CN109810415A - It is a kind of using pentaerythrite modified melamine-formaldehyde resin/piperazine pyrophosphate compound as the expansion type flame retardant of carbon forming agent - Google Patents
It is a kind of using pentaerythrite modified melamine-formaldehyde resin/piperazine pyrophosphate compound as the expansion type flame retardant of carbon forming agent Download PDFInfo
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- CN109810415A CN109810415A CN201910085070.4A CN201910085070A CN109810415A CN 109810415 A CN109810415 A CN 109810415A CN 201910085070 A CN201910085070 A CN 201910085070A CN 109810415 A CN109810415 A CN 109810415A
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- China
- Prior art keywords
- flame retardant
- formaldehyde resin
- pentaerythrite
- melamine
- carbon forming
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 44
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 41
- -1 pentaerythrite modified melamine-formaldehyde Chemical class 0.000 title claims abstract description 41
- 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 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 29
- 229920000877 Melamine resin Polymers 0.000 title claims abstract description 27
- 229920001276 ammonium polyphosphate Polymers 0.000 claims abstract description 13
- 239000004114 Ammonium polyphosphate Substances 0.000 claims abstract description 11
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims abstract description 11
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000012024 dehydrating agents Substances 0.000 claims abstract description 4
- 239000004088 foaming agent Substances 0.000 claims abstract description 4
- 238000013329 compounding Methods 0.000 claims abstract description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 7
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 229920002866 paraformaldehyde Polymers 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 229920001807 Urea-formaldehyde Polymers 0.000 claims 1
- 238000006266 etherification reaction Methods 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims 1
- 229920000137 polyphosphoric acid Polymers 0.000 claims 1
- 239000004743 Polypropylene Substances 0.000 abstract description 27
- 229920001155 polypropylene Polymers 0.000 abstract description 11
- MWFNQNPDUTULBC-UHFFFAOYSA-N phosphono dihydrogen phosphate;piperazine Chemical compound C1CNCCN1.OP(O)(=O)OP(O)(O)=O MWFNQNPDUTULBC-UHFFFAOYSA-N 0.000 abstract description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000460 chlorine Substances 0.000 abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 14
- 238000012360 testing method Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000003610 charcoal Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- MYOXMAQGEINAEF-UHFFFAOYSA-N [C].N1=NN=CC=C1 Chemical compound [C].N1=NN=CC=C1 MYOXMAQGEINAEF-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 3
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004079 fireproofing Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 241000220324 Pyrus Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- OOSUHIIJYDMCCW-UHFFFAOYSA-N cyanamide;formaldehyde Chemical compound O=C.NC#N OOSUHIIJYDMCCW-UHFFFAOYSA-N 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940031098 ethanolamine Drugs 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical class O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000021017 pears Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- 229920001693 poly(ether-ester) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of using pentaerythrite modified melamine-formaldehyde resin/piperazine pyrophosphate compound as carbon forming agent, melamine cyanurate is foaming agent, ammonium polyphosphate is dehydrating agent, passes through expansion type flame retardant (IFR) made of mixing compounding.The mass fraction of the IFR each component is as follows: ammonium polyphosphate 70~80%, pentaerythrite modified melamine-formaldehyde resin 10~20%, melamine cyanurate 2~5% and piperazine pyrophosphate 7~12%.The IFR not only has good fire retardation to polypropylene, but also is substantially free of chlorine, therefore more safety and environmental protection.In addition, polypropylene flame redardant color obtained is preferable.
Description
Technical field
It is specifically a kind of with the modified trimerization of pentaerythrite the present invention relates to a kind of novel expansion type flame retardant
Cyanamide formaldehyde resin/piperazine pyrophosphate compound is the expansion type flame retardant of carbon forming agent, belongs to chemical industry and high molecular material auxiliary agent
Field.
Background technique
Expansion type flame retardant (IFR) is one kind by acid source (dehydrating agent), carbon source (carbon forming agent) and gas source (foaming agent) three
The composite flame retardant system being grouped as has many advantages, such as that the high and low cigarette of flame retarding efficiency, low toxicity, additive amount are few, meets current fire proofing
Press down the requirement of cigarette, low toxicity, and is considered as that (Tang Shuo, Jin Yujuan, Qian Lijun are swollen for the Green Flammability agent of one kind with development potential
The progress Chinese Plastics of swollen type fire retardant, 2012, (8): 1-8).Nevertheless, but IFR used at present there is also resistances
Fuel efficiency fruit is still poor, influences the problems such as big with the poor compatibility of polymer, on polymer physics performance.
Carbon forming agent is the basis to form expanded charred layer, is one of the key substance for influencing IFR flame retardant effect.Therefore, it opens
Send out carbon forming agent novel and be always the emphasis of IFR research.
The carbon forming agent used earliest is mainly some polyols, such as pentaerythrite, dipentaerythritol, starch, mountain
Pears alcohol etc..These carbon forming agents are water-soluble big, the poor compatibility with material, precipitation easy to migrate, and it is poor at charcoal and thermal stability, add
Dosage is big, so that the performances degradation such as mechanics of material.These problems seriously hinder the development of IFR.To solve above ask
Topic, has carried out a large amount of research to carbon forming agent both at home and abroad, many novel carbon forming agents has been developed, such as thermoplastic polyurethane carbon forming agent
(Bugajny M,Bras M L,Bourbigot S,et al. Thermoplastic polyurethanes as
carbonization agents in intumescent blends part 1:fire retardancy of
polypropylene/ thermoplastic polyurethane/ammonium polyphosphate blends.J
Fire Sci, 1999,17 (6): 494-513), thermoplastic phenolic resin carbon forming agent (Zhong Y, Wu W, Wu R, et al.The
flame retarding mechanism of the novolac as char agent with the fire
retardant containing phosphorous–nitrogen in thermoplastic poly(ether ester)
Elastomer system.Polym Degr Stab, 2014,105 (1): 166-177), novel polyamide carbon forming agent (Yi J,
Liu Y,Pan D.Synthesis,thermal degradation,and flame retardancy of a novel
charring agent aliphatic—aromatic polyamide for intumescent flame retardant
Polypropylene.J Appl Polym Sci, 2012,127 (2): 1061-1068) etc..These carbon forming agents are although overcome
The disadvantages of traditional carbon forming agent water solubility greatly, is easily precipitated, thermal stability is poor, but it is undesirable at charcoal, thus be not widely applied.
In recent years, the successful use of macro molecular triazine carbon forming agent made the flame retardant effect of IFR be significantly improved.It has concurrently
At the double action of charcoal and foaming, and the compatibility for being insoluble in water and polymer is good.The IFR being combined by it and APP is not only
Flame retardant effect is more traditional to be obviously improved, and the water resistance of fire proofing and mechanical performance also significantly improve (Feng C,
Zhang Y,Liu S,et al.Synthesis of novel triazine charring agent and its effect
in intumescent flame-retardant polypropylene.J Appl Polym Sci,2012,123(6):3
208-3 216；Feng C,Liang M,Jiang J,et al.Synergistic effect of a novel triazine
charring agent and ammonium polyphosphate on the flame retardant properties
of halogen-free flame retardant polypropylene composites. Thermochimica Acta,
2016, s 627-629:83-90), therefore, triazine carbon forming agent causes extensive attention both domestic and external.At present about this kind of at charcoal
There are many report of agent.Nevertheless, but this kind of carbon forming agent there is also following problems: 1) it mainly with Cyanuric Chloride, unit amine
(such as ethanol amine, butylamine) and polyamine (such as ethylenediamine, piperazine) are raw material, as made from condensation and polycondensation.Due to three
Polychlorostyrene cyanogen replaces not exclusively, and 1.0% or so chlorine is typically contained in product, cannot fully meet user to the Halogen of fire retardant
It is required that there are still certain safety problems；2) a large amount of sodium chloride-containing waste water is generated in production process, it is difficult to administer.In addition, by
A large amount of low boiling point solvent (such as acetone) is used in production process, solvent loss is big, causes serious air pollution.Exactly
Due to problem of environmental pollution, the carbon forming agent also non-large-scale production at home affects its popularization and use；3) flame retardant effect and
Water resistance needs to be further increased, and the water resistance of fire proofing made from it is not able to satisfy quality mark both domestic and external still
It is quasi-.In view of the above problems, patent is according to the design and synthesis such as the fire retardant mechanism of IFR and the structure feature of triazine carbon forming agent one kind
Novel macro molecular triazine carbon forming agent-pentaerythrite modified melamine-formaldehyde resin (season such as Tang Linsheng, Zhu Xin, Yang Jingwei penta
Tetrol modified melamine-formaldehyde resin and preparation method thereof, number of patent application: 201910072232.0,2019-01-25).
Pentaerythrite is grafted on melamine resin by the carbon forming agent by being etherified, and not only successfully solves pentaerythrite water
The problems such as dissolubility is big, poor compatibility with polymer, and it had not only contained pentaerythrite structural unit, but also contained triazine ring structure
Unit, thus have into charcoal and foaming effect concurrently.But the thermal stability of pentaerythrite modified melamine-formaldehyde resin and at charcoal
Property slightly worse, weightlessness only 210 DEG C or so of thermal decomposition temperature of 2%, it is less desirable separately as the effect of carbon forming agent, and fire-retardant production
Product Yi Bianhuang.
Summary of the invention
In view of the above problems, inventor of the invention is to using pentaerythrite modified melamine-formaldehyde resin as carbon forming agent
IFR formula and preparation method conduct in-depth research, as a result, it has been found that passing through compound thermal stability and the pyrophosphoric acid good at charcoal
Piperazinyl instinct overcomes the shortcomings that pentaerythrite modified melamine-formaldehyde resin is as carbon forming agent, and with pentaerythrite modified three
Melamine-formaldehyde resin/piperazine pyrophosphate compound is carbon forming agent, and melamine cyanurate is foaming agent, and ammonium polyphosphate is
Dehydrating agent, by mixing the IFR for compounding out and there is good fire retardation to polypropylene.
The composition of the IFR and the mass fraction of each component are as follows:
Further, the pentaerythrite modified melamine-formaldehyde resin is with melamine, paraformaldehyde and season
Penta tetrol is raw material, is prepared by three-step reactions such as methylolation, polycondensation and etherificates.
The IFR not only has good fire retardation to polypropylene, but also is substantially free of chlorine, therefore more safety and environmental protection.
In addition, fire-retardant PP color obtained is preferable.
Specific embodiment
Hereinafter, preferred embodiments of the present invention will be described, it should be understood that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
Unless otherwise indicated, percentage employed in the present invention is mass percent.
Polypropylene (abbreviation PP) used herein is the PP of asphalt in Shenli Refinery, Co., Ltd, Sinopec production
SP179 type copolymer polypropylene and the PP H8020 of China National Petroleum share Chemical Co., Ltd.'s Lanzhou Petrochemical Company production are equal
Poly- polypropylene, the two w in mass ratio (PP SP179): w (PP H8020)=3:1 are used in mixed way；Ammonium polyphosphate (abbreviation APP) and
Melamine cyanurate (MCA) is Shouguang WeiDong Chemical Co., Ltd.'s production；Piperazine pyrophosphate is the research of Sichuan fine chemistry industry
Designing institute's production；The self-control of pentaerythrite modified melamine-formaldehyde resin.
The preparation of fire-retardant PP sample: by PP and IFR by certain mass ratio at double screw extruder (20~30rpm of revolving speed)
In at 190~200 DEG C squeeze out mix, be granulated.Particle after drying is using tablet press machine in 200~210 DEG C, 5MPa pressure lower die
It is molded, it is subsequently placed under 5MPa pressure and is cold-pressed, then be cut into the batten of required specification for performance test use.
Flame retardant property test: limit oxygen index (LOI) is using (the Jiangning county's analysis of JF-3 type oxygen index measurer
Instrument plant) it is measured according to GB/T2046-1993, test sample is having a size of 100mm × 6.5mm × 1.6mm；Testing vertical flammability is adopted
It is tested with CZF-3 type horizontal vertical burning analyzer (analysis instrument factory, Jiangning county) with reference to GB/T2408-1996, sample
Having a size of 100mm × 13mm × 1.6mm.
Embodiment 1
The preparation of pentaerythrite modified melamine-formaldehyde resin, the specific steps are as follows:
126g (1.0mol) melamine, 225g (7.5mol) paraformaldehyde and 1L deionized water are added equipped with reflux
In the 2L three-necked flask of condenser pipe, blender and thermometer, material pH is adjusted with the sodium hydroxide solution that mass fraction is 10%
To 9 or so, 75 DEG C of reaction 1h are then heated to.Temperature of charge is then down to 55 DEG C, adds 613g (4.5mol) Ji Wusi
Alcohol adjusts material pH to 1.5 or so with the hydrochloric acid that mass fraction is 20%, and in 55 ± 5 DEG C of reaction 2.5h, then is warming up to 80
± 5 DEG C of the reaction was continued 2h.Material pH to 9 or so is adjusted with the sodium hydroxide solution that mass fraction is 10% after reaction, it is cold
But it to room temperature, filters, filter cake is washed 3 times with the deionized water of 1L × 3, and gained filter cake obtains 292g white powder in 150 DEG C of dry 3h
Shape product.The yield of product is 99.2%, and the solubility of product is 0.22g/100mL water, temperature when product weightlessness 2%
(T2wt%), 5% when temperature (T5wt%), 10% when temperature (T10wt%) and temperature (T when maximum heat weight loss ratemax) respectively
It is 213.1 DEG C, 235.4 DEG C, 256.0 DEG C and 357.0 DEG C.
Embodiment 2
It is a kind of to be hindered by the intumescent of carbon forming agent of pentaerythrite modified melamine-formaldehyde resin/piperazine pyrophosphate compound
Agent is fired, forms and the quality of each component is as follows: ammonium polyphosphate 750g, pentaerythrite modified melamine-formaldehyde resin 130g,
Melamine cyanurate 30g, piperazine pyrophosphate 90g.Conventional powder mixer or high-speed mixer and mixing is added in the above component
10~20min obtains IFR.
Flame retardant property evaluation test is carried out by previously described method to the above IFR, the results are shown in Table 1.In table 1
The result shows that IFR made from the present embodiment has good flame retardant effect to PP, when its additive amount accounts for the 28% of material gross mass
When, testing vertical flammability is just by V-0 grades, t1And t1It is only respectively 1.12s and 2.45s, and the color of fire-retardant PP is not apparent from change
It is yellow.
Embodiment 3
It is a kind of to be hindered by the intumescent of carbon forming agent of pentaerythrite modified melamine-formaldehyde resin/piperazine pyrophosphate compound
Agent is fired, forms and the quality of each component is as follows: ammonium polyphosphate 750g, pentaerythrite modified melamine-formaldehyde resin 110g,
Melamine cyanurate 30g, piperazine pyrophosphate 110g.Conventional powder mixer or high-speed mixer and mixing is added in the above component
10~20min obtains IFR.
Flame retardant property evaluation test is carried out by previously described method to the above IFR, the results are shown in Table 1.In table 1
The result shows that IFR made from the present embodiment also has good flame retardant effect to PP, but flame retardant effect is slightly worse than embodiment 1, when
When its additive amount accounts for the 28% of material gross mass, testing vertical flammability is only by V-1 grades, t1And t1Respectively 5.24s and
10.63s, but the color of fire-retardant PP is whiter.
Embodiment 4
It is a kind of to be hindered by the intumescent of carbon forming agent of pentaerythrite modified melamine-formaldehyde resin/piperazine pyrophosphate compound
Agent is fired, forms and the quality of each component is as follows: ammonium polyphosphate 750g, pentaerythrite modified melamine-formaldehyde resin 130g,
Melamine cyanurate 50g, piperazine pyrophosphate 70g.Conventional powder mixer or high-speed mixer and mixing is added in the above component
10~20min obtains IFR.
Flame retardant property evaluation test is carried out by previously described method to the above IFR, the results are shown in Table 1.In table 1
The result shows that IFR made from the present embodiment also has preferable flame retardant effect to PP, but flame retardant effect is worse than embodiment 1 and reality
Example 2 is applied, when its additive amount accounts for the 28% of material gross mass, testing vertical flammability is only by V-2 grades, t1And t1Only it is respectively
7.74s and 17.58s, and dripped when burning.
Comparative example 1
It is a kind of using pentaerythrite modified melamine-formaldehyde resin as the expansion type flame retardant of carbon forming agent, composition and each group
The quality divided is as follows: ammonium polyphosphate 750g, pentaerythrite modified melamine-formaldehyde resin 220g, melamine cyanurate
30g.Conventional powder mixer is added in the above component or 10~20min of high-speed mixer and mixing obtains IFR.
Flame retardant property evaluation test is carried out by previously described method to the above IFR, the results are shown in Table 1.In table 1
The result shows that IFR made from the present embodiment also has preferable flame retardant effect to PP, but flame retardant effect is significantly worse than embodiment,
When its additive amount accounts for the 30% of material gross mass, testing vertical flammability could be by V-0 grades, and the color of fire-retardant PP slightly becomes
It is yellow.
The flame retardant property of the fire-retardant PP of table 1
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
Claims (3)
1. a kind of expansion type flame retardant, which is characterized in that with pentaerythrite modified melamine-formaldehyde resin/piperazine pyrophosphate
Compound is carbon forming agent, and melamine cyanurate is foaming agent, and ammonium polyphosphate is dehydrating agent, by swollen made of mixing compounding
Swollen type fire retardant.
2. expansion type flame retardant according to claim 1, which is characterized in that the mass fraction of each component is as follows: polyphosphoric acid
Ammonium 70~80%, pentaerythrite modified melamine-formaldehyde resin 10~20%, melamine cyanurate 2~5% and burnt phosphorus
Mcpp acid 7~12%.
3. expansion type flame retardant according to claim 1, which is characterized in that the pentaerythrite modified cyanurotriamide first
Urea formaldehyde is to be made using melamine, paraformaldehyde and pentaerythrite as raw material by methylolation, polycondensation and etherification reaction.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN114015115A (en) * | 2021-10-25 | 2022-02-08 | 沈阳工业大学 | Preparation method of intumescent flame retardant based on piperazine pyrophosphate/melamine cyanurate/ammonium polyphosphate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102304250A (en) * | 2011-09-07 | 2012-01-04 | 上海日之升新技术发展有限公司 | High-melt-index halogen-free flame-retarding polypropylene and preparation method thereof |
-
2019
- 2019-01-29 CN CN201910085070.4A patent/CN109810415B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102304250A (en) * | 2011-09-07 | 2012-01-04 | 上海日之升新技术发展有限公司 | High-melt-index halogen-free flame-retarding polypropylene and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 《化工百科全书》编辑委员会编: "《化工百科全书 第1卷 锕系元素的锕系后元素-丙烯酰胺聚合物 a-bing》", 30 December 1990, 化学工业出版社 * |
| 唐海珊: "哌嗪类磷酸盐的合成及其在阻燃聚丙烯中的应用研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
| 朱健生等: "密胺甲醛树脂包覆改性聚磷酸铵", 《高分子材料科学与工程》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN114015115A (en) * | 2021-10-25 | 2022-02-08 | 沈阳工业大学 | Preparation method of intumescent flame retardant based on piperazine pyrophosphate/melamine cyanurate/ammonium polyphosphate |
| CN114015115B (en) * | 2021-10-25 | 2023-03-28 | 沈阳工业大学 | Preparation method of intumescent flame retardant based on piperazine pyrophosphate/melamine cyanurate/ammonium polyphosphate |
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