CN101061127A - 1,4-hydroquinone functionalized phosphinates and phosphonates - Google Patents

1,4-hydroquinone functionalized phosphinates and phosphonates Download PDF

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Publication number
CN101061127A
CN101061127A CNA2005800391790A CN200580039179A CN101061127A CN 101061127 A CN101061127 A CN 101061127A CN A2005800391790 A CNA2005800391790 A CN A2005800391790A CN 200580039179 A CN200580039179 A CN 200580039179A CN 101061127 A CN101061127 A CN 101061127A
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deutero
composition
epoxy
resin
quinhydrones
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M·V·汉森
L·D·廷伯莱克
K·马松内
O·胡滕洛赫
G·舍尔哈格
M·马泽
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BASF SE
Lanxess Solutions US Inc
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BASF SE
Crompton Corp
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/51Phosphorus bound to oxygen
    • C08K5/53Phosphorus bound to oxygen bound to oxygen and to carbon only
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02Phosphorus compounds
    • C07F9/28Phosphorus compounds with one or more P—C bonds
    • C07F9/30Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/32Esters thereof
    • C07F9/3205Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/3229Esters of aromatic acids (P-C aromatic linkage)
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02Phosphorus compounds
    • C07F9/28Phosphorus compounds with one or more P—C bonds
    • C07F9/38Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40Esters thereof
    • C07F9/4003Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4021Esters of aromatic acids (P-C aromatic linkage)

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Abstract

There is presented novel 1,4-hydroquinone derivatized phosphinates and phosphonates. The novel compositions here presented are useful as polymer curing agents and as flame retardants. Where R, R' each independently are the same or different aryl, aralkyl or alkyl comprising from one to 15 carbon atoms.

Description

1, phosphinate that 4-is hydroquinone functionalized and phosphonic acid ester
The application requires the U.S. Provisional Patent Application No.60/611 of submission on September 21st, 2004,782 right of priority.
Summary of the invention
Present invention relates in general to novel 1,4-quinhydrones and 1, the phosphinate that the 4-naphthoquinones is functionalized and the preparation of phosphonic acid ester and they are as the purposes of the flame retardance element of epoxy-resin systems.Phosphinate of the present invention and phosphonic acid ester can be used as the curing agent for epoxy resin with reinforced flame retardant performance.Though phosphinate of the present invention and phosphonic acid ester can be used for cured epoxy resin separately, combine as the co-curing agent with polyol and can find bigger applicability.1,4-quinhydrones or 1, phosphinate/phenolic varnish that the 4-naphthoquinones is functionalized and phosphonic acid ester/novolac resin co-curing agent is suitable for fire-retardant printed-wiring board (PWB).The present invention also can be used as the co-curing agent in the epoxy-resin systems of prepreg (prepreg), veneer sheet, especially copper clad laminate, and described prepreg, veneer sheet, especially copper clad laminate can be used for making the not electronic component of halogen-containing flame retardant.
Background of invention
Matrix material based on Resins, epoxy gets the nod in multiple application for a long time substantially, and because this matrix material of its versatility continues to have sizable importance.A specific examples of this application includes, but are not limited to, and is used for printed circuit board (PCB) (printed-wiring board (PWB), electric veneer sheet PWB).The Resins, epoxy that is used for is wherein processed easily and has especially been obtained popularizing owing to it.The feature of those Resins, epoxy also is favorable mechanical and chemical property, toughness and for example to the patience of multiple organic solvent, and show good chemical reagent resistance and moisture resistance.These performances make epoxide resin material can adapt to multiple application purpose, and make the material of forming matrix material obtain favourable use.
Usually, can easily Resins, epoxy be machined for the PWB composite applications by making prepreg (B-stage (B-staging)).For example, use the resin impregnation base material, this base material is inorganic or organic toughener of fiber, pile fabric and fabric or textile materials form normally.This can be by realizing with the resin solution coated substrate in easy volatilization or the volatilizable solvent.Can comprise that roller coat, dip-coating, spraying and their combination apply by multiple familiar technology.This prepreg of heating desolvates and partly solidifies this resin to remove in baking oven then.Advantageously, the prepreg that obtains after this processing can not adhere to certainly, but they should not be completely crued yet.In addition, prepreg should show storage stability.Being processed in the composite material subsequently, this prepreg should apply under the heat and the condition of pressure fusible so that as far as possible closely and for good and all bond together with toughener or insertion component and the material that provides for matrix material; That is, crosslinked epoxy resin-base must and toughener, and the interface that material to be bonded together such as metal, pottery, inorganic and organic materials form height adheres to.
Flame retardant resistance is an important performance for some application that relates to polymer materials.In some purposes, flame retardant resistance has been endowed first priority, and this is because for example danger that human and goods and materials is caused in the structural material that is used for aircraft and motor vehicle structure and is used for public transport.In electronic application, flame retardant resistance is necessary, because element may produce sizable localized hyperthermia on veneer sheet.The calcination of veneer sheet may cause the loss of assembling electronic component thereon.In addition, for the human fire savety of the device that comprises the PWB element, guarantee high explosion-proof/flameproof protection level.
Therefore, in the preparation of the veneer sheet that contains Resins, epoxy, in composition epoxy resin, introduce various additives and/or reactive component has been a convention with the flame retardant resistance of improving the gained veneer sheet.Used the fire retardant matter of many types, yet, up to the present commercial the most frequently used be for example tetrabromo-bisphenol of halogen-containing compound.Usually by this material being introduced Resins, epoxy with the diglycidylether reaction of dihydroxyphenyl propane.Usually, in order to reach required flame retardancy level (in standard " Underwriters Laboratory " test method UL 94, reaching V-0), require the level of this brominated fire retardant matter to satisfy: based on the gross weight in the product, the bromine content that provides is that 10wt% is to 25wt%.
Usually, halogen-containing fire retarding epoxide resin is considered to safety and effectively as those that comprise tetrabromo-bisphenol.Yet, use and more and more do not favored based on the fire retarding epoxide resin system of halogen-containing chemical substance.For these type materials, hope can be satisfied the needs of flame retardant resistance and show and identical or bigger mechanical property, toughness and the solvent resistance that halogenated materials provided used at present and the advantage of moisture resistance.
A kind of such method that is proposed by numerous research workers is to use phosphine flame retardant.Referring to for example, EP 0 384 939; EP 0 384 940; EP 0 408 990; DE 4 308 185; DE 4 308 187; WO 96/07685; WO 96/07686; U.S. Patent No. 5,648,171; U.S. Patent No. 5,587,243; U.S. Patent No. 5,576,357; U.S. Patent No. 5,458,978; And U.S. Patent No. 5,376,453; All documents are incorporated herein by reference in this integral body.In all these reference, by forming a kind of preparation, then its linking agent with amino crosslinker such as Dyhard RU 100, sulfanilamide (SN) or some other nitrogenous element is solidified to form the thermosetting polymer network derived from the fire retardant of phosphorus compound and the reaction of Resins, epoxy.
The specific examples of commercially available phosphorus based flame retardant additives comprises Antiblaze TM1045 (Albright and Wilson Ltd, United Kingdom), it is a phosphonic acid ester.Phosphoric acid ester also is used as additive, for example, PX-200 (Diahachi, Japan).The disclosed commercially available reactive P contained compound that is suitable for Resins, epoxy comprise Sanko HCA and SankoHCA-HQ (Sanko Chemical Co., Ltd., Japan).
The phosphonic acid ester that alkyl and aryl replace also is used for fire retarding epoxide resin.More particularly, phosphonic C 1-C 4Therefore alkyl ester is valuable, because they comprise a high proportion of phosphorus, and can give resin flame retardant properties comprising them.Yet, being used for preparing the surrogate of the Resins, epoxy of electric veneer sheet as halogenated fire-retardants, phosphonic acid ester is not also accepted extensively, because often cause undesirable performance.For example, these phosphonic acid esters are known softening agent and therefore often show undesirable low second-order transition temperature (T by its veneer sheet that forms g).Another defective is to use these phosphonic acid esters to improve the tendency of gained cured epoxy resin absorption moisture with the amount of the flame retardant resistance that is enough to provide necessary.The water absorption of cured layer pressing plate is very important because when be introduced into temperature be approximately 260 ℃ liquid solder bathe in the time (printed-wiring board (PWB) make in exemplary steps), the veneer sheet of contained high levels moisture often bubbles and lost efficacy.
Other method of giving flame retardant resistance relates to uses resin material and mineral filler, as the not halogen-containing fire retarded epoxy resin composition of binding substances preparation of aluminum trihydrate (EP 0 795 570 A1) or magnesium hydroxide (JP 2001213980 A2).Depend on physicals, these materials may make the processing of Resins, epoxy become more difficult, because they are insoluble to resin system.In addition, may need quite high load level, this performance that can detract.Usually referring to, U.S. Patent No. 6,097,100, WO01/42359 and the reference that is used to describe various mineral fillers quoted in them.
Be the hydroxyaryl phosphine oxide co-curing agent that epoxy-resin systems provides not other trial of halogen-containing fire retardant to comprise to be used for Resins, epoxy, described epoxy-resin systems is advantageously used in prepreg, veneer sheet, copper clad laminate and printed-wiring board (PWB).Fire-retardant co-curing agent like this is in U.S. Patent No. 6,887, discloses in 950.
An object of the present invention is to provide economical, useful 1,4-quinhydrones or 1, phosphinate that the 4-naphthoquinones is functionalized and functionalized phosphonic acid ester are as the flame retardant composition that is used for cured epoxy resin.Of the present invention 1,4-quinhydrones or 1, phosphinate that the 4-naphthoquinones is functionalized and the preparation of functionalized phosphonic acid ester are used for the hydrolysis-stable and the application heat-staple, not halogen-containing epoxy-resin systems of PWB material can find special effectiveness.
It is halogen-containing 1 that another object of the present invention provides, 4-quinhydrones or 1, and phosphinate that the 4-naphthoquinones is functionalized and functionalized phosphonic acid ester composition epoxy resin, it can be used as the surrogate of the tetrabromo-bisphenol of non-combustible high pressure laminate in using.
These and other objects of the present invention and advantage will be found out from following detailed description.
The present invention relates to be used for the structure (I) of flame-proofed polymer material (particularly including printed-wiring board (PWB)) and the preparation of phosphinate (II) and phosphonic acid ester.
Figure A20058003917900081
R and R ' limit below.
Except top quinhydrones based structures I and II, the applicant also discloses the naphthalene compound of diol substituted in the present invention, that is: according to 1 of structure III and IV, and phosphinate that the 4-naphthoquinones is functionalized and phosphonic acid ester.
Figure A20058003917900082
Unless context has needs in addition, when relating to quinhydrones hereinafter, be to be understood that these naphthalenediol compositions also are described.
More particularly, the present invention relates to be used for preparing prepreg, veneer sheet, and the fire retarding epoxide resin of copper clad laminate particularly, this prepreg, veneer sheet and particularly copper clad laminate are used under the situation of not using halogen contained compound makes electronic component.The invention still further relates to the method for flame retardant thermoset resins and the manufacture method of fire-retardant printed-wiring board (PWB), prepreg and veneer sheet.
Curable, the fire retarding epoxide resin that is fit to be used for to make resin formulation, prepreg and veneer sheet can be reacted with the advancement of halogen-containing Resins, epoxy not by structure (I) and compound (II) and prepare.The hydroxyl structure of structure I, II, III and IV part easily with standard epoxy in epoxide group react.By using suitable reactive chemistry metering can in the copolymer products resin, obtain various molecular weight.The Resins, epoxy that is fit to is, but is not limited to novolac epoxy and bisphenol A diglycidyl ether.Quinhydrones of the present invention and naphthoquinones can also be used as curing agent for epoxy resin.The use of can using alone or combine of these solidifying agent with other solidifying agent that is fit to such as lacquer resins.
Can be the compound of structure I and II is functionalized to obtain the epoxy intermediate of structure I A and IIA in the reactive site of phenol.For example, the compound of structure I and II can react to produce difunctional epoxy compound with Epicholorohydrin.Can use then with the same mode of commercial epoxy resin and use these compounds, that is, they can be used as Resins, epoxy, can improve or promote with difunctionality oxy-compound such as dihydroxyphenyl propane, or solidify with the solidifying agent that is fit to.
Figure A20058003917900091
Structure III forms similar epoxy compounds with IV when reacting to Epicholorohydrin.
Composition of the present invention is described to " not halogen-containing ".Should be understood that, add Epicholorohydrin and may add the chlorine of trace, to form structure (IA) and epoxidised compound (IIA) as reactant.Similarly, the halogen of trace may be present in the phosphinate and phosphonic acid ester of structure I, II, III and IV.Such halogen is not enough to influence significantly flame retardant resistance.The halogen that has a trace is negligible as the by product of the precursor of making the present application composition.
R, R ' are identical or different aryl, aralkyl, alkenyl independently of one another or contain C 1-C 15Alkyl.Aryl comprises phenyl, xenyl, naphthyl and is selected from the analogue that following group replaces: the alkoxyl group of straight chain or branching such as methoxy or ethoxy, the alkyl of straight chain or branching such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group and nonyl substituting group.Kiki alkenyl group comprises vinyl, propenyl and butenyl, and condition is the ability that this substituting group can not hinder phosphorus compound and selected polymkeric substance to react.For example, when R is phenylene, the R of suitable replacement be adjacent-,-or, be commonly referred to ortho-cresol base, meta-cresol base or p-cresol base to hydroxyl-methyl-phenyl.Alkyl can be the saturated substituting group of straight chain, branching or ring-type of a common 1-15 carbon atom, comprises methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl and decyl substituting group.The feature of aralkyl can be by one or more alkyl carbon atoms keyed jointing aromatic kernels.The example of aralkyl comprises hydrocinnamyl or benzene butyl substituting group.
A preferred embodiment is to use compound 1B:2,5-dihydroxy phenyl-phenyl phosphinic acid 2,6-dimethyl-phenylester and 2B:2, two (2, the 6-3,5-dimethylphenyl) esters of 5-dihydroxy phenyl phosphonic acids.2, the existence of 6-3,5-dimethylphenyl structure division provides improved moisture resistance, thermotolerance and good chemical stability.
Figure A20058003917900101
Compound I B Compound I IB
Can prepare aforesaid compound and preparaton to influence curing speed, strengthen flame retardant resistance and to improve physicals with extra additive and filler.These compounds and preparaton are intended to be used for making the prepreg and the glass enhancement layer pressing plate of the manufacturing that is used for printed-wiring board (PWB).
Generally speaking, 1,4-quinhydrones or 1, both account for the about 85 moles of % of about 25-of the epoxy curing agent part of Resins, epoxy phosphinate that the 4-naphthoquinones is functionalized or phosphonic acid ester or they.Advantageously, this quinhydrones or naphthoquinones partly provide explosion-proof/flameproof protection, and can influence the structure and the electrical property of gained electricity veneer sheet sharply.This quinhydrones or naphthoquinones part can be 90 moles of % or even 100 moles of % of curing agent for epoxy resin part.
The poly-hydroxy mixture also comprises the phenols co-crosslinking composition with two or more hydroxy functionalities, and can comprise any suitable phenols component, as the resin that obtains by the reaction of phenol or alkylated phenol and formaldehyde, for example novolac resin, resole, Dicyclopentadiene (DCPD) phenol phenolic varnish; Or other hydroxy-functionalized polymer's resin of the cinnamic residue of hydroxyl for example.The multifunctional phenolic monomers and/or the oligomeric compound that are fit to comprise three (hydroxy phenyl) methane; Three (hydroxy phenyl) ethane; 1,3, the 5-trihydroxybenzene; Four phenolic group ethane; 3,4,5-trihydroxybenzoic acid (also claiming gallic acid) or derivatives thereof, or pyrogallol (also claiming 1); Or 1,2,4-trihydroxybenzene (also claiming hydroxyhydrochinon); 1,8,9-trihydroxy-anthracene (also claiming Dithranol or dithranol), or 1,2,10-trihydroxy-anthracene (also claiming leucoalizarin (anthrarobine)); 2,4, the 5-trihydroxy-pyrimidine; And the mixture of these compounds and reaction product.Other phenols component can also be referring to U.S. Patent No. 6,645,631, and its disclosure is hereby incorporated by.If necessary, can be with the phenols component blend of monomer, oligopolymer and polymkeric substance, with preparation phenols co-crosslinking composition.
Preferred poly-hydroxy co-crosslinking material is that class novolac resin that comprises resol, Cresol Formaldehyde Resin and their mixture.Perhaps most preferred poly-hydroxy novolac resin is those of residue that comprise azaheteroaryl, phenol and aldehyde, and this resin can be selected from: benzoguanamine phenol formaldehyde resin, acetylguanamine phenol formaldehyde resin, melamine phenol formaldehyde resin, benzoguanamine Cresol Formaldehyde Resin, acetylguanamine Cresol Formaldehyde Resin, melamine Cresol Formaldehyde Resin and their mixture.Phenols, many other reaction product that contain between azaheteroaryl and the aldehyde will be used for forming suitable hydroxy-containing resin by those skilled in the art's approval.
On the other hand, the present invention includes curable composition epoxy resin, it comprises:
Resins, epoxy;
Co-crosslinking poly-hydroxy mixture, it comprises:
1,4-quinhydrones or 1, phosphinate that the 4-naphthoquinones is functionalized and functionalized phosphonic acid ester, or both and
This poly-hydroxy mixture also comprises phenols co-crosslinking composition, and said composition comprises above-mentioned phenols component with two or more hydroxy functionalities.
In some embodiments, Resins, epoxy is novolac epoxy, and in other embodiments, and Resins, epoxy can be based on Epicholorohydrin and dihydroxyphenyl propane, and perhaps in other embodiment still, Resins, epoxy is based on Epicholorohydrin and Bisphenol F.Curable composition epoxy resin preferably has the phosphorus content of the about 5wt% of about 0.2wt%-, and wherein approximately the about 4wt% of 1wt%-is slightly typical.Approximately the about 3wt% of 2wt%-is especially preferred.Usually, the poly-hydroxy mixture has the total hydroxy radical content with the needed stoichiometric about 50 moles of about 150 moles of % of %-of existing epoxy resin cure, wherein under many circumstances hydroxy radical content for being preferred with the about 125 moles of % of the needed stoichiometric about 75 moles of %-of epoxy resin cure.Still preferred can be that hydroxy radical content is with the about 110 moles of % of the needed stoichiometric about 85 moles of %-of epoxy resin cure.
In many embodiments, the hydroxyl structure of 1 mole of about 99 moles of % of %-is the novolac resin oh group partly in the curing agent mixture, and the hydroxyl structure of about 15 moles of about 75 moles of % of %-is typical for the novolac resin oh group partly in the curing agent mixture.In addition, the hydroxyl structure of about 1 mole of about 99 moles of % of %-partly is 1 in curing agent mixture, 4-quinhydrones or 1,4-naphthaquinone part, and the hydroxyl structure of about 25 moles of about 85 moles of % of %-partly is 1 in curing agent mixture, 4-quinhydrones or 1,4-naphthaquinone partly are typical.
Aspect another, provide a kind of matrix material of resin impregnation of the present invention, this matrix material comprises enhancement component and partly solidified at least fire retarded epoxy resin composition described herein.This matrix material comprises that glass filler, glass fibre or glass fabric also randomly comprise the copper foil layer on the matrix material that adheres to this resin impregnation.This type of veneer sheet generally includes the glass fabric layer of a plurality of resin impregnations, and they are pressed into the structure that can not be separated into the stratified integration basically of its structure usually.Though often selecting glass is strongthener, also provide within the scope of the present invention to comprise carbon fiber, aromatic polyamide fibre and quartzy matrix material.
The present invention relates to 1 of described herein and poly-hydroxy co-curing agent blend, phosphinate that 4-quinhydrones or naphthoquinones are functionalized and the phosphonic acid ester purposes in the Resins, epoxy preparaton.Typical curable preparaton is made of following material, but be not limited to following material, A) of the present invention 1,4-quinhydrones or 1, phosphinate that the 4-naphthoquinones is functionalized and functionalized phosphonic acid ester, perhaps they both, B) novolac resin, C) Resins, epoxy or Resins, epoxy binding substances, D) filler or filler binding substances, E) curing catalyst, and F) suitable solvent or solvent binding substances.This preparaton can also comprise additive that those skilled in the art select or reactive component to obtain the performance of some needs.
A preferred embodiment of the present invention is 1,4-quinhydrones or 1, phosphinate that the 4-naphthoquinones is functionalized and functionalized phosphonic acid ester or their both as with the purposes of the blend of poly-hydroxy novolac resin.By means of the solvent that is fit to, described herein 1,4-quinhydrones or 1, phosphinate that the 4-naphthoquinones is functionalized and functionalized phosphonic acid ester dissolve easily as the mixture with various novolac resins.These resin solutions provide the resin solidification solution of giving excellent processing and easy usability.These resin solidification solution are stable and suppress 1,4-quinhydrones or 1, the crystallization of the phosphinate that the 4-naphthoquinones is functionalized and functionalized phosphonic acid ester or selected phenolic varnish.Perhaps, under the situation of selecting, can be by with 1,4-quinhydrones or 1, both form blend with the phenolic varnish melt blending that is fit to phosphinate that the 4-naphthoquinones is functionalized and functionalized phosphonic acid ester or they.If this novolac resin is a solid, so 1,4-quinhydrones or 1, the mixture of phosphinate that the 4-naphthoquinones is functionalized and functionalized phosphonic acid ester or they both and novolac resin can be used as the processing of solid blend thing and with solid-state use.An optional embodiments is with 1,4-quinhydrones or 1, and phosphinate that the 4-naphthoquinones is functionalized and functionalized phosphonic acid ester or their both and novolac resin add in the curable resin preparaton individually.
Except as otherwise noted, or as can be seen by context, term lacquer resins and analogue are meant and comprise the hydroxy-functional resin combination that it comprises one or more replacements or unsubstituted phenolic compound and one or more aldehyde, the condensation product of preferred formaldehyde.As following pointed, this resinoid can randomly comprise heteroaryl component such as melamine and guanamines.
Be suitable for making prepreg and veneer sheet curable, fire retarded epoxy resin composition can be by 1,4-quinhydrones or 1, the phosphinate, 1 that the 4-naphthoquinones is functionalized, 4-quinhydrones or 1, the preparaton of the phosphonic acid ester that the 4-naphthoquinones is functionalized or they both and novolac resin and commercially available Resins, epoxy prepares.1,4-quinhydrones or 1, the phosphinate, 1 that the 4-naphthoquinones is functionalized, 4-quinhydrones or 1, the phosphonic acid ester that the 4-naphthoquinones is functionalized or their both products distribution make to be solidified and some physical property of uncured resin is affected easily.The performance that relates to is for example, but to be not limited to molecular weight, viscosity, second-order transition temperature and gelation point.The types and sources of the aromatic hydroxy that exists in its reason and the curing agent mixture is relevant.
Resins, epoxy can with phenols co-crosslinking composition together 1,4-quinhydrones or 1, the phosphinate, 1 that the 4-naphthoquinones is functionalized, 4-quinhydrones or 1, both are crosslinked for the phosphonic acid ester that the 4-naphthoquinones is functionalized or they.Phenols co-crosslinking composition comprises novolac resin, as phenol-formaldehyde resin, cresol-formaldehyde resin and their mixture.The polymkeric substance of phenol, azaheteroaryl and aldehyde also is fit to.Example comprises benzoguanamine-phenol-formaldehyde resin, acetylguanamine-phenol-formaldehyde resin, melamine-phenol-formaldehyde resin, benzoguanamine-cresol-formaldehyde resin, acetylguanamine-cresol-formaldehyde resin, melamine-cresol-formaldehyde resin and their mixture.
This co-curing composition also comprises the phenolic material with two or more hydroxy functionalities.Typical phenolic compound is:
A) resin that is obtained by the reaction of phenol or alkylated phenol and formaldehyde is as novolac resin or resole.
B) polyhydroxy aromatic material, as: aforesaid three (hydroxy phenyl) methane; Three (hydroxy phenyl) ethane; 1,3, the 5-trihydroxybenzene; Four phenolic group ethane etc.
Preferred phenols co-curing component is that class novolac resin that comprises phenol formaldehyde resin, Cresol Formaldehyde Resin and their mixture.Preferred poly-hydroxy novolac resin comprises the residue of azaheteroaryl, phenol and aldehyde, and these resins can be selected from: benzoguanamine phenol formaldehyde (PF), acetylguanamine phenol formaldehyde (PF), melamine phenol formaldehyde (PF), benzoguanamine cresoform, acetylguanamine cresoform, melamine cresoform and their mixture.Phenols, many other reaction product that contain between azaheteroaryl and the aldehyde will be used for forming suitable hydroxy-containing resin for those skilled in the art's approval.
The poly-hydroxy novolac resin that comprises phenol/aldehyde copolymer (as multipolymer of the residue of the benzene that replaces of one or more or various other hydroxyl of comprising the phenol (as cresols or dihydroxyphenyl propane) of formaldehyde and phenol or replacement) is especially preferred in some embodiments.This component and of the present invention 1,4-quinhydrones or 1, phosphinate that the 4-naphthoquinones is functionalized and functionalized phosphonic acid ester are together as the co-curing agent.The phenol novolac resin is the commercial materials that easily obtains, and is characterized by general chemical structure V usually:
Figure A20058003917900151
Wherein R can represent hydrogen, alkyl such as methyl etc.
The novolac resin that is fit to comprises, for example, but is not limited to: can be from HexionSpecialty Chemicals, and the Durite that Inc. obtains SD-1708, SL-1710, SD-1502, SD-1702, SD-1731, SD-1734, SD-241A, SD-423A, RD-2414, SD-5132, SD-7280, SD-1502, SD-500C; Can be from GP-2074,5300,5833, the 834D54 of Georgia Pacific acquisition; Can be from HRJ-11040,1166,1583,2210,2355,2901, CRJ-406 and the FRJ-425/200 of Schenectady International acquisition.
In some cases, comprise that the poly-hydroxy novolac resin of multipolymer is especially preferred, this multipolymer comprises the reaction product of azaheteroaryl, phenol and aldehyde.As pointed before this, these resins can be selected from benzoguanamine phenol formaldehyde (PF), acetylguanamine phenol formaldehyde (PF), melamine phenol formaldehyde (PF), benzoguanamine cresoform, acetylguanamine cresoform, melamine cresoform and their mixture.Phenols, many other reaction product that contain between azaheteroaryl and the aldehyde will be used for forming suitable hydroxy-containing resin for those skilled in the art's approval.If desired, can use other aldehyde and/or other triaizine compounds.As at " Encyclopedia of PolymerScience and Engineering ", the 2nd edition, the 11st volume, the 50th page; Or at " Kirk-Othmer Encyclopedia of Chemical Technology ", the 4th edition, the 18th volume, disclosed such these resins for preparing in the 606th page.
Being suitable for representative Resins, epoxy of the present invention is shown in Epoxy Resins Chemistry and Technology, second edition,Edit (MarcelDekker, Inc.New York, 1988) by Clayton A.May, Chemistry and Technology of Epoxy Resins,Edit (Blackie Academic ﹠amp by B.Ellis; Professional, Glasgow, 1993), Handbook of Epoxy Resins,In H.E.Lee and K.Neville work (McGraw Hill, New York, 1967) and EP 1116774 A2.The Resins, epoxy that is fit to is, but be not limited to, based on bis-phenol and polyphenol, for example dihydroxyphenyl propane, tetramethyl-dihydroxyphenyl propane, Bisphenol F, bisphenol S, four benzene hydroxyl ethanes, Resorcinol, 4,4 '-Resins, epoxy of biphenyl, dihydroxy naphthlene, with derived from phenolic varnish, phenol for example: formaldehyde novolac, cresols: formaldehyde novolac, bisphenol-A phenolic varnish, biphenyl-, toluene-, dimethylbenzene-or the phenol of sym-trimethylbenzene-modification: the Resins, epoxy of formaldehyde novolac, derived from the aminotriazine novolac resin and the heterocyclic ring epoxy resins of p-aminophenol and cyanuric acid.In addition, for example, derived from 1, the aliphatic epoxy resin of 4-butyleneglycol, glycerine and Dicyclopentadiene (DCPD) skeleton is fit to.Many epoxy-resin systems that other is fit to are obtainable and are also thought to be fit to by those skilled in the art.
Use each molecule on average to have more than 1, preferably at least 1.8, more preferably the Resins, epoxy of at least 2 epoxy group(ing) is normally favourable.Under most preferred situation, this Resins, epoxy is the novolac epoxy that each molecule has at least 2.5 epoxy group(ing).In wide region of the present invention, this Resins, epoxy can be to have more than 11, any saturated or undersaturated aliphatic series of 2-epoxy group(ing), alicyclic, aromatics or heterogeneous ring compound.The example of heterocyclic ring oxygen compound is diglycidyl glycolylurea or triglycidyl group isocyanuric acid ester (TGIC).
Resins, epoxy does not preferably contain low alkyl group aliphatic series substituent Resins, epoxy, for example glycidyl ether of the glycidyl ether of phenol phenolic varnish or bisphenol-f.Preferred Resins, epoxy is novolac epoxy (be sometimes referred to as the epoxidation lacquer resins, this term is intended to contain epoxy phenol novolac resin and cresol novolac epoxy varnish resin they both).
Novolac epoxy (comprising the cresol novolac epoxy varnish resin) can be easily for example with trade(brand)name D.E.N. TM, Quatrex TM, (trade mark of Dow Chemical Company) and Epon TM(Hexion Specialty Chemicals, the trade mark of Inc) is purchased.
1,4-quinhydrones or 1, phosphinate that the 4-naphthoquinones is functionalized and functionalized phosphonic acid ester or they both can be randomly as the fire retardant of a lot of thermosets and thermoplastic resin, for example multipolymer of polycarbonate, polyester, vinyl ester, cyanate, polymeric amide, polyimide, polyolefine (comprising polyethylene, polypropylene, poly--the 4-methylpentene, polystyrene), acrylonitrile-styrene-divinyl, urethane and many other materials; But the fire retardant that more particularly, is used for Resins, epoxy is general method.
Those skilled in the art can be with 1,4-quinhydrones or 1, both are transformed into the functional group of any number phosphinate that the 4-naphthoquinones is functionalized and functionalized phosphonic acid ester or they, for example, but be not limited to, ether, carbonic ether, carbamate and ester change the performance of material to improve the consistency in given resin system.Particularly, can be in the Resins, epoxy preparaton with these materials directly as linking agent.These materials are intended to be used for fire-retardant printed-wiring board (PWB).In addition, the resin of the present invention's description can be prepared to influence curing speed, strengthen flame retardant resistance and to improve physicals with extra additive and filler.
In addition, the present composition can be mixed with common additive with present composition with other fire retardant material to improve performance.These altogether-the FR material can be inorganic or organic, and can be reactivity or additive kind compound.The example of inorganic additives types of material includes but not limited to, hibbsite (ATH), magnesium hydroxide, hydrated barta, lime carbonate, titanium dioxide and silicon-dioxide.Be particularly useful altogether-the FR filler is ATH.The self-gravitation character of co-curing agent of the present invention can further be enhanced to satisfy UL-94 V-0 requirement by adding suitable fire-retardant auxiliary.Aforesaid other filler will be thought flame retardant properties useful by those skilled in the art.The example of organic class additive or reactive component comprises, but be not limited to, triphenylphosphate, Resorcinol two (two-2,6-xylyl phosphoric acid ester), 9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound, dihydroxyphenyl propane two (phenylbenzene-phosphoric acid ester), melamines, melamine phosphate, melamine borate and many other materials well known to those skilled in the art.
Can use filler to influence physicals and to reduce cost in the present invention.Usually, filler and toughener comprise glass fibre, granulated glass sphere (solid or hollow), silicon-dioxide or the silicon carbide whisker etc. of mica, talcum, kaolin, wilkinite, wollastonite, glass fibre, glass fabric, glassmat, grinding.Many these materials are at Encyclopedia of MaterialsScience and Engineering, and the 3rd rolls up, the 1745-1759 page or leaf, and MIT press, Cambridge, MA enumerates in (1986), and its disclosure is hereby incorporated by.The binding substances of filler is preferred in some embodiments; As under the situation of the glass fabric of prepreg that is used for printed-wiring board (PWB) and veneer sheet, toughener constitutes the major part of matrix material of the present invention yet in other embodiments.
The curing catalyst or the catalyzer that are fit to that can be used for this preparaton comprise, still are not limited to, and replacement or unsubstituted imidazoles be imidazoles, glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole etc. for example.Other catalyzer comprises tertiary amine and acid amides.Also can use phosphine catalyst, for example triphenylphosphine.Also can use separately or combine with other catalyzer and use Lewis acid, this is convention to those skilled in the art.The example of typical Lewis acid comprises the oxide compound and the oxyhydroxide of zinc, tin, silicon, aluminium, boron and iron; Also can use boron trifluoride or boric acid.
Put into practice according to the present invention, the matrix material of resin impregnation is provided, it comprises the curable compositions at least a and described herein in filler or the toughener, and this matrix material solidifies at least in part.For example, of the present invention 1,4-quinhydrones or 1, phosphinate that the 4-naphthoquinones is functionalized and functionalized phosphonic acid ester mixture, polyhydroxy resin and Resins, epoxy are advantageously used in the manufacturing of the prepreg that is used for preparing printed-wiring board (PWB) and veneer sheet.The resin that to describe preparation by this paper and one or more solidifying agent and optional promotor (one or more) are mixed and are applied on the woven fiber glass.In being generally 150 ℃-200 ℃ baking oven, the sheet material or the prepreg of resin impregnation solidified several minutes at least in part then; For example 1-5 minute.
In order to prepare the sort of veneer sheet that is used for printed-wiring board (PWB), pile up the layer of resin impregnation shown in it with a plurality of prepregs are adjacent one another are.Each side at this stacked body provides copper foil layer, for example multilayer.Then this stacked body (comprising layer of cloth and paper tinsel layer) is arrived 50psi 20 in press, compacting 1 hour or longer time are to prepare the veneer sheet of compacting under the pressure of preferred 30-35psi, 170-220 ℃ high temperature.Therefore veneer sheet comprises a plurality of fused layers of the glass fabric of resin impregnation.If desired, depend on required structure, can use more or less preimpregnation bed of material or paper tinsel layer.
In embodiment subsequently, use hereinafter to be referred as:
The ATH hibbsite
DEN 438 can be from the epoxidised novolaks resin of Dow Chemical Co acquisition
Dowanol PM 1-methoxyl group-2-propyl alcohol
The DSC dsc
The FR fire retardant
The 2MI glyoxal ethyline
31The nuclear magnetic resonance spectrum of P NMR phosphorus
The PWB printed-wiring board (PWB)
Phr part/hundred part resin
The Tg second-order transition temperature
SD-1708 can be from Hexion Specialty Chemicals, the phenol that Inc obtains
Formaldehyde resin (novolac resin)
The TGA thermogravimetric analysis
Embodiment
Embodiment 1.
2,5-dihydroxy phenyl-phenyl phosphinic acid 2, the preparation of 6-dimethyl-phenylester (Compound I B):
With 2 of 390g (3.2mol), the 6-xylenol adds in the reaction vessel and is heated to 60 ℃, produces melt.Subsequently, under agitation, add 572g (3.2mol) phenyl dichloro phosphine.After two hours, temperature is risen to 95 ℃, rise to 135 ℃ then and kept two hours, rise to 185 ℃ and keep two hours to remove HCl gas.Mixture is cooled to envrionment temperature and adds 2.1 liters of toluene.In 0.5 hour, add stoichiometric water.Observe this reaction mixture and rise to 45 ℃ maximum value, and under agitation in 4 hours, return to envrionment temperature from envrionment temperature.The acetate that adds 1.8g (0.03mol) is as catalyzer.This mixture heating up to 80-85 ℃, and was added 1 of 3.4mol continuously in 6 hours, 4-benzoquinones (4.7 liters solution in toluene).Finish after the interpolation, stirred this mixture 20 hours down at 95 ℃.By crystallization with the crude product purifying.This material has 172 ℃ fusing point and dissolves in acetone.By 31This product is identified in P NMR spectrum and ultimate analysis.
Embodiment 2.
2, the preparation of two (2, the 6-3,5-dimethylphenyl) esters (Compound I IB) of 5-dihydroxy phenyl phosphonic acids.
Can be with 2 of 100.0g, the 6-xylenol adds in the reaction vessel and is heated to 60 ℃, produces melt.The phosphorus trichloride that under agitation can dropwise add subsequently, 56.2g.Temperature can be continued to rise to 95 ℃ after 2 hours, keep 2 hours; Rising to 135 ℃ kept 2 hours; Rise to 185 ℃ and keep 2 hours to remove HCl.Mixture can be cooled to envrionment temperature and can add 200 gram toluene.In 0.5 hour, can add 7.38g water, and can under situation about not heating, stir 4 hours.Can add 400g toluene.Can add 0.22g acetate as catalyzer.This mixture heating up 80-90 ℃ can be arrived, and 1 of 44.2g, 4-benzoquinones can be in 6 hours, added.Down this reaction mixture was heated other 10-20 hour at 110 ℃.Can be by crystallization or column chromatography with the crude product purifying.Can pass through 31This product is identified in P NMR spectrum and ultimate analysis.
Embodiment 3.
Use compound 1 as co-curing agent prepared layer pressing plate
Preparation 64.5phr passes through 2 of embodiment 1 preparation, 5-dihydroxy phenyl-phenyl phosphinic acid 2,6-dimethyl-phenylester and the 17.7phr SD-1708 solution in 127phr Dowanol PM.100phr DEN 438 Resins, epoxy and 0.0013phr glyoxal ethyline are added in the solution." the glass fabric synusia carries out about 2 minutes of B-stageization to form prepreg to eight 12 * 12 of gained varnish impregnations then in the baking oven under 170 ℃.The 1 ounce copper foil sheet in eight 11 * 11 " prepreg and 2 outsides 12 * 12 " is stacked, and at 185 ℃, 33PSI down compacting 160 minutes to produce veneer sheet.
Embodiment 4.
Use 2,5-dihydroxy phenyl-phenyl phosphinic acid 2,6-dimethyl-phenylester are as the co-curing agent, and ATH is as being total to-FR material preparation veneer sheet:
Preparation 64.6phr passes through 2 of embodiment 1 preparation, 5-dihydroxy phenyl-phenyl phosphinic acid 2,6-dimethyl-phenylester and the 17.7phr SD-1708 solution in 127phr Dowanol PM.100phr DEN 438,78.2phr ATH and 0.0010phr glyoxal ethyline are added in this solution to form slurry.Eight 12 * 12 " 7628 glass fabric synusia also carry out B-stageization under 170 ℃ to use the gained varnish impregnation.The 1 ounce copper foil sheet in eight 11 * 11 " prepreg and 2 outsides 12 * 12 " is stacked, and at 185 ℃, 33PSI down compacting 160 minutes to produce veneer sheet.
Embodiment 5.
Use 2, two (2, the 6-3,5-dimethylphenyl) esters of 5-dihydroxy phenyl phosphonic acids are as the description of the veneer sheet of co-curing agent:
Can be with 2 of 72.5phr embodiment 2, two (2, the 6-3,5-dimethylphenyl) esters of 5-dihydroxy phenyl phosphonic acids and 17.7phr SD 1708 stir with 127phr Dowanol PM.Can add 100phr DEN 438 and 0.0013phr glyoxal ethyline then.Gained varnish can flood eight 12 * 12 " 7628 glass fabric synusia, and can under 170 ℃, carry out B-stageization.The 1 ounce copper foil sheet in eight 11 * 11 " prepreg and 2 outsides 12 * 12 " can be stacked, and can be at 185 ℃, 33PSI down compacting 160 minutes to produce veneer sheet.
Embodiment 6.
Veneer sheet by the preparation of phenolic varnish solidifying agent:
Use the unique solidifying agent prepared layer pressing plate that is used for Resins, epoxy according to the novolac resin conduct of structure V according to the step of embodiment 3.
The performance of the material by the foregoing description preparation provides in table 1.
Table 1
Preparaton numbering (phr)
Composition/embodiment 4 3 6
DEN 438 100 100 100
Structure 1B 2,5-dihydroxy phenyl-phenyl phosphinic acid 2,6-dimethyl-phenylester 64.6 64.5 Do not have
SD-1708 17.7 17.7 72.6
2-MI 0.001 0.001 0.05
ATH 78.2 Do not have Do not have
The veneer sheet performance
TGA. 15% ℃ 344 376 387
Tg ℃ (passing through DSC) 116 133 174
T-260, 2Minute Not failure Not failure N/A
T-288, 2Minute >90 46 N/A
Pressure cooker/immersed solder (% moisture content/grade; 5=is best) 0.218/5 0.219/5 N/A/5
UL-94 combustion test Ave T1/T2 18/13 44/0 67/0
Total combustion time 3, second 155 219 335
Burning is observed Weak flame, 1 inch (2.5cm) of slow edge burning, self-gravitation Weak flame, 2 inches (5cm) of slow edge burning, self-gravitation Veneer sheet all burns down
Footnote:
1. TGA experiment: analytic sample in thermogravimetric analyzer.Under nitrogen atmosphere, with 10 ℃/minute speed the temperature in the analyser is elevated to 700 ℃ maximum value from room temperature.The temperature that is write down is the temperature when 5% mass loss takes place.
2. T-260 is meant by IPC (Association Connecting ElectronicsIndustries) the use thermomechanical analyzer (TMA) that limits and is determined at the detection method of 260 ℃ of lower leaf times.Use detection side's religious name 2.4.24.1.Similarly carrying out T-288 to measure the stratified time, is under 288 ℃ temperature still.
3. total combustion time of five test samples, wherein each sample has two kinds of flames application.
Data in the table 1 show: comprise 2, and 5-dihydroxy phenyl-phenyl phosphinic acid 2, the preparaton of 6-dimethyl-phenylester shows the inherent flame retardant properties.Though these preparatons are not optimized with regard to V-0 FR performance, from very weak flame front and self-gravitation characteristic, its inherent FR performance is conspicuous.By contrast, non-FR control sample has much strong flame front, and this flame front causes this veneer sheet sample all to burn down.
Use the basic preparatons of these of this material to show very good thermostability by following character representation: with the temperature value of the approaching higher TGA 5wt% loss of non-fire-retardant control sample, and considerably beyond the T-260 and the T-288 result of pb-free solder application need.

Claims (20)

1. composition, it comprises according to 1 of following structure I, II, III, IV, 4-quinhydrones deutero-phosphinate, 1,4-quinhydrones deutero-phosphonic acid ester, 1,4-naphthoquinones deutero-phosphinate, 1,4-naphthoquinones deutero-phosphonic acid ester, or their binding substances:
Figure A2005800391790002C1
Wherein R, R ' are identical or different aryl, aralkyl or the alkyl that contains 1-15 carbon atom independently of one another, but for structure I, R cannot be methyl or ethyl, and for structure I I, R and R ' cannot be methyl, ethyl or sec.-propyl simultaneously.
2. the composition of claim 1, wherein structure I is 2,5-dihydroxy phenyl-phenyl phosphinic acid 2,6-dimethyl-phenylester.
3. the composition of claim 1, wherein structure I I is 2, two (2, the 6-3,5-dimethylphenyl) esters of 5-dihydroxy phenyl phosphonic acids.
4. polymer composition, it comprises in the structure of claim 1 one or more.
5. the polymer composition of claim 4, wherein this polymkeric substance is a thermosetting resin.
6. the polymer composition of claim 4, wherein this polymkeric substance is a thermoplastic resin.
7. the composition of claim 5, wherein this polymkeric substance is a Resins, epoxy.
8. the composition of claim 7, wherein this Resins, epoxy also reacts with phenolic varnish.
9. the composition of claim 8, it also comprises strongthener.
10. the composition of claim 9, wherein this strongthener is glass, carbon, polyaramide or quartzy fiber.
11. the composition of claim 9 wherein partly solidifies this resin and strongthener to form prepreg.
12. the compacted lift pressing plate that forms by a plurality of prepregs according to claim 11.
13. according to the veneer sheet of claim 12, it also comprises Copper Foil.
14. the composition of claim 7, wherein this structure is selected from 2,5-dihydroxy phenyl-phenyl phosphinic acid 2,6-dimethyl-phenylester, 2, two (2, the 6-3,5-dimethylphenyl) esters of 5-dihydroxy phenyl phosphonic acids; 2,5-dihydroxyl naphthyl-phenyl phosphinic acid 2,6-dimethyl-phenylester; 2, two (2, the 6-3,5-dimethylphenyl) ester or their binding substancess of 5-dihydroxyl naphthyl-phosphonic acids.
15. the resin of claim 13, wherein this 1,4-quinhydrones deutero-phosphonic acid ester is selected from 2,5-dihydroxy phenyl-phenyl-phosphonic acid 2,6-dimethyl-phenylester or 2,5-dihydroxy phenyl phosphonic acids two (2, the 6-3,5-dimethylphenyl) ester, 2,5-dihydroxyl naphthyl-phenyl phosphinic acid 2,6-dimethyl-phenylester, 2, two (2, the 6-3,5-dimethylphenyl) ester or their binding substancess of 5-dihydroxyl naphthyl-phosphonic acids.
16. Resins, epoxy, it comprises according to 1 of following structure I, II, III, IV, 4-quinhydrones deutero-phosphinate, 1,4-quinhydrones deutero-phosphonic acid ester, 1,4-naphthoquinones deutero-phosphinate, 1, the reaction product of 4-naphthoquinones deutero-phosphonic acid ester or their binding substances and Epicholorohydrin:
Figure A2005800391790003C1
Wherein R, R ' are identical or different aryl, aralkyl or the alkyl that contains 1-15 carbon atom independently of one another.
17. Resins, epoxy, it comprises 1,4-quinhydrones deutero-phosphinate, 1,4-quinhydrones deutero-phosphonic acid ester, 2,5-naphthalenediol deutero-phosphinate, 2, the reaction product of 5-naphthalenediol deutero-phosphonic acid ester or their binding substances and Epicholorohydrin.
18. the composition of claim 1, wherein structure III is 2,5-dihydroxyl naphthyl-phenyl phosphinic acid 2,6-dimethyl-phenylester
19. the composition of claim 1, wherein structure I V is 2, two (2, the 6-3,5-dimethylphenyl) esters of 5-dihydroxyl naphthyl-phosphonic acids.
20. composition, it comprises according to 1 of following structure I, II, III, IV, 4-quinhydrones deutero-phosphinate, 1, and 4-quinhydrones deutero-phosphonic acid ester, 1,4-naphthoquinones deutero-phosphinate, 1,4-naphthoquinones deutero-phosphonic acid ester or their binding substances:
Figure A2005800391790004C1
Wherein R, R ' are identical or different aryl, aralkyl or the alkyl that contains 1-15 carbon atom independently of one another;
And polymkeric substance.
CNA2005800391790A 2004-09-21 2005-09-21 1,4-hydroquinone functionalized phosphinates and phosphonates Pending CN101061127A (en)

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