CN1563168A - Method for preparing nano composite material of polyethylene/montmorillonite - Google Patents
Method for preparing nano composite material of polyethylene/montmorillonite Download PDFInfo
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Abstract
A method for preparing polyethylene/imvite nanocomposite includes decorating layered inorganic nanoimvite with organic intercalator by applying cation exchanging process; processing decorated imvite with dispersing agent for forming uniform colloid solution of imvite and styrene; adding initiator, comonomer and antioxygen in colloid solution; mixing with polyethylene uniformly and obtaining the polyethylene/imivite nanocomposite through extruding and pelletizing.
Description
Technical field
The present invention relates to a kind of preparation method of polyethylene/montmorillonite nanometer composite material, relate in particular to the novel method that a kind of method with fusion-grafting prepares polyethylene/montmorillonite intercalation or exfoliated nano-composite.The invention belongs to polymeric material field.
Background technology
Since 1987 by Japanese Toyota researchdevelopment center synthetic nylon 6/ clay nano hybrid materials, this material is under the prerequisite of losing shock strength, toughness and transparency hardly, can improve the tensile strength and (the Usuki A.and Kojoma Y. such as tensile modulus, bending strength and composite bending modulus, heat-drawn wire, flame retardant resistance and barrier properties for gases of material significantly, Polym.Prepr., 28-447,1987), cause extensive concern and the interest of people to nano composite polymer-montmorillonoid material.Polyethylene be output big, use wider general-purpose plastics, the polyethylene nano composite material is at poly high performance and improve aspect such as its range of application and have important practical value.But polyethylene is not simply just to mix to obtain nano composite material with polynite, have only the interlayer of polynite is opened, form intercalation or exfoliated structure, could improve performance greatly, so the quality of polynite and polymer phase capacitive directly has influence on performance of composites.Polyethylene is a non-polar polymer, and the consistency of it and polynite is relatively poor, is difficult to obtain the nano composite material of excellent performance, so the most in-situ inserted polymeric method (Chinese patent application number: 99119653.8 that adopt of people; 00105797.9; 00107654.X; 02119744.X) prepare polyethylene/montmorillonite nanometer composite material, but this method must set about carrying out polymerization from vinyl monomer, but the polyethylene that polymerization is good directly can not be carried out modification, and its limitation is arranged.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of preparation method of polyethylene/montmorillonite nanometer composite material is proposed, technology is simple, do not need specific installation, only with common plastics extruder tool, cost is low, is suitable for scale operation, and the performance of material keeps original poly performance substantially, and its shock strength, barrier and thermostability are improved.
For realizing such purpose, in technical scheme of the present invention, at application for a patent for invention " preparation method of the in-situ inserted polymkeric substance of nano imvite-vinylbenzene " (application number: on the basis 03115777.7), earlier polynite is modified with organic intercalation agent, the polynite of modified is handled with dispersion agent again, be mixed and made into vinylbenzene/montmorillonite Composite colloid with vinylbenzene then, in composite gel, add monomer altogether, initiator and oxidation inhibitor, mix on high-speed mixer with polyethylene then, on twin screw extruder, carry out fusion-grafting at last and extrude, thereby prepare polyethylene/montmorillonite intercalation or exfoliated nano-composite.
The inventive method is carried out as follows:
1, adopting base exchange method that organic intercalation agent is carried out in the inorganic nano polynite modifies, with nano imvite powder and solvent ratio high-speed stirring on high-speed mixer in 1: 1～500 (weight ratios), rotating speed is 500-4500 rev/min, makes to form stable suspension system; Other presses organic intercalation agent and solvent the mixed of 1: 1～100 (weight ratios), stirring makes it abundant dissolving, then with this solution by joining in the suspension of polynite with the weight ratio of montmorillonite suspension liquid 1: 1～300, under 20-300 ℃ of temperature vigorous stirring 0.5-80 hour.After the filtration throw out is washed with hot solvent, the hot solvent consumption is equivalent to 2-50 times of weight of precipitate, stirs 0.5-10 hour, filters.Washing process repeats 2-5 time, to remove wherein remaining organism, with final product in 60 ℃ of following vacuum-dryings.
2, be to mix 5-60 minute on 500-6000 rev/min the high-speed mixer with the dispersion agent of organo montmorillonite 80-99.9 part of obtaining in the step 1 and 0.1-20 part (by weight), thereby make the polynite that can form stable and uniform colloidal solution with vinylbenzene at 30-120 ℃, rotating speed.
3, nano imvite in the step 2 and styrene monomer are at room temperature mixed with magnetic stirrer by weight 0.01～20: 1, the initiator, 0.3 ‰-100% oxidation inhibitor and the common monomer of 1%-300% that add the 0.5%-15% be equivalent to styrene monomer weight again, stir, make colloid mixture.
4, be 1～75: 100 colloid mixture with weight ratio with polyethylene be to mix 3-45 minute on 500-8000 rev/min the high-speed mixer at rotating speed; in common twin screw extruder, extrude then; extruder temperature is 120-300 ℃; rotating speed is 70-900 rev/min; the residence time of material in screw rod is 1-10 minute; after the material of extruding cools off through the water-cooled cooling tank; be granulation on 100-3000 rev/min the dicing machine at rotating speed, promptly get polyethylene/montmorillonite intercalation or exfoliated nano-composite.
Polyethylene of the present invention is polyethylene wax, ultra-low density polyethylene, new LDPE (film grade), linear low density polyethylene, high density polyethylene(HDPE), ultrahigh molecular weight polyethylene(UHMWPE), or the mixture of their compositions.
Inorganic nano polynite of the present invention is of a size of nano level at least on the one dimension direction, the disperse phase yardstick is the 1-100 nanometer.
Solvent of the present invention is toluene, dimethylbenzene, perhydronaphthalene, whiteruss, kerosene, water, ethanol, methyl alcohol, acetone, ethylene dichloride or sherwood oil.
Organic intercalation agent of the present invention is the hexadecyl brometo de amonio, the n-cetyltrimethyl ammonium, dimethyl benzene ethyl dodecyl chlorination ammonium, octadecyl bromination ammonium, cetyl trimethylammonium bromide, methylacryoyloxyethyl-benzyl-alkyl dimethyl ammonium chloride, hexadecyl-phenyl-azo pyridine ammonium chloride, vinyl benzyl-dimethyl dodecyl chlorination ammonium, vinyl benzyl-dimethyl cetyl chloride ammonium, methylacryoyloxyethyl-benzyl-dimethyl brometo de amonio, the 3,5-dimethylphenyl octadecyl ammonium chloride, hexadecyl-phenyl-azo pyridine brometo de amonio, two octadecyl bromination ammoniums, dimethyl stearyl ammonium chloride, vinyl benzyl-dimethyl dodecyl bromination ammonium, or the mixture of their compositions.
Dispersion agent of the present invention is whiteruss, Resins, epoxy, silane coupling agent, metatitanic acid coupling agent, silicone oil, vulcabond, glycerine, ethylene glycol, ethylene waxes, ethyl acetate, methyl methacrylate, or the mixture of their compositions.
Initiator of the present invention is azo-bis-isobutyl cyanide (AIBN), dicumyl peroxide (DCP), benzoyl peroxide (BPO), t-butyl peroxide (TBP), or the mixture of being made up of them.
Monomer altogether of the present invention is the mixture of vinylformic acid, α-Jia Jibingxisuan, acrylamide, methyl glycidyl ester, maleic anhydride, hexanolactam, vinyl pyrrolidone, methyl methacrylate or their compositions, but is the response type monomer of a class electron donor.
Oxidation inhibitor of the present invention is antioxidant 1010, oxidation inhibitor 1098, oxidation inhibitor 168, antioxidant 264, anti-oxidant DLTP, dihydroxyphenyl propane, antioxidant BHT or triphenyl phosphite, or the mixture of being made up of them.
The present invention's employing in-situ inserted polymerization different from the past is equipped with the method for polyethylene/montmorillonite intercalation or exfoliated nano-composite, polynite that utilization was handled and styrene monomer can form stable colloid and styrene monomer is easy and the characteristics of polyethylene fusion-grafting, method with fusion-grafting prepares polyethylene/montmorillonite intercalation or exfoliated nano-composite, not only overcome polyethylene and polynite and be difficult to the blended weakness, and obtained polyethylene/montmorillonite nanometer composite material, method is simple, equipment is simple, is convenient to scale operation.The polyethylene/montmorillonite intercalation or the exfoliated nano-composite of the present invention's preparation are compared with pure polyethylene, had higher shock strength, barrier and thermostability, have wide industrial to be worth and application prospect.
Embodiment
Following embodiment further specifies of the present invention, rather than limits the scope of the invention.
Embodiment 1
Add 32 gram vinyl benzyl-dimethyl cetyl chloride amine in 500 milliliters beaker, 35 milliliters of concentrated hydrochloric acids and 100 gram deionized waters are heated to 85 ℃ with this solution, make vinyl benzyl-dimethyl cetyl chloride ammonium intercalator.In addition, 35 gram polynites are dispersed in the solvent deionized water of 90 ℃ of 500 grams, stir.The solution that will contain vinyl benzyl-dimethyl cetyl chloride ammonium intercalator then joins in the suspended dispersed liquid of this polynite, and vigorous stirring 1.5 hours.After overanxious white precipitate placed 1000 milliliters beaker, add 500 gram hot water, stirred 1 hour, and filtration.This process repeats more than three times, to remove wherein residual ammonium salt.Final product filtration and cooling drying is standby.Be to mix 15 minutes on 600 rev/mins the high-speed mixer then with the organo montmorillonite that makes 25 grams and the 0.3 dispersant liq paraffin that restrains, thereby make the polynite that can form stable and uniform colloidal solution with vinylbenzene at 70 ℃, rotating speed.The above-mentioned polynite that obtains 15 grams and 10 gram vinylbenzene are made it to mix with magnetic stirrer in large beaker; add 0.05 gram initiator benzoyl peroxide; 2 grams are monomer vinylformic acid and 0.1 gram antioxidant 1010 altogether; stir; mix with 500 gram linear low density polyethylenes again; in common twin screw extruder, extrude then and make pellet; extruder temperature is 160 ℃ of feeding sections; 165 ℃ of compression sections; 180 ℃ of 170 ℃ of homogenizing zones and die temperatures; rotating speed is 240 rev/mins; the residence time of material in screw rod is 3 minutes; after the material of extruding cools off through the water-cooled cooling tank; through the dicing machine pelletizing; obtain pellet; 80 ℃ of dryings are 24 hours in baking oven; promptly get polyethylene/montmorillonite nanometer composite material; this material is compared with not compound preceding linear low density polyethylene, and its shock strength improves more than 40%; 10 ℃ of heat decomposition temperature raisings and barrier have improved 1 times.
Embodiment 2
Add 85 gram hexadecyl trimethyl ammonium bromide in 500 milliliters beaker, 40 milliliters of concentrated hydrochloric acids and 150 gram deionized waters are heated to 90 ℃ with this solution, make the cetyl trimethylammonium bromide intercalator.In addition, 36 gram polynites are dispersed in the solvent deionized water of 90 ℃ of 400 grams, stir.The solution that will contain the cetyl trimethylammonium bromide intercalator then joins in the dispersion liquid of this polynite, and vigorous stirring 2 hours.After overanxious white precipitate placed 500 milliliters beaker, add 350 gram hot water, stirred 2.5 hours, and filtration.This process repeats more than three times, to remove wherein residual ammonium salt.Final product filtration and cooling drying is standby.Be to mix 30 minutes on 750 rev/mins the high-speed mixer then with the organo montmorillonite that makes 30 grams and the 1 dispersion agent vulcabond that restrains, thereby make the polynite that can form stable and uniform colloidal solution with vinylbenzene at 80 ℃, rotating speed.The above-mentioned polynite that obtains 25 grams and 30 gram vinylbenzene are made it to mix with magnetic stirrer in large beaker; add 0.1g initiator azo-bis-isobutyl cyanide; 40 grams are monomer hexanolactam and 6 gram oxidation inhibitor 168 altogether; stir; mix with 500 gram high density polyethylene(HDPE)s again; in common twin screw extruder, extrude then and make pellet; extruder temperature is 165 ℃ of feeding sections; 175 ℃ of compression sections; 190 ℃ of 180 ℃ of homogenizing zones and die temperatures; rotating speed is 300 rev/mins; the residence time of material in screw rod is 2.5 minutes; after the material of extruding cools off through the water-cooled cooling tank; through the dicing machine pelletizing; obtain pellet; 80 ℃ of dryings are 30 hours in baking oven; promptly get polyethylene/montmorillonite nanometer composite material; this material is compared with compound preceding pure high density polyethylene(HDPE), and its shock strength improves more than 45%; 20 ℃ of heat decomposition temperature raisings and barrier have improved 1.2 times.
Embodiment 3
Add 56 gram 3,5-dimethylphenyl octadecyl chlorination amine in 500 milliliters beaker, 30 milliliters of concentrated hydrochloric acids and 180 gram deionized waters are heated to 120 ℃ with this solution, make 3,5-dimethylphenyl octadecyl ammonium chloride intercalator.In addition, 40 gram polynites are dispersed in the solvent deionized water of 120 ℃ of 350 grams, stir.The solution that will contain 3,5-dimethylphenyl octadecyl ammonium chloride intercalator then joins in the dispersion liquid of this polynite, and vigorous stirring 5 hours.After overanxious white precipitate placed 500 milliliters beaker, add 300 gram hot water, stirred 3 hours, and filtration.This process repeats more than three times, to remove wherein residual ammonium salt.Final product filtration and cooling drying is standby.Be to mix 45 minutes on 800 rev/mins the high-speed mixer then with the organo montmorillonite that makes 25 grams and the 1.8 dispersion agent methyl methacrylates that restrain, thereby make the polynite that can form stable and uniform colloidal solution with vinylbenzene at 75 ℃, rotating speed.The above-mentioned polynite that obtains 20 grams and 50 gram vinylbenzene are made it to mix with magnetic stirrer in large beaker; add 0.2g initiator t-butyl peroxide (TBP); 15 grams are monomer vinyl pyrrolidone and 3 gram oxidation inhibitor dihydroxyphenyl propanes altogether; stir; mix with 200 gram high density polyethylene(HDPE)s and 350 gram ultrahigh molecular weight polyethylene(UHMWPE)s again; in common twin screw extruder, extrude then and make pellet; extruder temperature is 180 ℃ of feeding sections; 185 ℃ of compression sections; 200 ℃ of 190 ℃ of homogenizing zones and die temperatures; rotating speed is 150 rev/mins; the residence time of material in screw rod is 4 minutes; after the material of extruding cools off through the water-cooled cooling tank; through the dicing machine pelletizing; obtain pellet; 80 ℃ of dryings are 30 hours in baking oven; promptly get polyethylene/montmorillonite nanometer composite material; this material is compared with compound preceding pure polyethylene, and its shock strength improves more than 30%; 15 ℃ of heat decomposition temperature raisings and barrier have improved 1.4 times.
Embodiment 4
In 500 milliliters beaker, add 60 gram methylacryoyloxyethyl-benzyl-dimethyl amine bromides and 20 gram octadecyl bromination amine, 45 milliliters of concentrated hydrochloric acids and 200 gram deionized waters, this solution is heated to 120 ℃, makes methylacryoyloxyethyl-benzyl-dimethyl brometo de amonio and octadecyl bromination ammonium mixing intercalator.In addition, 50 gram polynites are dispersed in the solvent deionized water of 100 ℃ of 350 grams, stir.The solution that will contain above-mentioned mixing intercalator then joins in the dispersion liquid of this polynite, and vigorous stirring 3 hours.After overanxious white precipitate placed 500 milliliters beaker, add 400 gram hot water, stirred 2 hours, and filtration.This process repeats more than three times, to remove wherein residual ammonium salt.Final product filtration and cooling drying is standby.Be to mix 35 minutes on 2000 rev/mins the high-speed mixer then with the dispersion agent metatitanic acid coupling agents of the organo montmorillonite that makes 35 grams and 1.2 grams and the 3 dispersion agent ethylene glycol that restrain, thereby make the polynite that can form stable and uniform colloidal solution with vinylbenzene at 50 ℃, rotating speed.The above-mentioned polynite that obtains 30 grams and 3 gram vinylbenzene are made it to mix with magnetic stirrer in large beaker; add 0.1g initiator azo-bis-isobutyl cyanide (AIBN) and 0.2 gram initiator dicumyl peroxide (DCP); 1 gram is monomer maleic anhydride and 0.5 gram oxidation inhibitor antioxidant 264 and 1 gram oxidation inhibitor triphenyl phosphite altogether; stir; mix with 600 gram new LDPE (film grade)s again; in common twin screw extruder, extrude then and make pellet; extruder temperature is 140 ℃ of feeding sections; 145 ℃ of compression sections; 165 ℃ of 160 ℃ of homogenizing zones and die temperatures; rotating speed is 240 rev/mins; the residence time of material in screw rod is 3 minutes; after the material of extruding cools off through the water-cooled cooling tank; through the dicing machine pelletizing; obtain pellet; 60 ℃ of dryings are 24 hours in baking oven; promptly get polyethylene/montmorillonite nanometer composite material; this material is compared with compound preceding pure new LDPE (film grade), and its shock strength improves more than 50%; 12 ℃ of heat decomposition temperature raisings and barrier have improved 1.1 times.
Claims (9)
1, a kind of preparation method of polyethylene/montmorillonite nanometer composite material is characterized in that carrying out as follows:
1) adopt base exchange method that organic intercalation agent is carried out in the inorganic nano polynite and modify, with nano imvite powder and solvent by weight 1: 1～500 on high-speed mixer high-speed stirring, rotating speed is 500-4500 rev/min, makes the stable suspension system of formation; In addition organic intercalation agent is mixed by weight 1: 1～100 with solvent, stirring makes it abundant dissolving, then with this solution by joining in the suspension of polynite with the weight ratio of montmorillonite suspension liquid 1: 1～300, under 20-300 ℃ of temperature vigorous stirring 0.5-80 hour.After the filtration throw out is washed with hot solvent, the hot solvent consumption is equivalent to 2-50 times of weight of precipitate, stirs 0.5-10 hour, filters.Washing process repeats 2-5 time, to remove wherein remaining organism, with final product in 60 ℃ of following vacuum-dryings;
2) be to mix 5-60 minute on 500-6000 rev/min the high-speed mixer by weight with the dispersion agent of organo montmorillonite 80-99.9 part of obtaining in the step 1 and 0.1-20 part, make the polynite that can form stable and uniform colloidal solution with vinylbenzene at 30-120 ℃, rotating speed;
3) nano imvite in the step 2 and styrene monomer are at room temperature mixed with magnetic stirrer by weight 0.01～20: 1, add 0.5 ‰-15% the initiator be equivalent to styrene monomer weight, 0.3 ‰-100% oxidation inhibitor and the common monomer of 1%-300% again, stir, make colloid mixture;
4) be 1～75: 100 colloid mixture with weight ratio with polyethylene be to mix 3-45 minute on 500-8000 rev/min the high-speed mixer at rotating speed; in common twin screw extruder, extrude then; extruder temperature is 120-300 ℃; rotating speed is 70-900 rev/min; the residence time of material in screw rod is 1-10 minute; after the material of extruding cools off through the water-cooled cooling tank; be granulation on 100-3000 rev/min the dicing machine at rotating speed, promptly get polyethylene/montmorillonite intercalation or exfoliated nano-composite.
2, the preparation method of polyethylene/montmorillonite nanometer composite material as claimed in claim 1, it is characterized in that described polyethylene is polyethylene wax, ultra-low density polyethylene, new LDPE (film grade), linear low density polyethylene, high density polyethylene(HDPE), ultrahigh molecular weight polyethylene(UHMWPE), or the mixture of their compositions.
3, the preparation method of polyethylene/montmorillonite nanometer composite material as claimed in claim 1 is characterized in that described inorganic nano polynite is of a size of nano level at least on-Wei direction, and the disperse phase yardstick is the 1-100 nanometer.
4, the preparation method of polyethylene/montmorillonite nanometer composite material as claimed in claim 1 is characterized in that described solvent is toluene, dimethylbenzene, perhydronaphthalene, whiteruss, kerosene, water, ethanol, methyl alcohol, acetone, ethylene dichloride or sherwood oil.
5, the preparation method of polyethylene/montmorillonite nanometer composite material as claimed in claim 1, it is characterized in that described organic intercalation agent is the hexadecyl brometo de amonio, the n-cetyltrimethyl ammonium, dimethyl benzene ethyl dodecyl chlorination ammonium, octadecyl bromination ammonium, cetyl trimethylammonium bromide, methylacryoyloxyethyl-benzyl-alkyl dimethyl ammonium chloride, hexadecyl-phenyl-azo pyridine ammonium chloride, vinyl benzyl-dimethyl dodecyl chlorination ammonium, vinyl benzyl-dimethyl cetyl chloride ammonium, methylacryoyloxyethyl-benzyl-dimethyl brometo de amonio, the 3,5-dimethylphenyl octadecyl ammonium chloride, hexadecyl-phenyl-azo pyridine brometo de amonio, two octadecyl bromination ammoniums, dimethyl stearyl ammonium chloride, vinyl benzyl-dimethyl dodecyl bromination ammonium, or the mixture of their compositions.
6, the preparation method of polyethylene/montmorillonite nanometer composite material as claimed in claim 1, it is characterized in that described dispersion agent is whiteruss, Resins, epoxy, silane coupling agent, metatitanic acid coupling agent, silicone oil, vulcabond, glycerine, ethylene glycol, ethylene waxes, ethyl acetate, methyl methacrylate, or the mixture of their compositions.
7, the preparation method of polyethylene/montmorillonite nanometer composite material as claimed in claim 1, it is characterized in that described initiator is azo-bis-isobutyl cyanide (AIBN), dicumyl peroxide (DCP), benzoyl peroxide (BPO), t-butyl peroxide (TBP), or the mixture of forming by them.
8, the preparation method of polyethylene/montmorillonite nanometer composite material as claimed in claim 1 is characterized in that described monomer altogether is the mixture of vinylformic acid, α-Jia Jibingxisuan, acrylamide, methyl glycidyl ester, maleic anhydride, hexanolactam, vinyl pyrrolidone, methyl methacrylate or their compositions.
9, the preparation method of polyethylene/montmorillonite nanometer composite material as claimed in claim 1, it is characterized in that described oxidation inhibitor is antioxidant 1010, oxidation inhibitor 1098, oxidation inhibitor 168, antioxidant 264, anti-oxidant DLTP, dihydroxyphenyl propane, antioxidant BHT or triphenyl phosphite, or the mixture of forming by them.
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| CN103805147A (en) * | 2012-11-12 | 2014-05-21 | 长江大学 | Oil-based drilling fluid organic soil activator |
| CN104744842A (en) * | 2015-03-24 | 2015-07-01 | 合肥会通新材料有限公司 | Polystyrene composite material reinforced by in situ-polymerization of montmorillonite intercalation and preparation method of polystyrene composite material |
| CN107216492A (en) * | 2017-07-12 | 2017-09-29 | 徐州诺克非医药科技有限公司 | A kind of preparation method of the nano composite water absorbing material of montmorillonoid-containing |
| CN108864530A (en) * | 2018-05-31 | 2018-11-23 | 安徽电信器材贸易工业有限责任公司 | A kind of optical cable composite material |
| CN109346655A (en) * | 2018-09-21 | 2019-02-15 | 江苏微能电子科技有限公司 | Over capacity stablizes lithium battery and preparation method thereof |
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| CN110975930A (en) * | 2019-11-28 | 2020-04-10 | 万华化学集团股份有限公司 | Preparation method of isomerization catalyst and method for catalyzing vitamin A isomer conversion by using isomerization catalyst |
| CN112852390A (en) * | 2019-11-28 | 2021-05-28 | 中国石油化工股份有限公司 | Organic clay and preparation method and application thereof |
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| CN103805147A (en) * | 2012-11-12 | 2014-05-21 | 长江大学 | Oil-based drilling fluid organic soil activator |
| CN104744842A (en) * | 2015-03-24 | 2015-07-01 | 合肥会通新材料有限公司 | Polystyrene composite material reinforced by in situ-polymerization of montmorillonite intercalation and preparation method of polystyrene composite material |
| CN107216492A (en) * | 2017-07-12 | 2017-09-29 | 徐州诺克非医药科技有限公司 | A kind of preparation method of the nano composite water absorbing material of montmorillonoid-containing |
| CN108864530A (en) * | 2018-05-31 | 2018-11-23 | 安徽电信器材贸易工业有限责任公司 | A kind of optical cable composite material |
| CN109346655A (en) * | 2018-09-21 | 2019-02-15 | 江苏微能电子科技有限公司 | Over capacity stablizes lithium battery and preparation method thereof |
| CN109517292A (en) * | 2018-10-12 | 2019-03-26 | 安徽优丽普科技有限公司 | A kind of excellent anti-aging PVC board and preparation method thereof of thermal stability |
| CN109371475A (en) * | 2018-10-12 | 2019-02-22 | 中国石油化工股份有限公司 | A kind of spinning process of ultra-high molecular weight polyethylene |
| CN109371475B (en) * | 2018-10-12 | 2021-04-06 | 中国石油化工股份有限公司 | Spinning method of ultra-high molecular weight polyethylene |
| CN110975930A (en) * | 2019-11-28 | 2020-04-10 | 万华化学集团股份有限公司 | Preparation method of isomerization catalyst and method for catalyzing vitamin A isomer conversion by using isomerization catalyst |
| CN112852390A (en) * | 2019-11-28 | 2021-05-28 | 中国石油化工股份有限公司 | Organic clay and preparation method and application thereof |
| CN110975930B (en) * | 2019-11-28 | 2022-08-05 | 万华化学集团股份有限公司 | Preparation method of isomerization catalyst and method for catalyzing vitamin A isomer conversion by using isomerization catalyst |
| CN116240006A (en) * | 2021-12-07 | 2023-06-09 | 天津大港油田滨港集团博弘石油化工有限公司 | Modified nano thick oil viscosity reducer and preparation method thereof |
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