CN100365035C - Phosphorous polymer having phenolic structure and its use - Google Patents
Phosphorous polymer having phenolic structure and its use Download PDFInfo
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- CN100365035C CN100365035C CNB001235249A CN00123524A CN100365035C CN 100365035 C CN100365035 C CN 100365035C CN B001235249 A CNB001235249 A CN B001235249A CN 00123524 A CN00123524 A CN 00123524A CN 100365035 C CN100365035 C CN 100365035C
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Abstract
The present invention discloses a novel phosphorus containing polymer in a phenolic structure and simultaneously discloses the purposes of the polymer for preparing prepregs, composite materials, laminated objects, printed circuit boards and electronic packaging materials. A product prepared from the phosphorus containing polymer of the present invention has the advantages of favorable processability, no need of an additional flame retardant, high flame retardancy and high heat resistance.
Description
The present invention relates to phosphorous polymer of a kind of tool phenolic structure and uses thereof.This phosphorous polymer can be used as the solidifying agent of composition epoxy resin, and after the reaction of itself and epoxyhalopropane, itself also can be used as the Resins, epoxy composition.The flame-retarding characteristic and high heat resistance and the toxic substances such as not halogen-containing or antimonous oxide that have the UL94V-O standard by the prepared product of this base polymer.
Matrix material, especially epoxide resin material have been widely used in fields such as for example application, electric insulation, building building materials, tackiness agent and lajminated material because of having simple and easy processibility, high security, superior mechanicalness and chemical property.The veneer sheet made from Resins, epoxy particularly, because this resinoid is strong to the bounding force of strongtheners such as glasscloth, and there is not volatile component when solidifying and molding shrinkage is little, therefore the veneer sheet of gained has advantages such as use range is wide, physical strength is good, electric insulating quality is good, chemical proofing is good, and can be widely used in electric and electronic product.
Yet because the fine-line and the highdensity requirement of printed circuit board (PCB) improved day by day, veneer sheet also is required to have more excellent electrical properties, mechanical properties and heat-resisting processibility.Glass tansition temperature (Tg) after the FR4 veneer sheet of at present wide usefulness solidifies is about 130 ℃ mostly, thus in the printed circuit board (PCB) processing procedure, surpass 200 ℃ cutting and boring processing, and break easily or plate bursting in the welding processing procedure more than 270 ℃.Therefore the various laminate sheet materials of emphasizing to have high heat stability and high glass tansition temperature are just successively in the active development.In addition, to another important requirement of veneer sheet for need have flame retardant resistance.Owing to often be used in the vehicles such as aircraft, automobile and public transportation, be directly connected to the safety of lives and properties, so the flame retardant resistance of printed circuit board (PCB) be definitely necessary.
For making veneer sheet have flame retardant resistance, must import and have the material that to isolate flame and reduce ignition quality.The veneer sheet that Resins, epoxy/glass fibers is maintained, can use halogen contained compound, particularly brominated Resins, epoxy and solidifying agent, and cooperate for example flame retardant of antimonous oxide class, in the hope of reaching harsh requirement (as the UL94V-O grade) to the veneer sheet flame-retarding characteristic.Yet Resins, epoxy desires to reach the level as UL94V-O, and its bromine content needs up to 17% to 21%, and must be used antimonous oxide or other fire retardants.But antimonous oxide has been listed in carcinogenic substance; And bromine not only can produce acrid free radical and hydrogen bromide in combustion processes, and the aromatics of high bromine content more can produce the bromination furans and the bromination two English compounds of severe toxicity, has a strong impact on health and environment.Therefore the recovery of substrate and processing all become serious problems.As mentioned above, seeking a kind of new fire retardant material is very urgent with the problem of environmental pollution that improves present veneer sheet and caused in fact.
Phosphorus series compound has been widely studied and has used the fire retardant that has the environmental protection notion as a new generation.For example use the organic compound (for example triphenyl, trityl phosphoric acid ester, phosphoric acid etc.) that contains red phosphorus or phosphorus to substitute halogen compounds as fire retardant, to improve the flame retardant resistance of macromolecular material or gel-type resin.In resin, need to add and just can be effective in a large number yet directly add this compounds, and the characteristic that can directly influence resin base material electrical properties etc. and cause difficulty in the practicality for example.In recent years, cooperate environmental protection and safety to consider, to use phosphatization Resins, epoxy to substitute the prescription of brominated epoxy resin as fire-retardant basal plate, for example United States Patent (USP) 5,376, use for No. 453 the phosphoric acid ester of band epoxy group(ing) to cooperate nitrogenous ring-type solidifying agent to make veneer sheet, but, therefore add multiple phosphoric acid ester epoxide in order to remedy the standard that the phosphorus content deficiency promptly is difficult to reach UL94V-O; United States Patent (USP) 5,458, then utilize for No. 978 epoxy phosphate ester to cooperate nitrogen-containing epoxy thermoset and metal composite as solidifying agent, about 175 ℃ of its finished glass tansition temperature, flame-retardant nature then only reaches UL94V-O edge (42 seconds with respect to threshold value 50 seconds) and United States Patent (USP) 5,506, No. 313 those disclosed herein.Yet above-mentioned patent all fails to reach required difficult right property and high heat resistance.
The object of the present invention is to provide a kind of phosphorous polymer of tool phenolic structure, to overcome the shortcoming of prior art.
The present invention relates to phosphorous polymer of a kind of tool phenolic structure and uses thereof simultaneously.Can make preimpregnation thing, matrix material, lajminated material, printed circuit board (PCB) and the electronic package material etc. of tool flame retardant resistance and high heat resistance by this polymkeric substance.
The objective of the invention is to realize by following manner: a kind of phosphorous polymer of tool phenolic structure is characterized by and has following repeating unit:
Wherein, R
1And R
2Can be identical or different, and represent H, C
1-20Alkyl, phenoxy group, phenyl-C
1-4Phenyl-the C that replaces through hydroxyl on alkyl, the phenyl ring
1-4Alkyl;
R
aFor can be through C
1-4Phenylene, singly-bound that alkyl replaces
Or-CHR
3-, this R
3Be H, C
1-4Alkyl, CH
2=CH, phenyl, furyl, C
1-4The C that replaces through hydroxyl on alkyl phenyl or the phenyl ring
1-4Alkyl phenyl;
(b) be selected from following formula (b1) or (b2) the phosphorous repeating unit of any one:
R wherein
1, R
2, and R
aDefinition as described above, and
X is Sauerstoffatom or electron pair,
T is Sauerstoffatom or chemical bond,
R ' and R " can be identical or different, and be C
1-18Alkyl, phenyl or phenyl-C
1-6Alkyl, or
Can represent
R
iAnd R
jCan be identical or different, and be hydrogen or C
1-18Alkyl; Or
Wherein each substituting group such as above-mentioned definition; And
Choose wantonly
Wherein
Or
R
bBe H, C
1-4Alkyl, CH
2=CH, phenyl, furyl, C
1-4The C that replaces through hydroxyl on alkyl phenyl or the phenyl ring
1-4Alkyl phenyl,
R
cBe NH
2, OH, C
1-10Alkyl, phenyl or benzoyl.
The phosphorous polymer of tool phenolic structure of the present invention can be used as the solidifying agent of composition epoxy resin.About a kind of composition epoxy resin, its phosphorous polymer that contains tool phenolic structure of the present invention is as solidifying agent again in the present invention in view of the above.
Moreover the phosphorous epoxy polymer of the relevant again a kind of tool phenolic structure of the present invention is must the person with the epoxyhalopropane reaction by the phosphorous polymer of tool phenolic structure of the present invention.
In addition, the relevant again a kind of composition epoxy resin of the present invention, its phosphorous epoxy polymer that contains tool phenolic structure of the present invention is as Resins, epoxy composition person.
Again, the relevant again a kind of composition epoxy resin of the present invention, it contains phosphorous polymer of the present invention as solidifying agent and contain phosphorous epoxy polymer of the present invention as Resins, epoxy composition person.
Composition epoxy resin of the present invention can be according to prior art method, in not using under the halid situation, cooperates the silicon Rankine, makes electronic package material after mixing, pulverize, playing ingot, again through hot-forming and must meet the electronic packing body of environmental protection condition.This electronic packing body flame retardant effect, heat stable property, dimensional stability and electrical properties etc. all meet and even be much better than the standard of present product, be applicable to the electronic product of making electronics, space, traffic etc., and in order to make printed circuit board (PCB) and multilayer circuit board etc.
Among the present invention, comprise epoxy chloropropane and epoxy bromopropane in order to the epoxyhalopropane that makes the phosphorous epoxy polymer of tool phenolic structure with the phosphorous polymer reaction of tool phenolic structure.
R among the present invention
aAnd R
bShown " C
1-4Alkyl " reach " C
1-4Alkyl phenyl " or " C that replaces through hydroxyl on the phenyl ring
1-4Alkyl phenyl " in C
1-4Examples of alkyl comprises methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, second butyl, tributyl etc.
R ' and R " shown in " phenyl-C
1-6Alkyl " in C
1-6Examples of alkyl comprises above-mentioned C
1-4The cited person of alkyl reaches amyl group, hexyl etc.
R
cShown C
1-10Examples of alkyl comprises above-mentioned C
1-6The described person of alkyl reaches heptyl, octyl group, nonyl, decyl etc.
R ' and R " shown in C
1-8Examples of alkyl comprises above-mentioned C
1-10The cited person of alkyl reaches 11 carbon backs, ten dicarbonyls, 13 carbon backs, 14 carbon backs, 15 carbon backs, 16 carbon backs, 17 carbon backs, 18 carbon backs etc.
R
1And R
2Shown C
1-20Examples of alkyl comprises above-mentioned C
1-18The cited person of alkyl reaches 19 carbon backs, 20 carbon backs etc.
Repeating unit in the phosphorous polymer of tool phenolic structure of the present invention (a) be derived from phenolic resinoid for example resol, cresol novolac resin, xylenol resol, phenol resol, isobutyl-phenol resol, the ninth of the ten Heavenly Stems phenol resol, bisphenol A phenolic resin, bisphenol F phenolic resin, bis-phenol resol, the polyphenol of melamine resin etc. and tool following formula repeating unit:
R in the formula
1And R
21 to 10 value is shown in definition, and Z as described above.
Repeating unit in the phosphorous polymer of tool phenolic structure of the present invention (b1) is the reaction product derived from the compound reaction gained of the phosphorous-chlorine functional group shown in the compound of above-mentioned phenolic resinoid and the following formula:
All symbols define as described above in the formula.
Repeating unit in the phosphorous polymer of tool phenolic structure of the present invention (b2) is the reaction product derived from the compound reaction gained of the phosphorous-chlorine functional group shown in the compound of above-mentioned phenolic resinoid and the following formula:
All symbols define as described above in the formula.
The repeating unit (c) that exists according to circumstances in the phosphorous polymer of tool phenolic structure of the present invention is derived from trimeric cyanamide (melamines) compound, cyanuric acid (cyanuric acid) compound and guanamines class (guanamine) compound such as benzene guanidine (benzoquanamine) etc.
Of the present invention contain Resins, epoxy used in the composition epoxy resin of phosphorous polymer as solidifying agent of tool phenolic structure can be phosphorous or not the phosphorated epoxy compounds as polymerized unit, the preferred embodiments of this polymerized unit for example comprises, bis-phenol (bisphenol), phenol, dihydroxy-benzene, connection phenol (biphenol), naphthalene, nitrogen heterocyclic ring, phenolic compound, siloxanyl monomers, the glycidyl ether of polysiloxane etc. (glycidyl ether), glycidyl amine (glycidyl amine), epihydric alcohol sulfide (glycidyl thiocther) and/or Racemic glycidol carboxylicesters (glycidyl carbonyl ester) etc.
The diglycidylether of bis-phenol can be diglycidylether that for example comprises dihydroxyphenyl propane glycidyl ether, Bisphenol F glycidyl ether, dihydroxyphenyl propane D glycidyl ether, bisphenol S glycidyl ether, tetramethyl-dihydroxyphenyl propane glycidyl ether, tetramethyl-Bisphenol F glycidyl ether, tetramethyl-dihydroxyphenyl propane D glycidyl ether, tetramethyl-bisphenol S glycidyl ether, tetrabromo-bisphenol etc., with and the derivative of glycidyl amine, epihydric alcohol sulfide and Racemic glycidol carboxylicesters etc.
The glycidyl ether example of connection phenol comprises, for example 4,4 '-Lian phenol glycidyl ether, 3,3 '-dimethyl-4,4 '-Lian phenol glycidyl ether, 3,3 ', 5,5 '-tetramethyl--4,4 '-Lian phenol glycidyl ether etc., with and the derivative of glycidyl amine, epihydric alcohol sulfide and Racemic glycidol carboxylicesters etc.
The glycidyl ether example of dihydroxy-benzene comprises, for example Resorcinol glycidyl ether, Resorcinol glycidyl ether, isobutyl-Resorcinol glycidyl ether etc., with and the derivative of glycidyl amine, epihydric alcohol sulfide and Racemic glycidol carboxylicesters etc.
The polyglycidyl ether example of phenolic aldehyde comprises, for example phenolic aldehyde polyglycidyl ether, cresols phenolic aldehyde polyglycidyl ether, bisphenol-A phenolic polyglycidyl ether etc., with and the derivative of glycidyl amine, epihydric alcohol sulfide and Racemic glycidol carboxylicesters etc.
Nitrogenous heterocyclic glycidyl ether example comprises, for example glycidyl ether of trimeric cyanamide glycidyl ether, benzene guanidine and the glycidyl ether of cyanuric acid etc., with and the derivative of glycidyl amine, epihydric alcohol sulfide and Racemic glycidol carboxylicesters etc.
Also can use the polyglycidyl ether of other polyphenol, example comprises, three (4-hydroxy phenyl) methane polyglycidyl ether, three (4-hydroxy phenyl) ethane polyglycidyl ether, three (4-hydroxy phenyl) propane polyglycidyl ether, three (4-hydroxy phenyl) butane polyglycidyl ether, three (3-methyl-4-hydroxy phenyl) methane polyglycidyl ether, three (3 for example, 5-dimethyl-4-hydroxy phenyl) methane polyglycidyl ether, four (4-hydroxy phenyl) ethane polyglycidyl ether, four (3,5-dimethyl-4-hydroxy phenyl) ethane polyglycidyl ether etc.
Electricity can use the mixture of above-mentioned various epoxy compoundss.
In the above-mentioned epoxy compounds, the preferably is polymer with bis phenol A glycidyl ether, Resorcinol glycidyl ether of tool difunctionality base etc., three (4-hydroxy phenyl) methane polyglycidyl ether of tool trifunctional base etc., compound or its mixtures such as tool four functional groups' four (4-hydroxy phenyl) ethane polyglycidyl ethers and cresols phenolic aldehyde polyglycidyl ether.
Again, the example of other epoxy compoundss is, for example with the various epoxy compoundss of the compound gained of hydrogen peroxide direct oxidation tool double bond structure, comprise the Dicyclopentadiene (DCPD) epoxide,
The epoxy compounds of the epoxide of styrene derivatives and cyclenes class etc. also all can be used in the composition of the present invention.
Composition epoxy resin of the present invention, except with the above-mentioned polymkeric substance of the present invention as the solidifying agent, still can optionally be used known not phosphorus curing agent, look closely composition must final character and decide.
Not phosphorus curing agent alleged among the present invention for example comprises, contain can with the compound of the active group of epoxy reaction, example is, for example amine compound, polyphenol, phenolic compound, naphthalene, siloxanes, polysiloxane, polythiol and poly carboxylic acid etc. or its mixture.
Suitable amine compound example comprises, for example dicyan diamide, two amido ditans etc.
Suitable polyphenol example for example comprises dihydroxy-benzene and bis-phenol such as dihydroxyphenyl propane, Bisphenol F, dihydroxyphenyl propane D, bisphenol S, tetramethyl-dihydroxyphenyl propane, tetramethyl-Bisphenol F, tetramethyl-dihydroxyphenyl propane D, tetramethyl-bisphenol S, three (4-hydroxy phenyl) methane, three (4-hydroxy phenyl) ethane, three (4-hydroxy phenyl) propane, three (4-hydroxy phenyl) butane, three (3-methyl-4-hydroxy phenyl) methane, three (3,5-dimethyl-4-hydroxy phenyl) methane, four (4-hydroxy phenyl) ethane, four (3,5-dimethyl-4-hydroxy phenyl) ethane etc.
Suitable phenolic compound example comprises, for example the phenol formaldehyde condensation body of phenol formaldehyde condensation body, cresols phenol formaldehyde condensation body, bisphenol-A phenolic condensation body, trimeric cyanamide-phenol.
The relevant again a kind of composition epoxy resin of the present invention, its contain react gained by the phosphorous polymer of tool phenolic structure of the present invention and epoxyhalopropane the phosphorous epoxy polymer of tool phenolic structure as the Resins, epoxy composition, and solidifying agent.
In this composition epoxy resin, except the phosphorous epoxy polymer of tool phenolic structure of the present invention as the Resins, epoxy composition, also can contain aforesaid phosphorous or not phosphorous epoxy compounds as the Resins, epoxy composition.
Can be the phosphorous polymer of tool phenolic structure of the present invention with solidifying agent used in the composition epoxy resin, also can be the known not phosphorus curing agent of above stated specification.
In the composition epoxy resin of the present invention, the addition of solidifying agent is decided on the reactive behavior hydrogen equivalent of each solidifying agent and the epoxy equivalent (weight) of Resins, epoxy, but usually, epoxy equivalent (weight) with respect to Resins, epoxy is 100%, the reactive behavior hydrogen equivalent of solidifying agent is generally 10 to 100%, and more preferably 50 to 90%.
Composition epoxy resin of the present invention can be applicable to the application in high heat-stable material field, as lajminated material, integrated circuit board encapsulation material, electronic package material, high heat-resisting powder body coating, engineering plastic, or the like.
In the composition epoxy resin of the present invention, also can optionally add curing catalyst, solvent, catalyzer and other additives.
Curing catalyst used among the present invention is for example tertiary amine, three grades of phosphines, quaternary ammonium salt, quaternary alkylphosphonium salt and imidazolium compoundss etc., and these curing catalysts can use separately also can mix two or more uses.
Tertiary amine comprises for example triethylamine, tributylamine, dimethyl amine ethanol, three (N, N-dimethyl amine ylmethyl) phenol, N, N-dimethyl amido cresols etc.
Three grades of phosphines comprise for example triphenyl phosphine.
Quaternary ammonium salt comprises for example Tetramethylammonium chloride, tetramethylammonium bromide, iodate tetramethyl-ammonium, chlorination triethylbenzene ammonium methyl, bromination triethylbenzene ammonium methyl, iodate triethylbenzene ammonium methyl etc.
Quaternary alkylphosphonium salt comprises for example chlorination 4-butyl-phosphonium, the Xiuization 4-butyl-phosphonium, the iodate 4-butyl-phosphonium, 4-butyl-phosphonium acetate title complex, tetraphenylphosphonium chloride, the Xiuization tetraphenylphosphoniphenolate, the iodate tetraphenylphosphoniphenolate, the tonsilon triphenyl phosphonium, bromination Yi base triphenyl phosphonium, iodate Yi base triphenyl phosphonium, Yi base triphenyl phosphonium acetate title complex, Yi base triphenyl phosphonium phosphorylated ligand compound, chlorination propyl group triphenyl phosphonium, bromination propyl group triphenyl phosphonium, iodate propyl group triphenyl phosphonium, the chlorinated butyl triphenyl phosphonium, bromination Ding base triphenyl phosphonium, iodate Ding base triphenyl phosphonium.
Imidazolium compounds comprises for example glyoxal ethyline, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-dodecyl imidazoles and 2-heptadecyl imidazoles.
Preferable curing catalyst is that imidazolium compounds is Ji quaternary alkylphosphonium salt is good with glyoxal ethyline, 2-phenylimidazole, Yi base triphenyl phosphonium acetate title complex and bromination Ding base triphenyl phosphonium especially.
If use curing catalyst, its usage quantity is preferably 0.005 to 5.0 weight % of composition gross weight, is preferably 0.05 to 4.5 weight %, and more preferably 0.1 to 4.0 weight % is preferably 0.15 to 3.0 weight %.
Though can shorten the reaction times if add excessive curing catalyst, easily generate by product and the applicability of product is had detrimentally affect.The equal variation of electrical properties, moisture resistance, water-absorbent when being used for circuit card lamination object for example; If the promotor addition is too little, then speed of response is unfavorable for the industry utilization excessively slowly.
But in the present composition also mat add solvent and adjust the viscosity of composition, range of viscosities should be adjusted to 20 to 500cps/25 ℃, viscosimetric analysis system placed 25 ℃ of thermostatic baths 4 hours with this composition, used Brookfield (Brookfield) viscometer in 25 ℃ of measurers.
The available solvent is for example organic aromatic hydrocarbon based, ketone, protic solvent, ethers and ester class etc.
Organic aromatic hydrocarbon based for example toluene, dimethylbenzene of comprising.
Ketone comprises for example acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK).
Protic solvent comprises for example N, dinethylformamide, N, N-diethylformamide, dimethyl sulfoxide (DMSO).
Ethers comprises for example ethylene glycol monomethyl ether, propylene glycol monomethyl ether.
The ester class comprises for example ethyl acetate, isopropyl acid ethyl ester.
Employed catalyzer can be for example methanol solution of 10% triphenylphosphine (catalyst A) etc. in the present composition.
Spendable other additives are this skill additive commonly used, for example modification agent, thermo-stabilizer, photostabilizer, ultraviolet absorbers and softening agent etc. among the present invention.
The present invention comprises being used for high heat-stable material field also relevant for the purposes of resin combination of the present invention, as lajminated material, integrated circuit board encapsulation material, electronic package material, high heat-resisting powder body coating, engineering plastic etc.But resin combination of the present invention also mat contains leaching method dipping base material and makes the preimpregnation thing.The base material that impregnation is used can use organic or inorganic material such as paper, glass, metal, carbon fiber, boron fibre, match network imitative (cellophane) and organic polymer etc.
Resin combination of the present invention can be made the lajminated material that comprises Copper Foil, fiber support thing and resin combination of the present invention according to prior art method.For example, glasscloth can be contained and be dipped in the resin combination of the present invention, then, heating dry this cloth of the universe and the dry preimpregnation thing of the universe.Gained preimpregnation thing can be preserved the several months long under room temperature, it preserves extremely excellence of character.This preimpregnation thing can further give moulding and make composite material laminated board, also can be used for the bonding coat of preimpregnation thing separately, or after one or more preimpregnation thing is made up, gets veneer sheet behind surface thereof or two surperficial upward placement Copper Foils and with pressurized, heated.The dimensional stability of gained veneer sheet, chemical proof, erosion resistance, water absorbability and electrical properties etc. all are much better than the standard of present product, be applicable to the electric product of making electronics, space, traffic etc., and in order to make printed circuit board (PCB) and multilayer circuit board etc.
Disclosed composition epoxy resin also can not use under the halid situation by known method, cooperates the silicon Rankine, makes electronic package material after mixing, pulverize, playing ingot, again through hot-forming and must meet the electronic packing body of environmental protection condition.This electronic packing body flame retardant effect, heat stable property, dimensional stability and electrical properties etc. all meet and even be much better than the standard of present product, be applicable to the electronic product of making electronics, space, traffic etc., and in order to make printed circuit board (PCB) and multilayer circuit board etc.
In sum, the invention provides a kind of phosphorous polymer and epoxy polymer thereof of the novel tool phenolic structure with excellent flame resistivity, thermostability and mechanical properties and contain composition epoxy resin of these polymkeric substance and uses thereof.
Below in conjunction with accompanying drawing shown in the following example the present invention is described in further detail, but these embodiment and are not in order to limit the scope of the invention only in order to explanation the present invention.
Epoxy equivalent (weight) hereinafter and solids component are to record by following method:
Epoxy equivalent (weight) (EEW, Epoxy Equivalent Weight): make Resins, epoxy be dissolved in chlorobenzene: in the solvent of chloroform=1: 1, carry out titration with the HBr/ Glacial acetic acid, measure according to the method for ASTM D1652, wherein indicator is a Viola crystallina.
Viscosity (Viscosity): epoxy resin varnish of the present invention placed 25 ℃ of thermostatic baths 4 hours, with Brookfield (Brookfield) viscometer in 25 ℃ of measurers.
Solids component (Solid content): varnish sample 1 gram of extracting epoxy resin composition, in 60 minutes non-volatile part measured weight percents of 150 ℃ of bakings.
Phenol-formaldehyde A: factory is produced by the Changchun artificial resin, and with the phenol formaldehyde condensation body that trade(brand)name PF5110 sells, its hydroxyl equivalent is 108g/eq.
Bakelite B: the company of changing into is produced by FDAC, and with the melamine-based phenol formaldehyde condensation body that contains of trade(brand)name Melane 9000 sales, its hydroxyl equivalent is 118g/eq.
Bakelite C: factory is produced by the Changchun artificial resin, and with the phenol formaldehyde condensation body that trade(brand)name BN7135 sells, its hydroxyl equivalent is 124g/eq.
Resins, epoxy 1: factory is produced by the Changchun artificial resin, the diglycidylether of the dihydroxyphenyl propane of selling with trade(brand)name BE188EL, and its epoxy equivalent (weight) is between 185 to 195g/eq, hydrolyzable chlorine is below the 200ppm, viscosity is between 11,000 to 15, between 000cps/25 ℃.
Resins, epoxy 2: factory is produced by the Changchun artificial resin, the diglycidylether of the tetrabromo-bisphenol of selling with trade(brand)name BEB530A80, and its epoxy equivalent (weight) is between 430 to 450g/eq, and bromine content is between 18.5 to 20.5 weight %.
Resins, epoxy 3: factory is produced by the Changchun artificial resin, the diglycidylether of the tetrabromo-bisphenol of selling with trade(brand)name BEB526A80, and its epoxy equivalent (weight) is between 410 to 430g/eq, and bromine content is between 19.0 to 21.0 weight %.
Resins, epoxy 4: factory is produced by the Changchun artificial resin, and with the Resins, epoxy that trade(brand)name CNE-200T sells, its epoxy equivalent (weight) is about 200g/eq.
Solidifying agent A represents the DMF solution of 10% dicyan diamide.
Catalyst A is represented the methanol solution of 10% triphenylphosphine.
Curing catalyst is represented the DMF solution of 10%2-Methylimidazole.
[synthesis example 1] contains phosphorous polymer A synthetic of repeating unit (a) and (b) tool phenolic structure
Use 3 liter of five neck flask as reaction vessel, this flask is with the device of control and displays temperature and pressure, in wherein adding 615 gram phosphorus vinegar chlorine (POC13) and 5.4 gram Magnesium Chloride Anhydrouss, be warming up to 100 ℃, and in 2 hours, add 750 gram phenol with given pace, add the back that finishes and continue reaction 2 hours.Then, under uniform temp, add 600 gram phenol-formaldehyde As (OH equivalent 108g/eq) and continue reaction 2 hours, add 1000 gram methyl ethyl ketones then, behind distilled water wash three times, decompression is heated up in a steamer and is desolventized, obtain the phosphorous Resin A of the flaxen tool phenolic structure of 1670 grams, its OH equivalent is 442g/eq.
[synthesis example 2] contains phosphorous polymer B synthetic of repeating unit (a) and (b) and (c) tool phenolic structure
Except that using bakelite B (the OH equivalent is 120g/eq) and containing the melamine-based alternative phenol-formaldehyde A, all the other are all identical with synthesis example 1, and obtain the phosphorous polymer B of tool phenolic structure, and its OH equivalent is 460g/eq.
[synthesis example 3] contains phosphorous polymer C synthetic of repeating unit (a) and (b) tool phenolic structure
Remove and use dihydroxyphenyl propane-resol (bakelite C, its OH equivalent is 120g/eq) to substitute beyond the phenol-formaldehyde A, all the other are all identical with synthesis example 1, and obtain the phosphorous polymer C of tool phenolic structure, and its OH equivalent is 482g/eq.
Synthesize the phosphorous resin that contains epoxy group(ing) and tool phenolic structure with following synthesis example 4-5:
The phosphorous epoxy polymer A's of [synthesis example 4] tool phenolic structure is synthetic
Use 3 liter of five neck flask as reaction vessel, this flask is with the device of control and displays temperature and pressure, and can be with the condensation of condistillation mixture and the isolating device of water, epoxyhalopropane, the phosphorous resin A of the tool phenolic structure that adding 700 gram synthesis examples 1 make in flask and 880 gram epoxy chloropropane, the gained mixture is after being stirred to uniform dissolution under the normal atmosphere, under the 190mmHg absolute pressure, heat to 70 ℃, and under the equilibrium temperature and pressure of this solution, in four hours, add 49.3% sodium hydroxide solution of 154.7 grams with given pace.Decompression was heated up in a steamer and is removed residual epoxy chloropropane and solvent after reaction was finished.The Resins, epoxy crude product of gained is dissolved in the solution of methyl ethyl ketone and deionized water, to wash the sodium-chlor that removes in the resin, the decompression that continues is heated up in a steamer except that methyl ethyl ketone, obtains the phosphorous epoxy polymer A of the hazel tool phenolic structure of 780 grams, and its epoxy equivalent (weight) is 468g/eq.
The phosphorous epoxy resin B's of [synthesis example 5] tool phenolic structure is synthetic
Except that the phosphorous polymer B of the tool phenolic structure that uses synthesis example 2 to make substituted the phosphorous polymer A of tool phenolic structure, all the other were all identical with synthesis example 4, and the phosphorous epoxy polymer B of acquisition tool phenolic structure, its epoxy equivalent (weight) is 490g/eq.
Embodiment 1 to 6 and comparative example 1 to 2
Composition epoxy resin of the present invention, its prescription are shown in the embodiment 1-6 of table 1.Comparative example 1 and 2 is a control group.
At room temperature, in the container that is equipped with agitator and condenser, above synthetic phosphorous epoxy resin and solidifying agent, curing catalyst, solvent are deployed into phosphorous epoxy resin composition according to the adding proportion shown in the table 1:
The composite formula of each embodiment of table 1 and comparative example
| Composite formula (g) | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 1 | Comparative example 2 |
| The phosphorous epoxy polymer A of synthesis example 4 | 180 | |||||||
| The phosphorous epoxy polymer B of synthesis example 5 | 180 | |||||||
| Resins, epoxy 1 | 160 | 140 | 100 | 150 | ||||
| Resins, epoxy 2 | 125 | |||||||
| Resins, epoxy 3 | 40 | 125 | ||||||
| The phosphorous polymer A of synthesis example 1 | 200 | 240 | ||||||
| The phosphorous polymer B of synthesis example 2 | 190 | 190 | 210 | |||||
| Solidifying agent A | 40 | 180 | 15 | 250 | 260 | |||
| The methanol solution of catalyst A 10% triphenyl phosphine | 1 | 1 | 1 | 1 | 1 | 1 | ||
| The DMF solution of curing catalyst 10%2-Methylimidazole | 0.625 | 0.625 |
Property detection
With glasscloth contain be dipped in the foregoing description 1 to 6 and 1 to 2 synthetic phosphorous epoxy resin composition of comparative example after, through 150 ℃ of dry preimpregnation things that become of the universe, again through DSC (scan-type calorimeter, TA2910) (differential scanning calorimeter, TA2910) test its glass tansition temperature, measure its calorific loss situation with thermo-gravimetric analysis (TGA), and test its flame retardant resistance with combustion test, the result is as shown in table 2, and the made preimpregnation thing tool flame retardant resistance of the present composition and its thermogravimetric loss temperature and glass tansition temperature also improve a lot of as shown in Table 2.
Table 2 is through flame retardant resistance, thermostability and the glass tansition temperature of 180 ℃ of bakings preimpregnation thing after 120 minutes
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 1 | Comparative example 2 | |
| Combustion test * | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
| 1% thermogravimetric loss temperature | 305 | 312 | 310 | 330 | 303 | 301 | 250 | 250 |
| Tg(℃) | 185 | 193 | 198 | 185 | 205 | 207 | 132 | 150 |
Annotate: * combustion test (flame test): according to the method for UL94V-0.
Respectively that eight above-mentioned various preimpregnation things are superimposed, it respectively places the Copper Foil of 35 microns of a slices up and down, pressing under 185 ℃ of temperature, pressure 25Kg/cm2 and obtain the laminate of this preimpregnation thing and glasscloth, the detailed analysis result is as shown in table 3, all can reach the required standards by its various test events of laminate made from the present composition as can be known in the table, as shown in table 3.
Table 3 after adding hot pressing, the test result of substrate rerum natura
| Analysis project | Condition and specification | Embodiment 1 | Embodiment 2 | Embodiment 6 | Comparative example 2 |
| Soldering resistance | IPC260 ℃ of specification＞10 | By | By | By | By |
| Stripping strength | IPC specification＞8lb/in | 8.50 | 8.70 | 8.70 | 8.90 |
| Surface resistivity | IPC specification＞10 12 | 2.57*10 15 | 2.25*10 15 | 4.56*10 15 | 3.57*10 15 |
| Body resistance | IPC specification＞10 10 | 1.08*10 14 | 9.56*10 13 | 1.87*10 14 | 1.06*10 14 |
| Specific inductivity | IPC specification＜5.4 | 4.5 | 4.6 | 4.6 | 4.6 |
| The dissipation factor | -- | 0.018 | 0.020 | 0.018 | 0.020 |
| Tg(℃) | DSC | 190 | 203 | 210 | 153 |
In summary, preimpregnation thing and the laminate thereof made with the present composition, particularly the glass tansition temperature is better for the tool flame retardant resistance, at least reach 190 ℃ even, also all satisfactory specifications even better such as the soldering resistance of its finished product, stripping strength, surface resistivity, body resistance, specific inductivity and the dissipation factor up to more than 200 ℃.
[embodiment 7 and 8]
Phosphorous epoxy resin composition of the present invention can be mixed with the encapsulation material of embodiment 7 and embodiment 8 according to the prescription shown in 4 of tabulating down.Comparative example 3 and comparative example 4 are control group.Pulverize behind the various composition uniform mixing with each prescription, and after mixing with two roller mullers again through pulverizing, playing ingot and obtain to encapsulate and use material.Each encapsulation is carried out moulding and character test with material, and the result is as shown in table 5.
The phosphorous encapsulant compositions prescription of table 4
| Composite formula (g) | Embodiment 7 | Embodiment 8 | Comparative example 3 | Comparative example 4 |
| Resins, epoxy 4 | 540 | - | 790 | 790 |
| The phosphorous epoxy polymer B of synthesis example 5 | - | 620 | - | - |
| Resins, epoxy 2 | - | - | - | 3 |
| The phosphorous polymer A of synthesis example 1 | 650 | - | - | - |
| Resol | - | 400 | 400 | 400 |
| The melting silica | 2800 | 2800 | 2800 | 2800 |
| Catalyst A | 5.2 | 5.2 | 5.2 | 5.2 |
| Silane | 14.2 | 14.2 | 14.2 | 14.2 |
| Carbon black | 7.2 | 7.2 | 72 | 7.2 |
| Wax | 11 | 11 | 11 | 11 |
| Antimonous oxide | - | - | - | 7.2 |
Property detection after the phosphorous packaged material moulding of table 5
| Project | Condition | Embodiment 7 | Embodiment 8 | Comparative example 3 | Comparative example 4 |
| Melting viscosity | 175℃ | 50 pools | 52 pools | 79 pools | 83 pools |
| Gelation time | 160℃ | 28 seconds | 27 seconds | 28 seconds | 29 seconds |
| Flame retardant resistance | UL 94V-0 | By | By | Do not pass through | By |
| Mobility | - | 70 centimeters | 68 centimeters | 59 centimeters | 55 centimeters |
| The glass tansition temperature | DSC | 165℃ | 167℃ | 160℃ | 163℃ |
Packaged material by preparing with the present composition as can be known in the table 5 all is being better than reference examples aspect melt viscosity, gelation time, flame retardant resistance, mobility and the glass tansition temperature after the moulding.
Claims (11)
1. the phosphorous polymer of a tool phenolic structure is characterized in that having following repeating unit:
R wherein
1And R
2Can be identical or different, and represent H, C
1-20Alkyl, phenoxy group, phenyl-C
1-4Phenyl-the C that replaces through hydroxyl on alkyl, the phenyl ring
1-4Alkyl,
R
aFor can be through C
1-4The phenylene that alkyl replaces, singly-bound,
Or-CHR
3-, this R
3Be H, C
1-4Alkyl, CH
2=CH, phenyl, furyl, C
1-4The C that replaces through hydroxyl on alkyl phenyl or the phenyl ring
1-4Alkyl phenyl;
(b) be selected from following formula (b1) or (b2) the phosphorous repeating unit of any one:
R wherein
1, R
2And R
aDefinition as described above, and
X is Sauerstoffatom or electron pair,
T is Sauerstoffatom or chemical bond,
R ' and R " can be identical or different, and be C
1-18Alkyl, phenyl or phenyl-C
1-6Alkyl, or
Can represent
R
iAnd R
jCan be identical or different, and be hydrogen or C
1-18Alkyl: or
Wherein each substituting group such as above-mentioned definition, and
Choose wantonly
Wherein
Or
R
bBe H, C
1-4Alkyl, CH
2=CH, phenyl, furyl, C
1-4The C that replaces through hydroxyl on alkyl phenyl or the phenyl ring
1-4Alkyl phenyl,
R
cBe NH
2, OH, C
1-10Alkyl, phenyl or benzoyl.
2. composition epoxy resin, it is characterized in that comprising (A) Resins, epoxy and (B) phosphorous polymer of tool phenolic structure as claimed in claim 1 as solidifying agent.
3. composition epoxy resin as claimed in claim 2, it is characterized in that this Resins, epoxy with glycidyl ether, glycidyl amine, epihydric alcohol sulfide and/or the Racemic glycidol carboxylicesters of at least one compound of from bis-phenol, phenol, dihydroxy-benzene, connection phenol, naphthalene, nitrogen heterocyclic ring, phenolic compound, siloxanyl monomers, polysiloxane, selecting as polymerized unit.
4. composition epoxy resin, comprise that (A) is by the phosphorous polymer of the described tool phenolic structure of claim 1 and the Resins, epoxy of epoxyhalopropane reaction gained, the phosphorous polymer of this tool phenolic structure system is with the hydroxyl and epoxyhalopropane reaction of contained repeating unit (a), reach (B) contain can with the solidifying agent of the active group of epoxy reaction.
5. composition epoxy resin as claimed in claim 4 is characterized in that this solidifying agent selects from the cohort that amine compound, polyphenol, phenolic compound, naphthalene, siloxanyl monomers, polysiloxane, polythiol and poly carboxylic acid are formed.
6. composition epoxy resin as claimed in claim 4 is characterized in that this solidifying agent is the phosphorous polymer of the described tool phenolic structure of claim 1.
7. as any described composition epoxy resin in the claim 2 to 6, it is characterized in that with respect to the Resins, epoxy epoxy equivalent (weight) be 100, the reactive behavior hydrogen equivalent of solidifying agent is 10 to 100.
8. composition epoxy resin as claimed in claim 7 is characterized in that said composition also contains curing catalyst.
9. composition epoxy resin as claimed in claim 8 is characterized in that this curing catalyst selects from the cohort that tertiary amine, three grades of phosphines, quaternary ammonium salt, quaternary alkylphosphonium salt and imidazolium compoundss are formed.
10. as claim 7 or 8 described composition epoxy resins, the consumption that it is characterized in that this curing catalyst is 0.005 to 5.0 weight % of composition epoxy resin gross weight.
11. claim 2 or 4 described composition epoxy resins are making lajminated material, as the application in integrated circuit board packaged material, electronic package material, high heat-resisting powder coating, the engineering plastics.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001235249A CN100365035C (en) | 2000-08-18 | 2000-08-18 | Phosphorous polymer having phenolic structure and its use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001235249A CN100365035C (en) | 2000-08-18 | 2000-08-18 | Phosphorous polymer having phenolic structure and its use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1339518A CN1339518A (en) | 2002-03-13 |
| CN100365035C true CN100365035C (en) | 2008-01-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001235249A Expired - Lifetime CN100365035C (en) | 2000-08-18 | 2000-08-18 | Phosphorous polymer having phenolic structure and its use |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1333014C (en) * | 2003-08-08 | 2007-08-22 | 长春人造树脂厂股份有限公司 | Halogen-free resin composition |
| CN101153107B (en) * | 2006-09-28 | 2011-02-16 | 长春人造树脂厂股份有限公司 | Fire retardant resin composition |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3998789A (en) * | 1973-09-11 | 1976-12-21 | Sumitomo Bakelite Company, Limited | Flame resistant thermosetting resin composition and method for preparing same |
| JPS5695929A (en) * | 1979-12-28 | 1981-08-03 | Mitsubishi Gas Chem Co Inc | Production of laminated sheet |
| US5346743A (en) * | 1992-03-13 | 1994-09-13 | Kabushiki Kaisha Toshiba | Resin encapsulation type semiconductor device |
| CN1167495A (en) * | 1995-09-29 | 1997-12-10 | 东芝化学株式会社 | Hologen-free flame-retardant epoxy resin composition, and prepreg and laminate containing the same |
| CN1171122A (en) * | 1994-12-23 | 1998-01-21 | 巴斯福股份公司 | Process for preparing dyed melamine-formaldehyde condensation products |
| CN1230569A (en) * | 1998-04-01 | 1999-10-06 | 大八化学工业株式会社 | Flame-retarded resin composition |
-
2000
- 2000-08-18 CN CNB001235249A patent/CN100365035C/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3998789A (en) * | 1973-09-11 | 1976-12-21 | Sumitomo Bakelite Company, Limited | Flame resistant thermosetting resin composition and method for preparing same |
| JPS5695929A (en) * | 1979-12-28 | 1981-08-03 | Mitsubishi Gas Chem Co Inc | Production of laminated sheet |
| US5346743A (en) * | 1992-03-13 | 1994-09-13 | Kabushiki Kaisha Toshiba | Resin encapsulation type semiconductor device |
| CN1171122A (en) * | 1994-12-23 | 1998-01-21 | 巴斯福股份公司 | Process for preparing dyed melamine-formaldehyde condensation products |
| CN1167495A (en) * | 1995-09-29 | 1997-12-10 | 东芝化学株式会社 | Hologen-free flame-retardant epoxy resin composition, and prepreg and laminate containing the same |
| CN1230569A (en) * | 1998-04-01 | 1999-10-06 | 大八化学工业株式会社 | Flame-retarded resin composition |
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|---|---|
| CN1339518A (en) | 2002-03-13 |
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