CN117567978B - Preparation method of benzoxazine modified polyurethane electronic adhesive - Google Patents
Preparation method of benzoxazine modified polyurethane electronic adhesive Download PDFInfo
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- CN117567978B CN117567978B CN202410051403.2A CN202410051403A CN117567978B CN 117567978 B CN117567978 B CN 117567978B CN 202410051403 A CN202410051403 A CN 202410051403A CN 117567978 B CN117567978 B CN 117567978B
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 34
- 239000004814 polyurethane Substances 0.000 title claims abstract description 34
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000000853 adhesive Substances 0.000 title claims abstract description 27
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 25
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 25
- 239000010452 phosphate Substances 0.000 claims abstract description 25
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229960005323 phenoxyethanol Drugs 0.000 claims abstract description 24
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 21
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 15
- KBZFDRWPMZESDI-UHFFFAOYSA-N 5-aminobenzene-1,3-dicarboxylic acid Chemical compound NC1=CC(C(O)=O)=CC(C(O)=O)=C1 KBZFDRWPMZESDI-UHFFFAOYSA-N 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000004359 castor oil Substances 0.000 claims abstract description 12
- 235000019438 castor oil Nutrition 0.000 claims abstract description 12
- 239000012975 dibutyltin dilaurate Substances 0.000 claims abstract description 12
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 12
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 12
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 12
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 59
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 29
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- 238000010992 reflux Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- 230000018044 dehydration Effects 0.000 claims description 17
- 238000006297 dehydration reaction Methods 0.000 claims description 17
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- VCXRQDUGDLCNEH-UHFFFAOYSA-N 2h-1,2-benzoxazine;phosphoric acid Chemical compound OP(O)(O)=O.C1=CC=C2C=CNOC2=C1 VCXRQDUGDLCNEH-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- MDNWOSOZYLHTCG-UHFFFAOYSA-N Dichlorophen Chemical compound OC1=CC=C(Cl)C=C1CC1=CC(Cl)=CC=C1O MDNWOSOZYLHTCG-UHFFFAOYSA-N 0.000 claims description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 7
- 229940035437 1,3-propanediol Drugs 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 7
- 239000000203 mixture Substances 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 4
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006683 Mannich reaction Methods 0.000 abstract description 2
- 125000002252 acyl group Chemical group 0.000 abstract description 2
- 238000005660 chlorination reaction Methods 0.000 abstract description 2
- 238000005886 esterification reaction Methods 0.000 abstract description 2
- 238000006467 substitution reaction Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 9
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 2
- -1 benzoxazine chlorobenzene Chemical compound 0.000 description 2
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004100 electronic packaging Methods 0.000 description 2
- 239000006261 foam material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/3844—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing one nitrogen atom in the ring
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6662—Compounds of group C08G18/42 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of electronic adhesives and discloses a preparation method of benzoxazine modified polyurethane electronic adhesives, which comprises the steps of preparing bis (benzoxazine-containing double-cage phosphate) phenoxyethanol by sequentially carrying out acyl chlorination reaction, esterification reaction, mannich reaction, substitution reaction on raw materials such as 5-amino isophthalic acid, thionyl chloride, double-cage cyclic phosphate, 2' -methylene bis (4-chlorophenol) and the like, and then adding the obtained mixture into polycaprolactone dihydric alcohol and toluene diisocyanate to obtain a component A. The preparation method comprises the steps of taking castor oil, 1, 3-propylene glycol and dibutyltin dilaurate as raw materials, preparing a component B, and finally uniformly mixing the component A and the component B to obtain the benzoxazine modified polyurethane electronic adhesive. The benzoxazine modified polyurethane electronic adhesive prepared by the invention has excellent heat resistance and flame retardance.
Description
Technical Field
The invention relates to the technical field of electronic adhesives, in particular to a preparation method of benzoxazine modified polyurethane electronic adhesive.
Background
With the continuous development of the precision and the miniaturization of electronic devices and logic circuits, the performance requirements of electronic products on the electronic adhesive are more and more strict, and the polyurethane electronic adhesive has the advantages of low hardness, good elasticity, high bonding strength and the like, and is an electronic packaging material widely applied to electronic appliances. However, with the continuous development and maturity of the electronic industry, the size of devices in the electronic equipment is gradually reduced, the density of the devices in unit volume is higher and higher, the temperature of the equipment is continuously increased during operation, so that heat is rapidly accumulated, and the heat resistance and flame retardance of the electronic equipment are vital to the safe operation of the whole system.
The benzoxazine resin has the advantages of low viscosity, moisture resistance, heat resistance, flame retardance and the like, is widely applied to the fields of electronics, electrics, aerospace, automobile industry and the like, and can be used for preparing high-performance packaging materials such as heat resistance, moisture resistance and the like by introducing the benzoxazine resin into materials such as electronic packaging and the like.
The patent publication No. CN116987378B discloses a super-temperature-resistant benzoxazine-polyurethane foam material, a preparation method and application thereof, and the patent prepares a benzoxazine-group-containing polyurethane, and takes the polyurethane as a matrix to prepare the benzoxazine resin foam material, which has excellent temperature resistance, but does not improve the flame retardant property of the foam material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of benzoxazine-modified polyurethane electronic adhesive, which is used for preparing the phenoxyethanol containing bis (double-cage-ring-containing phosphate benzoxazine), wherein the prepared monomer contains two double-cage-ring phosphate structures and two benzoxazine structures, and the polyurethane electronic adhesive prepared by taking the benzoxazine-modified polyurethane electronic adhesive as a matrix has excellent heat resistance and flame retardance.
The preparation method of the benzoxazine-modified polyurethane electronic adhesive comprises the following steps:
step (1), adding polycaprolactone dihydric alcohol and bis (double-cage-ring-containing phosphate benzoxazine) phenoxyethanol into a flask, carrying out vacuum dehydration, adding toluene diisocyanate into the flask, reacting for 3-6h at 80-90 ℃, and cooling to room temperature after the reaction is finished to obtain a component A;
step (2), adding castor oil and 1, 3-propylene glycol into a flask, dehydrating in vacuum, adding dibutyl tin dilaurate into the flask, and uniformly mixing to obtain a component B;
and (3) adding the component A and the component B into a flask, uniformly mixing, and curing for 1-3 hours at 70-90 ℃ to obtain the benzoxazine modified polyurethane electronic adhesive.
Preferably, in the step (1), the mass ratio of polycaprolactone diol, bis (benzoxazine containing double-cage phosphate) phenoxyethanol and toluene diisocyanate is 100: (50-100): (100-180).
Preferably, in the step (2), the mass ratio of castor oil, 1, 3-propylene glycol and dibutyltin dilaurate is 100: (4-10): (0.05-0.1).
Preferably, in the step (3), the mass ratio of the component A to the component B is (20-60): 100.
preferably, in the step (1), the preparation method of the bis (benzoxazine containing double-cage phosphate) phenoxyethanol comprises the following steps:
s1, adding 5-amino isophthalic acid and thionyl chloride into a dimethylbenzene solvent, heating to 60-90 ℃, carrying out reflux reaction for 3-8h, and evaporating the solvent under reduced pressure to obtain an intermediate 1;
s2, adding the intermediate 1 into an acetone solvent, adding double-cage cyclic phosphate and triethylamine into the acetone solvent, heating to 50-60 ℃, carrying out reflux reaction for 2-5h, cooling to room temperature after the reaction is finished, carrying out suction filtration, washing with deionized water, and drying to obtain an intermediate 2;
s3, adding 2,2' -methylenebis (4-chlorophenol), formaldehyde and the intermediate 2 into dioxane solvent, stirring and mixing for 10-20min, heating to 90-100 ℃, carrying out reflux reaction for 5-10h, carrying out reduced pressure distillation to remove the solvent after the reaction is finished, washing with deionized water, and drying to obtain an intermediate 3;
s4, adding the intermediate 3 and ethylene glycol into the N, N-dimethylformamide solvent, heating to 110-130 ℃, stirring and reacting for 2-5h, after the reaction is finished, distilling under reduced pressure to remove the solvent, washing with deionized water, and drying to obtain the bis (benzoxazine containing double-cage cyclic phosphate) phenoxyethanol.
Preferably, in the step S1, the molar ratio of 5-aminoisophthalic acid to thionyl chloride is 1: (2-2.5).
Preferably, in the step S2, the molar ratio of the intermediate 1 to the double-cage cyclic phosphate to the triethylamine is 1: (2-2.6): (1.5-3).
Preferably, in the step S3, the molar ratio of the 2,2' -methylenebis (4-chlorophenol), formaldehyde and the intermediate 2 is 1: (4-5): (1-1.4).
Preferably, in the step S4, the molar ratio of the intermediate 3 to the ethylene glycol is 1: (1.6-2.2).
The invention has the beneficial effects that:
the invention uses raw materials such as 5-amino isophthalic acid, thionyl chloride, double-cage cyclic phosphate, 2' -methylene bis (4-chlorophenol) and the like to sequentially carry out acyl chlorination reaction, esterification reaction, mannich reaction and substitution reaction to prepare the double (double-cage cyclic phosphate benzoxazine) phenoxyethanol, and then the phenoxyethanol is added into polycaprolactone dihydric alcohol and toluene diisocyanate to obtain the component A. The preparation method comprises the steps of taking castor oil, 1, 3-propylene glycol and dibutyltin dilaurate as raw materials, preparing a component B, and finally uniformly mixing the component A and the component B to obtain the benzoxazine modified polyurethane electronic adhesive.
The benzoxazine-modified polyurethane electronic adhesive prepared by the invention contains a double-cage-ring phosphate structure, and when heated and combusted, the double-cage-ring phosphate structure can generate polyphosphoric acid and metaphosphoric acid with strong dehydration property, so that the dehydration and carbonization of materials can be promoted, and as the polyphosphoric acid and metaphosphoric acid are not easy to volatilize, a compact protective layer can be formed on the surface of the materials, the transportation and energy transfer of the materials and external substances are prevented, and a better flame retardant effect is achieved.
The benzoxazine-modified polyurethane electronic adhesive prepared by the invention contains a benzoxazine structure, can absorb heat when heated, and performs ring-opening reaction to form a network-like structure with high crosslinking density containing nitrogen atoms, namely the benzoxazine, so that the heat resistance of the material is further improved. The benzoxazine modified polyurethane electronic adhesive prepared by the invention has excellent heat resistance and flame retardance.
Drawings
FIG. 1 is a scheme for the preparation of bis (biscaged cyclic phosphate benzoxazine) phenoxyethanol according to the present invention.
Detailed Description
In order to make the technical problems, technical solutions and comparison effects to be solved more apparent, the present invention will be described in further detail with reference to examples. It should be understood that the detailed description and specific examples, while indicating the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
The preparation method of the double-cage cyclic phosphate comprises the following steps: 33.6g of pentaerythritol and 38.3g of phosphorus oxychloride are added into 100mL of 1, 4-dioxane solvent, the temperature is raised to 80 ℃, the reflux reaction is carried out for 3 hours, after the reaction is finished, the mixture is cooled to room temperature, filtered, recrystallized by ethanol and dried, and the double-cage cyclic phosphate is obtained.
Example 1: (1) Adding 20mmol of 5-amino isophthalic acid and 45mmol of thionyl chloride into a dimethylbenzene solvent, heating to 80 ℃, carrying out reflux reaction for 5 hours, and evaporating the solvent under reduced pressure to obtain an intermediate 1;
(2) Adding 50mmol of the intermediate 1 into an acetone solvent, adding 120mmol of double-cage cyclic phosphate and 100mmol of triethylamine into the acetone solvent, heating to 55 ℃, carrying out reflux reaction for 4 hours, cooling to room temperature after the reaction is finished, carrying out suction filtration, washing with deionized water, and drying to obtain an intermediate 2;
(3) 80mmol of 2,2' -methylenebis (4-chlorophenol), 400mmol of formaldehyde and 90mmol of intermediate 2 are added into dioxane solvent, stirred and mixed for 16min, then heated to 100 ℃, reflux reacted for 8h, after the reaction is finished, the solvent is distilled off under reduced pressure, washed by deionized water and dried to obtain intermediate 3;
(4) Adding 50mmol of intermediate 3 and 90mmol of ethylene glycol into an N, N-dimethylformamide solvent, heating to 120 ℃, stirring for reaction for 3 hours, after the reaction is finished, distilling under reduced pressure to remove the solvent, washing with deionized water, and drying to obtain bis (benzoxazine containing double-cage cyclic phosphate) phenoxyethanol;
(5) 100g of polycaprolactone dihydric alcohol and 50g of bis (double-cage-ring-containing phosphate benzoxazine) phenoxyethanol are added into a flask for vacuum dehydration, 150g of toluene diisocyanate is added into the flask, the reaction is carried out for 4 hours at 85 ℃, and after the reaction is finished, the mixture is cooled to room temperature, so that a component A is obtained;
(6) 200g of castor oil and 10g of 1, 3-propanediol are added into a flask, vacuum dehydration is carried out, then 0.2g of dibutyltin dilaurate is added into the flask, and the mixture is uniformly mixed to obtain a component B;
(7) Adding 40g of the component A and 200g of the component B into a flask, uniformly mixing, and curing for 2 hours at 80 ℃ to obtain the benzoxazine-modified polyurethane electronic adhesive.
Example 2: (1) 20mmol of 5-amino isophthalic acid and 45mmol of thionyl chloride are added into a dimethylbenzene solvent, the temperature is raised to 80 ℃, the reflux reaction is carried out for 8 hours, and the solvent is distilled off under reduced pressure to obtain an intermediate 1;
(2) Adding 50mmol of the intermediate 1 into an acetone solvent, adding 110mmol of double-cage cyclic phosphate and 90mmol of triethylamine, heating to 55 ℃, carrying out reflux reaction for 5h, cooling to room temperature after the reaction is finished, carrying out suction filtration, washing with deionized water, and drying to obtain an intermediate 2;
(3) 80mmol of 2,2' -methylenebis (4-chlorophenol), 350mmol of formaldehyde and 110mmol of intermediate 2 are added into dioxane solvent, stirred and mixed for 18min, then heated to 90 ℃, reflux reacted for 10h, after the reaction is finished, the solvent is distilled off under reduced pressure, washed by deionized water and dried to obtain intermediate 3;
(4) Adding 50mmol of intermediate 3 and 90mmol of ethylene glycol into an N, N-dimethylformamide solvent, heating to 120 ℃, stirring for reaction for 4 hours, after the reaction is finished, distilling under reduced pressure to remove the solvent, washing with deionized water, and drying to obtain bis (benzoxazine containing double-cage cyclic phosphate) phenoxyethanol;
(5) 100g of polycaprolactone dihydric alcohol and 62g of bis (double-cage-ring-containing phosphate benzoxazine) phenoxyethanol are added into a flask for vacuum dehydration, 170g of toluene diisocyanate is added into the flask, the reaction is carried out for 5 hours at 80 ℃, and after the reaction is finished, the mixture is cooled to room temperature, so that a component A is obtained;
(6) 200g of castor oil and 15g of 1, 3-propanediol are added into a flask, vacuum dehydration is carried out, then 0.2g of dibutyltin dilaurate is added into the flask, and the mixture is uniformly mixed to obtain a component B;
(7) 60g of the component A and 200g of the component B are added into a flask, uniformly mixed and cured for 2 hours at 90 ℃ to obtain the benzoxazine-modified polyurethane electronic adhesive.
Example 3: (1) 20mmol of 5-amino isophthalic acid and 50mmol of thionyl chloride are added into a dimethylbenzene solvent, the temperature is raised to 80 ℃, the reflux reaction is carried out for 6 hours, and the solvent is distilled off under reduced pressure to obtain an intermediate 1;
(2) Adding 50mmol of the intermediate 1 into an acetone solvent, adding 130mmol of double-cage cyclic phosphate and 140mmol of triethylamine into the acetone solvent, heating to 55 ℃, carrying out reflux reaction for 5h, cooling to room temperature after the reaction is finished, carrying out suction filtration, washing with deionized water, and drying to obtain an intermediate 2;
(3) Adding 80mmol of 2,2' -methylenebis (4-chlorophenol), 360mmol of formaldehyde and 100mmol of intermediate 2 into a dioxane solvent, stirring and mixing for 18min, heating to 100 ℃, carrying out reflux reaction for 7h, removing the solvent by reduced pressure distillation after the reaction is finished, washing with deionized water, and drying to obtain an intermediate 3;
(4) Adding 50mmol of intermediate 3 and 90mmol of ethylene glycol into an N, N-dimethylformamide solvent, heating to 130 ℃, stirring and reacting for 5 hours, after the reaction is finished, distilling under reduced pressure to remove the solvent, washing with deionized water, and drying to obtain bis (benzoxazine containing double-cage cyclic phosphate) phenoxyethanol;
(5) 100g of polycaprolactone dihydric alcohol and 74g of bis (double-cage-ring-containing phosphate benzoxazine) phenoxyethanol are added into a flask for vacuum dehydration, 160g of toluene diisocyanate is added into the flask, the reaction is carried out for 5 hours at 85 ℃, and after the reaction is finished, the mixture is cooled to room temperature, so that a component A is obtained;
(6) 200g of castor oil and 10g of 1, 3-propanediol are added into a flask, vacuum dehydration is carried out, then 0.15g of dibutyltin dilaurate is added into the flask, and the mixture is uniformly mixed to obtain a component B;
(7) Adding 80g of the component A and 200g of the component B into a flask, uniformly mixing, and curing for 3 hours at 80 ℃ to obtain the benzoxazine-modified polyurethane electronic adhesive.
Example 4: (1) Adding 20mmol of 5-amino isophthalic acid and 48mmol of thionyl chloride into a dimethylbenzene solvent, heating to 80 ℃, carrying out reflux reaction for 5 hours, and evaporating the solvent under reduced pressure to obtain an intermediate 1;
(2) Adding 50mmol of the intermediate 1 into an acetone solvent, adding 120mmol of double-cage cyclic phosphate and 140mmol of triethylamine into the acetone solvent, heating to 55 ℃, carrying out reflux reaction for 5h, cooling to room temperature after the reaction is finished, carrying out suction filtration, washing with deionized water, and drying to obtain an intermediate 2;
(3) Adding 80mmol of 2,2' -methylenebis (4-chlorophenol), 380mmol of formaldehyde and 90mmol of intermediate 2 into a dioxane solvent, stirring and mixing for 15min, heating to 95 ℃, carrying out reflux reaction for 10h, removing the solvent by reduced pressure distillation after the reaction is finished, washing with deionized water, and drying to obtain an intermediate 3;
(4) Adding 50mmol of intermediate 3 and 80mmol of ethylene glycol into an N, N-dimethylformamide solvent, heating to 120 ℃, stirring and reacting for 5 hours, after the reaction is finished, distilling under reduced pressure to remove the solvent, washing with deionized water, and drying to obtain bis (benzoxazine containing double-cage cyclic phosphate) phenoxyethanol;
(5) Adding 100g of polycaprolactone dihydric alcohol and 86g of bis (double-cage-ring-containing phosphate benzoxazine) phenoxyethanol into a flask, carrying out vacuum dehydration, adding 100g of toluene diisocyanate into the flask, reacting for 6 hours at 85 ℃, and cooling to room temperature after the reaction is finished to obtain a component A;
(6) 200g of castor oil and 8g of 1, 3-propanediol are added into a flask, vacuum dehydration is carried out, then 0.14g of dibutyltin dilaurate is added into the flask, and the mixture is uniformly mixed to obtain a component B;
(7) 100g of the component A and 200g of the component B are added into a flask, uniformly mixed and cured for 3 hours at 90 ℃ to obtain the benzoxazine-modified polyurethane electronic adhesive.
Example 5: (1) 20mmol of 5-amino isophthalic acid and 45mmol of thionyl chloride are added into a dimethylbenzene solvent, the temperature is raised to 80 ℃, the reflux reaction is carried out for 6 hours, and the solvent is distilled off under reduced pressure to obtain an intermediate 1;
(2) Adding 50mmol of the intermediate 1 into an acetone solvent, adding 120mmol of double-cage cyclic phosphate and 100mmol of triethylamine into the acetone solvent, heating to 60 ℃, carrying out reflux reaction for 2h, cooling to room temperature after the reaction is finished, carrying out suction filtration, washing with deionized water, and drying to obtain an intermediate 2;
(3) Adding 80mmol of 2,2' -methylenebis (4-chlorophenol), 380mmol of formaldehyde and 80mmol of intermediate 2 into a dioxane solvent, stirring and mixing for 15min, heating to 100 ℃, carrying out reflux reaction for 10h, removing the solvent by reduced pressure distillation after the reaction is finished, washing with deionized water, and drying to obtain an intermediate 3;
(4) Adding 50mmol of intermediate 3 and 90mmol of ethylene glycol into an N, N-dimethylformamide solvent, heating to 120 ℃, stirring and reacting for 5 hours, after the reaction is finished, distilling under reduced pressure to remove the solvent, washing with deionized water, and drying to obtain bis (benzoxazine containing double-cage cyclic phosphate) phenoxyethanol;
(5) Adding 100g of polycaprolactone dihydric alcohol and 100g of bis (double-cage-ring-containing phosphate benzoxazine) phenoxyethanol into a flask, carrying out vacuum dehydration, adding 160g of toluene diisocyanate into the flask, reacting for 5 hours at 90 ℃, and cooling to room temperature after the reaction is finished to obtain a component A;
(6) 200g of castor oil and 15g of 1, 3-propanediol are added into a flask, vacuum dehydration is carried out, then 0.2g of dibutyltin dilaurate is added into the flask, and the mixture is uniformly mixed to obtain a component B;
(7) 120g of the component A and 200g of the component B are added into a flask, uniformly mixed and cured for 3 hours at 80 ℃ to obtain the benzoxazine-modified polyurethane electronic adhesive.
Comparative example 1: (1) Adding 80mmol of 2,2 '-methylenebis (4-chlorophenol), 400mmol of formaldehyde and 90mmol of 5-amino isophthalic acid into dioxane solvent, stirring and mixing for 16min, heating to 100 ℃, carrying out reflux reaction for 8h, removing the solvent by reduced pressure distillation after the reaction is finished, washing with deionized water, and drying to obtain 2,2' -methylenebis (benzoxazine-containing chlorobenzene);
(2) 50mmol of 2,2' -methylenebis (containing benzoxazine chlorobenzene) and 90mmol of glycol are added into an N, N-dimethylformamide solvent, the temperature is raised to 120 ℃, the mixture is stirred and reacted for 3 hours, after the reaction is finished, the solvent is removed by reduced pressure distillation, deionized water is used for washing, and the benzoxazine-containing phenoxyethanol intermediate is obtained by drying;
(3) 100g of polycaprolactone dihydric alcohol and 50g of benzoxazine-containing phenoxyethanol intermediate are added into a flask for vacuum dehydration, 150g of toluene diisocyanate is added into the flask, the reaction is carried out for 4 hours at 85 ℃, and after the reaction is finished, the mixture is cooled to room temperature, so that a component A is obtained;
(4) 200g of castor oil and 10g of 1, 3-propanediol are added into a flask, vacuum dehydration is carried out, then 0.2g of dibutyltin dilaurate is added into the flask, and the mixture is uniformly mixed to obtain a component B;
(5) Adding 40g of the component A and 200g of the component B into a flask, uniformly mixing, and curing for 2 hours at 80 ℃ to obtain the benzoxazine-modified polyurethane electronic adhesive.
The oxygen index of the material was measured using an oxygen index meter.
The burn rating of the material was tested using a horizontal vertical burn tester.
Table 1: oxygen index and combustion grade test results for each example and comparative example
As can be seen from table 1, the flame retardant properties of examples 1 to 5 are better than comparative example 1 because the addition of the double cage ring phosphate to the electronic paste in examples 1 to 5 can increase the flame retardant properties of the electronic paste, whereas the flame retardant properties of comparative example 1 are inferior because the double cage ring phosphate is not contained.
The heat resistance of the material is tested by using a thermal weightlessness instrument, the temperature range is 50-600 ℃ and the heating rate is 15 ℃/min under the nitrogen atmosphere.
Table 2: results of heat resistance test of examples and comparative examples
T 5% The decomposition temperature is 5% of the weight of the material; t (T) 50% Is the decomposition temperature at which the material loses 50% of weight.
As can be seen from table 2, the heat resistance of examples 1 to 5 and the heat resistance of comparative example 1 are both superior because the benzoxazine structures are contained in examples 1 to 5 and comparative example 1, and when heated, the benzoxazine structures can absorb heat to form a high-density cross-linked network structure, further enhancing the heat resistance of the materials, and in addition, the double cage cyclic phosphate esters contained in examples 1 to 5 can promote the dehydration and carbonization of the materials to increase the heat resistance of the materials, so that the heat resistance of examples 1 to 5 is superior to comparative example 1.
And testing the mechanical properties of the material by using a universal tensile tester.
The hardness of the material was tested using a shore a durometer.
Table 3: tensile Strength and hardness test results for examples and comparative examples
As shown in Table 3, the benzoxazine-modified polyurethane electronic gum prepared by the invention has excellent mechanical properties.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
Claims (8)
1. The preparation method of the benzoxazine modified polyurethane electronic adhesive is characterized by comprising the following steps of:
(1) Adding 5-amino isophthalic acid and thionyl chloride into a dimethylbenzene solvent, heating to 60-90 ℃, carrying out reflux reaction for 3-8h, and evaporating the solvent under reduced pressure to obtain an intermediate 1;
(2) Adding the intermediate 1 into an acetone solvent, adding double-cage cyclic phosphate and triethylamine into the acetone solvent, heating to 50-60 ℃, carrying out reflux reaction for 2-5h, cooling to room temperature after the reaction is finished, carrying out suction filtration, washing with deionized water, and drying to obtain an intermediate 2;
(3) Adding 2,2' -methylenebis (4-chlorophenol), formaldehyde and an intermediate 2 into a dioxane solvent, stirring and mixing for 10-20min, heating to 90-100 ℃, carrying out reflux reaction for 5-10h, removing the solvent by reduced pressure distillation after the reaction is finished, washing with deionized water, and drying to obtain an intermediate 3;
(4) Adding the intermediate 3 and ethylene glycol into an N, N-dimethylformamide solvent, heating to 110-130 ℃, stirring and reacting for 2-5h, after the reaction is finished, distilling under reduced pressure to remove the solvent, washing with deionized water, and drying to obtain bis (double-cage-ring-containing phosphate benzoxazine) phenoxyethanol;
(5) Adding polycaprolactone dihydric alcohol and bis (benzoxazine containing double-cage phosphate) phenoxyethanol into a flask for vacuum dehydration, adding toluene diisocyanate into the flask, reacting for 3-6h at 80-90 ℃, and cooling to room temperature after the reaction is finished to obtain a component A;
(6) Adding castor oil and 1, 3-propylene glycol into a flask, dehydrating in vacuum, adding dibutyl tin dilaurate into the flask, and uniformly mixing to obtain a component B;
(7) Adding the component A and the component B into a flask, uniformly mixing, and curing for 1-3 hours at 70-90 ℃ to obtain the benzoxazine-modified polyurethane electronic adhesive.
2. The method for preparing the benzoxazine-modified polyurethane electronic gum according to claim 1, wherein in the step (1), the molar ratio of 5-amino isophthalic acid to thionyl chloride is 1: (2-2.5).
3. The method for preparing the benzoxazine-modified polyurethane electronic gum according to claim 1, wherein in the step (2), the molar ratio of the intermediate 1 to the double-cage cyclic phosphate to the triethylamine is 1: (2-2.6): (1.5-3).
4. The method for preparing the benzoxazine-modified polyurethane electronic gum according to claim 1, wherein in the step (3), the molar ratio of 2,2' -methylenebis (4-chlorophenol), formaldehyde and intermediate 2 is 1: (4-5): (1-1.4).
5. The method for preparing the benzoxazine-modified polyurethane electronic gum according to claim 1, wherein in the step (4), the molar ratio of the intermediate 3 to the ethylene glycol is 1: (1.6-2.2).
6. The method for preparing the benzoxazine-modified polyurethane electronic gum according to claim 1, wherein in the step (5), the mass ratio of polycaprolactone diol, bis (double-cage-ring-containing phosphate benzoxazine) phenoxyethanol and toluene diisocyanate is 100: (50-100): (100-180).
7. The method for preparing the benzoxazine-modified polyurethane electronic gum according to claim 1, wherein in the step (6), the mass ratio of castor oil, 1, 3-propanediol and dibutyltin dilaurate is 100: (4-10): (0.05-0.1).
8. The method for preparing the benzoxazine-modified polyurethane electronic gum according to claim 1, wherein in the step (7), the mass ratio of the component a to the component B is (20-60): 100.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101463046A (en) * | 2008-11-20 | 2009-06-24 | 西华大学 | Caged bicyclic phosphate flame retardant, and preparation and use thereof |
| CN105001265A (en) * | 2015-07-07 | 2015-10-28 | 苏州凯马化学科技有限责任公司 | Preparation method for flame retardant double-phosphorus-cage cyclic phosphate compound |
| CN110283289A (en) * | 2019-07-22 | 2019-09-27 | 上海瑞仪化工科技有限公司 | A kind of phosphorous benzoxazine resin of high flame retardant and its preparation method and application |
| US10781345B1 (en) * | 2017-11-27 | 2020-09-22 | Yantai Darbond Technology Co., Ltd. | Method of preparing polyurethane hot melt adhesive with high temperature resistance |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101463046A (en) * | 2008-11-20 | 2009-06-24 | 西华大学 | Caged bicyclic phosphate flame retardant, and preparation and use thereof |
| CN105001265A (en) * | 2015-07-07 | 2015-10-28 | 苏州凯马化学科技有限责任公司 | Preparation method for flame retardant double-phosphorus-cage cyclic phosphate compound |
| US10781345B1 (en) * | 2017-11-27 | 2020-09-22 | Yantai Darbond Technology Co., Ltd. | Method of preparing polyurethane hot melt adhesive with high temperature resistance |
| CN110283289A (en) * | 2019-07-22 | 2019-09-27 | 上海瑞仪化工科技有限公司 | A kind of phosphorous benzoxazine resin of high flame retardant and its preparation method and application |
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