CN114380975B - Flame-retardant polyurethane and preparation method thereof - Google Patents
Flame-retardant polyurethane and preparation method thereof Download PDFInfo
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- CN114380975B CN114380975B CN202210213651.3A CN202210213651A CN114380975B CN 114380975 B CN114380975 B CN 114380975B CN 202210213651 A CN202210213651 A CN 202210213651A CN 114380975 B CN114380975 B CN 114380975B
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- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
- C08G18/696—Polymers of conjugated dienes containing heteroatoms other than oxygen and other than the heteroatoms of copolymerised vinyl monomers
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- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
- C08G18/698—Mixtures with compounds of group C08G18/40
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Abstract
The invention provides flame-retardant polyurethane and a preparation method thereof, and belongs to the technical field of new material preparation. The flame-retardant polyurethane comprises a component A and a component B, wherein the component A comprises the following components in parts by weight: 40-60 parts of hydroxyl-terminated polybutadiene, 10-30 parts of polymer polyol, 10-30 parts of polypropylene glycol, 5-10 parts of cross-linking agent and 5-10 parts of flame retardant; the component B is isocyanate; the weight ratio of the component A to the component B in the polyurethane is 1.4-1.6:1. The invention simultaneously adds DOPO and HTPB, can ensure good mechanical property and flame retardant property, has lower requirements on equipment and environment, and has simple process, convenient operation and good economy.
Description
Technical Field
The invention belongs to the technical field of new materials, and relates to flame-retardant polyurethane and a preparation method thereof.
Background
Polyurethane (PU) is a block polymer produced by reacting a diisocyanate or polyisocyanate (hard segment) with a polyol having 2 or more hydroxyl groups (soft segment). The PU main chain contains a plurality of carbamate groups, so that a large number of hydrogen bonds can be formed in molecules and among molecules, physical crosslinking can occur in the molecular chain, and the hard segments and the soft segments are aggregated due to the thermodynamic incompatibility of the soft and hard phases of crosslinking, so that microphase separation phenomenon is generated, namely, the soft and hard segments are uniformly and alternately distributed to play a role of elastic crosslinking, so that the polyurethane has the excellent mechanical property and various characteristics of insulativity, oil resistance, hydrolysis resistance, low temperature resistance and the like, and is widely applied to a plurality of fields of ships, aerospace, military industry and the like. However, polyurethane is extremely easy to burn, its oxygen index is only about 19.2%, and the amount of released combustion smoke is large, which limits its application to a great extent, and therefore, the design and synthesis of flame-retardant polyurethane become very important.
The reactive phosphorus-containing flame retardant 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and the derivative structure thereof contain P-H bond, have high addition activity to hydroxyl-terminated polybutadiene (HTPB) in PU, and are combined with HTPB in a covalent bond form, so that DOPO is introduced into PU molecular chain, and the reactive flame-retardant polyurethane can be generated, and has the advantages of no halogen, no toxicity, no migration and lasting flame retardant property. The HTPB is a liquid telechelic polymer, and can react with a chain extender and a cross-linking agent at room temperature or high temperature to generate a three-dimensional network structured condensate, and the condensate has excellent mechanical properties, in particular hydrolysis resistance, acid and alkali resistance, wear resistance, low temperature resistance and excellent electrical insulation. Therefore, the addition of the two main components ensures the mechanical property and the flame retardant property of the polyurethane at the same time.
Patent CN201910348766.1 discloses polyurethane which is flame-retarded by synergism of ammonium polyphosphate and magnesium hydroxide, not only maintains the heat-insulating property of polyurethane, but also combines good flame-retardant properties of ammonium polyphosphate and magnesium hydroxide, but essentially belongs to an additive flame retardant, and has the defects of easy migration, poor compatibility with a matrix and the like. Patent CN95104528.8 discloses a polyurethane elastomer which uses polydiene polyol and castor oil as main components, and the addition of castor oil can effectively raise mechanical properties of tensile strength, etc., and the prepared polyurethane elastomer has good buffering property, but lower hardness.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide novel flame-retardant polyurethane and a preparation method thereof, and the novel flame-retardant polyurethane is characterized in that two components, namely HTPB and DOPO, are simultaneously added, and are combined in a covalent bond mode, so that the problems of poor compatibility of a flame retardant and the polyurethane and easy loss of the flame retardant are solved, and the polyurethane has excellent mechanical property and flame retardant property.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the flame-retardant polyurethane comprises an A component and a B component, wherein the weight ratio of the A component to the B component is 1.4-1.6:1. the component A comprises the following components in parts by weight: 40-60 parts of hydroxyl-terminated polybutadiene, 10-30 parts of polymer polyol, 10-30 parts of polypropylene glycol, 5-10 parts of cross-linking agent and 5-10 parts of flame retardant. The component B is isocyanate.
Further, the polymer polyol is one, two or more than two of polycaprolactone diol, polycaprolactone triol and polytetrahydrofuran diol. The polymer polyol has a number average molecular weight of 200 to 1000.
Further, the cross-linking agent comprises one or more of trimethylolethane and trimethylolpropane.
Further, the flame retardant is 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
Further, the isocyanate is one or more of diphenylmethane diisocyanate, toluene diisocyanate and polymethylene polyphenyl polyisocyanate.
A preparation method of flame-retardant polyurethane comprises the following steps:
in the first step, each component in the component A is put into a reaction vessel according to the weight proportion, the hydroxyl-terminated polybutadiene (HTPB) structure has a super-conjugated effect, the electron cloud density on olefinic carbon is reduced, the nucleophile flame retardant (DOPO) is favorable to be close to olefinic carbon atoms, DOPO has a phosphacycle structure, and P atoms have lone pair electrons and undergo nucleophilic addition reaction with carbon-carbon double bonds on HTPB, so that HTPB and DOPO are combined in a covalent bond form to generate HTPB-DOPO. Stirring for 2-3h in a vacuum environment with a certain preset rotating speed and a temperature of 100-120 ℃ until DOPO is reacted completely, and cooling to 50-70 ℃ to obtain colorless transparent liquid.
Secondly, the colorless transparent liquid and the component B are mixed according to the weight ratio of 1.4-1.6:1 into a reaction vessel, and reacting the-NCO groups in the isocyanate of the component B with various alcohols of the component A and the-OH groups in the HTPB-DOPO to generate-NHCOO-groups, thereby introducing the DOPO into polyurethane chains, and converting the structure of the polyurethane chains into a three-dimensional network structure by using a cross-linking agent. The mixed solution is stirred for 3-8 minutes at room temperature until the mixed solution is uniformly mixed, and light yellow viscous liquid is obtained. Pouring the light yellow viscous liquid into a mould, and solidifying at normal temperature.
Further, the preset rotating speed is 1000-2000 rpm.
The HTPB and DOPO are combined in a covalent bond mode, and the reaction process is as follows:
compared with the prior art, the invention has the beneficial effects that:
(1) The HTPB is selected as the soft segment of the polyurethane, and the prepared polyurethane has high strength and good performance, the tensile strength at room temperature can reach 33.15MPa, the elastic modulus can reach 1050.84MPa, and the hardness can reach Shore 93D.
(2) The polyurethane belongs to reactive flame-retardant polyurethane, which is different from the conventional method of adding the flame retardant into the base material by a physical mixing method in the prior art, is connected into a polyurethane chain in a covalent bond mode, has no problems of poor compatibility of the flame retardant and the polyurethane and easy loss of the flame retardant, and has lasting flame retardance.
(3) The invention provides solvent-free type bi-component polyurethane, which has no volatilization problem, and the raw materials are nontoxic and harmless to organisms and the environment, and belongs to environment-friendly polyurethane. And has low requirements on equipment and environment, simple process and convenient operation.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way.
Comparative example 1
(1) Preparation of component A
And (2) stirring 50 parts of hydroxyl-terminated polybutadiene, 20 parts of polycaprolactone triol, 20 parts of polypropylene glycol and 10 parts of trimethylolpropane for 2 hours at the rotating speed of 1000 revolutions per minute and the vacuum temperature of 120 ℃ in parts by weight, and cooling to 60 ℃ after uniform mixing to obtain the component A.
(2) 60 parts of component A and 40 parts of component B (4, 4' -diphenylmethane diisocyanate) are taken in the same container, and stirred at room temperature for 5min until the components are uniformly mixed, thus obtaining the solvent-free double-component polyurethane.
Comparative example 2
(1) Preparation of component A
According to parts by weight, stirring 30 parts of polycaprolactone triol, 30 parts of polypropylene glycol, 10 parts of trimethylolpropane and 10 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide for 2 hours under the conditions of 1000 revolutions per minute and vacuum 120 ℃, and cooling to 60 ℃ after uniform mixing to obtain the component A.
(2) 60 parts of component A and 40 parts of component B (4, 4' -diphenylmethane diisocyanate) are taken in the same container, and stirred at room temperature for 5min until the components are uniformly mixed, thus obtaining the solvent-free double-component polyurethane.
Example 1
(1) Preparation of component A
50 parts of hydroxyl-terminated polybutadiene, 10 parts of polycaprolactone dihydric alcohol, 30 parts of polypropylene glycol, 10 parts of trimethylolpropane and 5 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are stirred for 3 hours under the conditions of 1000 revolutions per minute and vacuum 120 ℃ in parts by weight, and the mixture is cooled to 50 ℃ after being uniformly mixed, so that the component A is obtained.
(2) Taking 56 parts of the component A and 40 parts of the component B (4, 4' -diphenylmethane diisocyanate) in the same container, and stirring at room temperature for 5min until the components are uniformly mixed to obtain the solvent-free double-component polyurethane.
Example 2
(1) Preparation of component A
60 parts of hydroxyl-terminated polybutadiene, 10 parts of polycaprolactone triol, 10 parts of polypropylene glycol, 5 parts of trimethylolethane and 10 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are stirred for 3 hours under the conditions of rotating speed of 1500 rpm and vacuum 100 ℃ and are uniformly mixed, and then the temperature is reduced to 70 ℃ to obtain the component A.
(2) 60 parts of component A and 40 parts of component B (toluene diisocyanate) are taken in the same container, and stirred at room temperature for 6min until the components are uniformly mixed, thus obtaining the solvent-free double-component polyurethane.
Example 3
(1) Preparation of component A
According to parts by weight, 40 parts of hydroxyl-terminated polybutadiene, 25 parts of polycaprolactone dihydric alcohol, 25 parts of polypropylene glycol, 10 parts of trimethylolpropane and 10 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are stirred for 2.5 hours under the conditions of 1600 revolutions per minute and vacuum 110 ℃, and the mixture is cooled to 50 ℃ after being uniformly mixed, so that the component A is obtained.
(2) 60 parts of component A and 40 parts of component B (toluene diisocyanate) are taken in the same container, and stirred at room temperature for 8min until the components are uniformly mixed, so that the solvent-free double-component polyurethane is obtained.
Example 4
(1) Preparation of component A
55 parts of hydroxyl-terminated polybutadiene, 15 parts of polytetrahydrofuran glycol, 15 parts of polypropylene glycol, 10 parts of trimethylolpropane and 10 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are stirred for 2 hours under the conditions of the rotating speed of 1200 revolutions per minute and the vacuum temperature of 110 ℃ and are cooled to 55 ℃ after being uniformly mixed, so that the component A is obtained.
(2) Taking 64 parts of A component and 40 parts of B component (4, 4' -diphenylmethane diisocyanate) in the same container, and stirring at room temperature for 7min until the components are uniformly mixed to obtain the solvent-free double-component polyurethane.
Example 5
(1) Preparation of component A
50 parts of hydroxyl-terminated polybutadiene, 30 parts of polycaprolactone triol, 10 parts of polypropylene glycol, 8 parts of trimethylolpropane and 8 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are stirred for 3 hours under the conditions of 1000 revolutions per minute and vacuum 100 ℃ in parts by weight, and the mixture is cooled to 70 ℃ after being uniformly mixed, so that the component A is obtained.
(2) Taking 56 parts of the component A and 40 parts of the component B (4, 4' -diphenylmethane diisocyanate) in the same container, and stirring at room temperature for 3min until the components are uniformly mixed to obtain the solvent-free double-component polyurethane.
Example 6
(1) Preparation of component A
According to parts by weight, stirring 45 parts of hydroxyl-terminated polybutadiene, 25 parts of polycaprolactone dihydric alcohol, 20 parts of polypropylene glycol, 5 parts of trimethylolethane and 10 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide for 2 hours at the rotating speed of 2000 rpm under the vacuum condition of 120 ℃, and cooling to 60 ℃ after uniform mixing to obtain the component A.
(2) 60 parts of component A and 40 parts of component B (polymethylene polyphenyl polyisocyanate) are taken in the same container, and stirred at room temperature for 5min until the components are uniformly mixed, so that the solvent-free bi-component polyurethane is obtained.
Example 7
(1) Preparation of component A
60 parts of hydroxyl-terminated polybutadiene, 15 parts of polycaprolactone triol, 20 parts of polypropylene glycol, 10 parts of trimethylolethane and 10 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are stirred for 3 hours under the conditions of 1000 revolutions per minute and vacuum 120 ℃ in parts by weight, and the mixture is cooled to 65 ℃ after being uniformly mixed, so that the component A is obtained.
(2) 60 parts of component A and 40 parts of component B (4, 4' -diphenylmethane diisocyanate) are taken in the same container, and stirred at room temperature for 6min until the components are uniformly mixed, thus obtaining the solvent-free double-component polyurethane.
Example 8
(1) Preparation of component A
60 parts of hydroxyl-terminated polybutadiene, 15 parts of polycaprolactone triol, 15 parts of polytetrahydrofuran diol, 30 parts of polypropylene glycol, 10 parts of trimethylolpropane and 10 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are stirred for 3 hours under the conditions of 1000 revolutions per minute and vacuum 120 ℃ and cooled to 50 ℃ after being uniformly mixed, so that the component A is obtained.
(2) 60 parts of component A and 40 parts of component B (polymethylene polyphenyl polyisocyanate) are taken in the same container, and stirred at room temperature for 8min until the components are uniformly mixed, so that the solvent-free bi-component polyurethane is obtained.
Example 9
(1) Preparation of component A
50 parts of hydroxyl-terminated polybutadiene, 20 parts of polycaprolactone triol, 20 parts of polypropylene glycol, 5 parts of trimethylolpropane and 10 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are stirred for 2 hours under the conditions of 1000 revolutions per minute and vacuum 120 ℃ in parts by weight, and the mixture is cooled to 70 ℃ after being uniformly mixed, so that the component A is obtained.
(2) 60 parts of component A and 40 parts of component B (polymethylene polyphenyl polyisocyanate) are taken in the same container, and stirred at room temperature for 5min until the components are uniformly mixed, so that the solvent-free bi-component polyurethane is obtained.
Tensile properties were tested according to GB/T1040-2018, hardness according to GB/T2411-2008, hardness with a Shore D durometer, limiting oxygen index according to GB/T2406-2008.
TABLE 1
The results of the solvent-free two-component polyurethane mechanical and flame-retardant tests prepared in examples 1-9 and comparative examples 1-2 are shown in Table 1, and it can be seen from the above table that the mechanical parameters such as tensile strength, elastic modulus and hardness of the examples are obviously higher than those of the comparative examples, and can reach 33.15MPa, 1050.84MPa and Shore 93D respectively, so that the mechanical properties are obviously increased. Meanwhile, the oxygen index of the embodiment can reach 26.6%, and the flame retardant property is greatly improved due to the introduction of DOPO. Therefore, the mechanical property and the flame retardant property of the polyurethane can be obviously improved by simultaneously adding the HTPB and the DOPO.
The examples described above represent only embodiments of the invention and are not to be understood as limiting the scope of the patent of the invention, it being pointed out that several variants and modifications may be made by those skilled in the art without departing from the concept of the invention, which fall within the scope of protection of the invention.
Claims (3)
1. The flame-retardant polyurethane is characterized by comprising an A component and a B component, wherein the weight ratio of the A component to the B component is 1.4-1.6:1, a step of; the component A comprises the following components in parts by weight: 40-60 parts of hydroxyl-terminated polybutadiene, 10-30 parts of polymer polyol, 10-30 parts of polypropylene glycol, 5-10 parts of cross-linking agent and 5-10 parts of flame retardant; the polymer polyol is one or more of polycaprolactone diol, polycaprolactone triol and polytetrahydrofuran diol; the number average molecular weight of the polymer polyol is 200-1000; the cross-linking agent is one or more of trimethylolethane and trimethylolpropane; the flame retardant is 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide; the component B is isocyanate; the isocyanate is more than one of diphenylmethane diisocyanate, toluene diisocyanate and polymethylene polyphenyl polyisocyanate.
2. A method for preparing the flame retardant polyurethane of claim 1, comprising the steps of:
firstly, putting all components in the component A into a reaction vessel according to weight proportion, and combining hydroxyl-terminated polybutadiene HTPB in the component A and a flame retardant DOPO in a covalent bond mode to generate HTPB-DOPO; stirring for 2-3h in a vacuum environment with preset rotating speed and 100-120 ℃ until DOPO is reacted completely, and cooling to 50-70 ℃ to obtain colorless transparent liquid; secondly, mixing the colorless transparent liquid obtained in the first step with the component B according to the proportion of 1.4-1.6:1, stirring for 3-8 minutes at room temperature until the mixture is uniformly mixed to obtain light yellow viscous liquid; pouring the light yellow viscous liquid into a mould, and solidifying at normal temperature.
3. The method for preparing flame retardant polyurethane according to claim 2, wherein the preset rotation speed is 1000-2000 rpm.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103059255A (en) * | 2012-12-20 | 2013-04-24 | 常州大学 | Preparation method of anti-flaming polyurethane elastomer based on tung oils |
| CN110790890A (en) * | 2019-11-22 | 2020-02-14 | 大连理工大学 | Polyurethane elastomer for metal composite sandwich plate core material and use method thereof |
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| CN103012729B (en) * | 2012-12-20 | 2014-10-29 | 常州大学 | Preparation method for linseed oil-based flame retardant polyurethane elastomer |
| CN103030965B (en) * | 2012-12-20 | 2014-10-29 | 常州大学 | Method for preparing castor-oil-based flame-retardant polyurethane elastomer |
| CN107151213B (en) * | 2016-03-03 | 2020-08-07 | 中国石油化工股份有限公司 | Halogen-free flame-retardant tung oil polyol and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103059255A (en) * | 2012-12-20 | 2013-04-24 | 常州大学 | Preparation method of anti-flaming polyurethane elastomer based on tung oils |
| CN110790890A (en) * | 2019-11-22 | 2020-02-14 | 大连理工大学 | Polyurethane elastomer for metal composite sandwich plate core material and use method thereof |
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