CN102219785B - Triazine-containing benzoxazine, triazine-containing benzoxazine polymer, and preparation method thereof - Google Patents
Triazine-containing benzoxazine, triazine-containing benzoxazine polymer, and preparation method thereof Download PDFInfo
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 title claims abstract description 103
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920000642 polymer Polymers 0.000 title abstract description 3
- 239000000178 monomer Substances 0.000 claims abstract description 74
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 21
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 14
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
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- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 21
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- 239000000243 solution Substances 0.000 claims description 16
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 15
- -1 ethynyl phenyl Chemical group 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 12
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 229960001701 chloroform Drugs 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- JXYITCJMBRETQX-UHFFFAOYSA-N 4-ethynylaniline Chemical compound NC1=CC=C(C#C)C=C1 JXYITCJMBRETQX-UHFFFAOYSA-N 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 claims 1
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- 238000010438 heat treatment Methods 0.000 abstract description 5
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- 125000003367 polycyclic group Chemical group 0.000 abstract 1
- 125000001424 substituent group Chemical group 0.000 abstract 1
- 150000003918 triazines Chemical class 0.000 abstract 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 21
- 238000001723 curing Methods 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
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- 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 6
- 239000002585 base Substances 0.000 description 6
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- 230000011218 segmentation Effects 0.000 description 6
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- CVNOWLNNPYYEOH-UHFFFAOYSA-N 4-cyanophenol Chemical compound OC1=CC=C(C#N)C=C1 CVNOWLNNPYYEOH-UHFFFAOYSA-N 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 150000005130 benzoxazines Chemical class 0.000 description 3
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- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 3
- 229920006391 phthalonitrile polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QYYCVMYAGCAAKW-UHFFFAOYSA-N 4-prop-2-ynoxybenzamide Chemical compound NC(=O)C1=CC=C(OCC#C)C=C1 QYYCVMYAGCAAKW-UHFFFAOYSA-N 0.000 description 2
- 101100391174 Dictyostelium discoideum forC gene Proteins 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000002679 ablation Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 125000001207 fluorophenyl group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
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- 238000010189 synthetic method Methods 0.000 description 2
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- ALQPJHSFIXARGX-UHFFFAOYSA-N 2-ethynylaniline Chemical compound NC1=CC=CC=C1C#C ALQPJHSFIXARGX-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 241001442654 Percnon planissimum Species 0.000 description 1
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention relates to triazine-containing benzoxazine, a triazine-containing benzoxazine polymer, and a preparation method thereof. The preparation method is characterized by: adopting cyanophenol as a raw material; adopting trifluoromethanesulfonic acid or trifluoroacetic acid as a catalyst; synthesizing triazine-containing trihydric phenol (TP for short) in dichloromethane or chloroform or acetone at a common temperature; adopting the synthesized TP, formaldehyde and aminated compounds as reaction raw materials; adopting a alkali as the catalyst, and carrying out a reaction in a alcohol solvent or a ether solvent to synthesize a series of triazine-containing polycyclic benzoxazine monomers (BZ for short) which have not been reported; heating the BZ to carry out a ring-opening polymerization to form polybenzoxazine (PBZ for short). A structural formula of the monomer BZ is shown as follow, substituents R are shown in the specification. The synthesized novel monomer provided by the present invention contains a triazine ring structure, such that the triazine content in the PBZ resin can be substantially raised so as to notably improve heat resistance, residual carbon rate, fire resistance property and wave transmission property of the PBZ.
Description
Technical field
The present invention relates to a kind of novel benzoxazine monomer and polymkeric substance thereof, particularly, containing benzoxazine, Polybenzoxazine and their preparation method of triazine, belong to technical field of polymer materials.
Background technology
Polybenzoxazine has excellent mechanical property, resistance toheat, flame retardant properties and electrical insulation capability, has been subject in recent years people and has paid close attention to widely and study.Yet, along with the development of the new and high technologies such as aerospace, electronic apparatus, information technology, also more and more higher to the requirement of material property.Need development to there is high glass-transition temperature (T
g), the Polybenzoxazine of high thermal stability and the contour performance of high flame retardant.
As everyone knows, triazine ring has very high thermostability and flame retardant properties.Therefore, in Polybenzoxazine, introduce thermotolerance, flame retardant properties and the carbon residue rate that triazine ring can improve Polybenzoxazine.In addition, triazine has lower specific inductivity, can prepare Polybenzoxazine electromagnetic wave transparent material.
The report of triazine introducing Polybenzoxazine at present also seldom.The Ishida seminar of U.S. Case Western Reserve University is at " Thermal properties of phthalonitrile functional polybenzoxazines " [Thermochimica Acta, 2000,357-358:195-203], " Thermal Study on the Copolymers of Phthalonitrile and Phenylnitrile-Functional Benzoxazines " [J.Appl.Polym.Sci., 1999,73:2937-2949] and " High-Performance Maleimide and Nitrile-Functionalized Benzoxazines with Good Processibility for Advanced Composites " [J.Appl.Polym.Sci., 2006,101:548-558] monocycle and dicyclo benzoxazine intermediate and the polymkeric substance thereof of the cyano-containing of having reported for work in three pieces of articles and patent US1996:5973144 < < High Char Yield Benzoxazines > >, and cyano group is catalytically conveted to triazine ring is studied.The Huimin Qi seminar of East China University of Science is at " Synthesis and characteristic of polybenzoxazine with phenylnitrile functional group " [Polym.Adv.Technol., 2009,20:268-272] also reported for work in article monocycle and dicyclo benzoxazine intermediate and the polymkeric substance thereof of cyano-containing, and the catalyzed polymerization of cyano group is studied.The Xiaobo Liu seminar of University of Science and Technology of China Electronics is at " Synthesis and characterization of a novel bisphthalonitrile containing benzoxazine " [e.Polym.Lett., 2007, 1:512-518] and " Synthesis and thermal properties of the thermosetting resin based on cyano functionalized benzoxazine " [Polym.Degrad.Stab., 2008, 93:739-744] in article and patent CN2006:1876615 < < double-terminal phthalonitrile, resin, in cured article and its production and use > >, also reported for work monocycle and the dicyclo benzoxazine intermediate of cyano-containing, and the catalyzed polymerization of cyano group and transformation efficiency thereof are studied.
Yet their preparation method first prepares the benzoxazine monomer that contains cyano group, then by the method for heating or catalysis, realize the conversion of solidifying of benzoxazine monomer and cyano group.The main drawback of this method is the transformation efficiency of cyano group not high (transformation efficiency < 40%), possible reason is, the corsslinking molecular chain network solidifying to form has limited the motion of cyano group, make no matter to adopt raising solidification value still to add the methods such as catalyzer, all improve unsatisfactorily the transformation efficiency of cyano group, in final product Polybenzoxazine, the content of triazine ring is lower, unfavorable to the performance of raising Polybenzoxazine.
In order to improve the content of triazine in Polybenzoxazine, thereby improve significantly the performance of Polybenzoxazine, such as thermotolerance, flame retardant resistance, ablation resistance, wave etc., from the monomer new approaches of can yet be regarded as of starting with.
Summary of the invention
The object of this invention is to provide a kind of many rings benzoxazine monomer, its polymkeric substance and their preparation method containing triazine.
The technical scheme that the present invention takes is: first take 4-hydroxybenzonitrile as raw material, with trifluoromethanesulfonic acid or trifluoroacetic acid, make catalyzer, in methylene dichloride, chloroform or acetone, normal temperature spends the night.Trimerization reaction through 4-hydroxybenzonitrile, synthesizes the trihydric phenol containing triazine--2,4,6-tri-(4-hydroxy phenyl)-1,3,5-s-triazine (being called for short TP).Then TP, formaldehyde and the aminated compounds synthesizing of take is reaction raw materials, with alkali as a catalyst, in alcohols or ether solvent, reacts, and synthesized a series of many rings benzoxazine monomer BZ containing triazine that report for work that have no.Finally heating BZ makes its ring-opening polymerization form Polybenzoxazine PBZ.
Containing many rings benzoxazine monomer of triazine, its structural formula is
Wherein R (as shown in Fig. 1) is: phenyl (a), p-methylphenyl (pt), between aminomethyl phenyl (mt), o-methyl-phenyl-(ot), 3,5-3,5-dimethylphenyl (35m), to ethynyl phenyl (papa), between ethynyl phenyl (mapa), to propargyloxy (appe), to fluorophenyl (pfa), adjacent fluorophenyl (ofa), 2,6-difluorophenyl (26fa), 2-methyl-6-fluorophenyl (6ot), p-nitrophenyl (pna), m-nitro base (mna), O-Nitrophenylfluorone (ona), 3,5-dinitrophenyl (35na), to cyano-phenyl (pca), fluoro-4 cyano-phenyls of 3-(3f4ca), 4-nitro-2-cyano-phenyl (4n2ca), 4-nitro-2,3-dicyano phenyl (4n23ca), to carboxyl phenyl (paba), to carboxylic acid sodium phenyl (pabass), adjacent carboxyl phenyl (oaba), to formic acid ester group phenyl (pabe), p-sulfonic acid base phenyl (pabsa), p-sulfonic acid sodium base phenyl (pabsass), ortho-sulfonic acid base phenyl (oabsa), 2,4-disulfonic acid base phenyl (2ab14sa), cyclohexyl (ca), methyl (m), ethyl (ea), n-hexyl (nha), allyl group (ala), 2-hydroxyethyl (2ea), 4-(trimethoxy is silica-based) propyl group (kh550) or 4-(dimethoxy-methyl is silica-based) propyl group (kh660).
The preparation method of the described many rings benzoxazine monomer containing triazine, step following (reaction scheme is shown in Fig. 1):
(a) under room temperature, in methylene chloride, trichloromethane, acetone or tetrahydrofuran (THF), add raw material to cyano group phenol, catalyzer trifluoromethanesulfonic acid or trifluoroacetic acid, mixed solution at room temperature reacts 2-3h, gained purified solution is dried and (preferably uses alkali liquid washing, and with solvent extraction, combining extraction liquid, pressure reducing and steaming solvent, vacuum-drying) must be containing the trihydric phenol TP of triazine after;
(b) the trihydric phenol TP, aminated compounds, the formaldehyde that under room temperature, in solvent dioxane, ethanol, methyl alcohol, chloroform, toluene or tetrahydrofuran (THF), add step (a) to obtain, mixed solution reacts 3-4h under reflux conditions, gained purified solution is dried and (preferably uses alkali liquid washing, and with solvent extraction, combining extraction liquid, pressure reducing and steaming solvent, vacuum-drying) must be containing many rings benzoxazine monomer BZ of triazine after.
Solvent in above-mentioned steps (a), to the weight part ratio of cyano group phenol, catalyzer, be 60～80: 10～40: 02～2.
In above-mentioned steps (b), the weight part ratio of solvent, trihydric phenol TP, aminated compounds, formaldehyde is 30～80: 10～30: 20～70: 20～60.
Described aminated compounds is aniline, to substituted aniline, saturated or unsaturated fatty amine or the fatty amine that contains silicon.
The polymkeric substance of above-mentioned monomer,, containing the Polybenzoxazine PBZ of triazine ring, its structural formula is as follows:
The same aforementioned monomer of the optional substituting group of R wherein, resulting polymers is crosslinked network-like macromole.
The preparation method who contains the Polybenzoxazine PBZ of triazine ring, comprises that step is as follows:
(1) preparation is containing many rings benzoxazine monomer (preparation method is the same) of triazine;
(2) by gained, the many rings benzoxazine monomer containing triazine solidifies, concrete steps are: the many rings benzoxazine monomer containing triazine is poured in rectangle aluminium matter mould, in Constant Temp. Oven, the Polybenzoxazine obtaining containing triazine ring is solidified in segmentation, curing temperature-rise period is: within the scope of 100-260 ℃, time variable control gradient increased temperature, isothermal curing 1-3h after 10 ℃ or 20 ℃ of every risings of temperature.
Contain the solidification process monitoring of many rings benzoxazine monomer (being called for short benzoxazine monomer below) of triazine:
For the solidify reaction process of benzoxazine monomer of the present invention, we use DSC and FTIR to research and analyse.By TP and aniline, be raw material gained benzoxazine monomer-2,4,6-tri-(3-phenyl-3,4 dihydros-2H-1,3-benzoxazine-6 base)-1,3, the DSC spectrogram demonstration of 5-s-triazine (being called for short BZ-a), the fusing point of BZ-a is 158.8 ℃, initial polymerization temperature is 205.5 ℃, maximum ring-opening polymerization exothermic peak temperature is 227 ℃, and heat release end temp is 245 ℃.The explanation of the curing FTIR spectrogram of segmentation, monomer after 160 ℃ of curing 2h, the charateristic avsorption band 1496cm of benzoxazine
-1, 1230cm
-1and 942cm
-1slightly reduce.Illustrate that being heated to 160 ℃ of benzoxazine monomers does not have open loop substantially.Monomer after 180 ℃ of curing 2h, the charateristic avsorption band 1496cm of benzoxazine
-1, 1230cm
-1and 942cm
-1basic disappearance.Phenolic hydroxyl group charateristic avsorption band 3435cm
-1occur, now benzoxazine open loop is completely described.When sample is further after 200 ℃ and 220 ℃ of curing 2h, belong to the charateristic avsorption band 1262cm of tertiary amine
-1further strengthen, illustrate that benzoxazine enters partial cross-linked formation polymkeric substance.When sample is further after 240 ℃ of curing 2h, 1262cm
-1the absorption at place is substantially constant, illustrates that benzoxazine has been cross-linked to form polymkeric substance completely.
The thermal characteristics of Polybenzoxazine of the present invention:
The thermal characteristics of Polybenzoxazine is mainly analyzed by DMA and TGA, and test acquired results is in Table 1.
The thermal characteristics of table 1 Polybenzoxazine
Table 1 is the thermal characteristics of Polybenzoxazine resin, and in accompanying drawing, DMA and TGA spectrogram can be seen, the Tg of P (BZ-a) is 322 ℃, and in nitrogen atmosphere, 5% and 10% thermal weight loss temperature is respectively 374 ℃ and 423 ℃, and carbon yield is 64%.In air atmosphere, 5% and 10% thermal weight loss temperature is respectively 403 ℃ and 453 ℃.As a comparison, the benzoxazine monomer that we have listed by cyano-containing directly solidifies the thermal characteristics data of gained Polybenzoxazine.By table, we can find out, contrast monocycle Polybenzoxazine P (NBZ-m) and dicyclo Polybenzoxazine P (NBZ-b), and the Tg of P (BZ-a) has improved respectively 92 ℃ and 64 ℃, and its thermostability also increases.Illustrate that the raising of triazine ring content in Polybenzoxazine resin has improved the thermal characteristics of Polybenzoxazine resin greatly.
The present invention adopts a kind of new synthetic method: allow cyano group first form triazine ring, and then synthetic benzoxazine monomer it is heating and curing obtain the Polybenzoxazine that amounts of triazine is high.Concrete steps are the raw material phenol first synthesizing containing triazine, and then to take containing the phenol of triazine, formaldehyde, aminated compounds be the synthetic benzoxazine monomer containing triazine of raw material, and finally heating makes its ring-opening polymerization form Polybenzoxazine containing the benzoxazine monomer of triazine.Due to the benzoxazine monomer adopting containing triazine, just do not need cyano group in solidification process to be converted into this single step reaction of triazine ring, so in Polybenzoxazine, amounts of triazine is very high, also greatly reduce heat curing temperature simultaneously.
The present invention has the following advantages:
1, in the novel monomeric of synthesized of the present invention, contain triazine structure, can greatly improve the content of triazine in gained Polybenzoxazine resin, thereby can significantly improve thermotolerance, carbon residue rate, flame retardant resistance and the wave penetrate capability of Polybenzoxazine.
2, resulting Polybenzoxazine P (BZ-a) has excellent thermal characteristics, T
gup to 322 ℃; In nitrogen atmosphere, 5% and 10% thermal weight loss temperature is respectively 374 ℃ and 423 ℃; In air atmosphere, 5% and 10% thermal weight loss temperature is respectively up to 403 ℃ with 453 ℃.Can be used for making 250 ℃ of above high temperature materials that use.
3, gained Polybenzoxazine P (BZ-a) has higher carbon yield.At N
2in atmosphere, be heated to 800 ℃, carbon yield is 64%, can prepare ablation resistant material.
4, gained benzoxazine monomer BZ-a of the present invention has lower solidification value.Owing to not needing to carry out the thermal transition of cyano group in solidification process, therefore reduced the solidification value containing cyanogen benzoxazine.
5, raw material used in the present invention: to cyano group phenol, paraformaldehyde, formalin and various amines etc., the overwhelming majority is commerical prod, and cost is lower.
6, the synthetic method of benzoxazine monomer used herein and the curing process of Polybenzoxazine are simple and easy to do, are applicable to most of factories and carry out suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is containing the preparation feedback route of many rings benzoxazine monomer of triazine;
Fig. 2 is benzoxazine BZ-a's
1h and
13c NMR spectrogram;
Fig. 3 is the FTIR spectrogram of benzoxazine BZ-a;
Fig. 4 is the MS spectrogram of benzoxazine BZ-a;
Fig. 5 is the DSC spectrogram of benzoxazine BZ-a;
Fig. 6 is the curing FTIR spectrogram of benzoxazine BZ-a;
Fig. 7 is the DMA spectrogram of Polybenzoxazine P (BZ-a);
Fig. 8 is the TGA spectrogram of Polybenzoxazine P (BZ-a).
Embodiment
Below by specific examples, the present invention is specifically described, it is important to point out: this example is only applicable to further illustrate of the present invention, but do not limit to its scope.Those skilled in the art, after reading this patent, are apparent in the various improvement of having done without prejudice to essence of the present invention, all belong to the claimed scope of the present invention.
Synthetic containing the trihydric phenol (TP) of triazine ring: add successively 10.0g 4-hydroxybenzonitrile, 1.8mL trifluoromethanesulfonic acid, 40mL methylene dichloride in 100mL flask, at room temperature react 2h, obtain yellow suspension liquid.With the 1N NaOH aqueous solution and deionized water wash for several times, stratification, get methylene dichloride concentrated mutually after, obtain white solid.Productive rate 92%.
1H?NMR(300MHz，CDCl
3，ppm)：6.97(d，6H，Ph-H)，8.55(d，6H，Ph-H)，10.29(s，3H，Ph-O-H).
Synthetic containing many rings benzoxazine monomer (BZ-a) of triazine: add successively 1.0g TP, 0.504g paraformaldehyde, 0.76mL aniline, 0.5mL triethylamine, 50mL dehydrated alcohol in 100mL there-necked flask, stir miscible, be warming up to gradually backflow, and react 4h under reflux temperature, obtain yellow benzoxazine monomer solution.Reaction mixture is steamed and desolventized, and gained crude product is with obtaining light yellow crystal, productive rate 81% after anhydrous diethyl ether recrystallization.
1H?NMR(300MHz，CDCl
3，ppm)：4.80(s，6H，N-CH
2-Ph)，5.47(s，6H，N-CH
2-O)，6.93-8.53(m，24H，Ar-H).
13C?NMR(75MHz，CDCl
3，ppm)：δ170.6(Triazine?ring-C)，158.2，148.1，129.5，129.1，128.9，127.8，121.9，120.8，118.6，117.3(Ar-C)，80.3(N-CH
2-O，oxazine?ring)，50.6(N-CH
2-Ph，oxazine?ring).FTIR(KBr，cm
-1)：3037，2916(Ph-H)，1601，1521，1364(triazine)，1583，1496(Ph)，941(oxazine?ring)，1232(stretch，C-O-C).HRMS(ESI)：Calcd?for?C
45H
36N
6O
3(M+H)
+：709.2882，found：709.2907.Anal.calcd?for?C
45H
36N
6O
3：C，76.25％；H，5.12％；N，11.86％.Found：C，76.27％；H，5.12％；N，11.84％.
Synthetic containing the trihydric phenol (TP) of triazine ring: add successively 10.0g 4-hydroxybenzonitrile, 1.6mL trifluoroacetic acid, 40mL methylene dichloride in 100mL flask, at room temperature react 3h, obtain yellow suspension liquid.With the 1N NaOH aqueous solution and deionized water wash for several times, stratification, get methylene dichloride concentrated mutually after, obtain white solid.Productive rate 90%.
1H?NMR(300MHz，CDCl
3，ppm)：6.97(d，6H，Ph-H)，8.55(d，6H，Ph-H)，10.29(s，3H，Ph-O-H).
Synthetic containing many rings benzoxazine monomer (BZ-a) of triazine: add successively 1.0g TP, 1.36mL 37% formalin, 0.76mL aniline, 0.5mL triethylamine, 30mL dioxane in 100mL there-necked flask, stir miscible, be warming up to gradually backflow, and react 3h under reflux temperature, obtain yellow benzoxazine monomer solution.Reaction mixture is steamed and desolventized, and gained crude product is with obtaining light yellow crystal, productive rate 86% after dehydrated alcohol recrystallization.
Synthetic containing the trihydric phenol (TP) of triazine ring: add successively 10.0g 4-hydroxybenzonitrile, 1.6mL trifluoroacetic acid, 35mL chloroform in 100mL flask, at room temperature react 2h, obtain yellow suspension liquid.With the 1N NaOH aqueous solution and deionized water wash for several times, stratification, get methylene dichloride concentrated mutually after, obtain white solid.Productive rate 93%.
1H?NMR(300MHz，CDCl
3，ppm)：6.97(d，6H，Ph-H)，8.55(d，6H，Ph-H)，10.29(s，3H，Ph-O-H).
Synthetic containing many rings benzoxazine monomer (BZ-a) of triazine: add successively 1.0g TP, 1.36mL 37% formalin, 0.76mL aniline, 0.5mL triethylamine, 30mL dioxane in 100mL there-necked flask, stir miscible, be warming up to gradually backflow, and react 3h under reflux temperature, obtain yellow benzoxazine monomer solution.Reaction mixture is steamed and desolventized, and gained crude product is with obtaining light yellow crystal, productive rate 86% after dehydrated alcohol recrystallization.
In 100mL there-necked flask, add successively 1.0g TP, 0.504g paraformaldehyde, 0.76mL aniline, 25mL chloroform, stir misciblely, be warming up to gradually backflow, and react 5h under reflux temperature, obtain yellow benzoxazine monomer solution.Reaction mixture is steamed and desolventized, and gained crude product is with obtaining light yellow crystal, productive rate 77% after re-crystallizing in ethyl acetate.
Embodiment 4 is synthetic containing many rings benzoxazine monomer (BZ-ala) of triazine
Synthetic containing the trihydric phenol (TP) of triazine ring: with embodiment 1.
Synthetic containing many rings benzoxazine monomer (BZ-ala) of triazine: in 50mL there-necked flask, add successively 2.0g TP, 1.01g paraformaldehyde, 0.74mL allyl amine, stir miscible, be warming up to gradually 90 ℃ of reaction 2h, obtain yellow benzoxazine monomer solution.Reaction mixture is steamed and desolventized, and gained crude product is with obtaining light yellow crystal, productive rate 89% after anhydrous diethyl ether recrystallization.
1H?NMR(300MHz，CDCl
3，ppm)：4.74(s，6H，N-CH
2-Ph)，5.43(s，6H，N-CH
2-O)，3.39(d，6H，N-CH
2-CH)，5.20(d，3H，＝CH
2)，5.23(d，3H，＝CH
2)，5.94(m，3H，-CH＝)，6.93-8.53(m，9H，Ar-H).
13C?NMR(75MHz，CDCl
3，ppm)：δ168.8(Triazine?ring-C)，157.1，126.9，128.1，127.2，122.3，119.5(Ar-C)，129.1(-CH＝CH
2)，111.3(-CH＝CH
2)，53.6(N-CH
2-CH＝)，83.2(N-CH
2-O，oxazine?ring)，49.9(N-CH
2-Ph，oxazine?ring).FTIR(KBr，cm
-1)：3123(＝C-H)，3033，2912(Ph-H)，1642(C＝C)，1605，1522，1367(triazine)，1495(Ph)，944(oxazine?ring)，1230(stretch，C-O-C).HRMS(ESI)：Calcd?for?C
36H
36N
6O
3(M+H)
+：601.2849，found：601.2852.Anal.calcdfor?C
36H
36N
6O
3：C，71.98％；H，6.04％；N，13.99％.Found：C，71.77％；H，6.10％；N，14.04％.
Synthetic containing the trihydric phenol (TP) of triazine ring: with embodiment 1.
Synthetic containing many rings benzoxazine monomer (BZ-appe) of triazine: add successively 1.0g TP, 0.504g paraformaldehyde, 112g 4-aminocarbonyl phenyl propargyl ether, 1.0mL aqueous sodium carbonate, 30mL dioxane in 100mL there-necked flask, stir miscible, be warming up to gradually backflow, and react 4h under reflux temperature, obtain yellow benzoxazine monomer solution.Reaction mixture is steamed and desolventized, and gained crude product is with obtaining light yellow crystal, productive rate 76% after anhydrous diethyl ether recrystallization.
1H?NMR(300MHz，CDCl
3，ppm)：2.50(s，3H，≡C-H)，4.67(s，6H，O-CH
2-C≡)，4.72(s，6H，N-CH
2-Ph)，5.40(s，6H，N-CH
2-O)，6.23-7.83(m，21H，Ar-H).
13C?NMR(75MHz，CDCl
3，ppm)：168.1(Triazine?ring-C)，157.3，149.0，129.1，129.1，128.2，127.0，120.5，118.6，118.2，116.1(Ar-C)，76.1(-C≡CH)，84.7(-C≡CH)，64.7(O-CH
2-C≡)，79.2(N-CH
2-O，oxazine?ring)，49.5(N-CH
2-Ph，oxazine?ring).FTIR(KBr，cm
-1)：3190(≡C-H)，3035，2914(Ph-H)，2112(C≡C)，1600，1519，1364(triazine)，1581，1495(Ph)，940(oxazine?ring)，1232(stretch，C-O-C).HRMS(ESI)：Calcd?for?C
54H
42N
6O
6(M+H)
+：871.3166，found：871.3170.Anal.calcd?for?C
54H
42N
6O
6：C，74.47％；H，4.86％；N，9.65％.Found：C，74.33％；H，4.82％；N，9.64％.
Synthetic containing the trihydric phenol (TP) of triazine ring: with embodiment 1.
Synthetic containing many rings benzoxazine monomer (BZ-appe) of triazine: add successively 1.0g TP, 0.504g paraformaldehyde, 112g 4-aminocarbonyl phenyl propargyl ether, 30mL dioxane in 100mL there-necked flask, stir miscible, be warming up to gradually backflow, and react 5h under reflux temperature, obtain yellow benzoxazine monomer solution.Reaction mixture is steamed and desolventized, and gained crude product is with obtaining light yellow crystal, productive rate 72% after anhydrous diethyl ether recrystallization.
Synthetic containing the trihydric phenol (TP) of triazine ring: with embodiment 1.
Synthetic containing many rings benzoxazine monomer (BZ-appa) of triazine: add successively 1.0g TP, 0.504g paraformaldehyde, 0.99g 4-acetylenylaniline, 30mL dioxane, 1mL wet chemical in 100mL there-necked flask, stir miscible, be warming up to gradually backflow, and react 5h under reflux temperature, obtain yellow benzoxazine monomer solution.Reaction mixture is steamed and desolventized, and gained crude product is with obtaining light yellow crystal, productive rate 68% after anhydrous diethyl ether recrystallization.
1H?NMR(300MHz，CDCl
3，ppm)：3.02(s，3H，≡C-H)，4.75(s，6H，N-CH
2-Ph)，5.44(s，6H，N-CH
2-O)，5.92-7.55(m，21H，Ar-H).
13C?NMR(75MHz，CDCl
3，ppm)：169.3(Triazinering-C)，158.6149.9，129.7，129.8，128.6，128.0，120.4，120.1，118.2，117.5(Ar-C)，81.1(-C≡CH)，72.1(-C≡CH)，76.1(N-CH
2-O，oxazine?ring)，51.54(N-CH
2-Ph，oxazine?ring).FTIR(KBr，cm
-1)：3172(≡C-H)，3030，2911(Ph-H)，2097(C≡C)，1601，1522，1366(triazine)，1583，1496(Ph)，942(oxazine?ring)，1235(stretch，C-O-C).HRMS(ESI)：Calcd?for?C
51H
36N
6O
3(M+H)
+：781.2849，found：781.2844.Anal.calcd?for?C
51H
36N
6O
3：C，78.44％；H，4.65％；N，10.76％.Found：C，78.39％；H，4.62％；N，10.60％.
Synthetic containing the trihydric phenol (TP) of triazine ring: with embodiment 1.
Synthetic containing many rings benzoxazine monomer (BZ-appa) of triazine: add successively 1.0g TP, 0.504g paraformaldehyde, 0.99g 4-acetylenylaniline in 100mL there-necked flask, 50mL methyl alcohol, N, N-diethyl α-amino isopropyl alcohol, stir miscible, be warming up to gradually backflow, and react 5h under reflux temperature, obtain yellow benzoxazine monomer solution.Reaction mixture is steamed and desolventized, and gained crude product is with obtaining light yellow crystal, productive rate 62% after anhydrous diethyl ether recrystallization.
Synthetic containing the trihydric phenol (TP) of triazine ring: with embodiment 1.
Synthetic containing many rings benzoxazine monomer (BZ-mapa) of triazine: add successively 1.0g TP, 0.504g paraformaldehyde, 0.99g 2-acetylenylaniline, 30mL dioxane in 100mL there-necked flask, stir miscible, be warming up to gradually backflow, and react 5h under reflux temperature, obtain yellow benzoxazine monomer solution.Reaction mixture is steamed and desolventized, and gained crude product is with obtaining light yellow crystal, productive rate 69% after anhydrous diethyl ether recrystallization.
1H?NMR(300MHz，CDCl
3，ppm)：3.01(s，3H，≡C-H)，4.75(s，6H，N-CH
2-Ph)，5.44(s，6H，N-CH
2-O)，5.91-7.86(m，21H，Ar-H).
13C?NMR(75MHz，CDCl
3，ppm)：169.2(Triazinering-C)，158.6149.9，129.7，129.3，128.6，128.6，120.4，120.1，112.2，119.2(Ar-C)，80.9(-C≡CH)，71.8(-C≡CH)，76.0(N-CH
2-O，oxazine?ring)，51.3(N-CH
2-Ph，oxazine?ring).FTIR(KBr，cm
-1)：3171(≡C-H)，3030，2910(Ph-H)，2096(C≡C)，1601，1522，1366(triazine)，1580，1493(Ph)，942(oxazine?ring)，1235(stretch，C-O-C).HRMS(ESI)：Calcd?for?C
51H
36N
6O
3(M+H)
+：781.2849，found：781.2843.Anal.calcd?for?C
51H
36N
6O
3：C，78.44％；H，4.65％；N，10.76％.Found：C，78.38％；H，4.632％；N，10.60％.
Synthetic containing the trihydric phenol (TP) of triazine ring: with embodiment 1.
Synthetic containing many rings benzoxazine monomer (BZ-pt) of triazine: add successively 1.0g TP, 1.36mL 37% formalin, 0.92mL4-monomethylaniline, 0.5mL triethylamine, 30mL dioxane in 100mL there-necked flask, stir miscible, be warming up to gradually backflow, and react 3h under reflux temperature, obtain yellow benzoxazine monomer solution.Reaction mixture is steamed and desolventized, and gained crude product is with obtaining light yellow crystal, productive rate 88% after anhydrous diethyl ether recrystallization.
1H?NMR(300MHz，CDCl
3，ppm)：2.35(s，9H，-CH
3)，4.73(s，6H，N-CH
2-Ph)，5.52(s，6H，N-CH
2-O)，6.33-8.22(m，21H，Ar-H).
13C?NMR(75MHz，CDCl
3，ppm)：δ170.7(Triazinering-C)，158.2，1478.1，129.5，129.1，128.3，127.8，121.2，120.0，117.6，115.6(Ar-C)，80.4(N-CH
2-O，oxazine?ring)，50.9(N-CH
2-Ph，oxazine?ring)，22.4(-CH
3).FTIR(KBr，cm
-1)：3032，2912(Ph-H)，1601，1521，1364(triazine)，1580，1492(Ph)，940(oxazine?ring)，1231(stretch，C-O-C).HRMS(ESI)：Calcd?for?C
48H
42N
6O
3(M+H)
+：751.3318，found：751.3302.Anal.calcd?forC
48H
42N
6O
3：C，76.78％；H，5.46％；N，11.19％.Found：C，76.67％；H，5.32％；N，11.24％.
Embodiment 11 is synthetic containing many rings benzoxazine monomer (BZ-ca) of triazine
Synthetic containing the trihydric phenol (TP) of triazine ring: with embodiment 1.
Synthetic containing many rings benzoxazine monomer (BZ-ca) of triazine: in 50mL there-necked flask, add successively 2.0g TP, 1.01g paraformaldehyde, 0.82mL hexahydroaniline, stir miscible, be warming up to gradually 90C reaction 2h,, obtain yellow benzoxazine monomer solution.Reaction mixture is steamed and desolventized, and gained crude product is with obtaining light yellow crystal, productive rate 89% after anhydrous diethyl ether recrystallization.
1H?NMR(300MHz，CDCl
3，ppm)：1.46(m，18H，Cyclohexyl-CH
2-)，1.52(m，12H，Cyclohexyl-CH
2-)，2.67(t，3H，Cyclohexyl-CH-N)，4.75(s，6H，N-CH
2-Ph)，5.44(s，6H，N-CH
2-O)，6.93-7.65(m，9H，Ar-H).
13C?NMR(75MHz，CDCl
3，ppm)：δ168.8(Triazinering-C)，157.1，126.9，128.1，127.2，122.3，119.5(Ar-C)，83.2(N-CH
2-O，oxazine?ring)，49.9(N-CH
2-Ph，oxazine?ring).48.9，30.5，27.4，21.6(Cyclohexyl-C).FTIR(KBr，cm
-1)：3033，2912(Ph-H)，1642(C＝C)，1605，1522，1367(triazine)，1495(Ph)，943(oxazine?ring)，1230(stretch，C-O-C).HRMS(ESI)：Calcd?for?C
45H
54N
6O
3(M+H)
+：727.4257，found：727.4243.Anal.calcd?forC
45H
54N
6O
3：C，74.35％；H，7.49％；N，11.56％.Found：C，74.27％；H，7.50％；N，11.54％.
Embodiment 12 is containing the preparation of the Polybenzoxazine P (BZ-a) of triazine ring
The BZ-a monomer of 0.9g triazine ring is poured in aluminium matter rectangular die, gradient increased temperature in Constant Temp. Oven, the Polybenzoxazine P (BZ-a) obtaining containing triazine ring is solidified in segmentation, and curing temperature-rise period is: 140 ℃/2h, 160 ℃/2h, 180 ℃/2h, 200 ℃/2h, 220 ℃/2h, 240 ℃/2h.
Embodiment 13 is containing the preparation of the Polybenzoxazine P (BZ-a) of triazine ring
The BZ-a monomer of 0.5g triazine ring is poured in aluminium matter rectangular die, gradient increased temperature in Constant Temp. Oven, the Polybenzoxazine P (BZ-a) obtaining containing triazine ring is solidified in segmentation, and curing temperature-rise period is: 160 ℃/2h, 180 ℃/3h, 200 ℃/3h, 220 ℃/1h, 240 ℃/1h.
Embodiment 14 is containing the preparation of the Polybenzoxazine P (BZ-ala) of triazine ring
The BZ-ala monomer of 1.2g triazine ring is poured in aluminium matter rectangular die, gradient increased temperature in Constant Temp. Oven, the Polybenzoxazine P (BZ-ala) obtaining containing triazine ring is solidified in segmentation, and curing temperature-rise period is: 140 ℃/2h, 160 ℃/2h, 180 ℃/2h, 200 ℃/2h, 220 ℃/2h, 240 ℃/2h.
Embodiment 15 is containing the preparation of the Polybenzoxazine P (BZ-appe) of triazine ring
The BZ-appe monomer of 1.6g triazine ring is poured in aluminium matter rectangular die, gradient increased temperature in Constant Temp. Oven, the Polybenzoxazine P (BZ-a) obtaining containing triazine ring is solidified in segmentation, and curing temperature-rise period is: 140 ℃/1h, 160 ℃/1h, 180 ℃/2h, 200 ℃/2h, 220 ℃/2h, 240 ℃/2h, 260 ℃/2h.
Claims (4)
1. containing many rings benzoxazine monomer of triazine, it is characterized in that, its structural formula is
Wherein R is: phenyl, p-methylphenyl, to ethynyl phenyl, cyclohexyl, allyl group.
2. the preparation method of the many rings benzoxazine monomer containing triazine according to claim 1, is characterized in that, step is as follows:
(a) under room temperature, in methylene chloride, trichloromethane, acetone or tetrahydrofuran (THF), add raw material to cyano group phenol, catalyzer trifluoromethanesulfonic acid or trifluoroacetic acid, mixed solution at room temperature reacts 2-3h, must be containing the trihydric phenol TP of triazine after gained purified solution is dried;
(b) the trihydric phenol TP, aminated compounds, the formaldehyde that under room temperature, in solvent dioxane, ethanol, methyl alcohol, chloroform, toluene or tetrahydrofuran (THF), add step (a) to obtain, mixed solution reacts 3-4h under reflux conditions, must be containing many rings benzoxazine monomer BZ of triazine after gained purified solution is dried; Described aminated compounds is aniline, 4-monomethylaniline, 4-acetylenylaniline, hexahydroaniline or allyl amine.
3. the preparation method of the many rings benzoxazine monomer containing triazine according to claim 2, is characterized in that, solvent in step (a), to the weight part ratio of cyano group phenol, catalyzer, is 60～80:10～40:0.2～2.
4. the preparation method of the many rings benzoxazine monomer containing triazine according to claim 2, is characterized in that, in step (b), the weight part ratio of solvent, trihydric phenol TP, aminated compounds, formaldehyde is 30～80:10～30:20～70:20～60.
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| JP6464525B2 (en) * | 2015-05-11 | 2019-02-06 | 国立大学法人東京工業大学 | Thermosetting composition and novel compound |
| CN105566312B (en) * | 2015-12-29 | 2019-04-19 | 高鼎精细化工(昆山)有限公司 | Oxo nitrogen containing three azacyclo-s is for benzocyclohexane and preparation method thereof |
| CN111100291B (en) * | 2018-10-25 | 2021-08-31 | 中国科学院上海硅酸盐研究所 | Preparation method of polybenzoxazine-reinforced three-dimensional graphene foam |
| CN110438577A (en) * | 2019-07-26 | 2019-11-12 | 温多利遮阳材料（德州）股份有限公司 | Polypropylene flame redardant composite material and its product |
| CN112778292B (en) * | 2020-12-25 | 2022-09-02 | 长沙新材料产业研究院有限公司 | Benzoxazine compound and preparation method thereof |
| CN113248158B (en) * | 2021-05-31 | 2021-10-29 | 安徽鑫民玻璃股份有限公司 | High-heat-resistance explosion-proof glass and production process thereof |
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| EP1297948A2 (en) * | 2001-09-29 | 2003-04-02 | Mitsubishi Polyester Film GmbH | Hydrolysis-resistant, transparent, amorphous film made from a crystallizable thermoplastic and process for its production |
| CN1654539A (en) * | 2004-02-02 | 2005-08-17 | 田村化研株式会社 | Thermosetting resin compositions and film articles |
| CN1667023A (en) * | 2004-03-09 | 2005-09-14 | 三菱工程塑料株式会社 | Flame-retardant polyamide resin composition and extrusion-molded product |
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| EP0964096A2 (en) * | 1998-06-11 | 1999-12-15 | Ciba SC Holding AG | Process for improving the photochemical and thermal stability of dyeings and printings of polyester fibrous materials |
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| EP1297948A2 (en) * | 2001-09-29 | 2003-04-02 | Mitsubishi Polyester Film GmbH | Hydrolysis-resistant, transparent, amorphous film made from a crystallizable thermoplastic and process for its production |
| CN1654539A (en) * | 2004-02-02 | 2005-08-17 | 田村化研株式会社 | Thermosetting resin compositions and film articles |
| CN1667023A (en) * | 2004-03-09 | 2005-09-14 | 三菱工程塑料株式会社 | Flame-retardant polyamide resin composition and extrusion-molded product |
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