CN101124298A - Reactive flame retardant and flame-retardant resin processed article - Google Patents

Reactive flame retardant and flame-retardant resin processed article Download PDF

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CN101124298A
CN101124298A CNA2006800054861A CN200680005486A CN101124298A CN 101124298 A CN101124298 A CN 101124298A CN A2006800054861 A CNA2006800054861 A CN A2006800054861A CN 200680005486 A CN200680005486 A CN 200680005486A CN 101124298 A CN101124298 A CN 101124298A
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resin
retardant
flame
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make
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管野敏之
菅田好信
柳瀬博雅
重原淳孝
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Fuji Electric Co Ltd
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Abstract

Disclosed is a reactive flame retardant which provides a resin with excellent flame retardance even when it is added in a small amount while being prevented from bleedout. Also disclosed is a flame-retardant resin processed article obtained by using such a reactive flame retardant. An organophosphorus compound represented by the general formula (I) below, wherein at least one or more of X<1>-X<3> represent a group containing phosphorus and having a terminal unsaturated group, is used as a reactive flame retardant which is reactive with resins. A flame-retardant resin processed article can be obtained by solidifying the resin composition containing the organophosphorus compound and then reacting it through heating or application of radiation.

Description

Reactive flame retardant and flame-retardant resin processed article
Technical field
The present invention relates to the flame-retardant resin processed article that is used for the fire retardant of molded resin and so on and uses this fire retardant.More specifically, the flame-retardant resin processed article that the present invention relates to not halogen-containing non-halogen-based flame retardants and use this fire retardant.
Background technology
Have good mouldability or the processing characteristics that is used for resins for universal use and engineering plastics separately as the thermoplastic resin of polyester and polymeric amide with as the thermosetting resin of Resins, epoxy, therefore physical strength and electrical characteristic are used to comprise various fields such as electricity and electronics always.In addition, require for preventing that aspect the security that high temperature catches fire be fire-retardant by the goods of these resins being processed the resin treatment made from molding.For example, provide as the standard of UL94 grade as flame retardant resistance.
Common known halogen species can make goods of resin treatment etc. fire-retardant effectively.By add halogen-based flame retardants in resin, goods that make resin treatment etc. have flame retardant resistance.Allegedly provide the mechanism of flame retardant resistance as follows by halogen-based flame retardants.That is, the halogenation free radical mainly is to produce by thermolysis, and the halogenation free radical of generation captures the organic free radical as Combustion Source, stops the incendiary chain reaction, thereby shows high flame retardant.
Yet the fire retardant that contains a large amount of halogen compounds depends on that combustion conditions may produce dioxin etc., therefore from reducing the viewpoint of environmental pressure, in recent years the requirement that reduces halogen quantity is constantly increased.Therefore, investigated the non-halogen-based flame retardants of various not halogen-containing based compounds.
Investigated inorganic combustion inhibitor such as metal hydroxides and red phosphorus, be derived from the triazinyl fire retardant of urea, organophosphorus based flameproofing such as phosphoric acid ester etc. are as the non-halogen-based flame retardants of this class.
Yet not having as the metal hydroxides of aluminium hydroxide or magnesium hydroxide provides the very effect of high flame retardant, so resin must mix with a large amount of metal hydroxidess.Therefore, the easy variation of the mouldability of resin, the physical strength of the moulded parts of making etc. descends easily, thereby causes the problem that the application of the goods etc. of available resin treatment is restricted.In addition,,, produce obnoxious flavour, reduce mouldability and cause bleed owing to disperse insufficient red phosphorus to suppress electrical characteristic easily although red phosphorus has the high flame retardant effect.
On the other hand, for example, following patent documentation 1 discloses the piperazine salt of the acid phosphoric acid ester with phosphorinane structure or has the Alkylenediamine salt of 1-6 carbon atom to be used as is the fire retardant of organophosphorus base, as phosphoric acid ester.
In addition, following patent documentation 2 discloses a kind of fire retardant that is used for mainly the resin formed by the aromatic phosphate acid ester of for example mono phosphoric acid ester phenyl ester or mono phosphoric acid ester toluene ester with as the aliphatic amine of piperazine.
In addition, following patent documentation 3 discloses a kind of phosphorated phenolic compound, as the fire retardant that fire retarding epoxide resin is provided, this compound provides good fire retardation with the halogen-free flame-retardant agent prescription, provide moulded parts good physicals, as thermotolerance and water tolerance, and the binding property in the electrician uses with veneer sheet.
In addition, following patent documentation 4 discloses a kind of organic cyclic phosphorus compound with difunctionality hydroxyl, especially can be as the stablizer of polymer composition or as fire retardant.
In addition, following patent documentation 5 discloses a kind of organo phosphorous compounds, and it has allyl group as unsaturated link(age) at this compound end.
Patent documentation 1:JP 2002-20394 A
Patent documentation 2:JP 2002-80633 A
Patent documentation 3:JP 2002-138096 A
Patent documentation 4:JP 5-331179 A
Patent documentation 5:JP 2004-315672 A
Summary of the invention
The problem to be solved in the present invention
Disclose as above patent documentation 1-5, the fire retardant of being made up of organo phosphorous compounds is carried out various researchs, and can obtain multiple organophosphorous fire retardant at present.Yet the flame retardant resistance of these organophosphorous fire retardants is all not enough, so resin must mix with the various fire retardants of high density.
In addition, do not have in the organophosphorus based compound that in above patent documentation 1-3, discloses a kind of in molecule, have can with resin Composition reactive activity group, therefore flame retardant compositions moves in resin easily, thereby causes flame retardant compositions to volatilize when molding and pollute the problem on surface that mould or fire retardant are exuded to the goods of resin treatment.
Has the effect of the sex flame retardant that reacts in the resin that hydroxyl etc. can be combined in the active group in the Resins, epoxy at the organophosphorus based compound described in the above patent documentation 4.Yet, in having hydroxyl etc. to be combined in the resin of the reactive group in the conventional olefin resin, can not form cross-link bond.Equally in this case, flame retardant compositions moves in resin easily, thereby causes flame retardant compositions to volatilize when molding and pollute mould or fire retardant is exuded to the problem on surface of the goods of resin treatment.
In addition, the organo phosphorous compounds energy and the resin reaction that in above patent documentation 5, disclose, the effect of the sex flame retardant that reacts.But, be liquid under this compound room temperature, therefore compound is oozed out with the existence of the product of resin reaction.In addition, the heat decomposition temperature of organo phosphorous compounds is low, and its flame retardance element evaporates with resin kneading and molding the time easily.Therefore, in some situation, in the goods of molding fire retardant contain quantity not sufficient, so just can not provide fire retardation.Therefore, mouldability or poor in processability that the moulded parts of organo phosphorous compounds is arranged.
Therefore, the purpose of this invention is to provide: reactive flame retardant, even good flame retardant resistance and thermotolerance also can be provided when this reactive flame retardant joins resin on a small quantity, can prevent oozing out of this fire retardant etc., and moulded parts has good mechanical characteristics, electrical characteristic, dimensional stability and mouldability; The flame-retardant resin processed article of using this fire retardant also is provided.
The method of dealing with problems
The present inventor has carried out extensive studies in view of the above problems.The feature of the reactive flame retardant of the present invention that result of study obtains is, contains the following general formula (I) or (II) organo phosphorous compounds of expression, and this organo phosphorous compounds has unsaturated end group:
Figure A20068000548600071
In the formula, X 1To X 3Expression-OH or by the group of following formula (A) expression, X independently of one another 4The group of expression singly-bound or following formula (B) expression, X 1To X 3In one or more groups of representing following formula (A) expression separately, contain CH at this group end 2=CH-CH 2-;
Figure A20068000548600081
In the formula, R 1Expression CH 2=CH-CH 2-, the aryl that is less than or equal to 12 carbon atoms is arranged or the aralkyl that is less than or equal to 12 carbon atoms, R is arranged 2And R 3Represent hydrogen atom, CH independently of one another 2=CH-CH 2-, the aryl that is less than or equal to 12 carbon atoms is arranged or the aralkyl that is less than or equal to 12 carbon atoms is arranged, Y represent singly-bound ,-NH-or-O-;
Figure A20068000548600082
In the formula, R 4To R 9Expression is selected from following group separately: phenyl, benzyl, Alpha-Naphthyl, betanaphthyl, p-xenyl, phenoxy group, benzyloxy, alpha-naphthoxy base, β-naphthyloxy, p-biphenylyloxy (biphenyloxy), (CH 2=CH-CH 2) 2N-, CH 2=CH-CH 2NH-, CH 2=CH-CH 2O-and CH 2=CH-CH 2-, R 10Expression H or CH 2=CH-CH 2-, R 4To R 10In at least one is illustrated in this group end and contains CH 2=CH-CH 2-group, R 4To R 8Can be identical or different mutually.
According to reactive flame retardant of the present invention, use the organo phosphorous compounds that has at least one unsaturated end key in the molecule, therefore, this unsaturated end key because the heat that is used to react or irradiation and and resin-bonded.Therefore, flame retardant compositions can stable existence in resin, so just can prevent that fire retardant from oozing out, even when adding a small amount of fire retardant, also can provide flame retardant resistance for a long time.
In addition, organo phosphorous compounds of the present invention contains one or more phosphorus atom in its any molecule, so this compound can easily produce the P free radical with high flame retardant effect.In addition, when compound contained easily dissociative P-C key, this compound produced the P free radical with high flame retardant effect probably.Therefore, can improve flame retardant resistance.
In addition, the heat decomposition temperature of organo phosphorous compounds can improve, because this compound has high molecular, and is stable aspect energy.Therefore, this compound can prevent fire retardant mediate with resin and molding during evaporate and the heat can prevent fire retardant because of molding time the or shearing and decompose, thereby improved the mouldability of compound.In addition, this compound contains a large amount of carbon, thereby can obtain the so-called effect of burning, and improves flame retardant resistance by produce and deposit the cigarette ash component when resin decomposes at this.
Simultaneously, flame-retardant resin processed article of the present invention can or be used the resin combination that contains reactive flame retardant and resin by molding, by heating or radiation resin and the reaction of this reactive flame retardant are made then, wherein the feature of flame-retardant resin processed article is, total amount with flame-retardant resin processed article is a benchmark, contains 1-20 quality % reactive flame retardant.
According to flame-retardant resin processed article of the present invention,, make the flame retardant compositions stable existence in resin because make the unsaturated link(age) and the resin reaction of organo phosphorous compounds end by heating or radiation.As a result, can prevent that fire retardant from oozing out, flame retardant effect can improve.Therefore, even also can provide flame retardant resistance for a long time when the add-on of reactive flame retardant is low to moderate 1-20 quality % in whole flame-retardant resin processed article.
In addition, by the combination between fire retardant and the resin, resin crosslinks forms tridimensional network.Therefore, can make molded resin, the product of the resin treatment of making thus can show excellent chemical stability, thermotolerance, mechanical characteristics, electrical characteristic, dimensional stability, flame retardant resistance and mouldability.Particularly can improve thermotolerance and physical strength.In addition, resin can be molded as thin type.
In above-mentioned flame-retardant resin processed article, resin combination preferably contains two or more reactive flame retardants, and wherein at least a reactive flame retardant is polyfunctional.
According to this on the one hand, because the crosslinked speed of reaction of following can be controlled by being used in combination the different mutually fire retardant of multiple reactivity, therefore can prevent because the contraction of the resin due to the carrying out fast of crosslinking reaction etc.In addition, add the uniform tridimensional network that multifunctional fire retardant causes being formed with organo phosphorous compounds, therefore improve thermotolerance and flame retardant resistance, and can obtain more stabilized resins of physicals.
In addition, in above-mentioned flame-retardant resin processed article, resin combination also preferably removes and comprises reactive flame retardant, also is included as the fire retardant of cyclic nitrogen compound, and this compound has at least one unsaturated group at its end.
According to this on the one hand, have at the compound end under the situation of cyclic nitrogen compound of at least one unsaturated group, by the combination of fire retardant and interlaminar resin, resin also is cross-linked to form tridimensional network.Therefore, when the whole cost of multiple fire retardant descends because of being used in combination multiple fire retardant, can make molded resin, the product of thus obtained resin treatment can have excellent chemical stability, thermotolerance, mechanical characteristics, electrical characteristic, dimensional stability, flame retardant resistance and mouldability.In addition, added nitrogen and also improved consistency with resin, particularly in the situation of using polyamide-based resins as resin.
In addition, in above-mentioned flame-retardant resin processed article, resin combination also comprises another kind of reactive fire retardant that do not have except reactive flame retardant.This resin combination should contain a certain amount of another kind of fire retardant in polymeric matrix, this fire retardant and reactive flame retardant combination make this fire retardant can not influence the thermal property and the mechanical characteristics of the goods of resin treatment, and can not ooze out.
According to this on the one hand, be used in combination reactive flame retardant and another kind ofly do not have reactive fire retardant, as phosphate-based, melamine-based, metal hydroxides or silica-based fire retardant, compare with the situation of only using reactive flame retardant, because provide synergy can additionally improve flame retardant resistance, and can reduce the cost of fire retardant.
In addition, in flame-retardant resin processed article, resin combination preferably also contains linking agent, and described linking agent is polyfunctional monomer or the oligopolymer that has unsaturated group at its main framing end.
According to this on the one hand, by the combination of fire retardant and interlaminar resin, resin crosslinks forms tridimensional network.Therefore, can make molded resin, the product of thus obtained resin treatment has excellent chemical stability, thermotolerance, mechanical characteristics, electrical characteristic, dimensional stability, flame retardant resistance and mouldability.
In addition, in flame-retardant resin processed article, be benchmark with the flame-retardant resin processed article total amount, flame-retardant resin processed article preferably also contains 1-45 amount % mineral filler.Particularly, be benchmark with the flame-retardant resin processed article total amount, flame-retardant resin processed article preferably contains 1-10 quality % laminated clay as mineral filler, and this laminated clay can obtain by the lamination silicate layer.According to this on the one hand, can make the goods of resin treatment, it is inhibited because of contraction and the decomposition due to crosslinked, and this goods have good dimensional stability.In addition, will obtain laminated clay by the lamination silicate layer and add fashionablely as mineral filler, laminated clay is dispersed in the resin with nano level, with the resin formation mixed structure.Thermotolerance, physical strength that makes the flame-retardant resin processed article of making like this etc. is improved.
In addition, in flame-retardant resin processed article, be benchmark with the total amount of flame-retardant resin processed article, flame-retardant resin processed article preferably also contains 5-50 quality % fortifying fibre.According to this on the one hand, add the physical strength that fortifying fibre can improve the goods of resin treatment, as tensile strength, compressive strength, flexural strength or shock strength.In addition, can prevent that the physicals that causes because of humidity and temperature from descending.
In addition, in flame-retardant resin processed article, flame-retardant resin processed article preferably by with dosage irradiated electrons bundle or gamma-rays more than or equal to 10kGy, is made by the reaction between resin and the reactive flame retardant.According to this on the one hand, after resin solidifies by molding etc., can be undertaken crosslinkedly, therefore can make the goods of resin treatment with high productivity by irradiation.In addition, under the dosage of above-mentioned scope, can prevent because of underdosage forms uneven tridimensional network, and because of oozing out that the linking agent of remained unreacted causes.Particularly, with 10-45kGy dosage irradiation the time, can also prevent the distortion that the internal stress, contraction etc. of the goods of the resin treatment that causes because of oxygenolysis product that excess dosage produces cause.
In addition, in flame-retardant resin processed article, flame-retardant resin processed article is also preferably by making in the reaction between resin and the reactive flame retardant under high 5 ℃ or the higher temperature than resin combination molding temperature.According to this on the one hand, do not need to carry out radiating irradiation apparatus etc.Particularly, this flame-retardant resin processed article is applicable to the resin combination that contains thermosetting resin.
Aspect flame-retardant resin processed article another, flame-retardant resin processed article preferably is selected from following a kind of: moulded parts, coated film and sealing material.As mentioned above, flame-retardant resin processed article of the present invention has good flame retardant resistance, and can prevent to ooze out.Therefore, except can be used as conventional molded resin, it can be used as formation coated film such as coating agent, or is suitable as the sealing material of semi-conductor, liquid crystal material etc.
In flame-retardant resin processed article on the other hand, flame-retardant resin processed article is preferably used as electric component or electronic unit.As mentioned above, flame-retardant resin processed article of the present invention has good thermotolerance, mechanical characteristics, electrical characteristic, dimensional stability, flame retardant resistance and mouldability, therefore, be especially suitable for use as electric component or the electronic unit that above-mentioned physicals is had special strict demand.
The invention effect
According to the present invention, can provide: non-halogen radical reactive flame retardant even this fire retardant also can provide good flame retardant resistance to resin when joining resin on a small quantity, can prevent to ooze out simultaneously etc.; And provide the flame-retardant resin processed article of using this reactive flame retardant.
Description of drawings
Shown in Figure 1 is the TG graphic representation of fire retardant.
Shown in Figure 2 is the figure of the relation between flame-retardant resin processed temperature of articles and the physical strength.
Embodiment
Below, will describe the present invention in detail.
Reactive flame retardant of the present invention is to have with the reactive of resin and the reactive flame retardant of flame retardant resistance is provided because of this reactivity and resin-bonded, it is characterized in that the reactive organo phosphorous compounds that this reactive flame retardant contains following general formula (I) or (II) represents:
Figure A20068000548600121
In the formula, X 1To X 3The group of expression-OH or following formula (A) expression independently of one another, X 4The group of expression singly-bound or following formula (B) expression, X 1To X 3In one or more groups of representing following formula (A) expression separately, and contain CH at this group end 2=CH-CH 2-;
Figure A20068000548600122
In the formula, R 1Expression CH 2=CH-CH 2-, the aryl that is less than or equal to 12 carbon atoms is arranged or the aralkyl that is less than or equal to 12 carbon atoms, R is arranged 2And R 3Represent hydrogen atom, CH independently of one another 2=CH-CH 2-, the aryl that is less than or equal to 12 carbon atoms is arranged or the aralkyl that is less than or equal to 12 carbon atoms is arranged, Y represent singly-bound ,-NH-or-O-;
Figure A20068000548600123
In the formula, R 4To R 9Expression is selected from following group separately: phenyl, benzyl, Alpha-Naphthyl, betanaphthyl, p-xenyl, phenoxy group, benzyloxy, alpha-naphthoxy base, β-naphthyloxy, p-biphenylyloxy, (CH 2=CH-CH 2) 2N-, CH 2=CH-CH 2NH-, CH 2=CH-CH 2O-and CH 2=CH-CH 2-group, R 10Expression H or CH 2=CH-CH 2-, R 4To R 10In at least one end that is illustrated in group contain CH 2=CH-CH 2-group, R 4To R 9Can be identical or different mutually.
By above-mentioned general formula (I) and the organo phosphorous compounds of the present invention of any expression (II) be that phosphorus is the compound of pentavalent, this compound has one or more allyl group (CH 2=CH-CH 2-), these allyl groups each naturally at the unsaturated link(age) of the end of this compound.At this, allyl group is or to apply the functional group of irradiation described below etc. and resin-bonded by heating.
Because the organo phosphorous compounds of the invention described above is a powder characteristics in room temperature, even have when not staying in the moulded parts with the product of resin reaction, compound also oozes out hardly.In addition, the heat decomposition temperature of organo phosphorous compounds of the present invention is higher than the heat decomposition temperature of popular response organo phosphorous compounds, this compound is being stablized (more energetically stable) more than the popular response organo phosphorous compounds aspect the energy, therefore its flame retardant compositions evaporation hardly during molding, the goods of resin treatment have good mouldability or processing characteristics.In addition, organo phosphorous compounds of the present invention contains many aromatic rings in its molecule, so carbide productive rate height, can easily form the carbon (char) (pyrolysis residue) that heat or oxygen is had very big shielding effect.In addition, therefore the phosphorus content height of organo phosphorous compounds of the present invention can easily produce the phosphorus free radical with high flame retardant effect when thermolysis.In addition, organo phosphorous compounds of the present invention has the space molecular structure, and therefore described compound is reactive to the resin height, and can improve the physical strength of the molded resin of making.Even in the situation that molded resin is made up of thermoplastic resin, molded resin can have the mechanical and physical performance suitable with the molded resin of thermosetting resin.
The organo phosphorous compounds of general formula (I) expression preferably has two or more allyl groups in its any one molecule.In addition, this compound preferably has two or more phosphorus atom in its any one molecule.In addition, the phosphorus content of this compound is preferably 6-20 quality %.
In addition, the example that has the aryl that is less than or equal to 12 carbon atoms in the general formula (I) comprises :-C 6H 5(phenyl) ,-C 6H 5OH (hydroxy phenyl) ,-C 6H 5-C 6H 5OH (Hydroxybiphenyl) ,-α-C 10H 7(Alpha-Naphthyl) and-β-C 10H 7(betanaphthyl).
In addition, there is the example of the aralkyl that is less than or equal to 12 carbon atoms to comprise-CH 2-C 6H 5(benzyl).
In addition, the Y in the general formula (A) preferably represents singly-bound.When Y represented singly-bound, this compound had dissociative P-C key easily, and this compound just is easy to generate the phosphorus free radical when thermolysis like this, therefore can further improve flame retardant resistance.
The object lesson of the organo phosphorous compounds of general formula (I) expression comprises that compound shown below (I-1) is to (I-6).
Figure A20068000548600151
These compounds separately can by for example have with following formula (d) or (e) acyl chloride reaction of phenol resins and the structure of the structure of expression with formula (A) expression synthesize.
Figure A20068000548600161
In addition, the organo phosphorous compounds by general formula (II) expression preferably has two or more allyl groups in its any one molecule.In addition, the phosphorus content of this compound is preferably 6-20 quality %.
In addition, the object lesson by the organo phosphorous compounds of general formula (II) expression comprises that compound shown below (II-1) is to (II-17).
Figure A20068000548600181
Figure A20068000548600191
Figure A20068000548600201
Figure A20068000548600211
Figure A20068000548600221
These compounds separately can be synthetic by for example following method, and this method comprises: at first synthetic three (3-allyl group-4-hydroxy phenyl) phosphine oxide or three (4-hydroxy phenyl) phosphine oxides are as skeleton; Make this skeleton and phosphonyl chloride reaction with required functional group.It should be noted that three (3-allyl group-4-hydroxy phenyl) phosphine oxide or three (4-hydroxy phenyl) phosphine oxides can synthesize in the following manner: make the hydroxyl and the reaction of chloro trimethyl silane of 2-allyl group-4-bromophenol or 4-bromophenol, thereby provide-OSi (CH 3) 3Form; Make the reaction of this products therefrom and metallic lithium, on the bromine position, carry out lithiumation (lithiate); Make 3 moles products therefrom and 1 mole phosphoryl chloride reaction; Right-OSi (CH after this reaction 3) 3Part is hydrolyzed, and this part is restored be hydroxyl.
For example, the compound by formula (II-1) expression can synthesize in the following manner: at first synthetic three (3-allyl group-4-hydroxy phenyl) phosphine oxide is as skeleton; Make the reaction of this skeleton and diphenyl phosphonyl chloride.
Next, the flame-retardant resin processed article of using above-mentioned reactive flame retardant is described.
Flame-retardant resin processed article of the present invention comprises reactive flame retardant and resin, the organo phosphorous compounds that this reactive flame retardant contains top general formula (I) or (II) represents.Flame-retardant resin processed article can be made by the following method: to comprising with the resin combination total amount is that the resin combination of the 1-20 quality % reactive flame retardant of benchmark carries out molding, perhaps this resin combination is made coated film; By heating or application of radiation, resin and reactive flame retardant are reacted to each other.
Thermoplastic resin and thermosetting resin separately can be as the resins in the flame-retardant resin processed article of the present invention, without any special restriction.
The example of thermoplastic resin comprises: polyamide-based resins; Polyester-based resin such as polybutylene terephthalate resin or polyethylene terephthalate; The polyacrylic based resin; Polyimide-based resin; Polycarbonate resin; Polyurethane-based resin; Polystyrene-based resin such as polystyrene, vinylformic acid nitrile-styrol copolymer or vinylformic acid nitrile-butadiene-styrene copolymer; Polyacetal base resin; Polyolefin resin; Polyphenylene oxide resin; Polyphenylene sulfide and polybutadiene.Wherein, from mechanical characteristics, polyamide-based resins, polybutylene terephthalate resin, polyethylene terephthalate resin, polycarbonate resin, polyacrylic based resin, polyacetal base resin or polyphenylene oxide resin are preferably used in aspects such as thermotolerance.
The example of thermosetting resin comprises Resins, epoxy, urethane resin, unsaturated polyester resin, phenol resins, urea resin, melamine resin, Synolac and silicone resin.Wherein, from mechanical characteristics, Resins, epoxy is preferably used in aspects such as thermotolerance, phenol resins, unsaturated polyester resin or urea resin.
With the resin combination total amount is benchmark, and the content of above-mentioned reactive flame retardant is necessary for 1-20 quality %, preferred 1-15 quality %.When reactive flame retardant content during less than 1 quality %, because of the crosslinked deficiency that the reaction between reactive flame retardant and the resin produces, the machinery of the goods of the resin treatment of making, hot and electric physicals deficiency can not reach sufficient flame retardant resistance.On the other hand, it is also inadvisable that the content of reactive flame retardant surpasses 20 quality %, because reactive flame retardant is excessive, may produce the unreacted monomer of reactive flame retardant or the gas of decomposition, perhaps the product of low dimerization may ooze out, and the mechanical characteristics of the goods of the resin treatment of making descends.
Below preferred: flame-retardant resin processed article of the present invention contains two or more from the above-mentioned general formula (I) or (II) the reactive different compound mutually of the organo phosphorous compounds of expression, i.e. the quantity of two or more above-mentioned functional groups in a molecule different organo phosphorous compounds mutually; With at least a be the organo phosphorous compounds of multifunctional reactive flame retardant.Be used in combination the mutual different multiple reactive flame retardant of number of functional groups and can control crosslinked required speed of reaction, and can prevent resin combination shrinking fast because of crosslinking reaction.In addition, use multifunctional reactive flame retardant can cause forming uniform tridimensional network, and improve the physical strength of the goods of resin treatment by organo phosphorous compounds, for example, tensile strength, compressive strength, flexural strength or shock strength.
In addition, flame-retardant resin processed article of the present invention preferably except that above-mentioned general formula (I) or (II) expression organo phosphorous compounds, also comprise reactive flame retardant, this reactive flame retardant is made up of the cyclic nitrogen compound (below be called " multifunctional cyclic compound ") that the end at compound has at least one unsaturated group.In addition, be 1 mass parts more preferably with organo phosphorous compounds of the present invention, the content of reactive nitrogenous compound is the 0.5-10 mass parts.
The object lesson that has this compounds of unsaturated group at multifunctional cyclic compound end comprises: diacrylate, dimethacrylate, diallyl thing (diallylate), triacrylate, trimethacrylate, triallyl thing (triallylate), tetraacrylate, tetramethyl-acrylate and tetraallyl thing (tetraallylate).Wherein, aspect reactive, more preferably acrylate is as diacrylate, triacrylate or tetraacrylate.The example of cyclic nitrogen compound comprises isocyanuric acid ring and cyanogen urea acid ring.
The object lesson of multifunctional cyclic compound comprises the derivative of acid of above-mentioned cyanogen urea or isocyanuric acid, polyfunctional monomer or oligopolymer are as the diacrylate of isocyanuric acid EO-sex change, the triacrylate and the three isocyanuric acid triacrylates of isocyanuric acid EO-sex change.
In addition, flame-retardant resin processed article of the present invention preferably contains the another kind of reactive fire retardant (below be called " another kind of fire retardant ") that do not have except that above-mentioned reactive flame retardant.The preferred example of this another kind of fire retardant comprises: metal hydroxides is representative with aluminium hydroxide and magnesium hydroxide for example; Phosplate such as triphenylphosphate and Tritolyl Phosphate; Condensed phosphoric acid esters such as dihydroxyphenyl propane two (xenyl) phosphoric acid ester and Resorcinol two (xenyl) phosphoric acid ester; Ammonium polyphosphate; Many phosphamides; Red phosphorus; Phosphoguanidine; The derivative of acid of cyanogen urea or isocyanuric acid; With non-halogen-based flame retardants such as melamine derivative.
In addition, these another kind of fire retardants can use separately separately, and perhaps two or more are used in combination.With the resin combination total amount is benchmark, and the content of another kind of fire retardant is preferably 1-20 quality %, more preferably 3-15 quality %, and fire retardant oozes out and the mechanical property of the goods of resin treatment descends to prevent.
In addition, flame-retardant resin processed article of the present invention also preferably contain a kind of do not have flame retardant resistance but can with the linking agent of resin reaction.It should be noted that used term among the present invention " do not have flame retardant resistance but can with the linking agent of resin reaction " refers to have bridging property but linking agent itself that do not have flame retardant resistance.The reactive flame retardant that has cross-linking properties and flame retardant resistance simultaneously got rid of in this term, as above-mentioned " cyclic nitrogen compound that has at least one unsaturated group at the compound end ".
The polyfunctional monomer or the oligopolymer that have unsaturated group at its main framing end can be preferably used as this class linking agent, and the example of this class linking agent comprises the functional compound of difunctionality to four by following general formula (a) to (c) expression.At this, M represents main framing, R 11To R 14Expression has the functional group of unsaturated end group separately, (a) represents difunctional compound, (b) represents the trifunctional compound, (c) represents four functional compounds.
Figure A20068000548600251
Its object lesson comprises the structure of being represented by following general formula, and in each general formula, main framing M is an aliphatic alkyl, as glycerine or pentaerythritol derivative; Aromatic ring is as trimellitic acid, pyromellitic acid, tetrahydrofuran (THF) or trimethylene trioxane; And bis-phenol.
Figure A20068000548600252
Figure A20068000548600261
The object lesson of difunctional monomer or oligopolymer comprises diacrylate, comprise the diacrylate of Bisphenol F-EO-sex change, diacrylate, diacrylate tripropylene glycol ester, polypropyleneglycol diacrylate, polyethyleneglycol diacrylate and the pentaerythritol diacrylate monostearate of dihydroxyphenyl propane-EO-sex change, and their dimethacrylate and diallyl thing.
In addition, the object lesson of trifunctional monomer or oligopolymer comprises triacrylate, as the triacrylate of pentaerythritol triacrylate, Viscoat 295, TriMethylolPropane(TMP) PO-sex change and the triacrylate of TriMethylolPropane(TMP) EO-sex change, and their trimethacrylate and triallyl thing.
In addition, the object lesson of four functional monomers or oligopolymer comprises two (TriMethylolPropane(TMP)) tetraacrylate and tetramethylol methane tetraacrylates.
Linking agent can obtain in the following manner, make a kind of functional group that has a unsaturated group as end of being selected from allyl bromide 98, vinyl carbinol, allylamine, methacrylic bromine, methallyl alcohol and the methyl allylamine and be selected from trimellitic acid, pyromellitic acid, tetrahydrofuran (THF) tetracarboxylic acid, 1,3,5-trihydroxybenzene, glycerine, tetramethylolmethane and 2,4,6-three (chloromethyl)-1,3, a kind of reaction as main framing M in the 5-trioxane makes.
With respect to 1 mass parts reactive flame retardant, content of crosslinking agent is the 0.5-10 mass parts.
In addition, flame-retardant resin processed article of the present invention also contains, for example mineral filler, fortifying fibre, any in the perhaps various additives.
The adding mineral filler can improve the physical strength and the dimensional stability of the goods of resin treatment.In addition, mineral filler can be used as the absorption reaction sex flame retardant, and reactive flame retardant is dispersed in base substance in the resin combination.
Can use any general known mineral filler, its typical example comprises: copper powder, iron powder, nickel powder, zinc powder, glass putty, Stainless Steel Powder, aluminium powder, bronze, silver powder etc.; Pyrogenic silica; Pure aluminium silicate; Calucium Silicate powder; Silicic acid; Moisture Calucium Silicate powder; Hydrated aluminium silicate; Granulated glass sphere; Carbon black; Silica powder; White mica; Talcum; Mica; Clay; Titanium oxide; Ferric oxide; Zinc oxide; Lime carbonate; Magnesiumcarbonate; Magnesium oxide; Calcium oxide; Sal epsom; Potassium titanate; And diatomite.These mineral fillers can be used separately separately, perhaps two kinds or more of being used in combination.In addition, these mineral fillers can adopt general known surface treatment agent to handle separately.In the present invention, in these fillers, the preferred laminated clay that obtains by the lamination silicate layer that uses is as mineral filler especially.The clay that term " laminated clay that obtains by the lamination silicate layer " refers to have following structure, in this structure lamination separately the thickness length that is about a 1nm and a side be about the silicate layer of 100nm.Therefore, laminated clay is dispersed in the resin with nano level, with the resin formation mixed structure.As a result, the thermotolerance, physical strength etc. of flame-retardant resin processed article have been improved.The mean particle size of laminated clay is preferably and is less than or equal to 100nm.The example of laminated clay comprises montmorillonite, kaolinite and mica.Wherein, preferred montmorillonite is because montmorillonite has good dispersiveness.Laminated clay can carry out surface treatment, to improve its dispersiveness in resin.This laminated clay can be to be purchased product, for example, can use " Nanomer " (trade(brand)name is made by NISSHOIWAI BENTONITE) or " Somasif " (trade(brand)name is made by Co-op Chemical).
In addition, be benchmark with the total amount of flame-retardant resin processed article, the content of mineral filler is preferably 1-45 quality %, more preferably 1-20 quality %.Inorganic filler content is inadvisable less than 1 quality %, because the physical strength deficiency of flame-retardant resin processed article, the dimensional stability of goods is not enough.Also inadvisable when inorganic filler content surpasses 45 quality %, because flame-retardant resin processed article becomes fragility.In addition, when flame-retardant resin processed article contained laminated clay, with respect to the total amount of flame-retardant resin processed article, laminated clay content was preferably 1-10 quality %.Should point out that laminated clay can use separately, perhaps be used in combination with other any mineral filler.
Add fortifying fibre and can improve for example physical strength and the dimensional stability of moulded parts.The example of fortifying fibre comprises: glass fibre, carbon fiber and steel fiber.Consider in intensity with aspect the binding property of resin or mineral filler, preferably use glass fibre.Can be used alone fortifying fibre, perhaps two or more fiber combinations be used.Fiber can be handled with general known surface treatment agent such as silane coupling agent.
Preferred especially surface treated glass fibre is as above-mentioned fortifying fibre, and this fibrid has more preferably applied resin.In this case, can further improve binding property with thermoplastic polymer.
Can use general known silane coupling agent as the surface treatment agent that is used for fortifying fibre, the object lesson of silane coupling agent comprises the silane coupling agent that has at least one alkoxyl group and at least one reactive functional groups separately, described alkoxyl group is selected from methoxy or ethoxy, and described reactive functional groups is selected from amino, vinyl, acrylic, methacrylic acid group, epoxide group, thiohydroxy, halogen atom and isocyanate group.
Resin to the coating that is used for fortifying fibre has no particular limits, and its example comprises urethane resin and Resins, epoxy.
With the flame-retardant resin processed article total amount is benchmark, and the content of fortifying fibre is preferably 5-50 quality %, or 10-45 quality % more preferably.This content is inadvisable less than 5 quality %, because the physical strength of flame-retardant resin processed article descends its dimensional stability deficiency.It is also inadvisable that this content surpasses 50 quality %, because be difficult to resin processed.
Except said components, can also add a certain amount of any binder component commonly used in the flame-retardant resin processed article of the present invention, for example crystal nucleating agent, tinting material, antioxidant, releasing agent, softening agent, thermo-stabilizer, lubricant and UV inhibitor, make physicals such as thermotolerance as the object of the invention, weathering resistance and shock-resistance are not subjected to tangible infringement.In addition, as described below, when being reacted to each other because of UV-light, resin and reactive flame retardant can use UV initiator etc.
Tinting material is had no particular limits, but preferably when using the radiation that describes below, do not show the tinting material that fades.For example, preferably use mineral dye such as blood red, iron oxide black, carbon, or chrome yellow, or metal complexes such as phthalocyanine pigment.
Flame-retardant resin processed article of the present invention can obtain in the following manner, and resin combination is carried out molding or coated film, makes resin and reactive flame retardant reaction by heating or radiation then.
Resin combination can adopt general known method to carry out molding.For example, contain the situation of thermoplastic resin at resin combination, thermoplastic resin and reactive flame retardant are melted and mediate makes pellet.Then, adopt general known method such as injection moulding, extrusion molding, vacuum moulding or blowing are carried out molding to pellet.Fusion (melding) and kneading step can use common fusion and mediate processing units, as single shaft or biaxial extruder, and the Banbury mixing roll, kneader or mixing roll carry out.Mediating temperature can suitably select according to the type of thermoplastic resin.For example, in the polyamide-based resins situation, mediate and preferably carry out at 240-280 ℃.Can set suitable condition of moulding, but have no particular limits.In this step, crosslinked can't carrying out in advance, therefore, winding part extra during molding can circulate as thermoplastic resin.
On the other hand, in the thermosetting resin situation, as top situation, thermosetting resin and reactive flame retardant are melted and pellet is made in kneading.Then, can adopt for example general known method such as injection moulding, molding is carried out in compression moulding or die casting.
In preparation coated film situation, resin combination can apply with original state.Perhaps, resin combination can suitably dilute with solvent etc., solution that preparation can apply or suspension, this solution or suspension carry out drying by general known method, the preparation coated film can adopt as roller coat, spraying, the coating process of dip-coating or spin coating prepares coated film, and the coating process that adopts is had no particular limits.
In the resin combination, the unsaturated link(age) of reactive flame retardant end and resin reaction promote because of heating or irradiation radiating crosslinking reaction, so flame retardant compositions stably are present in the resin.
When adopting heating when making the mode of reactive flame retardant and resin reaction, resin and reactive flame retardant be preferably than resin moulded temperature high 5 ℃ or higher temperature, reacts under more preferably high 10 ℃ or the higher temperature.
When adopting the irradiation conduct to carry out crosslinked mode, can use electron beam, alpha-ray, gamma-rays, X-ray, UV-light etc.Used term " irradiation " refers to generalized irradiation among the present invention, except that particle beam such as electron beam or alpha-ray, specifically also comprises hertzian wave, as X-ray or UV-light.
Irradiation preferably adopts above-mentioned electron beam or gamma-rays to carry out.General known rumbatrons etc. can be used for electron beam irradiation, are preferably greater than or equal the acceleration energy of 2.5MeV.Can use the irradiation apparatus in general known co-60 radiation source etc. to be used for the gamma-rays radiation.
Use the irradiation apparatus in general known co-60 radiation source etc. can be used for the gamma-rays radiation.Preferred gamma-ray reason be gamma-ray penetrance greater than electron beam, therefore can carry out uniform irradiation.But gamma-rays has high radiance, thereby must control the dosage of this ray, to prevent excess radiation.
Radiation dose during irradiation is preferably more than or equals 10kGy, or 10-45kGy more preferably.The goods that radiation dose within this scope can make resin treatment have a good physical owing to crosslinked.Radiation dose is inadvisable less than 10kGy, and reason is owing to the crosslinked tridimensional network that forms is inhomogeneous, and unreacted linking agent may ooze out.Radiation dose is also inadvisable greater than 45kGy, and reason is that the internal stress of the goods of the resin treatment that produced because of the oxygenolysis product still keeps, and causes distortion, contraction etc.
Flame-retardant resin processed article of the present invention also has good mechanical characteristics except having good thermotolerance and flame retardant resistance, electrical characteristic, dimensional stability and mouldability.Therefore, the goods of this resin treatment can be suitable for requiring the electric component and the electronic unit of high heat resistance and high flame retardant, are used for trolley part or optics, for example: the parts that are used to support the contact of Mgs, isolating switch etc.; Substrate such as printed board; The encapsulation of unicircuit; Or the shell of electric component.
The object lesson of electric component or electronic unit comprises: dash receiver; Switchboard; Mgs; Isolating switch; Transformer; Electromagnetic contactor; Circuit brake; Rly.; Umformer; Various transmitters; Various motors; Semiconducter device, as diode, transistor and unicircuit.
The goods of resin treatment can be suitable for trolley part, as: cooling fan; Collision bumper; Braking top; Internal part such as panel; Sliding part; Transmitter; Or motor.
The goods of resin treatment not only can be used as the goods of molding, and can be used as the fire-retardant coated film on moulded parts, the fiber etc.
In addition, the goods of this resin treatment for example are used for, sealing covers and when isolated above-mentioned electric component or electronic unit such as semiconducter device, can provide good thermotolerance and good flame retardant resistance.Promptly, for example, resin combination sealing with cured resin, and is carried out above-mentioned reaction by heating or radiation, thus the flame retardant resistance sealing material that the goods of resin treatment can be sealed with the electronic unit or the electrical element of opposing as semi-conductor chip or ceramic condenser.Sealing can be by casting, perfusion, and die casting, injection moulding, compression moulding etc. are carried out.The electronic unit or the electric component that will seal had no particular limits, and its example comprises: liquid crystal, unicircuit, transistor, thyristor, diode and electrical condenser.
Embodiment
[0125] below, with the present invention of way of example more detailed description.But the present invention is not subjected to the restriction of these embodiment.
[0126]＜synthetic organo phosphorous compounds 〉
(embodiment 1) [synthetic compound (I-1)]
43.28g (205mmol) phenoxy group phosphinylidyne dichloro and 200ml are added in the 500ml four neck flasks through the distillatory ethyl acetate, and this flask is equipped with the return line of band drying tube, and mechanical stirring device, nitrogen induce one to manage and dropping funnel.Mixture is in the nitrogen, stirs in 0-5 ℃.During the stirring,, in mixture, slowly add the mixed solution of 19.89g (205mmol) diallyl amine and 41.52g (410mmol) triethylamine by this dropping funnel, add finish after, the gained mixture is in room temperature reaction 3 hours, 70 ℃ of reactions are 12 hours then.After the product cooling, Triethylammonium chloride salt is by removing by filter, and solution decompression concentrates, and removes like this and desolvates and excessive amine.Afterwards, resistates underpressure distillation, the cut of 144-146 ℃/5mmHg of collection.Therefore, make 47.73g phenoxy group phosphinylidyne monochloro list (N, N-diallyl) acid amides (below be called " POPAC ") (productive rate is 85%).Should point out, infrared absorption spectrum, NMR and TOF-mass spectrum confirm that this compound is POPAC.
[0127] infrared absorption spectrum (cm -1): v (C=C)1635, v (ring)1604,1495, v (P=O, POC)1280,1195,1040, v (CN)945
1The H-NMR spectrum (δ, ppm): phenyl-H 7.15 (2H), 7.33 (3H) ,-CH=5.55 (2H) ,-CH 2-5.10 (4H) ,=CH 23.50 (4H)
TOF-mass spectrum (M/Z): 273 (molecular weight of calculating=271.7)
Next, the phenol resins and 4.8g (200mmol) sodium hydride of general formula (d) expression below 250ml dimethyl formamide (below be called " DMF "), the 30.64g (100mmol) added in the 500ml four neck flasks, this flask has been equipped with above-mentioned device.Mixture is under the nitrogen, and stirs.When almost not observing the bubble hydrogen of generation, this mixture is heated to 80 ℃, and reacts 2 hours.Afterwards, product is cooled to 0-5 ℃.Cooling period, by dropping funnel slow mixed solution that adds 54.35g (200mmol) POPAC and 100ml DMF solution in this product, all mixtures reacted 3 hours under this temperature, then 60 ℃ of reactions 12 hours.Afterwards, solvent is removed by underpressure distillation, is decreased to original about 1/3 up to the products therefrom volume.The viscous liquid of this generation is added drop-wise in the 3L water under the vigorous stirring, the faint yellow waxy substance of collecting precipitation.After this material washes with water, dry down in 60 ℃ of decompressions and heating, thereby make 75.2g target compound (productive rate is 97%).
The infrared absorption spectrum of this compound, the mass spectral result of NMR and TOF-is as follows, above determining shown in the structure of compound (I-1).
Infrared absorption spectrum (cm -1): v (C=C)1635, v (ring)1604,1495, v (P=O, POC)1280,1195,1040, v (CN)945, v (OH)3380
1The H-NMR spectrum (δ, ppm) :-OH 9.2 (1H), phenyl-H 6.85-7.55 (22H) ,-CH=5.60 (4H), allyl group-CH 2-5.15 (8H) ,=CH 23.50 (8H), CH 31.95 (3H)
TOF-mass spectrum (M/Z): 779 (molecular weight of calculating=776.82)
Figure A20068000548600311
(embodiment 2) [synthetic compound (I-2)]
According to carrying out, except following: use 39.97g (205mmol) phenyl phosphonyl chloride to substitute phenoxy group phosphinylidyne dichloro with embodiment 1 identical operations; The cut of 122-124 ℃/5mmHg is collected in underpressure distillation, therefore, makes 43.50g phenyl phosphonic monochloro list (N, N-diallyl) acid amides (below be called " PPAC ") (productive rate is 83%).Should point out, infrared absorption spectrum, NMR and TOF-mass spectrum confirm that this compound is PPAC.
Infrared absorption spectrum (cm -1): v (C=C)1635, v (ring)1604,1495, v (P=O, POC)1280, v (CN)945
1The H-NMR spectrum (δ, ppm): phenyl-H 6.85 (2H), 7.10 (3H) ,-CH=5.45 (2H) ,-CH 2-4.95 (4H) ,=CH 23.35 (4H)
TOF-mass spectrum (M/Z): 257 (molecular weight of calculating=255.7)
Next, in the phenol resins and 7.05g (300mmol) sodium hydride adding 500ml four neck flasks with following general formula (e) expression of 250mlDMF, 42.55g (100mmol), this flask has been equipped with above-mentioned device.Mixture is under the nitrogen, and stirs.When almost not observing the bubble hydrogen of generation, this mixture is heated to 80 ℃, and reacts 2 hours.Afterwards, product is cooled to 0-5 ℃.Cooling period, by dropping funnel slow mixed solution that adds 76.73g (300mmol) PPAC and 100ml DMF solution in this product, all mixtures reacted 3 hours under this temperature, then 60 ℃ of reactions 12 hours.Afterwards, solvent is removed by underpressure distillation, is decreased to original about 1/3 up to the products therefrom volume.The viscous liquid of this generation is added drop-wise in the 3L water under the vigorous stirring, the faint yellow waxy substance of collecting precipitation.After this material washes with water, dry down in 60 ℃ of decompressions and heating, thereby make 104.2g target compound (productive rate is 96%).
The infrared absorption spectrum of this compound, the mass spectral result of NMR and TOF-is as follows, above determining shown in the structure of compound (I-2).
Infrared absorption spectrum (cm -1): v (C=C)1635, v (ring)1604,1495, v (P=O, POC)1280,1195,1040, v (CN)945
1The H-NMR spectrum (δ, ppm): phenyl-H 6.85-7.55 (31H) ,-CH=5.60 (6H), allyl group-CH 2-5.15 (12H) ,=CH 23.50 (12H), CH 31.6-1.85 (9H)
TOF-mass spectrum (M/Z): 1085 (molecular weight of calculating=1083.2)
Figure A20068000548600321
(embodiment 3) [synthetic compound (I-3)]
153.32g (1.00mol) phosphoryl chloride and 200ml are added in the 500ml four neck flasks through the distillatory chloroform, and this flask is equipped with the device identical with embodiment 1.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring, by this dropping funnel, the phenol resins and 41.52g (410mmol) triethylamine that slowly add general formula (d) expression above the 30.64g (100mmol) in mixture are dissolved in the mixed solution that the 100ml chloroform makes, after interpolation finishes, mixture is in room temperature reaction 3 hours, and 70 ℃ of reactions are 12 hours then.After the product cooling, Triethylammonium chloride salt is by removing by filter, and the solution decompression distillation is removed, and removes like this and desolvates and excessive amine.Afterwards, in resistates, add 200ml tetrahydrofuran (THF) (below be called " THF "), the solution that makes is returned the reactor of front.
Next, slowly add the 200ml solution of 54.93g (300mmol) naphthyl alcohol potassium in THF by dropping funnel in above-mentioned solution, all solution refluxed 6 hours at boiling point then in room temperature reaction 3 hours.Product is cooled to room temperature, by dropping funnel slow mixed solution that adds 22.82g (400mmol) allylamine and 40.50g (400mmol) triethylamine in this product, and all mixture room temperature reactions 3 hours, boiling point refluxed 12 hours down then.Afterwards, the products therefrom concentrating under reduced pressure, volume is decreased to original about 1/3 like this.Afterwards, the viscous liquid of this gained is added drop-wise in the 3L water under the vigorous stirring the faint yellow waxy substance of collecting precipitation.After this material washes with water, dry down in 60 ℃ of decompressions and heating, thereby make 98.4g target compound (productive rate is 81%).
The infrared absorption spectrum of this compound, the mass spectral result of NMR and TOF-is as follows, above determining shown in the structure of compound (I-3).
Infrared absorption spectrum (cm -1): v (NH)3360,1620, v (C=C)1635, v (ring)1604,1495, v (P=O, POC)1280,1195,1040, v (CN)945
1The H-NMR spectrum (δ, ppm): allyl group-H 6.85-7.55 (33H) ,-CH=5.60 (3H), allyl group-CH 2-5.15 (6H),＞NH 3.65 (3H) ,=CH 23.50 (6H), CH 31.85 (3H)
TOF-mass spectrum (M/Z): 1044 (molecular weight of calculating=1042)
(embodiment 4) [synthetic compound (I-4)]
76.67g (0.50mol) phosphoryl chloride and 200ml THF are added in the 1000ml four neck flasks, and this flask is equipped with the device identical with embodiment 1.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring, by this dropping funnel, slowly add 500ml chlorination allyl group magnesium at the 1.O-mol/l of THF solution in mixture, all mixtures are in room temperature reaction 3 hours, then 60 ℃ of reactions 10 hours.Afterwards, solvent is removed by underpressure distillation being less than or equal under the temperature of room temperature, becomes the solution in the chloroform.The magnesium chloride throw out that produces is by removing by filter, and solution decompression concentrates, and is adjusted to 300ml.Then, this gained solution returns the reactor of front.
Next, in above-mentioned solution, slowly add the phenol resins of 30.64g (100mmol) following formula (d) expression and the solution that 41.52g (410mmol) triethylamine is dissolved in the 200ml chloroform, all solution room temperature reactions 3 hours, 60 ℃ were reacted 12 hours then.After the product cooling, throw out is by removing by filter, and solution drying, and curing are under reduced pressure removed excessive reagent and solvent like this, and whole resistatess are dissolved in the 400ml chloroform, gained solution are returned the reactor of front.In this solution, slowly add 53.57g (500mmol) benzylamine and 50.64g (500mmol) triethylamine by dropping funnel and be dissolved in the mixed solution that the 200ml chloroform makes, all mixture room temperature reactions 3 hours, 60 ℃ were reacted 12 hours then.Excess reagent and solvent are removed in decompression, obtain waxy substance, this material are dispersed in the 3L water, to its stirring.Filter the faint yellow waxy substance of collecting precipitation.This material washes with water and is dry, thereby makes 79.6g target compound (productive rate is 94%).
The infrared absorption spectrum of this compound, the mass spectral result of NMR and TOF-is as follows, above determining shown in the structure of compound (I-4).
Infrared absorption spectrum (cm -1): v (NH)3360,1620, v (C=C)1635, v (ring)1604,1495, v (P=O, POC)1280,1195,1040, v (CN)945
1The H-NMR spectrum (δ, ppm): allyl group-H 6.85-7.55 (27H) ,-CH=5.60 (3H), allyl group-CH 2-5.15 (6H), benzyl-CH 24.3 (6H),＞NH 3.65 (3H) ,=CH 23.50 (6H), CH 31.85 (3H)
TOF-mass spectrum (M/Z): 888 (molecular weight of calculating=885.92)
(embodiment 5) [synthetic compound (I-5)]
Phenol resins, 250ml DMF and 2.35g (100mmol) sodium hydride of 30.64g (100mmol) following formula (d) expression are added in the 500ml four neck flasks, and this flask is equipped with the device identical with embodiment 1.Mixture is under the nitrogen and stirs.When almost not observing the bubble hydrogen of generation,, reacted 2 hours mixture heating up to 80 ℃.Afterwards, product is cooled to 0-5 ℃.Cooling period slowly adds the mixed solution of 25.58g (100mmol) PPAC (referring to embodiment 2) and 100ml DMF by dropping funnel in gains, all mixtures reacted 12 hours in 60 ℃ then this thermotonus 3 hours.Afterwards, solvent is removed by underpressure distillation, is decreased to original about 1/3 up to the product volume.The viscous liquid of gained is added drop-wise in the 3L water under the vigorous stirring the faint yellow waxy substance of collecting precipitation.After washing with water, this material is in 60 ℃, and decompression and heating are dry down, thereby make 104.2g target compound (productive rate is 96%).
The infrared absorption spectrum of this compound, the mass spectral result of NMR and TOF-is as follows, above determining shown in the structure of compound (I-5).
Infrared absorption spectrum (cm -1): v (OH)3380, v (C=C)1635, v (ring)1604,1495, v (P=O, POC)1280,1195,1040, v (CN)945
1The H-NMR spectrum (δ, ppm) :-OH 9.35 (2H), phenyl-H 6.85-7.55 (17H) ,-CH=5.60 (2H), allyl group-CH 2-5.15 (4H) ,=CH 23.50 (4H), CH 31.85 (3H)
TOF-mass spectrum (M/Z): 528 (molecular weight of calculating=525.6)
(embodiment 6) [synthetic compound (I-6)]
The phenol resins and 4.8g (200mmol) sodium hydride of 250ml DMF, 30.64g (100mmol) following formula (d) expression are added in the four neck flasks, and this flask is equipped with the device identical with embodiment 1.Mixture is under the nitrogen and stirs.When almost not observing the bubble hydrogen of generation,, reacted 2 hours mixture heating up to 80 ℃.Afterwards, product is cooled to 0-5 ℃.Cooling period by dropping funnel, slowly adds the mixed solution of 27.17g (100mmol) POPAC (referring to embodiment 1) and 100ml DMF in product, all mixtures reacted 12 hours in 60 ℃ then this thermotonus 3 hours.Then, product stirs in 0-5 ℃.During the stirring, under the nitrogen,, in product, slowly add 53.7g (200mmol) two phenoxy group phosphinylidyne monochloros (diphenylphosphoric chloride) and be dissolved in the solution that 100ml DMF makes by dropping funnel.After dropwising, gains are this thermotonus 3 hours, then in room temperature reaction 6 hours, again in 80 ℃ of reactions 24 hours.Afterwards, solvent is removed by underpressure distillation, is decreased to original about 1/3 up to the product volume.The viscous liquid of gained is added drop-wise in the 3L water under the vigorous stirring the faint yellow waxy substance of collecting precipitation.After washing with water.This material is in 60 ℃, and decompression and heating are dry down, thereby make 91.5g target compound (productive rate is 91%).
The infrared absorption spectrum of this compound, the mass spectral result of NMR and TOF-is as follows, above determining shown in the structure of compound (I-6).
Infrared absorption spectrum (cm -1): v (C=C)635, v (ring)1604,1495, v (P=O, POC)1280,1195,1040, v (CN)945 (v (OH)3200 disappear)
1The H-NMR spectrum (δ, ppm): phenyl-H 6.85-7.55 (37H) ,-CH=5.60 (2H), allyl group-CH 2-5.15 (4H) ,=CH 23.50 (4H), CH 31.85 (3H)
TOF-mass spectrum (M/Z): 1008 (molecular weight of calculating=1005.92)
(embodiment 7) [synthetic compound (II-1)]
21.3g (100mmol) 2-allyl group-4-bromophenol, 12.1g (120mmol) triethylamine (below be called " TEA ") and 120ml are added in the 300ml four neck flasks through distillatory tetrahydrofuran (THF) (below be called " THF "), and this flask is equipped with return line, dropping funnel, nitrogen inlet tube and the mechanical stirring device that has calcium chloride tube.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring, in mixture, slowly add 11.0g (120mmol) chloro trimethyl silane by dropping funnel.After dropwising, gains are at this thermotonus 1 hour, room temperature reaction 6 hours.Afterwards, by concentrating under reduced pressure, remove desolvate, excessive Trimethylamine 99 and excess chlorine be for trimethyl silane, resistates washes with water and carries out drying.Therefore, quantitatively obtain 2-allyl group-4-bromo-1-trimethylsiloxy benzene.
Next, the product that previous step is made (2-allyl group-4-bromo-1-trimethylsiloxy benzene) all join with above-mentioned four identical neck flasks in.Add 150ml through distillatory THF in this flask, mixture is under the nitrogen.When stirring the mixture, in this mixture, add 1.39g (200mmol) metal lithium bands gradually, with the slight boiling point reflux state that keeps causing because of reaction heat.After interpolation finishes, gains reaction 8 hours.Afterwards, remove excessive metallic lithium, thereby quantitatively obtain 2-allyl group-4-lithium generation (lithio)-1-trimethylsiloxy benzole soln.
Next, with 15.3g (100mmol) phosphoryl chloride and 100ml through distillatory THF be added to above-mentioned four identical neck flasks in.When stirring the mixture for 0-5 ℃, under the nitrogen, by dropping funnel whole (2-allyl group-4-lithium generation-1-trimethylsiloxy benzene) solution that previous step obtains is slowly added in this mixture, all mixtures are this thermotonus 3 hours, then in room temperature reaction 12 hours.Afterwards, add 30ml 1N hydrochloric acid in products therefrom, all mixture stirred 3 hours in 50 ℃.Solution decompression concentrates.The resistates water and the hexane wash of this solution from recrystallizing methanol, thereby obtain 41.1g white needles compound [three (3-allyl group-4-hydroxy phenyl) phosphine oxide (below be called " AHP ")] (productive rate is 92%).Should point out that ultimate analysis and TOF-mass spectrum confirm that this compound is AHP.
Ultimate analysis: C:72.77% (72.62%), H:6.04% (6.11%), O:14.22% (14.33%), P:6.97% (6.94%)
TOF-mass spectrum (M/Z): 448 (molecular weight of calculating=446.51)
Then, with 22.3g (50.0mmol) AHP, 20.2g (200mmol) TEA and 150ml through distillatory dimethyl formamide (below be called " DMF ") be added to above-mentioned four identical neck flasks in.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring, in mixture, slowly add 34.0g (150mmol) diphenyl phosphonyl chloride by dropping funnel and be dissolved in the solution that 100ml DMF makes.After dropwising, gains are this thermotonus 3 hours, then in room temperature reaction 6 hours, again in 80 ℃ of reactions 24 hours.Afterwards, product drying under reduced pressure and curing are dissolved in chloroform then.Product washes with water, and chloroform dewaters with anhydrous sodium sulphate, filter, and drying under reduced pressure and curing, thereby make 51.3g target compound (productive rate is 91%).
The infrared absorption spectrum of this compound, the mass spectral result of NMR and TOF-is as follows, above determining shown in the structure of compound (II-1).
Infrared absorption spectrum (cm -1): v (CH2=CH)1625, v (ring)1604,1500, v (P=O)1200-1300, v (P-O-C)1210,950 (v (OH)3200 disappear)
1The H-NMR spectrum (δ, ppm): phenyl C-H 7.0-7.5 (39H), allyl group C-H 3.5-4.0,5.1-6.0 (15H)
TOF-mass spectrum (M/Z): 1049,1050,1051 (molecular weight of calculating=1047.01)
(embodiment 8) [synthetic compound (II-2)]
94.95g (500mmol) phenyl phosphonyl chloride and 200ml THF are added to 300-ml four neck flasks, and this flask is equipped with the device identical with embodiment 7.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring, in this mixture, slowly add the mixed solution of 48.6g (500mmol) diallyl amine and 50.5g (500mmol) TEA by dropping funnel.After dropwising, the gained mixture is this thermotonus 6 hours, then in room temperature reaction 24 hours.Remove by filter hydrochloride, the resistates concentrating under reduced pressure.Afterwards, the product underpressure distillation is collected in the cut of 176-180 ℃/4mmHg.Therefore, make 108.5g phenyl phosphonic monochloro list (N, N-diallyl) acid amides (below be called " PPAC ") (productive rate is 85%).
With 22.3g (50.0mmol) AHP (referring to embodiment 7), 20.2g (200mmol) TEA and 100ml distillatory dimethyl formamide (DMF) be added to above-mentioned four identical neck flasks in.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring,, in mixture, slowly add 12.8g (50.0mmol) PPAC and be dissolved in the solution that 50ml DMF makes by dropping funnel.After dropwising, gained mixture thing is this thermotonus 3 hours, then in room temperature reaction 6 hours, again in 80 ℃ of reactions 24 hours.Then, product stirs in 0-5 ℃.During the stirring, under the nitrogen,, in product, slowly add 26.9g (100mmol) two phenoxy group phosphinylidyne monochloros and be dissolved in the solution that 100ml DMF makes by dropping funnel.After dropwising, gains are this thermotonus 3 hours, then in room temperature reaction 6 hours, again in 80 ℃ of reactions 24 hours.Afterwards, product drying under reduced pressure and curing are dissolved in chloroform then.Products therefrom washes with water, and chloroform dewaters with anhydrous sodium sulphate, filter, and drying under reduced pressure and curing, thereby make 48.5g target compound (productive rate is 93%).
The infrared absorption spectrum of this compound, the mass spectral result of NMR and TOF-is as follows, above determining shown in the structure of compound (II-2).
Infrared absorption spectrum (cm -1): v (CH2=CH)1625, v (ring)1602,1495, v (P=O)1200-1300, v (P-O-C)1210,980 (v (OH)3200 disappear)
1The H-NMR spectrum (δ, ppm): phenyl C-H 7.0-7.5 (34H), allyl group C-H 3.4-4.1,5.1-6.1 (25H)
TOF-mass spectrum (M/Z): 1132,1133,1134 (molecular weight of calculating=1130.06)
(embodiment 9) [synthetic compound (II-3)]
Obtain 29.53g three (4-hydroxy phenyl) phosphine oxide (below be called " HPP ") (productive rate is 90.5%) according to the mode identical, substitute 2-allyl group-4-bromophenol except using 17.3g (mmol) 4-bromophenol with embodiment 7.Should point out that ultimate analysis and TOF-mass spectrum confirm that the compound that obtains in previous step is HPP.
Ultimate analysis: C:66.16% (66.25%), H:4.92% (4.84%), O:19.62% (19.61%), P:9.30% (9.50%)
TOF-mass spectrum (M/Z): 328 (molecular weight of calculating=326.30)
Next, 46.0g (300mmol) phosphoryl chloride and 100ml THF are added to 300-ml four neck flasks, this flask is equipped with and above-mentioned identical device.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring,, in mixture, slowly add 16.3g (50.0mmol) HPP and 10.1g (100mmol) TEA and be dissolved in the solution that 100ml THF makes by dropping funnel.After dropwising, the gained mixture is this thermotonus 6 hours, then in room temperature reaction 24 hours.Afterwards, remove by filter amine salt, remove by underpressure distillation and desolvate and excessive phosphorus chloride, thereby quantitatively obtain three [(P-dichlor-phosphoryl oxygen base) phenyl] phosphine oxide (below be called " DCPPP ").
Then, the product (DCPPP) that previous step is obtained all be added to above-mentioned four identical neck flasks in.Add 100ml THF in this flask, mixture is under the nitrogen.When stirring the mixture for 0-5 ℃,, in mixture, slowly add 48.59g (500mmol) diallyl amine and 50.5g (500mmol) TEA and be dissolved in the solution that 100ml THF makes by dropping funnel.After dropwising, the gained mixture is this thermotonus 6 hours, then in room temperature reaction 24 hours.Afterwards, remove by filter amine salt, the resistates concentrating under reduced pressure makes it become chloroformic solution more then.Products therefrom washes with water, uses anhydrous sodium sulfate drying, filters, and drying under reduced pressure and curing make 46.3g target compound (productive rate is 86%).
The infrared absorption spectrum of this compound, the mass spectral result of NMR and TOF-is as follows, above determining shown in the structure of compound (II-3).
Infrared absorption spectrum (cm -1): v (CH2=CH)1625, v (ring)1594,1495, v (P=O)1200-1300, v (P-O-C)1210,980 (v (OH)3200 disappear)
1The H-NMR spectrum (δ, ppm): phenyl C-H 7.0-7.5 (12H), allyl group C-H 3.4-4.1,5.1-6.1 (60H)
TOF-mass spectrum (M/Z): 1043,1044,1045 (molecular weight of calculating=1041.2)
(embodiment 10) [synthetic compound (II-4)]
Make 33.6g target compound (productive rate is 84%) according to the mode identical, except substituting diallyl amine with 28.6g (500mmol) allylamine with embodiment 9.
The infrared absorption spectrum of this compound, the mass spectral result of NMR and TOF-is as follows, above determining shown in the structure of compound (II-4).
Infrared absorption spectrum (cm -1): v (NH)3280,1640, v (CH2=CH)1625, v (ring)1594,1495, v (P=O)1200-1300, v (P-O-C)1210,980 (v (OH)3200 disappear)
1The H-NMR spectrum (δ, ppm): phenyl C-H 7.0-7.5 (12H), N-H 4.7 (6H), allyl group C-H3.2-4.3,5.0-6.1 (30H)
TOF-mass spectrum (M/Z): 802,803,804 (molecular weight of calculating=800.2)
(embodiment 11) [synthetic compound (II-5)]
Make 37.9g target compound (productive rate is 94%) according to the mode identical, substitute diallyl amine except using 29.0g (500mmol) vinyl carbinol with embodiment 9.
The infrared absorption spectrum of this compound, the mass spectral result of NMR and TOF-is as follows, above determining shown in the structure of compound (II-5).
Infrared absorption spectrum (cm -1): v (CH2=CH)1625, v (ring)1594,1495, v (P=O)1200-1300, v (P-O-C)1210,980 (v (OH)3200 disappear)
1The H-NMR spectrum (δ, ppm): phenyl C-H 7.0-7.5 (12H), allyl group C-H 3.4-4.0,5.1-6.1 (30H)
TOF-mass spectrum (M/Z): 808,809,811 (molecular weight of calculating=806.7)
(embodiment 12) [synthetic compound (II-6)]
Make 33.0g target compound (productive rate is 93%) according to the mode identical, substitute diallyl amine by 50.4g (500mmol) chlorination allyl group magnesium at the solution of THF except using 100ml with embodiment 9.
The infrared absorption spectrum of this compound, the mass spectral result of NMR and TOF-is as follows, above determining shown in the structure of compound (II-6).
Infrared absorption spectrum (cm -1): v (CH2=CH)1625, v (ring)1594,1495, v (P=O)1200-1300, v (P-O-C)1210,980 (v (OH)3200 disappear)
1The H-NMR spectrum (δ, ppm): phenyl C-H 7.0-7.5 (12H), allyl group C-H 3.5-4.0,5.2-6.0 (30H)
TOF-mass spectrum (M/Z): 712,713,714 (molecular weight of calculating=710.5)
(embodiment 13) [synthetic compound (II-7)]
153.2g (1.00mol) phosphoryl chloride and 100ml THF are added in the 300-ml four neck flasks, and this flask has been equipped with the device identical with embodiment 7.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring,, in mixture, slowly add the mixed solution of 48.6g (500mmol) diallyl amine and 50.5g (500mmol) TEA by dropping funnel.After dropwising, the gained mixture is this thermotonus 6 hours, then in room temperature reaction 24 hours.Afterwards, remove by filter amine salt, underpressure distillation removes and desolvates and excessive phosphorus chloride.The resistates underpressure distillation is collected in the cut of 98-101 ℃/5mmHg like this.Therefore, make 78.1g dichlor-phosphoryl base (N, N-diallyl) acid amides (below be called " DCPA ") (productive rate is 73%).
With 64.2g (300mmol) DCPA and 100ml THF be added to above-mentioned four identical neck flasks in. mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring,, in mixture, slowly add 16.3g (50.0mmol) HPP (referring to embodiment 9) and 30.3 (300mmol) TEA and be dissolved in the solution that 100ml THF makes by dropping funnel.After dropwising, the gained mixture is this thermotonus 6 hours, then in room temperature reaction 24 hours.Afterwards, remove by filter amine salt, underpressure distillation removes desolvates and excessive DCPA.Whole resistatess are returned said apparatus, add 100ml THF to dissolve this resistates.Next, solution is under the nitrogen, stirs in 0-5 ℃.During the stirring,, in mixture, slowly add 34.3g (600mmol) allylamine and 30.3g (300mmol) TEA and be dissolved in the solution that 100ml THF makes by dropping funnel.After dropwising, gains are this thermotonus 6 hours, then in room temperature reaction 24 hours.After removing by filter amine salt, underpressure distillation removes and desolvates and excess amine.Resistates is dissolved in chloroform, and product washes with water, uses anhydrous sodium sulfate drying, filters, and drying under reduced pressure and curing make 40.1g target compound (productive rate is 87%).
The infrared absorption spectrum of this compound, the mass spectral result of NMR and TOF-is as follows, above determining shown in the structure of compound (II-7).
Infrared absorption spectrum (cm -1): v (NH)3280,1640, v (CH2=CH)1625, v (ring)1594,1495, v (P=O)1200-1300, v (P-O-C)1210,980 (v (OH)3200 disappear)
1The H-NMR spectrum (δ, ppm): phenyl C-H 7.0-7.5 (12H), N-H 4.7 (3H), allyl group C-H3.4-4.2,5.0-6.0 (45H)
TOF-mass spectrum (M/Z): 923,924,925 (molecular weight of calculating=921.0)
(embodiment 14) [synthetic compound (II-8)]
12.2g (500mmol) MAGNESIUM METAL and 250ml diethyl ether are added to 500-ml four neck flasks, and this flask has been equipped with the device identical with embodiment 7.Mixture is under the nitrogen, adds a small amount of iodine, to activate this mixture.By dropping funnel, in the gained mixture, slowly add 63.3g (500mmol) benzyl chloride, to keep slight boiling point reflux state.After dropwising, gains reaction 3 hours under boiling point refluxes is then in room temperature reaction 3 hours.During this period, whole MAGNESIUM METAL reactions, thereby quantitatively obtain the zephiran chloride magnesium solution.
Next, 153.3g (1.00mol) phosphoryl chloride and 100ml of diethyl ether are added in the four neck flasks same as described above.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring, by dropping funnel, the benzyl magnesium chloride that previous step is obtained all is added in the mixture.After dropwising, gains are this thermotonus 6 hours, then in room temperature reaction 24 hours.Afterwards, magnesium salts is by removing by filter, and underpressure distillation removes and desolvates and excessive phosphorus chloride.The resistates underpressure distillation is collected in the cut of 99-102 ℃/5mmHg like this.Therefore, obtain 81.5g benzyl phosphonyl dichloride (below be called " BzPDC ") (productive rate is 78%).Should point out that the TOF-mass spectrum confirms that this compound is BzPDC.
TOF-mass spectrum (M/Z): 211,212,213 (molecular weight of calculating=209.0)
Next, 52.3g (250mmol) BzPDC and 150ml THF are added to above-mentioned four identical neck flasks in.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring,, in mixture, slowly add 24.3g (250mmol) diallyl amine and 50.5g (500mmol) TEA and be dissolved in the solution that 150ml THF makes by dropping funnel.After dropwising, the gained mixture is this thermotonus 6 hours, then in room temperature reaction 24 hours.Afterwards, remove by filter amine salt, underpressure distillation removes and desolvates and excess amine then.The resistates underpressure distillation is collected in the cut of 128-133 ℃/4mmHg like this.Therefore, make 51.3g benzyl phosphono monochloro list (N, N-diallyl) acid amides (below be called " BzPAC ") (productive rate is 76%).Should point out that the TOF-mass spectrum confirms that this compound is BzPAC.
TOF-mass spectrum (M/Z): 271,272,273 (molecular weight of calculating=269.8)
Next, 16.3g (50.0mmol) HPP (referring to embodiment 9) and 100ml DMF are added to above-mentioned four identical neck flasks in.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring,, in mixture, slowly add 40.5g (150mmol) BzPAC and 30.3g (300mmol) TEA and be dissolved in the solution that 100ml DMF makes by dropping funnel.After dropwising, the gained mixture is this thermotonus 6 hours, then in room temperature reaction 24 hours.After removing by filter amine salt, underpressure distillation removes and desolvates and excess amine.Resistates is dissolved in chloroform, and product washes with water, uses anhydrous sodium sulfate drying, filters, and drying under reduced pressure and curing make 35.2g target compound (productive rate is 91%).
The infrared absorption spectrum of this compound, the mass spectral result of NMR and TOF-is as follows, above determining shown in the structure of compound (II-8).
Infrared absorption spectrum (cm -1): v (CH2=CH)1625, v (ring)1594,1495, v (P=O)1200-1300, v (P-O-C)1210,980 (v (OH)3200 disappear)
1The H-NMR spectrum (δ, ppm): phenyl C-H 7.0-7.5 (27H), benzyl-CH2-4.7 (6H), allyl group C-H 3.4-4.2,5.0-6.0 (30H)
TOF-mass spectrum (M/Z): 1028,1029,1030 (molecular weight of calculating=1026.0)
(embodiment 15) [synthetic compound (II-9)]
12.2g (500mmol) MAGNESIUM METAL and 150ml diethyl ether are added to 500-ml four neck flasks, and this flask has been equipped with the device identical with embodiment 7.Mixture is under the nitrogen, adds a small amount of iodine, to activate this mixture.By dropping funnel, in the gained mixture, slowly add the diethyl ether solution of 103.1g (500mmol) α-bromonaphthalene of 300ml, to keep slight boiling point reflux state.After dropwising, the reaction 6 hours under boiling point refluxes of gained mixture is then in room temperature reaction 6 hours.During this period, all MAGNESIUM METAL reactions quantitatively obtain bromination Alpha-Naphthyl magnesium solution.
Then, 153.3g (1.00mol) phosphoryl chloride and 100ml diethyl ether are added to 1, in the 000-ml four neck flasks, this flask is equipped with and above-mentioned identical device.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring,, in mixture, slowly add whole bromination Alpha-Naphthyl magnesium solutions that previous step makes by dropping funnel.After dropwising, the gained mixture is this thermotonus 6 hours, then in room temperature reaction 24 hours.Afterwards, remove by filter magnesium salts after, underpressure distillation removes desolvates and excessive phosphorus chloride, makes 117.6g Alpha-Naphthyl phosphonyl dichloride (below be called " α NPDC ") (productive rate is 96%).Should point out that the TOF-mass spectrum confirms that above-claimed cpd is α NPDC.
TOF-mass spectrum (M/Z): 256,257,258 (molecular weight of calculating=254.0)
Next, 61.3g (250mmol) α NPDC and 150ml THF are added to 500-ml four neck flasks, this flask is equipped with and above-mentioned identical device.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring,, in mixture, slowly add the THF solution of 50.4g (500mmol) the chlorination allyl group magnesium of 200ml by dropping funnel.After dropwising, the gained mixture is this thermotonus 6 hours, then in room temperature reaction 24 hours.Afterwards, remove by filter amine salt, solvent is removed by underpressure distillation then.The resistates underpressure distillation is collected in the cut of 158-162 ℃/4mmHg like this.Therefore, make 66.7g P-allyl group, P-(Alpha-Naphthyl) phosphonyl chloride (below be called " A α NPC ") (productive rate is 84%).Should point out that the TOF-mass spectrum confirms that this compound is A α NPC.
TOF-mass spectrum (M/Z): 253,254,255 (molecular weight of calculating=250.7)
Next, 16.3g (50.0mmol) HPP (referring to embodiment 9), 30.3 (300mmol) TEA and 100ml DMF are added to 300-ml four neck flasks, this flask is equipped with and above-mentioned identical device.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring,, in mixture, slowly add the DMF solution of 37.6g (150mmol) the A α NPC of 150ml by dropping funnel.After dropwising, the gained mixture is this thermotonus 6 hours, then in room temperature reaction 24 hours.After removing by filter amine salt, underpressure distillation removes and desolvates and excess amine.Resistates is dissolved in chloroform, and product washes with water, uses anhydrous sodium sulfate drying, filters, and drying under reduced pressure and curing make 46.6g target compound (productive rate is 91%).
The infrared absorption spectrum of this compound, the mass spectral result of NMR and TOF-is as follows, above determining shown in the structure of compound (II-9).
Infrared absorption spectrum (cm -1): v (CH2=CH)1625, v (ring)1603,1594,1495, v (P=O)1200-1300, v (P-O-C)1210,980 (v (OH)3200 disappear)
1The H-NMR spectrum (δ, ppm): aromatics C-H 6.8-7.5 (33H), allyl group C-H 3.4-4.2,5.0-6.1 (15H)
TOF-mass spectrum (M/Z): 970,971,972 (molecular weight of calculating=968.9)
(embodiment 16) [synthetic compound (II-10)]
According to the mode identical with embodiment 15, make 116.5g betanaphthyl phosphonyl dichloride (below be called " β NPDC ") (productive rate is 95%), substitute α-bromonaphthalene except using 103.1g (500mmol) β-bromonaphthalene.Should point out that the TOF-mass spectrum confirms that this compound is β NPDC.
TOF-mass spectrum (M/Z): 256,257,258 (molecular weight of calculating=254.0)
Next, 61.3g (250mmol) β NPDC and and 150ml THF are added to above-mentioned four identical neck flasks in.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring,, in mixture, slowly add the solution that 28.6g (500mmol) allylamine and 101g (1.00mol) TEA are dissolved in 200ml THF by dropping funnel.After dropwising, the gained mixture is this thermotonus 6 hours, then in room temperature reaction 24 hours.Afterwards, remove by filter magnesium salts after, solvent is removed by underpressure distillation then.The resistates underpressure distillation is collected in the cut of 168-170 ℃/4mmHg like this.Therefore, make 97.9g betanaphthyl phosphono monochloro list (N-allyl group) acid amides (below be called " β NPAC ") (productive rate is 74%).Should point out that the TOF-mass spectrum confirms that this compound is β NPAC.
TOF-mass spectrum (M/Z): 266,267,268 (molecular weight of calculating=264.5)
Next, 16.3g (50.0mmol) HPP (referring to embodiment 9), 30.3g (300mmol) TEA and 100ml DMF are added to above-mentioned four identical neck flasks in.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring, in mixture, slowly add the DMF solution of 39.7g (150mmol) the β NPAC of 150ml by dropping funnel.After dropwising, the gained mixture is this thermotonus 6 hours, then in room temperature reaction 24 hours.After removing by filter amine salt, underpressure distillation removes and desolvates and excess amine.Resistates is dissolved in chloroform, and products therefrom washes with water, uses anhydrous sodium sulfate drying, filters, and drying under reduced pressure and curing make 50.0g target compound (productive rate is 92%).
The infrared absorption spectrum of this compound, the mass spectral result of NMR and TOF-is as follows, above determining shown in compound (II-10) structure.
Infrared absorption spectrum (cm -1): v (NH)3320,1640, v (CH2=CH)1625, v (ring)1600,1495, v (P=O)1200-1300, v (P-O-C)1210,980 (v (OH)3200 disappear)
1The H-NMR spectrum (δ, ppm): aromatics C-H 6.9-7.5 (33H), N-H 4.8 (3H), allyl group C-H3.4-4.2,5.0-6.1 (15H)
TOF-mass spectrum (M/Z): 1015,1016,1017 (molecular weight of calculating=1013.95)
(embodiment 17) [synthetic compound (II-11)]
2.2g (500mmol) MAGNESIUM METAL and 250ml diethyl ether are added to 500-ml four neck flasks, and flask has been equipped with the device identical with embodiment 7.Mixture is under the nitrogen, adds a small amount of iodine, to activate this mixture.By dropping funnel, in the gained mixture, slowly add 116.1g (500mmol) 4-bromo biphenyl and be dissolved in the solution that the 150ml diethyl ether makes, to keep slight boiling point reflux state.After dropwising, the reaction 3 hours under boiling point refluxes of gained mixture is then in room temperature reaction 3 hours.During this period, all MAGNESIUM METAL reactions quantitatively obtain bromination 4-xenyl magnesium.
Next, 153.3g (1.00mol) phosphoryl chloride and 100ml diethyl ether are added to above-mentioned four identical neck flasks in.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring,, in mixture, slowly be added in whole chlorine (bromine) change 4-xenyl magnesium solution that previous step obtains by dropping funnel.After dropwising, the gained mixture is this thermotonus 6 hours, then in room temperature reaction 24 hours.Afterwards, remove by filter magnesium salts, underpressure distillation removes and desolvates and excessive phosphorus chloride then.Resistates is recrystallization from the mixed solvent of sherwood oil/benzene, makes 97.6g 4-xenyl phosphonyl dichloride (below be called " BPPDC "), is white needle-like crystals (productive rate is 72%).Should point out that the TOF-mass spectrum confirms that this white needle-like crystals is BPPDC.
TOF-mass spectrum (M/Z): 273,274,275 (molecular weight of calculating=271.1)
Then, 67.8g (250mmol) BPPDC and 150ml THF are added to above-mentioned four identical neck flasks in.By dropping funnel, 25.2g (250mmol) the chlorination allyl group magnesium that slowly adds 100ml in mixture is dissolved in the solution of THF.After dropwising, the gained mixture is this thermotonus 6 hours, then in room temperature reaction 24 hours.Afterwards, remove by filter magnesium salts, solvent is removed by underpressure distillation then.Resistates is recrystallization from sherwood oil/benzene mixed solvent, makes 59.5g P-allyl group, and P-(4-xenyl) phosphonyl chloride (below be called " ABPC ") is white needle-like crystals (productive rate is 86%).Should point out that the TOF-mass spectrum confirms that this compound is ABPC.
TOF-mass spectrum (M/Z): 268,269,270 (molecular weight of calculating=276.7)
Next, 16.3g (50.0mmol) HPP (referring to embodiment 9), 30.3g (300mmol) TEA and 100ml DMF are added to above-mentioned four identical neck flasks in.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring,, in mixture, slowly add the DMF solution of 41.5g (150mmol) ABPC of 150ml by dropping funnel.After dropwising, the gained mixture is this thermotonus 6 hours, then in room temperature reaction 24 hours.After removing by filter amine salt, underpressure distillation removes and desolvates and excess amine.Resistates is dissolved in chloroform, and gains wash with water, uses anhydrous sodium sulfate drying, filters, and drying under reduced pressure and curing make 46.6g target compound (productive rate is 91%).
The infrared absorption spectrum of this compound, the mass spectral result of NMR and TOF-is as follows, above determining shown in compound (II-11).
Infrared absorption spectrum (cm -1): v (CH2=CH)1625, v (ring)1603,1594,1495, v (P=O)1200-1300, v (P-O-C)1210,980 (v (OH)3200 disappear)
1The H-NMR spectrum (δ, ppm): aromatics-H 7.0-7.5 (39H), allyl group C-H 3.3-4.2,5.0-6.1 (15H)
TOF-mass spectrum (M/Z): 1049,1050,1051 (molecular weight of calculating=1047.1)
(embodiment 18) [synthetic compound (II-12)]
105.5g (500mmol) phenoxy group phosphinylidyne dichloro and 150ml THF are added to 500-ml four neck flasks, and flask has been equipped with the device identical with embodiment 7.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring,, in mixture, slowly add 48.6g (500mmol) diallyl amine and 101g (1.00mol) TEA and be dissolved in the solution that 150ml THF makes by dropping funnel.After dropwising, the gained mixture is this thermotonus 6 hours, then in room temperature reaction 24 hours.After removing by filter amine salt, underpressure distillation removes desolvates and excessive amine.The resistates underpressure distillation is collected in the cut of 122-126 ℃/5mmHg like this.Therefore, make 116.8g phenoxy group phosphinylidyne monochloro list (N, N-diallyl) acid amides (below be called " POPAC ") (productive rate is 86%).Should point out that the TOF-mass spectrum confirms that this compound is POPAC.
TOF-mass spectrum (M/Z): 273,274,275 (molecular weight of calculating=271.1)
Next, 16.3g (50.0mmol) HPP (referring to embodiment 9), 30.3g (300mmol) TEA and 100ml DMF are added to above-mentioned four identical neck flasks in.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring,, in mixture, slowly add the DMF solution of 40.8g (150mmol) POPAC of 150ml by dropping funnel.After dropwising, the gained mixture is this thermotonus 6 hours, then in room temperature reaction 24 hours.After removing by filter amine salt, underpressure distillation removes and desolvates and excess amine.Resistates is dissolved in chloroform, and products therefrom washes with water, uses anhydrous sodium sulfate drying, filters, and drying under reduced pressure and curing make 46.6g target compound (productive rate is 91%).
The infrared absorption spectrum of this compound, the mass spectral result of NMR and TOF-is as follows, above determining shown in compound (II-12).
Infrared absorption spectrum (cm -1): v (CH2=CH)1625, v (ring)1600,1595,1495, v (P=O)1200-1300, v (P-O-C)1210,980
1H-NMR spectrum (δ, ppm): aromatics C-H 7.0-7.5 (27H), allyl group C-H 3.3-4.2,5.0-6.1 (30H)
TOF-mass spectrum (M/Z): 1034,1035,1036 (molecular weight of calculating=1032.0)
(embodiment 19) [synthetic compound (II-13)]
230.0g (1.50mol) phosphoryl chloride and 150ml THF are added to 500-ml four neck flasks, and this flask has been equipped with the device identical with embodiment 7.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring, in mixture, slowly add 108.2g (1.00mol) benzylalcohol and 152g (1.50mol) TEA by dropping funnel and be dissolved in the solution that 200ml THF makes.After dropwising, the gained mixture is this thermotonus 6 hours, then in room temperature reaction 24 hours..After removing by filter the amine salt of generation, excessive phosphoryl chloride, TEA and solvent are removed in underpressure distillation, make 207.0g benzyloxy phosphinylidyne dichloro (benzylphosphoric dichloride is called " Bz0PDC " below) (productive rate is 92%).Should point out that the TOF-mass spectrum confirms that this compound is BzOPDC.
TOF-mass spectrum (M/Z): 227,228,229 (molecular weight of calculating=225.0)
Next, 112.5g (500mmol) BzOPDC and 150ml THF are added in the 500-ml four neck flasks, this flask is equipped with and above-mentioned identical device.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring,, in mixture, slowly add 48.6g (500mmol) diallyl amine and 101g (1.00mol) TEA and be dissolved in the solution that 150ml THF makes by dropping funnel.After dropwising, the gained mixture is this thermotonus 6 hours, then in room temperature reaction 24 hours.Afterwards, remove by filter amine salt, underpressure distillation removes and to desolvate and excessive amine then, obtains 125.7g benzyloxy phosphinylidyne monochloro list (N, N-diallyl) acid amides (below be called " BzOPAC "), is resistates (productive rate is 88%).Should point out that the TOF-mass spectrum confirms that this compound is BzOPAC.
TOF-mass spectrum (M/Z): 287,288,289 (molecular weight of calculating=285.7)
Next, 16.3g (50.0mmol) HPP (referring to embodiment 9), 30.3g (300mmol) TEA and 100ml DMF are added to above-mentioned four identical neck flasks in.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring,, in mixture, slowly add the DMF solution of 42.9g (150mmol) BzOPAC of 150ml by dropping funnel.After dropwising, the gained mixture is this thermotonus 6 hours, then in room temperature reaction 24 hours.After removing by filter amine salt, underpressure distillation removes and desolvates and excess amine.Resistates is dissolved in chloroform, and products therefrom washes with water, uses anhydrous sodium sulfate drying, filters, and drying under reduced pressure and curing make 46.6g target compound (productive rate is 91%).
The infrared absorption spectrum of this compound, the mass spectral result of NMR and TOF-is as follows, above determining shown in compound (II-13).
Infrared absorption spectrum (cm -1): v (CH2=CH)1625, v (ring)1603,1594,1495, v (P=O)1200-1300, v (P-O-C)1210,980
1The H-NMR spectrum (δ, ppm): aromatics C-H 6.9-7.5 (27H), benzyl-CH 2-4.4 (6H), allyl group C-H 3.3-4.2,5.0-6.2 (30H)
TOF-mass spectrum (M/Z): 1076,1077,1078 (molecular weight of calculating=1074.1)
(embodiment 20) [synthetic compound (II-14)]
230.0g (1.50mol) phosphoryl chloride and 150ml THF are added in the 500-ml four neck flasks, and this flask has been equipped with the device identical with embodiment 7.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring,, in mixture, slowly add the pure and mild 152g of 144.2g (1.00mol) α-naphthalene (1.50mol) TEA and be dissolved in the solution that 200ml THF makes by dropping funnel.After dropwising, the gained mixture is this thermotonus 6 hours, then in room temperature reaction 24 hours.After removing by filter the amine salt of generation, excessive phosphoryl chloride, TEA and solvent are removed in underpressure distillation, thereby make 245.3g of alpha-naphthoxy base phosphinylidyne dichloro (α-naphthylphosphoric dichloride is called " α NOPDC " below) (productive rate is 94%).Should point out that the TOF-mass spectrum confirms that this compound is α NOPDC.
TOF-mass spectrum (M/Z): 263,264,265 (molecular weight of calculating=261.0)
Next, 130.5g (500mmol) α NOPDC and 150ml THF are added to above-mentioned four identical neck flasks in.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring,, in mixture, slowly add 48.6g (500mmol) diallyl amine and 101g (1.00mol) TEA and be dissolved in the solution that 150ml THF makes by dropping funnel.After dropwising, the gained mixture is this thermotonus 6 hours, then in room temperature reaction 24 hours.Afterwards, remove by filter amine salt, underpressure distillation removes and desolvates and excess amine then.Therefore, make 146.4g alpha-naphthoxy base phosphinylidyne monochloro list (N, N-diallyl) acid amides (below be called " α NOPAC "), be resistates (productive rate is 91%).Should point out that the TOF-mass spectrum confirms that this compound is α NOPAC.
TOF-mass spectrum (M/Z): 323,324,325 (molecular weight of calculating=321.8)
[0200] next, 16.3g (50.0mmol) HPP (referring to embodiment 9), 30.3g (300mmol) TEA and 100ml DMF are added to above-mentioned four identical neck flasks in.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring,, in mixture, slowly add 48.3g (150mmol) α NOPAC and be dissolved in the solution that 150ml DMF makes by dropping funnel.After dropwising, the gained mixture is this thermotonus 6 hours, then in room temperature reaction 24 hours.After removing by filter amine salt, underpressure distillation removes and desolvates and excess amine.Resistates is dissolved in chloroform, and products therefrom washes with water, uses anhydrous sodium sulfate drying, filters, and drying under reduced pressure and curing make 52.6g target compound (productive rate is 89%).
The infrared absorption spectrum of this compound, the mass spectral result of NMR and TOF-is as follows, above determining shown in compound (II-14).
Infrared absorption spectrum (cm -1): v (CH2=CH)1625, v (ring)1604,1595,1495, v (P=O)1200-1300, v (P-O-C)1210,980
1H-NMR spectrum (δ, ppm): aromatics C-H 7.0-7.6 (33H), allyl group C-H 3.3-4.2,5.0-6.1 (30H)
TOF-mass spectrum (M/Z): 1184,1185,1186 (molecular weight of calculating=1182.2)
(embodiment 21) [synthetic compound (II-15)]
230.0g (1.50mol) phosphoryl chloride and 150ml THF are added in the 500-ml four neck flasks, and this flask has been equipped with the device identical with embodiment 7.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring,, in mixture, slowly add the pure and mild 152g of 144.2g (1.00mol) β-naphthalene (1.50mol) TEA and be dissolved in the solution that 200ml THF makes by dropping funnel.After dropwising, the gained mixture is this thermotonus 6 hours, then in room temperature reaction 24 hours.After removing by filter the amine of generation, excessive phosphorus chloride, TEA and solvent are removed in underpressure distillation, thereby make 237.5g β-naphthyloxy phosphinylidyne dichloro (below be called " β NOPDC ") (productive rate is 91%).Should point out that the TOF-mass spectrum confirms that this compound is β NOPDC.
TOF-mass spectrum (M/Z): 263,264,265 (molecular weight of calculating=261.0)
Next, 130.5g (500mmol) β NOPDC and 150ml THF are added to above-mentioned four identical neck flasks in.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring,, in mixture, slowly add 48.6g (500mmol) diallyl amine and 101g (1.00mol) TEA and be dissolved in the solution that 150ml THF makes by dropping funnel.After dropwising, the gained mixture is this thermotonus 6 hours, then in room temperature reaction 24 hours.Afterwards, remove by filter amine salt, underpressure distillation removes and desolvates and excess amine then.Therefore, obtain 144.8g β-naphthyloxy phosphinylidyne monochloro list (N, N-diallyl) acid amides (below be called " β NOPAC ") (productive rate is 90%) into resistates.Should point out that the TOF-mass spectrum confirms that this compound is β NOPAC.
TOF-mass spectrum (M/Z): 323,324,325 (molecular weight of calculating=321.8)
Next, 16.3g (50.0mmol) HPP (referring to embodiment 9), 30.3g (300mmol) TEA and 100ml DMF are added to above-mentioned four identical neck flasks in.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring,, in mixture, slowly add 48.3g (150mmol) β NOPAC and be dissolved in the solution that 150ml DMF makes by dropping funnel.After dropwising, the gained mixture is this thermotonus 6 hours, then in room temperature reaction 24 hours.After removing by filter amine salt, underpressure distillation removes and desolvates and excess amine.Resistates is dissolved in chloroform, and products therefrom washes with water, uses anhydrous sodium sulfate drying, filter, and drying under reduced pressure and curing, thus make 53.8g target compound (productive rate is 91%).
The infrared absorption spectrum of this compound, the mass spectral result of NMR and TOF-is as follows, above determining shown in compound (II-15).
Infrared absorption spectrum (cm -1): v (CH2=CH)1625, v (ring)1600,1594,1495, v (P=O)1200-1300, v (P-O-C)1210,980
1The H-NMR spectrum (δ, ppm): aromatics C-H 6.9-7.5 (33H), allyl group C-H 3.3-4.2,5.0-6.2 (30H)
TOF-mass spectrum (M/Z): 1184,1185,1186 (molecular weight of calculating=1182.2)
(embodiment 22) [synthetic compound (II-16)]
230.0g (1.50mol) phosphoryl chloride and 150ml THF are added to 500-ml four neck flasks, and this flask has been equipped with the device identical with embodiment 7.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring,, in mixture, slowly add 170.2g (1.00mol) the pure and mild 152g of 4-xenyl (1.50mol) TEA and be dissolved in the solution that 200ml THF makes by dropping funnel.After dropwising, the gained mixture is this thermotonus 6 hours, then in room temperature reaction 24 hours.After removing by filter the amine of generation, excessive phosphoryl chloride, TEA and solvent are removed in underpressure distillation, make to be called " BPOPDC " below the 267.0g 4-biphenylyloxy phosphinylidyne dichloro (biphenylphosphoric dichloride)) (productive rate is 93%).Should point out that the TOF-mass spectrum confirms that this compound is BPOPDC.
TOF-mass spectrum (M/Z): 289,290,291 (molecular weight of calculating=287.1)
Next, 143.6g (500mmol) BPOPDC and 150ml THF are added to above-mentioned four identical neck flasks in.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring,, in mixture, slowly add 48.6g (500mmol) diallyl amine and 101g (1.00mol) TEA and be dissolved in the solution that 150ml THF makes by dropping funnel.After dropwising, the gained mixture is this thermotonus 6 hours, then in room temperature reaction 24 hours.Afterwards, remove by filter amine salt, underpressure distillation removes and desolvates and excess amine then.Therefore, make 156.5g 4-biphenylyloxy phosphinylidyne monochloro list (N, N-diallyl) acid amides into resistates (below be called " BPOPAC ") (productive rate is 90%).Should point out that the TOF-mass spectrum confirms that this compound is BzOPAC.
TOF-mass spectrum (M/Z): 349,350,351 (molecular weight of calculating=347.8)
Next, 16.3g (50.0mmol) HPP (referring to embodiment 9), 30.3g (300mmol) TEA and 100ml DMF are added to above-mentioned four identical neck flasks in.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring,, in mixture, slowly add the DMF solution of 52.2g (150mmol) BPOPAC of 150ml by dropping funnel.After dropwising, the gained mixture is this thermotonus 6 hours, then in room temperature reaction 24 hours.After removing by filter amine salt, underpressure distillation removes and desolvates and excess amine.Resistates is dissolved in chloroform, and products therefrom washes with water, uses anhydrous sodium sulfate drying, filters, and drying under reduced pressure and curing make 57.3g target compound (productive rate is 91%).
The infrared absorption spectrum of this compound, the mass spectral result of NMR and TOF-is as follows, above determining shown in compound (II-16).
Infrared absorption spectrum (cm -1): v (CH2=CH)1625, v (ring)1603,1594,1495, v (P=O)1200-1300, v (P-O-C)1210,980
1The H-NMR spectrum (δ, ppm): aromatics C-H 6.8-7.5 (39H), allyl group C-H 3.3-4.2,5.0-6.1 (30H)
TOF-mass spectrum (M/Z): 1262,1263,1264 (molecular weight of calculating=1260.3)
(embodiment 23) [synthetic compound (II-17)]
22.3g (50.0mmol) AHP (referring to embodiment 7), 20.2g (200mmol) TEA and 100ml are added to the four neck flasks identical with embodiment 7 through distillatory DMF.Mixture is under the nitrogen, stirs in 0-5 ℃.During the stirring, under the nitrogen,, in mixture, slowly add 40.3g (150mmol) two phenoxy group phosphinylidyne monochloros and be dissolved in the solution that 150ml DMF makes by dropping funnel.After dropwising, the gained mixture is this thermotonus 3 hours, then in room temperature reaction 6 hours, again in 80 ℃ of reactions 24 hours.Afterwards, products therefrom drying under reduced pressure and curing are dissolved in chloroform then.Products therefrom washes with water, and chloroform dewaters with anhydrous sodium sulphate, filter, and drying under reduced pressure and curing, thus make 52.6g target compound (productive rate is 92%).
The infrared absorption spectrum of this compound, the mass spectral result of NMR and TOF-is as follows, above determining shown in compound (II-17).
Infrared absorption spectrum (cm -1): v (CH2=CH)1625, v (ring)1602,1495, v (P=O)1200-1300, v (P-O-C)1210,980, (v (OH)3200 disappear)
1The H-NMR spectrum (δ, ppm): phenyl C-H 7.0-7.5 (39H), allyl group C-H 3.4-4.1,5.1-6.1 (15H)
TOF-mass spectrum (M/Z): 1144,1145,1146 (molecular weight of calculating=1142.99)
＜fire retardant physicals test 〉
[test case 1]
With TG/DTA 6200 (Seiko Instruments Inc. manufacturing), raise the under the following conditions temperature of each compound is measured the thermogravimetric curve (TG curve) of following each organo phosphorous compounds, and described condition comprises, sample size is 5mg, and temperature rise rate is 10 ℃/min.In addition, be determined under the nitrogen productive rate of carbide in the time of 600 ℃.Fig. 1 illustrates the TG curve of following each organo phosphorous compounds, and table 1 illustrates the productive rate of the carbide of each compound.
Figure A20068000548600521
Table 1
Compound (I-6) Compound (II-17) Compound (III-1)
Phosphorus content 9.24 11.00 6.95
The productive rate of carbide 31.30 33.00 2.10
* 1Under the nitrogen, the productive rate in the time of 600 ℃
Clearly illustrate that by top test result, the heat decomposition temperature of organo phosphorous compounds of the present invention [compound (I-6) or compound (II-17)] is higher than common organo phosphorous compounds [compound (III-1)], and than common organo phosphorous compounds more stable aspect the energy, therefore its flame retardance element can evaporate when molding hardly, and the goods of resin treatment have good mouldability or processing characteristics.In addition, the phosphorus content height of organo phosphorous compounds of the present invention, it shows high carbonization produce rate, demonstration can easily form the carbon (pyrolysis residue) of the high shielding effect of heat or oxygen, and high flame retardant can be provided.
＜preparation flame-retardant resin processed article 〉
(embodiment 24)
With 47.3 mass parts as 6/66 nylon copolymer of thermoplastic resin (by UBE INDUSTRIES, LTD. make: 2123B), 30 mass parts as the glass fibre of fortifying fibre (by ASAHI FIBER GLASSCo., Ltd. make: 03.JAFT2Ak25, every fiber of this glass fibre has carried out surface treatment with silane coupling agent, the length of each fiber is about 3mm), 0.5 mass parts is as the carbon black of tinting material, 0.2 mass parts antioxidant (made by Ciba-Geigy: IRGANOX 1010), as 6 mass parts particle diameters of mineral filler is that the talcum of 2 μ m is (by Nippon Talc Co., Ltd. make) and the clay of 5 mass parts nano level particle diameters (make by Nissho Iwai Bentonite: NANOMER 1.30T) and 11 mass parts mix mutually as the reactive flame retardant of representing by following formula (I-4) of fire retardant, all component uses the side-flow type biaxial extruder (by The Japan Steel Works, LTD. make) mediate at 280 ℃, make resin granular material.After 4 hours, (made by FUNUC: α 50C) carry out molding under the condition below, described condition comprises that resin temperature is 280 ℃ to above-mentioned resin granular material, and die temperature is 80 ℃ with injection moulding machine in 105 ℃ of dryings.
Afterwards, use cobalt 60, with 25kGy dosage the goods of above-mentioned molding are carried out the irradiation gamma-radiation, thereby make the goods of the resin treatment of embodiment 24 as irradiation source.
(embodiment 25)
With 51.3 mass parts as 66 nylon copolymers of thermoplastic resin (by UBE INDUSTRIES, LTD.:2020B), 25 mass parts as the glass fibre of fortifying fibre (by ASAHI FIBER GLASS Co., Ltd. make: 03.JAFT2Ak25, every fiber of this glass fibre has carried out surface treatment with silane coupling agent, the length of each fiber is about 3mm), 0.5 mass parts is as the carbon black of tinting material, 0.2 mass parts antioxidant (made by Ciba-Geigy: IRGANOX 1010), as the particle diameter of 6 mass parts of mineral filler is that the talcum of 2 μ m is (by Nippon Talc Co., Ltd. make) and the clay of 5 mass parts nano level particle diameters (make by Nissho Iwai Bentonite: NANOMER 1.30T) and 12 mass parts mix mutually as the reactive flame retardant of representing by following formula (I-3) of fire retardant, all component uses the side-flow type biaxial extruder (by TheJapan Steel Works, LTD. make) mediate at 280 ℃, make resin granular material.After 4 hours, (made by FUNUC: α 50C) carry out molding under the condition below, described condition comprises that resin temperature is 280 ℃ to above-mentioned resin granular material, and die temperature is 80 ℃ with injection moulding machine in 105 ℃ of dryings.
Afterwards, use cobalt 60,, thereby make the goods of the resin treatment of embodiment 25 with the goods irradiation gamma-radiation of 25kGy dosage to above-mentioned molding as irradiation source.
(embodiment 26)
With 45.3 mass parts as 66 nylon of thermoplastic resin (by UBE INDUSTRIES, LTD.:2020B), as 10 mass parts particle diameters of mineral filler is that the talcum of 2 μ m is (by Nippon Talc Co., Ltd. make) and the clay of 5 mass parts nano level particle diameters (make by Nissho Iwai Bentonite: NANOMER 1.30T), 0.5 mass parts is as the carbon black of tinting material, as the reactive flame retardant that 8 mass parts of fire retardant are represented by the reactive flame retardant and the 6 mass parts following formulas (I-5) of following formula (I-3) expression, 0.2 mass parts antioxidant (made by Ciba-Geigy: IRGANOX 1010) mixes mutually.
Said mixture carries out fusion with the side-flow type biaxial extruder at 280 ℃.In addition, 25 mass parts as the glass fibre of fortifying fibre (by ASAHI FIBER GLASS Co., Ltd. make: 03.JAFT2Ak25, every fiber of this glass fibre has carried out surface treatment with silane coupling agent, the length of each fiber is about 3mm) sneak into above-mentioned molten mixture by extruding kneading from a side, thus make resin granular material.Afterwards, above-mentioned resin granular material is in 105 ℃ of dryings after 4 hours, (make by FUNUC: α 50C) carry out molding under the usual conditions below with injection moulding machine, described condition comprises that barrel temperature is 280 ℃, die temperature is 80 ℃, injection pressure is 78.4MPa, and injection speed is 120mm/s, and be 15 seconds cooling time.
Afterwards, use cobalt 60,, make the goods of the resin treatment of embodiment 26 with the goods irradiation gamma-radiation of 25kGy dosage to above-mentioned molding as irradiation source.
(embodiment 27)
Make the goods of the resin treatment of embodiment 27 under the condition identical with embodiment 26, except following difference: (by UBE INDUSTRIES, LTD. makes: 2020B) as thermoplastic resin to use 46.3 mass parts, 66 nylon; (by SANKO CHEMICAL CO., Ltd. makes: BCA) as fire retardant for the reactive flame retardant of 8 mass parts following formulas (I-4) expression and the another kind of organophosphorous fire retardant of 5 mass parts.
(embodiment 28)
With 45.2 mass parts as 66 nylon of thermoplastic resin (by UBE INDUSTRIES, LTD. make: 2020B), as 6 mass parts particle diameters of mineral filler is that the talcum of 2 μ m is (by Nippon Talc Co., Ltd. make) and the clay of 5 mass parts nano level particle diameters (make by Nissho Iwai Bentonite: NANOMER1.30T), 0.5 mass parts is as the carbon black of tinting material, as 9 mass parts of fire retardant reactive flame retardant by following formula (I-1) expression, 2 mass parts multifunctional cyclic compounds are (by Nippon Kasei Chemical Co., LTD. make: TAIC) and the another kind of organophosphorous fire retardant of 7 mass parts (by SANKO CHEMICAL CO., Ltd. make: BCA), 0.3 mass parts antioxidant (made by Ciba-Geigy: IRGANOX 1010) mixes mutually.
Said mixture carries out fusion with the side-flow type biaxial extruder at 280 ℃.In addition, 25 mass parts as the glass fibre of fortifying fibre (by ASAHI FIBER GLASS Co., Ltd. make: 03.JAFT2Ak25, every fiber of this glass fibre has carried out surface treatment with silane coupling agent, the length of each fiber is about 3mm) sneak into above-mentioned molten mixture by extruding kneading from a side, thus make resin granular material.Afterwards, above-mentioned resin granular material is in 105 ℃ of dryings after 4 hours, (make by FUNUC: α 50C) carry out molding under the usual conditions below with injection moulding machine, described condition comprises that barrel temperature is 280 ℃, die temperature is 80 ℃, injection pressure is 78.4MPa, and injection speed is 120mm/s, and be 15 seconds cooling time.
Afterwards, use cobalt 60,, thereby make the goods of the resin treatment of embodiment 28 with the goods irradiation gamma-radiation of 25kGy dosage to above-mentioned molding as irradiation source.
(embodiment 29)
Make moulded parts according to the condition identical with embodiment 26, except following difference: 48.3 mass parts as the polybutylene terephthalate resin of thermoplastic resin (by Toray Industries, Inc. make: TORAYCON 1401X06), reactive flame retardant as the expression of 10 mass parts following formulas (I-1) of fire retardant, the another kind of organophosphorous fire retardant of 5 mass parts is (by SANKO CHEMICAL CO., Ltd. make: BCA) and 2 mass parts multifunctional cyclic compounds (by TOAGOSEI CO., LTD. make: M-315), as 10 mass parts particle diameters of mineral filler is that the talcum of 2 μ m is (by Nippon Talc Co., Ltd. make) and 4 mass parts nano level particle diameter clays (make by Nissho Iwai Bentonite: NANOMER 1.30T), 20 mass parts as the glass fibre of fortifying fibre (by ASAHI FIBER GLASS Co., Ltd. make: 03.JAFT2Ak25, every fiber of this glass fibre has carried out surface treatment with silane coupling agent, the length of each fiber is about 3mm), 0.5 mass parts is mediated under 245 ℃ kneading temperature as the carbon black of tinting material and the antioxidant of 0.2 mass parts (made by Ciba-Geigy: IRGANOX 1010), makes resin granular material like this; Resin granular material was in 130 ℃ of dryings 3 hours; Barrel temperature during molding is changed into 250 ℃.
Afterwards, use Sumitomo Heavy Industries, the accelerator that Ltd. makes under the 4.8MeV acceleration voltage, with the radiation dose of the 40kGy goods irradiated electrons bundle to above-mentioned molding, makes the goods of the resin treatment of embodiment 29.
(embodiment 30)
Make moulded parts under the condition identical with embodiment 26, except following: the thermocatalyst that also adds 3 mass parts in the system of embodiment 26 (is made by NOF CORPORATION: Nofmer BC).
Afterwards, above-mentioned moulded parts in 245 ℃ of reactions 8 hours, thereby makes the goods of the resin treatment of embodiment 30 under heating condition.
(embodiment 31)
Under the condition identical, make slim moulded parts (thickness t is 0.6mm) with embodiment 28, except following difference: in the system of embodiment 28, also add 7 mass parts UV initiators (be used in combination IRGANOX 651 and IRGANOX 369 with 2: 1 ratios, make) by Ciba-Geigy.
Afterwards, to the light of above-mentioned moulded parts irradiation ultrahigh pressure mercury lamp 2 minutes, optical wavelength was 365nm, and illumination is 150mW/cm 2Thereby, make the goods of the resin treatment of embodiment 31.
(embodiment 32)
With 45 mass parts silicon-dioxide (silicon-dioxide 530, make by FUJI SILYSIA CHEMICAL LTD.) be dispersed in the moulding resin of thermosetting epoxy resin base of 45 mass parts, this resin is by mixing 100 mass parts main agents (by NAGASE CHEMICAL CO., LTD. make: XNR 4012) with 50 mass parts solidifying agent (by NAGASE CHEMICAL CO., LTD. make: XNH 4012) and 1 mass parts curing catalyst (by NAGASE CHEMICAL CO., LTD. make: FD 400) make, the reactive flame retardant that adds the expression of 10 mass parts following formulas (I-5) in above-mentioned dispersion is as fire retardant, thereby makes moulded parts.
Afterwards, above-mentioned moulded parts is in 100 ℃ of reactions 1 hour, thereby makes the goods of the resin treatment of embodiment 32 (sealing agent).
(embodiment 33)
A kind of moulded parts, be to be used for making in the Resins, epoxy (by Shin-Etsu Chemical Co., Ltd. makes: SEMICOAT 115) of sealing semiconductor by 8 mass parts are added 92 mass parts as the reactive flame retardant of the following formula (I-5) of fire retardant expression.
Afterwards, above-mentioned moulded parts is in 150 ℃ of reactions 4 hours, thereby makes the goods of the resin treatment of embodiment 33 (sealing agent).
(embodiment 34)
With 47.3 mass parts as 6/66 nylon copolymer of thermoplastic resin (by UBE INDUSTRIES, LTD. make: 2123B), 30 mass parts as the glass fibre of fortifying fibre (by ASAHI FIBER GLASSCo., Ltd. make: 03.JAFT2Ak25, every fiber of this glass fibre has carried out surface treatment with silane coupling agent, the length of each fiber is about 3mm), 0.5 mass parts is as the carbon black of tinting material, 0.2 mass parts antioxidant (made by Ciba-Geigy: IRGANOX 1010), as 7 mass parts particle diameters of mineral filler is that the talcum of 2 μ m is (by Nippon Talc Co., Ltd. make) and the clay of 5 mass parts nano level particle diameters (make by Nissho Iwai Bentonite: NANOMER 1.30T) and 10 mass parts mix mutually as the reactive flame retardant of representing by following formula (II-4) of fire retardant, all component uses the side-flow type biaxial extruder (by The Japan Steel Works, LTD. make) mediate at 280 ℃, thus make resin granular material.After 4 hours, (made by FUNUC: α 50C) carry out molding under the condition below, described condition comprises that resin temperature is 280 ℃ to above-mentioned resin granular material, and die temperature is 80 ℃ with injection moulding machine in 105 ℃ of dryings.
Afterwards, use cobalt 60, with 25kGy dosage the goods of above-mentioned molding are carried out the irradiation gamma-radiation, thereby make the goods of the resin treatment of embodiment 34 as irradiation source.
(embodiment 35)
Make the goods of the resin treatment of embodiment 35 under mixing composition identical with embodiment 34 and condition of moulding, except following difference: (by UBE INDUSTRIES, LTD. makes: 2020B) as thermoplastic resin to use 46.3 mass parts, 66 nylon; Using 7 mass parts particle diameters is that the talcum (by Nippon TalcCo., Ltd. make) and the clay of 4 mass parts nano level particle diameters of 2 μ m (made by Nissho Iwai Bentonite: NANOMER 1.30T) as mineral filler; With use 12 mass parts by the reactive flame retardant of following formula (I-8) expression as fire retardant.
(embodiment 36)
Add 42.3 mass parts as 66 nylon of thermoplastic resin (by UBE INDUSTRIES, LTD.:2020B), (Silia 530 as 11 mass parts silicon-dioxide of mineral filler, make by FUJI SILYSIACHEMICAL LTD.) and the clay of 4 mass parts nano level particle diameters (make by Nissho Iwai Bentonite: NANOMER 1.30T), 0.5 mass parts is as the carbon black of tinting material, as the reactive flame retardant that 6 mass parts of fire retardant are represented by the reactive flame retardant and the 6 mass parts following formulas (II-9) of following formula (II-8) expression, 0.2 mass parts antioxidant (made by Ciba-Geigy: IRGANOX 1010) also mixes mutually.
Said mixture carries out fusion with the side-flow type biaxial extruder at 280 ℃.In addition, 30 mass parts as the glass fibre of fortifying fibre (by ASAHI FIBER GLASS Co., Ltd. make: 03.JAFT2Ak25, every fiber of this glass fibre has carried out surface treatment with silane coupling agent, the length of each fiber is about 3mm) sneak into above-mentioned molten mixture by extruding kneading from a side, thus make resin granular material.Afterwards, above-mentioned resin granular material is in 105 ℃ of dryings after 4 hours, (make by FUNUC: α 50C) carry out molding under the usual conditions below with injection moulding machine, described condition comprises that barrel temperature is 280 ℃, die temperature is 80 ℃, and injection pressure is 78.4MPa, and injection speed is 120mm/s, be 15 seconds cooling time, thereby make the moulded parts that can be used for electric component or electronic unit or automobile.
Afterwards, use cobalt 60,, thereby make the goods of the resin treatment of embodiment 36 with the goods irradiation gamma-radiation of 25kGy dosage to above-mentioned molding as irradiation source.
(embodiment 37)
Make the goods of the resin treatment of embodiment 37 under mixing composition identical with embodiment 36 and condition of moulding, except following difference: (by UBE INDUSTRIES, LTD. makes: 2020B) as thermoplastic resin to use 38.3 mass parts, 66 nylon; (by SANKO CHEMICAL CO., Ltd. makes: BCA) as fire retardant to use the reactive flame retardant of 9 mass parts following formulas (II-8) expressions and the another kind of organophosphorous fire retardant of 7 mass parts.
(embodiment 38)
Make the goods of the resin treatment of embodiment 38 under mixing composition identical with embodiment 36 and condition of moulding, except following difference: (by UBE INDUSTRIES, LTD. makes: 2020B) as thermoplastic resin to use 44.2 mass parts, 66 nylon; (by ASAHIFIBER GLASS Co., Ltd. makes: 03.JAFT2Ak25), every fiber of this glass fibre has carried out surface treatment with silane coupling agent, and the length of each fiber is about 3mm as fortifying fibre to use 25 mass parts glass fibre; Use 0.5 mass parts carbon black as tinting material; Use 0.3 mass parts antioxidant (made by Ciba-Geigy: IRGANOX 1010); Using 7 mass parts particle diameters is that the talcum (by Nippon Talc Co., Ltd. make) and the clay of 4 mass parts nano level particle diameters of 2 μ m (made by Nissho Iwai Bentonite: NANOMER 1.30T) as mineral filler; Use 10 mass parts following formulas (II-1) expressions reactive flame retardant, 2 mass parts multifunctional cyclic compounds (by Nippon Kasei Chemical Co., LTD. makes: TAIC) and the another kind of organophosphorous fire retardant of 7 mass parts (make by Clariant: EXOLIT OP 1230) as fire retardant.
(embodiment 39)
Add 51.3 mass parts as the polybutylene terephthalate resin of thermoplastic resin (by TorayIndustries, Inc. make: TORAYCON 1401X06), reactive flame retardant as the expression of 10 mass parts following formulas (II-12) of fire retardant, the another kind of organophosphorous fire retardant of 7 mass parts is (by SANKOCHEMICAL CO., Ltd. make: BCA) and 2 mass parts multifunctional cyclic compounds (by TOAGOSEI CO., LTD. make: M-315), as 5 mass parts particle diameters of mineral filler is that the talcum of 2 μ m is (by NipponTalc Co., Ltd. make) and the clay of 4 mass parts nano level particle diameters (make by Nissho Iwai Bentonite: NANOMER 1.30T), 0.5 mass parts is as carbon black and the 0.2 mass parts antioxidant (made by Ciba-Geigy: IRGANOX 1010) and the mixing mutually of tinting material.
Said mixture carries out fusion with the side-flow type biaxial extruder at 245 ℃.In addition, 20 mass parts as the glass fibre of fortifying fibre (by ASAHI FIBER GLASS Co., Ltd. make: 03.JAFT2Ak25, every fiber of this glass fibre has carried out surface treatment with silane coupling agent, the length of each fiber is about 3mm) sneak into above-mentioned molten mixture by extruding kneading from a side, thus make resin granular material.Afterwards, above-mentioned resin granular material is in 130 ℃ of dryings after 3 hours, (make by FUNUC: α 50C) carry out molding under the usual conditions below with injection moulding machine, described condition comprises that barrel temperature is 280 ℃, die temperature is 80 ℃, and injection pressure is 78.4MPa, and injection speed is 120mm/s, be 15 seconds cooling time, thereby make the moulded parts that can be used for electric component or electronic unit or automobile.
Afterwards, use Sumitomo Heavy Industries, the accelerator that Ltd. makes under the 4.8MeV acceleration voltage, with the radiation dose of the 40kGy goods irradiated electrons bundle to above-mentioned molding, thereby makes the goods of the resin treatment of embodiment 39.
(embodiment 40)
Make moulded parts in the condition identical, except following difference: in the system of embodiment 36, also add 3 mass parts thermocatalysts and (make by NOF CORPORATION: Nofmer BC) with embodiment 36.
Afterwards, above-mentioned moulded parts in 245 ℃ of reactions 8 hours, thereby makes the goods of the resin treatment of embodiment 40 under heating condition.
(embodiment 41)
Under the condition identical, make slim moulded parts (thickness t is 0.6mm) with embodiment 38, except following difference: in the system of embodiment 38, also add 7 mass parts UV initiators (be used in combination IRGANOX 651 and IRGANOX 369 with 2: 1 ratios, make) by Ciba-Geigy.
Afterwards, to the light of above-mentioned moulded parts irradiation ultrahigh pressure mercury lamp 2 minutes, optical wavelength was 365nm, and illumination is 150mW/cm 2Thereby, make the goods of the resin treatment of embodiment 41.
(embodiment 42)
With 45 mass parts silicon-dioxide (silicon-dioxide 530, make by FUJI SILYSIA CHEMICAL LTD.) be dispersed in the moulding resin of thermosetting epoxy resin base of 45 mass parts, this resin is by mixing 100 mass parts main agents (by NAGASE CHEMICAL CO., LTD. make: XNR 4012) with 50 mass parts solidifying agent (by NAGASE CHEMICAL CO., LTD. make: XNH 4012) and 1 mass parts curing catalyst (by NAGASE CHEMICAL CO., LTD. make: FD 400) make, the reactive flame retardant that adds the expression of 10 mass parts following formulas (II-5) in above-mentioned dispersion is as fire retardant, thereby makes moulded parts.
Afterwards, above-mentioned moulded parts is in 100 ℃ of reactions 1 hour, thereby makes the goods of the resin treatment of embodiment 42 (sealing agent).
(embodiment 43)
A kind of moulded parts, be to be used for making in the Resins, epoxy (by Shin-Etsu ChemicalCo., Ltd. makes: SEMICOAT 115) of sealing semiconductor by 6 mass parts are added 94 mass parts as the reactive flame retardant of the following formula (II-11) of fire retardant expression.
Afterwards, above-mentioned moulded parts is in 150 ℃ of reactions 4 hours, thereby makes the goods of the resin treatment of embodiment 43 (sealing agent).
(embodiment 44)
With 51.3 mass parts as 66 nylon of thermoplastic resin (by UBE INDUSTRIES, LTD. make: 2020B), 25 mass parts as the glass fibre of fortifying fibre (by ASAHI FIBER GLASS Co., Ltd. make: 03.JAFT2Ak25, every fiber of this glass fibre has carried out surface treatment with silane coupling agent, the length of each fiber is about 3mm), 0.5 mass parts is as the carbon black of tinting material, 0.2 mass parts antioxidant (made by Ciba-Geigy: IRGANOX 1010), as 6 mass parts particle diameters of mineral filler is that the talcum of 2 μ m is (by Nippon Talc Co., Ltd. make) and the clay of 5 mass parts nano level particle diameters (make by Nissho Iwai Bentonite: NANOMER 1.30T), mix mutually with the reactive flame retardant by following formula (I-6) expression of 12 mass parts as fire retardant, all component uses the side-flow type biaxial extruder (by The Japan Steel Works, LTD. make) mediate at 280 ℃, thus make resin granular material.In 105 ℃ of dryings after 4 hours, above-mentioned resin granular material (is made by FUNUC: α 50C) carry out molding under the usual conditions below with injection moulding machine, described condition comprises that barrel temperature is 280 ℃, die temperature is 80 ℃, injection pressure is 78.4MPa, injection speed is 120mm/s, and be 15 seconds cooling time.
Afterwards, use cobalt 60, with 25kGy dosage the goods of above-mentioned molding are carried out the irradiation gamma-radiation, thereby make the goods of the resin treatment of embodiment 44 as irradiation source.
(embodiment 45)
Under mixing composition identical and condition of moulding, make the goods of the resin treatment of embodiment 45 with embodiment 44, except following difference: use 12 mass parts by the reactive flame retardant of following formula (II-17) expression as fire retardant.
(comparative example 1 to 20)
The goods of each resin treatment are to make under mixing identical with embodiment 24 to 43 and condition of moulding in the comparative example 1 to 20, except following difference: be not blended in each reactive flame retardant of the present invention among the embodiment 24 to 43.
(comparative example 21)
Under the condition identical, make the goods of the resin treatment of comparative example 21 with embodiment 28, except following difference: (by SANKO CHEMICAL CO., Ltd. makes: BCA) as the fire retardant among the embodiment 28 only to add the another kind of organophosphorous fire retardant of 20 mass parts.
(comparative example 22)
Under the condition identical, make the goods of the resin treatment of comparative example 22 with embodiment 38, except following difference: (by SANKO CHEMICAL CO., Ltd. makes: BCA) as the fire retardant among the embodiment 38 only to add the another kind of organophosphorous fire retardant of 20 mass parts.
(comparative example 23)
Under the condition identical, make the goods of the resin treatment of comparative example 23 with embodiment 44, except following difference: use 12 mass parts by the reactive flame retardant of following formula (III-1) expression as the fire retardant among the embodiment 44.
(the physicals test of flame-retardant resin processed article)
[test case 2]
Goods to each resin treatment in embodiment 24 to 43 and the comparative example 1 to 22, the testing plate (inch wide * 3.2,5 inches long * 1/2 inch thick) that preparation meets UL-94 is used for the flame retardant resistance test and meets glowing filament (glow-wire) testing plate (square of 60mm of IEC60695-2 method (GWFI), thickness is 1.6mm), these testing plate are carried out UL 94 tests, glow wire test (according to IEC) and solder heat resistance test.In addition, the goods of all resin treatment all ooze out test, carry out 3 hours at 300 ℃.Table 2 and table 3 are listed jointly and are finished fruit.
In UL 94 tests, testing plate is vertically installed and is contacted 10 seconds with the flame of Bunsen burner, writes down combustion time.After the fire extinguishing, this testing plate contacts 10 seconds again with flame, writes down combustion time.Measure total combustion time, for the second time the scorching hot time after the fire extinguishing, determine whether to exist the drippage product to light cotton.
In addition, the glow wire test can following mode carry out, the nichrome wire (being made up of 80% nickel and 20% chromium) that uses diameter 4mm is as glowing filament, this glowing filament is by bending, rive to prevent its tip, and the K type (Chromel-Alumel) that uses diameter 0.5mm is as temperature plug, and using the thermopair pressure load is that 1.0 ± 0.2N and temperature are 850 ℃ condition.Adopt the standard of not lighted less than 30 seconds and cotton paper below sample the combustion time after the contact as determining flammable standard (GWFI).
In the solder heat resistance test, the size changing rate after 10 seconds in the fusion welding that is immersed in 350 ℃ is shown.
Table 2
Flame retardant resistance (UL-94) Arrive the combustionmaterial (Kindler) of anchor clamps Because of the drippage product is lighted absorbent cotton The glow wire test 300 ℃ of oozing out after 3 hours Size changing rate in the solder heat resistance test (%)
Embodiment 24 V-0 No No By No 4
Embodiment 25 V-0 No No By No 3
Embodiment 26 V-0 No No By No 3
Embodiment 27 V-0 No No By No 5
Embodiment 28 V-0 No No By No 5
Embodiment 29 V-0 No No By No 6
Embodiment 30 V-0 No No By No 11
Embodiment 31 V-0 No No By No 18
Embodiment 32 V-0 No No By No 5
Embodiment 33 V-0 No No By No 27
Embodiment 34 V-0 No No By No 3
Embodiment 35 V-0 No No By No 3
Embodiment 36 V-0 No No By No 3
Embodiment 37 V-0 No No By No 6
Embodiment 38 V-0 No No By No 6
Embodiment 39 V-0 No No By No 7
Embodiment 40 V-0 No No By No 11
Embodiment 41 V-0 No No By No 15
Embodiment 42 V-0 No No By No 19
Embodiment 43 V-0 No No By No 25
Table 3
Comparative example Flame retardant resistance (UL-94) Arrive the combustionmaterial (Kindler) of anchor clamps Because of the drippage product is lighted absorbent cotton The glow wire test 300 ℃ of oozing out after 3 hours Size changing rate in the solder heat resistance test (%)
1 HB Have Have Do not pass through No Distortion *
2 HB Have Have Do not pass through No Distortion *
3 HB Have Have Do not pass through No Distortion *
4 HB Have Have Do not pass through No 29
5 HB Have Have Do not pass through No 33
6 HB Have Have Do not pass through No Distortion *
7 HB Have Have Do not pass through No Distortion *
8 HB Have Have Do not pass through No Distortion *
9 HB Have Have Do not pass through No Distortion *
10 HB Have Have Do not pass through No Distortion *
11 HB Have Have Do not pass through No Distortion *
12 HB Have Have Do not pass through No Distortion *
13 HB Have Have Do not pass through No Distortion *
14 HB Have Have Do not pass through No 28
15 HB Have Have Do not pass through No 32
16 HB Have Have Do not pass through No Distortion *
17 HB Have Have Do not pass through No Distortion *
18 HB Have Have Do not pass through No Distortion *
19 HB Have Have Do not pass through No Distortion *
20 HB Have Have Do not pass through No Distortion *
22 V-2 No Have By Have Distortion *
23 V-2 No Have By Have Distortion *
Distortion *: distortion at once after the immersion
By the result shown in table 2 and the table 3 as can be known, the goods of the resin treatment of all embodiment all have the flame retardant resistance (that is, the goods of every kind of resin treatment have good flame retardant resistance) of V-0 separately and have passed through the glow wire test.In addition, in the goods of each resin treatment of all embodiment, the size changing rate after the solder heat resistance test is less than or equal to 27%.In addition, even, do not observe fire retardant yet and ooze out at 300 ℃ after 3 hours.
On the other hand, the goods of each resin treatment of comparative example 1 to 20 do not contain arbitrary reactive flame retardant of the present invention, and these goods have the flame retardant resistance (that is flame retardant resistance deficiency) of HB and do not pass through the glow wire test.And for the size changing rate after the solder heat resistance test, it is relatively poor comparing with each embodiment.
In addition, the goods of comparative example 21 and 22 resin treatment have used non-reacted organophosphorus based flameproofing as fire retardant, and these goods have the flame retardant resistance (that is, the flame retardant resistance deficiency) of V-2, and observe after 3 hours at 300 ℃ and to ooze out.
[test case 3]
With PHYSICA UDS 200 (making) by Nihon SiberHegner, measure the storage modulus of goods of each resin treatment of embodiment 44, embodiment 45 and comparative example 23 below under the condition, described condition comprises: temperature range is 45-350 ℃, temperature rise rate is 5 ℃/min, driving frequency is 1Hz, and what apply is deformed into 0.2%.Fig. 2 illustrates these results.
The result of Fig. 2 shows that embodiment 44 and 45 has used organo phosphorous compounds of the present invention separately, and their physical strength is good.
On the other hand, the physical strength of the goods of the resin treatment of comparative example 23 is relatively poor.
Industrial applicability
The present invention is applicable to molded resin, such as electric component and electronic unit, as the goods of halogen-containing flame-retardant resin processed not.

Claims (13)

1. reactive flame retardant comprises with the following formula (I) or (II) organo phosphorous compounds of expression, and described organo phosphorous compounds has unsaturated end group:
Figure A2006800054860002C1
In the formula, X 1To X 3The group of expression-OH or following formula (A) expression independently of one another, X 4The group of expression singly-bound or following formula (B) expression, X 1To X 3In one or more groups of representing following formula (A) expression separately, and contain CH at the group end 2=CH-CH 2-;
Figure A2006800054860002C2
In the formula, R 1Expression CH 2=CH-CH 2-, the aryl that is less than or equal to 12 carbon atoms is arranged or the aralkyl that is less than or equal to 12 carbon atoms, R is arranged 2And R 3Represent hydrogen atom, CH independently of one another 2=CH-CH 2-, the aryl that is less than or equal to 12 carbon atoms is arranged or the aralkyl that is less than or equal to 12 carbon atoms is arranged, Y represent singly-bound ,-NH-or-O-;
Figure A2006800054860003C1
In the formula, R 4To R 9Expression is selected from following group separately: phenyl, benzyl, Alpha-Naphthyl, betanaphthyl, p-xenyl, phenoxy group, benzyloxy, alpha-naphthoxy base, β-naphthyloxy, p-biphenylyloxy, (CH 2=CH-CH 2) 2N-, CH 2=CH-CH 2NH-, CH 2=CH-CH 2O-and CH 2=CH-CH 2-, R 10Expression H or CH 2=CH-CH 2-, R 4To R 10In at least one is illustrated in the group end and contains CH 2=CH-CH 2-group, R 4To R 9Mutually can be identical or different.
2. flame-retardant resin processed article, make in the following manner, the resin combination that comprises described reactive flame retardant of claim 1 and resin is carried out molding or coated film,, make the reaction of resin and reactive flame retardant then by heating or radiation; With the flame-retardant resin processed article total amount is benchmark, and this flame-retardant resin processed article comprises the reactive flame retardant of 1-20 quality %.
3. flame-retardant resin processed article as claimed in claim 2 is characterized in that described resin combination contains two or more reactive flame retardants, and wherein at least a is polyfunctional.
4. as claim 2 or 3 described flame-retardant resin processed article, it is characterized in that described resin combination removes and comprises reactive flame retardant, also is included as the fire retardant of cyclic nitrogen compound, this compound has at least one unsaturated group at its end.
5. as each described flame-retardant resin processed article among the claim 2-4, it is characterized in that described resin combination also comprises the fire retardant of another kind of anergy.
6. as each described flame-retardant resin processed article among the claim 2-5, it is characterized in that described resin combination also comprises linking agent, this linking agent is polyfunctional monomer or the oligopolymer that unsaturated group is arranged at its main framing end.
7. as each described flame-retardant resin processed article among the claim 2-6, it is characterized in that, is benchmark with the total amount of flame-retardant resin processed article, and these goods also comprise 1-45 quality % mineral filler.
8. flame-retardant resin processed article as claimed in claim 7 is characterized in that, is benchmark with the total amount of flame-retardant resin processed article, and these goods also comprise laminated clay that 1-10 quality % obtains by the lamination silicate layer as mineral filler.
9. as each described flame-retardant resin processed article among the claim 2-8, it is characterized in that, is benchmark with the total amount of flame-retardant resin processed article, and these goods also comprise 5-50 quality % fortifying fibre.
10. as each described flame-retardant resin processed article among the claim 2-9, it is characterized in that described goods are to make by carrying out irradiation with electron beam or gamma-rays with the dosage more than or equal to 10kGy, make reacting between resin and the reactive flame retardant.
11., it is characterized in that described goods are to react under high 5 ℃ or higher temperature than the molding temperature of resin combination by resin and reactive flame retardant to make as each described flame-retardant resin processed article among the claim 2-9.
12. as each described flame-retardant resin processed article among the claim 2-11, it is characterized in that, described goods comprise be selected from following a kind of: moulded parts, coated film and sealing material.
13., it is characterized in that described goods are as electric component or electronic unit as each described flame-retardant resin processed article among the claim 2-12.
CNA2006800054861A 2005-02-21 2006-02-16 Reactive flame retardant and flame-retardant resin processed article Pending CN101124298A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102926202A (en) * 2012-09-25 2013-02-13 台州学院 Flame-retardant coating and preparation method and application thereof
CN107868188A (en) * 2016-09-23 2018-04-03 台光电子材料股份有限公司 Phosphorus-containing ethylene polyphenylene ether, resin composition containing the same, and product thereof
CN110938234A (en) * 2018-09-25 2020-03-31 中山台光电子材料有限公司 Flame-retardant compound, method for producing same, resin composition, and article thereof
CN111853652A (en) * 2020-06-30 2020-10-30 圣晖***集成集团股份有限公司 Emergency lamp and manufacturing method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102926202A (en) * 2012-09-25 2013-02-13 台州学院 Flame-retardant coating and preparation method and application thereof
CN107868188A (en) * 2016-09-23 2018-04-03 台光电子材料股份有限公司 Phosphorus-containing ethylene polyphenylene ether, resin composition containing the same, and product thereof
CN110938234A (en) * 2018-09-25 2020-03-31 中山台光电子材料有限公司 Flame-retardant compound, method for producing same, resin composition, and article thereof
CN110938234B (en) * 2018-09-25 2021-06-08 中山台光电子材料有限公司 Flame-retardant compound, method for producing same, resin composition, and article thereof
CN111853652A (en) * 2020-06-30 2020-10-30 圣晖***集成集团股份有限公司 Emergency lamp and manufacturing method thereof

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