CN102731768A - Method for preparing polyether glycol by using melamine as initiator - Google Patents
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Abstract
The invention provides a method for preparing polyether glycol by using melamine as an initiator. The method comprises the steps that: melamine is mixed with an organic solvent, such that a slurry is prepared; the slurry is subjected to an addition polymerization reaction with oxidized olefin with the catalytic effect of alkali metal under certain temperature and pressure; an obtained initial product is subjected to further post-treatment, such that a series of polyether glycol products with an average molecular weight of 300-5000 and a hydroxyl value of 400-30mgKOH/g can be obtained. The method provided by the invention is simple. With the method, a series of polyether glycol products containing imine triazine structural units and having different molecular weights and hydroxyl values can be prepared. The obtained product is improved in auto-catalysis, thermal stability, flame retardance, and other physical and mechanical properties of polyurethane products.
Description
Technical field
The present invention relates to prepare the method for polyether glycol, being specially a kind of is the method that initiator prepares polyether glycol with the trimeric cyanamide.
Background technology
Trimeric cyanamide and verivate thereof are with the special molecular structure of thermally-stabilised and rich nitrogen; In nitrogen, phosphorus flame-retardant system, playing the part of the key player that nitrogenous source is provided; As addition type nitrogen flame retardant such as trimeric cyanamide, organic derivative of the phosphoric acid salt of trimeric cyanamide, pyrophosphate salt, polyphosphoric acid salt, borate, cyanate and other trimeric cyanamide or the like.Forefathers have attempted various the above-mentioned fire retardant that contains trimeric cyanamide being carried out fire-retardant method with the physics addition manner to polyurethane system, have improved the flame retardant properties of polyurethane product.But the mode that this physics adds also can reduce some physical and mechanical properties of goods undoubtedly.
More early stage USP; US 4293657, US 4745133, US 5087384, US 5106883 disclose with the trimeric cyanamide powder of certain grain size and traditional polyether glycol; Method preparation through adding dispersion agent and other auxiliary agent contains the method for trimeric cyanamide polyether glycol, and further prepares polyurethane foam with isocyanic ester; Than the patent in later stage, US 5569682, US 6103140, US 6599952 disclose stability, the reduction method of viscosity of the mixture of further raising trimeric cyanamide and traditional polyethers; Bring into play the method for its flame retardant effect to greatest extent through the formulating of recipe of optimizing.Above technology, trimeric cyanamide all are to join in the middle of the polyurethane product with the mode that physics adds, although brought into play considerable flame retardant effect, have all likewise influenced the physical and mechanical properties of goods to some extent.
Triazine ring is the stable fragrant heterocycle structure unit of a carbon containing, nitrogen;
; For many years; People are devoted to be introduced in the middle of the polyurethane system; To improve goods thermostability, flame retardant resistance and physical and mechanical properties.Early stage technology, the trimerization through vulcabond obtains containing the unitary POLYMETHYLENE POLYPHENYLISOCYANATE of triazine ring structure, and important effect has been brought into play in the thermostability of urethane, the raising of flame retardant properties., through with tricyanic acid be initiator, with oxyethane, propylene oxide under catalytic condition substep addition, polymerization make the polyethers that contain triazine ring structure, also thermally-stabilisedly, fire-retardant made contribution for what improve polyurethane product thereafter.
The structural unit of imino-triazine;
; Except a stable triazine ring; Also connecting three imino-s, nitrogen content 68%.This particular structural unit is introduced in the molecular structure of polyether glycol, can improves the integrated performance index that comprises flame retardant properties of polyurethane product undoubtedly greatly.
CN200410027331.0 discloses " method for preparing flame retarding polyether with trimeric cyanamide ", prepares melamino-formaldehyde preshrunk thing by trimeric cyanamide and formaldehyde earlier at alkaline condition, adds the resin that the hydramine preparation is referred to as MELA thereafter again.The MELA resin further mixes with traditional polyether glycol and obtains the trimeric cyanamide flame retardant polyether polyol.Method provides and has been incorporated into the method in the polyurethane system to trimeric cyanamide with " imino-triazine " structural unit.But product is not the polyether glycol of the imido-triazine structural units on the essential meaning, but by the polyether glycol of terpolycyantoamino-formaldehyde resin modification.And owing to well-known reason, the package stability extreme difference of melamino-formaldehyde precondensate, thereby the polyether glycol that is difficult to obtain having stability.
CN201010104605.7 discloses " compound method of the novel flame retardant polyether polyol that hard bubbles "; Mix initiator through adopting polyol compound and trimeric cyanamide to form, at 0-0.5Mpa pressure, under 50 ℃ of-150 ℃ of temperature condition; With basic metal is catalyzer; Obtain the purpose product with the propylene oxide polymerization, product is used for the hard-foam polyurethane goods, has brought into play good stability, oxygen index height, good flame retardation effect, effect with low cost.Product essence is a kind ofly to be the polyether glycol of initiator with the trimeric cyanamide and to be the mixture of initiator polyether glycol with the polyol, to a certain degree limit the widespread use in other polyurethane product.In addition; Well-known; Reactive hydrogen on the trimeric cyanamide carboxamido-group is compared with the reactive hydrogen on the polyol, and reactive behavior is very different, and mixing initiator trimeric cyanamide under reaction conditions is to be in solid state shape; Thereby the speed of itself and the initial addition reaction of propylene oxide receives great limitation, and then the control of the molecular weight of trimeric cyanamide polyether glycol, hydroxyl value can be limited to.
The realization all not yet in effect of known technology is the target that the initiator preparation contains the serial polyether glycol of the purified different molecular-weight average of imido grpup triazine structural units, hydroxyl value with the trimeric cyanamide.
Summary of the invention
The present invention just is being based on above technical problem; Provide technology simple, through can obtaining containing the serial polyether glycol of imido grpup triazine structural units different molecular weight and hydroxyl value behind the polyaddition reaction, the autocatalysis of polyurethane product, thermally-stabilised, fire-retardant and other physical and mechanical properties is all improved a kind of be the method that initiator prepares polyether glycol with the trimeric cyanamide.
Technical scheme of the present invention is:
A kind of is the method that initiator prepares polyether glycol with the trimeric cyanamide, may further comprise the steps:
(1) preparation slurry: is that 1:2-1:10 mix with organic solvent according to mol ratio with trimeric cyanamide
The preparation slurry; Described organic solvent is the aprotic polar organic solvent; The dialkyl ether that comprises divalent alcohol, glycol; Glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, alkylating acid amides, N; The mixture of any one or a few in dinethylformamide, the DMAC N,N;
As preferably, organic solvent is selected DMAC N,N or ethylene glycol diethyl ether for use.
(2) polyreaction: is 110 ℃-180 ℃ with mixed slurry in temperature, and pressure is 0-1MPa, as preferably; Reaction pressure is 0.2-0.6MPa; Reaching with basic metal is under the catalytic condition of catalyzer, carries out polyaddition reaction with olefin oxide, and the mol ratio of olefin oxide and trimeric cyanamide is 6-110:1; Before polyaddition reaction, massfraction is dissolved greater than 10% trimeric cyanamide.Obtain the polyether glycol of different molecular weight and hydroxyl value behind the polyaddition reaction; Described olefin oxide is the mixture of oxyethane or propylene oxide or oxyethane and propylene oxide.Oxyethane or propylene oxide can prepare respectively and contain single segment polyether glycol; Also known method be can adopt, oxyethane, propylene oxide production block or end hydroxy polyether polyvalent alcohol alternately added stage by stage.
Described catalyzer is KOH, NaOH, CH
ONa or CH
3OK, the addition of catalyzer are the 0.5%-3% of trimeric cyanamide mass content.
The molecular-weight average of the serial polyether glycol of different molecular-weight average and hydroxyl value is 300-5000, and hydroxyl value is 400-30mg KOH/g, recently realizes through the mole that changes trimeric cyanamide and olefin oxide.Hydroxyl value be in the 1g sample hydroxyl the milligram number of suitable Pottasium Hydroxide (KOH), represent with mg KOH/g.
All contain an imino-triazine structural units in each molecule of polyether glycol:
.
Disposable reinforced before olefin oxide adopts and reacts, through the definite terminal point that reacts of the variation of reaction pressure; Or batch charging in the reaction process, can avoid reaction pressure too high, or the mode of continuous charging, realize constant voltage, isothermal reaction through the control feed rate.Reaction can be adopted still reaction intermittently, also can realize the process of successive reaction through known engineering.
With the trimeric cyanamide is the method that initiator prepares polyether glycol; It is mixed with slurry with trimeric cyanamide and organic solvent; Slurry directly carries out polyaddition reaction with olefin oxide under certain temperature, pressure, basic metal catalytic condition, the initial product that obtains gets the method for the serial polyether glycol product of molecular-weight average 300-5000, hydroxyl value 400-30mg KOH/g through further aftertreatment.
The temperature of polyaddition reaction is 110 ℃-180 ℃; As preferably; The temperature of polyaddition reaction is 135 ℃-165 ℃, and experiment is found, when being lower than 100 ℃; Opening takes place in trimeric cyanamide and olefin oxide hardly, mainly be because the reactive behavior of reactive hydrogen on the trimeric cyanamide carboxamido-group far below traditional initiator.From the initial addition on the adjusting trimeric cyanamide carboxamido-group and the purpose of transfer reaction speed thereafter; So that obtain molecular weight polyether glycol goods as far as possible uniformly; Particularly prepare under the situation of high hydroxyl value polyether glycol at the olefin oxide/trimeric cyanamide with low mol ratio, it is necessary suitably improving temperature of reaction.But the too high meeting of temperature of reaction makes the form and aspect deterioration of product.So select for use suitable temperature better to the form and aspect of product.
Selected organic solvent has certain dissolubility and the reaction product polyether glycol is had unlimited solvent borne trimeric cyanamide under the condition of certain reaction temperature and certain pressure; Simultaneously, under the reaction working condition, do not react with initial feed and product.Such solvent system has been guaranteed the activity of reactive hydrogen and olefin oxide opening on the trimeric cyanamide carboxamido-group; Overcome that the gas-solid interface reaction can only take place on the melamine particles surface olefin oxide and the difficult problem that influences speed of reaction, realized the target of trimeric cyanamide dissolving-reaction among the present invention-product dissolution process process.Under the reaction working condition, the said organic solvent attribute that does not react with initial feed and product has been avoided the generation of by product.Extreme case has certain dissolubility like water to trimeric cyanamide, but the existence meeting of water forms sweet ether in reaction process; The organic cpds of band carbonyl like aldehydes, comes down to the process of hydroxyalkylation reaction to the dissolution process of trimeric cyanamide.
Slurry according to the invention is the slurry that is hybridly prepared into by trimeric cyanamide and organic solvent, and the mass ratio of trimeric cyanamide and organic solvent should satisfy in reaction and has at least under the working condition 10% trimeric cyanamide to be in the dissolved state.Strengthen the consumption of solvent, the meltage of trimeric cyanamide strengthens or dissolving fully, though can improve the time of speed of response and shortening reaction, the yield of solvent can infinitely strengthen, and the energy expenditure of recovery is also big more.The requirement of comprehensive initial addition reaction speed and the factor of economic aspect, selecting the mass ratio of trimeric cyanamide and organic solvent is 1:2-1:10.
Base metal catalysts according to the invention comprises NaOH, KOH, CH
3ONa, CH
3OK. better suited is KOH; Catalyst consumption is 0.5%-3%, preferred 0.8%-1.2% of a trimeric cyanamide quality percentage composition.Experiment finds that base metal catalysts helps the addition reaction speed of accelerated reaction initial stage trimeric cyanamide and olefin oxide, helps the realization of technological process of the present invention.Although other traditional positively charged ions, amphoteric catalyst also can be used for the opening of olefin oxide, poor effect.
Compared with prior art, beneficial effect of the present invention is:
(1) serial polyether glycol according to the invention is as a kind of new system of urethane raw, can be widely used in that polyurethane product is thermally-stabilised, fire-retardant, the improvement of autocatalysis and other physical and mechanical properties.
(2) polyether glycol of the present invention has submissive oxidic polyethylene, its chlorinated polypropylene segment, is rich in the molecular structure of the reactive hydrogen on hydroxyl and the imide, thereby also is suitable for the modification of other organic polymer.
(3) solvent system that adopts among the present invention has been guaranteed the activity of reactive hydrogen and olefin oxide opening on the trimeric cyanamide carboxamido-group, has overcome that the gas-solid interface reaction can only take place on the melamine particles surface olefin oxide and the difficult problem that influences speed of reaction.
(4) the said organic solvent attribute that does not react with initial feed and product that adopts among the present invention has been avoided the generation of by product.
Embodiment
Below in conjunction with embodiment the present invention is made further detailed description.
But should this be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.
Embodiment 1:
A kind of is the method that initiator prepares polyether glycol with the trimeric cyanamide, may further comprise the steps:
(1) preparation slurry: is that 1:2-1:10 is mixed with slurry with trimeric cyanamide and organic solvent according to mol ratio; Organic solvent is the aprotic polar organic solvent; The dialkyl ether that comprises divalent alcohol, glycol; Glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, alkylating acid amides, N; The mixture of any one or a few in dinethylformamide, the DMAC N,N;
(2) polyreaction: is that 110 ℃-180 ℃, pressure are 0-1MPa and are under the catalytic condition of catalyzer with basic metal with mixed slurry in temperature, carries out polyaddition reaction with olefin oxide, obtains the polyether glycol of different molecular weight and hydroxyl value; Olefin oxide is the mixture of oxyethane or propylene oxide or oxyethane and propylene oxide.The mol ratio of olefin oxide and trimeric cyanamide is 6-110:1.Catalyzer is KOH, NaOH, CH
ONa or CH
3OK, the addition of catalyzer are the 0.5%-3% of trimeric cyanamide quality.
The reaction principle of trimeric cyanamide and olefin oxide
R
1, R
2, R
3All do
R
4, R
5, R
6All do
Embodiment 2:
Trimeric cyanamide/propylene oxide=1:11 (mol ratio) is mixed with slurry; After the DMAC N,N mixing and stirring with 126g (1mol) trimeric cyanamide and 600g, join in the autoclave of 2L then; Add 3g KOH solid, sealed reactor.Charge into the N of 0.5MPa
2, after pressure testing was air tight, the vacuum tightness that will react gas reactor with circulation ability of swimming vacuum pump was evacuated to-0.08～-0.09MPa, fill N again
2Displacement is found time twice.Under this vacuum tightness, negative pressure sucks the 660g propylene oxide, fills N again
2Pressurize 1MPa is warming up to 140 ± 5 ℃ then, treats that pressure drop is low to moderate stopped reaction when no longer changing in the still, and cooling obtains reddish-brown clarification viscous liquid, this liquid mass conservation of weighing, and trimeric cyanamide and propylene oxide reaction are complete; In this liquid, adding its pH value of oxalic acid adjusting is 8-9, is warming up to 50 ℃, with 0.5 hour, adds 6g SiO again in the stirring
2-Al
2O
3Sorbent material stirred 1 hour; Behind the suction filtration-0.08～-0.09MPa vacuum tightness, 160 ℃ of distillations go out all DMAC N,N solvents, obtain anhydrous, molecular-weight average near 800 polyether glycol, are designated as MP800-1.
Embodiment 3:
Trimeric cyanamide/propylene oxide=1:11 (mol ratio) makes polyether glycol.
Except that changing organic solvent into ethylene glycol diethyl ether and aftertreatment distillation temperature is 120 ℃, and other experiment condition and post-processing operation are all with instance 2.Obtain reddish-brown clarification viscous liquid, this liquid mass conservation of weighing, trimeric cyanamide and propylene oxide reaction are complete; Obtain anhydrous, molecular-weight average near 800 polyether glycol, be designated as MP800-2.
Embodiment 4:
Trimeric cyanamide/propylene oxide=1:9 (mol ratio) makes polyether glycol.
The add-on of removing propylene oxide is 540g, and temperature of reaction is outside 150 ± 5 ℃, and other experiment condition and post-processing operation are all with instance 2.Obtain reddish-brown clarification viscous liquid, this liquid mass conservation of weighing, trimeric cyanamide and propylene oxide reaction are complete; Obtain anhydrously, molecular-weight average is designated as MP660-1 near 660 polyether glycol.
Embodiment 5:
Trimeric cyanamide/propylene oxide=1:7 (mol ratio) makes polyether glycol.
The add-on of removing propylene oxide is 420g, and temperature of reaction is outside 150-160 ℃, and other experiment condition post-processing operation is all with instance 2.Obtain dark red brown clarification viscous liquid, this liquid mass conservation of weighing, trimeric cyanamide and propylene oxide reaction are complete; Obtain anhydrously, molecular-weight average is designated as MP550-1 near 550 polyether glycol.
Embodiment 6:
Trimeric cyanamide/propylene oxide=1:6.5 (mol ratio) makes polyether glycol.
The add-on of removing propylene oxide is 390g, and temperature of reaction is outside 160-165 ℃, and other experiment condition post-processing operation is all with instance 2.Obtain dark red brown clarification viscous liquid, this liquid mass conservation of weighing, trimeric cyanamide and propylene oxide reaction are complete; Obtain anhydrous, molecular-weight average near 510 polyether glycol, be designated as MP510-1.
Embodiment 7:
Trimeric cyanamide/propylene oxide=1:6 (mol ratio) makes polyether glycol.
The add-on of removing propylene oxide is 360g, and temperature of reaction is outside 160-165 ℃, and other experiment condition post-processing operation is all with instance 2.Obtain dark red brown clarification viscous liquid, this liquid mass conservation of weighing, trimeric cyanamide and propylene oxide reaction are complete; Obtain anhydrous, molecular-weight average near 480 polyether glycol, be designated as MP480-1.
Embodiment 8:
Trimeric cyanamide/oxyethane=1:10 (mol ratio) makes polyether glycol.
After the DMAC N,N mixing and stirring with 75.6g (0.6mol) trimeric cyanamide and 600g, join in the autoclave of 2L, add the 1gKOH solid, sealed reactor.Charge into the 0.5MPa high-purity N
2, after pressure testing is air tight, with circulation ability of swimming vacuum pump will react gas reactor be evacuated to-0.08～-0.09MPa vacuum tightness, fill N again
2Displacement is found time twice.Fill 0.2MPa N again
2Pressurize is warming up to 160 ± 5 ℃, in the molten stainless steel that oxyethane is housed is irritated, charges into N
2, make to add the flow container constant voltage, under this temperature to 0.6MPa; In reaction kettle, be pressed into 280g oxyethane through the liquid feeding valve is intermittent; This process remains pressure 0.35-0.5MPa in the still, treats that pressure drop is low to moderate stopped reaction when no longer changing in the still, obtains puce clarification viscous liquid; This liquid mass conservation of weighing, trimeric cyanamide and reacting ethylene oxide are complete; Last handling process is with instance 2, obtains anhydrous, molecular-weight average near 590 polyether glycol, is designated as ME590-1.
Embodiment 9:
Trimeric cyanamide/oxyethane=1:8 (mol ratio) makes polyether glycol.
Except that the add-on of oxyethane is the 220g, other experiment condition and post-processing operation are all with instance 8.Obtain atropurpureus clarification viscous liquid, this liquid mass conservation of weighing, trimeric cyanamide and reacting ethylene oxide are complete; Obtain anhydrous, molecular-weight average near 500 polyether glycol, be designated as ME500-1.
Embodiment 10:
Trimeric cyanamide/oxyethane=1:6 (mol ratio) makes polyether glycol
Except that the add-on of oxyethane is the 160g, other experiment condition and post-processing operation are all with instance 8.Obtain atropurpureus clarification viscous liquid, this liquid mass conservation of weighing, trimeric cyanamide and reacting ethylene oxide are complete; Obtain anhydrous, molecular-weight average near 400 polyether glycol, be designated as ME400-1.
Embodiment 11:
Trimeric cyanamide/propylene oxide/oxyethane=1:20:20 (mol ratio) makes polyether glycol.
After the ethylene glycol diethyl ether mixing and stirring with 63g (0.5mol) trimeric cyanamide and 300g, join in the autoclave of 2L, add the 0.7gKOH solid, sealed reactor.Charge into the 0.5MPa high-purity N
2, after pressure testing is air tight, with circulation ability of swimming vacuum pump will react gas reactor be evacuated to-0.08～-0.09MPa vacuum tightness, fill N again
2Displacement is found time twice.Under this vacuum tightness, negative pressure sucks the 580g propylene oxide, fills N again
2Pressurize 0.2MPa is warming up to 160 ± 5 ℃, when pressure no longer descends in the question response still, in the molten stainless steel that oxyethane is housed is irritated, charges into N
2, make to add the flow container constant voltage to 0.6MPa, under this temperature, in reaction kettle, be pressed into 440g oxyethane through the liquid feeding valve is intermittent, this process remains pressure 0.35-0.5MPa in the still, when treating that pressure drop is extremely invariable in the still, stopped reaction.Obtain pale red brown clarification viscous liquid, this liquid mass conservation of weighing, trimeric cyanamide and two kinds of alkene all react completely; Except that distillation temperature is 120 ℃, other last handling process is with instance 2, obtains anhydrous, molecular-weight average near 2150 polyether glycol, is designated as MPE2150-2.
The performance analysis index of the polyether glycol that makes in the foregoing description is following:
Viscosity adopts NDJ-7 Shanghai balance equipment factory rotational viscosimeter, presses GB/T 12008.7-2010 method and measures.
Hydroxyl value is pressed GB/T 12008.3-2009 method and is measured.
Molecular-weight average and theoretical hydroxyl value are the data calculateds that obtains according to total matter balance and triazine ring imido grpup structure.
Can find out that from last table all more theoretical hydroxyl value of actual measurement hydroxyl value is bigger, mainly be because product molecule triazine ring is connected with imido grpup, and imido grpup and test agent reaction generate stable compound, make test value bigger than normal.Product viscosity all reduces with the increase of molecular-weight average fast, and this is that the soft segment that connects on the ring is long more because triazine ring is a stiffening ring, and the flexibility of molecule is big more, and viscosity reduces big more.PH value shows slightly alkalescence, is owing to after product removes basic catalyst, contain due to the imido grpup in the product molecule.
Claims (9)
1. one kind is the method that initiator prepares polyether glycol with the trimeric cyanamide, it is characterized in that may further comprise the steps:
(1) preparation slurry: is that 1:2-1:10 is mixed with slurry with trimeric cyanamide and organic solvent according to mol ratio;
(2) polyreaction: is that 110 ℃-180 ℃, pressure are 0-1MPa and are under the catalytic condition of catalyzer with basic metal with mixed slurry in temperature, carries out polyaddition reaction with olefin oxide, obtains the polyether glycol of different molecular weight and hydroxyl value;
Described organic solvent is the aprotic polar organic solvent; Dialkyl ether for divalent alcohol, glycol; Glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, alkylating acid amides, N; The mixture of any one or a few in dinethylformamide, the DMAC N,N;
Described olefin oxide is the mixture of oxyethane or propylene oxide or oxyethane and propylene oxide.
2. according to claim 1 a kind of be the method that initiator prepares polyether glycol with the trimeric cyanamide, it is characterized in that: described organic solvent is DMAC N,N or ethylene glycol diethyl ether.
3. according to claim 1 a kind of be the method that initiator prepares polyether glycol with the trimeric cyanamide, it is characterized in that: described catalyzer is KOH, NaOH, CH
3ONa or CH
3OK, the addition of catalyzer are the 0.5%-3% of trimeric cyanamide mass percent.
4. according to claim 1 a kind of be the method that initiator prepares polyether glycol with the trimeric cyanamide, it is characterized in that: the mol ratio of said olefin oxide and trimeric cyanamide is 6-110:1.
5. according to claim 1 a kind of be the method that initiator prepares polyether glycol with the trimeric cyanamide, it is characterized in that: described polyaddition reaction temperature is 135 ℃-165 ℃.
6. according to claim 1 a kind of be the method that initiator prepares polyether glycol with the trimeric cyanamide, it is characterized in that: said polyaddition reaction pressure is 0.2-0.6MPa.
7. according to claim 1 a kind of be the method that initiator prepares polyether glycol with the trimeric cyanamide; It is characterized in that: the molecular-weight average of the polyether glycol of described different molecular weight and hydroxyl value is 300-5000; Hydroxyl value is 400-30mg KOH ∕ g, recently realizes through the mole that changes trimeric cyanamide and olefin oxide.
8. according to claim 1 a kind of be the method that initiator prepares polyether glycol with the trimeric cyanamide, it is characterized in that: all contain an imino-triazine structural units in each molecule of said polyether glycol:
.
9. according to claim 1 a kind of be the method that initiator prepares polyether glycol with the trimeric cyanamide, it is characterized in that: the reinforced mode that described olefin oxide adopts is disposable reinforced before for reaction, or batch charging in the reaction process, or continuous charging.
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| CN110078885A (en) * | 2019-05-27 | 2019-08-02 | 江苏钟山化工有限公司 | A kind of combined polyether glycol and its application with fire-retardant and autocatalytic cleavage energy |
| CN110078885B (en) * | 2019-05-27 | 2021-06-18 | 江苏钟山化工有限公司 | Combined polyether polyol with flame retardant and autocatalytic properties and application thereof |
| CN111019113A (en) * | 2019-12-05 | 2020-04-17 | 万华化学（宁波）容威聚氨酯有限公司 | Aminopolyether polyol for pure LBA system, preparation method thereof and polyurethane rigid foam prepared by using aminopolyether polyol |
| CN111019113B (en) * | 2019-12-05 | 2023-03-03 | 万华化学（宁波）容威聚氨酯有限公司 | Amino polyether polyol for pure LBA system, preparation method thereof and polyurethane rigid foam prepared by using amino polyether polyol |
| CN111363135A (en) * | 2020-03-14 | 2020-07-03 | 浙江恒丰新材料有限公司 | Preparation method and application of melamine-ethylene oxide/propylene oxide copolymer polyether polyol |
| CN114395120A (en) * | 2021-12-22 | 2022-04-26 | 山东一诺威新材料有限公司 | Preparation method of flame-retardant high-temperature-resistant polyether polyol |
| CN114395120B (en) * | 2021-12-22 | 2023-11-10 | 山东一诺威新材料有限公司 | Preparation method of flame-retardant high-temperature-resistant polyether polyol |
| CN117106167A (en) * | 2023-08-02 | 2023-11-24 | 江苏斯德瑞克化工有限公司 | Macromolecular polyether polyol and preparation method thereof |
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