CN112480372A - Phosphorus-containing compound with amino group, epoxy resin composition, preparation method and application - Google Patents
Phosphorus-containing compound with amino group, epoxy resin composition, preparation method and application Download PDFInfo
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- CN112480372A CN112480372A CN201910858202.2A CN201910858202A CN112480372A CN 112480372 A CN112480372 A CN 112480372A CN 201910858202 A CN201910858202 A CN 201910858202A CN 112480372 A CN112480372 A CN 112480372A
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- phosphorus
- containing compound
- epoxy resin
- flame retardant
- amino group
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- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 47
- 239000011574 phosphorus Substances 0.000 title claims abstract description 47
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 150000001875 compounds Chemical class 0.000 title claims abstract description 34
- 125000003277 amino group Chemical group 0.000 title claims abstract description 32
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 31
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 31
- 239000000203 mixture Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000003063 flame retardant Substances 0.000 claims abstract description 60
- 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 claims abstract description 58
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 18
- -1 phosphorus compound Chemical class 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 abstract description 6
- 230000000996 additive effect Effects 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 3
- 230000009477 glass transition Effects 0.000 abstract description 3
- 239000011229 interlayer Substances 0.000 abstract description 3
- 230000000704 physical effect Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 24
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000002156 mixing Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 229960000583 acetic acid Drugs 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012362 glacial acetic acid Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- KEYLJVFXWVSVSP-UHFFFAOYSA-N hydroxymethyl dimethyl phosphite Chemical compound P(OCO)(OC)OC KEYLJVFXWVSVSP-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 4
- 229920003180 amino resin Polymers 0.000 description 4
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 239000012796 inorganic flame retardant Substances 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000011094 fiberboard Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IDCBOTIENDVCBQ-UHFFFAOYSA-N TEPP Chemical compound CCOP(=O)(OCC)OP(=O)(OCC)OCC IDCBOTIENDVCBQ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AVEFMZWGJBABMS-UHFFFAOYSA-N bis[(1,2,2,6,6-pentamethylpiperidin-4-yl)oxy]phosphoryl bis(1,2,2,6,6-pentamethylpiperidin-4-yl) phosphate Chemical compound O(P(OC1CC(N(C(C1)(C)C)C)(C)C)(=O)OP(=O)(OC1CC(N(C(C1)(C)C)C)(C)C)OC1CC(N(C(C1)(C)C)C)(C)C)C1CC(N(C(C1)(C)C)C)(C)C AVEFMZWGJBABMS-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000001617 migratory effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3211—Esters of acyclic saturated acids which can have further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3264—Esters with hydroxyalkyl compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a phosphorus-containing compound with amino, an epoxy resin composition, a preparation method and application thereof, wherein the phosphorus-containing compound with amino is shown as the following formula I; compared with an additive flame retardant which is easy to separate out, the phosphorus-containing compound with the amino group is more stable in the composite material, the glass transition temperature can reach more than 180 ℃, the flame retardant property is excellent, the physical property is excellent, the interlayer peeling strength can also reach more than 1N/mm, the high stability can be still kept after baking, and the phosphorus-containing compound with the amino group has a good application prospect and a high application value.
Description
Technical Field
The invention belongs to the field of flame retardants, and relates to a phosphorus-containing compound with amino groups, an epoxy resin composition, a preparation method and application.
Background
Epoxy resin prepreg has been widely used in the fields of electronic and electrical products such as printed circuit boards and insulating materials in transformers, and in order to meet the flame retardant requirements of materials, brominated epoxy resin is often used as a resin matrix of the flame retardant prepreg. However, bromine-containing epoxy resins generate a large amount of toxic gases harmful to human bodies when burned; meanwhile, the glass fiber/epoxy resin prepreg prepared by the existing solvent method process can cause the problems of environmental pollution such as difficult solvent volatilization and recovery. With the environmental protection concerns, halogen-based flame retardants are gradually being replaced.
The phosphorus-containing flame retardant can realize flame retardance by inhibiting flame, heat loss caused by molten drops, surface blocking caused by phosphorus-containing acid, accumulation of an acid catalytic carbon layer, prevention of further oxidation of carbon by carbon deposition and the like, and decomposition products and combustion products of the phosphorus-containing flame retardant are few in corrosivity and toxic substances and are a better choice in flame retardant materials.
CN103113711A discloses a preparation method of a low-dielectric halogen-free flame-retardant glass fiber prepreg, which utilizes the phosphorus-nitrogen synergistic flame-retardant effect and the low dielectric property of polyphenyl ether, adopts a two-step process that a phosphorus flame retardant and hydroxyl-terminated polyphenyl ether respectively react with epoxy resin to prepare low-dielectric flame-retardant epoxy resin, then compounds the low-dielectric flame-retardant epoxy resin with liquid epoxy resin, and uniformly mixes the low-dielectric flame-retardant epoxy resin with a latent curing agent to prepare a resin system for the prepreg; and then preparing a glue film from the resin system for the prepreg by adopting a glue film machine, and compounding the glue film with glass fiber or fabric by a compound machine to prepare the low-dielectric halogen-free flame-retardant prepreg. The glass fiber prepreg prepared by the method has excellent flame retardant property and small dielectric constant, meets the production process of a two-step method of hot-melt prepreg, and is suitable for large-scale production of the prepreg for electronic and electric appliances. But its flame retardancy can still be improved.
CN105713041A discloses a preparation method of an intumescent flame retardant containing sterically hindered amine and having an antioxidant function, which comprises the step of carrying out ester exchange reaction on tetraethyl pyrophosphate and 1,2,2,6, 6-pentamethylpiperidinol under the action of a catalyst to obtain a target product of tetra (1,2,2,6, 6-pentamethyl-4-piperidyl) pyrophosphate. The secondary amino group on the piperidine ring in the steric hindrance amine structure in the system can effectively capture alkyl free radicals and alkyl oxygen free radicals in the polymer combustion process, so that the alkyl free radicals and the alkyl oxygen free radicals lose activity, have the function of circularly capturing the free radicals, can delay the induction stage of polymer combustion, and can inhibit the development stage of polymer combustion; the hindered amine group has the functions of catalyzing esterification into carbon, blocking and cooling, and effectively improving the graphitization degree and the strength of the carbon layer after the polymer is combusted, so that the flame retardant efficiency is greatly improved. The method brings oxidation resistance to the flame retardant, and the flame retardant performance of the flame retardant is not improved.
CN102071032A discloses a flame retardant containing amino resin and a preparation method thereof, wherein the flame retardant comprises a phosphorus-nitrogen flame retardant, an inorganic flame retardant and amino resin; the phosphorus-nitrogen flame retardant is coated with an inorganic flame retardant, and the inorganic flame retardant is coated with amino resin; the weight percentage of the phosphorus-nitrogen flame retardant, the inorganic flame retardant and the amino resin is 100: 1-30. The flame retardant provided by the method is applied to the flame-retardant process of the plant fiber board, the physical and chemical properties, the processing property and the use property of the plant fiber board are not damaged, and the combustion smoke concentration and the toxicity of the flame-retardant wood material under fire can be reduced. The method is mainly applied to plant fiber boards and is limited in application.
At present, the application of the existing flame retardant still has certain limitation, and how to develop a flame retardant with environmental protection and good flame retardance has important significance for the application of the flame retardant.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a phosphorus-containing compound with amino, an epoxy resin composition, a preparation method and application thereof, so as to solve the problems of unstable performance, poor flame retardant property and environmental pollution of the existing flame retardant.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an amino group-containing phosphorus compound, wherein the amino group-containing phosphorus compound has the following formula I:
wherein, R, R1、R2Independently selected from substituted or unsubstituted C1～C5The linear or branched alkylene group of (a), e is an integer of 0 to 20 (for example, 0, 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20), k is an integer of 0 to 30 (for example, 0, 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30), and h is an integer of 0 to 2 (for example, 0, 1, 2).
The term "substituted" as used herein means that any one or more hydrogen atoms on the designated atom is replaced with a substituent selected from the designated group, provided that the designated atom does not exceed a normal valence and that the result of the substitution is a stable compound.
Compared with an additive flame retardant which is easy to precipitate, the phosphorus-containing compound with the amino group provided by the invention is more stable in the composite material and has better physical properties.
Said C of the invention1～C5The straight chain alkylene group of (A) means C1、C2、C3、C4Or C5Linear alkylene of (2) or C1、C2、C3、C4Or C5Branched alkylene groups of (1).
Preferably, said R, R1、R2Independently selected from unsubstituted C1～C5A linear alkylene group of (a).
Preferably, the value of e is an integer of 0-5.
Preferably, the value of k is an integer of 10-25.
Preferably, the phosphorus-containing compound having an amino group is preferably
Any one of them.
In a second aspect, the present invention provides a method for preparing a phosphorus-containing compound having an amino group according to the first aspect, the method comprising: the phosphorus-containing flame retardant with the reactive group is obtained by a substitution reaction of a compound containing-P-OH and an amino compound.
In a third aspect, the present invention provides an epoxy resin composition comprising the phosphorus-containing compound having an amino group according to the first aspect.
Preferably, the epoxy resin composition comprises the following components in parts by weight: 80 to 120 parts (for example, 80 parts, 85 parts, 90 parts, 95 parts, 100 parts, 105 parts, 110 parts, 115 parts, 120 parts, etc.), 20 to 50 parts (for example, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, etc.) of a phosphorus compound having an amino group, and 0.2 to 1 part (for example, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 part, etc.) of 2-methylimidazole.
Preferably, the epoxy resin composition further comprises dicyandiamide.
In a fourth aspect, the present invention provides a use of the epoxy resin composition according to the third aspect in a flame retardant material.
The epoxy resin composition provided by the invention has a good flame retardant effect, and can be widely applied to flame retardant materials.
Compared with the prior art, the invention has the following beneficial effects:
compared with an additive flame retardant which is easy to separate out, the phosphorus-containing compound with the amino group is more stable in the composite material, the glass transition temperature can reach more than 180 ℃, the flame retardant property is excellent, the physical property is excellent, the interlayer peeling strength can also reach more than 1N/mm, the high stability can be still kept after baking, and the phosphorus-containing compound with the amino group has a good application prospect and a high application value.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A phosphorus-containing compound with an amino group has the following structure:
the preparation method comprises the following steps:
adding 1mol of diethylenetriamine and 1mol of dimethyl hydroxymethyl phosphite, 200mL of ethanol, 0.1mol of sodium hydroxide and 0.1g of DMAP into a three-neck flask with a magnetic stirring thermometer, heating until the ethanol refluxes, reacting for 12h, then adding hydrochloric acid until the pH value is 7, filtering and washing, and removing impurities to obtain the phosphorus-containing flame retardant with the structure.
1H NMR(400MHz,DMSO-d6):δ＝5.00-5.03(s,2H,-N 2H),3.48-3.50(d,6H,-P-O-CH3),3.03-3.06(s,2H,-P-C 2H-),2.85-2.88(t,2H,-NH-CH2-C 2H-NH2),2.65-2.68(t,2H,-NH-C 2H-CH2-NH2),2.51-2.55(s,4H,-NH-C 2H-C 2H-NH-).
Example 2
A phosphorus-containing compound with an amino group has the following structure:
the preparation method comprises the following steps:
(1) under nitrogen atmosphere, putting 200mL of glacial acetic acid, 0.5mol of dimethyl phosphite and 0.5mol of maleic acid into a three-port 500mL glass reactor with a stirring device, stirring, dissolving 0.5mmol of Pb catalyst into 20mL of glacial acetic acid at the stirring temperature of 60 ℃, then adding the mixture into a reaction system in a dropwise manner, reacting for 12h, and then separating a product;
1H NMR(400MHz,DMSO-d6)δ＝13.52-13.54(s,1H,-CH-CO-OH),12.98-13.00(s,1H,-CH2-CO-OH),3.47-3.49(d,6H,-P-O-C 3H),2.85-2.90(t,1H,-CH-),2.78-2.81(d,2H,-C 2H-).
(2) mixing 1mol and 2mol of thionyl chloride of the product obtained in the step (1) with 200mL of chloroform, reacting at a reflux temperature, and then adding 1mol of ethylenediamine and 0.1mol of triethylamine to react for 30min to obtain a product B;
1H NMR(400MHz,DMSO-d6)δ＝13.52-13.54(s,1H,-CH-CO-OH),8.20-8.22(s,2H,-N 2H),8.12-8.15(s,1H,-CO-NH-),3.47-3.49(d,6H,-P-O-C 3H),2.88-2.92(t,1H,-CH-),2.68-2.72(m,4H,-C 2H-CO-NH-C 2H-),2.60-2.63(m,2H,-C 2H-NH2).
(3)1mol of diethylenetriamine and 1mol of hydroxymethyl dimethyl phosphite, 200mL of ethanol, 0.1mol of sodium hydroxide and 0.1g of DMAP, heating until the ethanol refluxes, reacting for 6h, then adding hydrochloric acid until the pH value is 7, and separating a product C;
1H NMR(400MHz,DMSO-d6):δ＝5.00-5.03(s,2H,-N 2H),3.48-3.50(d,6H,-P-O-CH3),3.03-3.06(s,2H,-P-C 2H-),2.85-2.88(t,2H,-NH-CH2-C 2H-NH2),2.65-2.68(t,2H,-NH-C 2H-CH2-NH2),2.51-2.55(s,4H,-NH-C 2H-C 2H-NH-).
(4) and mixing the product B with the product C, and adding a small amount of triethylamine for mixing reaction to obtain the phosphorus-containing flame retardant with the structure.
1H NMR(400MHz,DMSO-d6):δ＝3.48-3.50(d,12H,-P-O-CH3).
Due to-CH in the hydrogen spectrum2-the peaks are all doped together, taking into account-NH2The active hydrogen peak may be inaccurate, so that only the characteristic peak (-P-O-CH) is determined3) The molecular weight of the final product was calculated to be 444.89 (theoretical value: 445).
Example 3
A phosphorus-containing compound with an amino group has the following structure:
the preparation method comprises the following steps:
(1) under nitrogen atmosphere, putting 200mL of glacial acetic acid, 0.5mol of dimethyl phosphite and 0.5mol of maleic acid into a three-port 500mL glass reactor with a stirring device, stirring, dissolving 0.5mmol of Pb catalyst into 20mL of glacial acetic acid at the stirring temperature of 60 ℃, then adding the mixture into a reaction system in a dropwise manner, reacting for 12h, and then separating a product;
1H NMR(400MHz,DMSO-d6)δ＝13.52-13.54(s,1H,-CH-CO-OH),12.98-13.00(s,1H,-CH2-CO-OH),3.47-3.49(d,6H,-P-O-C 3H),2.85-2.90(t,1H,-CH-),2.78-2.81(d,2H,-C 2H-).
(2) mixing 3mol of the product obtained in the step (1), 2mol of thionyl chloride and 600mL of chloroform, reacting at a reflux temperature, and then adding 3mol of ethylenediamine and 0.3mol of triethylamine to react for 0.5h to obtain a product;
(3)1mol of diethylenetriamine and 1mol of hydroxymethyl dimethyl phosphite, 200mL of ethanol, 0.1mol of sodium hydroxide and 0.1g of DMAP, heating until the ethanol refluxes, reacting for 6h, then adding hydrochloric acid until the pH value is 7, and separating the product;
1H NMR(400MHz,DMSO-d6):δ＝5.00-5.03(s,2H,-N 2H),3.48-3.50(d,6H,-P-O-CH3),3.03-3.06(s,2H,-P-C 2H-),2.85-2.88(t,2H,-NH-CH2-C 2H-NH2),2.65-2.68(t,2H,-NH-C 2H-CH2-NH2),2.51-2.55(s,4H,-NH-C 2H-C 2H-NH-).
(4) and (3) mixing the product obtained in the step (2) with the product obtained in the step (3), and adding a small amount of triethylamine for mixing reaction to obtain the phosphorus-containing flame retardant with the structure.
1H NMR(400MHz,DMSO-d6):δ＝3.47-3.49(d,24H,-P-O-CH3).
Since the nuclear magnetic hydrogen spectrum parts of the polymer are doped together, only characteristic peaks are judged, and the molecular weight of the finally obtained product is 884.12 (the theoretical value is 885) through calculation.
Example 4
A phosphorus-containing compound with an amino group has the following structure:
the preparation method comprises the following steps:
(1) under nitrogen atmosphere, putting 200mL of glacial acetic acid, 0.5mol of dimethyl phosphite and 0.5mol of maleic acid into a three-port 500mL glass reactor with a stirring device, stirring, dissolving 0.5mmol of Pb catalyst into 20mL of glacial acetic acid at the stirring temperature of 60 ℃, then adding the mixture into a reaction system in a dropwise manner, reacting for 12h, and then separating a product;
(2) mixing 10mol of the product obtained in the step (1), 2mol of thionyl chloride and 2000mL of chloroform, reacting at a reflux temperature, and then adding 10mol of ethylenediamine and 0.3mol of triethylamine to react for 5 hours to obtain a product;
(3)1mol of diethylenetriamine and 1mol of hydroxymethyl dimethyl phosphite, 200mL of ethanol, 0.1mol of sodium hydroxide and 0.1g of DMAP, heating until the ethanol refluxes, reacting for 6h, then adding hydrochloric acid until the pH value is 7, and separating the product;
(4) and (3) mixing the product obtained in the step (2) with the product obtained in the step (3), and adding a small amount of triethylamine for mixing reaction to obtain the phosphorus-containing flame retardant with the structure.
1H NMR(400MHz,DMSO-d6):δ＝3.47-3.49(d,66H,-P-O-CH3).
The molecular weight of the final product was calculated to be 2423.99 (theoretical 2425).
Example 5
A phosphorus-containing compound with an amino group has the following structure:
the preparation method comprises the following steps:
(1) under nitrogen atmosphere, putting 200mL of glacial acetic acid, 0.5mol of dimethyl phosphite and 0.5mol of maleic acid into a three-port 500mL glass reactor with a stirring device, stirring, dissolving 0.5mmol of Pb catalyst into 20mL of glacial acetic acid at the stirring temperature of 60 ℃, then adding the mixture into a reaction system in a dropwise manner, reacting for 12h, and then separating a product;
(2) mixing 1mol of the product obtained in the step (1), 2mol of thionyl chloride and 200mL of chloroform, reacting at a reflux temperature, and then adding 1mol of ethylenediamine and 0.3mol of triethylamine to react for 12 hours to obtain a product;
(3)1mol of diethylenetriamine and 1mol of hydroxymethyl dimethyl phosphite, 200mL of ethanol, 0.1mol of sodium hydroxide and 0.1g of DMAP, heating until the ethanol refluxes, reacting for 6h, then adding hydrochloric acid until the pH value is 7, and separating the product;
(4) and (3) mixing the product obtained in the step (2) with the product obtained in the step (3), and adding a small amount of triethylamine for mixing reaction to obtain the phosphorus-containing flame retardant with the structure.
1H NMR(400MHz,DMSO-d6):δ＝3.47-3.49(d,156H,-P-O-CH3).
The molecular weight of the final product was calculated to be 5723.89 (theoretical 5725).
An epoxy resin composition is provided, which comprises the following components:
100 parts of bisphenol A type epoxy resin (the epoxy equivalent is 450g/eq), 30 parts of flame-retardant curing agent, if the curing agent is complemented, the curing agent is complemented by dicyandiamide, and 0.5 part of 2-methylimidazole. Wherein the flame retardant curing agent is the phosphorus-containing compound with amino groups provided in examples 1-5, respectively.
Comparative example 1
The only difference from the epoxy resin composition containing the phosphorus-containing composition having an amino group of example 1 was that 30 parts by weight of the flame retardant curing agent was replaced with a dicyandiamide curing agent used in an amount sufficient for curing the epoxy resin.
Comparative examples 2 to 3
30 parts by weight (comparative example 2) and 45 parts by weight (comparative example 3) of triphenyl phosphate as a flame retardant were added to the base of comparative example 1.
Performance testing
The epoxy resin compositions provided in examples 1 to 5 and comparative examples 1 to 3 were prepared into copper clad laminates according to a known conventional method, and the following tests were carried out:
(1)Tg: differential Scanning Calorimetry (DSC) according to the DSC method defined in IPC-TM-650 at 2.4.25Measuring;
(2) interlayer peel strength PS: testing the peel strength of the plate according to the experimental conditions of 'after thermal stress' in the IPC-TM-6502.4.8 method;
(3) dielectric constant (Dk) and dielectric loss factor (Df): testing the dielectric constant Dk and the dielectric loss Df of the board by adopting an SPDR method under the frequency of 10 GHz;
(5) combustibility: testing according to UL-94 vertical burning test standard;
(6) flame retardant stability: soaking the copper-clad plate in water for 1h, drying and measuring the combustibility of the copper-clad plate again;
(7) mobility: and baking the copper-clad plate at 150 ℃ for 2h, and testing the weight difference percentage before and after baking.
The results of the tests on the examples and comparative examples are shown in Table 1:
TABLE 1
As can be seen from the examples and performance tests, the copper-clad plate prepared by using the phosphorus-containing flame retardant with the reactive group provided by the invention has excellent performance, and the comparison of the examples shows that the phosphorus-containing flame retardant provided by the preparation examples 3-5 has better effect. The comparison between the embodiment and the comparative example shows that the additive flame retardant can affect the glass transition temperature, the peel strength and other properties of the copper-clad plate, and the additive flame retardant has a migratory type and part of additive flame retardant is soluble in water, so that the flame retardant stability is extremely poor.
The applicant states that the phosphorus-containing compound with amino group, the epoxy resin composition, the preparation method and the application of the present invention are illustrated by the above examples, but the present invention is not limited to the above detailed method, that is, the present invention is not meant to be implemented by relying on the above detailed method. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The phosphorus-containing compound with the amino group is characterized by having the following formula I:
wherein, R, R1、R2Independently selected from substituted or unsubstituted C1～C5E is an integer of 0 to 20, k is an integer of 0 to 30, and h is an integer of 0 to 2.
2. The phosphorus-containing compound having amino group as claimed in claim 1, wherein R, R1、R2Independently selected from unsubstituted C1～C5A linear alkylene group of (a).
3. The phosphorus-containing compound with amino groups as claimed in claim 1 or 2, wherein e is an integer of 0 to 5.
4. The phosphorus-containing compound with amino groups as claimed in any of claims 1 to 3, wherein k is an integer of 10 to 25.
5. The phosphorus-containing compound having amino group according to any one of claims 1 to 4, wherein the phosphorus-containing compound having amino group is preferably
Any one of them.
6. The method for preparing a phosphorus compound having an amino group according to any one of claims 1 to 5, wherein the method comprises: the phosphorus-containing flame retardant with the reactive group is obtained by a substitution reaction of a compound containing-P-OH and an amino compound.
7. An epoxy resin composition comprising the phosphorus-containing compound having an amino group according to any one of claims 1 to 5.
8. The epoxy resin composition according to claim 7, wherein the epoxy resin composition comprises the following components in parts by weight: 80-120 parts of bisphenol A type epoxy resin, 20-50 parts of phosphorus-containing compound with amino and 0.2-1 part of 2-methylimidazole.
9. The epoxy resin composition according to claim 7 or 8, wherein the epoxy resin composition further comprises dicyandiamide.
10. Use of the epoxy resin composition according to any one of claims 7 to 9 in flame retardant materials.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2754319A (en) * | 1948-07-01 | 1956-07-10 | Union Carbide & Carbon Corp | Production of diesterified phosphono derivatives of polyfunctional organic compounds |
| DE2212390A1 (en) * | 1971-03-18 | 1972-09-21 | Interstab Ltd | Curing agents for epoxy resins - produced by condensation of polyamines with aldehydes or ketones,and sec phosphites |
| US4125575A (en) * | 1975-07-18 | 1978-11-14 | Compagnie Francaise De Produits Industriels | Phosphonylated amides |
| JPS5998150A (en) * | 1982-11-26 | 1984-06-06 | Adeka Argus Chem Co Ltd | Halogen-containing resin composition |
| CN109336927A (en) * | 2018-10-26 | 2019-02-15 | 洪湖市泰科技有限公司 | A kind of preparation method of phosphine system reactive flame retardant monomer |
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2019
- 2019-09-11 CN CN201910858202.2A patent/CN112480372B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2754319A (en) * | 1948-07-01 | 1956-07-10 | Union Carbide & Carbon Corp | Production of diesterified phosphono derivatives of polyfunctional organic compounds |
| DE2212390A1 (en) * | 1971-03-18 | 1972-09-21 | Interstab Ltd | Curing agents for epoxy resins - produced by condensation of polyamines with aldehydes or ketones,and sec phosphites |
| US4125575A (en) * | 1975-07-18 | 1978-11-14 | Compagnie Francaise De Produits Industriels | Phosphonylated amides |
| JPS5998150A (en) * | 1982-11-26 | 1984-06-06 | Adeka Argus Chem Co Ltd | Halogen-containing resin composition |
| CN109336927A (en) * | 2018-10-26 | 2019-02-15 | 洪湖市泰科技有限公司 | A kind of preparation method of phosphine system reactive flame retardant monomer |
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