CN107501539A - Aldehyde radical functional polyethers polyol copolymer and its preparation method and application - Google Patents
Aldehyde radical functional polyethers polyol copolymer and its preparation method and application Download PDFInfo
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- CN107501539A CN107501539A CN201710916415.7A CN201710916415A CN107501539A CN 107501539 A CN107501539 A CN 107501539A CN 201710916415 A CN201710916415 A CN 201710916415A CN 107501539 A CN107501539 A CN 107501539A
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
Abstract
This application discloses a kind of aldehyde radical functional polyethers polyol copolymer, its chemical formula is:Wherein, A11Selected from C1~C3One kind in alkylidene;R11, R12, R13, R14Independently selected from hydrogen, alkyl, in one kind;R10Selected from hydrogen, methyl,At least one of;R101, R102, R103, R104, R105Independently selected from hydrogen, C1~C4One kind in alkyl;M, n are positive integer, meet 1≤n≤50,1≤m≤50.Aldehyde radical functional polyethers polyol copolymer in the present invention has 350~20000Da number-average molecular weight, and the aldehyde radical functional polyethers polyol copolymer reactivity is high, and field is synthesized available for polyurethane.
Description
Technical field
The application is related to a kind of aldehyde radical functional polyethers polyol copolymer and its preparation method and application, belong to polyalcohol and
Its preparation field.
Background technology
PPG, be that main chain contains ehter bond (- R-O-R-), end group or side base contain 2 or more than 2 hydroxyls (-
OH oligomer).It is using low molecular weight polyols, polyamine or compound containing active hydrogen as initiator, exists with oxyalkylene
Ring-opening polymerisation forms under catalyst action.Suitable oxyalkylene includes, such as propylene oxide (expoxy propane), ethylene oxide
(oxirane).Polyalcohol initiator has the trihydroxylic alcohol such as the dihydric alcohols such as propane diols, ethylene glycol, glycerine trimethylolpropane and season penta
The polyalcohols such as tetrol, xylitol, sorbierite, sucrose;Amine initiator is diethylamine, diethylenetriamine etc..PPG, it is all
Such as polyoxypropyleneglycol, Polyoxyethylene glycol and polytetrahydrofuran diol, for polyurethane field, generally produced to polyurethane
Product bring excellent performance.
The high polymer material of function containing aldehyde radical can must crosslink reaction with amino, can improve the damp and hot of material to a certain extent
Stability.The A of Chinese patent CN 104498649 disclose a kind of being answered without chrome leather with macromolecule containing aldehyde with self-assembling function
Tanning agent, contain aldehyde radical (methyl) acrylic resin and three block nonionic parents polyurethane tree by select appropriate molecular structure
Fat, covalently cross-linked, imparting product better performance is produced with the amino in material using aldehyde radical.
Polyurethane material is widely used in auto industry, mechanical industry, electrical equipment and measurement instrument industry, leather due to excellent performance
With the field such as shoemaking industry, medical treatment and physical culture.In many application fields, for example, for can be by polyalcohol (such as polyether polyols
Alcohol) prepare polyurethane, it is desirable to assign its excellent combination property, contain as the B of Chinese patent CN 101871024 disclose one kind
The preparation method of the polyurethane-acrylate resin tanning agent of aldehyde radical.It is neat by unsaturated aldehyde, specific polymerizable nonionic polyurethane
Polymers participation is free-radical polymerized, and the polyurethane segment of aldehyde radical, nonionic is introduced into acrylate resins, obtained polymer copolymerization
Resin contains aldehyde radical, and covalently cross-linked, the soft and full feel of imparting leather can be produced with materials with hide glue fibril.
However, not yet provided in PPG preparation field so far polynary to how to prepare aldehyde radical functional polyethers
Any solution of alcohol problem or at least gratifying solution.
The content of the invention
According to the one side of the application, there is provided a kind of aldehyde radical functional polyethers polyol copolymer, it has very high
Reactivity, for preparing polyurethane.
The aldehyde radical functional polyethers polyol copolymer, shown in its chemical formula such as formula (I):
Wherein, A11Selected from C1~C3One kind in alkylidene;
R11, R12, R13, R14One kind in hydrogen, alkyl;
R10Selected from hydrogen, methyl,At least one of;R101, R102, R103, R104, R105Solely
On the spot selected from hydrogen, C1~C4One kind in alkyl;
M, n are positive integer, meet 1≤n≤50,1≤m≤50.
Preferably, A in the formula (I)11For methylene;R11, R12, R13, R14Independently selected from hydrogen, C1~C4In alkyl
It is a kind of.
Preferably, A in the formula (I)11For methylene;R11, R12, R13, R14Independently selected from hydrogen, C1~C2In alkyl
It is a kind of.
Preferably, A in the formula (I)11For methylene;R11, R12, R13, R14One kind in hydrogen, methyl.
Preferably, shown in its chemical formula such as formula (II):
Wherein, R20Selected from hydrogen, methyl,At least one of;M, n are positive integer, meet 1≤n
≤ 50,1≤m≤50.
Preferably, the m, n are positive integer, meet 2≤n≤25,2≤m≤25.
It is highly preferred that the m, n are positive integer, meet 5≤n≤20,5≤m≤20.
Preferably, the number-average molecular weight of the aldehyde radical functional polyethers polyol copolymer is 350~20000Da.
Preferably, the number-average molecular weight of the aldehyde radical functional polyethers polyol copolymer is 700~10000Da.
It is highly preferred that the number-average molecular weight of the aldehyde radical functional polyethers polyol copolymer is 800~5000Da.
The another aspect of the application, there is provided the method for preparing above-mentioned aldehyde radical functional polyethers polyol copolymer, at least wrap
Containing following steps:
(1) raw material to hydroxyaryl formaldehyde and substituted epoxy compound, in the presence of catalyst I, backflow will be contained
Reaction 1~8 hour, obtain structural formula as shown in formula (VI) to hydroxyaryl formaldehyde epoxide ether;
Wherein, A60Selected from C1~C3One kind in alkylidene;
R61, R62, R63, R64One kind in hydrogen, alkyl;
Described being selected to hydroxyaryl formaldehyde has at least one of compound shown in formula (III):
The substituted epoxy compound, which is selected from, has at least one of compound shown in formula (IV):
Wherein, R30, R31, R32, R33One kind in hydrogen, alkyl;
A40Selected from C1~C3One kind in alkylidene;The one kind of X in halogen;
(2) under non-active gas atmosphere, step (1) resulting structures formula as shown in formula (VI) to hydroxyaryl formaldehyde ring
With epoxide in the presence of catalyst II, 30~120 DEG C are reacted 1~8 hour oxygen compound ether, obtain the aldehyde radical official
Can polyether polyols alcohol copolymer;
Wherein, epoxide, which is selected from, has at least one of compound shown in formula (V):
Wherein, R50Selected from hydrogen, methyl,At least one of;R501, R502, R503, R504,
R505Independently selected from hydrogen, C1~C4One kind in alkyl.
Preferably, R in the formula (III)30, R31, R32, R33Independently selected from hydrogen, C1~C4One kind in alkyl.
Preferably, R in the formula (III)30, R31, R32, R33Independently selected from hydrogen, C1~C2One kind in alkyl.
Preferably, R in the formula (III)30, R31, R32, R33One kind in hydrogen, methyl.
Preferably, R in the formula (III)30, R31, R32, R33It is hydrogen.
Preferably, A in the formula (IV)40Selected from C1~C2One kind in alkylidene;The one kind of X in Cl, Br, I.
Preferably, A in the formula (IV)40For methylene;X is Cl.
Preferably, R in the formula (V)50Selected from hydrogen, methyl,At least one of;R501,
R502, R503, R504, R505Independently selected from hydrogen, C1~C2One kind in alkyl.
Preferably, R in the formula (V)50Selected from hydrogen, methyl,At least one of;R501,
R502, R503, R504, R505One kind in hydrogen, methyl.
Preferably, A in formula (VI)60For methylene;R61, R62, R63, R64Independently selected from hydrogen, C1~C4One in alkyl
Kind.It is further preferred that A in formula (V)60For methylene;R61, R62, R63, R64One kind in hydrogen, methyl.
Preferably, specific reaction condition is in step (1):Hydroxyaryl formaldehyde, catalyst I, organic solvent will be mixed
Close uniformly, be heated to flowing back in the case where non-active gas protect atmosphere, then add substituted epoxy compound, back flow reaction, obtain
As shown in formula (VI) to hydroxyaryl formaldehyde epoxide ether.
Preferably, it is to the mass ratio of hydroxyaryl formaldehyde, substituted epoxy compound and catalyst I described in step (1)
1:1~5:1~8.
Preferably, it is to the mass ratio of hydroxyaryl formaldehyde, substituted epoxy compound and catalyst I described in step (1)
1:2~4:3~6.
Preferably, the catalyst I is selected from least one of carbonate of alkali metal.
Preferably, the carbonate of the alkali metal is selected from least one of Anhydrous potassium carbonate, natrium carbonicum calcinatum.
Preferably, the organic solvent is selected from least one of absolute ethyl alcohol, tetrahydrofuran, dioxane.
Preferably, organic solvent is with being 1 to the mass ratio of hydroxyaryl formaldehyde:10~50.
Preferably, organic solvent is with being 1 to the mass ratio of hydroxyaryl formaldehyde:20~25.
Preferably, the condition of back flow reaction described in step (1) is 50~90 DEG C of back flow reactions 1~3 hour.
Preferably, the condition of back flow reaction described in step (1) is 65~85 DEG C of back flow reactions 2 hours.
Preferably, described in step (2) as shown in formula (V) to hydroxyaryl formaldehyde epoxide ether, epoxy compound
Thing and catalyst II mass ratio are 10:0.1~10:0.1~10.
Preferably, described in step (2) as shown in formula (V) to hydroxyaryl formaldehyde epoxide ether, epoxy compound
Thing and catalyst II mass ratio are 10:3~8:0.3~2.
Preferably, the catalyst II is in tetra-n-butyl ammonium acetate, tetra-n-butyl ammonium fluoride, tetra-n-butyl ammonium bromide
At least one.
Preferably, reaction condition reacts 2~6 hours for 50~85 DEG C in step (2).
Mode is preferably carried out as one kind, the method for preparing above-mentioned aldehyde radical functional polyethers polyol copolymer, is at least wrapped
Include following steps:
A. according to the mass fraction, by 1 part of parahydroxyben-zaldehyde, the carbonate of 1~8 part of alkali metal, 20~50 parts it is organic molten
Agent is sequentially added in 500mL four-hole bottles, is well mixed, and is led to nitrogen protection, is heated to flowing back;Stirring, 1~5 part of epoxy chlorine is added dropwise
Propane, it is then refluxed for reaction 1~8 hour;Parahydroxyben-zaldehyde glycidol ether is obtained after product is purified;
B. according to the mass fraction, by 10 parts of parahydroxyben-zaldehyde glycidol ethers, 0.1~10 part of epoxide, 0.1~
10 parts of catalyst are added in there-necked flask, lead to nitrogen, stirring reaction 1~20 hour, adds acidic methanol and tetrahydrofuran is quenched
Go out reaction, respectively with after n-hexane, water sedimentation, be dissolved in acid tetrahydrofuran, kept for 5 hours, product is through washing, dry aldehyde
Base functional polyethers polyol copolymer.
A kind of aldehyde radical functional polyethers polyol copolymer in the application, using parahydroxyben-zaldehyde and epoxychloropropane as original
Material, reacts under the carbonate effect of alkali metal, after purified, obtains parahydroxyben-zaldehyde glycidol ether;Then it is being catalyzed
In the presence of agent, homopolymerization occurs with epoxide, it is purified to obtain aldehyde radical functional polyethers polyol copolymer.
Aldehyde radical functional polyethers polyol copolymer described herein is used to prepare polyurethane.
The another aspect of the application, there is provided a kind of polyurethane, it is polynary that its preparing raw material includes above-mentioned aldehyde radical functional polyethers
At least one of aldehyde radical functional polyethers polyol copolymer that alcohol copolymer and/or the above method are prepared.
It is used for the purposes for preparing polyurethane, described poly- ammonia according to the aldehyde radical functional polyethers polyol copolymer of the present invention
Ester, can be more by polyester known to aldehyde radical functional polyethers polyol copolymer disclosed by the invention and the art engineer
The combined polymerization of at least one of first alcohol, PPG, small molecule polyol, small molecule polyamine and polyisocyanates obtains.
The small molecule polyol is the polyalcohol that carbon number is no more than 6;Small molecule polyamine is that carbon number does not surpass
Cross 6 polyamine.
The preparation method of the polyurethane, including at least following steps:
PPG, aldehyde radical functional polyethers polyol copolymer are dissolved in anhydrous solvent, are warming up to 50~120 DEG C,
Polyisocyanates and catalyst are added, reacts 2~6 hours, obtains polyurethane.
Preferably, the PPG is selected from polyethylene glycol dihydric alcohol, polypropylene glycol diols, PolyTHF binary
At least one of alcohol.
Preferably, the molecular weight of the PPG is 600~5000Da.It is further preferred that the polyether polyols
The molecular weight of alcohol is 1000~3000Da.
It is sub- that the polyisocyanates is selected from toluene di-isocyanate(TDI) (TDI), 1,4- tetramethylene diisocyanates, 1,6- six
It is methyl diisocyanate (HDI), the dimethylene diisocyanates of 1,12- ten, hexamethylene -1,3- or 1,4- diisocyanate, different
Isophorone diisocyanate (IPDI), diphenyl methane 4,4- diisocyanate (MDI), double-hexyl methane diisocyanate
(HMDI), 1, hexamethylene-diisocyanate (HDI), polymethylene multi-phenenyl isocyanate (PAPI), the isocyanic acid of phenylenedimethylidyne two
Ester (XDI), naphthalene -1,5- diisocyanate (NDI), Methylcyclohexyl diisocyanate (HTDI), tetramethylxylene two
Isocyanates (TMXDI), hydrogenation methylenebis phenyl isocyanate (H12At least one of MDI).
Preferably, the polyisocyanates is selected from IPDI (IPDI), toluene di-isocyanate(TDI)
(TDI), 1,6- hexamethylene diisocyanates (HDI), double-hexyl methane diisocyanate (HMDI), diphenyl methane 4,4-
Diisocyanate (MDI), toluene di-isocyanate(TDI) (TDI), hydrogenation methylenebis phenyl isocyanate (H12MDI at least one in)
Kind.
Preferably, the catalyst is selected from least one of organic tin salt.
Preferably, the catalyst is dibutyl tin dilaurate.
Preferably, the solvent is selected from least one of DMF, DMSO, DMAC, NMP.
Preferably, the reaction condition reacts 3~5 hours for 60~100 DEG C.
Preferably, the matter of the PPG, aldehyde radical functional polyethers polyol copolymer, polyisocyanates and catalyst
Amount part is compared for 10~50:5~50:2~100:0.1~0.3.
Preferably, the matter of the PPG, aldehyde radical functional polyethers polyol copolymer, polyisocyanates and catalyst
Amount part is compared for 15~30:10~35:20~60:0.1~0.3.
In the application, the non-active gas protection atmosphere is selected from least one of nitrogen, helium, neon, argon gas.
In the application, " alkyl " refers to the group formed by losing any one hydrogen atom on alkane compound molecule.Alkane
Hydrocarbon compound includes cycloalkane, linear paraffin, branched paraffin.
In the application, C1~C2、C1~C4Etc. the carbon number for referring both to group and being included.
Beneficial effect caused by the application energy includes:
1) aldehyde radical functional polyethers polyol copolymer produced by the present invention has 350~20000Da number-average molecular weight, should
Aldehyde radical functional polyethers polyol copolymer reactivity is high, and field is synthesized available for polyurethane.
2) aldehyde radical functional polyethers polyol copolymer produced by the present invention, the anti-hydrolytic performance and mechanical property being prepared
Energy.
Brief description of the drawings
Fig. 1 is the nuclear magnetic resoance spectrum hydrogen spectrogram of parahydroxyben-zaldehyde glycidol ether in embodiment 1.
Fig. 2 is the nuclear magnetic resoance spectrum hydrogen spectrogram of aldehyde radical functional polyethers polyol copolymer in embodiment 1.
Embodiment
The application is described in detail with reference to embodiment, but the application is not limited to these embodiments.
Unless otherwise instructed, the raw material in embodiments herein and catalyst are bought by commercial sources.
Analysis method is as follows in embodiments herein:
Proton nmr spectra analysis is carried out using AVANCE III HD (Bruker-BioSpin) nuclear magnetic resonance spectrometer.
In the application, PolyTHF dihydric alcohol is abbreviated as PTMEG, and molecular weight is about 2000.
The aldehyde radical functional polyethers polyol copolymer C1 of embodiment 1 preparation
(1) synthesis of parahydroxyben-zaldehyde glycidol ether
6.0 grams of para hydroxybenzenes are added in the 500mL four-necked bottles that one carries agitator, reflux condensing tube, nitrogen ascending pipe
Formaldehyde, 20.4 grams of Anhydrous potassium carbonates and 144 grams of absolute ethyl alcohols, lead to nitrogen, be heated with stirring in 80 DEG C, 30 minutes and be added dropwise 10.8 grams
Epoxychloropropane, back flow reaction two hours;Potassium carbonate, filtrate decompression distillation are filtered to remove, product is dissolved in ethyl acetate, water
Wash, organic phase is dried using anhydrous magnesium sulfate, is evaporated under reduced pressure, and is crossed post and is obtained parahydroxyben-zaldehyde glycidol ether.Its nuclear magnetic resonance
It is as shown in Figure 1 to compose hydrogen spectrogram.
(2) synthesis of aldehyde radical functional polyethers polyol copolymer
In the 100mL there-necked flasks that one carries agitator, nitrogen ascending pipe, 7.0g parahydroxyben-zaldehyde glycidols are added
Ether, 2.0g phenol glycidyl ethers, lead to nitrogen, add 1.2g tetrabutylammonium acetate ammoniums, 55 DEG C are reacted 2 hours;Add 5mL tetrahydrochysene furans
Mutter, add 20mL acidic methanols (HCl:Methanol=1:10) quenching reaction, successively using n-hexane, water sedimentation.It is dissolved in 20mL
Acid tetrahydrofuran (HCl:Tetrahydrofuran=1:10) 2 hours, are stood, using water sedimentation, aldehyde radical functional polyethers polyalcohol is obtained and is total to
Polymers, it is designated as C1.
Shown in its chemical formula such as formula (II), wherein,Nuclear magnetic resonance
It is as shown in Figure 2 to compose hydrogen spectrogram.
The aldehyde radical functional polyethers polyol copolymer C2 of embodiment 2 preparation
(1) synthesis of parahydroxyben-zaldehyde glycidol ether
6 grams of para hydroxybenzene first are added in the 500mL four-necked bottles that one carries agitator, reflux condensing tube, nitrogen ascending pipe
Aldehyde, 28 grams of natrium carbonicum calcinatums and 120 grams of dioxane, lead to nitrogen, be heated with stirring to 10.8 grams of epoxies of dropwise addition in 80 DEG C, 30 minutes
Chloropropane, 80 degree are reacted two hours;Sodium carbonate, filtrate decompression distillation are filtered to remove, product is dissolved in ethyl acetate, washes, have
Machine is mutually dried using anhydrous magnesium sulfate, is evaporated under reduced pressure, and is crossed post and is obtained parahydroxyben-zaldehyde glycidol ether.
(2) synthesis of aldehyde radical functional polyethers polyol copolymer
In the 100mL there-necked flasks that one carries agitator, nitrogen ascending pipe, 7.0g parahydroxyben-zaldehyde glycidols are added
Ether, 3.0 grams of expoxy propane, lead to nitrogen, add 0.5g tetrabutyl ammonium fluorides, 30 DEG C are reacted 6 hours;5mL tetrahydrofurans are added, then
Add 20mL acidic methanols (HCl:Methanol=1:10) quenching reaction, successively using n-hexane, water sedimentation.It is dissolved in 20mL acidity four
Hydrogen furans (HCl:Tetrahydrofuran=1:10) 2 hours, are stood, using water sedimentation, obtains aldehyde radical functional polyethers polyol copolymer, is remembered
For C2.Shown in its chemical formula such as formula (II), wherein, R20For hydrogen, n=20, m=28.
The hydrogen nuclear magnetic resonance spectrogram of the parahydroxyben-zaldehyde glycidol ether obtained in the present embodiment and the survey in embodiment 1
Test result is identical.
The aldehyde radical functional polyethers polyol copolymer C3 of embodiment 3 preparation
(1) synthesis of parahydroxyben-zaldehyde glycidol ether
6 grams of para hydroxybenzene first are added in the 500mL four-necked bottles that one carries agitator, reflux condensing tube, nitrogen ascending pipe
Aldehyde, 20.4 grams of Anhydrous potassium carbonates and 150 grams of tetrahydrofurans, lead to nitrogen, be heated with stirring to 10.8 grams of rings of dropwise addition in 65 DEG C, 30 minutes
Oxygen chloropropane, back flow reaction two hours;Potassium carbonate, filtrate decompression distillation are filtered to remove, product is dissolved in ethyl acetate, washed,
Organic phase is dried using anhydrous magnesium sulfate, is evaporated under reduced pressure, and is crossed post and is obtained parahydroxyben-zaldehyde glycidol ether.
(2) synthesis of aldehyde radical functional polyethers polyol copolymer
In the 100mL there-necked flasks that one carries agitator, nitrogen ascending pipe, 7.0g parahydroxyben-zaldehyde glycidols are added
Ether, 7.0 grams of 1,2- epoxy butanes lead to nitrogen, add 1.5g tetrabutylammonium acetate ammoniums, and 50 DEG C are reacted 4 hours;Add 5mL tetrahydrochysene furans
Mutter, add 20mL acidic methanols (HCl:Methanol=1:10) quenching reaction, successively using n-hexane, water sedimentation.It is dissolved in 20mL
Acid tetrahydrofuran (HCl:Tetrahydrofuran=1:10) 2 hours, are stood, using water sedimentation, aldehyde radical functional polyethers polyalcohol is obtained and is total to
Polymers, it is designated as C3.Shown in its chemical formula such as formula (II), wherein, R20For methyl, n=8, m=19.
Test result in the parahydroxyben-zaldehyde glycidol ether embodiment 1 obtained in the present embodiment is identical.
The polyurethane J1 of embodiment 4 preparation
10.0 grams of PolyTHF dihydric alcohol PTMEG 2000 are added in 250mL a bite bottles and 6.5 grams of aldehyde radical functions are gathered
Ethoxylated polyhydric alcohol copolymer (C1), add 160mL and dry DMF, be warming up to 95 DEG C, add 1.6 grams of IPDI, dibutyl tin dilaurate
2 drops, react 4 hours, obtain polyurethane, be designated as J1.
The polyurethane J2 of embodiment 5 preparation
10.0 grams of PolyTHF dihydric alcohol PTMEG 2000 are added in 250mL a bite bottles and 5.2 grams of aldehyde radical functions are gathered
Ethoxylated polyhydric alcohol copolymer (C2), add 160mL and dry DMF, be warming up to 80 DEG C, add 1.5 grams of MDI, dibutyl tin dilaurate 1
Drop, react 5 hours, obtain polyurethane, be designated as J2.
The polyurethane J3 of embodiment 6 preparation
10.0 grams of PolyTHF dihydric alcohol PTMEG 2000 are added in 250mL a bite bottles and 8.4 grams of aldehyde radical functions are gathered
Ethoxylated polyhydric alcohol copolymer (C3), add 160mL and dry DMF, be warming up to 100 DEG C, add 2.1 grams of H12MDI, dibutyl tin cinnamic acid
Tin 3 drips, and reacts 5 hours, obtains polyurethane, be designated as J3.
The Mechanics Performance Testing of embodiment 7
Mechanics Performance Testing is carried out to sample J1-J3;Wherein, the measure of tensile property is according to method in GB/T13022-91
Measure.Test result is as shown in table 1.
Table 1
From table 1 it follows that the flame retardant polyurethane J1-J3 being prepared has excellent mechanical property.
It is described above, only it is several embodiments of the application, any type of limitation is not done to the application, although this Shen
Please with preferred embodiment disclose as above, but and be not used to limit the application, any person skilled in the art, do not taking off
In the range of technical scheme, make a little variation using the technology contents of the disclosure above or modification is equal to
Case study on implementation is imitated, is belonged in the range of technical scheme.
Claims (10)
1. a kind of aldehyde radical functional polyethers polyol copolymer, it is characterised in that shown in its chemical formula such as formula (I):
Wherein, A11Selected from C1~C3One kind in alkylidene;
R11, R12, R13, R14One kind in hydrogen, alkyl;
R10Selected from hydrogen, methyl,At least one of;R101, R102, R103, R104, R105Independently
Selected from hydrogen, C1~C4One kind in alkyl;
M, n are positive integer, meet 1≤n≤50,1≤m≤50.
2. aldehyde radical functional polyethers polyol copolymer according to claim 1, it is characterised in that A in the formula (I)11For
Methylene;R11, R12, R13, R14Independently selected from hydrogen, C1~C4One kind in alkyl.
3. aldehyde radical functional polyethers polyol copolymer according to claim 1, it is characterised in that its chemical formula such as formula (II)
It is shown:
Wherein, R20Selected from hydrogen, methyl,At least one of;M, n are positive integer, meet 1≤n≤50,1
≤m≤50。
4. the aldehyde radical functional polyethers polyol copolymer according to any one of claims 1 to 3, it is characterised in that the aldehyde
The number-average molecular weight of base functional polyethers polyol copolymer is 350~20000Da.
5. prepare the method for the aldehyde radical functional polyethers polyol copolymer described in any one of Claims 1-4, it is characterised in that
Including at least following steps:
(1) raw material to hydroxyaryl formaldehyde and substituted epoxy compound, in the presence of catalyst I, back flow reaction 1 will be contained
~8 hours, obtain structural formula as shown in formula (VI) to hydroxyaryl formaldehyde epoxide ether;
Wherein, A60Selected from C1~C3One kind in alkylidene;
R61, R62, R63, R64One kind in hydrogen, alkyl;
Described being selected to hydroxyaryl formaldehyde has at least one of compound shown in formula (III):
The substituted epoxy compound, which is selected from, has at least one of compound shown in formula (IV):
Wherein, R30, R31, R32, R33One kind in hydrogen, alkyl;
A40Selected from C1~C3One kind in alkylidene;The one kind of X in halogen;
(2) under non-active gas atmosphere, step (1) resulting structures formula as shown in formula (VI) to hydroxyaryl formaldehyde epoxidation
With epoxide in the presence of catalyst II, 30~120 DEG C are reacted 1~8 hour compound ether, are obtained the aldehyde radical function and are gathered
Ethoxylated polyhydric alcohol copolymer;
Wherein, epoxide, which is selected from, has at least one of compound shown in formula (V):
Wherein, R50Selected from hydrogen, methyl,At least one of;R501, R502, R503, R504, R505It is independent
Ground is selected from hydrogen, C1~C4One kind in alkyl.
6. according to the method for claim 5, it is characterised in that specific reaction condition is in step (1):Will be to hydroxyl virtue
Base formaldehyde, catalyst I, organic solvent are well mixed, and are heated to flowing back in the case where non-active gas protect atmosphere, are then added substitution
Epoxide, back flow reaction, obtain structural formula as shown in formula (VI) to hydroxyaryl formaldehyde epoxide ether.
7. the method according to claim 5 or 6, it is characterised in that to hydroxyaryl formaldehyde, substitution described in step (1)
Epoxide and catalyst I mass ratio are 1:1~5:1~8;
The catalyst I is selected from least one of carbonate of alkali metal.
8. according to the method for claim 6, it is characterised in that the organic solvent is selected from absolute ethyl alcohol, tetrahydrofuran, two
At least one of ring of oxygen six.
9. according to the method for claim 5, it is characterised in that pair of the structural formula as shown in formula (VI) described in step (2)
The mass ratio of hydroxyaryl formaldehyde epoxide ether, epoxide and catalyst II is 10:0.1~10:0.1~10;
The catalyst II is selected from least one of tetra-n-butyl ammonium acetate, tetra-n-butyl ammonium fluoride, tetra-n-butyl ammonium bromide.
10. a kind of polyurethane, it is characterised in that the aldehyde radical function that its preparing raw material includes described in any one of Claims 1-4 is gathered
In the aldehyde radical functional polyethers polyol copolymer that any one of ethoxylated polyhydric alcohol copolymer and/or claim 5 to 9 method are prepared
At least one.
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CN111378114B (en) * | 2018-12-31 | 2023-03-14 | 江苏苏博特新材料股份有限公司 | Aldehyde-group modified polyether intermediate, preparation method thereof and application thereof in preparation of slow-setting type micromolecule phosphonic acid-based superplasticizer |
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