CN113372385B - Phosphorus-benzene bisphenol polymer and preparation method and application thereof - Google Patents
Phosphorus-benzene bisphenol polymer and preparation method and application thereof Download PDFInfo
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- CN113372385B CN113372385B CN202110630018.XA CN202110630018A CN113372385B CN 113372385 B CN113372385 B CN 113372385B CN 202110630018 A CN202110630018 A CN 202110630018A CN 113372385 B CN113372385 B CN 113372385B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 44
- YYPXKRAXSNFGJH-UHFFFAOYSA-N C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.[P].C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.[P].C1=CC=CC=C1 YYPXKRAXSNFGJH-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 12
- IBDMRHDXAQZJAP-UHFFFAOYSA-N dichlorophosphorylbenzene Chemical compound ClP(Cl)(=O)C1=CC=CC=C1 IBDMRHDXAQZJAP-UHFFFAOYSA-N 0.000 claims abstract description 7
- TXFOLHZMICYNRM-UHFFFAOYSA-N dichlorophosphoryloxybenzene Chemical compound ClP(Cl)(=O)OC1=CC=CC=C1 TXFOLHZMICYNRM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 5
- -1 tetramethyl bisphenol compound Chemical class 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims description 38
- 239000003822 epoxy resin Substances 0.000 claims description 26
- 229920000647 polyepoxide Polymers 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000004848 polyfunctional curative Substances 0.000 claims description 6
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 239000006184 cosolvent Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 16
- 239000011574 phosphorus Substances 0.000 abstract description 16
- 230000009477 glass transition Effects 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 239000004033 plastic Substances 0.000 abstract description 5
- 229920003023 plastic Polymers 0.000 abstract description 5
- 239000002861 polymer material Substances 0.000 abstract 1
- 239000011342 resin composition Substances 0.000 description 41
- 238000000034 method Methods 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 17
- 238000012360 testing method Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 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 class N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 239000003063 flame retardant Substances 0.000 description 8
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 7
- 239000011889 copper foil Substances 0.000 description 7
- 238000000105 evaporative light scattering detection Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- IXHXEDWHGKBGDN-UHFFFAOYSA-N C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.OC1=C(C=CC=C1)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.OC1=C(C=CC=C1)C1=CC=CC=C1 IXHXEDWHGKBGDN-UHFFFAOYSA-N 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 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 2
- 238000007731 hot pressing Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- KMRIWYPVRWEWRG-UHFFFAOYSA-N 2-(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)benzene-1,4-diol Chemical compound OC1=CC=C(O)C(P2(=O)C3=CC=CC=C3C3=CC=CC=C3O2)=C1 KMRIWYPVRWEWRG-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
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- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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- 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
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- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
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- 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
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- Epoxy Resins (AREA)
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Abstract
The invention provides a phosphorus-benzene bisphenol polymer and a preparation method and application thereof, and relates to the technical field of high polymer materials. The structure of the phosphorus-benzene bisphenol polymer is shown as a formula I or a formula II, and the phosphorus-benzene bisphenol polymer is obtained by reacting phenylphosphonic dichloride or phenyl dichlorophosphate with a tetramethyl bisphenol compound. The phosphorus content of the phosphorus-benzene bisphenol polymer is up to more than 5 percent, the phosphorus-benzene bisphenol polymer is easy to be added into a resin solvent for modulation, the manufactured electronic plastic has better flame retardance and heat resistance, and the manufactured plate has the advantages of high tearing strength, high glass transition temperature, proper hardness of the electronic plate and the like.
Description
Technical Field
The invention relates to the technical field of high molecular materials, in particular to a phosphorus-benzene bisphenol polymer and a preparation method and application thereof.
Background
The brominated flame retardant is a common flame retardant in printed circuit boards, and the tetrabromobisphenol A type epoxy resin is a common brominated flame retardant which has good flame retardance. Based on the requirement of environmental protection, the bromine flame retardant is replaced by the common phosphorus flame retardant.
In recent years, phosphorus-containing epoxy resins synthesized by phenanthrene type phosphorus-containing compounds such as 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) or 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide (ODOPB) and epoxy resins are widely used for manufacturing halogen-free FR-4 copper-clad glass fiber laminated plates, and the obtained halogen-free copper clad plates have good comprehensive performance, but have the problems of high water absorption, low heat resistance and the like.
Patent application with publication number CN1435446A discloses a halogen-free flame-retardant polycarbonate which is prepared by mixing and granulating phenylphosphonyl chloride and bisphenol compounds. However, this material is obtained by direct kneading, and the components in the composition are complicated, and there is no definite composition, and an alkali metal or alkaline earth metal arylsulfonic acid needs to be further added to increase the flame retardant effect, and it cannot be directly added to or dissolved in a solvent as a flame retardant in the resin of the printed wiring board.
Disclosure of Invention
In view of the above, it is necessary to provide a phenylphenol polymer having a phosphorus content of 5% or more, which can be easily added to a resin solvent for preparation, and which can be used to produce an electronic plastic having good flame retardancy and heat resistance, and a sheet having high tear strength, high glass transition temperature, and suitable hardness for electronic sheets.
The structure of the phosphorus-benzene bisphenol polymer provided by the invention is shown as a formula I or a formula II:
wherein n is 2-5, and R is selected from: CH (CH)3CCH3、
One kind of (1).
The phosphorus-benzene bisphenol polymer has the phosphorus content of more than 5 percent, is easy to be added into a resin solvent for modulation, the manufactured electronic plastic has better flame retardance and heat resistance, and the manufactured plate has the advantages of high tearing strength, high glass transition temperature, high electronic plate size stability and smoothness and the like.
The invention also provides a preparation method of the phosphorus-benzene bisphenol polymer, which is carried out according to a synthetic route shown in a formula III or a formula IV:
mixing phenylphosphonic dichloride or phenyl dichlorophosphate and a tetramethyl bisphenol compound, adding a solvent and a cosolvent, and carrying out reflux reaction to obtain the compound shown in the formula I or the formula II.
In one embodiment, the tetramethylbisphenol compound is selected from: tetramethyl bisphenol A,
In one embodiment, the solvent is selected from: toluene.
In one embodiment, the co-solvent is selected from: one or two of pyridine and 4-dimethylamino pyridine.
In one embodiment, the reflux reaction temperature is 120-180 ℃ and the reaction time is 10-20 hours.
In one embodiment, the molar ratio of the phenylphosphonic dichloride or phenyl dichlorophosphate to the tetramethylbisphenol compound is 1: (1-2).
In one embodiment, the reflux reaction further comprises a purification step after completion of the reflux reaction: and washing the product with tetrahydrofuran or water, and distilling to remove the solvent to obtain the purified target product.
The invention also provides an epoxy resin composition which comprises the phosphorus-benzene bisphenol polymer.
In one embodiment, the epoxy resin composition comprises the following raw materials in parts by weight: 90-110 parts of phenolic epoxy resin, 40-60 parts of a phosphorus-benzene bisphenol polymer, 25-35 parts of a hardener, 0.05-0.2 part of a hardener accelerator and 140-160 parts of an organic solvent.
The invention also provides an application of the phosphorus-benzene bisphenol polymer or the epoxy resin composition in preparing a laminated plate.
Compared with the prior art, the invention has the following beneficial effects:
the phosphorus-benzene bisphenol polymer has the phosphorus content of more than 5 percent, is easy to be added into a resin solvent for modulation, and the manufactured electronic plastic has better flame retardance and heat resistance, and the manufactured plate has the advantages of high tearing strength, high glass transition temperature, high electronic plate size stability and smoothness and the like.
Drawings
FIG. 1 shows the NMR spectrum of a phenylphenol polymer A1.
FIG. 2 shows the NMR spectrum of the phenylphenol bisphenol A4.
Detailed Description
To facilitate an understanding of the invention, a more complete description of the invention will be given below in terms of preferred embodiments. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In the following examples and comparative examples, the starting materials were either commercially available or formulated by conventional methods unless otherwise specified.
Example 1
(1) A phosphorus benzene bisphenol polymer A1 is prepared by the following method:
erecting a reaction bottle, arranging a thermometer and a return pipe on the reaction bottle, condensing with water at 0 ℃, adding 2.84g of tetramethyl bisphenol A, 10ml of toluene and 10ml of pyridine into the reaction bottle, stirring for dissolving, then adding 0.49g of phenylphosphonyl dichloride in batches one by one, introducing nitrogen, heating to 140 ℃ for heating and stirring reaction, after reacting for 16 hours, stopping the reaction, adding THF (tetrahydrofuran) to clean the crude product, and then carrying out reduced pressure distillation to obtain a product A1 with the structure shown in formula V, wherein the yield is more than 80%. The molecular MASS of MASS detection is 2316.7, n is 5, and the phosphorus content is 6.68%. The results of hydrogen nuclear magnetic resonance spectroscopy (model number Mercury-VX200MHz, nuclear magnetic resonance spectrometer manufactured by Varian corporation) are shown in FIG. 1.
(2) The epoxy resin composition is prepared by taking A1 as a raw material, and is specifically prepared by the following method:
the raw materials were weighed out in the ratios in table 2, placed in a stirrer, stirred at room temperature, and mixed well to obtain resin composition C1.
(3) The resin composition C1 is used as a raw material to prepare a laminated plate, and the laminated plate is prepared by the following method:
7628 glass fiber cloth was coated with the resin composition C1 by a roll coater so that the resin and glass fiber cloth were impregnated in an amount of 43%, and the resultant was dried by heating at 180 ℃ for 2 to 5 minutes in a dryer to prepare prepregs in a semi-cured state, and eight prepregs were laminated to each other, and one copper foil of 1oz was laminated on each of the outermost layers on both sides. Then, the resultant was hot-pressed to obtain a copper foil-coated laminate D1. Wherein the hot pressing conditions are as follows: heating to 200 deg.C at a heating rate of 2.0 deg.C/min, and hot pressing at 200 deg.C under a pressure of 25 kg/sq.cm (initial pressure of 12 kg/sq.cm) for 90 min.
Example 2
(1) A phosphorus benzene bisphenol polymer A2 is prepared by the following method:
substantially the same procedure as in example 1 for the preparation of a phenylphenol polymer was conducted, except that the reflux reaction time was 6 hours, to obtain product A2. The yield was 88.1%, the MASS of the MASS detection molecule 1942, n-4, and the phosphorus content was 6.92%.
(2) The epoxy resin composition is prepared by taking A2 as a raw material, and is specifically prepared by the following method:
the raw materials were weighed out in the ratios in table 2, placed in a stirrer, stirred at room temperature, and mixed well to obtain resin composition C2.
(3) The resin composition C2 is used as a raw material to prepare a laminated plate, and the laminated plate is prepared by the following method:
a laminate D2 was obtained in the same manner as in example 1 except that the resin composition C2 was replaced with the resin composition.
Example 3
(1) A phosphorus benzene bisphenol polymer A3 is prepared by the following method:
substantially the same procedure as in example 1 for preparing a phosphorus-benzene bisphenol polymer was conducted, except that 2.84g of tetramethylbisphenol A was replaced with 3.24g
The product A3 with the structure shown in formula VI is obtained, the yield is 86%, the MASS detection molecular weight is 1405, n is 3, and the phosphorus content is 5.33%.
(2) The epoxy resin composition is prepared by taking A3 as a raw material, and is specifically prepared by the following method:
the raw materials were weighed out in the ratios in table 2, placed in a stirrer, stirred at room temperature, and mixed well to obtain resin composition C3.
(3) The resin composition C3 is used as a raw material to prepare a laminated plate, and the laminated plate is prepared by the following method:
a laminate D3 was obtained in the same manner as in example 1 except that the resin composition C3 was replaced with the resin composition.
Example 4
(1) A phosphorus benzene bisphenol polymer A4 is prepared by the following method:
the procedure was substantially the same as that for the preparation of the phenylphenol bisphenol polymer in example 1, except that 0.49g of phenylphosphonyl dichloride was replaced with 0.53g of phenyl dichlorophosphate to give product A4 represented by the formula VII at a yield of 89%, a MASS molecular weight of 1357.4, n-3 and a phosphorus content of 5.8%. The results of hydrogen nuclear magnetic resonance spectroscopy (model number Mercury-VX200MHz, nuclear magnetic resonance spectrometer manufactured by Varian corporation) are shown in FIG. 2.
(2) The epoxy resin composition is prepared by taking A4 as a raw material, and is specifically prepared by the following method:
the raw materials were weighed out in the ratios in table 2, placed in a stirrer, stirred at room temperature, and mixed well to obtain resin composition C4.
(3) The resin composition C4 is used as a raw material to prepare a laminated plate, and the laminated plate is prepared by the following method:
a laminate D4 was obtained in the same manner as in example 1 except that the resin composition C4 was replaced with the resin composition.
Example 5
(1) A phosphorus benzene bisphenol polymer A5 is prepared by the following method:
substantially the same procedure as in example 4 was conducted to prepare a phenylphenol polymer except that 2.84g of tetramethylbisphenol A was replaced with 3.24g of
The product A5 with the structure shown in formula VIII is obtained, the yield is 83%, the MASS detection molecular weight is 2058, n is 3, and the phosphorus content is 5.64%.
(2) The epoxy resin composition is prepared by taking A5 as a raw material, and is specifically prepared by the following method:
the raw materials were weighed out in the ratios in table 2, placed in a stirrer, stirred at room temperature, and mixed well to obtain resin composition C5.
(3) The resin composition C5 is used as a raw material to prepare a laminated plate, and the laminated plate is prepared by the following method:
a laminate D5 was obtained in the same manner as in example 1 except that the resin composition C5 was replaced with the resin composition.
Comparative example 1
(1) An epoxy resin composition is prepared by the following steps:
the raw materials were weighed in the raw material ratios in table 2, placed in a stirrer, stirred at room temperature, and mixed uniformly to obtain resin composition E1.
(3) The resin composition E1 is used as a raw material to prepare a laminated plate, and the laminated plate is prepared by the following method:
a laminate F1 was obtained in the same manner as in example 1 except that the resin composition was changed to the resin composition E1.
Comparative example 2
(1) An epoxy resin composition is prepared by the following steps:
the raw materials were weighed in the raw material ratios in table 2, placed in a stirrer, stirred at room temperature, and mixed uniformly to obtain resin composition 2.
(3) The resin composition E2 is used as a raw material to prepare a laminated plate, and the laminated plate is prepared by the following method:
a laminate F2 was obtained in the same manner as in example 1 except that the resin composition was changed to the resin composition E2.
Comparative example 3
(1) An epoxy resin composition is prepared by the following steps:
the raw materials were weighed in the raw material ratios in table 2, placed in a stirrer, stirred at room temperature, and mixed uniformly to obtain resin composition E3.
(3) The resin composition E3 is used as a raw material to prepare a laminated plate, and the laminated plate is prepared by the following method:
a laminate F3 was obtained in the same manner as in example 1 except that the resin composition was changed to the resin composition E3.
Comparative example 4
(1) A phosphorus benzene bisphenol polymer B2 is prepared by the following method:
substantially the same procedure as in example 1 was conducted to produce a phenylphenol polymer, except that the reflux reaction temperature was 100 ℃ and the reaction time was 16 hours, to obtain product B2. MASS detection molecule MASS less than 1000, reduced reactivity.
(2) The epoxy resin composition is prepared by taking B2 as a raw material, and is specifically prepared by the following method:
the raw materials were weighed in the raw material ratios in table 2, placed in a stirrer, stirred at room temperature, and mixed uniformly to obtain resin composition E4.
(3) The resin composition E2 is used as a raw material to prepare a laminated plate, and the laminated plate is prepared by the following method:
a laminate F4 was obtained in the same manner as in example 1 except that the resin composition was changed to the resin composition E4.
Comparative example 5
(1) A phosphorus benzene bisphenol polymer B3 is prepared by the following method:
substantially the same procedure as in example 1 was conducted to produce a phenylphenol polymer, except that the reflux reaction temperature was 200 ℃ and the reaction time was 16 hours, to obtain product B3. The MASS detection product has complex components, n is more than 8, and the phosphorus content is less than 1%.
(2) The epoxy resin composition is prepared by taking B3 as a raw material, and is specifically prepared by the following method:
the raw materials were weighed in the raw material ratios in table 2, placed in a stirrer, stirred at room temperature, and mixed uniformly to obtain resin composition E5.
(3) The resin composition E3 is used as a raw material to prepare a laminated plate, and the laminated plate is prepared by the following method:
a laminate F5 was obtained in the same manner as in example 1 except that the resin composition was changed to the resin composition E5.
Comparative example 6
A phosphorus benzene bisphenol polymer B1 is prepared by the following method:
the preparation method of the phosphorus-benzene bisphenol polymer in the example 1 is basically the same, except that the cosolvent pyridine is not added. Product B1 was obtained. MASS detection molecule MASS less than 1000, reduced reactivity.
The raw materials, yields, phosphorus contents, solubilities, etc. of the phosphorus-phenyl-bisphenol polymers in examples and comparative examples are shown in Table 1.
TABLE 1 raw materials, reaction conditions, yields and solubilities of the phenylphenol bisphenol polymers in examples and comparative examples
As can be seen from the above table, the phenylphenol polymer a 1-a 5 of the embodiments of the present invention has stable components and high solvent compatibility, and can be conveniently prepared and mixed with other plastics or substrate applications.
The raw material composition ratios of the resin compositions in examples and comparative examples are shown in Table 2.
TABLE 2 raw material composition (parts by weight) of the resin compositions in examples and comparative examples
Wherein, the novolac epoxy resin adopts KEP-1138 (Korea KOLON), the BDP is bisphenol A-bis (diphenyl phosphate) (CAS number: 5945-33-5, Taiwan Liu and chemical industry), and the hardener (curing agent) adopts EPICLON HPC-8000-65T.
Experimental example 1
The performance tests were performed on each laminate in the examples and the comparison as follows:
(1) glass transition temperature test: the glass transition temperature (Tg) was measured using a Dynamic Mechanical Analyzer (DMA). The glass transition temperature test specification is IPC-TM-650.2.4.25C and No. 24C test method of The Institute for Interconnecting and Packaging Electronic Circuits (IPC).
(2) Water absorption test: a pressure cooker boil out test (PCT) was performed, and the laminate was placed in a pressure vessel and tested for high humidity resistance at 121 ℃, saturation humidity (100% r.h.) and 1.2 atm for 2 hours.
(3) Testing the thermal expansion coefficient and the expansion rate in the Z-axis direction: the thermal expansion of the sample was measured by a thermal expansion analyzer of TA instruments model TA 2940 under 50 ℃ to 26 DEG CTemperature rise rate of 5 degrees per minute at 0 ℃ and 3X 3mm of test sample2The thermal expansion coefficient in the thickness direction (Z-axis direction) and the expansion rate in the Z-axis direction of the laminate sample were measured.
(4) Thermal decomposition temperature test: the temperature at which the mass is reduced by 5% compared to the initial mass, i.e., the thermal decomposition temperature, is measured by a thermogravimetric analyzer (TGA).
(5) Lead-free solder test: five copper foil-containing substrates with the size of 290mm multiplied by 210mm are subjected to Lead free IR reflow for 3 times, and then whether the appearance of the copper foil substrate has the phenomenon of plate explosion or not is observed.
(6) And (3) testing the tearing strength: the peel strength refers to the adhesion of the copper foil to the substrate, and is usually expressed in terms of the amount of force required to peel the copper foil from the surface of the substrate vertically per inch (25.4mm) of width. MIL-P-55110E specifies a 1oz copper foil substrate and a specification of 8 lb/in.
(7) Flame resistance test: the printed circuit board was fixed in a vertical position by a vertical burning test method using UL94V, burned with a bunsen burner, and its self-ignition extinction and combustion-supporting characteristics were compared.
(8) And (3) rubber discharge layering detection: the appearance of the laminate was inspected. If the lamination and the filler are layered and precipitated among the components of the laminated plate, the resin distribution is not uniform or the filler distribution is not uniform, the phenomenon of glue discharging and layering is indicated (judged as NG, namely No Good); if the phenomenon does not exist, the phenomenon of rubber discharge delamination does not exist (the judgment result is OK).
(9) And (3) flatness test: the laminate of A4 size was inspected and laid flat on a granite marble table. If the laminated plate can be flatly pasted on the platform, and the appearance is smooth and uniform, and has no uneven wrinkles or lines or particle bulges, the flatness is good; if the appearance is not smooth and uneven, or there are uneven wrinkles or lines or particle protrusions, the flatness is inferior.
The test results are shown in table 3.
TABLE 3 Properties of laminates in examples and comparative examples
As can be seen from Table 3, the laminates D1 to D5 prepared from the phosphorus-benzene bisphenol polymers A1 to A5 of examples 1 to 5 of the present invention as the flame retardant or the epoxy resin of the hardener have excellent heat resistance and dimensional stability, good smoothness and no sealant drainage layer. The laminate of the comparative example was poor in flatness, delamination of the binder (e.g., F1, F3, F5), poor in flame retardancy (e.g., F2, F5), or low in tear strength (e.g., F4).
Comparing laminated board F4, D2, D1 and F5, polymerization amount n is 2 ~ 5 and is good, n is too low (< 2), and phosphorus benzene bisphenol polymer phosphorus content is on the high side, and tear strength is on the low side, and n is too high (> 5), and phosphorus content is on the low side, and the flame retardant efficiency variation only has V1 grade, and laminated board thermal stability variation, and the solder resistance variation, the planarization is poor, also has the phenomenon of binder removal layering.
Comparing laminates F2, D1 and F3, the addition amount of the phosphorus-benzene bisphenol polymer is too low, the tear strength of the laminate is low, the addition amount of the phosphorus-benzene bisphenol polymer is too high, the heat resistance of the laminate is poor, the thermal stability is poor, and the solder resistance test is poor.
Comparative laminates F1, D1 and D4, compared to the conventional BDP, used the phenylphosphonic bisphenol polymer of the present invention (R is CH)3CCH3) The obtained laminated plate has the advantages of high Tg, high heat resistance, high thermal stability, strong tearing strength, no adhesive discharge seal layer and good smoothness.
Comparative laminates F1, D3 and D5, compared to the conventional BDP, used the phenylphosphonic bisphenol polymer of the present invention (R is
) The obtained laminated plate has the advantages of high Tg, high heat resistance, high thermal stability, strong tearing strength, no adhesive discharge seal layer and good smoothness.
The Tg, heat resistance and thermal stability of the comparative laminates F1, D1 and D3 were better for D1 and D3 than for the commonly used BDP.
The Tg, heat resistance and thermal stability of the comparative laminates F1, D4 and D5 were better for D4 and D5 than for the commonly used BDP.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (7)
1. The epoxy resin composition is characterized by comprising the following raw materials in parts by weight: 90-110 parts of phenolic epoxy resin, 40-60 parts of a phosphorus-benzene bisphenol polymer, 25-35 parts of a hardener, 0.05-0.2 part of a hardener accelerator and 140-160 parts of an organic solvent; the structure of the phosphorus-benzene bisphenol polymer is shown as a formula I or a formula II:
wherein n is 3-5, and R is selected from: CH (CH)3CCH3、
One of (1);
the preparation method of the phosphorus-benzene bisphenol polymer is carried out according to a synthetic route shown in a formula III or a formula IV:
mixing phenylphosphonic dichloride or phenyl dichlorophosphate and a tetramethyl bisphenol compound, adding a solvent and a cosolvent, and carrying out reflux reaction at the reflux reaction temperature of 120-110 ℃ for 10-20 hours to obtain the compound shown in the formula I or the formula II.
2. The epoxy resin composition of claim 1, wherein the tetramethylbisphenol compound is selected from the group consisting of: tetramethyl bisphenol A,
3. The epoxy resin composition of claim 1, wherein the solvent is selected from the group consisting of: toluene.
4. The epoxy resin composition of claim 1, wherein the co-solvent is selected from the group consisting of: one or two of pyridine and 4-dimethylamino pyridine.
5. The epoxy resin composition according to claim 1, wherein the molar ratio of phenylphosphonyl dichloride or phenyl dichlorophosphate to the tetramethylbisphenol compound is 1: (1-2).
6. The epoxy resin composition according to any one of claims 1 to 5, further comprising a purification step after completion of the reflux reaction: and washing the product with tetrahydrofuran or water, and distilling to remove the solvent to obtain the purified target product.
7. Use of the epoxy resin composition of claim 1 in the preparation of a laminate.
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