CN112759714B - Preparation method of high-toughness graft copolymer - Google Patents
Preparation method of high-toughness graft copolymer Download PDFInfo
- Publication number
- CN112759714B CN112759714B CN201911000105.6A CN201911000105A CN112759714B CN 112759714 B CN112759714 B CN 112759714B CN 201911000105 A CN201911000105 A CN 201911000105A CN 112759714 B CN112759714 B CN 112759714B
- Authority
- CN
- China
- Prior art keywords
- acrylate
- latex
- parts
- vinyl chloride
- salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and relates to a method for grafting vinyl chloride on acrylate latex with large particle size, in particular to a preparation method of a high-toughening graft copolymer, and the vinyl chloride graft copolymer with the toughening effect remarkably improved can be obtained through the method. The preparation method comprises the steps of preparing acrylate latex, expanding the latex diameter and carrying out vinyl chloride graft copolymerization. The preparation method of the invention adopts soluble inorganic salt as expanding agent, and is used for agglomerating acrylic ester latex particles and then carrying out vinyl chloride suspension polymerization.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to a method for grafting vinyl chloride on acrylate latex with large particle size, in particular to a preparation method of a high-toughening graft copolymer, and the vinyl chloride graft copolymer with the toughening effect remarkably improved can be obtained through the method.
Background
Pure polyvinyl chloride (PVC) resin has the defects of high brittleness and poor mechanical property, and at present, a synthetic impact modifier is usually blended and mixed with the PVC resin to fully disperse the impact modifier into the PVC resin for overcoming. Common impact modifiers such as MBS (methyl methacrylate-butadiene-styrene), ACR (acrylate copolymer), CPE (chlorinated polyethylene), etc. are used in this way to improve the properties of polyvinyl chloride resins. In the toughening modifiers MBS and ACR resin which are microscopically in a core-shell structure, the main function is the rubber phase component in the core, and the factors such as the crosslinking degree, the particle size and the like determine the toughening modification effect of the final PVC resin. The rubber particle component in a dispersed independent state and the chloroethylene are directly grafted to prepare the copolymer PVC resin, so that the dispersed state of the rubber component in the PVC resin can be maintained, and the impact resistance of the rubber to the matrix polyvinyl chloride resin can be effectively maintained. The acrylate rubber polymer has less double bonds and other unstable structures in the molecular structure, is widely applied to the aspect of manufacturing weather-resistant PVC resin products, and has an outstanding toughening and modifying effect. For example, patent No. CN201210256716.9 provides a method, in which an acrylate latex having a cross-linked structure is prepared by a one-step process, and then acrylic ester monomer is added or not added to the system, and then the latex is graft-copolymerized with vinyl chloride in suspension, to obtain a graft copolymer having improved impact resistance and processing plasticization properties compared to the copolymer resin. However, the acrylate latex is prepared by a one-step method, the particle size of the obtained latex is small, the proportion of the latex is small and the particle size is increased limitedly although the polymerization operation of the additional monomer is carried out, so that the impact resistance of the final copolymer resin is not outstanding. Patent application No. CN201811177890.8 proposes that water-soluble strong acid solution is added into acrylic ester latex using protective polymer sol, small-particle-size latex particles are agglomerated into large particles by controlling the pH value of the system, and then vinyl chloride graft copolymerization is carried out, so as to prepare vinyl chloride graft copolymer with high toughness. In the process of agglomerating small-particle-size latex particles, the pH value of the system is a key factor, but the change range of the pH value of the latex is an extremely sensitive and narrow interval, factors such as acid liquor diffusion conditions, temperature changes and the like have great influence on the particle size of the latex, the difficulty in controlling the particle size of the latex particles and maintaining the stability of the latex system is high, and the resin with improved impact resistance effect cannot be obtained due to diameter expansion failure caused by glue residue or emulsion breaking phenomenon easily occurs.
Disclosure of Invention
In order to effectively control the particle size of the acrylate latex and maintain the stability of a latex system, the invention provides a preparation method of a high-toughening graft copolymer, which adopts soluble inorganic salt as an expanding agent to agglomerate acrylate latex particles and then carry out vinyl chloride suspension polymerization.
The invention is realized by adopting the following technical scheme:
the invention provides a preparation method of a high-toughness graft copolymer, which comprises the following steps:
step (1) preparation of acrylate latex:
mixing and stirring a monomer mixture consisting of 100 parts of acrylate monomers and 0.01-10 parts of crosslinking monomers with 150-250 parts of desalted water, 0.5-3.0 parts of emulsifying agent, 0.10-1.0 part of free radical thermal initiator and 0.01-0.3 part of strong base or alkaline salt, and reacting at 50-80 ℃ to obtain acrylate latex with 25-40 wt% of solid content and 0.050-0.100 mu m of number average particle diameter;
expanding the diameter of the latex in the step (2):
diluting the acrylate latex prepared in the step (1) to a solid content of 25-35 wt%, adding an inorganic salt aqueous solution with a concentration of 5-10 wt% and a pH value of 4.0-6.0 at a temperature of 20-40 ℃ under stirring, and agglomerating and expanding acrylate latex particles to a number average particle diameter of 0.10-0.40 mu m;
vinyl chloride graft copolymerization in step (3):
and (3) graft polymerizing the whole acrylate expanded diameter latex obtained in the step (2) with 110-200 parts of desalted water, 0.10-0.20 part of dispersing agent, 0.05-0.20 part of initiator, 0.001-0.20 part of alkaline salt and 100 parts of vinyl chloride monomer under the conditions of stirring and 55-65 ℃, discharging slurry after reaching specified pressure drop, and performing centrifugal dehydration, drying and screening to obtain the vinyl chloride graft copolymer containing the large-particle-size acrylate copolymer rubber particles.
The acrylic ester latex is an acrylic ester polymer emulsion with a rubber crosslinking structure obtained by adopting an emulsion polymerization process. Generally speaking, the impact resistance of the final copolymer resin has great correlation with the glass transition temperature of an acrylate polymer, namely the lower the glass transition temperature, the better the impact resistance, so that the acrylate monomer selected to be used refers to an acrylate monomer containing C2-C4 on an alkyl chain, and mainly comprises ethyl acrylate and butyl acrylate. In the acrylate monomer mixture, the butyl acrylate accounts for 80-100 wt%, and the ethyl acrylate content accounts for 20-0 wt%.
As an alternative to preparing the rubber phase-containing acrylate latex crosslinker, compounds which generally contain two or more non-conjugated copolymerizable double bonds in the molecular chain, diallyl phthalate, allyl methacrylate and 1, 4-butylene glycol dimethacrylate are used in the present invention due to the polymerization compatibility with the acrylate monomer. It may optionally be used in an amount of 0.01 to 10 parts, preferably 0.1 to 5.0 parts, per 100 parts of the acrylate monomer mixture. The use method is that the crosslinking monomer and the acrylate monomer are evenly blended and then participate in polymerization reaction together.
For the emulsion polymerization of acrylate monomers, a wide variety of emulsifiers can be used, both ionic and nonionic emulsifiers can be used. However, for the present invention, since the small-particle size latex particles are chemically agglomerated into large-particle size particles, chemically stable emulsifiers are not suitable, and anionic emulsifiers such as sodium lauryl sulfate and sodium dodecyl sulfonate are not suitable for use, the present invention particularly selects strongly basic saponified products of fatty acids having 12 to 18 carbon atoms (C12-C18) in the straight-chain alkyl groups, wherein the metal salts, including the sodium and potassium salts thereof, are water-soluble saponified at ordinary temperatures, and the potassium salts are mainly potassium salts, including potassium laurate, potassium oleate and potassium stearate, which can be used in an amount of 0.3 to 5.0 parts, preferably 0.5 to 3.0 parts, based on 100 parts of the acrylate monomer. When the amount is less than 0.5 part, the emulsion breaking phenomenon is liable to occur due to the decrease in the stability of the emulsion polymerization system, and when the amount is more than 3.0 parts, the particle diameter of the latex particles to be produced is too small, and even if the diameter is expanded to form large particles, too much diameter expanding agent is consumed, which affects the stability of the polymerization system.
The initiator used for the emulsion polymerization of the acrylic esters is preferably a water-soluble initiator. The persulfate thermal initiator has the advantages of low cost and small using amount, the usable persulfate initiator comprises potassium salt, sodium salt and ammonium salt, the selectable using amount is 0.01-2.0 parts, preferably 0.1-1.0 part based on 100 parts of polymerization monomer, and when the selectable using amount is less than 0.10 part, the induction period is too long, the polymerization time is prolonged, the using amount is insufficient at the later reaction stage, and the reaction is not thorough. When the amount is more than 1.0 part, the generation of radicals for initiating polymerization is excessive, the problems of latex average particle size reduction, concentrated reaction heat release, easy occurrence of rubber slag in a polymerization system and the like can be caused, and the yield and the quality of the acrylate latex are finally influenced.
The temperature for polymerization can be 40-90 ℃ under the condition of using persulfate thermal initiator, and the polymerization can be carried out in the range, but the reaction temperature is preferably 50-80 ℃ in the invention to ensure the polymerization efficiency.
It should be noted that, due to the use of persulfate initiator, the decomposition of persulfate will cause the pH value of the system to decrease during the polymerization reaction of acrylate, which will affect the emulsification and stabilization of the emulsifier, and too high a pH value will also cause the acceleration of the polymerization reaction, so it is necessary to ensure the stability of the pH value of the system. In the invention, a small amount of strong base or alkaline salt is adopted to neutralize hydrogen ions released by persulfate so as to ensure the stability of the pH value of the system. These bases include sodium hydroxide, potassium hydroxide, etc., and the basic salts include sodium carbonate, sodium bicarbonate, sodium pyrophosphate, etc., which may be optionally used in an amount of 0.001 to 0.5 parts, preferably 0.01 to 0.3 parts, based on 100 parts of the acrylate monomer mixture.
It is also important to note in the present invention that, in order to ensure the effective latex diameter expansion, the solid content of the latex obtained after the acrylate has reacted sufficiently cannot be too low, and according to the test results, the solid content is preferably 25 to 40 wt%, otherwise the latex diameter expansion effect is affected. Therefore, the water used in the polymerization of the acrylate latex is required to ensure the stability of the system and provide a high solid content, and accordingly the amount of the polymerization water can be selected from 110-400 parts, preferably 150-250 parts based on 100 parts of the acrylate monomer.
In the present invention, the particle size of the original latex should not be too small to obtain particles having a latex particle size of 0.100 to 0.400. mu.m after diameter expansion. By designing the polymerization and matching test formulation according to the above conditions of the present invention, it is preferable that the arithmetic mean particle diameter of the acrylate latex particles is 0.050 to 0.100. mu.m.
The key step of preparing the high-toughness copolymer in the invention is the diameter expansion operation of the acrylate latex. The invention selects weak acidic inorganic salt solution as expanding agent, the optional inorganic salt is mainly strong acid strong base salt with monovalent metal ions, and comprises sodium chloride, potassium chloride, sodium nitrate, potassium nitrate, sodium sulfate, potassium sulfate and the like. The inorganic salt solution is prepared by adding desalted water as a solvent and inorganic salt and stirring, and the optional concentration is 3.0-15 wt%, preferably 5.0-10.0 wt%. The solution for expanding salt is preferably a solution with a low pH value, optionally 3.0-7.0, preferably 4.0-6.0, so that the expanding effect of the salt solution can be sufficiently stabilized and the amount of salt used can be appropriately reduced. The dosage of the inorganic salt for expanding is 1.0-10 parts based on 100 parts of the dry acrylate adhesive, the expanding effect cannot be shown when the dosage is less than 1.0, and the rubber residue can be generated due to excessive dosage in the expanding process of the acrylic latex when the dosage is more than 10 parts. The acrylate dry-based adhesive is an acrylate copolymer in the acrylate latex obtained in the step (1). The preferred amount of the present invention is 2.0 to 8.0 parts.
As previously mentioned, the latex solids content should be diluted with water to a level in the range of 25-35 wt% and maintained at ambient conditions of 20-40 ℃ to facilitate the production of a stable expanded latex. If the solid content of the latex is higher than 35 wt%, glue residue is easy to appear in the process of dripping the salt solution. If the solid content is less than 25 wt%, the use amount of the salt solution for expanding the diameter is increased, which is not beneficial to the subsequent graft polymerization operation and the product performance. When the latex temperature is lower than 20 ℃ during the expanding operation, the emulsifier is possibly below the triple point, the protective activity of the emulsifier is reduced, and the latex agglomeration phenomenon is easily generated when the salt solution is expanded. When the temperature of the latex is higher than 40 ℃, the water on the surface of the latex is evaporated too fast, and the rubber slag is easy to generate in the diameter expanding process.
Under the above-mentioned operating conditions, the acrylic latex can be expanded from a calculated average particle diameter of 0.050 to 0.100. mu.m to a diameter of 0.100 to 0.400. mu.m, in which case the latex can be used for carrying out suspension graft polymerization with vinyl chloride.
In carrying out the suspension graft polymerization operation, the amount of water used as the dispersed phase is an important condition for ensuring the final graft copolymer product. In the present invention, the mass ratio of vinyl chloride monomer to water is selected to be 1.0/(1.0 to 3.0), preferably 1.0/(1.1 to 2.0), under the condition that the amount of the acrylate latex is determined. When the water content is more than 3.0, not only the polymerization reaction efficiency is reduced, but also the latex particle size after diameter expansion is influenced to a certain extent, so that the latex particle size is gradually reduced in the reaction process.
In the present invention, the suspension graft copolymerization of the expanded acrylic latex and vinyl chloride may use a polymeric dispersant for improving the stability of the suspension polymerization system, such dispersants include gelatin, polyvinyl alcohol, cellulose modified products, and the like. In the invention, hydroxypropyl methyl cellulose with 28-29 percent of methoxyl, 6.0-12.0 percent of hydroxypropyl and 40-60 mPa.s (2 percent aqueous solution, 25 ℃) is preferably selected, the dosage of the hydroxypropyl methyl cellulose is 0.10-0.20 part based on 100 parts of vinyl chloride monomer, and in the range, the stability of a polymerization system is good, the particle size of the copolymer resin particles is moderate, and the particle size distribution is reasonable. As a means for adjusting the plasticizer absorption property of the graft copolymer, it is recommended to use 0 to 0.10 part of water-soluble or oil-soluble polyvinyl alcohol having an alcoholysis degree of 35 to 55 mol% and a polymerization degree of 200-500 as a dispersion aid, and preferable oil-soluble dispersion aid include S202 of 3V sigma, and preferable water-soluble dispersion aid include Japanese synthetic chemistry LW-100, LW-200, and water-dispersible LM-20, LM-10HD and the like of Coly.
The initiator used in the suspension graft copolymerization of vinyl chloride is preferably an oil-soluble initiator, and includes diacyl peroxides such as dilauroyl peroxide, peroxyesters such as t-butyl peroxypivalate, dialkyl peroxydicarbonates such as cumyl peroxydicarbonate, and azo-compounds such as azobisisoheptonitrile. In the present invention, cumyl neodecanoate oxide, di (2-ethylhexyl) peroxydicarbonate, t-butyl peroxyneodecanoate, t-amyl peroxypivalate, and azobisisoheptonitrile are preferably used. The dosage of the polyvinyl chloride monomer is 0.05 to 0.20 portion based on 100 portions of vinyl chloride monomer.
In the suspension graft copolymerization of acrylate latex and vinyl chloride, a pH regulator can be used to improve the stability of the suspension polymerization system, a water-soluble bicarbonate and a monovalent soluble strong base salt are preferably used, and ammonium bicarbonate and sodium hydroxide are preferably used in the invention, and the amount of the ammonium bicarbonate and the sodium hydroxide is 0.001 to 0.20 part based on 100 parts of vinyl chloride monomer. The sodium hydroxide is used in a method different from that of the ammonium bicarbonate, and preferably, the sodium hydroxide is continuously added during the polymerization period, and the ammonium bicarbonate is mainly added at one time. Other additives used in vinyl chloride polymerization, including molecular weight regulators, metal complexing agents, anti-fish-eye agents, and the like, may also be used, and the present invention is not limited thereto.
The conversion rate (based on the total mass percentage of the polymerized vinyl chloride in the added vinyl chloride monomer) of the suspension graft copolymerization reaction of the acrylate latex and the vinyl chloride can be 65-95%, and the conversion rate is preferably 70-90% in the invention, because the excessively high conversion rate needs to prolong the polymerization reaction time, the production economy is reduced, the plasticizer absorption performance of the final resin product is reduced, and the thermal stability is deteriorated. When the pressure drop of the polymerization reaction reaches the requirement, a terminator can be added to end the reaction. The vinyl chloride graft polymerization terminator to be used in the present invention is not particularly limited, and any commonly used species such as Acetonide Thiosemicarbazone (ATSC), Diethylhydroxylamine (DEHA), monohydric or polyhydric phenols, and ester antioxidants can be used.
The preferred acrylate latex of the present invention is prepared as follows: adding desalted water, an emulsifier, strong base or alkaline salt and an acrylate monomer mixture containing a crosslinking monomer into a reactor, stirring and heating, introducing nitrogen to replace air in the reactor, then adding a free radical thermal initiator for polymerization, and generally determining that the monomer conversion rate is more than 95%, namely finishing the reaction to obtain the acrylate latex. The acrylate latex has an arithmetic mean particle diameter of 0.050 to 0.100 mu m and a solid content of 25 to 40 wt%.
During the diameter expanding operation, the diameter expanding salt solution is slowly dropped while the stirring state is maintained, so as to fully ensure the agglomeration of the inorganic salt on the latex particles.
The invention mainly adopts a suspension copolymerization process. The preferred suspension graft polymerization method of the present invention is: sequentially adding desalted water, a dispersing agent, an initiator, a water-soluble inorganic salt and the like into a clean pressure-resistant polymerization kettle at normal temperature, vacuumizing, adding a vinyl chloride monomer, starting stirring and fully mixing, then adding expanded acrylic ester latex, heating to a specified temperature for reaction, adding an auxiliary agent such as a polymerization terminator when the reaction pressure drop meets the requirement, and then carrying out operations such as degassing, slurry dehydration, drying and the like to obtain the vinyl chloride graft copolymer of the acrylic ester copolymer rubber particles with large particle size.
After the suspension graft polymerization of vinyl chloride is finished, unreacted monomers in the slurry should be removed, and the obtained copolymer resin slurry is dehydrated and dried to obtain the vinyl chloride graft copolymer product containing the acrylic ester latex particles.
The invention has the beneficial effects that: the vinyl chloride suspension graft copolymer resin obtained by the preparation method of the present invention contains 4 to 20 wt.% of the acrylate copolymer and 96 to 80 wt.% of the polyvinyl chloride resin. For the vinyl chloride graft copolymer of the acrylate latex, when the latex content is less than 4 wt%, the impact resistance of the vinyl chloride copolymer resin is not increased significantly, but when the latex content is more than 20 wt%, the impact resistance effect is not further increased significantly, and an excessively high acrylate latex content may cause latex particles to agglomerate in the vinyl chloride graft copolymer, which is difficult to disperse, and the impact resistance may be decreased.
The stability of the acrylic ester latex in the diameter expanding step is improved, the controllable range of the diameter expanding effect is large, and finally, the vinyl chloride graft copolymer resin not only has the stability of a polymerization system and the obvious particle size increasing effect of the diameter expanding latex, but also has excellent impact resistance.
Detailed Description
The present invention will be described in further detail in order to make the object and technical solution of the present invention more apparent. The experimental methods described in the following examples are all conventional methods unless otherwise specified; the specific techniques or conditions are not indicated in the examples, and the techniques or conditions are described in the literature in the field or according to the product specification; the reagents and materials are commercially available, unless otherwise specified.
The analysis and test method adopted by the invention is as follows:
(1) analytical test method
Particle size determination of copolymer latex and graft copolymer resin:
the particle size was measured using a Mastersizer 2000 laser particle sizer manufactured by Malvern.
② polymerization conversion rate of vinyl chloride: gravimetric method, the ratio of the mass of polyvinyl chloride in the copolymer resin to the mass of vinyl chloride monomer added;
③ apparent density: testing according to GB/T20022-.
Fourthly, the impact strength (23 ℃) of the notch of the simply supported beam is as follows: the sample preparation method is carried out according to the GB/T1043.1-2008 condition and the sample preparation method is carried out according to the following (2).
(2) The ingredients of the processing formula of the vinyl chloride copolymer resin are shown in Table 1:
TABLE 1 vinyl chloride graft copolymer resin processing compounding ratio
| Vinyl chloride graft copolymer resin | 100 portions of |
| Organotin 8831 | 1.5 parts of |
| Lubricant ZB-60 | 0.5 portion |
| Lubricant ZB-74 | 0.4 portion of |
| Calcium stearate | 0.5 portion |
A sample preparation method for a notch impact strength sample of a simply supported beam comprises the following steps: the acrylate latex vinyl chloride copolymer resin is weighed according to the formula and mixed with materials, the materials are kneaded in a high-speed mixer and mixed by an SK-160B double-roll mixing mill (175 +/-5 ℃ for 5 minutes), a primary stretched sheet is prepared, the sheet is weighed and cut, then the sheet with the thickness of 4mm is pressed on a hot press (180 +/-2 ℃ for 3 minutes), and the sheet is prepared into a simply supported beam impact sample strip according to the standard requirement for performance test.
The following examples and comparative examples illustrate the invention.
Example 1
(1) Preparation of acrylate latex
150.0 parts of desalted water, 5 parts of butyl acrylate, 0.8 part of diallyl phthalate, 3.0 parts of potassium laurate, 0.40 part of potassium chloride and 0.05 part of sodium hydroxide are added into a 2L glass kettle which is provided with a stirrer, a reflux condenser tube and a jacket, the air in the kettle is completely blown by nitrogen, the stirring is started, the temperature is raised to 70 ℃, and 0.20 part of potassium persulfate is added to initiate polymerization reaction. And after the conversion rate reaches more than 98%, the polymerization is considered to be finished. Finally, the acrylate latex with the solid content of 39.1 percent and the arithmetic mean particle diameter of 0.065 mu m is obtained.
(2) Latex expanding
25.5 parts (including 10 parts on a dry basis) of the obtained acrylic latex was diluted with desalted water at 20 ℃ until the solid content became 30% by weight, 5 parts of an aqueous solution of sodium chloride having a pH of 5.5 (adjusted with 0.1M hydrochloric acid solution) and a concentration of 5.0% by weight was added dropwise while stirring, whereupon the color of the latex was changed from bluish white to matt white, the arithmetic mean particle diameter of the latex was determined to be 0.310. mu.m, and the latex was filtered with a 40-mesh screen so as to be substantially free of scum.
(3) Vinyl chloride graft copolymerization
Adding 120 parts of desalted water, 0.15 part of hydroxypropyl methyl cellulose E50 (product of Dow chemical company), 0.05 part of polyvinyl alcohol S2020.06 part of cumyl peroxyneodecanoate, 0.14 part of di (2-ethylhexyl) peroxydicarbonate and 0.20 part of ammonium bicarbonate into a 10L pressure polymerization kettle, replacing the kettle with nitrogen, vacuumizing to be below-0.090 MPa, adding 100 parts of vinyl chloride monomer, stirring and mixing for 10 minutes at normal temperature, adding the expanded acrylate latex in the step (2), heating to 55 ℃ for reaction, adding 0.01 part of termination agent Diethylhydroxylamine (DEHA) when the pressure is reduced to 0.17MPa, degassing, dehydrating and drying the obtained polymer slurry to obtain the acrylate-vinyl chloride grafted copolymerAnd (4) branches. After polymerization is finished, the surfaces of the kettle wall, the stirring blades and the baffle are clean, a small amount of polymer agglomerates exist at the gas-liquid interface of the stirring shaft, and the drying quality of the polymer agglomerates is only 0.038 wt% of the mass of the graft copolymer. After the reaction, the total mass of the polymer was weighed, and the polymerization conversion of vinyl chloride was calculated to be 82.1%, and the content of the acrylic copolymer was calculated to be 10.9%. The vinyl chloride copolymer was analyzed to have an arithmetic mean particle diameter of 184 μm and an apparent density of 0.43g/mL, and after compounding, blending, processing into a sheet and sampling the copolymer according to the above-mentioned evaluation method, the impact strength of a simple beam notch at room temperature (23 ℃ C.) was determined to be 114kJ/m 2 。
Example 2
(1) Preparation of acrylate latex
200.0 parts of desalted water, 95 parts of butyl acrylate, 5 parts of ethyl acrylate, 3.6 parts of 1, 4-butanediol dimethacrylate, 2.0 parts of potassium stearate and 0.10 part of sodium pyrophosphate are added into a 2L glass kettle which is provided with a stirrer, a reflux condenser tube and a jacket, the air in the kettle is completely blown by nitrogen, the stirring is started, the temperature is raised to 52 ℃, and 0.75 part of ammonium persulfate is added to initiate polymerization reaction. And after the conversion rate reaches more than 95%, the polymerization is considered to be finished. Finally, the acrylic latex with the solid content of 33.3 percent and the arithmetic mean particle size of 0.0615 mu m is obtained.
(2) Latex expanding
45.0 parts (including 15 parts of dry base) of the obtained acrylic latex was added dropwise with stirring at 30 ℃ with 7.9 parts of an aqueous solution of sodium sulfate having a pH of 4.5 (adjusted with 0.05M sulfuric acid) and a concentration of 8.0% by weight, whereupon the latex color changed from bluish white to off-white, the arithmetic mean particle diameter of the latex was determined to be 0.198. mu.m, and the latex was filtered through a 40-mesh screen with substantially no scum.
(3) Vinyl chloride graft copolymerization
200 parts of desalted water, 0.20 part of hydroxypropyl methyl cellulose E50 (product of Dow chemical Co.), 0.03 part of polyvinyl alcohol S2020.03 part, 0.03 part of tert-butyl peroxyneodecanoate, 0.07 part of tert-amyl peroxypivalate and 0.06 part of ammonium bicarbonate are added into a 10L pressure polymerization kettle, the kettle is replaced by nitrogen, vacuum is pumped to be below-0.090 MPa, 100 parts of vinyl chloride monomer is added, stirring and mixing are carried out for 10 minutes at normal temperature, and then the mixture is addedAdding the expanded acrylate latex in the step (2), heating to 60 ℃ for reaction, adding 0.01 part of termination agent Diethylhydroxylamine (DEHA) when the pressure drop reaches 0.25MPa, degassing the obtained polymer slurry, dehydrating and drying to obtain the acrylate-vinyl chloride graft. After the polymerization is finished, a small amount of polymer agglomeration of the stirring shaft and the blades can be seen, the surface of the kettle wall is clean, and the drying quality of the agglomeration is only 0.062 wt% of the mass of the graft copolymer. After the reaction, the total mass of the polymer was weighed, and the polymerization conversion of vinyl chloride was calculated to be 84.0% and the content of the acrylic copolymer was calculated to be 15.2%. The vinyl chloride copolymer was analyzed to have an arithmetic mean particle diameter of 195 μm and an apparent density of 0.48g/mL, and after compounding, blending, processing and flaking and sampling the copolymer according to the above-mentioned evaluation method, the impact strength of a simple beam notch at normal temperature (23 ℃ C.) was measured to be 130kJ/m 2 。
Example 3
(1) Preparation of acrylate latex
180.0 parts of desalted water, 80 parts of butyl acrylate, 20 parts of ethyl acrylate, 1.0 part of allyl methacrylate, 0.7 part of potassium oleate and 0.15 part of sodium pyrophosphate are added into a 2L glass kettle provided with a stirrer, a reflux condenser tube and a jacket, the air in the kettle is purged by nitrogen, the stirring is started, the temperature is raised to 65 ℃, and 0.30 part of sodium persulfate is added to initiate polymerization reaction. And after the conversion rate reaches more than 98%, the polymerization is considered to be finished. Finally, the acrylic ester latex with the solid content of 35.3 percent and the arithmetic mean grain diameter of 0.086 mu m is obtained.
(2) Diameter enlargement of copolymerized latex
15.5 parts (including 5.5 parts on a dry basis) of the obtained acrylic latex was diluted with desalted water at 35 ℃ to 30% by weight, 4.1 parts of an aqueous solution of sodium sulfate having a pH of 4.8 (adjusted with 0.05M sulfuric acid solution) and a concentration of 6.0% by weight was added dropwise while stirring, whereupon the latex was changed from bluish white to off-white in color, the arithmetic mean particle diameter of the latex was determined to be 0.330. mu.m, and the latex was filtered through a 40-mesh screen so as to be substantially free of scum.
(3) Vinyl chloride graft copolymerization
110 parts of desalted water, 0.19 part of hydroxypropyl methyl cellulose F50 (product of Dow chemical Co.) and polyethylene are added into a 10L pressure polymerization kettle in proportion0.06 part of enol LW-100 (a product of Japan synthetic chemical company) and 0.090 part of di (2-ethylhexyl) peroxydicarbonate, replacing the interior of a kettle with nitrogen, vacuumizing to below-0.090 MPa, adding 100 parts of vinyl chloride monomer, stirring and mixing at normal temperature for 10 minutes, adding the expanded acrylate latex in the step (2), heating to 58 ℃ for reaction, continuously adding 0.20 part of sodium hydroxide within 3 hours, adding 0.01 part of termination agent Diethylhydroxylamine (DEHA) when the pressure drops to 0.30MPa, degassing the obtained polymer slurry, dehydrating and drying to obtain the vinyl chloride graft of acrylate. After the polymerization is finished, the kettle wall and the surface of the baffle are clean, a small amount of polymer is agglomerated at the stirring shaft and the blade end, and the dry mass of the polymer is 0.020 wt% of the mass of the graft copolymer. After the reaction, the total mass of the polymer was weighed, and the polymerization conversion of vinyl chloride was calculated to be 86% and the content of the acrylic copolymer was calculated to be 6.0%. The analysis revealed that the vinyl chloride copolymer resin particles had an arithmetic mean particle diameter of 137 μm and an apparent density of 0.45g/mL, and that the impact strength of a simple beam notched bar at room temperature (23 ℃ C.) was 61kJ/m when the copolymer was compounded, blended, processed into a sheet and sampled according to the above-mentioned evaluation method 2 。
Example 4
(1) Preparation of acrylate latex
180.0 parts of desalted water, 100 parts of butyl acrylate, 1.0 part of allyl methacrylate, 3.0 parts of potassium oleate and 0.10 part of sodium hydroxide are added into a 2L glass kettle provided with a stirrer, a reflux condenser tube and a jacket, the air in the kettle is purged by nitrogen, the stirring is started, the temperature is raised to 65 ℃, and 0.40 part of potassium persulfate is added to initiate polymerization reaction. And cooling for later use when the conversion rate reaches over 96 percent. Finally, the acrylic ester latex with the solid content of 35.4 percent and the arithmetic mean grain diameter of 0.060 mu m is obtained.
(2) Diameter enlargement of copolymer latex
22.6 parts (including 8.0 parts of a dry base) of the above acrylic latex was taken, 4.8 parts of a sodium chloride aqueous solution having a pH of 5.6 (adjusted with 0.10M nitric acid) and a concentration of 5.0 wt% was added dropwise thereto at 35 ℃ under stirring, whereupon the latex color changed from bluish white to off-white, the arithmetic mean particle diameter of the latex was determined to be 0.192. mu.m, and the latex was filtered through a 40-mesh screen with substantially no scum.
(3) Vinyl chloride graft copolymerization
Adding 150 parts of desalted water, 0.17 part of hydroxypropyl methyl cellulose FON50 (a product of shin-Etsu chemical company), 0.07 part of polyvinyl alcohol LW-200 (a product of Japan synthetic chemistry), 0.04 part of tert-butyl peroxyneodecanoate, 0.08 part of tert-amyl peroxypivalate and 0.22 part of ammonium bicarbonate into a 10L pressure polymerization kettle in proportion, replacing the kettle with nitrogen, vacuumizing to be below-0.090 MPa, adding 100 parts of vinyl chloride monomer, stirring and mixing for 10 minutes at normal temperature, adding the expanded acrylic latex in the step (2), heating to 63 ℃ for reaction, adding 0.01 part of termination agent Diethylhydroxylamine (DEHA) when the pressure is reduced to 0.33MPa, degassing, dehydrating and drying the obtained polymer slurry to obtain the vinyl chloride graft of acrylic ester. After polymerization, the kettle wall and the baffle surface are clean, a small amount of polymer lumps are formed at the stirring shaft and the blade end, and the dry mass of the polymer lumps is only 0.039 wt% of the mass of the graft copolymer. After the reaction, the total mass of the polymer was weighed, and the polymerization conversion of vinyl chloride was calculated to be 85% and the content of the acrylic copolymer was calculated to be 8.6%. The analysis revealed that the arithmetic mean particle diameter of vinyl chloride copolymer resin particles was 177 μm and the apparent density was 0.47g/mL, and that the impact strength of a simple beam notched bar at room temperature (23 ℃ C.) was 96kJ/m after compounding, blending, processing into a sheet and sampling the copolymer according to the above-mentioned evaluation method 2 。
Example 5
(1) Preparation of acrylate latex
200.0 parts of desalted water, 90 parts of butyl acrylate, 10 parts of ethyl acrylate, 1.2 parts of diallyl phthalate, 2.0 parts of potassium laurate, 0.40 part of potassium chloride and 0.20 part of sodium hydroxide are added into a 2L glass kettle provided with a stirrer, a reflux condenser tube and a jacket, the air in the kettle is purged by nitrogen, the stirring is started, the temperature is raised to 60 ℃, and 0.50 part of potassium persulfate is added to initiate polymerization reaction. And cooling for later use when the conversion rate reaches more than 95%. Finally, the acrylate latex with the solid content of 34.1 percent and the arithmetic mean particle size of 0.071 mu m is obtained.
(2) Diameter enlargement of copolymerized latex
26.4 parts (including 9.0 parts on a dry basis) of the above acrylic latex was taken, and 5.4 parts of a sodium chloride aqueous solution having a pH of 5.9 (adjusted with 0.10M hydrochloric acid solution) and a concentration of 4.0 wt% was added dropwise thereto at 37 ℃ under stirring, whereupon the latex color changed from bluish white to off-white, the arithmetic mean particle diameter of the latex was determined to be 0.288M, and the latex was filtered through a 40-mesh screen with substantially no scum.
(3) Vinyl chloride graft copolymerization
Adding 120 parts of desalted water, 0.19 part of hydroxypropyl methyl cellulose FON50 (a product of shin-Etsu chemical company), 0.02 part of polyvinyl alcohol LM-10HD (a product of Japan synthetic chemical company), 0.020 part of cumyl peroxyneodecanoate, 0.080 part of bis (2-ethylhexyl) peroxydicarbonate and 0.15 part of ammonium bicarbonate into a 10L pressure polymerization kettle in proportion, replacing the kettle with nitrogen, vacuumizing to below-0.090 MPa, adding 100 parts of vinyl chloride monomer, stirring and mixing for 10 minutes at normal temperature, adding the expanded acrylic ester latex in the step (2), heating to 55 ℃ for reaction, adding 0.01 part of terminator Diethylhydroxylamine (DEHA) when the pressure drops to 0.20MPa, degassing, dehydrating and drying the obtained polymer slurry to obtain the vinyl chloride graft of acrylic ester. After polymerization, the kettle wall and the baffle surface are clean, a small amount of polymer agglomerates are formed at the stirring shaft and the blade end, and the dry mass of the polymer agglomerates is only 0.030 wt% of the mass of the graft copolymer. After the reaction, the total mass of the polymer was weighed, and the polymerization conversion of vinyl chloride was calculated to be 83%, and the content of the acrylic copolymer was calculated to be 9.8%. The obtained vinyl chloride copolymer resin particles had an arithmetic mean particle diameter of 166 μm and an apparent density of 0.48g/mL, and after compounding, blending, processing into a sheet and sampling the copolymer according to the above-mentioned evaluation method, the impact strength of a simple beam notched bar at room temperature (23 ℃ C.) was measured to be 108kJ/m 2 。
Comparative example 1
The latex prepared in example 1 and the amount thereof were used without diameter expansion and by the same vinyl chloride graft copolymerization process, the results were: a little of caking is generated at the ends of the stirring shaft and the blades, the caking drying quality is 0.110 percent of the mass of the graft polymer, the vinyl chloride conversion rate is 82.8 percent, the content of the acrylic ester latex is 10.8 percent, the granularity of the vinyl chloride graft polymer is 190 mu m, the apparent density is 0.41g/mL, the graft copolymer is subjected to material preparation, blending, processing and sheet making according to the evaluation method, and the notch impact strength of the simply supported beam at the normal temperature (23 ℃) is measuredIs 71kJ/m 2 。
The acrylate latex graft copolymer without expansion is seen to have a lower impact strength.
Comparative example 2
The latex and the amount of the expanding agent prepared in example 2 were used, and the same amount of the expanding agent was used, except that the aqueous solution of the expanding agent was not subjected to pH adjustment, and the obtained expanded latex had an arithmetic mean particle diameter of 0.192. mu.m, and no scum was observed after filtration through a 40-mesh nylon mesh. The same vinyl chloride grafting process as in example 2 was used again, with the results: the wall and the baffle of the polymerization kettle are provided with pockmark-shaped agglomerates, the stirring shaft and the blade end are provided with agglomerates, and the dry mass of the agglomerates is 0.15 percent of the mass of the graft copolymer. The conversion rate of chloroethylene is 84.3%, the content of acrylic ester latex is 15.1%, the arithmetic mean particle diameter of graft copolymer particles is 213 micrometers, and apparent density is 0.48g/mL, after the graft copolymer is undergone the processes of proportioning, blending, processing and sheet-making and sample-making, the impact strength of simple beam notch under the normal temperature (23 deg.C) is measured and is 122kJ/m 2 。
It can be seen that the stability of the obtained graft copolymer system is poor when the expanding agent is not adjusted in pH value.
Comparative example 3
The diameter of the acrylic latex of example 1 was enlarged, and the pH of the solution was adjusted to 2.2 with the diameter-enlarging agent in a different place, and after the diameter of the acrylic latex was enlarged with the diameter-enlarging agent, a large amount of rice-like smear was filtered out from the enlarged acrylic latex, and the arithmetic mean particle diameter of the latex was 0.276. mu.m. The situation that the diameter expanding effect of the inorganic salt diameter expanding agent is influenced by too low pH value and too strong acidity of the diameter expanding agent solution is shown.
Comparative example 4
The acrylate latex of example 3 and the diameter expansion process were used except that the amount of desalted water used in the vinyl chloride grafting process was 320 parts. The final result is: the surfaces of the kettle wall and the baffle are free from agglomeration and skinning, the stirring shaft and the blade end are agglomerated, the mass of the agglomerated dry matter is 0.029 percent of the mass of the graft copolymer, the conversion rate of the chloroethylene is 85.55 percent, the arithmetic mean particle diameter of the graft polymer particles is 129 mu m, the apparent density is 0.45g/mL, the graft copolymer is subjected to burdening, blending, processing and flaking and sample preparation, and the notch punching of the simply supported beam at the normal temperature (23 ℃) is determinedThe impact strength is 45kJ/m 2 。
It can be seen that the impact resistance of the final polymer resin is lowered by using an excessive amount of desalted water in the graft copolymerization of vinyl chloride.
It should be understood that the above description is only a preferred embodiment of the present invention, and not intended to limit the present invention, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents may be made in the technical solutions described in the foregoing embodiments, or some technical features may be substituted. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A preparation method of a high-toughness graft copolymer is characterized by comprising the following steps:
step (1) preparation of acrylate latex:
mixing and stirring a monomer mixture consisting of 100 parts of acrylate monomers and 0.01-10 parts of crosslinking monomers with 150-250 parts of desalted water, 0.5-3.0 parts of emulsifying agent, 0.10-1.0 part of free radical thermal initiator and 0.01-0.3 part of strong base or alkaline salt, and reacting at 50-80 ℃ to obtain acrylate latex with 25-40 wt% of solid content and 0.050-0.100 mu m of number average particle diameter; the emulsifier is strong alkaline saponification metal salt of straight chain fatty acid with straight chain alkyl containing 12-18 carbon atoms, including sodium salt or potassium salt, and the straight chain fatty acid includes lauric acid, palmitic acid or stearic acid; the free radical thermal initiator is persulfate, including potassium salt, sodium salt or ammonium salt; the strong base comprises sodium hydroxide or potassium hydroxide, and the alkaline salt comprises sodium carbonate, sodium bicarbonate or sodium pyrophosphate;
expanding the diameter of the latex in the step (2):
diluting the acrylate latex prepared in the step (1) to a solid content of 25-35 wt%, adding an inorganic salt aqueous solution with a concentration of 5-10 wt% and a pH value of 4.0-6.0 at a temperature of 20-40 ℃ under stirring, and agglomerating and expanding acrylate latex particles to a number average particle diameter of 0.10-0.40 mu m; the using amount of the inorganic salt is 1.0-10 parts by 100 parts of acrylate dry-base adhesive, and the acrylate dry-base adhesive is the acrylate copolymer in the acrylate latex obtained in the step (1);
vinyl chloride graft copolymerization in step (3):
and (3) graft polymerizing the whole acrylate expanded diameter latex obtained in the step (2) with 110-200 parts of desalted water, 0.10-0.20 part of dispersing agent, 0.05-0.20 part of initiator, 0.001-0.20 part of alkaline salt and 100 parts of vinyl chloride monomer under the conditions of stirring and 55-65 ℃, discharging slurry after reaching specified pressure drop, and performing centrifugal dehydration, drying and screening to obtain the vinyl chloride graft copolymer containing the large-particle-size acrylate copolymer rubber particles.
2. The method for preparing the high toughness graft copolymer as claimed in claim 1, wherein the acrylate monomer in step (1) is an acrylate monomer having 2-4 carbon atoms in the alkyl chain, and the acrylate monomer contains 80-100 wt% of butyl acrylate and 20-0 wt% of ethyl acrylate.
3. The method for preparing a highly toughened graft copolymer according to claim 1, wherein the crosslinking monomer in the step (1) comprises diallyl phthalate, allyl methacrylate or 1, 4-butylene glycol dimethacrylate.
4. The method for preparing a highly toughened graft copolymer as claimed in claim 1, wherein the inorganic salt in the aqueous solution of the inorganic salt in the step (2) is sodium chloride, potassium chloride, sodium nitrate, potassium nitrate, sodium sulfate or potassium sulfate.
5. The method for preparing a highly toughened graft copolymer according to claim 1, wherein the dispersant in the step (3) comprises hydroxypropylmethylcellulose having a methoxy group content of 28 to 29%, a hydroxypropyl group content of 6.0 to 12.0%, and a viscosity of 40 to 60 mPa-s; the dispersion aid also comprises a dispersion aid agent, wherein the dispersion aid agent comprises water-soluble or oil-soluble polyvinyl alcohol with alcoholysis degree of 35-55 mol% and polymerization degree of 200-500, and the dosage of the dispersion aid agent is 0-0.10 part by mass based on 100 parts by mass of vinyl chloride monomer.
6. The method for preparing a highly toughened graft copolymer as claimed in claim 1, wherein the initiator in the step (3) comprises cumyl neodecanoate, di (2-ethylhexyl) peroxydicarbonate, t-butyl peroxyneodecanoate, t-amyl peroxypivalate or azobisisoheptonitrile.
7. The method of claim 1, wherein the alkali salt in step (3) comprises a water-soluble bicarbonate and a monovalent soluble strong base salt, wherein the water-soluble bicarbonate is ammonium bicarbonate and the monovalent soluble strong base salt is sodium hydroxide.
8. The method for preparing the highly toughened graft copolymer according to claim 1, comprising the steps of:
step (1) preparation of acrylate latex:
weighing 100 parts of acrylate monomer, 0.01-10 parts of crosslinking monomer, 150-250 parts of desalted water, 0.5-3.0 parts of emulsifier, 0.10-1.0 part of free radical thermal initiator and 0.01-0.3 part of strong base or alkaline salt, adding the desalted water, the emulsifier, the strong base or the alkaline salt and the acrylate monomer mixture containing the crosslinking monomer into a reactor, stirring and heating, introducing nitrogen to replace the air in the reactor, then adding the free radical thermal initiator for polymerization, and reacting at 50-80 ℃ to obtain the acrylate latex with 25-40 wt% of solid content and 0.050-0.100 mu m of number average particle diameter;
expanding the diameter of the latex in the step (2):
diluting the acrylate latex prepared in the step (1) to a solid content of 25-35 wt%, slowly dropwise adding an inorganic salt aqueous solution with a concentration of 5-10 wt% and a pH value of 4.0-6.0 at a temperature of 20-40 ℃ under a stirring condition, and agglomerating and expanding the acrylate latex particles to a number average particle diameter of 0.10-0.40 mu m;
vinyl chloride graft copolymerization in step (3):
preparing the whole acrylate expanded diameter latex obtained in the step (2), weighing 110-200 parts of desalted water, 0.10-0.20 part of dispersing agent, 0.05-0.20 part of initiator, 0.001-0.20 part of alkaline salt and 100 parts of vinyl chloride monomer, sequentially adding the desalted water, the dispersing agent, the initiator and the alkaline salt into a polymerization kettle at normal temperature, pumping vacuum, adding the vinyl chloride monomer, starting stirring and fully mixing, then adding the acrylate expanded diameter latex, then carrying out graft polymerization under the conditions of stirring and 55-65 ℃, discharging slurry after reaching specified pressure drop, and carrying out centrifugal dehydration, drying and screening operation to obtain the vinyl chloride graft copolymer containing the large-particle-size acrylate copolymer rubber particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911000105.6A CN112759714B (en) | 2019-10-21 | 2019-10-21 | Preparation method of high-toughness graft copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911000105.6A CN112759714B (en) | 2019-10-21 | 2019-10-21 | Preparation method of high-toughness graft copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112759714A CN112759714A (en) | 2021-05-07 |
| CN112759714B true CN112759714B (en) | 2022-08-12 |
Family
ID=75691578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911000105.6A Active CN112759714B (en) | 2019-10-21 | 2019-10-21 | Preparation method of high-toughness graft copolymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112759714B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1256279A (en) * | 1998-12-07 | 2000-06-14 | 中国石化齐鲁石油化工公司 | Synthesis of transparnt shock-resisting modifier |
| CN104558428A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | High-toughened chloroethylene grafted copolymer and preparation method thereof |
| CN109467646A (en) * | 2018-10-10 | 2019-03-15 | 中国石油化工股份有限公司 | A kind of preparation method of vinyl chloride graft copolymer |
-
2019
- 2019-10-21 CN CN201911000105.6A patent/CN112759714B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1256279A (en) * | 1998-12-07 | 2000-06-14 | 中国石化齐鲁石油化工公司 | Synthesis of transparnt shock-resisting modifier |
| CN104558428A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | High-toughened chloroethylene grafted copolymer and preparation method thereof |
| CN109467646A (en) * | 2018-10-10 | 2019-03-15 | 中国石油化工股份有限公司 | A kind of preparation method of vinyl chloride graft copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112759714A (en) | 2021-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2088162B1 (en) | Method for manufacturing polymer dispersions, dispersions created thereby and their application | |
| EP1984428B1 (en) | Process for producing cationically stabilized and water-redispersible polymer powder compositions | |
| CN113717309B (en) | Processing modified additive and preparation method thereof | |
| DE19958820A1 (en) | Process for the production of thermoplastic molding compositions | |
| CN101195669B (en) | Method for producing partial fluorine ethylene polymer | |
| EP0072900B1 (en) | Process for the preparation of vinyl-chloride polymers and copolymers by suspension polymerisation, and their use in lowering the viscosity of plastisols | |
| EP2497787B1 (en) | Vinyl chloride-based polymer | |
| CN112759714B (en) | Preparation method of high-toughness graft copolymer | |
| JP2017538789A (en) | Acrylic processing aid and vinyl chloride resin composition containing the same | |
| JP3121818B2 (en) | Aqueous acrylic polymer dispersion and method for producing the same | |
| CN112759717B (en) | Method for preparing graft copolymer having excellent impact strength | |
| KR101225937B1 (en) | Method for preparing polyvinyl chloride-based graft copolymer | |
| IE43835B1 (en) | Production of dispersions of polyvinyl acetate | |
| CN114426645B (en) | Preparation method of vinyl chloride copolymer with improved impact resistance | |
| CN114426646B (en) | Preparation method of vinyl chloride graft copolymer with excellent processability | |
| CN109467633A (en) | A kind of preparation method of vinyl chloride-acrylate copolymer | |
| JP3093106B2 (en) | Vinyl chloride resin | |
| JP3262700B2 (en) | Vinyl chloride resin | |
| KR100431453B1 (en) | Method for preparing polyvinyl resin having superior high impact property | |
| JPH06240086A (en) | Production of vinyl chloride resin composition | |
| JP3382714B2 (en) | Vinyl chloride graft resin | |
| KR101102272B1 (en) | Process for Vinyl Chloride Graft Copolymer Resin | |
| KR100645676B1 (en) | Methylmethacrylate-Butadien-Styrene Resin Composition for Impact Modifier and Method for Preparing the Same | |
| KR100684442B1 (en) | Processing aid composition for vinyl chloride resin | |
| JP4102229B2 (en) | Vinyl chloride resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |