CN101747371A - Non-halogen flame retardant hydrolysis resistant phosphorus-containing polyether/polyester polyol and preparation method thereof - Google Patents
Non-halogen flame retardant hydrolysis resistant phosphorus-containing polyether/polyester polyol and preparation method thereof Download PDFInfo
- Publication number
- CN101747371A CN101747371A CN200910273165A CN200910273165A CN101747371A CN 101747371 A CN101747371 A CN 101747371A CN 200910273165 A CN200910273165 A CN 200910273165A CN 200910273165 A CN200910273165 A CN 200910273165A CN 101747371 A CN101747371 A CN 101747371A
- Authority
- CN
- China
- Prior art keywords
- acid
- hydroxide
- oxide
- phosphine
- polyester polyol
- 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
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a non-halogen flame retardant hydrolysis resistant phosphorus-containing polyether/polyester polyol and a preparation method thereof. The method has the core of utilizing an industrial toxic by-product--phosphine as an original raw material to prepare the flame retardant hydrolysis resistant phosphorus-containing polyether/polyester polyol via multi-step reactions. The invention takes the phosphine as the original raw material, phosphine is a highly toxic gas and causes intoxication mainly by being inhaled from the respiratory tract, and the phosphine waste gas not only causes environmental pollution and harms human health, but also restricts production process control, safe production and comprehensive utilization of wastes. The process line of the invention provides a new way for the nuisanceless utilization of the phosphine, and the utilization of the phosphine gas is conductive to the healthy development of the phosphorus chemical industry. The obtained phosphorus-containing polyether/polyester polyol does not contain a phosphaester bond but is connected by a phosphorus-carbon bond, and the product has excellent hydrolysis resistant performance and adjustable phosphorus content, does not affect the storage property of the raw material, and has no corrosiveness on a mould.
Description
Technical field
The present invention relates to a kind of non-halogen flame retardant hydrolysis resistant phosphorus-containing polyether ether/polyester polyol and preparation method thereof.
Background technology
The industry polyvalent alcohol comprises polyether glycol and polyester polyol two big classes.Be to make initiator, the ring compound ring-opening polymerization is made with the compound that contains reactive hydrogen.The industrial application of polyether glycol comprises polyurethane material, coating, elastomer material, filamentary material, leatheroid, tamanori and seal gum, joint sealant and injection material, synthetic resins, tensio-active agent, brake fluid, hydraulic fluid and lubricating fluid, rocket propellant tamanori, makeup etc.Polyurethane industrial is the main application fields of polyvalent alcohol.
Polyurethane material has good use properties and processing characteristics, urethane foam light weight softness, insulation, ventilative, nontoxic, rebound resilience is good, compression set is little, the moisture-proof ageing-resistant performance is good, and multiple good characteristic such as oil resistant, organic solvent-resistant, sound insulation, insulation, be widely used in fields such as aviation, communications and transportation, building, decoration, industrial equipments, piping insulation, light industry, Home furniture.It is stronger that but the deadly defect of polyurethane products is a combustibility.Flex foam particularly, because density is little, specific surface area is big, heat insulating ability is good, its combustion problem is particularly outstanding, the oxygen index of self has only 14-16, so very easily lighted and burn.And once catch fire, burning is fierce rapidly, is difficult for putting out, a large amount of toxic smog that produces in its combustion processes, and the personnel that very easily cause suffocate and are poisoned to death.Since the urethane plastic mass production with since using, repeatedly fire disaster accident had taken place, people's lives and properties have caused massive losses, so improve the flame retardant properties of urethane, replacing non-flame-retarded foamed plastic with flame-retarded foamed plastic is trend of the times, is the inevitable requirement of public safety to material.
Prepare flame retardant polyurethane and adopt two kinds of method in common at present: add the fire retardant method and have the method for flame-retarding characteristic raw material with directly using.Preparation fire retardant that urethane adopted is the addition type organic or inorganic compound of ignition-proof elements such as chloride, bromine, nitrogen, phosphorus, antimony, aluminium, boron.Directly add fire retardant method simple equipments, foaming and fire-retardant can finishing synchronously, but it is very high that foam process requires, most fire retardants in foaming process, all can cause foam collapse bubble, shrink or ftracture, only there is fire retardant few in number to use, and flame retardant effect was not remarkable when these fire retardants added separately, and the foamy physical and mechanical properties that makes is relatively poor.Simultaneously, owing to use more chloride, bromine flame retardant, porous plastics combustion product gases toxicity is also bigger.Adopting halogen-free flame retardants is the polyurethane flame-proof technology trends, requires simultaneously to press down fuming and nontoxic gasization, and specific requirement improves to nonflammable (oxygen index 30) from self-extinguishing type (oxygen index 26).
Main raw material at urethane is polyvalent alcohol, isocyanic ester.In the raw molecule structure, introduce ignition-proof element, make in the PU flex foam molecule that makes and contain ignition-proof element, thereby obtain flame retardant properties.This kind method have the flame retardant properties persistence good, to advantages such as physical and mechanical properties influence are less.
The research of flame-proof polyol is the difficult problem that people pay close attention to using always.The research and development of China's flame retardant polyether polyol has also obtained certain progress in recent years.Wang Jingcun etc. (polyurethane industrial,, 20 (4): 11-15,45 in 2005) prepare route to the use for hard bubble of polyurethane flame-proof polyol and summarize.Domestic Tianjin Petrochemical Company institute successfully developed iron content series polyether glycol in 1999, have significantly fire-retardant and press down the cigarette effect, and when composite, the cooperative flame retardant effect is better with halogen-containing organic fire-retardant.The flame retardant grade series polyether glycol of Jiangsu Province Jiangyin YOBO Chemical Industry Co., Ltd. exploitation, not halogen-containing, elements such as P, Sb do not have corrosive nature to foaming machine.With its goods oxygen index 〉=20 of making, smoke density≤60%.Jinhua Chemical (Group) Corp., Ltd. is a main raw material with the propylene oxide, selects compound initiator, and ignition-proof element is introduced in the polyether glycol key, develops the JH-452R product of anti-the combustible polyether glycol through lab scale, pilot scale.Application test proves that this product has active height, viscosity is low, and is good with other auxiliary agent consistencies, is easy to characteristics such as construction, operation.Have tangible resistance to flame and low-smoke with its polyurethane product of making, its oxygen index reaches 20%-21%.Shaanxi Xi'an Inst. of Modern Chemistry carries out the positively charged ion ring-opening polymerization to 3-brooethyl-3-(2-cyanogen oxyethyl group) methyl oxygen butane (BMCMO), first in the polyether glycol molecular structure simultaneously introducing-Br (theoretical value is 34%) and-CN (theoretical value is 11%), made a kind of novel end hydroxy polyether polyvalent alcohol PBMCMO.Urethane with this polyether glycol preparation can have multiple properties such as fire-retardant, heat-resisting and oil resistant simultaneously.Side chain is contained the high reactivity chloro polyether glycol (CHIROL) of chloromethyl for Huaihai Institute of Technology and Qingdao University of Science and Technology and the method for the synthetic High Reactive Flame Retardant Polyether Polyol (HIROL) of tribromophenol sodium salt nucleophilic substitution is studied.The HIROL that makes is a clear amber in color liquid, and bromine content is 20%-25%, and viscosity is 0.75-0.88Paos, can be used for making the high-performance refractory flexible PU foam.The enterprise of domestic production flame retarding polyether is two families only at present, is respectively Huzhou innovation and Jiangyin friendly nation.The fire-retardant polyether polyols such as SPPG-280, POP-290 of Huzhou innovation are nitrogenous essential flame retardant polyurethane starting material.Flame retardant polyether polyol still waits exploitation at present as the raw material that is used in high-end foam field in the market of China.
In sum, flame retarding polyether (polyester) polyvalent alcohol of research contains halogens such as chlorine, bromine mostly at present, can not satisfy non-halogenated requirement.And not halogen-containing phosphorus-containing polyol is as basic structural unit basically with phosphoric acid ester.Because containing the phosphoric acid ester bond is phosphorus-to-oxygen bonds, hydrolysis does not influence production of polyurethane technology, reduces storage and asks qualitative.The hydrolysis problem that solves phosphorus-containing polyol is one of present most important technical barrier.The research of hydrolysis phosphor-containing flame-proof polyether glycol does not appear in the newspapers.
The objective of the invention is to overcome the deficiency that hydrolytic resistance is poor, content of halogen is high of existing urethane phosphonium flame retardant and phosphorous polyethers (polyester) polyvalent alcohol, make urethane reach halogen-free flameproof, low cigarette, nontoxic service requirements, and improve the processing characteristics of urethane.Utilize poisonous industrial by-products phosphuret-(t)ed hydrogen to be main raw material, the phosphorus-containing polyol for preparing a kind of hydrolysis, it can directly use as reactive flame retardant, also can be used as starting raw material, further synthetic macromolecule amount polyethers (polyester) polyvalent alcohol is as the raw material of halogen-free anti-inflaming polyurethane material.
The object of the present invention is achieved like this: a kind of non-halogen flame retardant hydrolysis resistant phosphorus-containing polyether ether/polyester polyol, and its general formula is as follows:
R wherein
1, R
2, R
3Can be identical, also can be different, they are one of following groups or its combination:
Hydrogen atom is if be trishydroxymethyl phosphine oxide or tris(hydroxymethyl)phosphine for hydrogen atom entirely;
-(CH
2) n-, n is an integer, can be straight chain, also can be corresponding branched chain isomer
-(CH
2CHCH
3O)
m--(CH
2CH
2O)
n-, m, n are zero or positive integer
-(O=C (CH
2)
mO)
n-, m, n are positive integer
The valency of phosphorus be+5 or+3 valencys, the perhaps mixture of the two.
A kind of method for preparing non-halogen flame retardant hydrolysis resistant phosphorus-containing polyether ether/polyester polyol,
(1) collection of phosphuret-(t)ed hydrogen and storage;
(2) phosphine gas through purifying, under acidic conditions, with formaldehyde reaction, preparation tetra methylol quaternary alkylphosphonium salt;
(3) quaternary alkylphosphonium salts prepare trishydroxymethyl phosphine oxide, tris(hydroxymethyl)phosphine or its mixture under alkaline condition;
(4) Zhi Bei methylol phosphide, promptly ring-opening polymerization takes place with epoxy compounds, lactone, lactide etc. in trishydroxymethyl phosphine oxide, tris(hydroxymethyl)phosphine or its mixture under catalyst action, obtains hydrolysis resistant phosphorus-containing polyether ether/polyester polyol.
In step (2) phosphine gas is fed the absorption tower, absorption liquid is formaldehyde/acid mixture, adopts the counter-current absorption mode.Absorption temperature is a room temperature-55 ℃, obtains quaternary alkylphosphonium salt solution after reaction is finished.
It is mineral acid, organic acid and polymeric acid that the acid of being adopted removes,
Mineral acid includes, but are not limited to hydrochloric acid, sulfuric acid, nitric acid, sulfurous acid, phosphoric acid, tetra-sodium, phosphorous acid, Hypophosporous Acid, 50, hypochlorous acid, perchloric acid, wolframic acid, phospho-wolframic acid, molybdic acid, phospho-molybdic acid;
The organic acid that is adopted comprises, but be not limited to formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, oleic acid, stearic acid, ricinolic acid, methylsulfonic acid, trifluoromethanesulfonic acid, hydroxyethylsulfonic acid, hydroxypropyl sulfonic acid, hydroxyl butyl sulfonic acid, phenylformic acid, toluylic acid, P-hydroxybenzoic acid, phenylium, Phenylsulfonic acid, p-methyl benzenesulfonic acid, naphthene sulfonic acid, naphthalene disulfonic acid;
The polymeric acid that is adopted includes, but not limited to polyacrylic acid, polymethyl acrylic acid, polyvinyl phenylbenzimidazole sulfonic acid, polyvinyl toluylic acid, polyvinylsulfonic acid, polyphosphoric acid.
In step (3), under protection of inert gas, alkali is heated up, joins fast in the aqueous solution of quaternary alkylphosphonium salt, behind the stirring reaction, separate the salt that reaction produces after, obtain trishydroxymethyl phosphine oxide, tris(hydroxymethyl)phosphine.
The alkali that is adopted is mineral alkali, organic bases, quaternary ammonium hydroxide or basic oxide.
Described mineral alkali comprises: as ammoniacal liquor, sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, hydrogen beryllium hydroxide, calcium hydroxide, magnesium hydroxide, strontium hydroxide, hydrated barta or aluminium hydroxide;
Organic bases comprises: Trimethylamine 99, triethylamine, tripropyl amine, Tributylamine, triamylamine, trolamine, pyridine or pyrroles;
Quaternary ammonium hydroxide comprises: tetramethylammonium hydroxide, tetraethylammonium hydroxide, hydroxide tetrapropylammonium or hydroxide hydrogen tetrabutylammonium;
Basic oxide comprise: Lithium Oxide 98min, sodium oxide, potassium oxide, rubidium oxide, beryllium oxide, magnesium oxide, calcium oxide, strontium oxide, barium oxide, zinc oxide, magnesium oxide or aluminum oxide.
In step (4), reaction vessel is a stainless steel cauldron, adds trishydroxymethyl phosphine oxide, tris(hydroxymethyl)phosphine or its mixture and catalyzer, nitrogen replacement 3 times in reactor, vacuumize then, after being warming up to preset temperature, slowly add propylene oxide, oxyethane or its mixture again, reaction pressure remains on below the certain value, after the control reaction temperature polyester scheduled time, be cooled to 80～90 ℃, hydroxyl value is surveyed in sampling, obtains thick polyethers; The qualified back of hydroxyl value adds pure water, phosphoric acid, Magnesium Silicate q-agent in reactor, be warming up to 105 ± 2 ℃, and vacuum hydro-extraction 5h after moisture is qualified, carries out vacuum filtration, obtains polyether glycol.
In step (4),, add reactor and weigh trishydroxymethyl phosphine oxide, tris(hydroxymethyl)phosphine or its mixture.Vacuumize, inflated with nitrogen three times, add rac-Lactide then, and the inferior tin of octoate catalyst, under preset temperature, be polymerized to the scheduled time, obtain head product. subsequently, reaction product is dissolved in methylene dichloride, do precipitation agent with ethanol and carry out purification process. the product behind the purifying is carried out vacuum-drying, remove the small molecules solvent, get polyester polyol.
Described catalyzer comprises mineral alkali, as sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, calcium hydroxide; Organic bases is as pyridine, pyrroles, Trimethylamine 99, triethylamine, tripropyl amine, Tributylamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, hydroxide tetrapropylammonium, hydroxide hydrogen tetrabutylammonium; Organometallic compound is as naphthalene sodium, naphthalene potassium, carbazole potassium, carbazole sodium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, zinc ethyl, magnesium ethide; The organo-metallic oxide compound is as aluminum isopropylate, aluminum ethoxide, propoxy-aluminium, butoxy aluminium, double metal cyanide, porphyrin metal complex, phthalocyanine metal complex compound.
Described catalyzer comprises: metal oxide such as tetrabutyl titanate, titanium isopropylate, stannous octoate; Metal hydride such as sodium hydride, potassium hydride KH, hydrolith; Strongly-acid compound such as methylsulfonic acid, trifluoromethanesulfonic acid, sulfuric acid, phosphoric acid, perchloric acid, trichoroacetic acid(TCA).
Non-halogen flame retardant hydrolysis resistant phosphorus-containing polyether ether/polyester polyol provided by the invention and preparation method thereof has following beneficial effect:
(1) with phosphuret-(t)ed hydrogen is starting raw material, phosphuret-(t)ed hydrogen is a kind of hypertoxic gas, mainly suck and cause poisoning by respiratory tract, phosphine waste gas has not only caused environmental pollution, endangered HUMAN HEALTH, and restricting production process control, safety in production and comprehensive utilization of waste materials, and technology circuit provided by the invention provides a new approach for the nuisanceless utilization of phosphuret-(t)ed hydrogen, and utilization helps the sound development of phosphorous chemical industry industry to phosphine gas.
(2) the phosphorous polyether/polyester polyvalent alcohol that obtains of the present invention, phosphoric acid ester bond not, and connect with phosphorus-to-carbon bonds, this product excellent hydrolysis resistance, phosphorus content is adjustable, does not influence the storge quality of raw material, simultaneously mould is not had corrodibility.
Embodiment
The phosphorous polyether/polyester polyvalent alcohol that the present invention obtains, its general formula is as follows:
R wherein
1, R
2, R
3Can be identical, also can be different, they are one of following groups or its combination:
Hydrogen atom is if be trishydroxymethyl phosphine oxide or tris(hydroxymethyl)phosphine for hydrogen atom entirely;
-(CH
2) n-, n is an integer, can be straight chain, also can be corresponding branched chain isomer
-(CH
2CHCH
3O)
m--(CH
2CH
2O)
n-, m, n are zero or positive integer
-(O=C (CH
2)
mO)
n-, m, n be positive integer phosphorus valency for+5 or+3 valencys, the perhaps mixture of the two, the perhaps mixture of the two, the two ratio depends on preparation condition and purification techniques.Obtain pure substance and mixture therefrom and when using, have suitable effect, can not add to separate directly and utilize.Complete preparation feedback can followingly be explained:
Reaction process is as follows:
1, prepares four methylol phosphonium salts by phosphine gas
The preparation feedback principle is as follows:
By the preparing tetra hydroxymethyl phosphorus quaternary alkylphosphonium salt, patent has been arranged.But the acid of being adopted can be other mineral acid, organic acid and polymeric acid except that hydrochloric acid that patent adopted, sulfuric acid.Mineral acid includes, but are not limited to nitric acid, sulfurous acid, phosphoric acid, tetra-sodium, phosphorous acid, Hypophosporous Acid, 50, hypochlorous acid, perchloric acid, wolframic acid, phospho-wolframic acid, molybdic acid, phospho-molybdic acid; The organic acid that is adopted comprises, but be not limited to formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, oleic acid, stearic acid, ricinolic acid, methylsulfonic acid, trifluoromethanesulfonic acid, hydroxyethylsulfonic acid, hydroxypropyl sulfonic acid, hydroxyl butyl sulfonic acid, phenylformic acid, toluylic acid, P-hydroxybenzoic acid, phenylium, Phenylsulfonic acid, p-methyl benzenesulfonic acid, naphthene sulfonic acid, naphthalene disulfonic acid; The polymeric acid that is adopted includes, but not limited to polyacrylic acid, polymethyl acrylic acid, polyvinyl phenylbenzimidazole sulfonic acid, polyvinyl toluylic acid, polyvinylsulfonic acid, polyphosphoric acid.Adopt the resulting quaternary alkylphosphonium salt of above-mentioned acid to have same reactive behavior and effect.Concrete operations are as follows:
Phosphine gas is fed the absorption tower, and absorption liquid is formaldehyde/acid mixture, adopts the counter-current absorption mode.Absorption temperature is a room temperature-55 ℃, obtains quaternary alkylphosphonium salt solution after reaction is finished, and surveys its content, is used for the next step.
2. the You quaternary alkylphosphonium salt prepares the trishydroxymethyl phosphorus polyvalent alcohol of different valence state
The preparation of trishydroxymethyl phosphine oxide or tris(hydroxymethyl)phosphine is raw material Yi the quaternary alkylphosphonium salt, prepares under alkaline condition.According to the difference of selected alkali, product can be pure trishydroxymethyl phosphine oxide, tris(hydroxymethyl)phosphine or the mixture of the two.No matter which kind of product all can directly use as the hydrolysis phosphorus-containing polyol.Be initiator with them simultaneously, proceed reaction, preparation high molecular hydrolysis resistant phosphorus-containing polyether ether (polyester) polyvalent alcohol.Reaction formula is as follows:
The alkali that reaction is adopted comprises that mineral alkali is (as ammoniacal liquor, sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, the hydrogen beryllium hydroxide, calcium hydroxide, magnesium hydroxide, strontium hydroxide, hydrated barta, aluminium hydroxide), organic bases (Trimethylamine 99, triethylamine, tripropyl amine, Tributylamine, triamylamine, trolamine, pyridine, the pyrroles), quaternary ammonium hydroxide (tetramethylammonium hydroxide, tetraethylammonium hydroxide, the hydroxide tetrapropylammonium, hydroxide hydrogen tetrabutylammonium), basic oxide (Lithium Oxide 98min, sodium oxide, potassium oxide, rubidium oxide, beryllium oxide, magnesium oxide, calcium oxide, strontium oxide, barium oxide, zinc oxide, magnesium oxide, aluminum oxide).Control reaction conditions (kind of alkali and concentration, temperature of reaction and time, feed rate etc.) can obtain different polyvalent alcohol products or its mixture.
Operation steps is as follows:
Under protection of inert gas, with alkali at a certain temperature, join fast in the aqueous solution of quaternary alkylphosphonium salt, stirring reaction is after the scheduled time, separate the salt that reaction produces after, obtain limpid thick liquid, productive rate 95%.According to the difference of employing key, can obtain pure trishydroxymethyl phosphine oxide, tris(hydroxymethyl)phosphine after the purification.Also can not add to separate and purify, directly use.
3, the preparation of hydrolysis phosphorus-containing polyol
The hydrolysis phosphorus-containing polyol is with prepared trishydroxymethyl phosphine oxide, and tris(hydroxymethyl)phosphine or the mixture of the two are initiator, with cyclic monomer (comprising epoxy monomer, lactone, lactide etc.) in the presence of catalyzer, carry out ring-opening polymerization and get.The feature of gained polyvalent alcohol is that phosphoric connects by phosphorus-to-carbon bonds, has avoided the weakness of phosphorus-to-oxygen bonds (phosphatide key) facile hydrolysis, thereby has had the feature of high hydrolysis resistance.
According to the characteristic of polymerization single polymerization monomer, the catalyzer that ring-opening reaction adopted is not quite similar.For the epoxies monomer, adoptable catalyzer comprises mineral alkali, as sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, calcium hydroxide; Organic bases is as pyridine, pyrroles, Trimethylamine 99, triethylamine, tripropyl amine, Tributylamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, hydroxide tetrapropylammonium, hydroxide hydrogen tetrabutylammonium; Organometallic compound, as naphthalene sodium, naphthalene potassium, carbazole potassium,, carbazole sodium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, zinc ethyl, magnesium ethide; The organo-metallic oxide compound is as aluminum isopropylate, aluminum ethoxide, propoxy-aluminium, butoxy aluminium; Double metal cyanide; Porphyrin metal complex; Phthalocyanine metal complex compound etc.
Polyreaction for lactone and lactide, can adopt catalyzer to comprise: metal oxide such as tetrabutyl titanate, titanium isopropylate, stannous octoate etc., metal hydride such as sodium hydride, potassium hydride KH, hydrolith etc., strongly-acid compound such as methylsulfonic acid, trifluoromethanesulfonic acid, sulfuric acid, phosphoric acid, perchloric acid, trichoroacetic acid(TCA) etc.
Catalyst consumption is decided by the requirement of final product molecular weight and hydroxyl value.
The epoxy monomer that reaction is adopted comprises oxyethane, propylene oxide, end epoxy group(ing) long chain alkane, phenyl ethylene oxide etc.These monomers may be used alone, can also be used in combination.
The polymerizable lactone that reaction is adopted comprises glycollide, rac-Lactide, butyrolactone, valerolactone, a few lactone, oenantholacton, caprylolactone, macrolide etc.
Reaction can adopt the mode of mass polymerization or solution polymerization to carry out at body.
Reaction formula can be expressed as:
Preparation polyether glycol operation steps is as follows:
In stainless steel cauldron, add trishydroxymethyl phosphine oxide, tris(hydroxymethyl)phosphine or its mixture of metering, catalyzer.Nitrogen replacement 3 times vacuumizes then, be warming up to preset temperature after, slowly add propylene oxide, oxyethane or its mixture again.Reaction pressure remains on below the certain value, after the control reaction temperature polyester scheduled time, is cooled to 80～90 ℃, and hydroxyl value is surveyed in sampling, obtains thick polyethers.The qualified back of hydroxyl value adds pure water, phosphoric acid, Magnesium Silicate q-agent in reactor, be warming up to 105 ± 2 ℃, and vacuum hydro-extraction 5h after moisture is qualified, carries out vacuum filtration, waits product.
The concrete operations step of preparation polyester polyol is as follows:
With trishydroxymethyl phosphine oxide, tris(hydroxymethyl)phosphine or its mixture of metering, add reactor and weigh.Vacuumize inflated with nitrogen three times.Add rac-Lactide then, and the inferior tin of octoate catalyst etc.Under preset temperature, be polymerized to the scheduled time, obtain head product. subsequently, reaction product is dissolved in methylene dichloride, does precipitation agent with ethanol and carry out purification process. the product behind the purifying is carried out vacuum-drying, remove the small molecules solvent, get product.
Embodiment:
Embodiment just lists and provides representational reaction conditions and step, but also not only comprises these contents, and according to the difference of employing raw material, relevant speciality technician can suitably adjust reaction conditions according to the ultimate principle of this patent.
Embodiment 1: the preparation of trishydroxymethyl phosphine oxide
Take by weighing 40g NaOH in advance, adding fills in the 1L single necked round bottom flask of 500ml distilled water, and magnetic agitation is dissolved NaOH fully.After treating that the NaOH aqueous solution is cooled to room temperature, drip 382.12g raw material tetra methylol sulfuric acid phosphonium, drip about time 1.5h room temperature reaction 10h by constant pressure funnel.
After reaction finishes, in solution, slowly drip dense HCl, regulate pH to neutral.Revolve inspissation and contract, 55-60 ℃, the water pump decompression, pact-0.09MPa removes to pour into behind most solvents and fills in the 500ml alcoholic acid 1L beaker, and preservative film seals, standing over night is fully to separate out salt, and suction filtration revolves inspissation once more and contracts, temperature 40-45 ℃, water pump decompression, pact-0.09MPa, after solvent-free substantially, pour in the 300ml ethanol, leave standstill a few hours fully to separate out salt, revolve steaming, solvent evaporated behind the suction filtration.With 200ml acetone extract separatory, solvent evaporated, as still have and salt out, but repeating step 4.Last solvent evaporated promptly gets product, for the transparent liquid 249g of viscosity is arranged slightly.
Embodiment 2: the preparation of tris(hydroxymethyl)phosphine
Take by weighing 80g NaOH in advance, adding fills in the 1L beaker of 400ml distilled water, and magnetic agitation is dissolved NaOH fully, is cooled to room temperature.In the 1L single necked round bottom flask, add 477.65g raw material THPS, vacuumize down, rapidly the above-mentioned 400ml NaOH aqueous solution of (should not surpass 1min) adding in the Ar protection.Behind the stirring at room reaction 20h, revolve inspissation and contract and remove most solvents, precipitation is separated out Na2SO4 in 500ml ethanol.Solvent evaporated behind the suction filtration is with 200ml acetone extract separatory (removing HCHO).As still have and salt out, but repeating step 3,4.Last solvent evaporated promptly gets product, for the transparent liquid 220g of certain viscosity is arranged.
Embodiment 3,
1.32g solid potassium hydroxide and 152g tris(hydroxymethyl)phosphine are added in the steel pressure reactor.Temperature is elevated to 120-125 ℃ subsequently, under vacuum decompression, keeps this temperature 40-50min, with existing moisture in the system of removing and other volatile impunty.Temperature is reduced to 105-115 ℃ subsequently, and begins to add propylene oxide (the total amount accumulative total of propylene oxide to be added is 628g).In the propylene oxide adition process, system pressure raises.The maintenance system constant pressure added all propylene oxide in 6 hours.Continue reaction 2-3 hour, all propylene oxide react.Treat that system temperature drops to about 80 ℃ and after pressure drops to normal pressure, refining according to ordinary method, obtained the phosphorous polyether glycol of 757g.Molecular weight is 715, and functionality is 3, and hydroxyl value is 235mgKOH/g.
Embodiment 4
1.32g solid potassium hydroxide and 134g trishydroxymethyl phosphine oxide are added in the steel pressure reactor.Vacuumize repeatedly, inflated with nitrogen is with oxidizing gas in the displacement still.Temperature is elevated to 120-125 ℃ subsequently, under vacuum decompression, keeps this temperature 40-50min, with existing moisture in the system of removing and other volatile impunty.Temperature is reduced to 105-115 ℃ subsequently, and begins to add propylene oxide (the total amount accumulative total of propylene oxide to be added is 628g).In the propylene oxide adition process, system pressure raises.Maintenance system pressure added all propylene oxide in 6 hours below 0.5MPa.Continue reaction 2-3 hour, all propylene oxide react.Treat that system temperature drops to about 80 ℃ and after pressure drops to normal pressure, refining according to ordinary method, obtained the phosphorous polyether glycol of 737g.Molecular weight is 680, and functionality is 3, and hydroxyl value is 247mgKOH/g.
Embodiment 5
1.32g solid potassium hydroxide and 152g tris(hydroxymethyl)phosphine are added in the steel pressure reactor.Temperature is elevated to 120-125 ℃ subsequently, under vacuum decompression, keeps this temperature 40-50min, with existing moisture in the system of removing and other volatile impunty.Temperature is reduced to 105-115 ℃ subsequently, and begins to add oxyethane (the total amount accumulative total of oxyethane to be added is 726g).In the oxyethane adition process, system pressure raises.The maintenance system constant pressure added all oxyethane in 4 hours below 0.5MPa.Continue reaction 1-2 hour, all oxyethane react.Treat that system temperature drops to about 80 ℃ and after pressure drops to normal pressure, refining according to ordinary method, obtained the phosphorous polyether glycol of 870g.Molecular weight is 796, and functionality is 3, and hydroxyl value is 211mgKOH/g.
Embodiment 6
To add the steel pressure reaction vessel that band stirs through CaH2 exsiccant refining 6-caprolactone 420g, trishydroxymethyl phosphine oxide 15.2g and stannous octoate.Vacuumize decompression, logical nitrogen, repeatable operation air to the still is all replaced.Reaction mixture is heated to 125-130 ℃.React after 24 hours, reduce temperature to room temperature.Mixture in the still is dissolved with methylene dichloride, remove by filter insolubless such as catalyzer.Filtrate is precipitated with excessive anhydrous diethyl ether/anhydrous methanol.Filter, obtain white cotton-shaped product.Put into vacuum drying oven, be dried to constant weight under 40 ℃, product 389g.Molecular weight of product is 416 by analysis, and functionality is 3, and hydroxyl value is 403mgKOH/g.
Embodiment 7
With 420g rac-Lactide (L type or DL type), trishydroxymethyl phosphine oxide 15.2g and urge the inferior tin of octoate catalyst adds the steel pressure reaction vessel that band stirs.Vacuumize decompression, logical nitrogen, repeatable operation air to the still is all replaced.Reaction mixture is heated to 140 ℃ of temperature, constant temperature polymerase 17 2 hours.Temperature is reduced to room temperature, adds methylene dichloride dissolving head product.Remove by filter catalyzer and insolubles.Subsequently filtrate is done precipitation agent with ethanol and carry out purification process. the white cotton-shaped product behind the purifying is carried out vacuum-drying at 50 ℃, remove small molecules solvent and volatilization component, obtain product 368g. by analysis the product molecular weight of product be 398, functionality is 3, hydroxyl value is 422mgKOH/g.
Claims (11)
1. non-halogen flame retardant hydrolysis resistant phosphorus-containing polyether ether/polyester polyol, its general formula is as follows:
Or
R wherein
1, R
2, R
3Can be identical, also can be different, they are one of following groups or its combination:
Hydrogen atom is if be trishydroxymethyl phosphine oxide or tris(hydroxymethyl)phosphine for hydrogen atom entirely;
-(CH
2) n-, n is an integer, can be straight chain, also can be corresponding branched chain isomer
-(CH
2CHCH
3O)
m--(CH
2CH
2O)
n-, m, n are zero or positive integer
-(O=C (CH
2)
mO)
n-, m, n are positive integer
The valency of phosphorus be+5 or+3 valencys, the perhaps mixture of the two.
2. method for preparing non-halogen flame retardant hydrolysis resistant phosphorus-containing polyether ether/polyester polyol, it is held to levy and is:
(1) collection of phosphuret-(t)ed hydrogen and storage;
(2) phosphine gas through purifying, under acidic conditions, with formaldehyde reaction, preparation tetra methylol quaternary alkylphosphonium salt;
(3) quaternary alkylphosphonium salts prepare trishydroxymethyl phosphine oxide, tris(hydroxymethyl)phosphine or its mixture under alkaline condition;
(4) Zhi Bei methylol phosphide, promptly ring-opening polymerization takes place with epoxy compounds, lactone, lactide etc. in trishydroxymethyl phosphine oxide, tris(hydroxymethyl)phosphine or its mixture under catalyst action, obtains hydrolysis resistant phosphorus-containing polyether ether/polyester polyol.
3. the method for preparing non-halogen flame retardant hydrolysis resistant phosphorus-containing polyether ether/polyester polyol according to claim 2, it is held to levy and is: in step (2) phosphine gas is fed the absorption tower, absorption liquid is formaldehyde/acid mixture, adopts the counter-current absorption mode.Absorption temperature is a room temperature-55 ℃, obtains quaternary alkylphosphonium salt solution after reaction is finished.
4. the method for preparing non-halogen flame retardant hydrolysis resistant phosphorus-containing polyether ether/polyester polyol according to claim 3, it is held to levy and is: it is mineral acid, organic acid and polymeric acid that the acid of being adopted removes,
Mineral acid includes, but are not limited to hydrochloric acid, sulfuric acid, nitric acid, sulfurous acid, phosphoric acid, tetra-sodium, phosphorous acid, Hypophosporous Acid, 50, hypochlorous acid, perchloric acid, wolframic acid, phospho-wolframic acid, molybdic acid, phospho-molybdic acid;
The organic acid that is adopted comprises, but be not limited to formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, oleic acid, stearic acid, ricinolic acid, methylsulfonic acid, trifluoromethanesulfonic acid, hydroxyethylsulfonic acid, hydroxypropyl sulfonic acid, hydroxyl butyl sulfonic acid, phenylformic acid, toluylic acid, P-hydroxybenzoic acid, phenylium, Phenylsulfonic acid, p-methyl benzenesulfonic acid, naphthene sulfonic acid, naphthalene disulfonic acid;
The polymeric acid that is adopted includes, but not limited to polyacrylic acid, polymethyl acrylic acid, polyvinyl phenylbenzimidazole sulfonic acid, polyvinyl toluylic acid, polyvinylsulfonic acid, polyphosphoric acid.
5. the method for preparing non-halogen flame retardant hydrolysis resistant phosphorus-containing polyether ether/polyester polyol according to claim 2; it is held to levy and is: in step (3) under protection of inert gas; alkali is heated up; join fast in the aqueous solution of quaternary alkylphosphonium salt; behind the stirring reaction; after separating the salt that reaction produces, obtain trishydroxymethyl phosphine oxide, tris(hydroxymethyl)phosphine.
6. the method for preparing non-halogen flame retardant hydrolysis resistant phosphorus-containing polyether ether/polyester polyol according to claim 5, it is held to levy and is: the alkali that is adopted is mineral alkali, organic bases, quaternary ammonium hydroxide or basic oxide.
7. the method for preparing non-halogen flame retardant hydrolysis resistant phosphorus-containing polyether ether/polyester polyol according to claim 6, it is held to levy and is: described mineral alkali comprises: as ammoniacal liquor, sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, hydrogen beryllium hydroxide, calcium hydroxide, magnesium hydroxide, strontium hydroxide, hydrated barta or aluminium hydroxide;
Organic bases comprises: Trimethylamine 99, triethylamine, tripropyl amine, Tributylamine, triamylamine, trolamine, pyridine or pyrroles;
Quaternary ammonium hydroxide comprises: tetramethylammonium hydroxide, tetraethylammonium hydroxide, hydroxide tetrapropylammonium or hydroxide hydrogen tetrabutylammonium;
Basic oxide comprise: Lithium Oxide 98min, sodium oxide, potassium oxide, rubidium oxide, beryllium oxide, magnesium oxide, calcium oxide, strontium oxide, barium oxide, zinc oxide, magnesium oxide or aluminum oxide.
8. the method for preparing non-halogen flame retardant hydrolysis resistant phosphorus-containing polyether ether/polyester polyol according to claim 2, it is held to levy and is: in step (4), reaction vessel is a stainless steel cauldron, in reactor, add the trishydroxymethyl phosphine oxide, tris(hydroxymethyl)phosphine or its mixture and catalyzer, nitrogen replacement 3 times, vacuumize then, after being warming up to preset temperature, slowly add propylene oxide again, oxyethane or its mixture, reaction pressure remains on below the certain value, after the control reaction temperature polyester scheduled time, is cooled to 80～90 ℃, hydroxyl value is surveyed in sampling, obtains thick polyethers; The qualified back of hydroxyl value adds pure water, phosphoric acid, Magnesium Silicate q-agent in reactor, be warming up to 105 ± 2 ℃, and vacuum hydro-extraction 5h after moisture is qualified, carries out vacuum filtration, obtains polyether glycol.
9. the method for preparing non-halogen flame retardant hydrolysis resistant phosphorus-containing polyether ether/polyester polyol according to claim 2, it is held to levy and is: in step (4), with trishydroxymethyl phosphine oxide, tris(hydroxymethyl)phosphine or its mixture, add reactor and weigh.Vacuumize, inflated with nitrogen three times, add rac-Lactide then, and the inferior tin of octoate catalyst, under preset temperature, be polymerized to the scheduled time, obtain head product. subsequently, reaction product is dissolved in methylene dichloride, do precipitation agent with ethanol and carry out purification process. the product behind the purifying is carried out vacuum-drying, remove the small molecules solvent, get polyester polyol.
10. the method for preparing non-halogen flame retardant hydrolysis resistant phosphorus-containing polyether ether/polyester polyol according to claim 8, it is held to levy and is: described catalyzer comprises mineral alkali, as sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, calcium hydroxide; Organic bases is as pyridine, pyrroles, Trimethylamine 99, triethylamine, tripropyl amine, Tributylamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, hydroxide tetrapropylammonium, hydroxide hydrogen tetrabutylammonium; Organometallic compound is as naphthalene sodium, naphthalene potassium, carbazole potassium, carbazole sodium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, zinc ethyl, magnesium ethide; The organo-metallic oxide compound is as aluminum isopropylate, aluminum ethoxide, propoxy-aluminium, butoxy aluminium, double metal cyanide, porphyrin metal complex, phthalocyanine metal complex compound.
11. the method for preparing non-halogen flame retardant hydrolysis resistant phosphorus-containing polyether ether/polyester polyol according to claim 9, it is held to levy and is: described catalyzer comprises: metal oxide such as tetrabutyl titanate, titanium isopropylate, stannous octoate; Metal hydride such as sodium hydride, potassium hydride KH, hydrolith; Strongly-acid compound such as methylsulfonic acid, trifluoromethanesulfonic acid, sulfuric acid, phosphoric acid, perchloric acid, trichoroacetic acid(TCA).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910273165A CN101747371A (en) | 2009-12-09 | 2009-12-09 | Non-halogen flame retardant hydrolysis resistant phosphorus-containing polyether/polyester polyol and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910273165A CN101747371A (en) | 2009-12-09 | 2009-12-09 | Non-halogen flame retardant hydrolysis resistant phosphorus-containing polyether/polyester polyol and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101747371A true CN101747371A (en) | 2010-06-23 |
Family
ID=42475046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910273165A Pending CN101747371A (en) | 2009-12-09 | 2009-12-09 | Non-halogen flame retardant hydrolysis resistant phosphorus-containing polyether/polyester polyol and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101747371A (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101982603A (en) * | 2010-10-22 | 2011-03-02 | 北京理工大学 | Halogen free phosphorous-nitrogen synergic antiflaming water-soluble polyurethane fabric coating agent and preparation method thereof |
| CN102093541A (en) * | 2010-12-07 | 2011-06-15 | 中山大学 | Application of aliphatic tertiary amine in cyclic ester ring opening polymerization and ring opening polymerization method of cyclic ester |
| CN103980313A (en) * | 2014-05-23 | 2014-08-13 | 厦门大学 | Phosphorus-nitrogen synergistic flame-retardant polyalcohol and preparation method thereof |
| CN104403094A (en) * | 2014-11-17 | 2015-03-11 | 江苏钟山化工有限公司 | Method for preparation of flame retardant polyether polyol based on modified phosphoric acid |
| CN105237757A (en) * | 2014-07-11 | 2016-01-13 | 中国石油化工股份有限公司 | Catalyst for ring-opening copolymerization of oxyalkylene and lactide |
| CN105801833A (en) * | 2016-03-25 | 2016-07-27 | 江阴职业技术学院 | Preparation method and application of reactive type halogen-free flame-retardant polyether glycol |
| CN106750248A (en) * | 2017-01-24 | 2017-05-31 | 中国科学技术大学 | A kind of hyperbranched flame retardant polyether polyol and preparation method thereof |
| CN107141467A (en) * | 2017-06-28 | 2017-09-08 | 山东诺威新材料有限公司 | The preparation method of phosphorus chlorine composite flame-proof polyethers |
| CN108411695A (en) * | 2018-02-05 | 2018-08-17 | 东莞嘉颐实业有限公司 | A kind of priming-free UV gloss oil and its preparation method and application |
| CN110078909A (en) * | 2019-04-28 | 2019-08-02 | 上海元业体育科技有限公司 | A kind of phosphorous silane-terminated polyether and preparation method thereof |
| CN110305308A (en) * | 2019-06-24 | 2019-10-08 | 万华化学（宁波）容威聚氨酯有限公司 | A kind of polyether polyol and preparation method thereof, a kind of hard polyurethane foam |
| CN110305281A (en) * | 2019-06-24 | 2019-10-08 | 万华化学（烟台）容威聚氨酯有限公司 | A kind of high-strength polyurethane hard bubble and preparation method thereof |
| CN111004379A (en) * | 2019-12-02 | 2020-04-14 | 浙江理工大学桐乡研究院有限公司 | Preparation method of flame-retardant polyol with high phosphorus content and multiple functionality degrees |
| CN112280019A (en) * | 2020-09-17 | 2021-01-29 | 昆明理工大学 | Reactive phosphorus-containing flame-retardant polyester polyol and preparation method thereof |
| WO2021047977A1 (en) | 2019-09-12 | 2021-03-18 | Huntsman International Llc | A tris (hydroxymethyl) phosphine oxide based polyester polyol and a resin composition obtained therefrom |
| CN112608443A (en) * | 2020-12-30 | 2021-04-06 | 江南大学 | Preparation method of heat-resistant flame-retardant UV (ultraviolet) curing waterborne polyurethane |
| CN113882029A (en) * | 2021-11-04 | 2022-01-04 | 唐山三友集团兴达化纤有限公司 | High-strength washable phosphorus-nitrogen flame-retardant viscose fiber and preparation method thereof |
| CN114957637A (en) * | 2022-06-28 | 2022-08-30 | 万华化学集团股份有限公司 | Phosphorus-containing polyol and polyurethane foam material prepared from same |
| CN117126365A (en) * | 2023-09-22 | 2023-11-28 | 广州银旭科技股份有限公司 | Flame-retardant polyurethane prepolymer, polyurethane material and preparation method of flame-retardant polyurethane prepolymer |
-
2009
- 2009-12-09 CN CN200910273165A patent/CN101747371A/en active Pending
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101982603A (en) * | 2010-10-22 | 2011-03-02 | 北京理工大学 | Halogen free phosphorous-nitrogen synergic antiflaming water-soluble polyurethane fabric coating agent and preparation method thereof |
| CN102093541A (en) * | 2010-12-07 | 2011-06-15 | 中山大学 | Application of aliphatic tertiary amine in cyclic ester ring opening polymerization and ring opening polymerization method of cyclic ester |
| CN102093541B (en) * | 2010-12-07 | 2013-12-18 | 中山大学 | Application of aliphatic tertiary amine in cyclic ester ring opening polymerization and ring opening polymerization method of cyclic ester |
| CN103980313A (en) * | 2014-05-23 | 2014-08-13 | 厦门大学 | Phosphorus-nitrogen synergistic flame-retardant polyalcohol and preparation method thereof |
| CN105237757A (en) * | 2014-07-11 | 2016-01-13 | 中国石油化工股份有限公司 | Catalyst for ring-opening copolymerization of oxyalkylene and lactide |
| CN104403094A (en) * | 2014-11-17 | 2015-03-11 | 江苏钟山化工有限公司 | Method for preparation of flame retardant polyether polyol based on modified phosphoric acid |
| CN105801833A (en) * | 2016-03-25 | 2016-07-27 | 江阴职业技术学院 | Preparation method and application of reactive type halogen-free flame-retardant polyether glycol |
| CN106750248A (en) * | 2017-01-24 | 2017-05-31 | 中国科学技术大学 | A kind of hyperbranched flame retardant polyether polyol and preparation method thereof |
| CN107141467A (en) * | 2017-06-28 | 2017-09-08 | 山东诺威新材料有限公司 | The preparation method of phosphorus chlorine composite flame-proof polyethers |
| CN108411695A (en) * | 2018-02-05 | 2018-08-17 | 东莞嘉颐实业有限公司 | A kind of priming-free UV gloss oil and its preparation method and application |
| CN110078909A (en) * | 2019-04-28 | 2019-08-02 | 上海元业体育科技有限公司 | A kind of phosphorous silane-terminated polyether and preparation method thereof |
| CN110078909B (en) * | 2019-04-28 | 2021-08-20 | 上海元业体育科技有限公司 | Phosphorus-containing silane terminated polyether and preparation method thereof |
| CN110305281A (en) * | 2019-06-24 | 2019-10-08 | 万华化学（烟台）容威聚氨酯有限公司 | A kind of high-strength polyurethane hard bubble and preparation method thereof |
| CN110305308A (en) * | 2019-06-24 | 2019-10-08 | 万华化学（宁波）容威聚氨酯有限公司 | A kind of polyether polyol and preparation method thereof, a kind of hard polyurethane foam |
| WO2021047977A1 (en) | 2019-09-12 | 2021-03-18 | Huntsman International Llc | A tris (hydroxymethyl) phosphine oxide based polyester polyol and a resin composition obtained therefrom |
| US12049536B2 (en) | 2019-09-12 | 2024-07-30 | Huntsman International Llc | Tris (hydroxymethyl) phosphine oxide based polyester polyol and a resin composition obtained therefrom |
| CN111004379A (en) * | 2019-12-02 | 2020-04-14 | 浙江理工大学桐乡研究院有限公司 | Preparation method of flame-retardant polyol with high phosphorus content and multiple functionality degrees |
| CN112280019A (en) * | 2020-09-17 | 2021-01-29 | 昆明理工大学 | Reactive phosphorus-containing flame-retardant polyester polyol and preparation method thereof |
| CN112608443A (en) * | 2020-12-30 | 2021-04-06 | 江南大学 | Preparation method of heat-resistant flame-retardant UV (ultraviolet) curing waterborne polyurethane |
| CN113882029A (en) * | 2021-11-04 | 2022-01-04 | 唐山三友集团兴达化纤有限公司 | High-strength washable phosphorus-nitrogen flame-retardant viscose fiber and preparation method thereof |
| CN113882029B (en) * | 2021-11-04 | 2023-10-10 | 唐山三友集团兴达化纤有限公司 | High-strength water-resistant phosphorus-nitrogen flame-retardant viscose fiber and preparation method thereof |
| CN114957637A (en) * | 2022-06-28 | 2022-08-30 | 万华化学集团股份有限公司 | Phosphorus-containing polyol and polyurethane foam material prepared from same |
| CN114957637B (en) * | 2022-06-28 | 2024-04-09 | 万华化学集团股份有限公司 | Phosphorus-containing polyol and polyurethane foam material prepared from same |
| CN117126365A (en) * | 2023-09-22 | 2023-11-28 | 广州银旭科技股份有限公司 | Flame-retardant polyurethane prepolymer, polyurethane material and preparation method of flame-retardant polyurethane prepolymer |
| CN117126365B (en) * | 2023-09-22 | 2024-03-08 | 广州银旭科技股份有限公司 | Flame-retardant polyurethane prepolymer, polyurethane material and preparation method of flame-retardant polyurethane prepolymer |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101747371A (en) | Non-halogen flame retardant hydrolysis resistant phosphorus-containing polyether/polyester polyol and preparation method thereof | |
| Cyriac et al. | Preparation of flame-retarding poly (propylene carbonate) | |
| CN105061711B (en) | A kind of end group is DOPO type reactive flame retardants of epoxy radicals and its preparation method and application | |
| CN103739832B (en) | A kind of manufacture method of cationic dye capable of dyeing fire retardant polyester resin | |
| CN105175735B (en) | A kind of branched Phosphorus-nitrogen flame retardant and preparation method thereof | |
| CN106750248B (en) | A kind of hyperbranched flame retardant polyether polyol and preparation method thereof | |
| CN104558570A (en) | Synthesis of phosphorus containing polyester polyol and application of phosphorus containing polyester polyol in polyurethane | |
| CN103102655A (en) | Inflaming retarding polyester film and preparation method thereof | |
| CN101514253A (en) | Environment-friendly flame-retarded unsaturated polyester resin and preparation method thereof | |
| CN103113619A (en) | Triazine ring containing caged organic phosphate flame retardant and preparation method thereof | |
| CN103819634A (en) | Block copolymer containing phosphorus and silicon and preparation method of block copolymer | |
| CN103113409A (en) | Triazine ring structure containing caged organic phosphate and preparation method thereof | |
| CN114456350B (en) | Silicate modified polymer foaming material for filling sealing | |
| CN104610571A (en) | Cardanol-based phosphatefire-retardant plasticizer and preparation method thereof | |
| CN108794525A (en) | A kind of preparation method of phosphonium flame retardant | |
| CN110643018B (en) | Bio-based flame-retardant epoxy resin containing nitrogen and phosphorus structures and preparation method thereof | |
| CN104592297A (en) | Flame-retardant glycol containing phenyl phosphate-based symmetrical structure and preparation method thereof | |
| CN107955155B (en) | Nitrogen-boron structure type flame-retardant polyether polyol and preparation method and application thereof | |
| CN110156840B (en) | Phosphorus-nitrogen flame retardant containing DOPO and preparation method thereof | |
| CN104592301A (en) | Flame retardant, preparation method as well as modified polydicyclopentadiene and preparation method | |
| CN109748935A (en) | A kind of new bio base phosphonitrile epoxy monomer and its biology base phosphorus nitrogen fire retarding epoxide resin obtained | |
| CN106496536A (en) | The preparation method of containing phosphorus silicon fire retardant polyethylene terephthalate | |
| CN103360566A (en) | Flame retardant rigid polyurethane foaming plastic | |
| CN109762020A (en) | A kind of transparency liquid fire retardant, preparation method and applications | |
| CN111763351B (en) | Reactive phosphaphenanthrene/phosphite ester biradical flame retardant, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: YICHANG MEILIN CHEMIAL TECHNOLOGY CO., LTD. Free format text: FORMER OWNER: HUBEI FORREST CHEMICAL INDUSTRY SCIENCE + TECHNOLOGY CO., LTD. Effective date: 20100820 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20100820 Address after: 443000 Development Center, Dongshan Development Zone, Yichang, Hubei, A-2098 Applicant after: Hubei Furuisi Chemical Technology Co., Ltd. Address before: 443000 Development Center, Dongshan Development Zone, Yichang, Hubei, A-2098 Applicant before: Hubei Furuisi Chemical Technology Co., Ltd. |
|
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20100623 |