major catalyst Expenditure Levels that amount is 5wt% optimal.
Wherein, the consumption of described petroleum resin modified catalyst is the 0.8wt%-1.0wt% of Petropols, described oil tree In the Petropols adding described melting in batches of fat modified catalyst, each addition is the 0.2- of Petropols 0.4wt%, it is therefore preferable to 0.2wt%, adds once every 30-40min.The present invention adopts catalyst in increments to add, it is possible to increase Catalytic efficiency reduces cost, and easily controllable reaction process, make peroxide major catalyst crack out enough freedom Base, forms multiple grafting sites in Petropols, and then forms a plurality of side chain, is cross-linked into the net high with nitrate paint COMPONENTS COMPATIBILITY Shape structure.
Wherein, described step(1)Petrochina resin heats up the temperature melting for 100-200 DEG C, described step(2)Middle grafting In modification, the temperature of resin is less than temperature 10-30 DEG C of the melting that heats up, and in described graft modification, the temperature of resin is less than and changes The boiling point of property monomer.Differ in the source of the raw material of Petropols, different manufacturers or same producer use different material, different work That skill draws even the consistent resin of appearance characteristics there is also the inconsistent situation of chemical constitution, therefore need according to different oil Resin adjusts the temperature of its melting that heats up.And the graft reaction initial stage, reaction can produce substantial amounts of water and release substantial amounts of heat, in order to Ensure that moisture smoothly flows out, avoid moisture to take away product again, temperature also to be prevented is too high to react too fast, generates unnecessary by-product Product, therefore need to control the temperature of resin in graft modification, and the temperature preferably controlling resin in graft modification is molten less than heating up 20 DEG C of the temperature melted, it is to avoid reaction temperature fluctuates excessive and produces the low side reaction product of multiple compatibilitys.
Wherein, described Petropols are C9 resin, and described modified monomer is maleic anhydride, described step(1)Petrochina tree Fat heats up the temperature melting for 170-180 DEG C, described step(2)In middle graft modification, the temperature of resin is less than 190 DEG C.Commercially available Petropols be obtained by the by-product of petroleum refining, be roughly divided into that carbon five is polymerized, carbon nine is polymerized, C 5/C nine copolymerization, DCPD Four big class such as polymerization, and due to need to be compatible with other components in nitrate paint, the animi resin of needs also must be have similar aromatic ring and Can addition product, be therefore more suitable in nitrate paint using C9 is petroleum resin modified, and further select maleic anhydride conduct Modified monomer, controlling reaction temperature condition, the modified C9 Petropols being finally obtained are high with the nitrate paint compatibility, and corresponding nitre Lacquer product has good paint film property(As tack, hardness, pliability).
Wherein, described step(1)And step(2)Carry out all in atmosphere, described atmosphere can for nitrogen or Carbon dioxide.
Beneficial effects of the present invention:1st, a kind of petroleum resin modified catalyst, high catalytic efficiency, catalytic efficiency ratio are provided Peroxide major catalyst is used merely to improve at least 50%, catalysate purity is high, need not go out decontamination by vacuum fractionation again; The 2nd, the preparation method of this kind of petroleum resin modified catalyst is provided, simple and practical, it is easy to industrialized production;3rd, provide a kind of stone The method of modifying of oleoresin, using the petroleum resin modified catalyst of the present invention, makes modified Petropols and nitrate paint phase Capacitive is high, and can be used in producing the nitrate paint of high mechanical properties, and the price of maleic acid modified rosin resin exists in recent years 13500 yuan/ton about, and utilize the modified Petropols price of method of modifying of the present invention to be 7000-9500 yuan/ton, significantly Reduce production cost.
Specific embodiment
The invention will be further described with the following Examples.
Embodiment 1
The modified petroleum resin of the present embodiment is prepared by following steps:
(1)Choose C9 Petropols and melt so as to heat up;
(2)Sequentially add modified monomer toward in the Petropols of melting and petroleum resin modified catalyst carries out graft modification, obtain To corresponding modified resin.
Wherein, described modified monomer is maleic anhydride, and the consumption of described modified monomer is the 5wt% of Petropols.
Wherein, the consumption of described petroleum resin modified catalyst is the 0.8wt% of Petropols, described petroleum resin modified In the Petropols adding described melting in batches of catalyst, each addition is the 0.2wt% of Petropols, every 30min Add once.
Wherein, described step(1)Petrochina resin heats up the temperature melting for 170 DEG C, described step(2)Middle graft modification The temperature of middle resin is less than 190 DEG C of the temperature of the melting that heats up.
Wherein, described step(1)And step(2)Carry out all in atmosphere, described atmosphere is nitrogen.
Wherein, described petroleum resin modified catalyst pass through by peroxide major catalyst, organic tin promoter and Imidazoles catalysis stabilizer physical agitation is mixed to prepare.
Wherein, described peroxide major catalyst is cumyl peroxide;Described organic tin promoter is February Dilaurylate;Described imidazoles catalysis stabilizer is 2-methylimidazole;Described peroxide major catalyst, organic tin help The part by weight of catalyst and imidazoles catalysis stabilizer is 1:1:1.
Embodiment 2
The modified petroleum resin of the present embodiment is prepared by following steps:
(1)Choose C9 Petropols and melt so as to heat up;
(2)Sequentially add modified monomer toward in the Petropols of melting and petroleum resin modified catalyst carries out graft modification, obtain To corresponding modified resin.
Wherein, described modified monomer is maleic anhydride, and the consumption of described modified monomer is the 15wt% of Petropols.
Wherein, the consumption of described petroleum resin modified catalyst is the 1.0wt% of Petropols, described petroleum resin modified In the Petropols adding described melting in batches of catalyst, each addition is the 0.25wt% of Petropols, every 40min adds once.
Wherein, described step(1)Petrochina resin heats up the temperature melting for 180 DEG C, described step(2)Middle graft modification The temperature of middle resin is less than 200 DEG C.
Wherein, described step(1)And step(2)Carry out all in atmosphere, described atmosphere is carbon dioxide.
Wherein, described petroleum resin modified catalyst pass through by peroxide major catalyst, organic tin promoter and Imidazoles catalysis stabilizer physical agitation is mixed to prepare.
Wherein, described peroxide major catalyst is cumyl peroxide;Described organic tin promoter is February Dilaurylate;Described imidazoles catalysis stabilizer is 2-methylimidazole;Described peroxide major catalyst, organic tin help The part by weight of catalyst and imidazoles catalysis stabilizer is 3:2:1.
Embodiment 3
The modified petroleum resin of the present embodiment is prepared by following steps:
(1)Choose C9 Petropols and melt so as to heat up;
(2)Sequentially add modified monomer toward in the Petropols of melting and petroleum resin modified catalyst carries out graft modification, obtain To corresponding modified resin.
Wherein, described modified monomer is maleic anhydride, and the consumption of described modified monomer is the 1wt% of Petropols.
Wherein, the consumption of described petroleum resin modified catalyst is the 0.9wt% of Petropols, described petroleum resin modified In the Petropols adding described melting in batches of catalyst, each addition is the 0.3wt% of Petropols, every 35min Add once.
Wherein, described step(1)Petrochina resin heats up the temperature melting for 160 DEG C, described step(2)Middle graft modification The temperature of middle resin is less than 180 DEG C.
Wherein, described step(1)And step(2)Carry out all in atmosphere, described atmosphere is nitrogen.
Wherein, described petroleum resin modified catalyst pass through by peroxide major catalyst, organic tin promoter and Imidazoles catalysis stabilizer physical agitation is mixed to prepare.
Wherein, described peroxide major catalyst is cumyl peroxide;Described organic tin promoter is February Dilaurylate;Described imidazoles catalysis stabilizer is 2-methylimidazole;Described peroxide major catalyst, organic tin help The part by weight of catalyst and imidazoles catalysis stabilizer is 2:2:1.
Embodiment 4
The modified petroleum resin of the present embodiment is prepared by following steps:
(1)Choose C9 Petropols and melt so as to heat up;
(2)Sequentially add modified monomer toward in the Petropols of melting and petroleum resin modified catalyst carries out graft modification, obtain To corresponding modified resin.
Wherein, described modified monomer is acrylic monomerss, and the consumption of described modified monomer is the 6wt% of Petropols.
Wherein, the consumption of described petroleum resin modified catalyst is the 0.8wt% of Petropols, described petroleum resin modified In the Petropols adding described melting in batches of catalyst, each addition is the 0.4wt% of Petropols, every 40min Add once.
Wherein, described step(1)Petrochina resin heats up the temperature melting for 120 DEG C, described step(2)Middle graft modification The temperature of middle resin is less than 140 DEG C.
Wherein, described step(1)And step(2)Carry out all in atmosphere, described atmosphere is nitrogen.
Wherein, described petroleum resin modified catalyst pass through by peroxide major catalyst, organic tin promoter and Imidazoles catalysis stabilizer physical agitation is mixed to prepare.
Wherein, described peroxide major catalyst is cumyl peroxide;Described organic tin promoter is February Dilaurylate;Described imidazoles catalysis stabilizer is 2-methylimidazole;Described peroxide major catalyst, organic tin help The part by weight of catalyst and imidazoles catalysis stabilizer is 2:1:1.
Embodiment 5
The modified petroleum resin of the present embodiment is prepared by following steps:
(1)Choose C9 Petropols and melt so as to heat up;
(2)Sequentially add modified monomer toward in the Petropols of melting and petroleum resin modified catalyst carries out graft modification, obtain To corresponding modified resin.
Wherein, described modified monomer is maleic anhydride, fumaric acid monomer and acrylic monomerss by weight 1:1:1 ratio is mixed The mixture closing, the consumption of described modified monomer is the 10wt% of Petropols.
Wherein, the consumption of described petroleum resin modified catalyst is the 1.0wt% of Petropols, described petroleum resin modified In the Petropols adding described melting in batches of catalyst, each addition be Petropols 0.2wt% it is therefore preferable to 0.2wt%, adds once every 30min.
Wherein, described step(1)Petrochina resin heats up the temperature melting for 115 DEG C, described step(2)Middle graft modification The temperature of middle resin is less than 130 DEG C.
Wherein, described step(1)And step(2)Carry out all in atmosphere, described atmosphere is nitrogen.
Wherein, described petroleum resin modified catalyst pass through by peroxide major catalyst, organic tin promoter and Imidazoles catalysis stabilizer physical agitation is mixed to prepare.
Wherein, described peroxide major catalyst is dibenzoyl peroxide, cumyl peroxide, methyl ethyl ketone peroxide By weight 1:1:The mixture of 1 mixing;Described organic tin promoter is lauryl mercaptan dibutyl tin, tin dilaurate two fourth Ji Xi, two (dodecyl sulfur) dibutyl tin by weight 1:1:The mixture of 1 mixing;Described imidazoles catalysis stabilizer is 2- Methylimidazole., 2- mercapto benzimidazole, 2-ethyl-4-methylimidazole by weight 1:1:The mixture of 1 mixing;Described peroxide The part by weight that compound major catalyst, organic tin promoter and imidazoles are catalyzed stabilizer is 10:7:2.
Embodiment 6
The modified petroleum resin of the present embodiment is prepared by following steps:
(1)Choose C9 Petropols and melt so as to heat up;
(2)Sequentially add modified monomer toward in the Petropols of melting and petroleum resin modified catalyst carries out graft modification, obtain To corresponding modified resin.
Wherein, described modified monomer is maleic anhydride, fumaric acid monomer by weight 2:The mixture of 1 ratio mixing, institute The consumption stating modified monomer is the 3wt% of Petropols.
Wherein, the consumption of described petroleum resin modified catalyst is the 0.8wt% of Petropols, described petroleum resin modified In the Petropols adding described melting in batches of catalyst, each addition is the 0.2wt% of Petropols, every 35min Add once.
Wherein, described step(1)Petrochina resin heats up the temperature melting for 150 DEG C, described step(2)Middle graft modification The temperature of middle resin is less than 160 DEG C.
Wherein, described step(1)And step(2)Carry out all in atmosphere, described atmosphere can for nitrogen or Carbon dioxide.
Wherein, described petroleum resin modified catalyst pass through by peroxide major catalyst, organic tin promoter and Imidazoles catalysis stabilizer physical agitation is mixed to prepare.
Wherein, described peroxide major catalyst be cumyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, Peroxidating 2, by weight 1 in 4- pentanedione:2:1:The mixture of 1 ratio mixing;Described organic tin promoter is February Dilaurylate, two (dodecyl sulfur) dibutyl tin, stannous octoate, dibutyltin diacetate by weight 2:1:1:1 ratio The mixture of example mixing;Described imidazoles catalysis stabilizer is 2-methylimidazole, 2- mercapto benzimidazole, 2- ethyl -4- first Base imidazoles, 2- phenylimidazole by weight 1:3:1:The mixture of 3 ratio mixing;Described peroxide major catalyst, organotin The part by weight of class promoter and imidazoles catalysis stabilizer is 5:3:2.
Embodiment 7
The modified petroleum resin of the present embodiment is prepared by following steps:
(1)Choose C9 Petropols and melt so as to heat up;
(2)Sequentially add modified monomer toward in the Petropols of melting and petroleum resin modified catalyst carries out graft modification, obtain To corresponding modified resin.
Wherein, described modified monomer is fumaric acid monomer and acrylic monomerss by weight 1:The mixture of 3 ratio mixing, The consumption of described modified monomer is the 4wt% of Petropols.
Wherein, the consumption of described petroleum resin modified catalyst is the 0.9wt% of Petropols, described petroleum resin modified In the Petropols adding described melting in batches of catalyst, each addition is the 0.3wt% of Petropols, every 33min Add once.
Wherein, described step(1)Petrochina resin heats up the temperature melting for 125 DEG C, described step(2)Middle graft modification The temperature of middle resin is less than 155 DEG C.
Wherein, described step(1)And step(2)Carry out all in atmosphere, described atmosphere is nitrogen.
Wherein, described petroleum resin modified catalyst pass through by peroxide major catalyst, organic tin promoter and Imidazoles catalysis stabilizer physical agitation is mixed to prepare.
Wherein, described peroxide major catalyst is cumyl peroxide, methyl ethyl ketone peroxide by weight 1:1 ratio The mixture of mixing;Described organic tin promoter is for lauryl mercaptan dibutyl tin, dibutyl tin laurate by weight 4:The mixture of 1 ratio mixing;Described imidazoles catalysis stabilizer is 2-methylimidazole, 2- phenylimidazole by weight 1:1 ratio The mixture of example mixing;Described peroxide major catalyst, organic tin promoter and imidazoles are catalyzed the weight of stabilizer Ratio is 10:9:9.
Embodiment 8
The modified petroleum resin of the present embodiment is prepared by following steps:
(1)Choose C9 Petropols and melt so as to heat up;
(2)Sequentially add modified monomer toward in the Petropols of melting and petroleum resin modified catalyst carries out graft modification, obtain To corresponding modified resin.
Wherein, described modified monomer is maleic anhydride and acrylic monomerss by weight 2:The mixture of 1 ratio mixing, institute The consumption stating modified monomer is the 9wt% of Petropols.
Wherein, the consumption of described petroleum resin modified catalyst is the 1.0wt% of Petropols, described petroleum resin modified In the Petropols adding described melting in batches of catalyst, each addition is the 0.2wt% of Petropols, every 38min Add once.
Wherein, described step(1)Petrochina resin heats up the temperature melting for 150 DEG C, described step(2)Middle graft modification The temperature of middle resin is less than 165 DEG C.
Wherein, described step(1)And step(2)Carry out all in atmosphere, described atmosphere is carbon dioxide.
Wherein, described petroleum resin modified catalyst pass through by peroxide major catalyst, organic tin promoter and Imidazoles catalysis stabilizer physical agitation is mixed to prepare.
Wherein, described peroxide major catalyst is dibenzoyl peroxide;Described organic tin promoter is 12 Dibutyltin mercaptide;Described imidazoles catalysis stabilizer is 2- phenylimidazole;Described peroxide major catalyst, organic tin help The part by weight of catalyst and imidazoles catalysis stabilizer is 10:5:1.
Comparative example 1-8
Successively with respect to embodiment 1-8, difference is that petroleum resin modified catalyst is cumyl peroxide to method and step.
Percent grafting test, the modified petroleum of embodiment 1-8 are carried out to the modified petroleum resin of embodiment 1-8, comparative example 1-8 The percent grafting of resin is 15%-20%, and yield is 90%-95%, and the percent grafting of the modified petroleum resin of comparative example 1-8 is 5%-10%, Yield is 80%-85%.This test shows, the high catalytic efficiency of the petroleum resin modified catalyst of the present invention, can effectively improve The percent grafting of Petropols, thus reach the purpose that Petropols replace rosin resin.
Embodiment 9-16
Successively with respect to embodiment 1-8, difference is that the Petropols chosen are C5 resin to method and step.
C9 Petropols resin 30% modified to nitrocotton 23%, organic solvent 47%, embodiment 1-8 is mixed dispersion Corresponding nitrate paint is obtained afterwards, and is applied on plank, being detected, performance is as shown in the table to the paint film after solidification
Project Index Test method
1st, paint film appearance Paint film flat smooth Range estimation
2nd, hardness(Double pendulum) ≥0.7 GB/T 1730 2007
3rd, pliability, mm ≤0.8 GB/T 1731 1993
4th, impact, cm ≥45 GB/T 1732 1993
5th, adhesive force(Draw circle), level ≤2 GB/T 1720 1979
As seen from the above table, it is applied to, using the modified C9 resin of the application method of modifying, the nitrate paint produced nitrate paint, produce There is good hardness, pliability, impact resistance and tack, and meet the requirement in GB 18583.Replaced using C9 resin Rosin resin, has not only surmounted rosin resin nitrate paint in performance, and cost reduces about 40-50%, and economic benefit is huge.
Finally it should be noted that above example is only in order to illustrating technical scheme, rather than the present invention is protected The restriction of shield scope, although having made to explain to the present invention with reference to preferred embodiment, those of ordinary skill in the art should Work as understanding, technical scheme can be modified or equivalent, without deviating from the reality of technical solution of the present invention Matter and scope.

Claims (10)

1. a kind of petroleum resin modified catalyst it is characterised in that:By peroxide major catalyst, organic tin promoter and Imidazoles catalysis stabilizer composition.
2. a kind of petroleum resin modified catalyst according to claim 1 it is characterised in that:Described peroxide main catalytic Agent is dibenzoyl peroxide, cumyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, peroxidating 2,4- pentanedione In at least one;
Described organic tin promoter is lauryl mercaptan dibutyl tin, dibutyl tin laurate, two (dodecyl sulfur) two At least one in butyl tin, stannous octoate, dibutyltin diacetate;
Described imidazoles catalysis stabilizer is 2-methylimidazole, 2- mercapto benzimidazole, 2-ethyl-4-methylimidazole, 2- benzene At least one in base imidazoles.
3. a kind of petroleum resin modified catalyst according to claim 1 it is characterised in that:Described peroxide main catalytic Agent is cumyl peroxide, and described organic tin promoter is dibutyl tin laurate, and described imidazoles catalysis is stable Agent is 2-methylimidazole.
4. a kind of petroleum resin modified catalyst according to claim 1 it is characterised in that:Described peroxide main catalytic Agent, organic tin promoter and imidazoles are catalyzed the weight of stabilizer ratio for 10:10-5:10-1.
5. a kind of petroleum resin modified catalyst described in claim 1-4 any one preparation method it is characterised in that:Will Peroxide major catalyst, organic tin promoter and imidazoles catalysis stabilizer stirring mixing, are obtained a kind of described stone Oleoresin modified catalyst.
6. a kind of petroleum resin modified catalyst described in claim 1-4 any one application process it is characterised in that:Bag Include following steps:
(1)Choose Petropols and melt so as to heat up;
(2)Sequentially add modified monomer toward in the Petropols of melting and petroleum resin modified catalyst carries out graft modification, obtain To corresponding modified resin.
7. a kind of petroleum resin modified catalyst according to claim 6 application process it is characterised in that:Described modification Monomer is at least one in maleic anhydride, fumaric acid monomer and acrylic monomerss, and the consumption of described modified monomer is oil tree The 1wt%-15wt% of fat.
8. a kind of petroleum resin modified catalyst according to claim 6 application process it is characterised in that:Described oil The consumption of resin modified catalyst is the 0.8wt%-1.0wt% of Petropols, and described petroleum resin modified catalyst in increments time adds Enter in the Petropols of described melting, each addition is the 0.2-0.4wt% of Petropols, adds once every 30-40min.
9. a kind of petroleum resin modified catalyst according to claim 6 application process it is characterised in that:Described step (1)Petrochina resin heats up the temperature melting for 100-200 DEG C, and in described graft modification, the temperature of resin is less than modified monomer Boiling point.
10. a kind of petroleum resin modified catalyst according to claim 6 application process it is characterised in that:Described stone Oleoresin is C9 resin, and described modified monomer is maleic anhydride, described step(1)Petrochina resin heat up melting temperature be 170-180 DEG C, described step(2))In middle graft modification, the temperature of resin is less than 190 DEG C.
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