CN105968350B - A kind of high tenacity polyethers urea type benzoxazine colophony and preparation method thereof - Google Patents
A kind of high tenacity polyethers urea type benzoxazine colophony and preparation method thereof Download PDFInfo
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- CN105968350B CN105968350B CN201610375685.7A CN201610375685A CN105968350B CN 105968350 B CN105968350 B CN 105968350B CN 201610375685 A CN201610375685 A CN 201610375685A CN 105968350 B CN105968350 B CN 105968350B
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- 229920000570 polyether Polymers 0.000 title claims abstract description 73
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000004202 carbamide Substances 0.000 title claims abstract description 48
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 20
- 229920002396 Polyurea Polymers 0.000 claims abstract description 20
- 238000004321 preservation Methods 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 150000001412 amines Chemical class 0.000 claims description 24
- 238000010792 warming Methods 0.000 claims description 18
- 239000000919 ceramic Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 125000005442 diisocyanate group Chemical group 0.000 claims description 8
- 229920002866 paraformaldehyde Polymers 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000009261 D 400 Substances 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000007711 solidification Methods 0.000 claims description 4
- 230000008023 solidification Effects 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims 1
- 229930185605 Bisphenol Natural products 0.000 claims 1
- 238000007605 air drying Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 239000001257 hydrogen Substances 0.000 abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 9
- 150000004893 oxazines Chemical class 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 229910052571 earthenware Inorganic materials 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- -1 aldehyde compound Chemical class 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229940106691 bisphenol a Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000005130 benzoxazines Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0683—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0688—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polyquinolines
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The invention discloses a kind of high tenacity polyethers urea type benzoxazine colophony and preparation method thereof, the structural formula of wherein high tenacity polyethers urea type benzoxazine colophony is:
Description
One, technical field
The present invention relates to a kind of high molecular material and preparation method thereof of low viscosity high tenacity, specifically a kind of high-ductilities
Property polyethers urea type benzoxazine colophony and preparation method thereof.
Two, background technology
Benzoxazine colophony is a kind of new type heterocycle thermosetting resin to grow up on the basis of traditional phenolic resin,
It is made after dehydrating condensation by phenolic compound, aminated compounds and aldehyde compound, then in catalyst or the condition of heating
Under, ring-opening polymerisation occurs, generates the nitrogenous and similar reticular structure with phenolic resin, it inherits the excellent performance of phenolic resin
Such as hot property, anti-flammability, good electrical property, while it also has and is shunk without small molecule release, volume approximation zero when solidification etc.
Characteristic.
But the crosslink density of benzoxazine is low, solidification temperature is high, and the big disadvantage of brittleness significantly limits benzoxazine
Application and popularization, therefore improve benzoxazine toughness become key.
Amine terminated polyether is a kind of oxyalkylene oligomer blocked by primary amine or secondary amine, and also known as polyetheramine or polyethers is more
Amine amine terminated polyether segment is simultaneously mainly used for polyureas, polyurethane synthesis material and epoxy with flexibility, amine terminated polyether well
Resin activity toughener.
Polyureas can be obtained by directly being reacted with polyisocyanates using polyamine, fast using amine and isocyanates reaction speed
And the characteristics of highly polar urea groups is easy to form urea hydrogen bond in polyureas molecular structure, polyureas is in expediting setting type finishing coat and corrosion
The fields such as protective coating are applied.
Polyether-type polyurea structure to gather by the polyester soft segment structure composition in the rigid structures and chain such as urea bond, soft segment structure
Urea has good compliance and elongation at break, and soft segment structure is longer, and branch is fewer, and the intermolecular active force of polyureas is got over
By force, structure is more regular, and tensile strength is also big;The phenyl ring of highly polar urea bond and rigidity also plays the intensity of polyureas in hard segment structure
Huge effect, in rigid structure, urea bond and phenyl ring are more, and intensity is bigger.
Three, invention content
The present invention is intended to provide a kind of high tenacity polyethers urea type benzoxazine colophony and preparation method thereof, skill to be solved
Art problem is to start with improving the brittleness of benzoxazine colophony from the angle of MOLECULE DESIGN.
High tenacity polyethers urea type benzoxazine colophony of the present invention, general structure are:
Wherein x indicates that the degree of polymerization of amine terminated polyether, n indicate the degree of polymerization of polyethers urea type benzoxazine colophony.
R indicates that the residue of diisocyanate, structural formula are:
(residue of MDI) or(residue of TDI).
The preparation method of high tenacity polyethers urea type benzoxazine colophony of the present invention, includes the following steps:
0.01mol diisocyanate and 0.02mol amine terminated polyethers are added in 50-100ml organic solvents, are warming up to 70
DEG C back flow reaction 4h, is prepared amine terminated polyether type polyureas;0.04mol paraformaldehydes and 0.01mol are added into reaction solution
Bisphenol-A is warming up to 85 DEG C of reaction 6h, and revolving removes solvent and water after reaction, is dried in vacuo up to polyethers urea type Ben Bing Evil
Piperazine is sticky yellow liquid, up to polyethers urea type benzoxazine colophony after solidification.
The diisocyanate is selected from '-diphenylmethane diisocyanate (MDI) or toluene di-isocyanate(TDI) (TDI).
The number-average molecular weight of the amine terminated polyether is 200-2500, and further the amine terminated polyether is D-230, D-
400 or D-2000.
The organic solvent is selected from DMF, DMAC or dioxane.
Curing process parameter is as follows:
The sticky yellow liquid of polyethers urea type benzoxazine is placed in ceramic crucible, ceramic crucible is then placed in air blast
In drying box, it is warming up to 100 DEG C of heat preservation 1h, 120 DEG C of heat preservation 1h, 150 DEG C of heat preservation 2h, 160 DEG C of heat preservation 2h, 180 DEG C of heat preservations successively
2h。
Reaction process is as follows:
R represents the residue of diisocyanate, and x represents the degree of polymerization of amine terminated polyether.
Amine terminated polyether, diisocyanate and the bisphenol-A raw material that the present invention uses all are linear long-chain, the polyethers urea of synthesis
Type benzoxazine branch is few, and the viscosity of product significantly reduces, and improves the processing performance of benzoxazine, polyethers urea groups drop
The low glass transition temperature of benzoxazine, and successfully realize the toughening of Dui benzoxazines.
Compared with the prior art, beneficial effects of the present invention are embodied in:
1, polyether segment is introduced Ben Bing Evil structures by resin of the present invention, assigns the high tenacity of benzoxazine colophony.
2, polyureas segment is introduced benzoxazine structure by resin of the present invention, assigns the rapid curing into benzoxazine, is improved
The mechanical strength of material.
3, it is linear long-chain in benzoxazine structure of the invention, few containing branch, ginseng product viscosity is low, and processing performance is superior.
4, resin of the present invention optimizes preparation process, and solvent can be with multiple choices, it is easy to accomplish industrialized production, cost
Cheap, yield is more than 80%.
Four, it illustrates
Fig. 1 is the appearance picture of high tenacity polyethers urea type benzoxazine colophony of the present invention.
Fig. 2 is the infrared spectrum of polyethers urea type benzoxazine of the present invention.1540cm in figure-1It is the characteristic peak of HN-CO-NH,
3330cm-1It is the absorption peak of the secondary amine of polyureas, 1695cm to have very strong absorption peak-1For the absorption peak of C=O in polyureas;, 935cm-1For the characteristic absorption peak for the phenyl ring that the characteristic peak of benzoxazine, Shi are connected Yu oxazine ring, 1102cm-1There is the very strong absorption peak to be
Ehter bond in polyethers, 1230cm-1For the ehter bond absorption peak of benzoxazine, 1378cm-1For the absorption peak of the C-N on benzoxazine.Root
According to the presence of these characteristic peaks, it was demonstrated that sample has the feature structure of polyureas and benzoxazine.
Fig. 3 is polyethers urea type benzoxazine of the present invention1H-NMR spectrum, with CDCl3For solvent, can be analyzed from figure
It arrives:It is solvent C DCl at δ=7.23Absorption peak, peak δ=5.3 indicates the proton of-O-CH2-N- hydrogen a in benzoxazine in figure
Peak, the proton peak of the Biao Shi oxazine ring-CH2- hydrogen of peak δ=4.3 b, δ=5.0 indicate polyureas in-NH- hydrogen c proton peak, δ=
3.6 indicate-CH in polyethers2The proton peak of hydrogen d, δ=1.2 indicate-CH in polyethers3The proton peak of hydrogen e, δ=2.2 are indicated in polyethers
The proton peak of CH hydrogen g, δ=2.0 indicate-CH in bisphenol-A3The proton peak of hydrogen f, peak δ=7.1-7.4 indicate the matter of Ar-H on phenyl ring
Sub- peak, to show that synthesized is required structure.
Fig. 4 is that the stress that the amine terminated polyether D-400 polyethers urea type benzoxazine colophonies of the present invention stretch answers curve, table 1
For its tensile property parameter.Two dumbbell shape standard batten test tensile properties are taken, take the fracture that it is averagely worth to resin strong
Degree is 27.11GPa, yield strength 33.29GPa, elasticity modulus 1181.97GPa, elongation at break 73.38%, fracture
Can be 19.58MJ/cm3, material is with the presence of yield point large deformation region, the size of the tensile toughness of energy to failure reaction material, this
Kind material has the characteristics that " Qiang Erren ", and toughness is greatly improved.
Fig. 5 is that the stress that the amine terminated polyether D-230 polyethers urea type benzoxazine colophonies of the present invention stretch answers curve, table 2
For its tensile property parameter.Two dumbbell shape standard batten test tensile properties are taken, it is taken averagely to be worth to resin fracture intensity
For 84.96GPa, Young's modulus 2632.74GPa, elongation at break 5.82%, energy to failure 2.92MJ/cm3, material according to
It is old that there is good intensity, toughness to be also greatly improved.
Fig. 6 is that the stress that the amine terminated polyether D-2000 polyethers urea type benzoxazine colophonies of the present invention stretch answers curve, table 3
For its tensile property parameter.Two dumbbell shape standard batten test tensile properties are taken, it is taken averagely to be worth to resin fracture intensity
For 0.3GPa, Young's modulus 0.46GPa, elongation at break 120.86%, energy to failure 0.22MJ/cm3, material is according to intensity
It is weaker, but its elongation at break is best, toughness is most preferably.
Five, specific implementation mode
The following describes the present invention in detail with reference to examples, but the present invention does not limit to following embodiment.
Embodiment 1:
The preparation method of high tenacity polyethers urea type benzoxazine colophony, includes the following steps in the present embodiment:
Prepare oligomer:2.5g '-diphenylmethane diisocyanates (MDI) and 8g amine terminated polyethers D-400 are added 50ml's
In DMAC, 4 hours of 70 DEG C of back flow reactions are warming up to, amine terminated polyether type polyureas is prepared;1.2g is added into reaction solution
Paraformaldehyde and 2.28g bisphenol-As are warming up to 85 DEG C of reaction 6h, and revolving removes solvent and water after reaction, is dried in vacuo to obtain the final product
Polyethers urea type benzoxazine is sticky yellow liquid.It tests its infrared and nuclear magnetic data and sees Fig. 2 and Fig. 3.
Cure test:The sticky yellow liquid of polyethers urea type benzoxazine is placed in ceramic crucible, then by ceramic earthenware
Crucible is placed in air dry oven, be warming up to successively 100 DEG C heat preservation 1h, 120 DEG C heat preservation 1h, 150 DEG C heat preservation 2h, 160 DEG C heat preservation 2h,
180 DEG C of heat preservation 2h obtain polyethers urea type benzoxazine colophony.Outside drawing such as Fig. 1, stress strain curve figure such as Fig. 4 and data such as table 1.
Table 1
Embodiment 2:
The preparation method of high tenacity polyethers urea type benzoxazine colophony, includes the following steps in the present embodiment:
Prepare oligomer:2.5g '-diphenylmethane diisocyanates (MDI) and 4.6g amine terminated polyethers D-230 are added
In the DMF of 100ml, 4 hours of 70 DEG C of back flow reactions are warming up to, amine terminated polyether type polyureas is prepared;Add into reaction solution
Enter 1.2g paraformaldehydes and 2.28g bisphenol-As, be warming up to 85 DEG C of reaction 6h, revolving removes solvent and water after reaction, and vacuum is dry
Dry polyethers urea type benzoxazine to obtain the final product, is sticky yellow liquid.
Cure test:The sticky yellow liquid of polyethers urea type benzoxazine is placed in ceramic crucible, then by ceramic earthenware
Crucible is placed in air dry oven, be warming up to successively 100 DEG C heat preservation 1h, 120 DEG C heat preservation 1h, 150 DEG C heat preservation 2h, 160 DEG C heat preservation 2h,
180 DEG C of heat preservation 2h obtain polyethers urea type benzoxazine colophony, and stress strain curve figure such as Fig. 5 and data are shown in Table 2.
Table 2
Embodiment 3:
The preparation method of high tenacity polyethers urea type benzoxazine colophony, includes the following steps in the present embodiment:
Prepare oligomer:2.5g '-diphenylmethane diisocyanates (MDI) and 40g amine terminated polyethers D-2000 are added
In the dioxane of 100ml, 4 hours of 70 DEG C of back flow reactions are warming up to, amine terminated polyether type polyureas is prepared;To reaction solution
Middle addition 1.2g paraformaldehydes and 2.28g bisphenol-As are warming up to 85 DEG C of reaction 6h, and revolving removes solvent and water after reaction, very
Sky is drying to obtain polyethers urea type benzoxazine, is sticky yellow liquid.
Cure test:The sticky yellow liquid of polyethers urea type benzoxazine is placed in ceramic crucible, then by ceramic earthenware
Crucible is placed in air dry oven, be warming up to successively 100 DEG C heat preservation 1h, 120 DEG C heat preservation 1h, 150 DEG C heat preservation 2h, 160 DEG C heat preservation 2h,
180 DEG C of heat preservation 2h obtain polyethers urea type benzoxazine colophony.Stress strain curve figure such as Fig. 6 and data are shown in Table 3.
Table 3
Embodiment 4:
The preparation method of high tenacity polyethers urea type benzoxazine colophony, includes the following steps in the present embodiment:
Prepare oligomer:1.74g toluene di-isocyanate(TDI)s (TDI) and 8g amine terminated polyethers D-400 are added the two of 100ml
In six ring of oxygen, 4 hours of 70 DEG C of back flow reactions are warming up to, amine terminated polyether type polyureas is prepared;It is added into reaction solution
1.2g paraformaldehydes and 2.28g bisphenol-As are warming up to 85 DEG C of reaction 6h, and revolving removes solvent and water, vacuum drying after reaction
It is sticky yellow liquid up to polyethers urea type benzoxazine.
Cure test:The sticky yellow liquid of polyethers urea type benzoxazine is placed in ceramic crucible, then by ceramic earthenware
Crucible is placed in air dry oven, be warming up to successively 100 DEG C heat preservation 1h, 120 DEG C heat preservation 1h, 150 DEG C heat preservation 2h, 160 DEG C heat preservation 2h,
180 DEG C of heat preservation 2h obtain polyethers urea type benzoxazine colophony.
Claims (4)
1. a kind of high tenacity polyethers urea type benzoxazine colophony, it is characterised in that its general structure is:
Wherein R indicates that the residue of diisocyanate, structural formula are:
2. a kind of preparation method of high tenacity polyethers urea type benzoxazine colophony described in claim 1, it is characterised in that including
Following steps:
0.01mol diisocyanate and 0.02mol amine terminated polyethers are added in 50-100ml organic solvents, 70 DEG C is warming up to and returns
Stream reaction 4h, is prepared amine terminated polyether type polyureas;0.04mol paraformaldehydes and 0.01mol bis-phenols are added into reaction solution
A is warming up to 85 DEG C of reaction 6h, and revolving removes solvent and water after reaction, is dried in vacuo up to polyethers urea type benzoxazine, is
Sticky yellow liquid, up to polyethers urea type benzoxazine colophony after solidification;
The diisocyanate is selected from '-diphenylmethane diisocyanate or toluene di-isocyanate(TDI);
The amine terminated polyether is D-230, D-400 or D-2000;
3. preparation method according to claim 2, it is characterised in that:
The organic solvent is selected from DMF, DMAC or dioxane.
4. preparation method according to claim 2, it is characterised in that curing process parameter is as follows:
The sticky yellow liquid of polyethers urea type benzoxazine is placed in ceramic crucible, ceramic crucible is then placed in forced air drying
In case, it is warming up to 100 DEG C of heat preservation 1h, 120 DEG C of heat preservation 1h, 150 DEG C of heat preservation 2h, 160 DEG C of heat preservation 2h, 180 DEG C of heat preservation 2h successively.
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