CN103992481A - Hyperbranched polyphosphazene flame retardant charring agent and preparing method thereof - Google Patents
Hyperbranched polyphosphazene flame retardant charring agent and preparing method thereof Download PDFInfo
- Publication number
- CN103992481A CN103992481A CN201410196403.8A CN201410196403A CN103992481A CN 103992481 A CN103992481 A CN 103992481A CN 201410196403 A CN201410196403 A CN 201410196403A CN 103992481 A CN103992481 A CN 103992481A
- Authority
- CN
- China
- Prior art keywords
- fire
- forming agent
- hyperbranched poly
- hexachlorocyclotriphosphazene
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 52
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 49
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title abstract description 21
- 238000000034 method Methods 0.000 title abstract description 11
- 229920002627 poly(phosphazenes) Polymers 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 claims description 30
- 238000002360 preparation method Methods 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 claims description 8
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- -1 4,4 '-dioxydiphenyl methane Chemical compound 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 4
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000004437 phosphorous atom Chemical group 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical group NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 4
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- WHJMGMTWMIGGQF-UHFFFAOYSA-N 1,1'-biphenyl;methanamine Chemical group NC.C1=CC=CC=C1C1=CC=CC=C1 WHJMGMTWMIGGQF-UHFFFAOYSA-N 0.000 claims description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical group NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- 229940058015 1,3-butylene glycol Drugs 0.000 claims description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical group CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 2
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical group CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims description 2
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical group CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 claims description 2
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 claims description 2
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical group NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 claims description 2
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 claims description 2
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 claims description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 2
- IWFHBRFJOHTIPU-UHFFFAOYSA-N 4,5-dichlorobenzene-1,2-diamine Chemical group NC1=CC(Cl)=C(Cl)C=C1N IWFHBRFJOHTIPU-UHFFFAOYSA-N 0.000 claims description 2
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 claims description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 2
- MERLDGDYUMSLAY-UHFFFAOYSA-N 4-[(4-aminophenyl)disulfanyl]aniline Chemical compound C1=CC(N)=CC=C1SSC1=CC=C(N)C=C1 MERLDGDYUMSLAY-UHFFFAOYSA-N 0.000 claims description 2
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical group NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 2
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims description 2
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000004367 cycloalkylaryl group Chemical group 0.000 claims description 2
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical group NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 claims description 2
- RLMGYIOTPQVQJR-UHFFFAOYSA-N cyclohexane-1,3-diol Chemical compound OC1CCCC(O)C1 RLMGYIOTPQVQJR-UHFFFAOYSA-N 0.000 claims description 2
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims description 2
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical group CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 claims description 2
- XOOMNEFVDUTJPP-UHFFFAOYSA-N naphthalene-1,3-diol Chemical compound C1=CC=CC2=CC(O)=CC(O)=C21 XOOMNEFVDUTJPP-UHFFFAOYSA-N 0.000 claims description 2
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 claims description 2
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 2
- RUOPINZRYMFPBF-UHFFFAOYSA-N pentane-1,3-diol Chemical compound CCC(O)CCO RUOPINZRYMFPBF-UHFFFAOYSA-N 0.000 claims description 2
- 125000004193 piperazinyl group Chemical group 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical group CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000004033 plastic Substances 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000005060 rubber Substances 0.000 abstract description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 abstract 1
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 238000005187 foaming Methods 0.000 abstract 1
- 238000005580 one pot reaction Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000003918 triazines Chemical class 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 235000019633 pungent taste Nutrition 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
Landscapes
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
An efficient hyperbranched polyphosphazene flame retardant charring agent is prepared by reacting hexachlorocyclotriphosphazene with a binary compound containing two active groups. The charring agent has characteristics of good foaming charring performance, excellent flame retardant effects and good processing performance, and can be widely used in plastics, rubber, coating, adhesives, and other polymer materials. A preparing method adopts a one-pot method, and has characteristics of continuous reaction process, short reaction time and high production efficiency. By controlling the mole ratio of the hexachlorocyclotriphosphazene to the binary compound, no end-capping agent is added in the reaction process. When compared with the addition of end-capping agents in synthesis processes in triazine type charring agent patents, the synthetic process of the charring agent is simplified.
Description
Technical field
The invention belongs to field of polymer material preparing technology, relate to a kind of expansion type flame-retarding char-forming agent and preparation method thereof, relate in particular to fire-retardant char-forming agent of a kind of hyperbranched poly phosphonitrile and preparation method thereof.
Background technology
Expansion type flame retardant is one of environment-friendly flame retardant agent type of widespread use in recent years, it has not only overcome halogenated flame retardant and when burning, has easily emitted pungency and corrosive gas and smog, many molten drops, shortcoming that easily personnel that cause suffocate, and has overcome the detrimentally affect that inorganic combustion inhibitor brings the mechanics of materials, processibility the subject of knowledge and the object of knowledge greatly due to addition.Expansion type flame retardant (IFR), because the charcoal layer of its unique fire retardant mechanism and Halogen, low cigarette, low toxicity, generation can prevent the characteristics such as polymkeric substance molten drop effectively, meets the requirement of preserving the ecological environment now.
Generally speaking, IFR comprises 3 parts, i.e. carbon source (being often polyol, as tetramethylolmethane), acid source (as ammonium polyphosphate) and source of the gas (as trimeric cyanamide).In traditional Intumscent Flame Retardant System polyphosphoric acid amine-tetramethylolmethane-trimeric cyanamide, tetramethylolmethane (PER) is a kind of compound with strong polarity, in use with bad, the easy reunion of macromolecular material consistency, exist poor heat stability, water-fast and poor durability, be easy to move to water-soluble large, the shortcoming such as addition is large, viscosity is high, processing characteristics is not good, charring rate is poor of matrix surface, greatly limited further applying of IFR.And existing triazines char-forming agent exists synthesis technique complexity, the shortcomings such as production cycle length.Therefore, the exploitation of novel char-forming agent is one of important directions of current expansion type flame retardant research.In recent years, phosphazene flame retardant as a kind of environmentally friendly flame retardant products development rapidly, is studied widely and is applied.
Phosphazene polymer is that a class skeleton has phosphorus, nitrogen Dan Shuanjian alternative arrangement as backbone structure, by connect different functional substituted radicals on phosphorus atom, obtain a class novel inorganic organic hybrid macromole of property, they have inorganics and organic excellent properties concurrently: be easy to functionalized, main chain is soft, optical clear, good biocompatibility, biodegradable etc., therefore be widely used in biological medicine material, fire retardant material, optical material etc.Have the characteristic that traditional organic polymer and inorganics hardly match, the phosphorus on main chain, nitrogen have been given its good flame retardant properties simultaneously; Organic constituent on side chain has been given the consistency good with matrix, and polyphosphonitrile environmental protection.Thereby can give the water tolerance that organic polymer matrix is good, high temperature resistant, low temperature resistant, resistance to solvent, oil resistant class and chemical, radiation hardness, mechanical property and optical transparence are good, photo and thermal stability is high and do not burn and the premium properties such as fire-retardant by the polyphosphonitrile of Choice and design different structure.
In the molecule of cyclic phosphazene compound, on phosphorus atom, contain two commutable active chlorine atoms, by various substitution reactions, can obtain multiple derivative, and phosphazene derivative has higher phosphorus, nitrogen content, this has just determined no matter be as flame retardant type functional materials or the flame-retardant additive of various materials, and this compounds is all with a wide range of applications and good application prospect.
Summary of the invention
The present invention is intended to overcome the deficiencies in the prior art, and the fire-retardant char-forming agent of hyperbranched poly phosphonitrile that a kind of thermostability is better, charring rate is higher is provided.
Another object of the present invention is to provide that a kind of reaction process is continuous, the reaction times is short, the preparation method of the fire-retardant char-forming agent of the simple above-mentioned hyperbranched poly phosphonitrile of synthesis technique.
For solving above technical problem, the technical scheme that the present invention takes is:
The fire-retardant char-forming agent of hyperbranched poly phosphonitrile, it has following general structure:
Wherein, Z is NH, N, S or O; R is a kind of in piperazine ring, straight chained alkyl, branched-chain alkyl, cycloalkyl and aryl.
Further, in R structure, also can contain one or more in S, O, N, Si and P atom.
Further, R can be on straight chain with between the straight chained alkyl of phenyl ring, a plurality of phenyl ring with aryl, cycloalkaryl or the cycloalkyl aryl of alkyl.
The preparation method of the above-mentioned fire-retardant char-forming agent of hyperbranched poly phosphonitrile, can represent by following reaction equation:
Wherein, HZ-R-ZH is the binary compound that contains two active groups, described active group can with hexachlorocyclotriphosphazene structure in chlorine atom generation substitution reaction;
Described preparation method comprises the steps:
(1), by hexachlorocyclotriphosphazene and general structure, being HZ-R-ZH, binary compound is dispersed in respectively in solvent, obtains hexachlorocyclotriphosphazene solution and binary compound solution;
(2), under the temperature condition of 0 ℃～10 ℃, in the described binary compound solution stirring, dropwise add described hexachlorocyclotriphosphazene solution, after dropwising, maintain temperature of reaction constant, continue reaction 1-4 hour; The mol ratio of described binary compound and described hexachlorocyclotriphosphazene is between 4:1～6:1;
(3) temperature of the reaction system through step (2) is increased to 30 ℃-70 ℃, and adds wherein acid binding agent, continue reaction 3-6 hour; The mol ratio of described acid binding agent and described hexachlorocyclotriphosphazene is between 6:1-7:1;
(4) temperature of the reaction system through step (3) is increased to 90 ℃-150 ℃, continues reaction 6-10 hour;
(5) stop stirring, and gained solid is carried out to suction filtration, washing, dry, obtain the fire-retardant char-forming agent of described hyperbranched poly phosphonitrile.
Preferably, the concentration of hexachlorocyclotriphosphazene solution described in step (1) is between 0.5mol/L～10mol/L.
Preferably, described binary compound is Ursol D, quadrol, hexanediamine, butanediamine, piperazine, N, N-dimethyl-1,3-propylene diamine, N-aminoethyl piperazine, 4,4 '-diaminodiphenyl oxide, DDS, 4,4 '-diaminodiphenylmethane, adjacent biphenyl methylamine, O-Phenylene Diamine, 1,2-propylene diamine, 1,3-propylene diamine, 2 methyl pentamethylenediamine, 2,6-tolylene diamine, 2,4 di amino toluene, 3 diethyl aminopropylamine, diethyl toluene diamine, hydroxyethylethylene diamine, 1,2-cyclohexanediamine, 4,5-dichloro O-Phenylene Diamine, 2,2 '-bis-[4-(4-amino-benzene oxygen phenyl)] propane, 3,3 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminodiphenyl sulfide, 4,4 '-diamino diphenyl disulfide, Resorcinol, pentanediol, 4,4 '-dihydroxy diphenyl ether, 4,4 '-dioxydiphenyl methane, BDO, ethylene glycol, 1,3 butylene glycol, 1,3-pentanediol, 1,3 cyclohexanediol, Isosorbide-5-Nitrae-cyclohexanediol, 2-ethyl-1,3-hexylene glycol, pyrocatechol, Resorcinol, 1,5-dihydroxy naphthlene, 1,3-naphthalenediol, 2,7 dihydroxy naphthalene, toluhydroquinone, 4,4 '-dihydroxyl diphenyl sulfide, 4,4 '-dihydroxyl diphenyl disulfide, Isosorbide-5-Nitrae-benzene dimethanethiol, 4,4 '-dimercapto diphenyl sulfide, 4, the combination of one or more in 4 '-dimercapto diphenyl disulfide and Isosorbide-5-Nitrae-thioresorcin.
Preferably, described acid binding agent is one or several mixtures that mix with arbitrary proportion in alkali metal hydroxide, alkaline carbonate or alkali metal hydrocarbonate; And the volumetric molar concentration of described acid binding agent is 1-10mol/L.
Further, described alkali metal hydroxide is NaOH or KOH; Described alkaline carbonate is Na
2cO
3or K
2cO
3; Described alkali metal hydrocarbonate is NaHCO
3or KHCO
3.
Preferably, drying conditions is vacuum-drying 2～10 hours at 50 ℃～100 ℃ in step (5), to reach good drying effect.
Due to the enforcement of above technical scheme, the present invention compared with prior art tool has the following advantages:
The present invention designs by dissaving structure, make full use of that super branched molecule end group is many, viscosity is low, easily process with other additive mixtures, high temperature easily becomes the advantages such as charcoal, prepared the fire-retardant char-forming agent of a kind of efficient polyphosphonitrile, weightless 1% temperature is all more than 340 ℃, the carbon residue amount of 600 ℃ of high temperature substantially can reach 60% and more than; It has fabulous charcoal, excellent flame retardant effect and the good processing characteristics of being foamed into, and owing to being hyperbranched structure, so flame retardant effect is lasting, there is not the problem of volatilization, stripping and migration, can be widely used in the macromolecular materials such as plastics, rubber, coating, tackiness agent.
Preparation method of the present invention adopts one kettle way, has reaction process continuous, and the reaction times is short, the feature that production efficiency is high.By controlling the mol ratio of hexachlorocyclotriphosphazene and binary compound, in reaction process, need not add end-capping reagent, and in building-up process, add end-capping reagent to compare in some triazines char-forming agent patents, simplified synthesis technique.
Accompanying drawing explanation
Fig. 1 is the infrared spectra comparison diagram of the prepared fire-retardant char-forming agent of hyperbranched poly phosphonitrile (a) of embodiment 1 and hexachlorocyclotriphosphazene (b).
Embodiment
Below in conjunction with accompanying drawing and specific embodiment, the present invention will be further described in detail, but be not limited to these embodiment.
Embodiment 1
0.2mol piperazine is dissolved in to 70mL ethanol, joins in the 500mL there-necked flask that reflux condensing tube, constant pressure funnel, agitator are housed, start stirring; 0.05mol hexachlorocyclotriphosphazene is dissolved in 100mL dioxane, and is dropwise added drop-wise in above-mentioned piperazine solution by constant pressure funnel, maintain the temperature at 0 ℃ and react 4 hours; Then temperature of reaction is risen to 50 ℃, 0.3molNaOH is dissolved in 20mL water, be slowly added drop-wise to above-mentioned reaction system, at this temperature, continue reaction 6 hours; Finally temperature of reaction is risen to 95 ℃ again, continue reaction 9 hours, stop stirring, suction filtration, washing while hot 3 times, 80 ℃ of vacuum-dryings 8 hours, obtains micro-yellow solid product 22.54g.
Products therefrom is carried out to ultimate analysis, and result shows, sample actual measurement C, and N, the quality percentage composition of H is respectively 39.2%, 30.5%, 6.37%, and C in the fire-retardant char-forming agent of hyperbranched poly phosphonitrile, N, the theoretical percentage composition of H is respectively 41.0%, 32.9%, 6.8%, and both are basically identical.Fig. 1 is the infrared spectrogram of products therefrom (a) and hexachlorocyclotriphosphazene (b), can find out 3420cm from Fig. 1 (a)
-1the stretching vibration peak that has occurred N-H, 2970-2840cm
-1for the stretching vibration peak of C-H, 1220cm
-1for the stretching vibration peak of P=N, 827cm
-1for the stretching vibration peak of C-N, and 567cm
-1the stretching vibration peak of the P-Cl at place is vanished from sight, and illustrates that Cl is substituted.Comprehensive above analysis, thinks that the fire-retardant char-forming agent of hyperbranched poly phosphonitrile of the present invention is successfully prepared.
The productive rate of the fire-retardant char-forming agent of hyperbranched poly phosphonitrile of the present embodiment gained is 95.4%, and the lower 357 ℃ of weightlessness of nitrogen atmosphere are that 1%, 600 ℃ of carbon residue amount is 68.1%.The fire-retardant char-forming agent of this hyperbranched poly phosphonitrile is joined in polypropylene matrix with 30% ratio, and its oxygen index is that 29, UL-94 reaches V-0 level.
In the present embodiment, the standard of oxygen index test institute foundation is ASTM D2863; The testing standard of vertical combustion UL-94 institute foundation is ASTM D3801-1996.
Embodiment 2
0.25mol quadrol is dissolved in to 25mL water, join the 500mL there-necked flask that reflux condensing tube, constant pressure funnel, agitator are housed, again the hexachlorocyclotriphosphazene of 0.05mol is dissolved in the tetrahydrofuran (THF) of 10mL, is dropwise added drop-wise in above-mentioned ethylenediamine solution, at 10 ℃, react 1 hour; Then be warming up to 70 ℃, by the Na of 0.32mol
2cO
3be dissolved in 40mL water, be slowly added drop-wise in this system, and continue reaction 3 hours at this temperature, be finally warming up to again 150 ℃, react 6 hours; Stop stirring, suction filtration, washing while hot 3 times is dried 2 hours at 100 ℃, obtains micro-yellow solid product 8.79g, and productive rate is 93.2%.In the present embodiment, the results of elemental analyses of products therefrom shows, C in the fire-retardant char-forming agent of hyperbranched poly phosphonitrile, and N, the theoretical percentage composition of H is respectively 28.4%, 43.1%, 7.1%, and measured value is respectively 27.2%, 42.5%, 6.18%, both are basically identical.Under nitrogen atmosphere, 342 ℃ of weightlessness of obtained flame-retardant char-forming agent are that 1%, 600 ℃ of carbon residue amount is 58.7%.
Embodiment 3:
0.3mol Ursol D is dissolved in to 100mL ethanol, join in the 500mL there-necked flask that reflux condensing tube, constant pressure funnel, agitator are housed, again the hexachlorocyclotriphosphazene of 0.05mol is dissolved in the benzene of 5mL, is dropwise added drop-wise in above-mentioned Ursol D solution, and at 5 ℃, react 3 hours; Then temperature of reaction is risen to 30 ℃, the KOH of 0.35mol is dissolved in the water of 50mL, be slowly added drop-wise in this reaction system, and continue reaction 8 hours at this temperature, be finally warming up to again 150 ℃, react 10 hours; Stop stirring, suction filtration, washing while hot 3 times, 50 ℃ of vacuum-dryings 10 hours, obtains micro-yellow solid product 36.7g, and productive rate is 94.6%.In the present embodiment, the results of elemental analyses of products therefrom shows, C in hyperbranched poly phosphonitrile char-forming agent, and N, the theoretical percentage composition of H is respectively 51.8%, 27.7%, 4.3%, and measured value is respectively 50.3%, 25.6%, 3.9%, both are basically identical.Under nitrogen atmosphere, 397 ℃ of weightlessness of obtained flame-retardant char-forming agent are that 1%, 600 ℃ of carbon residue amount is 69.8%.
Embodiment 4:
By 0.2mol4,4 '-diaminodiphenylsulfone(DDS) is dissolved in 80mL acetone, join in the 500mL there-necked flask that reflux condensing tube, constant pressure funnel, agitator are housed, again the hexachlorocyclotriphosphazene of 0.05mol is dissolved in to 10mL tetra-carbonoxides, dropwise be added drop-wise to above-mentioned 4, in 4 '-diaminodiphenylsulfone(DDS) solution, and at 10 ℃, react 1.5 hours; Then be warming up to 65 ℃, by 0.31molNaHCO
3be dissolved in 40mL water, be slowly added drop-wise in this reaction system, and continue reaction 3 hours at this temperature, be finally warming up to 110 ℃, then continue reaction 7 hours; Stop stirring, suction filtration, washing while hot 3 times, is dried 2 hours at 100 ℃, obtains white solid product 49.9g, and productive rate is 89.2%.In the present embodiment, the results of elemental analyses of product shows, C in hyperbranched poly phosphonitrile char-forming agent, and N, H, the theoretical percentage composition of S is respectively 51.6%, 11.8%, 3.5%, 11.4%, and measured value is respectively 50.3%, 10.3%, 2.9%, 10.5%, both are basically identical.Under nitrogen atmosphere, 387 ℃ of weightlessness of obtained flame-retardant char-forming agent are that 1%, 600 ℃ of carbon residue amount is 65.8%.
Embodiment 5:
0.25mol Resorcinol is dissolved in to 60mL ethanol, join the 500mL there-necked flask that reflux condensing tube, constant pressure funnel, agitator are housed, again the hexachlorocyclotriphosphazene of 0.05mol is dissolved in 50mL benzene, is dropwise added drop-wise in above-mentioned Resorcinol solution, and at 0 ℃, react 2 hours; Then the temperature of reaction system is risen to 60 ℃, by the K of 0.16mol
2cO
3be dissolved in 50mL water, be slowly added drop-wise in this reaction system, and continue reaction 7 hours at this temperature; Finally again the temperature of reaction system is risen to 100 ℃, continue reaction 9 hours; Stop stirring, suction filtration, washing while hot 3 times, 50 ℃ of vacuum-dryings 10 hours, obtains white solid product 24.5g, and productive rate is 86.2%.In the present embodiment, the results of elemental analyses of products therefrom shows, C in hyperbranched poly phosphonitrile char-forming agent, and N, the theoretical percentage composition of H is respectively 51.0%, 7.4%, 2.8%, and measured value is respectively 49.8%, 6.7%, 2.6%, both are basically identical.Under nitrogen atmosphere, 365 ℃ of weightlessness of obtained flame-retardant char-forming agent are that 1%, 600 ℃ of carbon residue amount is 60.4%.
Embodiment 6:
0.23mol ethylene glycol is dissolved in to 25mL acetone, join in the 500mL there-necked flask that reflux condensing tube, constant pressure funnel, agitator are housed, again 0.05mol hexachlorocyclotriphosphazene is dissolved in to 70mL tetrahydrofuran (THF), is dropwise added drop-wise in above-mentioned ethylene glycol solution, and react 2.5 hours at 3 ℃; Then the temperature of reaction system is risen to 56 ℃, by the KHCO of 0.32mol
3be dissolved in 40mL water, be slowly added drop-wise in this reaction system, and continue reaction 3 hours at this temperature; Finally the temperature of reaction system is risen to 89 ℃, then react 7 hours; Stop stirring, suction filtration, washing while hot 3 times, is dried 2 hours at 100 ℃, obtains white solid product 14.9g, and productive rate is 79.4%.In the present embodiment, the results of elemental analyses of product shows, C in hyperbranched poly phosphonitrile char-forming agent, and N, the theoretical percentage composition of H is respectively 25.2%, 11.0%, 6.3%, and measured value is respectively 24.9%, 10.5%, 5.9%, both are basically identical.Under nitrogen atmosphere, 335 ℃ of weightlessness of obtained flame-retardant char-forming agent are that 1%, 600 ℃ of carbon residue amount is 52.6%.
The fire-retardant char-forming agent of hyperbranched poly phosphonitrile of gained of the present invention, Heat stability is good, charring rate is high, no matter be to be used in conjunction with as char-forming agent and other acid sources, source of the gas, or self joins in polymeric matrix as fire retardant, can both reach desirable flame retardant effect.And the fire-retardant char-forming agent synthesis technique of hyperbranched poly phosphonitrile of the present invention is simple, and reaction process is continuous, and the reaction times is short, be applicable to very much suitability for industrialized production, there is fabulous fire-retardant application prospect.
Above the present invention is described in detail; its object is to allow the personage who is familiar with this art can understand content of the present invention and be implemented; can not limit the scope of the invention with this; the equivalence that all spirit according to the present invention are done changes or modifies, and all should be encompassed in protection scope of the present invention.
Claims (9)
1. the fire-retardant char-forming agent of hyperbranched poly phosphonitrile, is characterized in that: the fire-retardant char-forming agent of described hyperbranched poly phosphonitrile has following general structure:
Wherein, Z is NH, N, S or O; R is a kind of in piperazine ring, straight chained alkyl, branched-chain alkyl, cycloalkyl and aryl.
2. the fire-retardant char-forming agent of hyperbranched poly phosphonitrile according to claim 1, is characterized in that: in R structure, contain one or more in S, O, N, Si and P atom.
3. the fire-retardant char-forming agent of hyperbranched poly phosphonitrile according to claim 1 and 2, is characterized in that: R be on straight chain with between the straight chained alkyl of phenyl ring, a plurality of phenyl ring with aryl, cycloalkaryl or the cycloalkyl aryl of alkyl.
4. a preparation method for the fire-retardant char-forming agent of hyperbranched poly phosphonitrile claimed in claim 1, is characterized in that:
Described preparation method represents by following reaction equation:
Described preparation method comprises the steps:
(1), by hexachlorocyclotriphosphazene and general structure, being HZ-R-ZH, binary compound is dispersed in respectively in solvent, obtains hexachlorocyclotriphosphazene solution and binary compound solution;
(2), under the temperature condition of 0 ℃～10 ℃, in the described binary compound solution stirring, dropwise add described hexachlorocyclotriphosphazene solution, after dropwising, maintain temperature of reaction constant, continue reaction 1-4 hour; The mol ratio of described binary compound and described hexachlorocyclotriphosphazene is between 4:1～6:1;
(3) temperature of the reaction system through step (2) is increased to 30 ℃-70 ℃, and adds wherein acid binding agent, continue reaction 3-6 hour; The mol ratio of described acid binding agent and described hexachlorocyclotriphosphazene is between 6:1-7:1;
(4) temperature of the reaction system through step (3) is increased to 90 ℃-150 ℃, continues reaction 6-10 hour;
(5) stop stirring, and gained solid is carried out to suction filtration, washing, dry, obtain the fire-retardant char-forming agent of described hyperbranched poly phosphonitrile.
5. the preparation method of the fire-retardant char-forming agent of hyperbranched poly phosphonitrile according to claim 4, is characterized in that: in step (1), the concentration of hexachlorocyclotriphosphazene solution is between 0.5mol/L～10mol/L.
6. the preparation method of the fire-retardant char-forming agent of hyperbranched poly phosphonitrile according to claim 4, is characterized in that: described binary compound is Ursol D, quadrol, hexanediamine, butanediamine, piperazine, N, N-dimethyl-1,3-propylene diamine, N-aminoethyl piperazine, 4,4 '-diaminodiphenyl oxide, DDS, 4,4 '-diaminodiphenylmethane, adjacent biphenyl methylamine, O-Phenylene Diamine, 1,2-propylene diamine, 1,3-propylene diamine, 2 methyl pentamethylenediamine, 2,6-tolylene diamine, 2,4 di amino toluene, 3 diethyl aminopropylamine, diethyl toluene diamine, hydroxyethylethylene diamine, 1,2-cyclohexanediamine, 4,5-dichloro O-Phenylene Diamine, 2,2 '-bis-[4-(4-amino-benzene oxygen phenyl)] propane, 3,3 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminodiphenyl sulfide, 4,4 '-diamino diphenyl disulfide, Resorcinol, pentanediol, 4,4 '-dihydroxy diphenyl ether, 4,4 '-dioxydiphenyl methane, BDO, ethylene glycol, 1,3 butylene glycol, 1,3-pentanediol, 1,3 cyclohexanediol, Isosorbide-5-Nitrae-cyclohexanediol, 2-ethyl-1,3-hexylene glycol, pyrocatechol, Resorcinol, 1,5-dihydroxy naphthlene, 1,3-naphthalenediol, 2,7 dihydroxy naphthalene, toluhydroquinone, 4,4 '-dihydroxyl diphenyl sulfide, 4,4 '-dihydroxyl diphenyl disulfide, Isosorbide-5-Nitrae-benzene dimethanethiol, 4,4 '-dimercapto diphenyl sulfide, 4, the combination of one or more in 4 '-dimercapto diphenyl disulfide and Isosorbide-5-Nitrae-thioresorcin.
7. the preparation method of the fire-retardant char-forming agent of hyperbranched poly phosphonitrile according to claim 4, is characterized in that: described acid binding agent is one or several mixtures that mix with arbitrary proportion in alkali metal hydroxide, alkaline carbonate or alkali metal hydrocarbonate; And the volumetric molar concentration of described acid binding agent is 1-10mol/L.
8. the preparation method of the fire-retardant char-forming agent of hyperbranched poly phosphonitrile according to claim 7, is characterized in that: described alkali metal hydroxide is NaOH or KOH; Described alkaline carbonate is Na
2cO
3or K
2cO
3; Described alkali metal hydrocarbonate is NaHCO
3or KHCO
3.
9. the preparation method of the fire-retardant char-forming agent of hyperbranched poly phosphonitrile according to claim 4, is characterized in that: in step (5), drying conditions is vacuum-drying 2～10 hours at 50 ℃～100 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410196403.8A CN103992481A (en) | 2014-05-09 | 2014-05-09 | Hyperbranched polyphosphazene flame retardant charring agent and preparing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410196403.8A CN103992481A (en) | 2014-05-09 | 2014-05-09 | Hyperbranched polyphosphazene flame retardant charring agent and preparing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103992481A true CN103992481A (en) | 2014-08-20 |
Family
ID=51306839
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410196403.8A Pending CN103992481A (en) | 2014-05-09 | 2014-05-09 | Hyperbranched polyphosphazene flame retardant charring agent and preparing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103992481A (en) |
Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327276A (en) * | 2014-09-15 | 2015-02-04 | 江南大学 | Cross-linking type polyphosphazene-based organic dye selective adsorbent and preparation method thereof |
| CN104693442A (en) * | 2015-03-17 | 2015-06-10 | 苏州安鸿泰新材料有限公司 | Hyper-branched triazine charring agent and preparation method thereof |
| CN104725428A (en) * | 2014-10-12 | 2015-06-24 | 青岛科技大学 | Melamine modified polyamino cyclotriphosphazene and preparation method thereof |
| CN105330803A (en) * | 2015-11-13 | 2016-02-17 | 太原理工大学 | Triazine type hyperbranched polyurea charring agent and preparing method thereof |
| CN105399959A (en) * | 2015-12-23 | 2016-03-16 | 江南大学 | Polyphosphazene microsphere-based phenolic resin molding plastic additive and preparation method thereof |
| CN105503957A (en) * | 2016-02-02 | 2016-04-20 | 北京工商大学 | Double base compound based on phosphonitrile and triazine group and preparation method of double base compound |
| CN106380604A (en) * | 2016-03-10 | 2017-02-08 | 中南大学 | Preparation method and application of polycyclotriphosphazen porous material |
| CN106543473A (en) * | 2016-10-14 | 2017-03-29 | 北京工商大学 | A kind of phosphonitrile/triazine double-basis molecule fire retardant based on dopen Nano level metallic compound in situ and preparation method thereof |
| CN106674533A (en) * | 2016-11-28 | 2017-05-17 | 宋雪晶 | Preparation method and application of nitrogen-phosphorus synergistic flame retardant with dendrimer structure |
| CN107099012A (en) * | 2015-01-20 | 2017-08-29 | 大连理工大学 | A kind of triazine type sulfur-containing resin and its preparation method and application |
| CN108148327A (en) * | 2018-03-08 | 2018-06-12 | 廊坊崔氏电缆材料有限公司 | PVC charging pile CABLE MATERIALSs and preparation method thereof |
| CN108530682A (en) * | 2018-04-02 | 2018-09-14 | 北京工商大学 | A kind of micro- cross-linking flame-retardant system of the biradical molecule of phosphonitrile/triazine and its fire-retardant thermoplastic resin |
| CN108912336A (en) * | 2018-08-01 | 2018-11-30 | 河北大学 | A kind of active amino cross-linking type phosphazene derivative, preparation method and application and fire retarding epoxide resin |
| CN110079886A (en) * | 2019-05-10 | 2019-08-02 | 新昌县高纤纺织有限公司 | The preparation method of flame-retardant and anti-static knitting fabric |
| CN110975330A (en) * | 2019-12-17 | 2020-04-10 | 华东理工大学 | Synthesis method of novel rapid oil-water separation material |
| CN111548510A (en) * | 2020-06-02 | 2020-08-18 | 上海工程技术大学 | A kind of dendritic UPy damping agent and its preparation method and application |
| CN112409600A (en) * | 2020-11-10 | 2021-02-26 | 北华大学 | A kind of preparation method of hydrophobic tannin-modified polyphosphazene nanomaterial and its application in fire retardant coating |
| CN113234103A (en) * | 2021-05-28 | 2021-08-10 | 青岛大学 | Phosphazene flame retardant and preparation method and application thereof |
| CN113845725A (en) * | 2021-10-19 | 2021-12-28 | 青岛塑科高分子科技有限公司 | Flame-retardant polypropylene material with good water resistance and preparation method thereof |
| CN115232638A (en) * | 2021-04-22 | 2022-10-25 | 中国石油化工股份有限公司 | Heavy oil demulsifier and preparation method and application thereof |
| CN116376035A (en) * | 2023-03-22 | 2023-07-04 | 中国安全生产科学研究院 | Hyperbranched flame retardant containing MOFs and preparation method thereof |
| CN116478438A (en) * | 2023-05-05 | 2023-07-25 | 华东理工大学 | A kind of post-treatment impregnation body for PP parts and preparation method of flame-retardant PP parts |
| US11985841B2 (en) | 2020-12-07 | 2024-05-14 | Oti Lumionics Inc. | Patterning a conductive deposited layer using a nucleation inhibiting coating and an underlying metallic coating |
| US12069938B2 (en) | 2019-05-08 | 2024-08-20 | Oti Lumionics Inc. | Materials for forming a nucleation-inhibiting coating and devices incorporating same |
| US12101987B2 (en) | 2019-04-18 | 2024-09-24 | Oti Lumionics Inc. | Materials for forming a nucleation-inhibiting coating and devices incorporating same |
| US12113279B2 (en) | 2020-09-22 | 2024-10-08 | Oti Lumionics Inc. | Device incorporating an IR signal transmissive region |
| CN118812973A (en) * | 2024-09-19 | 2024-10-22 | 无锡方成包装科技股份有限公司 | A degradable modified PS plastic bowl and preparation method thereof |
| US12178064B2 (en) | 2018-02-02 | 2024-12-24 | Oti Lumionics Inc. | Materials for forming a nucleation-inhibiting coating and devices incorporating same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312815A (en) * | 1998-08-13 | 2001-09-12 | 大塚化学株式会社 | Cross-linked phenoxyphosphazene compound, process for producing same, flame retardant, flame-retar dant resin composition and molded flame-retardent resin |
| CN1551903A (en) * | 2001-09-03 | 2004-12-01 | 第一毛织株式会社 | Flame-retardant thermoplastic resin composition |
| CN1687189A (en) * | 2005-03-31 | 2005-10-26 | 上海交通大学 | Nano tube of cross linked polyphosphonitrile and preparation method thereof |
| WO2010132105A1 (en) * | 2009-05-12 | 2010-11-18 | Chemnano Materials Ltd | Sulfur functionalized polymers for separation of metals from gas and liquid and methods for preparation thereof |
| CN103333336A (en) * | 2013-06-04 | 2013-10-02 | 合肥安聚达新材料科技有限公司 | Preparation method of novel hyperbranched triazine char forming agent |
-
2014
- 2014-05-09 CN CN201410196403.8A patent/CN103992481A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312815A (en) * | 1998-08-13 | 2001-09-12 | 大塚化学株式会社 | Cross-linked phenoxyphosphazene compound, process for producing same, flame retardant, flame-retar dant resin composition and molded flame-retardent resin |
| CN1551903A (en) * | 2001-09-03 | 2004-12-01 | 第一毛织株式会社 | Flame-retardant thermoplastic resin composition |
| CN1687189A (en) * | 2005-03-31 | 2005-10-26 | 上海交通大学 | Nano tube of cross linked polyphosphonitrile and preparation method thereof |
| WO2010132105A1 (en) * | 2009-05-12 | 2010-11-18 | Chemnano Materials Ltd | Sulfur functionalized polymers for separation of metals from gas and liquid and methods for preparation thereof |
| CN103333336A (en) * | 2013-06-04 | 2013-10-02 | 合肥安聚达新材料科技有限公司 | Preparation method of novel hyperbranched triazine char forming agent |
Cited By (42)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327276A (en) * | 2014-09-15 | 2015-02-04 | 江南大学 | Cross-linking type polyphosphazene-based organic dye selective adsorbent and preparation method thereof |
| CN104725428B (en) * | 2014-10-12 | 2017-03-01 | 青岛科技大学 | Cyanurotriamide modified poly- amino ring three phosphonitrile and preparation method thereof |
| CN104725428A (en) * | 2014-10-12 | 2015-06-24 | 青岛科技大学 | Melamine modified polyamino cyclotriphosphazene and preparation method thereof |
| CN107099012B (en) * | 2015-01-20 | 2019-12-27 | 大连理工大学 | Triazine type sulfur-containing resin and preparation method and application thereof |
| CN107099012A (en) * | 2015-01-20 | 2017-08-29 | 大连理工大学 | A kind of triazine type sulfur-containing resin and its preparation method and application |
| CN104693442A (en) * | 2015-03-17 | 2015-06-10 | 苏州安鸿泰新材料有限公司 | Hyper-branched triazine charring agent and preparation method thereof |
| CN105330803B (en) * | 2015-11-13 | 2017-08-15 | 太原理工大学 | A kind of hyperbranched polyureas carbon forming agent of triazines and preparation method thereof |
| CN105330803A (en) * | 2015-11-13 | 2016-02-17 | 太原理工大学 | Triazine type hyperbranched polyurea charring agent and preparing method thereof |
| CN105399959A (en) * | 2015-12-23 | 2016-03-16 | 江南大学 | Polyphosphazene microsphere-based phenolic resin molding plastic additive and preparation method thereof |
| CN105399959B (en) * | 2015-12-23 | 2018-07-13 | 江南大学 | A kind of alkyd resin moulding material additive and preparation method thereof based on polyphosphazene microspheres |
| CN105503957A (en) * | 2016-02-02 | 2016-04-20 | 北京工商大学 | Double base compound based on phosphonitrile and triazine group and preparation method of double base compound |
| CN105503957B (en) * | 2016-02-02 | 2017-09-29 | 北京工商大学 | A kind of biradical compound based on phosphonitrile and triazine group and preparation method thereof |
| CN106380604B (en) * | 2016-03-10 | 2019-06-14 | 中南大学 | A kind of preparation method of polycyclic phosphazene porous material and use thereof |
| CN106380604A (en) * | 2016-03-10 | 2017-02-08 | 中南大学 | Preparation method and application of polycyclotriphosphazen porous material |
| CN106543473A (en) * | 2016-10-14 | 2017-03-29 | 北京工商大学 | A kind of phosphonitrile/triazine double-basis molecule fire retardant based on dopen Nano level metallic compound in situ and preparation method thereof |
| CN106543473B (en) * | 2016-10-14 | 2018-02-09 | 北京工商大学 | Biradical molecule fire retardant of a kind of phosphonitrile/triazine based on dopen Nano level metallic compound in situ and preparation method thereof |
| CN106674533A (en) * | 2016-11-28 | 2017-05-17 | 宋雪晶 | Preparation method and application of nitrogen-phosphorus synergistic flame retardant with dendrimer structure |
| US12178064B2 (en) | 2018-02-02 | 2024-12-24 | Oti Lumionics Inc. | Materials for forming a nucleation-inhibiting coating and devices incorporating same |
| CN108148327B (en) * | 2018-03-08 | 2020-11-13 | 廊坊崔氏电缆材料股份有限公司 | PVC charging pile cable material and preparation method thereof |
| CN108148327A (en) * | 2018-03-08 | 2018-06-12 | 廊坊崔氏电缆材料有限公司 | PVC charging pile CABLE MATERIALSs and preparation method thereof |
| CN108530682A (en) * | 2018-04-02 | 2018-09-14 | 北京工商大学 | A kind of micro- cross-linking flame-retardant system of the biradical molecule of phosphonitrile/triazine and its fire-retardant thermoplastic resin |
| CN108912336A (en) * | 2018-08-01 | 2018-11-30 | 河北大学 | A kind of active amino cross-linking type phosphazene derivative, preparation method and application and fire retarding epoxide resin |
| CN108912336B (en) * | 2018-08-01 | 2021-03-12 | 河北大学 | Active amino cross-linked phosphazene derivative, preparation method and application thereof, and flame-retardant epoxy resin |
| US12101987B2 (en) | 2019-04-18 | 2024-09-24 | Oti Lumionics Inc. | Materials for forming a nucleation-inhibiting coating and devices incorporating same |
| US12069938B2 (en) | 2019-05-08 | 2024-08-20 | Oti Lumionics Inc. | Materials for forming a nucleation-inhibiting coating and devices incorporating same |
| CN110079886A (en) * | 2019-05-10 | 2019-08-02 | 新昌县高纤纺织有限公司 | The preparation method of flame-retardant and anti-static knitting fabric |
| CN110975330A (en) * | 2019-12-17 | 2020-04-10 | 华东理工大学 | Synthesis method of novel rapid oil-water separation material |
| CN110975330B (en) * | 2019-12-17 | 2021-10-12 | 华东理工大学 | Synthesis method of rapid oil-water separation material |
| CN111548510A (en) * | 2020-06-02 | 2020-08-18 | 上海工程技术大学 | A kind of dendritic UPy damping agent and its preparation method and application |
| CN111548510B (en) * | 2020-06-02 | 2022-03-25 | 上海工程技术大学 | Dendritic UPy damping agent and preparation method and application thereof |
| US12113279B2 (en) | 2020-09-22 | 2024-10-08 | Oti Lumionics Inc. | Device incorporating an IR signal transmissive region |
| CN112409600A (en) * | 2020-11-10 | 2021-02-26 | 北华大学 | A kind of preparation method of hydrophobic tannin-modified polyphosphazene nanomaterial and its application in fire retardant coating |
| US11985841B2 (en) | 2020-12-07 | 2024-05-14 | Oti Lumionics Inc. | Patterning a conductive deposited layer using a nucleation inhibiting coating and an underlying metallic coating |
| CN115232638B (en) * | 2021-04-22 | 2024-01-30 | 中国石油化工股份有限公司 | Thickened oil demulsifier and preparation method and application thereof |
| CN115232638A (en) * | 2021-04-22 | 2022-10-25 | 中国石油化工股份有限公司 | Heavy oil demulsifier and preparation method and application thereof |
| CN113234103B (en) * | 2021-05-28 | 2023-07-25 | 青岛大学 | Phosphazene flame retardant, preparation method and application thereof |
| CN113234103A (en) * | 2021-05-28 | 2021-08-10 | 青岛大学 | Phosphazene flame retardant and preparation method and application thereof |
| CN113845725B (en) * | 2021-10-19 | 2023-03-21 | 青岛塑科高分子科技有限公司 | Flame-retardant polypropylene material with good water resistance and preparation method thereof |
| CN113845725A (en) * | 2021-10-19 | 2021-12-28 | 青岛塑科高分子科技有限公司 | Flame-retardant polypropylene material with good water resistance and preparation method thereof |
| CN116376035A (en) * | 2023-03-22 | 2023-07-04 | 中国安全生产科学研究院 | Hyperbranched flame retardant containing MOFs and preparation method thereof |
| CN116478438A (en) * | 2023-05-05 | 2023-07-25 | 华东理工大学 | A kind of post-treatment impregnation body for PP parts and preparation method of flame-retardant PP parts |
| CN118812973A (en) * | 2024-09-19 | 2024-10-22 | 无锡方成包装科技股份有限公司 | A degradable modified PS plastic bowl and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103992481A (en) | Hyperbranched polyphosphazene flame retardant charring agent and preparing method thereof | |
| CN103333336A (en) | Preparation method of novel hyperbranched triazine char forming agent | |
| CN102391545B (en) | Nitrogen and phosphorus containing flame retardant agent and preparation method thereof as well as application thereof | |
| CN103333493B (en) | Phosphorous macromole expandable flame retardant char-forming agent and preparation method thereof and consisting of expansion type flame retardant | |
| CN104693442B (en) | Hyper-branched triazine charring agent and preparation method thereof | |
| CN101914208B (en) | Phosphorus-containing and nitrogen-containing expansion type flame-retardant polymer and preparation method thereof | |
| CN101643651A (en) | Macromolecular intumescent flame resistance carbonizing agent with branching and crosslinking structure and preparation method and application thereof | |
| CN106543473B (en) | Biradical molecule fire retardant of a kind of phosphonitrile/triazine based on dopen Nano level metallic compound in situ and preparation method thereof | |
| CN106008993A (en) | Phosphorus-containing Schiff base structured flame retardant and preparation method thereof | |
| CN104497041A (en) | Melamine aminotrimethylene phosphonate and preparation method thereof | |
| CN102757580A (en) | Reaction type phosphorus-nitrogen fire retardant and synthesizing method thereof | |
| CN101974167A (en) | Intumescent flame retardant and synthesis method thereof | |
| CN104559204B (en) | Phosphorus-containing macromolecular intumescent flame-retardant charring agent with cross-linked structure as well as preparation method and application thereof | |
| CN106632468A (en) | A preparing method of an aminotris(methylenephosphonic acid) metal salt flame retardant | |
| CN101058730A (en) | Phosphorus-nitrogen type halogen-free ionic fire retardant, preparation method thereof and fire retarding polyvinyl alcohol material prepared from the same | |
| CN104072759B (en) | A kind of P-N system expansion reaction type fire retardant and preparation method thereof | |
| CN101429438A (en) | Phosphor-nitrogen expansion type combustion inhibitor and method of producing the same | |
| CN105295093A (en) | Ring phosphonitrile type additive flame retardant and preparation method thereof | |
| CN115703886A (en) | A kind of phosphorus-containing polysiloxane reactive flame retardant, preparation method and application | |
| CN111073037B (en) | A kind of high thermal stability intumescent flame retardant and preparation method thereof | |
| CN105601857B (en) | A kind of preparation method of macromolecular expanding fire retardant | |
| CN105801867B (en) | A kind of expansion type flame retardant and preparation method thereof based on biomass structure | |
| CN107652324B (en) | Three-source-in-one expansion type fire retardant and its synthetic method and application | |
| CN117263974B (en) | Dialkyl phosphinic acid ammonium salt and preparation method and application thereof | |
| CN106380485A (en) | DOPO-modified cyclophosphazene fire retardant and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140820 |