Summary of the invention
The object of the present invention is to provide a kind of synthesis works of isocyanate trimer with polyfunctionality unsaturated group
Skill.
It is a further object of the present invention to provide the isocyanate trimer for using the polyfunctionality unsaturated group, preparation contains
There is the method for the dispersion dispersion stabilizer of polyfunctionality unsaturated group.
Third object of the present invention is using the dispersion stabilizer synthesized polymer containing polyfunctionality unsaturated group
The methods and applications of object dispersion.
To realize the above goal of the invention, the invention adopts the following technical scheme:
According to the first aspect of the invention, a kind of isocyanate trimerization with polyfunctionality unsaturated group is provided
Body, structure are as follows:
Wherein, A, B, C separately indicate the aliphatic group containing 1~15 carbon, aromatic group, amide groups,
Lactone or ester group, alcohol ether or phenolic ether group, preferably di-substituted-phenyl replace formic acid ester group, cycloalkyl group, linear paraffin base.
R1, R2Separately indicate the aliphatic group containing 1~5 carbon, cyano or hydrogen atom.
As a kind of implementable solution, group B and group C are preferably identical.
As a kind of implementable solution, group R1With group R2It is preferred that identical.
According to the second aspect of the invention, the system of the isocyanate trimer of above-mentioned polyfunctionality unsaturated group is provided
Preparation Method is preferably prepared by following reaction as a preferred embodiment:
The preparation method of the isocyanate trimer of polyfunctionality unsaturated group includes: by diisocyanate I and insatiable hunger
It is added in reaction kettle with isocyanates II and III by the molar ratio of 1:0.9~1.2:0.9~1.2, catalyst is added, anti-
It is reacted at a temperature of answering, terminator is then added, obtain target compound.
According to the present invention, the preparation method of the isocyanate trimer of polyfunctionality unsaturated group, reaction temperature are preferred
It at 50~80 DEG C, reacts duration 3.5~5.0 hours, after terminator is added, when reaction is 0.5~1 hour a length of.
According to the present invention, the preferred toluene di-isocyanate(TDI) of diisocyanate (TDI), naphthalene diisocyanate (NDI), six methylenes
Group diisocyanate (HDI), methyl diphenylene diisocyanate (MDI), isophorone diisocyanate (IPDI), dicyclohexyl
Methane diisocyanate (HMDI), paraphenylene diisocyanate (PPDI), cyclohexane diisocyanate (CHDI), xyxylene two are different
Diphenyl diisocyanate (TMXDI) between cyanate (XDI), (HMDI), tetramethyl, norbornene alkyl diisocyanate (NBDI),
One of tetramethyl fourth diisocyanate (TMSDI) is a variety of, preferably toluene di-isocyanate(TDI) (TDI), tetramethyl Ding Eryi
Cyanate (TMSDI), paraphenylene diisocyanate (PPDI).
According to the present invention, unsaturated isocyanate is preferably phenylisocyanate (TMI), isocyanide acid acrylic acid between isopropenyl
One of ethyl ester (AOI), isocyanatomethyl ethyl acrylate are a variety of.
According to the present invention, the preparation process of the isocyanate trimer of polyfunctionality unsaturated group can choose in solvent
In the presence of react, suitable solvent be cyclohexanone, methylisobutylketone, n,N-Dimethylformamide, n,N-dimethylacetamide, second
One of acetoacetic ester, n-propyl acetate, isopropyl acetate, n-butyl acetate or isobutyl acetate are a variety of.
According to the present invention, the isocyanate trimer of the polyfunctionality unsaturated group after synthesis can be by isolating and purifying
After use, can also directly carry out subsequent reactions.It is preferred that removing unreacted diisocyanate or unsaturated isocyanide to reaction solution
Acid esters is carrying out subsequent reactions.
According to the present invention, the synthesis of the isocyanate trimer of polyfunctionality unsaturated group can be with or without catalysis
It is carried out in the presence of agent.It is preferable to use catalyst, common catalyst has organic phosphine and organic phosphine derivatives, organic amine, organic base
Or salt, metallic compound etc., preferably Mannich base, trialkyl phosphine catalyst, particularly preferred alkylamino radical sylvan.
As a kind of implementable solution, which is the object that di alkylamino group methyl and phenolic hydroxyl group are had in molecule
Matter reacts acquisition with dimethylamine and formaldehyde by phenol, p- isononyl phenol or bisphenol-A using Mannich reaction.
According to the present invention, the additive amount of catalyst is 0.1~0.3% (mass percent) of total amount of feeding.
According to the present invention, the adding manner of the catalyst minor tick can also be added in batches to be once added completely into,
It is preferred that three batches are added once every half an hour.
According to the present invention, the terminator is acids terminator, preferably sulfuric acid, phosphoric acid or chlorobenzoyl chloride, the acids end
Only the additive amount of agent is 0.3~0.5% (matter of total amount of feeding (the sum of diisocyanate I and unsaturated isocyanate II and III)
Measure percentage).
According to the present invention, under high temperature, isocyanic acid II or isocyanates III easily polymerize, and preferably addition polymerization inhibitor carries out anti-
It answers, such as hydroquinone or hydroquinone monomethyl ether, the dosage of polymerization inhibitor is total amount of feeding (diisocyanate I and unsaturated isocyanide
The sum of acid esters II and III) 0.001~0.3% (mass percent).
Preferably, the proportion of diisocyanate I and unsaturated isocyanate II and III are 1:0.9~1.2:0.9~1.2
(molar ratio), preferably 1:1:1 (molar ratio).
According to the third aspect of the present invention, the dispersion stabilizer containing polyfunctionality unsaturated group is provided, is
Prepared by being reacted by the isocyanate trimer of above-mentioned polyfunctionality unsaturated group with polyether polyol.
According to the present invention, the polyether polyol is that the polyethers that degree of functionality is 2~8 and molecular weight is 6000~15000 is more
The polyether polyol that first alcohol, preferably degree of functionality are 4~6 and molecular weight is 7000~13000.
According to the present invention, the polyether polyol that the present invention uses is that low molecule weight initiator is obtained through open loop of epoxy compound.
Initiator is one of sucrose, sorbierite, pentaerythrite, trimethylolpropane, glycerol or ethylene glycol or a variety of.Epoxy compound
Object is selected from one of ethylene oxide, propylene oxide, epoxy butane, oxinane or a variety of, optimization ethylene oxide and epoxy
The mixture of propane.
According to the present invention, the isocyanate trimer of polyfunctionality unsaturated group and polyether polyol are reacted, can be with
It is carried out in the case where being with or without catalyst by heating.It is preferable to use the catalysis of organic amine, organic phosphine or organic metal class
Agent particularly preferably uses organic tin catalyst.The dosage of catalyst is total amount of feeding (diisocyanate I and unsaturated isocyanide
The sum of acid esters II and III) 0.001~0.3% (mass percent).
According to the present invention, the isocyanate trimer of polyfunctionality unsaturated group and polyether polyol are reacted, can be with
It is carried out under conditions of being with or without solvent, suitable solvent is aromatic hydrocarbons, alkyl halide, aliphatic hydrocarbon, ester or ether solvent, preferably first
Benzene and butyl acetate.As a kind of implementable solution, preferably with prepare the consistent reaction dissolvent of isocyanate trimer process.
According to the present invention, the molar ratio of the isocyanate trimer of polyfunctionality unsaturated group and polyether polyol are as follows:
0.8~1.1:1, preferably 0.9~1.0:1.
According to the present invention, the isocyanate trimer of polyfunctionality unsaturated group and the reaction temperature of polyether polyol are
40~130 DEG C, preferably 70~100 DEG C;Reaction time preferably 0.1~5 hour, more preferable 1~3 hour.
According to the present invention, the isocyanate trimer of polyfunctionality unsaturated group and polyether polyol are reacted, can be with
Polymerization inhibitor is optionally added, as a kind of implementable solution, the polymerization inhibitor includes but is not limited to hydroquinone, to tert-butyl o
One of benzenediol, p-hydroxyanisole, methylnaphthohydroquinone, phenthazine and diphenylamines are a variety of.By weight, the polymerization inhibitor
Dosage be macromolecular Contents In Polyether Polyol total amount 0~1.5%, preferably 300~2000ppm.
According to the fourth aspect of the present invention, a kind of polymeric dispersions are provided, are prepared by following steps: using not
Saturation monomer polymerize by radical initiator in basic polyether polyalcohol with above-mentioned dispersion stabilizer and is obtained.
According to the present invention, the selection of the basic polyether polyalcohol is determined by the final use of polymeric dispersions,
Such as polymeric dispersions are used for the production of the soft bubble of massive polyurethane, just select general soft polyurethane foam polyether polyol, one
As hydroxyl value be 54~58mgKOH/g three-functionality-degree basic polyether polyalcohol;For the production of high rebound foam, just select high
Rebound foam polyether polyol, general hydroxyl value are the basis of the three-functionality-degree of the high activity of 33.5~36.5mgKOH/g or so
Polyether polyol.The heretofore described preferred hydroxyl value of basic polyether polyalcohol is the polyethers of the three-functionality-degree of 54~58mgKOH/g
Polyalcohol is as basic polyether polyol.
According to the present invention, in the method for preparing polymeric dispersions, unsaturated monomer includes styrene, methylbenzene second
One of alkene, ethyl styrene, acrylonitrile, methacrylonitrile, methyl methacrylate, acrylate are a variety of, preferably benzene
The mixture of ethylene and acrylonitrile.Based on the weight of polymeric dispersions product, the additive amount of monomer is about 20-60wt%, such as
Fruit uses the combination of styrene and acrylonitrile, preferably uses these monomers with the weight ratio of 0/100-80/20.
According to the present invention, the dispersion that the isocyanate trimer of polyfunctionality unsaturated group is synthesized with polyether polyol
Stabilizer, in the method for preparing polymeric dispersions, based on the weight of polymeric dispersions product, dispersion stabilizer is used
Amount is 0.5~10wt%, and preferably 1~6wt%, the dosage of base polymer polyalcohol is 30-70wt%.
According to the present invention, it in the method for preparing polymeric dispersions, as the initiator of free radical polymerization, can be used
Organic peroxide, common such as benzoyl peroxide, butyl peroctoates, peroxidating 2 ethyl hexanoic acid tert-pentyl ester are even
Nitrogen compound, it is common such as such as azodiisobutyronitrile (AIBN), azobis methylbutyronitrile (AMBN), two methyl isobutyrate of azo
(V601).Based on the weight of polymeric dispersions product, the additive amount of initiator is about 0.2~1wt%.
An embodiment according to the present invention, in the method for preparing polymeric dispersions, the basic polyether used is more
First alcohol is small molecule polyol (such as: ethylene glycol, glycerol, trimethylolpropane, pentaerythrite, sorbierite and sugar) or amine is (such as: three
Ethanol amine, ethylenediamine, toluenediamine etc.) pass through epoxide (such as: ethylene oxide, propylene oxide, epoxy butane) open loop
And it obtains.
According to the present invention, in the method for preparing polymeric dispersions, it can use and divide in polymeric dispersions preparation
Son amount regulator, such as alcohol, mercaptan, aromatic hydrocarbons, preferably methanol, ethyl alcohol, isopropanol, butanol, ethyl mercaptan, heptanthiol, spicy thioalcohol, 12
Alkyl hydrosulfide, toluene, ethylbenzene, dimethylbenzene.Particularly preferred isopropanol, lauryl mercaptan.
According to the present invention, it in the method for preparing polymeric dispersions, can be carried out by continuous process, wherein all
It is mixed with each other to raw material quantitative, is introduced continuously into reactor, at a certain temperature and after residence time reaction, be transferred to and deaerated
Journey;Or carried out by batch process, raw material is placed in reactor, then by monomer, initiator and one within given time
The mixture of a little raw materials is introduced into the reactor.
According to the present invention, in the method for preparing polymeric dispersions, the polymerization temperature of monomer is 80~140 DEG C, preferably
It is carried out at a temperature of 90~110 DEG C.
According to the present invention, in the method for preparing polymeric dispersions, after the completion of polymerization, polymerizate experience deaerated
Journey, to remove unreacted monomer and other additives.
According to the fifth aspect of the present invention, it provides and is moulded using polyurethane foam prepared by polymeric dispersions of the invention
Material.
According to the present invention, in the presence of the polyurethane foam plastics passes through catalysts for polyurethanes, foaming agent and crosslinking agent,
Polymeric dispersions are made to react and be made with isocyanates.
Polymeric dispersions account for the 10%~110% of the dosage of isocyanates;Catalysts for polyurethanes is relative to polymer point
The dosage of granular media is 0.015%~5%;Foaming agent is 2%~25% relative to the dosage of polymeric dispersions;Crosslinking agent is opposite
In polymeric dispersions dosage be 0.1%~5%;
Catalysts for polyurethanes be it is generally known, specific example include metallic catalyst for example stannous octoate, stannous oleate,
Dibutyl tin dilaurate, dibutyltin diacetate, tin and amines catalyst such as trimethylamine, triethylamine, triethylenediamine (TEDA), two
Methylethanolamine and bis- (2,2- dimethylamino)-ether.If available includes glycerol and diethanol amine using crosslinking agent.
Suitable foaming agent includes: water, acetone, carbon dioxide, halogenated hydrocarbons, aliphatic alkanes and cycloalkane.Auxiliary agent can be added as other,
Also fire retardant, surfactant, filler, dyestuff or pigment can be used.
Polyfunctionality isocyanates prepared by the present invention, reaction site is more, and activity is high, the dispersion stable prepared using it
Agent has the characteristics that reactivity is high, dispersion performance is good, has using the polymeric dispersions of dispersion stabilizer preparation excellent
Performance, be for some special system formulations by it.