CN106633022A - Preparation method and application of three-source integrated hyperbranched structure flame retardant - Google Patents
Preparation method and application of three-source integrated hyperbranched structure flame retardant Download PDFInfo
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- CN106633022A CN106633022A CN201611065776.7A CN201611065776A CN106633022A CN 106633022 A CN106633022 A CN 106633022A CN 201611065776 A CN201611065776 A CN 201611065776A CN 106633022 A CN106633022 A CN 106633022A
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- flame retardant
- hyperbranched
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- hydroxyl
- phosphoric acid
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 99
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229920006150 hyperbranched polyester Polymers 0.000 claims abstract description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 14
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000004814 polyurethane Substances 0.000 claims abstract description 9
- 229920002635 polyurethane Polymers 0.000 claims abstract description 9
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 7
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 20
- 239000000654 additive Substances 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000004970 Chain extender Substances 0.000 claims description 5
- 239000004971 Cross linker Substances 0.000 claims 1
- 238000006757 chemical reactions by type Methods 0.000 claims 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 2
- 239000004743 Polypropylene Substances 0.000 description 16
- 229920001155 polypropylene Polymers 0.000 description 16
- 229920000587 hyperbranched polymer Polymers 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- -1 inorganic acid compound Chemical class 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000003077 polyols Chemical class 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 229920005906 polyester polyol Polymers 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- 239000004114 Ammonium polyphosphate Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 3
- 229920001276 ammonium polyphosphate Polymers 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical class [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- ZHXAZZQXWJJBHA-UHFFFAOYSA-N triphenylbismuthane Chemical compound C1=CC=CC=C1[Bi](C=1C=CC=CC=1)C1=CC=CC=C1 ZHXAZZQXWJJBHA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a preparation method of a three-source integrated hyperbranched structure flame retardant. The preparation method of the three-source integrated hyperbranched structure flame retardant comprises the following steps: 1, adding hydroxyl terminated hyperbranched polyester and phosphoric acid into a reactor, and further adding a catalyst, namely phosphotungstic acid or p-toluenesulfonic acid; 2, heating to the temperature of 80 DEG C, and reacting for 4 hours under a vacuum condition; 3, washing with ethanol, and dissolving in acetone after drying; 4, adding ethylenediamine of which the molar ratio is equal to that of phosphoric acid to be reacted for 30 minutes, obtaining a precipitate, washing with ethanol for 3 times, and drying to obtain light yellow powder. The flame retardant obtained by adopting the method is mixed with acrylic acid, PP and the like, so that polyurethane flame-retardant PP with low viscosity and high mechanical properties can be obtained. The invention further discloses application of the three-source integrated hyperbranched structure flame retardant used as a polymer material.
Description
Technical Field
The invention belongs to the technical field of flame retardant preparation, and particularly relates to a preparation method and application of a three-source-integrated hyperbranched flame retardant.
Background
The intumescent flame retardant technology is a novel flame retardant technology developed in the middle of the 90 s of the 20 th century. When the Intumescent Flame Retardant (IFR) is used for flame-retarding plastics, an intumescent carbon layer is formed on the surface of the plastics to play roles in heat insulation, oxygen isolation, smoke suppression and molten drop prevention, and low smoke, low toxicity, no molten drop and no corrosive gas are generated. The phosphorus-nitrogen IFR is a composite flame retardant mainly comprising phosphorus, nitrogen and carbon as main components, and mainly comprises three parts: (1) the acid source, also called as a carbonization catalyst or a dehydrating agent, is usually an inorganic acid compound or an inorganic acid, has the function of promoting the generation of the carbonization compound, and has the following specific varieties: boric acid, ammonium phosphate salts, phosphoric acid esters, phosphoric acid salts, ammonium polyphosphate (APP), and the like; (2) carbon sources, also called char-forming agents, are mainly carbohydrates or polyols with a high carbon content, such as polymers (polyurethanes, etc.), starch, lignin, Pentaerythritol (PER), dipentaerythritol, etc.; (3) the gas source, also called a foaming source, can release inert gas to expand the carbon layer, mainly contains nitrogen compounds, and the specific types are as follows: melamine, urea, dicyandiamide, APP, and the like. IFR is mainly used for flame retarding in condensed phase by forming porous expanded carbon layer, which is formed by the following steps: (1) generating inorganic acid and polyesterified polyol which can be used as a dehydrating agent at a lower temperature; (2) at slightly higher temperatures, esterification reactions occur, with the potential for some release of small gaseous molecules; (3) the system is melted before or during esterification; (4) the non-combustible gas generated by the gas source and the water vapor generated by the reaction enable the melting system to further expand and foam, meanwhile, the polyol phosphate ester is further dehydrated and carbonized to form inorganic matters and carbon residues, and the system is further expanded and foamed; (5) forming a porous carbon foam layer.
At present, the three-source-in-one intumescent flame retardant is mainly composed of small molecules serving as an acid source, a carbon source and a gas source, such as phosphorus oxychloride (or phosphoric acid), melamine and pentaerythritol, and the obtained product has low molecular weight and poor compatibility with a polymer, and the mechanical property of the material is easily weakened by the existence of the small molecules.
Hyperbranched polymers have some unique properties due to their unique molecular structure. For example, good fluidity. The hyperbranched polymer has a highly branched molecular structure different from a random coil structure of a linear polymer in the traditional sense, has a compact molecular structure, has a spatial three-dimensional structure, shows Newtonian fluid behavior, and has a viscosity lower than that of the linear polymer with the same molecular weight. (iii) tailorable chemical properties. The linear polymer end groups have no significant effect on the properties of the polymer, whereas the hyperbranched polymer has a large number of terminal functional groups on the surface of the molecule, which have a significant effect on the properties of the hyperbranched polymer. The nature of the terminal groups of the hyperbranched polymer influences the reactivity, viscosity, polarity, crystallinity and glass transition temperature of the hyperbranched polymer. After the end group is modified, the property of the polymer is changed, and the application range of the polymer is expanded. More importantly, a large number of active end groups can be subjected to functional modification, so that the hyperbranched polymer has certain special functions.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of a three-source-one hyperbranched structure flame retardant. The invention utilizes a large amount of end groups and cutting chemical properties of the hyperbranched polymer to introduce amine phosphate groups into the hyperbranched polymer to obtain the flame retardant with high nitrogen and high phosphorus content. Fully modifying terminal hydroxyl groups of a Boltorn type hydroxyl-terminated hyperbranched polyester hyperbranched polymer to obtain an additive type 'three-source-one' intumescent flame retardant; partial end group modification is carried out on the Boltorn type hydroxyl-terminated hyperbranched polymer to obtain a reactive flame retardant, wherein one part of end groups are modified to be phosphate ammonium salt groups, and the other part of end groups are changed to be groups containing double bonds (or end hydroxyl groups are reserved), so that the reactive three-source-one intumescent flame retardant is obtained.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a three-source-one hyperbranched structure flame retardant comprises the following steps:
adding hydroxyl-terminated hyperbranched polyester and phosphoric acid into a reactor, and adding a catalyst phosphotungstic acid or p-toluenesulfonic acid;
step two, heating to 80 ℃, and reacting for 4 hours under a vacuum condition;
washing with ethanol, drying, and dissolving in acetone;
and step four, adding ethylenediamine with the molar ratio of phosphoric acid to react for 30 minutes to obtain a precipitate, washing with ethanol for three times, and drying to obtain light yellow powder.
According to the invention, when the molar ratio of the hydroxyl-terminated hyperbranched polyester to the phosphoric acid is less than 1:0.5, the reactive type 'three-source-one' hyperbranched structure flame retardant is obtained.
According to the invention, when the molar ratio of the hydroxyl-terminated hyperbranched polyester to the phosphoric acid is greater than or equal to 1:0.5, the additive type 'three-source-one' hyperbranched structure flame retardant is obtained.
The second purpose of the invention is to provide the application of the obtained three-in-one hyperbranched structure flame retardant, wherein the three-in-one hyperbranched structure flame retardant is used as a flame retardant for a high polymer material.
The third purpose of the invention is to provide the application of the obtained reactive type triple-source-integrated hyperbranched structure flame retardant, wherein the reactive type triple-source-integrated hyperbranched structure flame retardant is used as a chain extender or a crosslinking agent of a polyurethane reaction system.
The invention has the beneficial effects that: the hyperbranched polymer has good fluidity and a large number of cavities, and the flame retardant with the 'three-source-in-one' hyperbranched structure is added into a plastic material, so that the flame retardant effect can be realized, the processing technology performance can be improved, the mechanical property can be improved, and the like, and the hyperbranched polymer is a multifunctional flame retardant.
Detailed Description
The following will explain the preparation method of the "three-in-one" hyperbranched structure flame retardant of the present invention in detail with reference to the specific examples. It should be understood that the following examples are illustrative only and are not intended to limit the scope of the present invention.
The techniques used in the following examples are, unless otherwise specified, conventional techniques known to those skilled in the art; the instruments and equipment used, unless otherwise noted in this specification, are commonly available to those of ordinary skill in the art.
The invention takes hydroxyl-terminated hyperbranched polyester as a carbon source, phosphoric acid as an acid source and ethylenediamine as a gas source, and prepares the three-source-integrated flame retardant by controlling the molar ratio of the carbon source, the acid source and the gas source and controlling the reaction conditions of a reactor.
Example 1 preparation of reactive "three-in-one" hyperbranched flame retardant
Step one, adding hydroxyl-terminated hyperbranched polyester and phosphoric acid into a reactor, and adding a catalyst phosphotungstic acid or p-toluenesulfonic acid, wherein the molar ratio of the hydroxyl-terminated hyperbranched polyester to the phosphoric acid to the catalyst is 1:0.4: 0.5%;
step two, heating to 80 ℃, and reacting for 4 hours under a vacuum condition;
washing with ethanol, drying, and dissolving in acetone;
and step four, adding ethylenediamine with the molar ratio of phosphoric acid to react for 30 minutes to obtain a precipitate, washing with ethanol for three times, and drying to obtain light yellow powder, namely the reactive type triple-source integrated hyperbranched structure flame retardant.
The reaction equation of the reactive type 'three-source-one' hyperbranched structure flame retardant is as follows:
wherein,represents the internal structure of a hyperbranched polyester, the repeating unit of which is
Andrepresenting Boltorn type hyperbranched polyesters with different generations, wherein the small scale x represents that partial hydroxyl of x reacts with phosphoric acid in the Boltorn type hyperbranched polyesters; the subscript y indicates that the hydroxyl groups of the y moiety are not reacted in the Boltorn-type hyperbranched polyester.
In this embodiment, the hydroxyl-terminated hyperbranched polyester may be dissolved in a solvent (acetone, dioxane, dimethyl sulfoxide, etc.) before use.
According to the algebraic change, when the molar ratio of the hydroxyl-terminated hyperbranched polyester to the phosphoric acid is less than 1:0.5, the hydroxyl-terminated part of the hydroxyl-terminated hyperbranched polyester is modified, and the reserved hydroxyl-terminated part can be reserved or further modified into other groups to become a reactive flame retardant.
Example 2 application of reactive type 'three-in-one' hyperbranched structure flame retardant
The reactive triple-source-integrated hyperbranched structure flame retardant can be used as a chain extender or a cross-linking agent of a polyurethane reaction system to become the reactive triple-source-integrated flame retardant of the polyurethane system. The specific operation steps are as follows:
mixing part of flame-retardant modified hyperbranched polyester, polyester polyol and toluene diisocyanate in a certain proportion, adding catalyst triphenyl bismuth, defoaming after uniform mixing, and placing into a mold to be cured for 2d at 60 ℃. The polyester polyol of this embodiment may be replaced with other polyols, for example, raw materials of polyurethane such as polyether polyol and polybutadiene polyol; toluene diisocyanate may also be another polyisocyanate.
Taking the fourth generation hydroxyl-terminated hyperbranched polyester as an example, polyurethane obtained by mixing the fourth generation hydroxyl-terminated hyperbranched polyester as a chain extender with polyester polyol and toluene diisocyanate is tested for the mechanical property of the flame retardant property. The mixing ratio and the results are detailed in Table 1.
TABLE 1 comparison of the properties of polyurethanes obtained by mixing partially flame-retardant modified hydroxy hyperbranched polyesters with polyester polyols and toluene diisocyanate
And (4) conclusion: along with the increase of the chain extender, the LOI value is continuously increased, the tensile strength of the material is gradually increased, the elongation at break is gradually reduced, and the better the flame retardant effect is.
Example 3 application of reactive type 'three-in-one' hyperbranched structure flame retardant
The reactive type 'three-in-one' hyperbranched structure flame retardant can react with monomers containing double bonds (such as acrylic acid, oleic acid and the like) to obtain end groups containing the double bonds, and can be used as a reactive type 'three-in-one' flame retardant for olefin polymer materials. Taking the acrylic acid modified partial end group as an example, the reaction equation is as follows:
the preparation method comprises the following steps:
and (3) carrying out flame retardant modification on part of terminal groups of the hydroxyl-terminated hyperbranched polyester to obtain the reactive type triple-source-integrated hyperbranched structure flame retardant. In the Boltorn type hyperbranched polyester, hydroxyl groups of the y part which do not participate in the reaction react with carboxylic acid containing double bonds to obtain the flame retardant containing double bonds. For example: the preparation method comprises the following steps of (1) adding a catalyst of p-toluenesulfonic acid (0.5% of the mole number of acrylic acid), adding toluene as a water-carrying agent, reacting for 5-6 h in an oil bath at 140 ℃, vacuumizing, washing with water after the reaction is finished, and drying for later use. Adding the product and excessive phosphoric acid (for example, the mole number of the terminal hydroxyl groups of the modified hyperbranched polyester: the mole number of the phosphoric acid is 1:0.6) into a reactor, adding phosphotungstic acid or p-toluenesulfonic acid (0.5 percent of the mole number of the hydroxyl groups) as catalysts according to different generations, reacting for 4 hours under vacuum conditions, and washing with ethanol. After drying, dissolving in acetone, adding ethylenediamine with the molar ratio of phosphoric acid to react for 30 minutes to obtain precipitate, washing with ethanol for three times, and drying to obtain light yellow powder.
The flame-retardant hyperbranched polyester containing double bonds and polypropylene (PP) are subjected to thermomechanical reaction and blending in a twin-screw extruder according to a certain composition ratio to obtain the flame-retardant PP. The fourth generation flame-retardant hyperbranched polyester containing double bonds is used as a reactive flame retardant to be blended with PP to obtain the flame-retardant PP, and the performances are shown in the following table 2.
TABLE 2 proportion and comparison of the Properties of flame-retardant hyperbranched polyester containing double bonds with PP
And (4) conclusion:
(1) with the increase of the content of the reactive three-source-one hyperbranched structure flame retardant, the oxygen index (LOI) of the flame-retardant PP is increased, the flame-retardant grade is improved, and the combustion performance of the material is reduced;
(2) with the increase of the content of the flame retardant, the tensile strength of the material is gradually increased;
(3) as the flame retardant content increases, the elongation at break decreases;
(4) with the increase of the content of the flame retardant, the impact strength of the material is gradually increased;
(5) as the flame retardant content increases, the viscosity of the material gradually decreases.
In summary, the addition of the reactive triple-source-integrated hyperbranched structure flame retardant is beneficial to improving the mechanical property of the material, reducing the viscosity of the material and being beneficial to the molding processing of the material.
Example 4 preparation of additive type "three sources in one" hyperbranched structure flame retardant
Step one, adding hydroxyl-terminated hyperbranched polyester and phosphoric acid into a reactor, and adding a catalyst phosphotungstic acid or p-toluenesulfonic acid, wherein the molar ratio of the hydroxyl-terminated hyperbranched polyester to the phosphoric acid to the catalyst is 1:0.6: 0.5%;
step two, heating to 80 ℃, and reacting for 4 hours under a vacuum condition;
washing with ethanol, drying, and dissolving in acetone;
and step four, adding ethylenediamine with the molar ratio of phosphoric acid to react for 30 minutes to obtain a precipitate, washing with ethanol for three times, and drying to obtain light yellow powder, namely the additive type tri-source integrated hyperbranched structure flame retardant.
The reaction equation of the additive type 'three-source-one' hyperbranched structure flame retardant is as follows:
whereinRepresents Boltorn type hyperbranched polyesters of different generations;
represents the internal structure of a hyperbranched polyester, the repeating unit of which is
According to the algebraic change, when the molar ratio of the hydroxyl-terminated hyperbranched polyester to the phosphoric acid is more than or equal to 1:0.5, the hydroxyl-terminated hyperbranched polyester is completely modified to become the additive flame retardant.
Example 5 application of additive type triple-source-integrated hyperbranched structure flame retardant
The additive type 'three-source-one' hyperbranched structure flame retardant is used for a polypropylene system, and the flame retardant performance, the processing technology performance and the mechanical performance of the polypropylene system are researched. Adjusting the content of the flame retardant in a polypropylene system (different contents such as 5%, 10%, 15%, 20%, 25%, 30% and the like are added), and researching the influence rule of the flame retardant with different contents on the flame retardant property, the processing technology property and the mechanical property of the material.
(1) The influence rule of the flame retardants with different contents on the flame retardant property, the processing property and the mechanical property of the material is explained through data or tables, linear relations and the like. The results are shown in table 3, table 3 is the flame retardant PP obtained by mixing all modified hydroxyl terminated hyperbranched polyesters with PP in a certain ratio.
TABLE 3 comparison of the Properties of all modified hydroxyl-terminated hyperbranched polyesters with PP and of the flame-retardant PP obtained
And (4) conclusion:
(1) with the increase of the content of the additive type 'three-source-one' hyperbranched structure flame retardant, the oxygen index (LOI) of the flame-retardant PP is increased, the flame-retardant grade is improved, and the combustion performance of the material is reduced;
(2) with the increase of the content of the flame retardant, the tensile strength of the material is slightly reduced, then increased and finally slightly reduced, but still higher than that of PP without the flame retardant;
(3) the elongation at break is increased and the bending strength is gradually increased along with the increase of the content of the flame retardant;
(4) with the increase of the content of the flame retardant, the impact strength of the material is slightly reduced, then increased and finally slightly reduced;
(5) as the flame retardant content increases, the viscosity of the material gradually decreases.
In conclusion, the addition of the additive type 'three-source-one' hyperbranched structure flame retardant is beneficial to improving the mechanical property of the material, reducing the viscosity of the material and being beneficial to the molding processing of the material.
The embodiment 1-5 obtains the terminal groups containing nitrogen and phosphorus by carrying out flame retardant modification on the terminal hydroxyl hyperbranched polyester, has good flame retardant effect, and can improve the flame retardant property, reduce the viscosity and improve the mechanical property along with the addition of the flame retardant.
The above description is only a preferred embodiment of the present invention, and it should be noted that it is obvious to those skilled in the art that several modifications and decorations can be made without departing from the technology of the present invention, for example, the remaining terminal groups of the partially modified hyperbranched polyester can be modified by other modifications, such as anhydride modification, to obtain a "tri-source" flame retardant with carboxyl groups. Such modifications and refinements are also to be considered within the scope of the present invention.
Claims (5)
1. A preparation method of a three-source-one hyperbranched structure flame retardant is characterized by comprising the following steps:
adding hydroxyl-terminated hyperbranched polyester and phosphoric acid into a reactor, and adding a catalyst phosphotungstic acid or p-toluenesulfonic acid;
step two, heating to 80 ℃, and reacting for 4 hours under a vacuum condition;
washing with ethanol, drying, and dissolving in acetone;
and step four, adding ethylenediamine with the molar ratio of phosphoric acid to react for 30 minutes to obtain a precipitate, washing with ethanol for three times, and drying to obtain light yellow powder.
2. The preparation method of the "three-in-one" hyperbranched structure flame retardant of claim 1, wherein the reaction type "three-in-one" hyperbranched structure flame retardant is obtained when the molar ratio of the hydroxyl groups of the hydroxyl-terminated hyperbranched polyester to the phosphoric acid is less than 1: 0.5.
3. The preparation method of the triple-source all-in-one hyperbranched structural flame retardant of claim 1, wherein when the molar ratio of the hydroxyl group of the hydroxyl-terminated hyperbranched polyester to the phosphoric acid is greater than or equal to 1:0.5, an additive triple-source all-in-one hyperbranched structural flame retardant is obtained.
4. Use of a "tri-source" hyperbranched structured flame retardant obtained according to any of claims 1 to 3, characterized in that it is used as a flame retardant for polymeric materials.
5. Use of the "tri-source" hyperbranched structured flame retardant obtained according to any of claims 1 to 2, characterized in that it is used as a chain extender or cross-linker for polyurethane reaction systems.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107286370A (en) * | 2017-08-08 | 2017-10-24 | 青岛长荣化工科技有限公司 | A kind of nitrogen phosphorus flame retardant and preparation method thereof |
| CN109252240A (en) * | 2018-07-26 | 2019-01-22 | 东华大学 | The fused mass directly spinning preparation method of flame-proof antibiotic polyester fiber |
| CN109879907A (en) * | 2019-02-19 | 2019-06-14 | 四川大学 | Three-source integrated expanding fire retardant, hydridization expanding fire retardant and their preparation method and application with its grafting |
| CN110016130A (en) * | 2019-04-01 | 2019-07-16 | 东华大学 | The preparation method of phosphorus, nitrogen type flame retardant and flame-retardant textile based on hyper-branched polyester |
| CN110592950A (en) * | 2019-09-16 | 2019-12-20 | 东华大学 | Method for preparing flame-retardant cotton fabric without solvent |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007066383A1 (en) * | 2005-12-06 | 2007-06-14 | Toyo Boseki Kabushiki Kaisha | Phosphorated hyperbranched polymer and flame retardant resin composition |
| CN102304222A (en) * | 2011-06-16 | 2012-01-04 | 上海工程技术大学 | Hyperbranched polyphosphate flame retardant and preparation method thereof |
| CN102633999A (en) * | 2012-04-26 | 2012-08-15 | 陕西科技大学 | P-N flame retardant and preparation method thereof |
| CN103242627A (en) * | 2013-03-27 | 2013-08-14 | 宋雪晶 | Application of fatty acid ester end group hyperbranched polyester as high polymer material viscosity reducing and toughening agent |
-
2016
- 2016-11-28 CN CN201611065776.7A patent/CN106633022B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007066383A1 (en) * | 2005-12-06 | 2007-06-14 | Toyo Boseki Kabushiki Kaisha | Phosphorated hyperbranched polymer and flame retardant resin composition |
| CN102304222A (en) * | 2011-06-16 | 2012-01-04 | 上海工程技术大学 | Hyperbranched polyphosphate flame retardant and preparation method thereof |
| CN102633999A (en) * | 2012-04-26 | 2012-08-15 | 陕西科技大学 | P-N flame retardant and preparation method thereof |
| CN103242627A (en) * | 2013-03-27 | 2013-08-14 | 宋雪晶 | Application of fatty acid ester end group hyperbranched polyester as high polymer material viscosity reducing and toughening agent |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107286370B (en) * | 2017-08-08 | 2019-06-25 | 青岛长荣化工科技有限公司 | A kind of nitrogen-phosphorus flame retardant and preparation method thereof |
| CN107286370A (en) * | 2017-08-08 | 2017-10-24 | 青岛长荣化工科技有限公司 | A kind of nitrogen phosphorus flame retardant and preparation method thereof |
| CN109252240A (en) * | 2018-07-26 | 2019-01-22 | 东华大学 | The fused mass directly spinning preparation method of flame-proof antibiotic polyester fiber |
| CN109879907A (en) * | 2019-02-19 | 2019-06-14 | 四川大学 | Three-source integrated expanding fire retardant, hydridization expanding fire retardant and their preparation method and application with its grafting |
| CN109879907B (en) * | 2019-02-19 | 2021-09-14 | 四川大学 | Three-source integrated intumescent flame retardant, hybrid intumescent flame retardant grafted by three-source integrated intumescent flame retardant, and preparation methods and applications of three-source integrated intumescent flame retardant and hybrid intumescent flame retardant |
| CN110016130B (en) * | 2019-04-01 | 2021-08-03 | 东华大学 | Preparation method of phosphorus and nitrogen type flame retardant and flame-retardant fabric based on hyperbranched polyester |
| CN110016130A (en) * | 2019-04-01 | 2019-07-16 | 东华大学 | The preparation method of phosphorus, nitrogen type flame retardant and flame-retardant textile based on hyper-branched polyester |
| CN110592950B (en) * | 2019-09-16 | 2021-08-06 | 东华大学 | Method for preparing flame-retardant cotton fabric without solvent |
| CN110592950A (en) * | 2019-09-16 | 2019-12-20 | 东华大学 | Method for preparing flame-retardant cotton fabric without solvent |
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| CN110983784B (en) * | 2019-12-17 | 2022-07-12 | 太仓宝霓实业有限公司 | Improved environment-friendly flame retardant composition and preparation method thereof |
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| CN112724365B (en) * | 2020-11-30 | 2022-10-14 | 温州大学 | Flame-retardant hyperbranched polymer leather retanning agent |
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