CN112794949B - Preparation method of polybutadiene latex and prepared ABS resin - Google Patents
Preparation method of polybutadiene latex and prepared ABS resin Download PDFInfo
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- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/06—Butadiene
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- 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
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
- C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
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- 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
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The application provides a preparation method of polybutadiene latex, which is characterized in that functional monomers such as polyethylene glycol dimethacrylate and polypropylene glycol dimethacrylate are used for carrying out hydrophobic modification on nano-scale rutile titanium dioxide, and polybutadiene rubber is polymerized on the surface of the nano-scale rutile titanium dioxide to obtain the polybutadiene latex with a nano-scale rutile titanium dioxide inner core. The ABS resin prepared from the polybutadiene latex has a whiteness value of more than 90, and the impact resistance, tensile strength and bending strength of the ABS resin are also effectively improved.
Description
Technical Field
The invention belongs to the field of macromolecules, and particularly relates to a preparation method of polybutadiene latex and prepared ABS resin.
Background
ABS resin, the fifth most common plastic in the world, has a "sea-island" structure with polybutadiene rubber as a dispersed phase and styrene-acrylonitrile copolymer resin as a continuous phase. The ABS resin integrates the advantages of butadiene, styrene and acrylonitrile, so that the ABS resin has the characteristics of good dimensional stability, high chemical resistance, easy processing and forming, high impact resistance and the like, and is widely applied to the fields of home appliances, automobiles, electronics and the like.
With the improvement of the quality of life in recent years, in the field of household appliances in one of the application directions of ABS resins, people pay more attention to the appearance of household appliances, and many large-scale household appliance manufacturers are prompted to gradually take the apparent performance (such as whiteness) of ABS resin as a key factor for evaluating the quality of ABS resin products. Therefore, how to reduce the yellow index and improve the whiteness to obtain the ABS resin with excellent appearance quality has gradually become a hot problem to be solved urgently in the ABS industry.
CN109608782A discloses a preparation method of yellowing-resistant ABS resin, which introduces epoxy group in the grafting process, and utilizes the effect of the epoxy group and cyano group to slow down the cyclized yellowing reaction between acrylonitrile group in the ABS resin in the heating process, thereby reducing the yellow index of the ABS resin. The process of the reaction of the epoxy group and the cyano group introduced by the method is uncontrollable, and side reactions are more.
CN109942976A discloses a preparation method of yellowing-resistant and high-whiteness ABS resin, which introduces a polymeric phosphate monomer in the synthesis process of ABS grafted powder, and reduces the defects of the ABS resin, improves the self thermal oxidation aging resistance of the ABS resin, reduces the cross-linking aging degree of butadiene double bonds in the resin, prevents the cyclization reaction between cyano groups, and finally achieves the purposes of reducing the yellow index and improving the whiteness by chelating metal ions in a matrix resin. The polymerization type phosphate ester monomer adopted by the method is expensive and is not beneficial to large-scale industrial production.
CN103146133A discloses a nano TiO with anti-photoaging property 2 The preparation method of the ABS/ABS composite material comprises the step of extruding and granulating the ABS with nano TiO 2 Antioxidant, light stabilizer, ultraviolet absorbent, etc. are introduced into ABS resin system and rutile type nanometer TiO is utilized 2 The nano TiO with the light aging resistance is obtained by the excellent performance of long-acting shielding ultraviolet 2 An ABS composite material. But the method is to mix nano TiO by a physical blending method 2 Introducing ABS resin system and nano TiO 2 It is difficult to disperse uniformly in the resin and agglomeration easily occurs to cause a decrease in other properties of the ABS resin such as impact resistance.
Disclosure of Invention
The invention aims to provide a preparation method of polybutadiene latex, which is characterized in that functional monomers are used for carrying out hydrophobic modification on nano-scale rutile type titanium dioxide, and then polybutadiene rubber is polymerized on the surface of the nano-scale rutile type titanium dioxide to obtain the polybutadiene latex with nano-scale rutile type titanium dioxide inner core, so that the whiteness of ABS resin is improved on the premise of ensuring the mechanical properties such as the shock resistance and the like of the ABS resin.
The invention is realized by the following technical scheme:
in a first aspect, the present invention provides a process for the preparation of a polybutadiene latex, comprising the steps of:
adding 20-30 parts by weight of organic solvent, 1-5 parts by weight of titanium dioxide, 1-20 parts by weight of functional monomer and 60-100 parts by weight of first part of deionized water into a reactor, starting stirring, heating the reactor to 55-85 ℃ for heat preservation, adding 80-120 parts by weight of butadiene, 1-8 parts by weight of emulsifier, 0.1-3 parts by weight of electrolyte, 0.1-3 parts by weight of chain transfer agent, 0.1-3 parts by weight of initiator and 20-30 parts by weight of second part of deionized water into the reactor for polymerization reaction, stopping stirring when the particle size of polybutadiene latex is not less than 200nm and not more than 500nm, cooling the reactor to normal temperature, and filtering to obtain the polybutadiene latex.
Preferably, the method comprises the following steps:
adding 22-28 parts by weight of organic solvent, 1.5-4.5 parts by weight of titanium dioxide, 2-18 parts by weight of functional monomer and 70-90 parts by weight of first part of deionized water into a reactor, starting stirring, heating the reactor to 60-80 ℃ for heat preservation, after the heat preservation is carried out for 0.5-4.5 hours, adding 90-110 parts by weight of butadiene, 2-7 parts by weight of emulsifier, 0.5-2.5 parts by weight of electrolyte, 0.5-2.5 parts by weight of chain transfer agent, 0.5-2.5 parts by weight of initiator and 22-28 parts by weight of second part of deionized water into the reactor, continuing polymerization, stopping stirring when the particle size of polybutadiene latex is not less than 250nm and not more than 450nm, cooling the reactor to normal temperature, and filtering to obtain the polybutadiene latex.
In the method of the present invention, the organic solvent has a solubility of 20 parts by weight or more in 100 parts by weight of water at 25 ℃, and is preferably one or more selected from methanol, ethanol, N-propanol, isopropanol, N-butanol, isoamyl alcohol, ethylene glycol, N-dimethylformamide, and tetrahydrofuran, and more preferably ethylene glycol and/or isopropanol.
In the process of the present invention, the titanium dioxide is a nano-sized rutile titanium dioxide, preferably a rutile titanium dioxide having a size of 10 to 80nm, more preferably a rutile titanium dioxide having a size of 20 to 60 nm.
In the method, the functional monomer is one or more of polyethylene glycol dimethacrylate and polypropylene glycol dimethacrylate with the number average molecular weight of 200-10000.
In the method of the present invention, the emulsifier is an anionic emulsifier, preferably one or more of potassium oleate, potassium disproportionate abietate, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and sodium dioctyl sulfosuccinate, more preferably potassium oleate and/or potassium disproportionate abietate.
In the method of the invention, the electrolyte is one or more of potassium bicarbonate, potassium carbonate, sodium bicarbonate, sodium carbonate and sodium tripolyphosphate, and potassium bicarbonate and/or potassium carbonate are preferred.
In the method of the present invention, the chain transfer agent is one or two of n-dodecyl mercaptan and t-dodecyl mercaptan, and preferably t-dodecyl mercaptan.
In the process of the present invention, the initiator is selected from one or more of inorganic peroxides and organic peroxides, preferably one or more of potassium persulfate, sodium persulfate, ammonium persulfate, dicumyl peroxide, cumene hydroperoxide, more preferably potassium persulfate and/or sodium persulfate.
At present, a common method for introducing titanium dioxide into a resin system is physical blending, but a hydrophilic group (-OH) rich on the surface of titanium dioxide can cause the titanium dioxide to generate polar adsorption or moisture absorption during physical blending to generate agglomeration, so that the titanium dioxide is difficult to uniformly disperse in resin and has an obvious phase interface, which not only causes the mechanical property of the resin to be reduced, but also causes the titanium dioxide precipitation phenomenon in long-period use of the material to further influence the service performance and the service life of the product.
The invention mixes the nano-grade rutile type titanium dioxide with the functional monomer, and hydrophilic CH in the functional monomer 2 CH 2 O-group or CH 2 CH 2 CH 2 The O-group can generate hydrogen bond interaction with OH groups on the surface of the titanium dioxide so thatThe obtained functional monomer can be wrapped on the surface of the nano-scale rutile type titanium dioxide to obtain hydrophobic nano-rutile type titanium dioxide wrapped by polymerizable double bonds; then, polybutadiene was polymerized on the surface thereof to obtain a polybutadiene latex having a titanium dioxide core. According to the polybutadiene latex prepared by the method, the nano rutile type titanium dioxide can be uniformly dispersed in latex particles, so that the whiteness of the ABS resin prepared from the polybutadiene latex is improved; meanwhile, the nano rutile type titanium dioxide wrapped in the polybutadiene particles also improves the rigidity of the polybutadiene rubber particles without reducing the resin compatibility, so that the impact strength, the tensile strength and the bending strength of the prepared ABS resin are correspondingly improved.
In a second aspect, the present invention provides an ABS resin prepared from the polybutadiene latex prepared by the method of the present invention.
In the invention, the conventional technology in the field is to graft, coagulate, dehydrate and dry the prepared polybutadiene latex to obtain ABS rubber powder, and then to blend and granulate the ABS rubber powder with SAN resin to obtain ABS resin. The specific operation of obtaining the ABS rubber powder from the polybutadiene latex through grafting, coagulation, filtering, dehydration and drying can refer to pages 36-58 of the book "ABS resin production practice and application" written by Songzhou and the like, and the specific operation of obtaining the ABS resin through blending, extruding and granulating the ABS rubber powder and SAN resin can refer to pages 68-74 of the book.
The invention has the beneficial effects that:
the invention obtains the polybutadiene latex with the nanometer rutile titanium dioxide inner core by carrying out hydrophobic modification on the nanometer rutile titanium dioxide and polymerizing polybutadiene rubber on the surface of the nanometer rutile titanium dioxide. The ABS resin prepared from the polybutadiene latex prepared by the method provided by the invention has whiteness of more than 90, and the impact strength, the tensile strength and the bending strength of the resin are all improved to a certain extent.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
If the source information of the raw materials in the following examples and comparative examples of the present invention is not specifically described, the raw materials used in the examples or comparative examples are commercially available;
particle size test method of polybutadiene latex: according to the following steps of 1:40000 weight ratio polybutadiene samples were diluted with deionized water and tested by a malvern Nano-ZS90 particle sizer, the volume average particle size being the result.
Example 1
20kg of methanol, 1kg of rutile type titanium dioxide with the particle size of 20-40nm, 1kg of polyethylene glycol dimethacrylate with the number average molecular weight of 5000 and 90kg of a first part of deionized water are respectively added into a reactor and stirred, the reactor is heated to 55 ℃ and is kept warm for 0.1 hour, 110kg of butadiene, 2kg of potassium oleate, 1.9kg of potassium carbonate, 1.1kg of potassium bicarbonate, 0.1kg of n-dodecyl mercaptan, 1.5kg of potassium persulfate, 1.0kg of sodium persulfate and 20kg of a second part of deionized water are added into the reactor to continue polymerization, the particle size of latex in the reaction process is tested by a Malvern Nano-ZS90 particle size analyzer, the stirring is stopped when the particle size is 205nm, the reactor is cooled to the normal temperature, and the polybutadiene latex is obtained by filtering.
Examples 2 to 5
The differences between examples 2-5 and example 1 are shown in Table 1, and the remaining raw materials, experimental conditions and reaction steps are the same as those of example 1.
TABLE 1 differences between examples 2-5 and example 1
Comparative example 1
Respectively taking 108kg of deionized water, 100kg of butadiene, 2.2kg of potassium oleate, 2.3kg of disproportionated potassium rosinate, 1.5kg of potassium carbonate, 1.5kg of tert-dodecyl mercaptan, 0.9kg of potassium persulfate and 0.6kg of sodium persulfate, adding the materials into a reactor, starting stirring, heating the reactor to 75 ℃ for polymerization reaction, testing the particle size of latex in the reaction process by using a Malvern Nano-ZS90 type particle size analyzer, stopping stirring when the particle size is 352nm, cooling the reactor to normal temperature, and filtering to obtain polybutadiene latex.
Comparative example 2
Adding 20kg of methanol, 1kg of rutile type titanium dioxide with the particle size of 20-40nm and 90kg of a first part of deionized water into a reactor, starting stirring, heating the reactor to 55 ℃, keeping the temperature for 0.1 hour, adding 110kg of butadiene, 2kg of potassium oleate, 1.9kg of potassium carbonate, 1.1kg of potassium bicarbonate, 0.1kg of n-dodecyl mercaptan, 1.5kg of potassium persulfate, 1.0kg of sodium persulfate and 20kg of a second part of deionized water into the reactor, continuing polymerization, testing the particle size of latex in the reaction process by using a Malvern Nano-ZS90 type particle size meter, stopping stirring when the particle size is 214nm, reducing the reactor to the normal temperature, and filtering to obtain the polybutadiene latex.
ABS resins were prepared from the polybutadiene latices of the examples and comparative examples according to the invention and tested by injection molding into test specimens as follows:
1) Preparation of ABS graft latex
Into the reactor were charged 60kg (in terms of solid parts) of the polybutadiene latexes prepared in examples 1-5 and comparative examples 1 and 2, 100kg of deionized water, 0.001kg of FeSO 4 ·7H 2 O, 0.01kg of sodium pyrophosphate and 0.1kg of glucose, starting stirring, heating the reactor to 65 ℃, continuously adding a mixed pre-emulsion consisting of 0.2kg of cumene hydroperoxide, 30kg of styrene, 10kg of acrylonitrile, 0.5kg of tert-dodecyl mercaptan, 3kg of potassium oleate and 10kg of deionized water into the reactor, continuously adding the materials for 3 hours, heating the reactor to 75 ℃ after the materials are added, continuously reacting for 3 hours, cooling the reactor to the normal temperature, stopping stirring, and filtering to obtain the ABS grafted latex.
2) Preparation of ABS rubber powder
2kg MgSO 2 was added to the coagulation kettle 4 200kg of deionized water and stirring was switched on MgSO 4 Fully dissolving, and condensing the solutionHeating to 75 ℃, respectively adding 100kg of ABS grafted latex prepared in the step 1) into a coagulation kettle in a continuous feeding mode, wherein the continuous feeding time is 1 hour, heating the coagulation kettle to 90 ℃ after the feeding is finished, keeping the temperature for 1 hour, cooling the coagulation kettle to normal temperature, filtering, washing and dehydrating the coagulation slurry to obtain ABS wet rubber powder, and drying the ABS wet rubber powder at 65 ℃ by using a fluidized bed dryer until the water content is reduced<1% to obtain ABS rubber powder.
3) Preparation, injection molding and performance test of ABS resin
Adopting a double-screw extruder, taking SAN resin with LG chemical brand SA 30 as a blending continuous phase at 200-220 ℃, taking ABS rubber powder prepared in the step 2) as a blending dispersed phase, and respectively performing blending extrusion and granulation according to the polybutadiene rubber content of 15% to obtain the ABS resin.
Various test specimens are prepared on an injection molding machine at 190 ℃, and the whiteness, the impact strength, the tensile strength and the bending strength of the ABS resin are respectively obtained by testing according to ASTM D1925, ASTM D256, ASTM D638-2000 and ASTM D790-2000 standards, and the specific results are shown in Table 2.
TABLE 2ABS resin whiteness and mechanical Property test results
As can be seen from the test results of examples 1 to 5 and comparative examples 1 and 2, the ABS resin prepared using the polybutadiene latex prepared according to the present invention has excellent whiteness values and simultaneously the impact strength, tensile strength and flexural strength are effectively improved, compared to the ABS resin prepared from the polybutadiene latex prepared according to the comparative examples.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (11)
1. A method for preparing polybutadiene latex, which is characterized by comprising the following steps:
adding an organic solvent, titanium dioxide, a functional monomer and a first part of deionized water into a reactor, starting stirring, heating the reactor to 55-85 ℃ for heat preservation, adding butadiene, an emulsifier, an electrolyte, a chain transfer agent, an initiator and a second part of deionized water into the reactor for continuous polymerization reaction, stopping stirring when the particle size of polybutadiene latex is not less than 200nm and not more than 500nm, cooling the reactor to normal temperature, and filtering to obtain polybutadiene latex;
the titanium dioxide is rutile type titanium dioxide with the size of 10-80 nm;
the functional monomer is one or more of polyethylene glycol dimethacrylate and polypropylene glycol dimethacrylate with the number average molecular weight of 200-10000;
the titanium dioxide is used in an amount of 1 to 5 parts by weight relative to 80 to 120 parts by weight of butadiene.
2. The method of claim 1, wherein the components are used in amounts of: according to parts by weight, 20-30 parts of organic solvent, 1-5 parts of titanium dioxide, 1-20 parts of functional monomer, 60-100 parts of first part of deionized water, 80-120 parts of butadiene, 1-8 parts of emulsifier, 0.1-3 parts of electrolyte, 0.1-3 parts of chain transfer agent, 0.1-3 parts of initiator and 20-30 parts of second part of deionized water; the heat preservation time is 0.1-5 hours.
3. The method according to claim 1 or 2, wherein the organic solvent is selected from one or more of methanol, ethanol, N-propanol, isopropanol, N-butanol, isoamyl alcohol, ethylene glycol, N-dimethylformamide, and tetrahydrofuran.
4. The method according to claim 3, wherein the organic solvent is selected from ethylene glycol and/or isopropyl alcohol.
5. The method according to claim 1 or 2, wherein the emulsifier is an anionic emulsifier.
6. The method of claim 5, wherein the emulsifier is one or more of potassium oleate, potassium disproportionated rosin acid, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and sodium dioctyl sulfosuccinate.
7. The method according to claim 1 or 2, wherein the electrolyte is one or more of potassium bicarbonate, potassium carbonate, sodium bicarbonate, sodium carbonate, and sodium tripolyphosphate.
8. The method of claim 1 or 2, wherein the chain transfer agent is one or both of n-dodecyl mercaptan and t-dodecyl mercaptan.
9. The method according to claim 1 or 2, wherein the initiator is one or more selected from the group consisting of inorganic peroxides and organic peroxides.
10. The method according to claim 9, wherein the initiator is one or more of potassium persulfate, sodium persulfate, ammonium persulfate, dicumyl peroxide, and cumene hydroperoxide.
11. An ABS resin, characterized by being prepared from the polybutadiene latex prepared by the preparation process according to any one of claims 1 to 10.
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| JPH06102618A (en) * | 1992-09-21 | 1994-04-15 | Fuji Photo Film Co Ltd | Board for photographic printing paper |
| US7153573B2 (en) * | 2002-08-08 | 2006-12-26 | Kao Corporation | Polymer composite particle comprising metal oxide and silicone and/or fluorine and method of producing the same |
| CN101463171B (en) * | 2009-01-06 | 2011-12-14 | 山东日科化学股份有限公司 | Polychloroethylene mixture with excellent shock resistance and processability |
| FR2969158B1 (en) * | 2010-12-15 | 2013-01-18 | Arkema France | METHOD FOR CHOCY MODIFIERS AND SHOCK MODIFIED THERMOPLASTIC COMPOSITION HAVING IMPROVED HYDROLYTIC RESISTANCE |
| FR2969167B1 (en) * | 2010-12-15 | 2013-01-11 | Arkema France | MODIFIED THERMOPLASTIC COMPOSITION IMPROVED SHOCK |
| FR2969161B1 (en) * | 2010-12-15 | 2014-06-06 | Arkema France | NOVEL HEART-ECORCE MULTI-STEP POLYMER POWDER, PROCESS FOR PRODUCING THE SAME, AND COMPOSITION COMPRISING THE SAME |
| KR20150026838A (en) * | 2013-08-29 | 2015-03-11 | 주식회사 엘지화학 | Transparent ABS resin and transparent ABS resin composition |
| CN107189201B (en) * | 2017-06-09 | 2019-12-06 | 常州大学 | Inorganic oxide particle chemically modified by polymer, preparation method and application thereof |
| CN107619508A (en) * | 2017-09-25 | 2018-01-23 | 芜湖凯奥尔环保科技有限公司 | A kind of rubber composite |
| KR102288297B1 (en) * | 2017-09-29 | 2021-08-11 | 주식회사 엘지화학 | Method for preraing copolymer and copolymer |
| CN109853067A (en) * | 2019-03-01 | 2019-06-07 | 华东理工大学 | A kind of preparation method of viscose rayon delustring titanium dioxide |
| CN111073174B (en) * | 2019-12-25 | 2021-12-31 | 广东祺龙科技有限公司 | Odorless antistatic PVC composite material and preparation method thereof |
| CN111154041B (en) * | 2020-01-09 | 2022-07-12 | 万华化学集团股份有限公司 | Agglomerated latex for high impact ABS resin and preparation method thereof |
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