CN109694460A - Polyfunctionality unsaturated isocyanate tripolymer and its preparation and the application in dispersion stabilizer - Google Patents
Polyfunctionality unsaturated isocyanate tripolymer and its preparation and the application in dispersion stabilizer Download PDFInfo
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- CN109694460A CN109694460A CN201811512122.3A CN201811512122A CN109694460A CN 109694460 A CN109694460 A CN 109694460A CN 201811512122 A CN201811512122 A CN 201811512122A CN 109694460 A CN109694460 A CN 109694460A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
- C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
- C08G18/4845—Polyethers containing oxyethylene units and other oxyalkylene units containing oxypropylene or higher oxyalkylene end groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
Abstract
The invention discloses a kind of isocyanate trimer with polyfunctionality unsaturated group, structural formula is 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, substitution formic acid ester group, cycloalkyl group, linear paraffin base.R1, R2Separately indicate the aliphatic group containing 1~5 carbon, cyano or hydrogen atom.The invention further relates to the dispersion stabilizer for using the isocyanate trimer to prepare, polymeric dispersions and polyurethane foam plastics.There is preferable reactivity and dispersion stabilization using polymeric dispersions prepared by the stabilizer.
Description
Technical field
There is polyfunctionality unsaturated isocyanate tripolymer and its preparation process the present invention relates to one kind and dispersing surely
The application in agent is determined, specifically, being related to a kind of containing polyfunctionality unsaturated isocyanate and its preparation process, and use
It prepares the polymeric dispersions method of the dispersion stabilizer containing polyfunctionality unsaturated group.
Background technique
It is widely used in special material synthesis, water paint and UV curing field.The invention belongs to modified isocyanates
Tripolymer and its preparation field, in particular to a kind of Sulfamate modified isocyanate trimer and preparation method thereof.
Isocyanates (such as TDI, HDI) can polymerize under catalytic action generates isocyanuric acid ester six-membered ring structure (also known as
Tripolymer), it has a wide range of applications in fields such as coating, adhesive, elastomer, foamed plastics.Currently, trimerization polyisocyanates
Mainly there is the isocyanates based on TDI tripolymer and HDI trimer, containing unsaturated group because of the double bond containing different activities
And NCO group, especially contain polyfunctionality unsaturated group and isocyanate trimer.
It solves the problems, such as this, needs to develop the special technique of one kind and be used to develop with polyfunctionality unsaturated group
The preparation process of isocyanate trimer.
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.
Detailed description of the invention
Fig. 1 is the mass spectral analysis figure of the tripolymer compound of embodiment 2.
Fig. 2 is the infrared spectrum of the tripolymer compound of embodiment 2.
The mass spectral analysis figure of the tripolymer compound of Fig. 3 embodiment 3.
Fig. 4 is the infrared spectrum of the tripolymer compound of embodiment 3.
Specific embodiment
By specific embodiment example, the present invention will be described in detail.The scope of the present invention is not with specific embodiment
It is limited, but is defined in the claims.
In stabilizer synthesis and polymeric dispersions preparation of the invention, the abbreviation of compound used therefor and the explanation of meaning
It is as follows:
Polyether polyol A: the polyalcohol prepared by sorbierite and propylene oxide and reacting ethylene oxide.Hydroxyl value
28.0mgKOH/g, average functionality: 6；Average molecular weight: 12000；Viscosity: 25 DEG C of 1915cp@.
Polyether polyol B: the polyalcohol prepared by pentaerythrite and propylene oxide and reacting ethylene oxide.Hydroxyl value
22.4mgKOH/g, average molecular weight: 10000；Viscosity: 25 DEG C of 1318cp@.
Base polyol C: it is more that soft bubble polyethers is sprung back by glycerol and the height prepared with propylene oxide and reacting ethylene oxide
First alcohol, Wanhua Chemical Group Co., Ltd.,3135。
HEMA: hydroxyethyl methacrylate, Wanhua Chemical Group Co., Ltd.；
AOI: isocyanic acid ethyl acrylate, Liming chemical Inst；
TMI: phenylisocyanate between isopropenyl, Liming chemical Inst；
TDI: toluene di-isocyanate(TDI), Wanhua Chemical Group Co., Ltd.；
TMSDI: tetramethyl fourth diisocyanate, self-control；
Compare stabilizer: polyether polyol B is reacted with maleic anhydride, then with EO termination process, 25 DEG C of viscosity 4100cp@,
Degree of unsaturation 0.032meq/g.
Embodiment 1:
The synthesis of trimer catalyst:
50 DEG C of heating stirring 2h of 18.8g bisphenol-A and 54.4g dimethylamine solution are taken, 46.5g36% formalin, 2h is added dropwise
It is inside added dropwise, is warming up to 80 DEG C, after insulation reaction 2h, stop heating.It is evaporated under reduced pressure, receives after taking organic phase, sodium sulphate dry
Collect 130 DEG C, -0.095MPa yellow, viscous liquid, is dissolved in butyl acetate solvent and is configured to catalyst solution.
Embodiment 2:
The synthesis of TDI-TMI tripolymer:
Under logical N2 protection, 50.0gTDI, 115.5gTMI, 75g butyl acetate are added in reaction kettle, stirring is opened, adds
Heat is warming up to 60 DEG C, then divides 3 times and tetrabutylammonium hydroxide catalyst 2.4Kg is added in reaction kettle, be added every half an hour
Once, the isocyanate trimerization catalyst butyl acetate solution of the self-control phenols of methyl containing alkylamino radical of 11g5% is added dropwise, all adds
It is reacted after complete at 80 DEG C, every 1 hour detection NCO content, when the weight percentage of NCO is reduced to 4.9%, is cooled to 40 DEG C,
1g chlorobenzoyl chloride after stirring half an hour, stops reaction.Detect mass spectrometric data, MS m/z:576.5 (M+H)+As shown in Fig. 1.
Infrared spectrum: 2256.27cm-1 ,-NCO, such as attached drawing 2.
Embodiment 3:
The synthesis of AOI-TMSDI tripolymer:
Under logical N2 protection, 50gTMSDII, 71.9gTMI, 50g butyl acetate are added in reaction kettle, stirring is opened, adds
Heat is warming up to 60 DEG C, then divides 3 times and the self-control catalyst in 11g5% embodiment 1 is added in reaction kettle, every half an hour plus
Enter once, is reacted after all adding at 80 DEG C, every 1 hour detection NCO content, the weight percentage of NCO was reduced to 5.8%
When, 40 DEG C are cooled to, 1g chlorobenzoyl chloride after stirring half an hour, stops reaction.
60mgMEHQ (p methoxy phenol) is added and is warming up to 120 DEG C, vacuum takes off butyl acetate and unreacted isocyanide
Acid esters adds 120g butyl acetate, admittedly contain 50%.Detect mass spectrometric data, MS m/z:476.5 (M+H)+As shown in Fig. 3,
Infrared spectrum: 2256.27cm-1 ,-NCO, such as attached drawing 4.
Embodiment 4:
Dispersion stabilizer 1:500g polyether polyol A is added 0.25gMEHQ (p methoxy phenol), 0.05g lauric acid
Tin heats up 60 DEG C, and reaction solution prepared by 36g embodiment 2 is added dropwise, and after reacting 2h, is warming up to 100 DEG C, reacts 1h, and phosphoric acid is added and loses
It is living, solvent is sloughed, stabilizer 1,25 DEG C of viscosity 3621cp@, degree of unsaturation 0.084meq/g are obtained.As explanation, reactional equation
Formula is as follows:
Embodiment 5:
Dispersion stabilizer 2:500g polyether polyol B is added 0.25gMEHQ (p methoxy phenol), 0.05g lauric acid
Tin heats up 60 DEG C, and reaction solution prepared by 47g embodiment 3 is added dropwise, and after reacting 2h, is warming up to 100 DEG C, reacts 1h, and phosphoric acid is added and loses
It is living, solvent is sloughed, stabilizer 1,25 DEG C of viscosity 2615cp@, degree of unsaturation 0.079meq/g are obtained.As explanation, reactional equation
Formula is as follows:
Embodiment 6
It is prepared by polymeric dispersions 1:
500ml four-hole bottle is equipped with blender, heating device, temperature control device and feeder as reactor.In reactor
Middle addition basic polyether 55.4g (Wan Hua3156), 3.6g stabilizer 1 after nitrogen displacement, stirs slowly heating
To 110 DEG C, being continuously added to liftout (10.47g isopropanol, 85.71g basic polyether3156,36.55g propylene
Nitrile, 79.38g styrene, two methyl isobutyrate of 1.21g azo mixed liquor), control 115 DEG C~120 DEG C of temperature.In 100min
It is added dropwise, feeds intake and finish, aging reaction 1 hour, continue vacuum and take off list 2h, obtain product, measure product index.Hydroxyl value
29.80mgKOH/g, admittedly contain 44.5%, viscosity 5123mPaS.
Embodiment 7
It is prepared by polymeric dispersions 2:
500ml four-hole bottle is equipped with blender, heating device, temperature control device and feeder as reactor.In reactor
Middle addition basic polyether 55.4g (Wan Hua3156), 3.4g stabilizer 2 after nitrogen displacement, stirs slowly heating
To 110 DEG C, being continuously added to liftout (10.47g isopropanol, 85.71g basic polyether3156,39.83g propylene
Nitrile, 76.55g styrene, 1.21g azobisisovaleronitrile mixed liquor), control 115 DEG C~120 DEG C of temperature.It is added dropwise in 100min
It finishes, feeds intake and finish, aging reaction 1 hour, continue vacuum and take off list 2h, obtain product, measure product index.Hydroxyl value
30.04mgKOH/g, admittedly contain 44.3%, viscosity 4987mPaS.
Comparative example 1
500ml four-hole bottle is equipped with blender, heating device, temperature control device and feeder as reactor.In reactor
Middle addition basic polyether 55.4g (Wan Hua3156), 3.4g compares stabilizer and stirs and slowly rise after nitrogen displacement
110 DEG C of Wen Zhizhi, it is continuously added to liftout (10.47g isopropanol, 85.71g basic polyether3156,46.55g propylene
Nitrile, 69.83g styrene, two butyric acid dimethyl ester of 1.21g tetramethyl azo mixed liquor), control 115 DEG C~120 DEG C of temperature.
It is added dropwise in 100min, feeds intake and finish, aging reaction 1 hour, continued vacuum and take off list 2h, obtain product, there is visible of naked eyes
Grain object, detects partial size, the largest particles is at 10 μm or so.
Performance Properties Evaluation is as shown in table 1 below, polyurethane foam plastics preparation.
Table 1 combines material formula
The performance indicator and corresponding testing standard of the prepared polyurethane foam of test see the table below 2:
2 polyurethane foam performance of table
| Project | Testing standard | Embodiment 8 | Embodiment 9 | Embodiment 10 |
| VOC | VDA 278 90℃/0.5h | 45 | 35 | 60 |
| Smell, μ gC/g | VDA 270B3 80℃/2h | 2 | 2 | 3 |
| Tensile strength, Kpa | ISO1798 | 119 | 110 | 105 |
| Elongation at break, Kpa | ISO1798 | 90 | 90 | 85 |
Claims (19)
1. a kind of isocyanate trimer with polyfunctionality unsaturated group, structural formula 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, R2
Separately indicate the aliphatic group containing 1~5 carbon, cyano or hydrogen atom.
2. isocyanate trimer according to claim 1, wherein group B is identical as group C.
3. the preparation method of the isocyanate trimer with polyfunctionality unsaturated group of claims 1 or 2 comprising:
By diisocyanate I and unsaturated isocyanate II and III:
It is added in reaction kettle by the molar ratio of 1:0.9~1.2:0.9~1.2, catalyst is added, reacts at the reaction temperatures,
Then terminator is added, obtains target compound.
4. preparation method according to claim 3, wherein reaction temperature is 50~80 DEG C, and reaction duration 3.5~5.0 is small
When, after terminator is added, when reaction, is 0.5~1 hour a length of.
5. preparation method according to claim 3 or 4, wherein diisocyanate be selected from toluene di-isocyanate(TDI) (TDI),
Naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HDI), methyl diphenylene diisocyanate (MDI), isophorone
Diisocyanate (IPDI), dicyclohexyl methyl hydride diisocyanate (HMDI), paraphenylene diisocyanate (PPDI), hexamethylene two are different
Diphenyl diisocyanate (TMXDI) between cyanate (CHDI), xylylene diisocyanate (XDI), (HMDI), tetramethyl,
One of norbornene alkyl diisocyanate (NBDI), tetramethyl fourth diisocyanate (TMSDI) are a variety of, and preferably toluene two is different
Cyanate (TDI), tetramethyl fourth diisocyanate (TMSDI), paraphenylene diisocyanate (PPDI)；
Unsaturated isocyanate II or the III phenylisocyanate (TMI), isocyanic acid ethyl acrylate (AOI), different between isopropenyl
One of cyanate ethyl methacrylate is a variety of.
6. the preparation method according to any one of claim 3-5, wherein the isocyanates of polyfunctionality unsaturated group
The preparation of tripolymer is reacted in the presence of solvent, and solvent is cyclohexanone, methylisobutylketone, n,N-Dimethylformamide, N, N- bis-
One of methylacetamide, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate or isobutyl acetate are more
Kind.
7. the preparation method according to any one of claim 3-6, wherein the isocyanates of polyfunctionality unsaturated group
The synthesis of tripolymer carries out in the presence of being with or without catalyst, it is preferable to use catalyst, and catalyst is selected from organic phosphine and organic
One of phosphine-derivatives, organic amine, organic base or salt, metallic compound are a variety of, preferably Mannich base, trialkyl phosphine catalysis
Agent, particularly preferred alkylamino radical sylvan.
8. the preparation method according to any one of claim 3-7, wherein the terminator is acids terminator, preferably
Sulfuric acid, phosphoric acid or chlorobenzoyl chloride, the additive amount of the acids terminator be diisocyanate I and unsaturated isocyanate II and
0.3~0.5wt% of the sum of III.
9. the preparation method according to any one of claim 3-8, wherein add polymerization inhibitor such as hydroquinone or to benzene two
Phenol monomethyl ether is reacted.
10. a kind of dispersion stabilizer with polyfunctionality unsaturated group is by tool of any of claims 1 or 2
Have prepared by the isocyanate trimer of polyfunctionality unsaturated group reacts with polyether polyol.
11. dispersion stabilizer according to claim 10, wherein the polyether polyol is that degree of functionality is 2~8 and divides
The polyether polyol that son amount is 6000~15000, the polyether polyols that preferably degree of functionality is 4~6 and molecular weight is 7000~13000
Alcohol.
12. dispersion stabilizer described in 0 or 11 according to claim 1, wherein the isocyanide with polyfunctionality unsaturated group
The molar ratio of acid esters tripolymer and polyether polyol are as follows: 0.8~1.1:1, preferably 0.9~1.0:1；And/or
The reaction temperature of isocyanate trimer and polyether polyol with polyfunctionality unsaturated group is 40~130 DEG C,
It is preferred that 70~100 DEG C；Reaction time is 0.1~5 hour, more preferable 1~3 hour.
13. the described in any item dispersion stabilizers of 0-12 according to claim 1, wherein polyfunctionality unsaturated group it is different
Cyanate tripolymer optionally adds polymerization inhibitor with reacting for polyether polyol, and the polymerization inhibitor is selected from hydroquinone, to tertiary fourth
One of base catechol, p-hydroxyanisole, methylnaphthohydroquinone, phenthazine and diphenylamines are a variety of, by weight, the resistance
The dosage of poly- agent is the 0~1.5% of macromolecular polyether polyol total amount, preferably 300~2000ppm.
14. a kind of polymeric dispersions are prepared by following steps: using in unsaturated monomer and claim 10-13
Dispersion stabilizer described in one polymerize by radical initiator in basic polyether polyalcohol and is obtained.
15. polymeric dispersions according to claim 14, wherein the basic polyether polyalcohol be hydroxyl value be 54~
The basic polyether polyalcohol or hydroxyl value of the three-functionality-degree of 58mgKOH/g are the basis of the three-functionality-degree of 33.5~36.5mgKOH/g
Polyether polyol.
16. polymeric dispersions according to claim 14 or 15, wherein unsaturated monomer is selected from styrene, methylbenzene
One of ethylene, ethyl styrene, acrylonitrile, methacrylonitrile, methyl methacrylate, acrylate are a variety of, preferably
The mixture of styrene and acrylonitrile；And/or
Based on the weight of polymeric dispersions product, the additive amount of monomer is 20-60wt%.
17. polymeric dispersions described in any one of 4-16 according to claim 1, the weight based on polymeric dispersions, point
Granular media stabilizer usage amount is 0.5~10wt%, and preferably 1~6wt%, the dosage of base polymer polyalcohol is 30-70wt%.
18. using the polyurethane foam plastics of polymeric dispersions preparation described in any one of claim 14-17.
19. polyurethane foam plastics according to claim 18, wherein the polyurethane foam plastics is urged by polyurethane
In the presence of agent, foaming agent and crosslinking agent, make prepared by polymeric dispersions react with isocyanates.
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| CN113649067A (en) * | 2021-08-13 | 2021-11-16 | 万华化学(四川)有限公司 | Organic photocatalyst, preparation method and application thereof in synthesis of 2,3, 5-trimethylhydroquinone diester |
| WO2022136068A1 (en) | 2020-12-22 | 2022-06-30 | Covestro Deutschland Ag | A method for stably storing an isocyanate composition |
| CN114805740A (en) * | 2022-03-11 | 2022-07-29 | 广州五行材料科技有限公司 | Solvent-free TDI tripolymer urethane acrylate and preparation method thereof |
| EP4036138A1 (en) | 2021-01-28 | 2022-08-03 | Covestro Deutschland AG | A method for stably storing an isocyanate composition |
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| CN113649067A (en) * | 2021-08-13 | 2021-11-16 | 万华化学(四川)有限公司 | Organic photocatalyst, preparation method and application thereof in synthesis of 2,3, 5-trimethylhydroquinone diester |
| CN113649067B (en) * | 2021-08-13 | 2023-08-11 | 万华化学(四川)有限公司 | Organic photocatalyst, preparation method and application thereof in synthesis of 2,3, 5-trimethylhydroquinone diester |
| CN114805740A (en) * | 2022-03-11 | 2022-07-29 | 广州五行材料科技有限公司 | Solvent-free TDI tripolymer urethane acrylate and preparation method thereof |
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