CN113717326A - Bio-based polyester type hydrophilic cotton and preparation method thereof - Google Patents
Bio-based polyester type hydrophilic cotton and preparation method thereof Download PDFInfo
- Publication number
- CN113717326A CN113717326A CN202111119085.1A CN202111119085A CN113717326A CN 113717326 A CN113717326 A CN 113717326A CN 202111119085 A CN202111119085 A CN 202111119085A CN 113717326 A CN113717326 A CN 113717326A
- Authority
- CN
- China
- Prior art keywords
- bio
- reaction
- ethylene glycol
- terephthalic acid
- polyester type
- 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.)
- Pending
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229920000742 Cotton Polymers 0.000 title claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 114
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 27
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002028 Biomass Substances 0.000 claims abstract description 20
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 17
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 14
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 13
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 24
- 238000006068 polycondensation reaction Methods 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 18
- 239000002202 Polyethylene glycol Substances 0.000 claims description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 12
- 229920002678 cellulose Polymers 0.000 claims description 11
- 239000001913 cellulose Substances 0.000 claims description 11
- 150000002148 esters Chemical group 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 229920005610 lignin Polymers 0.000 claims description 10
- 239000003381 stabilizer Substances 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 6
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 6
- 229930006000 Sucrose Natural products 0.000 claims description 6
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 6
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 6
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 6
- 239000008107 starch Substances 0.000 claims description 6
- 235000019698 starch Nutrition 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 6
- 239000008158 vegetable oil Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 230000032050 esterification Effects 0.000 claims description 5
- 238000005886 esterification reaction Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 238000006385 ozonation reaction Methods 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 claims description 4
- 150000003077 polyols Chemical class 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 3
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229940095102 methyl benzoate Drugs 0.000 claims description 3
- 238000006011 modification reaction Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 238000006136 alcoholysis reaction Methods 0.000 claims description 2
- 238000004523 catalytic cracking Methods 0.000 claims description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 2
- 230000033444 hydroxylation Effects 0.000 claims description 2
- 238000005805 hydroxylation reaction Methods 0.000 claims description 2
- MCVVUJPXSBQTRZ-ONEGZZNKSA-N methyl (e)-but-2-enoate Chemical compound COC(=O)\C=C\C MCVVUJPXSBQTRZ-ONEGZZNKSA-N 0.000 claims description 2
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 claims description 2
- 238000004227 thermal cracking Methods 0.000 claims description 2
- 229960004793 sucrose Drugs 0.000 claims 3
- 239000002994 raw material Substances 0.000 abstract description 13
- 150000003254 radicals Chemical class 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000007385 chemical modification Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000003631 expected effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
- C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a bio-based polyester type hydrophilic sponge and a preparation method thereof, and the preparation method comprises the following steps: step one, preparing polyalcohol by using first biomass, and then carrying out chemical hydrocracking on the polyalcohol to obtain bio-based ethylene glycol; wherein, silicon dioxide with the mass fraction of 0.1-0.2% is added into the bio-based ethylene glycol and is uniformly mixed; catalyzing the second biomass to prepare bio-based terephthalic acid; step three, uniformly mixing the bio-based ethylene glycol and the bio-based terephthalic acid according to the molar ratio of 1:1-1.4, and adding the mixture into a polymerization kettle. In the invention, the terephthalic acid and the ethylene glycol which are used as main raw materials are prepared from renewable biomass with rich resources, so that the dependence on non-renewable chemical raw materials is reduced, particularly the non-grain biomass is used as the raw material to prepare the synthesized polyethylene terephthalate, the pressure of the raw material can not be relieved, and simultaneously the trouble caused by white pollution for a long time can be solved.
Description
Technical Field
The invention relates to the field of polyester type hydrophilic cotton, in particular to bio-based polyester type hydrophilic cotton and a preparation method thereof.
Background
PET, also known as polyethylene terephthalate, is generally obtained by the dehydration condensation of ethylene terephthalate, which is obtained by esterification of terephthalic acid with ethylene glycol. Although PET has many advantages and is popular with consumers, its own characteristics also bring about the disadvantage of poor hydrophilicity, further hindering its development and application.
At present, methods for improving the hydrophilicity of PET mainly comprise chemical modification and physical modification, and the chemical modification method is relatively stable, durable and effective, so that the method is widely adopted. The chemical modification includes copolymerization, surface chemical reaction and other methods, and the copolymerization method is an important method in chemical modifiers.
Although various improvement means are adopted, the overall performance and the hydrophilicity of the current PET material are not obviously improved, and the expected effect cannot be achieved.
Disclosure of Invention
The invention aims to provide a bio-based polyester type hydrophilic cotton and a preparation method thereof, and aims to solve the technical problem that the overall performance and hydrophilicity of the existing PET material are not obviously improved, and the expected effect cannot be achieved.
In order to achieve the purpose, the invention provides the following technical scheme:
according to one aspect of the present invention, there is provided a method for preparing a bio-based polyester type hydrophilic sponge, comprising the steps of:
step one, preparing polyalcohol by using first biomass, and then carrying out chemical hydrocracking on the polyalcohol to obtain bio-based ethylene glycol;
wherein, silicon dioxide with the mass fraction of 0.1-0.2% is added into the bio-based ethylene glycol and is uniformly mixed;
catalyzing the second biomass to prepare bio-based terephthalic acid;
step three, uniformly mixing the bio-based ethylene glycol and the bio-based terephthalic acid according to a molar ratio of 1:1-1.4, adding the mixture into a polymerization kettle, adding a catalyst and a stabilizer, uniformly mixing and stirring the mixture, and fully reacting the mixture, wherein the molar amount of the catalyst is 0.01-0.04% based on the total amount of the bio-based terephthalic acid; the molar amount of the stabilizer is 0.01-0.04%; wherein the reaction conditions at least satisfy: the reaction temperature is 240 ℃ and 250 ℃, the reaction pressure is 0-0.3MPa, and the reaction time is 3-4 h;
step four, after the reaction in the step three is finished, slowly adding polyhydric alcohol, continuously stirring in the adding process, after the reaction is finished, vacuumizing to perform polycondensation reaction to prepare bio-based polyethylene terephthalate, wherein the molar usage of the polyhydric alcohol is 0.6% based on the total amount of the bio-based terephthalic acid;
wherein the polycondensation reaction conditions at least satisfy: the polycondensation temperature is 280-;
modifying the obtained bio-based polyethylene glycol terephthalate by using an ozonization method, and carrying out closed polymerization reaction on monomer molecules containing hydrophilic groups and the bio-based polyethylene glycol terephthalate under the protection of inert gas to prepare the modified bio-based polyethylene glycol terephthalate with high hydrophilicity;
wherein the conditions of the modification reaction at least satisfy: the reaction temperature is 65-75 ℃, and the reaction time is 2-3 h.
Further, in step one, the first biomass is at least one of sucrose, starch, cellulose, lignin and vegetable oil:
wherein, sucrose, starch and cellulose are saccharified and fermented to prepare polyol;
preparing the cellulose and the lignin into the polyol by adopting one of thermal cracking, catalytic cracking, hydrogenation and catalytic dehydration methods;
the vegetable oil is made into the polyalcohol by adopting one of an excessive metal catalytic hydroxylation method, an ozone oxidation method and an alcoholysis method.
Further, in the first step, 0.01-0.04% of antimony oxide and 0.25-0.35% of titanium dioxide are added into the bio-based ethylene glycol in mass fraction;
preferably, the adding amount of the antimony oxide is 0.03%, and the adding amount of the titanium dioxide is 0.3%.
Further, in the step one, the particle size of the silicon dioxide is in the range of 10-25 nm;
preferably, the particle size of the silicon dioxide is 20nm, and the usage amount of the silicon dioxide is 0.1% of the mass fraction of the bio-based ethylene glycol.
Further, in the second step, the second biomass is sucrose, starch, cellulose, lignin and vegetable oil;
preferably, the second biomass is cellulose and lignin.
Further, in the third step, the reaction process of the bio-based terephthalic acid and the bio-based ethylene glycol at least comprises the following processes:
firstly, the bio-based terephthalic acid reacts with methanol, and dimethyl terephthalate is esterified to complete methyl esterification; wherein, after the reaction is finished, low-boiling-point substances are evaporated, and then the pure dimethyl terephthalate is obtained by rectification; the low-boiling-point substances comprise redundant water, methanol and methyl benzoate;
then, carrying out ester exchange reaction on the dimethyl terephthalate and the bio-based ethylene glycol by taking cadmium acetate and antimony trioxide as catalysts to form polyester oligomer, and distilling off methanol to ensure that the ester exchange is sufficient;
wherein the molar ratio of the dimethyl terephthalate to the bio-based ethylene glycol is 1:2.4, and the reaction conditions at least meet the following requirements: the temperature is 190 ℃ and 200 ℃;
and finally, antimony trioxide is used as a catalyst to perform self-polycondensation on the polyethylene terephthalate, ester exchange is performed, by means of reduced pressure and high temperature, the by-product ethylene glycol is continuously distilled off, the polymerization degree is improved, and the polyethylene terephthalate is prepared.
Further, in the fifth step, the monomer molecule containing the hydrophilic group is one of acrylic acid, methacrylic acid, methyl crotonate and sodium styrene sulfonate.
According to another aspect of the invention, the bio-based polyester type hydrophilic cotton prepared by the method is also provided.
Furthermore, the water contact angle is 76-65 degrees.
Compared with the prior art, the invention has the beneficial effects that:
in the invention, the terephthalic acid and the ethylene glycol which are used as main raw materials are prepared from renewable biomass with rich resources, so that the dependence on non-renewable chemical raw materials is reduced, and particularly, the non-grain biomass is used as the raw material to prepare the synthesized polyethylene terephthalate (PET), so that the raw material pressure can be relieved, and the trouble caused by white pollution for a long time can be solved.
Meanwhile, ozone is utilized to form free radicals on the surface of PET, and then the free radicals are combined with unsaturated bonds on monomer molecules containing hydrophilic groups under the conditions of liquid phase and no oxygen, so that the formed polymer has extremely strong hydrophilicity.
In addition, after ozone is adopted to form free radicals on the surface of PET, molecular monomers containing different functional groups can be grafted, so that different functions are achieved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
According to one aspect of the present invention, there is provided a method for preparing a bio-based polyester type hydrophilic sponge, comprising the steps of:
step one, preparing polyalcohol by using first biomass, and then carrying out chemical hydrocracking on the polyalcohol to obtain bio-based ethylene glycol;
wherein, silicon dioxide with the mass fraction of 0.1-0.2% is added into the bio-based ethylene glycol and is uniformly mixed;
catalyzing the second biomass to prepare bio-based terephthalic acid;
step three, uniformly mixing the bio-based ethylene glycol and the bio-based terephthalic acid according to a molar ratio of 1:1-1.4, adding the mixture into a polymerization kettle, adding a catalyst and a stabilizer, uniformly mixing and stirring the mixture, and fully reacting the mixture, wherein the molar amount of the catalyst is 0.01-0.04% based on the total amount of the bio-based terephthalic acid; the molar amount of the stabilizer is 0.01-0.04%; wherein the reaction conditions at least satisfy: the reaction temperature is 240 ℃ and 250 ℃, the reaction pressure is 0-0.3MPa, and the reaction time is 3-4 h;
step four, after the reaction in the step three is finished, slowly adding polyhydric alcohol, continuously stirring in the adding process, after the reaction is finished, vacuumizing to perform polycondensation reaction to prepare bio-based polyethylene terephthalate, wherein the molar usage of the polyhydric alcohol is 0.6% based on the total amount of the bio-based terephthalic acid;
wherein the polycondensation reaction conditions at least satisfy: the polycondensation temperature is 280-;
modifying the obtained bio-based polyethylene glycol terephthalate by using an ozonization method, and carrying out closed polymerization reaction on monomer molecules containing hydrophilic groups and the bio-based polyethylene glycol terephthalate under the protection of inert gas to prepare the modified bio-based polyethylene glycol terephthalate with high hydrophilicity;
wherein the conditions of the modification reaction at least satisfy: the reaction temperature is 65-75 ℃, and the reaction time is 2-3 h.
Terephthalic acid and ethylene glycol which are used as main raw materials are prepared from renewable biomass with rich resources, so that the dependence on non-renewable chemical raw materials is reduced, and particularly, non-grain biomass is used as a raw material to prepare synthetic polyethylene terephthalate (PET), so that the raw material pressure can be relieved, and meanwhile, the trouble caused by white pollution for a long time can be solved.
Meanwhile, ozone is utilized to form free radicals on the surface of PET, and then the free radicals are combined with unsaturated bonds on monomer molecules containing hydrophilic groups under the conditions of liquid phase and no oxygen, so that the formed polymer has extremely strong hydrophilicity.
In addition, after ozone is adopted to form free radicals on the surface of PET, molecular monomers containing different functional groups can be grafted, so that different functions are achieved.
To further illustrate the technical solution of the present invention, it will be further illustrated by the following examples.
The first embodiment is as follows:
the preparation method of the bio-based polyester type hydrophilic cotton comprises the following steps:
step one, under the condition of multi-metal catalysis at 150-200 ℃, cellulose is used as a reaction raw material to be subjected to continuous hydrocracking, separation and purification to obtain bio-based ethylene glycol;
then adding 0.1% of silicon dioxide with the particle size of 20nm, 0.03% of antimony oxide and 0.3% of titanium dioxide into the bio-based ethylene glycol to improve the efficiency of subsequent polycondensation reaction, and then uniformly mixing:
catalyzing lignin to prepare bio-based terephthalic acid, firstly pyrolyzing the lignin to generate an oxygen-containing compound, then cracking the oxygen-containing compound under the catalysis of a catalyst (phosphoric acid) to generate aromatic hydrocarbon, carrying out alkylation reaction on monocyclic aromatic hydrocarbon to generate xylene under a methanol environment, isomerizing the xylene through a modified catalyst (such as H-BEA) to generate paraxylene, and then carrying out catalytic oxidation and hydrogenation purification to prepare refined terephthalic acid;
step three, uniformly mixing the bio-based ethylene glycol and the bio-based terephthalic acid according to a molar ratio of 1:1.2, adding the mixture into a polymerization kettle, adding a catalyst and a stabilizer, uniformly mixing and stirring the mixture, and fully reacting the mixture, wherein the molar amount of the catalyst (ethylene glycol aluminum) is 0.04 percent, the molar amount of the stabilizer (phosphoric acid) is 0.04 percent, and the mixture is uniformly mixed and stirred and fully reacting the mixture, wherein the total amount of the bio-based terephthalic acid is calculated;
wherein the reaction conditions are as follows: the reaction temperature is 245 ℃, the reaction pressure is 0.2MPa, and the reaction time is 3.5 h;
step four, after the reaction in the step three is finished, slowly adding polyhydric alcohol (such as ethylene glycol) with the mole fraction of 0.6 percent (relative to PTA), continuously stirring in the adding process, fully reacting, vacuumizing and carrying out polycondensation reaction to obtain bio-based polyethylene terephthalate;
wherein, the conditions of the polycondensation reaction are as follows: the polycondensation temperature is 286 ℃, and the polycondensation time is 3.5 h;
and fifthly, modifying the obtained bio-based polyethylene glycol terephthalate by using an ozonization method, generating hydroperoxide (free radical) on the surface of the bio-based polyethylene glycol terephthalate, realizing grafting reaction on the surface of the bio-based polyethylene glycol terephthalate, and carrying out closed polymerization reaction on acrylic acid and the bio-based polyethylene glycol terephthalate under the protection of inert gas to prepare the modified bio-based polyethylene glycol terephthalate with high hydrophilicity.
Table 1 shows the performance parameters of the highly hydrophilic modified bio-based polyethylene terephthalate, wherein the number of the test samples is the same, and the range values are:
examples two to three
Following the procedure of example one, except that the mass fractions of antimony oxide, titanium dioxide and silicon dioxide were different, as shown in table 2:
as can be seen from table 2, as the amount of silica increases, not only the synthesis time and polymerization temperature increase, but also the target product acquisition rate tends to decrease.
Examples four to eight:
the process of example one is followed except for the catalyst, stabilizer and reaction conditions in step three, as shown in Table 3:
as can be seen from Table 3, the target product yield decreased with decreasing amounts of catalyst and stabilizer, and decreased target product yield was observed at reaction temperatures below or above 245 ℃, reaction pressures below or above 0.2MPa, and reaction times below or above 3.5 h.
Examples ninety-sixteen:
the process of example one was followed except that the polycondensation temperature and polycondensation time were varied as shown in Table 4:
TABLE 4
As is clear from Table 4, the highest PET acquisition rate was obtained under the reaction conditions of 286 ℃ and 3.5 hours of polycondensation time.
Example seventeen:
the method according to embodiment one, except that: the reaction process of the bio-based terephthalic acid and the bio-based ethylene glycol comprises the following steps:
firstly, the bio-based terephthalic acid reacts with slightly excessive methanol, and dimethyl terephthalate is esterified firstly to complete methyl esterification; wherein, after the reaction is finished, low-boiling-point substances are evaporated, and then the pure dimethyl terephthalate is obtained by rectification; the low-boiling-point substances comprise redundant water, methanol and methyl benzoate;
then, carrying out ester exchange reaction on the dimethyl terephthalate and the bio-based ethylene glycol by taking cadmium acetate and antimony trioxide as catalysts to form polyester oligomer, and distilling off methanol to ensure that the ester exchange is sufficient;
wherein the molar ratio of the dimethyl terephthalate to the bio-based ethylene glycol is 1:2.4, and the reaction conditions at least meet the following requirements: the temperature is 195 ℃;
and finally, antimony trioxide is used as a catalyst to perform self-polycondensation on the polyethylene terephthalate, ester exchange is performed, by means of reduced pressure and high temperature, the by-product ethylene glycol is continuously distilled off, the polymerization degree is improved, and the polyethylene terephthalate is prepared.
In the stage of methyl esterification and ester exchange, the ratio of equal groups is not considered;
in the ester exchange stage, the ratio of the number of groups is correspondingly adjusted according to the distilled amount of the ethylene glycol until the amount of the materials is close to the same amount.
The ethylene glycol was in slight excess.
Examples eighteen to twenty:
the process as in example seventeen except that the polycondensation reaction is conducted in stages in two reactors, the viscosity of the system is increased, and the reaction temperature and reaction pressure are varied as the degree of polycondensation reaction is increased.
As shown in table 5:
as can be seen from Table 5, the temperature of the pre-polycondensation in the previous stage was 282 ℃ and the reaction pressure was 2600 Pa; final polycondensation in the later stage: the reaction temperature was 285 ℃ and the reaction pressure was 80Pa, and the polymerization reaction was more sufficient.
According to another aspect of the invention, the bio-based polyester type hydrophilic cotton prepared by the method is also provided. Wherein, the water contact angle is 76 degrees to 65 degrees, and the hydrophilicity is better.
Table 6 shows the performance parameters of bio-based polyester hydrophilic foam finished products, wherein the number of the test samples is the same, and the range values are:
TABLE 6
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which includes the appended claims and their equivalents.
Claims (9)
1. The preparation method of the bio-based polyester type hydrophilic cotton is characterized by comprising the following steps:
step one, preparing polyalcohol by using first biomass, and then carrying out chemical hydrocracking on the polyalcohol to obtain bio-based ethylene glycol;
wherein, silicon dioxide with the mass fraction of 0.1-0.2% is added into the bio-based ethylene glycol and is uniformly mixed;
catalyzing the second biomass to prepare bio-based terephthalic acid;
step three, uniformly mixing the bio-based ethylene glycol and the bio-based terephthalic acid according to a molar ratio of 1:1-1.4, adding the mixture into a polymerization kettle, adding a catalyst and a stabilizer, uniformly mixing and stirring the mixture, and fully reacting the mixture, wherein the molar amount of the catalyst is 0.01-0.04% based on the total amount of the bio-based terephthalic acid; the molar amount of the stabilizer is 0.01-0.04%; wherein the reaction conditions at least satisfy: the reaction temperature is 240 ℃ and 250 ℃, the reaction pressure is 0-0.3MPa, and the reaction time is 3-4 h;
step four, after the reaction in the step three is finished, slowly adding polyhydric alcohol, continuously stirring in the adding process, after the reaction is finished, vacuumizing to perform polycondensation reaction to prepare bio-based polyethylene terephthalate, wherein the molar usage of the polyhydric alcohol is 0.6% based on the total amount of the bio-based terephthalic acid;
wherein the polycondensation reaction conditions at least satisfy: the polycondensation temperature is 280-;
modifying the obtained bio-based polyethylene glycol terephthalate by using an ozonization method, and carrying out closed polymerization reaction on monomer molecules containing hydrophilic groups and the bio-based polyethylene glycol terephthalate under the protection of inert gas to prepare the modified bio-based polyethylene glycol terephthalate with high hydrophilicity;
wherein the conditions of the modification reaction at least satisfy: the reaction temperature is 65-75 ℃, and the reaction time is 2-3 h.
2. The method for preparing bio-based polyester type hydrophilic sponge according to claim 1, wherein:
in step one, the first biomass is at least one of sucrose, starch, cellulose, lignin and vegetable oil:
wherein, sucrose, starch and cellulose are saccharified and fermented to prepare polyol;
preparing the cellulose and the lignin into the polyol by adopting one of thermal cracking, catalytic cracking, hydrogenation and catalytic dehydration methods;
the vegetable oil is made into the polyalcohol by adopting one of an excessive metal catalytic hydroxylation method, an ozone oxidation method and an alcoholysis method.
3. The method for preparing bio-based polyester type hydrophilic sponge according to claim 1, wherein:
in the first step, 0.01 to 0.04 percent of antimony oxide and 0.25 to 0.35 percent of titanium dioxide are added into the bio-based ethylene glycol in mass fraction;
preferably, the adding amount of the antimony oxide is 0.03%, and the adding amount of the titanium dioxide is 0.3%.
4. The method for preparing bio-based polyester type hydrophilic sponge according to claim 1, wherein:
in the first step, the particle size range of the silicon dioxide is 10-25 nm;
preferably, the particle size of the silicon dioxide is 20nm, and the dosage of the silicon dioxide is 0.1% of the mass fraction of the bio-based ethylene glycol.
5. The method for preparing bio-based polyester type hydrophilic sponge according to claim 1, wherein:
in the second step, the second biomass is cane sugar, starch, cellulose, lignin and vegetable oil;
preferably, the second biomass is cellulose and lignin.
6. The method for preparing bio-based polyester type hydrophilic sponge according to claim 1, wherein:
in the third step, the reaction process of the bio-based terephthalic acid and the bio-based ethylene glycol at least comprises the following processes:
firstly, the bio-based terephthalic acid reacts with methanol, and dimethyl terephthalate is esterified to complete methyl esterification; wherein, after the reaction is finished, low-boiling-point substances are evaporated, and then the pure dimethyl terephthalate is obtained by rectification; the low-boiling-point substances comprise redundant water, methanol and methyl benzoate;
then, carrying out ester exchange reaction on the dimethyl terephthalate and the bio-based ethylene glycol by taking cadmium acetate and antimony trioxide as catalysts to form polyester oligomer, and distilling off methanol to ensure that the ester exchange is sufficient;
wherein the molar ratio of the dimethyl terephthalate to the bio-based ethylene glycol is 1:2.4, and the reaction conditions at least meet the following requirements: the temperature is 190 ℃ and 200 ℃;
and finally, antimony trioxide is used as a catalyst to perform self-polycondensation on the polyethylene terephthalate, ester exchange is performed, by means of reduced pressure and high temperature, the by-product ethylene glycol is continuously distilled off, the polymerization degree is improved, and the polyethylene terephthalate is prepared.
7. The method for preparing bio-based polyester type hydrophilic sponge according to claim 1, wherein:
in the fifth step, the monomer molecule containing the hydrophilic group is one of acrylic acid, methacrylic acid, methyl crotonate and sodium styrene sulfonate.
8. A biobased polyester type hydrophilic sponge prepared by the method of any one of claims 1 to 7.
9. The bio-based polyester type hydrophilic sponge according to claim 8, wherein: the water contact angle is 76-65 degrees.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111119085.1A CN113717326A (en) | 2021-09-24 | 2021-09-24 | Bio-based polyester type hydrophilic cotton and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111119085.1A CN113717326A (en) | 2021-09-24 | 2021-09-24 | Bio-based polyester type hydrophilic cotton and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113717326A true CN113717326A (en) | 2021-11-30 |
Family
ID=78684680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111119085.1A Pending CN113717326A (en) | 2021-09-24 | 2021-09-24 | Bio-based polyester type hydrophilic cotton and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113717326A (en) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525416A (en) * | 2008-03-04 | 2009-09-09 | 东丽纤维研究所（中国）有限公司 | Biobased polyethylene terephthalate |
| US20100168372A1 (en) * | 2008-12-31 | 2010-07-01 | Corrado Berti | Bio-Based Terephthalate Polyesters |
| CN102586940A (en) * | 2012-03-15 | 2012-07-18 | 泉州海天材料科技股份有限公司 | Biomass polyester short fiber and preparation method thereof |
| CN102604053A (en) * | 2012-03-15 | 2012-07-25 | 泉州海天材料科技股份有限公司 | Method for preparing biomass polyester |
| CN103289020A (en) * | 2013-06-25 | 2013-09-11 | 周婕 | Modification method of medical polyethylene terephthalate (PET) |
| CN103665355A (en) * | 2012-09-13 | 2014-03-26 | 东华大学 | Preparation method of high-hydrophilicity full-bio-based polyester |
| CN104418997A (en) * | 2013-08-21 | 2015-03-18 | 中国科学院大连化学物理研究所 | Synthetic method of polyethylene glycol terephthalate from biomass glycol |
| CN104774321A (en) * | 2015-04-24 | 2015-07-15 | 广东顺德顺炎新材料有限公司 | Bio-based polyethylene glycol terephthalate and preparation method thereof |
| CN104854162A (en) * | 2012-10-29 | 2015-08-19 | 伍德-伊文达-菲瑟股份有限公司 | Process for producing a high-molecular-weight polyester or copolyester, and also polymer blends containing such |
| JP2016013704A (en) * | 2015-09-24 | 2016-01-28 | 大日本印刷株式会社 | Polyester resin composition laminate |
| CN108473666A (en) * | 2015-12-11 | 2018-08-31 | 埃维昂矿泉水有限公司 | Pet polymer with the resistive connection crystalline substance comonomer that can be biological source |
| US20190185617A1 (en) * | 2016-09-01 | 2019-06-20 | Nestec S.A. | Process for producing a bio-based polyethylene terephthalate (pet) polymer, entirely from bio-based materials |
-
2021
- 2021-09-24 CN CN202111119085.1A patent/CN113717326A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525416A (en) * | 2008-03-04 | 2009-09-09 | 东丽纤维研究所（中国）有限公司 | Biobased polyethylene terephthalate |
| US20100168372A1 (en) * | 2008-12-31 | 2010-07-01 | Corrado Berti | Bio-Based Terephthalate Polyesters |
| CN102586940A (en) * | 2012-03-15 | 2012-07-18 | 泉州海天材料科技股份有限公司 | Biomass polyester short fiber and preparation method thereof |
| CN102604053A (en) * | 2012-03-15 | 2012-07-25 | 泉州海天材料科技股份有限公司 | Method for preparing biomass polyester |
| CN103665355A (en) * | 2012-09-13 | 2014-03-26 | 东华大学 | Preparation method of high-hydrophilicity full-bio-based polyester |
| CN104854162A (en) * | 2012-10-29 | 2015-08-19 | 伍德-伊文达-菲瑟股份有限公司 | Process for producing a high-molecular-weight polyester or copolyester, and also polymer blends containing such |
| CN103289020A (en) * | 2013-06-25 | 2013-09-11 | 周婕 | Modification method of medical polyethylene terephthalate (PET) |
| CN104418997A (en) * | 2013-08-21 | 2015-03-18 | 中国科学院大连化学物理研究所 | Synthetic method of polyethylene glycol terephthalate from biomass glycol |
| CN104774321A (en) * | 2015-04-24 | 2015-07-15 | 广东顺德顺炎新材料有限公司 | Bio-based polyethylene glycol terephthalate and preparation method thereof |
| JP2016013704A (en) * | 2015-09-24 | 2016-01-28 | 大日本印刷株式会社 | Polyester resin composition laminate |
| CN108473666A (en) * | 2015-12-11 | 2018-08-31 | 埃维昂矿泉水有限公司 | Pet polymer with the resistive connection crystalline substance comonomer that can be biological source |
| US20190185617A1 (en) * | 2016-09-01 | 2019-06-20 | Nestec S.A. | Process for producing a bio-based polyethylene terephthalate (pet) polymer, entirely from bio-based materials |
Non-Patent Citations (2)
| Title |
|---|
| 芦长椿;: "生物基聚酯的技术现状与趋势", 纺织导报, no. 09, pages 57 - 60 * |
| 黄格省;李琰;闫捷;刘继文;: "生物质生产聚对苯二甲酸乙二醇酯原料", 石化技术与应用, vol. 31, no. 03, pages 240 - 245 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6175912B2 (en) | Method for producing polybutylene terephthalate | |
| CN107250207B (en) | Bio-based copolyester or copolymerized ethylene terephthalate | |
| US20100168373A1 (en) | Bio-Based Terephthalate Polyesters | |
| CN102617859B (en) | Method for preparing rosin modified organic silicon resin | |
| CN107915833B (en) | Fiber-grade bio-based polyester and preparation method thereof | |
| CN107955142B (en) | Process for preparing isosorbide-containing polyesters | |
| CN115785427B (en) | Composite catalyst and method for preparing aliphatic polycarbonate by using composite catalyst | |
| US20200291177A1 (en) | Diol composition and polyester | |
| CN115819261B (en) | Quaternized dihydroxyethyl terephthalate and preparation method and application thereof | |
| CN112920385A (en) | Preparation method of poly (butylene succinate) and copolymer thereof | |
| CN113929886B (en) | Long-chain branched PETG copolyester and preparation method thereof | |
| CN113801311B (en) | Polyester preparation method | |
| CN113717326A (en) | Bio-based polyester type hydrophilic cotton and preparation method thereof | |
| CN115785409B (en) | Titanium catalyst and preparation method thereof | |
| CN114479026B (en) | PBS preparation method without by-product tetrahydrofuran | |
| US20030232960A1 (en) | Poly(1,3-propylene-co-1,4:3,6-dianhydro-D-sorbitol terephthalate) and manufacturing process | |
| CN101250255B (en) | Preparation method of catalyst for synthesizing poly terephthalic acid 1, 3-propylene glycol ester | |
| CN114853579A (en) | Preparation method and application of cardanol-based chlorohydrin ether | |
| CN115057998B (en) | Method for jointly producing epsilon-caprolactone and polybutylene succinate | |
| CN115073417B (en) | Method for preparing lactide by catalyzing lactic acid with ternary composite catalyst | |
| CN112898554B (en) | Preparation method and application of ricinoleic acid polyoxypropylene ether | |
| WO2024045640A1 (en) | Method for preparing peit copolyester | |
| CN117362611A (en) | Method for synthesizing high-viscosity bio-based furan polyester | |
| CN117603439A (en) | Synthesis method of high-viscosity furan dicarboxylic acid polyester | |
| CN118772383A (en) | Polyethylene terephthalate method for synthesizing glycol ester |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211130 |
|
| RJ01 | Rejection of invention patent application after publication |