CN103772614A - One-step method for preparing grafted polyolefin wax emulsion - Google Patents
One-step method for preparing grafted polyolefin wax emulsion Download PDFInfo
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Abstract
The invention provides a one-step method for preparing grafted polyolefin wax. The one-step method comprises the following steps: grafting a graft comonomer onto a polyolefin wax main chain according to a solid phase graft technology to obtain comonomer grafted polyolefin wax; feeding a resolvent to the comonomer grafted polyolefin wax to resolve unreacted unsaturated polar monomers and dimethyl benzene, removing the resolvent, feeding an emulsifier, pyrosulfite, water and alkali, stirring for mixing, and ensuring the temperature to be any temperature or in any temperature range of 160 DEG C to 180 DEG C for heat-insulating reaction to obtain a grafted polyolefin wax emulsion. The method has the advantages that the consumption of harm resolvent dimethyl benzene, operation time and cost are greatly reduced; compared with those in a common grafted product, free maleic anhydride and dimethyl benzene in the grafted polyolefin wax prepared according to the method are removed more easily and completely.
Description
Technical field
The present invention relates to a kind of method of modified polyolefin, relate in particular to a kind of method of preparing graft polyolefin wax emulsion.
Background technology
Polyolefine is because density is little, cost is low, plasticity-is strong, and has certain erosion resistance and physical strength, as film, fiber and various profile applications in multiple fields.But polyolefine polarity is low, and Intermolecular Forces is little, therefore, polyolefine material covering with paint property, wetting ability, binding property or consistency are poor, bad with other material blend, filling or adhesive property.
Polyolefin-wax comprises the wax-like polyolefine of lower molecular weight, polyolefin-wax prepared by metallocene catalyst as disclosed in patent CN1206728A, more commonly formed after high temperature oxidation, chain rupture by polyolefine, in oxidising process, form carboxylic acid, polyolefinic polarity can be provided, but find in use procedure, Poly Propylene Wax polarity is still lower.Take glass fiber reinforced polypropylene composite material as example, glass fibre is very obvious to polypropylene enhancement, but because glass fibre is hydroaropic substance, great amount of hydroxy group is contained on surface, and polypropylene is lyophobic dust, therefore, glass fibre and polypropene blended after, because the two Physical Properties Difference is too large, glass fibre is difficult to disperse in polypropylene, causes glass-reinforced polypropylene interface performance very weak.
In order to expand the use of polyolefine in multiple fields, functional polyolefin or polyolefin-wax are effective meanss.Graft copolymerization is one of method of most important modified polyolefin, especially with the modification of polar comonomers, can provide binding property or the consistency of polyolefin resin.As PCT patent WO99/21902A discloses the vinyl monomer-grafted that contains S, N or O to ethylene/propene copolymer main chain; Chinese patent CN101724128B discloses the method for maleic anhydride inoculated polypropylene; U.S. US2005261436A1 disclose containing the β position of the polymers of vinyl monomers segment of carboxylic acid replace have containing-CN or-side chain of COOR group, thereby improve polyolefinic binding property and traumatic resistance energy; U.S. Pat 4041056 discloses maleic anhydride modified polyethylene wax; U.S. Pat 3481910 discloses unsaturated polycarboxylic acid and polyolefine graft reaction is prepared polyolefin-wax.
Polyolefin-wax emulsion all has a wide range of applications in multiple fields such as printing ink paint, releasing agent, dispersion agent, lubricant, treating compounds, at present, in developed country, polyolefin-wax has formed series product, and be oxidized on this basis, the chemical modification such as grafting, to improve use properties, polyolefin-wax emulsion is the one in modified polyolefin industrialization product.But sphere of learning is relatively less to the research of polyolefin-wax emulsion, a large amount of documents concentrates on Graft Modification of Polyolefine aspect, only there is a few patent references to report polyolefin-wax emulsion, as Chinese patent CN102020776A, CN101503519B disclose respectively a kind of preparation method of branched polyethylene wax emulsion, first in solution, carry out the modification of polyethylene wax, then add emulsifying agent, regulate pH value, obtain polythene wax emulsion; U.S. Pat 5290954 discloses thermolysis polyolefine and has obtained polyolefin-wax, then prepare the method for polar-modified polyolefin-wax, and the high-clarity emulsion that contains maleic anhydride modified Poly Propylene Wax disclosed, maleic anhydride inoculated polypropylene prepared by melt grafting under high temperature and water, tensio-active agent mixing certain hour, form emulsion.
In the above-mentioned technology of preparing polyolefin-wax emulsion, normally first polyolefin-wax is carried out to solution graft copolymerization or fusion-grafting, then carry out emulsification, solution method needs the poisonous organic solvents such as a large amount of dimethylbenzene, and product be difficult to separate, must product be separated from solvent by chromatography; Fusion-grafting at high temperature has a large amount of side reactions, makes PP wax flavescence blackening etc. and cannot carry out simple purification to product.
Therefore, need a kind of simple to operate, method of preparing graft polyolefin wax emulsion that production efficiency is higher.
Summary of the invention
Lack at present the method for preparing simply, efficiently graft polyolefin wax emulsion, therefore the invention provides a kind of single stage method and prepare the method for graft polyolefin wax emulsion, the present invention adopts solid phase grafting technology, after grafting, in reaction vessel, carry out emulsification, obtain graft polyolefin wax emulsion.
First aspect of the present invention is to provide a kind of method that single stage method is prepared graft polyolefin wax emulsion, and described method comprises the steps:
Step 2, adds solvent, and unreacted unsaturated polar monomer and xylene soluble, in described solvent, are then removed to solvent, and wherein, comonomer graft polyolefin wax is insoluble to or is slightly soluble in described solvent;
Step 3, adds emulsifying agent, pyrosulfite, water and alkali, is uniformly mixed the interval insulation reaction of the arbitrary temp within the scope of 160-180 ° of C or arbitrary temp; Obtain graft polyolefin wax emulsion.
In a preferred embodiment of the present invention, the method for removing solvent in step 2 is preferably: filtration unit is set in reaction container bottom, and by solvent filter, comonomer graft polyolefin wax is left in reaction vessel.
Wherein, described filtration unit at least comprises filtering net, and the aperture of filtering net is preferably 200-400 order.
In step 1, polyolefin-wax, unsaturated polar monomer, dimethylbenzene and initiator part by weight are preferably (500-2000): (10-100): (10-50): (10-50); More preferably (700-1800): (20-70): (10-40): (10-40); More preferably (1000-1500): (25-50): (15-30): (15-30).
Described polyolefin-wax can be low-molecular-weight wax-like polyolefine, or is obtained by oxidation of polyolefins cracking.Described polyolefine can be any olefin polymer, can be homopolymer, multipolymer or the mixture of the two.
In the present invention, described polyolefine is preferably any one or a few the mixture in the multipolymer that is selected from the multipolymer of alpha-olefin homo, alpha-olefin and other alkene, multiple alpha-olefin.
Wherein, described alpha-olefin is preferably the alpha-olefin of C2-C50, the more preferably alpha-olefin of C2-C30, the more preferably alpha-olefin of C2-C20, the more preferably alpha-olefin of C2-C12, as ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 1-heptene, 1-decene etc., more preferably ethene, propylene, 1-butylene, 1-amylene, 1-hexene, more preferably ethene, propylene, 1-butylene, most preferably be propylene.
In a preferred embodiment of the present invention, described polyolefin-wax is preferably polyethylene wax and/or Poly Propylene Wax, most preferably is Poly Propylene Wax.
Described unsaturated polar monomer is preferably and is selected from the monomer that contains following any one or multiple group: hydroxyl, sulfydryl, ester group, carboxyl, amide group, carbonyl, aldehyde radical, amino, cyano group, nitro, alkylsulfonyl, sulfonic group, phosphoryl, phosphonate group, halogen atom.
Described unsaturated polar monomer can be the mixture of a kind of monomer or various of monomer; And be preferably any one or a few the mixture being selected from unsaturated ester, unsaturated carboxylic acid, unsaturated acid anhydride, unsaturated alcohol, unsaturated nitrile, unsaturated amides; As vinylformic acid, methacrylic acid, alkyl acrylate, alkyl methacrylate, vinyl acetate, maleic anhydride, glycidyl acrylate, glycidyl methacrylate, vinyl cyanide, acrylamide etc.
Described alkyl acrylate is preferably vinylformic acid (C1-C12) alkyl ester, as methyl acrylate, ethyl propenoate, butyl acrylate, Ethyl acrylate, Octyl acrylate, decyl acrylate.
Described alkyl methacrylate is preferably methacrylic acid (C1-C12) alkyl ester, as methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, N-Hexyl methacrylate, Octyl methacrylate, decyl-octyl methacrylate.
Those skilled in the art can understand, and described unsaturated polar monomer refers to the polar monomer that contains carbon-to-carbon double bond or carbon-to-carbon triple bond, and the present invention is preferably the polar monomer that contains carbon-to-carbon double bond,
Graft copolymerization monomer of the present invention can be also the mixture of one or more unsaturated polar monomers and one or more unsaturated non-polar monomers, described unsaturated non-polar monomer is preferably alkene, can be many unsaturated olefins, the present invention is preferably alpha-olefin, wherein, described alpha-olefin is preferably the alpha-olefin of C2-C50, the more preferably alpha-olefin of C2-C30, the more preferably alpha-olefin of C2-C20, the more preferably alpha-olefin of C2-C12, as ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 1-heptene, 1-decene etc., more preferably ethene, propylene, 1-butylene, 1-amylene, 1-hexene, more preferably ethene, propylene, 1-butylene.
In a kind of preferred embodiment of the present invention, described graft copolymerization monomer does not contain unsaturated non-polar monomer; More preferably described graft copolymerization monomer is made up of one or more unsaturated polar monomers, most preferably is by a kind of unsaturated polar monomer and forms.
Described initiator can be any olefin polymerization catalysis known in the art, as radical initiator, cationic polymerization initiators, anionic polymerization initiator or coordination polymerization catalysts.
The present invention is preferably one or more radical initiators, can be peralcohol, azo-compound, persulfide, and is preferably superoxide.
Described azo-compound can be any one or a few the mixture in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo-bis-iso-dimethyl, azo diisobutyl amidine hydrochloride.
Described superoxide can be to be selected from hydrogen peroxide, alkyl hydrogen peroxide (being preferably alkyl peroxide), peroxidation two hydrocarbon (being preferably peroxidation dioxane), peroxidation two acyls, peroxy dicarbonate, as any one or a few the mixture in isopropyl benzene hydroperoxide, dicumyl peroxide, tertbutyl peroxide, di-t-butyl peroxide, dibenzoyl peroxide, peroxidized t-butyl perbenzoate, methylethyl ketone peroxide, cyclohexanone peroxide.The present invention is preferably any one or a few the mixture in dicumyl peroxide, di-t-butyl peroxide, dibenzoyl peroxide, methylethyl ketone peroxide, cyclohexanone peroxide.
Described persulfide can be to be selected from one or more persulphates, as ammonium persulphate, Potassium Persulphate, Sodium Persulfate.
Wherein, initiator can be once to feed intake, or batch charging, and the present invention does not limit.
The temperature of reaction of solid phase grafting described in step 1 is preferably 80-200 ° of C, more preferably 100-150 ° of C, more preferably 100-130 ° of C.
The reaction times of solid phase grafting described in step 1 is preferably 0.5-5 hour, more preferably 0.5-3 hour, more preferably 1-2 hour.
In step 2, described solvent is preferably any one or a few in alcohol, ketone, ester, halohydrocarbon, as methyl alcohol, ethanol, acetone, butanone, pentanone, pimelinketone, ethyl acetate, butylacetate, chloroform, methylene dichloride, ethylene dichloride etc.
In step 3, the weight ratio of polyolefin-wax and emulsifying agent, water, alkali, pyrosulfite is preferably (500-2000): (200-500): (1-10): (50-300): (10-50), more preferably (700-1800): (250-450): (3-6): (80-250): (15-40), more preferably (1000-1500): (300-400): (3-4): (100-200): (20-40).
Emulsifying agent, water, alkali, pyrosulfite can add simultaneously, or add successively according to the order of emulsifying agent, water, alkali, pyrosulfite, and the present invention does not limit.
Wherein, described emulsifying agent can be any one or a few the mixture being selected from alkylphenol polyoxyethylene, octadecyloxy phenyl original washing powder Soxylat A 25-7, fatty alcohol-polyoxyethylene ether, polyoxyethylene carboxylate, alkylsulphonic acid or alkylsulfonate, alkyl benzene sulphonate (ABS) or alkylbenzene sulfonate, Soxylat A 25-7 formaldehyde condensation products.
Wherein, described alkali is preferably alkali metal hydroxide, as KOH, NaOH or the mixture of the two.
Wherein, pyrosulfite is preferably ammonium salt and/or an alkali metal salt, as any one or a few mixture of ammonium pyrosulfite, Sodium Pyrosulfite, potassium pyrosulfite.
In step 3, the time of described insulation reaction is preferably 0.5-5 hour, more preferably 1-4 hour, more preferably 2-3 hour.
In step 3, the stir speed (S.S.) of described stirring is preferably 100-500r/min, more preferably 150-400r/min, more preferably 200-300r/min.
Second aspect of the present invention is to provide a kind of method that described single stage method prepares graft polyolefin wax emulsion in the application of preparing in glass fiber infiltration agent.
In second aspect of the present invention, polyolefin-wax is preferably Poly Propylene Wax.
In second aspect of the present invention, graft copolymerization monomer is preferably unsaturated polar monomer, and described unsaturated polar monomer is as defined in foregoing.
The defined term in first aspect of the present invention, can all be applied in second aspect of the present invention.
Third aspect of the present invention is to provide a kind of reactor of preparing graft polyolefin wax emulsion for single stage method, comprises that the top of reactor arranges opening for feed, and bottom is provided with liquid outlet opening; Be provided with filtering net in liquid outlet opening position, reactor bottom.
Wherein, filtering net aperture is preferably 200-400 order.
In the reactor that third aspect of the present invention provides, go out to be also provided with sealing cover at opening for feed.
In the reactor that third aspect of the present invention provides, in reactor, be provided with whipping appts.
The reactor that third aspect of the present invention provides is as follows for the preparation of the method for graft polyolefin wax emulsion:
Step 2, adds solvent from reactor opening for feed, and by unreacted graft copolymerization monomer and xylene soluble, wherein, the polyolefin-wax of comonomer grafting is insoluble to or is slightly soluble in described solvent; Filtering net by liquid outlet opening position, reactor bottom filters, and by liquid outlet opening, solvent is discharged;
Step 3 adds emulsifying agent, water, alkali and pyrosulfite in reactor, mixes, and 160-180 ° of C insulation reaction, obtains graft polyolefin wax emulsion;
After cooling the graft polyolefin wax emulsion obtaining, from discharge hole for discharge.
Wherein, the implication of polyolefin-wax, graft copolymerization monomer, initiator, solvent, emulsifying agent, alkali and pyrosulfite in aforesaid method, as first aspect of the present invention defines.The defined term in first aspect of the present invention, can all be applied in aforesaid method.
Wherein, in aforesaid method, in step 1 and step 3, reaction conditions defines as first aspect of the present invention.The defined term in first aspect of the present invention, can all be applied in aforesaid method.
This patent has utilized the high percentage of grafting that solid phase grafting has, low solvent and the feature of feed change intrinsic shape not, and at reactor discharge port, place reequips, and adds filtering net.In reactor, after solvent washing purifying solid phase grafting reactor product, directly add emulsified feedstock and carry out emulsion reaction.
Carry out by buying the Poly Propylene Wax grafted maleic anhydride of offshore company the process that emulsion is synthetic and in contrast to common Poly Propylene Wax first carry out grafting, then proceed step by step emulsion reaction by solution method or melt grafting in reactor with respect to domestic market major part, not only reduce in a large number the usage quantity of hazardous solvent dimethylbenzene, and activity duration and cost are greatly saved, and with respect to common graft product, the inventive method is removed free maleic anhydride and dimethylbenzene more easily and is more thorough.
Accompanying drawing explanation
Fig. 1 is reactor structural representation in the embodiment of the present invention.
Embodiment
Take graft polypropylene wax as example, below by embodiment, the present invention is described in detail and is described, so that better understand content of the present invention, but should be understood that, following embodiment does not limit the scope of the invention.
Reactor used as shown in Figure 1.
In the autoclave 1 with high speed agitator, add successively after 1kg Poly Propylene Wax (a gram Lay benefactor department provides), 30g maleic anhydride and 15g dimethylbenzene, intensification limit, limit uniform stirring 10 minutes, fully mixes each raw material.Add after 20g initiator dibenzoyl peroxide (BPO), for preventing maleic anhydride distillation volatilization, with sealing cover 11 strict seal reactors, continue to be warming up within the scope of 100-130 ° of C isothermal reaction 1-2 hour.
step 2, removes graft copolymerization monomer and dimethylbenzene
After finishing, reaction is cooled to below 40 ℃, add acetone from reactor opening for feed 10 after, fully stir, to dissolve free maleic anhydride and a small amount of dimethylbenzene (playing the effect of purification reaction product), the 200-400 order filter screen device 13 adding by discharge port 12 places is discharged acetone, and maleic anhydride inoculated polypropylene wax is retained in reactor 1.
Products therefrom is rendered as faint yellow solid particulate state, and infrared spectra detects, at 1790cm
-1there is the two keys of obvious C=O peak, illustrate that maleic anhydride is grafted on Poly Propylene Wax.
step 3, emulsification
In reactor 1, after acetone fully volatilizees, add successively after 300g emulsifying agent, 4g water, 180gKOH, 20g Sodium Pyrosulfite, stir, sealed high pressure reactor heats up.
Keep constant agitation speed 200-300r/mn, when temperature rises within the scope of 160-180 ° of C, isothermal reaction 2-3 hour.
After reaction finishes, be incubated half an hour, be cooled to normal temperature, open reactor, from discharge port 12 dischargings.
Emulsion appearance: oyster white.
Solid content: solid content can be adjusted within the scope of 10-50%, all emulsification smoothly.
Stability: described emulsion keeps more than 12 months, there is no layering at normal temperatures.
With glass fibre cohesiveness: compare with starch treating compound with sizing material for paraffin wax type fiberglass, adhesive property obviously improves, suitable with polyester, polyamide-based treating compound cohesiveness, and graft polypropylene wax prepared by the present embodiment and polyolefine have good consistency, therefore, alternative prior paraffin type glass fiber infiltration agent, is applied to glass fibre modified polyolefin field of compound material.
Embodiment 2
In the autoclave with high speed agitator, add successively after 1.5kg Poly Propylene Wax (a gram Lay benefactor department provides), 50g vinylformic acid glycidyl ether and 25g dimethylbenzene, intensification limit, limit uniform stirring 10 minutes, fully mixes each raw material.Add after 15g initiator dicumyl peroxide (DCP), continue to be warming up within the scope of 100-130 ° of C isothermal reaction 1-2 hour.
step 2, removes graft copolymerization monomer and dimethylbenzene
After finishing, reaction is cooled to below 40 ℃, after adding acetone, fully stir, to dissolve free vinylformic acid glycidyl ether and a small amount of dimethylbenzene, the 200-400 order filter screen device discharge acetone adding by going out reactor discharge port place, vinylformic acid glycidyl ether graft polypropylene wax is retained in reactor 1.
step 3, emulsification
After acetone fully volatilizees, in reactor, add successively 300g emulsifying agent, 3g water, 100g NaOH, 35g Sodium Pyrosulfite, stir, keep constant agitation speed, within the scope of 160-180 ° of C, isothermal reaction 2-3 hour.
After reaction finishes, be incubated half an hour, be cooled to normal temperature, open reactor, discharging.
Embodiment 3
In the autoclave with high speed agitator, add successively after 1.2kg Poly Propylene Wax (a gram Lay benefactor department provides), 43g methyl methacrylate and 18g dimethylbenzene, intensification limit, limit uniform stirring 10 minutes, fully mixes each raw material.Add in batches after 30g initiator dibenzoyl peroxide, continue to be warming up within the scope of 100-130 ° of C isothermal reaction 1-2 hour.
step 2, removes graft copolymerization monomer and dimethylbenzene
After finishing, reaction is cooled to below 40 ℃, after adding acetone, fully stir, to dissolve free methyl methacrylate and a small amount of dimethylbenzene, the 200-400 order filter screen device discharge acetone adding by going out reactor discharge port place, methyl-methacrylate grafted polypropylene wax is retained in reactor 1.
step 3, emulsification
After acetone fully volatilizees, in reactor, add successively 330g emulsifying agent, 3g water, 160g NaOH, 20g Sodium Pyrosulfite, stir, keep constant agitation speed, within the scope of 160-180 ° of C, isothermal reaction 2-3 hour.
After reaction finishes, be incubated half an hour, be cooled to normal temperature, open reactor, discharging.
Embodiment 4
In the autoclave with high speed agitator, add successively after 1.4kg Poly Propylene Wax (a gram Lay benefactor department provides), 33g vinylformic acid and 30g dimethylbenzene, intensification limit, limit uniform stirring 10 minutes, fully mixes each raw material.Add in batches after 25g initiator dibenzoyl peroxide, continue to be warming up within the scope of 100-130 ° of C isothermal reaction 1-2 hour.
step 2, removes graft copolymerization monomer and dimethylbenzene
After finishing, reaction is cooled to below 40 ℃, after adding acetone, fully stir, to dissolve free vinylformic acid and a small amount of dimethylbenzene, the 200-400 order filter screen device discharge acetone adding by going out reactor discharge port place, acrylic acid-grafted polypropylene wax is retained in reactor 1.
step 3, emulsification
After acetone fully volatilizees, in reactor, add successively 400g emulsifying agent, 4g water, 180g KOH, 20g Sodium Pyrosulfite, stir, keep constant agitation speed, within the scope of 160-180 ° of C, isothermal reaction 2-3 hour.
After reaction finishes, be incubated half an hour, be cooled to normal temperature, open reactor, discharging.
Embodiment 5
In the autoclave with high speed agitator, add successively after 1.2kg Poly Propylene Wax (a gram Lay benefactor department provides), 25g vinyl cyanide and 15g dimethylbenzene, intensification limit, limit uniform stirring 10 minutes, fully mixes each raw material.Add after 15g initiator dibenzoyl peroxide, continue to be warming up within the scope of 100-130 ° of C isothermal reaction 1-2 hour.
step 2, removes graft copolymerization monomer and dimethylbenzene
After finishing, reaction is cooled to below 40 ℃, after adding acetone, fully stir, to dissolve free vinyl cyanide and a small amount of dimethylbenzene, the 200-400 order filter screen device discharge acetone adding by going out reactor discharge port place, acrylonitrile grafting Poly Propylene Wax is retained in reactor 1.
step 3, emulsification
After acetone fully volatilizees, in reactor, add successively 400g emulsifying agent, 4g water, 180g KOH, 20g Sodium Pyrosulfite, stir, keep constant agitation speed, within the scope of 160-180 ° of C, isothermal reaction 2-3 hour.
After reaction finishes, be incubated half an hour, be cooled to normal temperature, open reactor, discharging.
Above specific embodiments of the invention be have been described in detail, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and alternative also all among category of the present invention.Therefore, equalization conversion and the modification done without departing from the spirit and scope of the invention, all should contain within the scope of the invention.
Claims (9)
1. single stage method is prepared a method for graft polyolefin wax emulsion, it is characterized in that, described method comprises the steps:
Step 1, under initiator and dimethylbenzene existence, by solid phase grafting technology, by the monomer-grafted graft copolymerization polyolefin-wax main chain that arrives, obtain comonomer graft polyolefin wax, wherein, in described graft copolymerization monomer, at least contain one or more unsaturated polar monomers;
Step 2, under≤40 ° of C conditions, adds solvent, and unreacted unsaturated polar monomer and xylene soluble, in described solvent, are then removed to solvent, and wherein, comonomer graft polyolefin wax is insoluble to or is slightly soluble in described solvent;
Step 3, adds emulsifying agent, pyrosulfite, water and alkali, is uniformly mixed the interval insulation reaction of the arbitrary temp within the scope of 160-180 ° of C or arbitrary temp; Obtain graft polyolefin wax emulsion.
2. method according to claim 1, is characterized in that, the method for removing solvent in step 2 is: filtration unit is set in reaction container bottom, and by solvent filter, comonomer graft polyolefin wax is left in reaction vessel.
3. method according to claim 1, it is characterized in that, polyolefin-wax, unsaturated polar monomer, dimethylbenzene and initiator part by weight are (500-2000): (10-100): (10-50): (10-50).
4. according to the method described in claim 1 or 3; it is characterized in that, described unsaturated polar monomer is selected from the monomer that contains following any one or multiple group: hydroxyl, sulfydryl, ester group, carboxyl, amide group, carbonyl, aldehyde radical, amino, cyano group, nitro, alkylsulfonyl, sulfonic group, phosphoryl, phosphonate group, halogen atom.
5. method according to claim 1, is characterized in that, the temperature of reaction of solid phase grafting described in step 1 is 80-200 ° of C; Reaction times is 0.5-5 hour.
6. method according to claim 1, is characterized in that, in step 3, the time of described insulation reaction is 0.5-5 hour, and the stir speed (S.S.) of described stirring is 100-500r/min.
7. according to the method described in claim 1,3 or 6, it is characterized in that, in step 3, the weight ratio of polyolefin-wax and emulsifying agent, water, alkali, pyrosulfite is (500-2000): (200-500): (1-10): (50-300): (10-50).
One kind as claimed in claim 1 method in the application of preparing in glass fiber infiltration agent.
9. a reactor of preparing graft polyolefin wax emulsion for single stage method, is characterized in that, comprises that the top of reactor arranges opening for feed, and bottom is provided with liquid outlet opening; Arrange in liquid outlet opening position, reactor bottom.
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| CN112709071A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Thermoplastic emulsion sizing agent for polypropylene-carbon fiber composite material and preparation method thereof |
| CN112500532A (en) * | 2020-12-14 | 2021-03-16 | 九洲生物技术（苏州）有限公司 | Multifunctional lubricant, and preparation method and application thereof |
| CN114716619A (en) * | 2021-01-06 | 2022-07-08 | 中国石油天然气股份有限公司 | Preparation method of maleic anhydride grafted styrene-butadiene rubber compatibilizer |
| CN114716619B (en) * | 2021-01-06 | 2024-03-01 | 中国石油天然气股份有限公司 | Preparation method of maleic anhydride grafted styrene-butadiene rubber compatibilizer |
| CN114957556A (en) * | 2022-06-14 | 2022-08-30 | 天津渤海中联石油科技有限公司 | Fluid loss additive, preparation method and application thereof, and oil-based drilling fluid |
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Application publication date: 20140507 |