CN104610530A - Flame retardant with bisphenol A groups, flame-retardant epoxy resin and flame-retardant composition - Google Patents
Flame retardant with bisphenol A groups, flame-retardant epoxy resin and flame-retardant composition Download PDFInfo
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- CN104610530A CN104610530A CN201510072386.1A CN201510072386A CN104610530A CN 104610530 A CN104610530 A CN 104610530A CN 201510072386 A CN201510072386 A CN 201510072386A CN 104610530 A CN104610530 A CN 104610530A
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Abstract
The invention discloses a flame retardant with bisphenol A groups, flame-retardant epoxy resin and a flame-retardant composition. The molecular structure of the flame retardant comprises bisphenol A groups connected to each other and groups (M base) with phosphorus-nitrogen frameworks formed by unsaturated phosphorus and nitrogen atoms, wherein the groups of phosphorus-nitrogen frameworks comprises at least 50wt% of groups (M1 base) with annular phosphorus-nitrogen frameworks formed by three phosphorus atoms and three nitrogen atoms, at most 30wt% of groups (M2 base) with chain-typed phosphorus-nitrogen frameworks formed by at most two phosphorus atoms and two nitrogen atoms, and at most 45wt% of groups (M3 base) with annular phosphorus-nitrogen frameworks formed by at least four phosphorus atoms and four nitrogen atoms. Therefore, the flame retardant has good flame retardance, and a cured product of the flame retardant has good heat-resistance, water resistance, cohesiveness, mechanical property and electrical property, and is an environment-friendly flame-retardant material with relatively good economy.
Description
Technical field
The present invention relates to the technical field of fire retardant matter, particularly relate to the flame retardant of band dihydroxyphenyl propane base, fire-retarded epoxy resin and flame-retardant composition.
Background technology
The electronic product being representative with mobile phone, computer, pick up camera, electronic game machine, the various products used be representative family expenses, office electric equipment products and the other field such as air-conditioning, refrigerator, television image, sound equipment articles for use, in order to safety, very most product all requires that it possesses flame retardant properties in various degree.
Required flame retardant properties or grade is reached in order to make product, traditional technology usually uses adds as aluminium hydroxide hydrate in material system, the inorganic fire-retarded material of the classes such as the metal hydroxides containing crystal water such as magnesium hydroxide hydrate, add as brominated bisphenol A with in system material, the brominated amount such as brominated bisphenol a type epoxy resin higher or organic chemicals that halogen-containing amount is higher, in order to improve the flame retardant resistance that these contain the organic chemicals of halogen, also usually add again in system if antimonous oxide etc. is to environment disagreeableness inorganic chemistry fire retardant material.
Owing to using halogen-containing fire retardant matter, can produce during its burning toxic substance without degradation property or difficult degradation as dioxin organic halogen chemical contamination environment, affect the mankind and animal health.
For the object of protection of the environment; the not halogen-containing compound such as phosphorous, nitrogenous is used to replace halogen contained compound as fire retardant; particularly at electronics, electrically, on Electric Industrial; employing has reactive simple function (only having an active reactive group in a molecule) 9; assorted-10-phospho hetero phenanthrene-10-the oxide compound of 10-dihydro-9-oxy is hereinafter referred to as DOPO); more adopt the derivative compound of DOPO as flame-retardant composition, add or do not add aluminium hydroxide hydrate, magnesium hydroxide hydrate reaches fire-retardant effect.
At electronic applications, resultant (the being called for short DOPO epoxy resin) widespread use usually using high cost, polyfunctional epoxy resin and the DOPO such as DOPO and novolac type epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol-A phenolic type epoxy resin to react is as the epoxide resin material of copper-clad plate purposes.
These use the copper-clad plate manufactured by DOPO epoxy resin, there is good flame retardant properties, but there is many defects in agglutinating value(of coal), thermotolerance, processibility etc., be not suitable for the needs of the high multilayer of manufacture modern communications needs, high reliability, high agglutinating value(of coal), good processing characteristics, and due to high cost, be unfavorable for spreading to and require the civil goods fields such as the consumer electronics of low cost as mobile phone etc.
Along with electronic industry is to the requirement of the factor such as pressure of the universal use of the further raising of short, little, thin, high multiple stratification, high reliability request, civilian consumer electronics and more and more severeer environmental pollution, market has the flame retardant resistance material of good flame retardant resistance, thermotolerance, good mechanical property in the urgent need to material.
Summary of the invention
In view of this, one aspect of the present invention provides a kind of flame retardant with good flame-retardance, thermotolerance, good mechanical property.
A kind of flame retardant with dihydroxyphenyl propane base, comprise the dihydroxyphenyl propane group that is connected with each other in its molecular structure and be with the group (M yl) of the phosphorus nitrogen skeleton be made up of unsaturated phosphorus, nitrogen-atoms, the group (M of the ring-type phosphorus nitrogen skeleton that the band that the group of described band phosphorus nitrogen skeleton comprises at least 50wt% is made up of three phosphorus, nitrogen-atoms
1base), the group (M of chain phosphorus nitrogen skeleton that is made up of two phosphorus, nitrogen-atoms at the most of the band of 30wt% at the most
2base) and the group (M of the ring-type phosphorus nitrogen skeleton be made up of at least four phosphorus, nitrogen-atoms of 45wt% at the most
3base).
Here M base refers to the phosphazenium groups with anti-flaming function.M
1i.e. ring three phosphonitrile base; M
2specific examples have single phosphonitrile and two phosphonitrile, it can adopt the conventional method in this area to synthesize; M
3specific examples have ring four phosphonitrile, ring five phosphonitrile and ring six phosphonitrile etc.Preferably, M
1accounting for more than the 80wt% of M total mass, particularly well, is 90 ~ 100wt%.
Further, it has such as formula the molecular structure shown in I:
In formula I, R represents aliphatic group containing at least one carbon atom or aromatic base; A, b, c are the integer being more than or equal to 1, b and c sum is more than or equal to 2, a, b and c three sum be more than or equal to 6, n be more than or equal to zero integer.
In above-mentioned flame retardant, if M
1content is less than 50wt%, or M
2more than 30wt%, then reacted resultant in use will damage the necessary performance such as thermotolerance, water tolerance and mechanical property with epoxy resin.
M
3content accounts for 45% of phosphazenium groups total mass at the most.If exceed this content, then reacted resultant in use will likely because viscosity is excessive, use inconvenience with epoxy resin, and make the bad results such as its performance suffers damage because molecular weight is excessive.
The dihydroxyphenyl propane hydroxyl that the molecular structure of flame retardant contains can as the avtive spot reacted with epoxy resin.Here term " flame retardant " i.e. flame-retardant compound can be such as some oligopolymer etc.
Another aspect of the invention provides a kind of fire-retarded epoxy resin with good flame-retardance, thermotolerance, good mechanical property.
A kind of fire-retarded epoxy resin, for by epoxy resin with as the resultant of above-mentioned flame retardant by being obtained by reacting.
The epoxy resin that the present invention couple and above-mentioned flame retardant react there is no special regulation, the compound containing epoxy group(ing) and epoxy resin.Such as with the difunctional epoxy resin that liquid bisphenol A type epoxy resin, liquid bisphenol F type epoxy resin, solid-state bisphenol A type epoxy resin, solid-state bisphenol f type epoxy resin, bisphenol-s epoxy resin, biphenyl type epoxy resin are representative, the above epoxy resin of trifunctional being representative with solid-state, liquid or semi-solid state novolac type epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol-A phenolic epoxy resin, acyclic isoprenoid type epoxy resin.Here, those skilled in the art it is easily understood that, when being certainly necessary, also the epoxy resin that the viscosity ratio such as alicyclic epoxy resin, chain type aliphatics type epoxy resin or ester formula epoxy resin are lower can be used, these epoxy resin can be used alone and also can two or more use together, and the present invention there is no special regulation to this.Above-mentioned epoxy resin both can a part or major part first participate in reaction, question response to a certain extent or add again after complete reaction other composition epoxy resin participate in reaction, also all required epoxy resin segmentations reaction or the reaction of disposable input can be dropped into, the present invention does not do special regulation, to obtain object under the prerequisite guaranteeing safety, environmental protection.
In order to fast reaction speed, save time and the energy, general needs add catalyzer in reaction system, the number of the present invention to the kind of catalyzer and add-on there is no special regulation, usually as imidazoles, triphenylphosphine and derivatives class thereof, tertiary amines, the General Catalyst that the epoxy resin such as quaternary ammonium salts and aldehydes matter react can use, these catalyzer both can be used alone, also can two or more be used in combination, usage quantity is reactive material whole between 100 ~ 20000ppm in contrast system generally, be more typically between 200 ~ 5000ppm.
Can according to the difference of viscosity in reactive system with other condition, adopt the method for solvent-free reaction or adopt the method adding solvent reaction in reaction system, the present invention there is no special regulation to reaction solvent, such as acetone, butanone, the ketones solvents such as pimelinketone, benzene, toluene, dimethylbenzene, the aromatic solvents such as xylol, methylene dichloride, trichloromethane, chlorobenzenes etc. are containing chlorinated solvents, ether, butyl ether, the ethers such as ethylene glycol monomethyl ether or ether alcohol kind solvent, petroleum solvent oil, butanols, the alcoholic solvents etc. such as isopropylcarbinol all can use, these solvents can be used alone, also can two kinds or several are used in combination, the number of usage quantity, can determine according to practical situation, be generally can make fire-retarded epoxy resin solid content be 5 ~ 100% consumption, particularly preferred for can make fire-retarded epoxy resin solid content be 20 ~ 100% consumption.
In order to fast reaction speed, generally carry out under the condition of heating, temperature of reaction is generally the scope of 40 ~ 250 DEG C, be more preferably the scope at 60 ~ 180 DEG C, the present invention does not do special regulation, with under the prerequisite guaranteeing safety and environmental protection, obtains object and selects to be as the criterion.
Further aspect of the present invention provides a kind of fire-retardant combination with good flame-retardance, thermotolerance, good mechanical property.
A kind of flame-retardant composition, is characterized in that, comprise fire-retarded epoxy resin described above.
Can only containing fire-retarded epoxy resin in above-mentioned flame-retardant composition, that also can add other has flame retardant resin, such as DOPO type epoxy resin, containing phosphorous epoxy resin, nitrogenous type epoxy resin, nitrogenous containing phosphorous epoxy resin, phosphorus containing phenolic resin, nitrogenous containing phosphorous resol, silicon-contained type epoxy resin and sulfur-type epoxy resin.Certainly also as required, the filler of solidifying agent, auxiliary agent, curing catalyst and halogen-free flame-retardance can be added.
Solidifying agent there is no special regulation in the present invention, and the material being typically used as epoxy curing agent all can be used as the solidifying agent of epoxy resin composition of the present invention.Specific examples can be aliphatic amide or the aromatic amines such as aminocompound, such as Dyhard RU 100, diethyl triamine, diaminodiphenylmethane, diaminodiphenylsulfone(DDS); Can also be two or more phenol-based compounds or mixture, such as, containing benzoxazine colophony, acid anhydrides, polyprotonic acid, boron trifluoride and complex compound thereof etc. in molecule such as dihydroxyphenyl propane, Bisphenol F, bisphenol S, linear phenolic resin, bisphenol A phenolic resin, these epoxy curing agents can be used alone, also can two kinds or several are used in combination, usage quantity is usually between the equivalence ratio 0.4 ~ 1.5 (eq) of contrast epoxy resin.
In epoxy resin ingredient of the present invention, in order to fast setting, usually need to add curing catalyst.The present invention to used curing catalyst without special regulation, use common epoxy resin curing accelerator, such as imidazoles, triphenylphosphine and derivatives class thereof, tertiary amines, quaternary ammonium salts, the General Catalyst of the epoxy curing agent such as boron trifluoride and derivatives class thereof curing reaction, these promotor both can be used alone, also can two or more be used in combination, the number of usage quantity, can be as required, with safety, environmental protection obtains object and is as the criterion, the present invention not specially provided for, usually, epoxy resin ingredient in contrast curing system, proper with 0.001% ~ 2.5%, more suitably scope is between 0.03% ~ 1.2%.
Filler is to increase its some function, character or reducing costs, can add as mineral fillers such as silicon-dioxide, diatomite, kaolin, calcium carbonate, mica, titanium dioxide, magnesium hydroxide, aluminium hydroxides in curing system, these mineral fillers can be used alone, also can two kinds or several are used in combination, usage quantity is generally advisable with the 500phr (phr represents the number contained by every hectogram) being no more than epoxy resin ingredient.
In above-mentioned flame-retardant composition, can be according to actual needs, some are added general in or special materials such as defoamer, coupling agent, toughner, flow agents in system, the present invention does not do special regulation to the kind and addition of adding auxiliary agent, as required, object can be obtained with safety, environmental protection and is as the criterion.
Another aspect of the invention provides a kind of preparation method of flame retardant, and the flame retardant obtained by this preparation method has good flame-retardance, thermotolerance, good mechanical property.
A preparation method for above-mentioned flame retardant resistance thing, is specially, and the muriate of above-mentioned M and dihydroxyphenyl propane being reacted through reacting to pass through, obtaining flame retardant.The concrete structure of M here and composition see above described in the structure of flame retardant resistance thing.
The concrete reaction adopted in above-mentioned preparation method can adopt method well known in the art, as phosphonitrilic chloride compound is having under solvent or solvent-free condition, use, is obtained by reacting with dihydroxyphenyl propane or its metal-salt for catalyzer in the basic conditions with the metal chlorides such as zinc chloride, magnesium chloride, aluminum chloride, boron trifluoride and complex compound thereof etc.These catalyzer can one or more be used in combination, there is no special regulation in the present invention.Muriatic example as M has conventional hexachlorocyclotriphosphazene, known solvent, catalyzer can be used to synthesize, also phosphorus pentachloride and ammonium chloride can be used to be synthesized after phosphorus chloride cyanogen compound according to known method, and purifying through physical method process or do not purify directly manufactures.
Another aspect of the invention provides a kind of purposes of flame retardant resistance thing, and it is for the solidifying agent of epoxy resin.
Can be used alone when being used as solidifying agent, also can be as used in combination in solidifying agent such as amine, acids, anhydrides, phenol-based compounds classes with other known epoxy curing agent.Time used in combination, special regulation be there is no to the usage ratio of various curing agent component in system.Under the condition of its mol ratio surplus, can with can react with it as after the substance reactions such as epoxy resin, end reaction base is the resultant of phenolic group, can separately or used in combination with one or several in above-mentioned known epoxy curing agent, for the ratio of usage quantity, without special regulation.
During above-mentioned solidifying agent for epoxy resin, it is suitable to Skill and method fillers such as calcium carbonate, silicon powder, diatomite, kaolin, magnesium hydroxide, aluminium hydroxide, terra alba, titanium dioxide, iron powder, copper powder, silver powder to add as required, also can add the thermoplastic resin classes such as ABS, PET, nylon, PC and use together in system.For these adding materials usage quantity number, use kind number, whether separately a kind ofly add that still to state middle interpolation used in combination, and not specially provided for, in general, not damage the performance of material.Certainly, in order to accelerate curing speed or add certain performance, usually, known epoxy resin curing accelerator can be added in system, as materials such as imidazoles, triphenylphosphine and derivative thereof, amine, boron trifluoride and complex compounds thereof, for the use of these adding materials, without specifying especially, its kind or quantitative proportion can be determined as required.In order to easy to use or increase some characteristic, can add as added ingredientss such as flow agent, defoamer, coupling agent, pigment, pigment, releasing agent, toughner in system, for the use of these adding materials, without specifying especially, its kind or quantitative proportion can be determined as required.
Another aspect of the invention provides a kind of purposes of flame-retardant composition, and it is for the composite metal substrate field of wiring board.The raw material of flame-retardant composition is by being solidificated in coating composite metal substrate being formed and has good flame-retardance energy, can wiring board be improved, such as electronic industry, electrically, Electric Industrial, communications and transportation, aerospace, toy industry etc. need the widespread use of the industry such as machine, equipment, instrument, instrument of wiring board.
Comprise the dihydroxyphenyl propane group that is connected with each other in this its molecular structure of flame retardant of the present invention and be with the group (M yl) of the phosphorus nitrogen skeleton be made up of unsaturated phosphorus, nitrogen-atoms, the group (M of the ring-type phosphorus nitrogen skeleton that the band that the group of described band phosphorus nitrogen skeleton comprises at least 50wt% is made up of three phosphorus, nitrogen-atoms
1base), the group (M of chain phosphorus nitrogen skeleton that is made up of two phosphorus, nitrogen-atoms at the most of the band of 30wt% at the most
2base) and the group (M of the ring-type phosphorus nitrogen skeleton be made up of at least four phosphorus, nitrogen-atoms of 45wt% at the most
3base), make this flame retardant have good flame retardant resistance thus, its cured article has good thermotolerance, water tolerance, agglutinating value(of coal) and mechanical property, electrical property, is a kind of fire retardant matter also with larger economy and environmental protection friendly.
Embodiment
Technical scheme of the present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
Chlordene ring three phosphorus cyanogen 173.83g (0.5mol), acetone 250ml, sodium methylate 108.04g (2.0mol) and dihydroxyphenyl propane 501.6g (2.2mol) is dropped into in three mouthfuls of 2000ml glass reactors of whipping appts, stir and lead to nitrogen while be warmed up to 40 DEG C, 20% sodium hydroxide solution 400g is instilled with 60min, keep 45 DEG C of temperature, stirring reaction 15 hours.After reaction, with the moisture in physical method removal system, refilter the insoluble substance in removal system, distill solvent in system, obtain flame retardant 667.0g, recording its phenolic group equivalent is 196.2g/eq, by this object resultant called after A.
With the triphenylphosphine dropping into liquid bisphenol A type epoxy resin 374g that epoxy equivalent (weight) is 187g/eq and above-mentioned A material 45g and 0.1g in three mouthfuls of 500ml glass reactors of whipping appts, be warmed up to 100 DEG C, react 8 hours, obtain the object epoxy resin 419.0g that epoxy equivalent (weight) is 238.0g/eq, add the epoxy resin solution that acetone is modulated into 60% again, by this object called after C.
Get the solution 100g (solids component is 60g) of above-mentioned C material, add the Dyhard RU 100 of 2.85g and appropriate DMF again, stir homogeneous after, add the glyoxal ethyline of 0.08g, wiring solution-forming, then obtains the standard copper-clad plate sample meeting the standard such as GB, UL, called after a copper-clad plate according to general copper-clad plate production process, the performance of test a copper-clad plate, its result represents in table-1.
Get the glyoxal ethyline of above-mentioned C material 100g, methyl tetrahydro phthalic anhydride 63g and 0.05g, after heating mixing is degassed, be poured in grinding tool, solidify 4 hours under temperature 120 DEG C of conditions, obtain the standard test specimen meeting the relevant criterion such as GB, UL standard, by this cured article called after cured article-1, the properties of test cured article-1, its result represents in table-2.
Embodiment 2
Ethylene dichloride 180g, phosphorus pentachloride 104.11g (0.5mol), ammonium chloride 26.75g (0.5mol) and magnesium chloride 20g is dropped into in three mouthfuls of 2000ml glass reactors of whipping appts.Stir and lead to nitrogen while be warmed up to 60 DEG C, and react under 60 DEG C of temperature condition after 6 hours, add sodium methylate 108.04g (2.0mol) again and dihydroxyphenyl propane 501.6g (2.2mol) continues reaction 12 hours, add solvent 300g, cross and filter insoluble substance, then solvent evaporated, obtain flame retardant 666.7g, recording its phenolic group equivalent is 196.5g/eq, by this object resultant called after B.
Be the liquid bisphenol A type epoxy resin 374g of 187g/eq and the triphenylphosphine of above-mentioned B substance 45g and 0.1g with dropping into epoxy equivalent (weight) in three mouthfuls of 500ml glass reactors of whipping appts, be warmed up to 100 DEG C, react 10 hours, obtain the object epoxy resin 419.0g that epoxy equivalent (weight) is 237.1g/eq, by this object called after D.
Get the solution 100g (solids component is 60g) of above-mentioned D material, add the Dyhard RU 100 of 2.85g and appropriate DMF again, stir homogeneous after, add the glyoxal ethyline of 0.08g, wiring solution-forming, then obtains the standard copper-clad plate sample meeting the standard such as GB, UL, called after b copper-clad plate according to general copper-clad plate production process, the performance of test b copper-clad plate, its result represents in table-1.
Embodiment 3
Bisphenol A type epoxy resin 100g that use market epoxy equivalent (weight) to be 230g/eq, market circulation, add A material 71.8g as described in Example 1, after adding appropriate acetone solution, add the glyoxal ethyline wiring solution-forming of 0.08g again, then the standard copper-clad plate sample meeting the standard such as GB, UL is obtained according to general copper-clad plate production process, called after c copper-clad plate, the performance of test c copper-clad plate, its result represents in table-1.
Comparative example 1
Be the linear phenolic epoxy resin 374g of 178g/eq and the triphenylphosphine of DOPO 38g and 0.1g with dropping into epoxy equivalent (weight) in three mouthfuls of 500ml glass reactors of whipping appts, be warmed up to 120 DEG C, react 5 hours, obtain the object epoxy resin 412g that epoxy equivalent (weight) is 232g/eq, by this object called after E.
Get above-mentioned E material 100g and add the Dyhard RU 100 of 3.0g and appropriate DMF again, stir homogeneous after, add the glyoxal ethyline of 0.08g, wiring solution-forming, then the standard copper-clad plate sample meeting the standard such as GB, UL is obtained according to general copper-clad plate production process, called after d copper-clad plate, the performance of test d copper-clad plate, its result represents in table-1.
Get the glyoxal ethyline of above-mentioned E material 100g, methyl tetrahydro phthalic anhydride 65g and 0.05g, after heating mixing is degassed, be poured in grinding tool, solidify 4 hours under temperature 120 DEG C of conditions, the obtained standard test specimen meeting the relevant criterion such as GB, UL standard, by this cured article called after cured article-2, the properties of test cured article-2, its result represents in table-2.
The test result following (in view of concrete testing method is well known to those skilled in the art, at this, method no longer being described in detail) of embodiment and comparative example:
The Performance comparision of table-1, copper-clad plate
Table-2, Solidified enzyme compares
The test data of above form, show that flame retardant of the present invention and derivative thereof are when being used in epoxy resin solidifying system and other system, have good flame retardant resistance, its cured article has good thermotolerance, water tolerance, agglutinating value(of coal) and mechanical property, electrical property.Flame retardant of the present invention belongs to the environment-friendly type flame-retardant material of novel environmental friendly of low cost, abundant raw material source, energy-saving and emission-reducing that properties is good.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (9)
1. the flame retardant with dihydroxyphenyl propane base, it is characterized in that, comprise the dihydroxyphenyl propane group that is connected with each other in its molecular structure and be with the group (M) of the phosphorus nitrogen skeleton be made up of unsaturated phosphorus, nitrogen-atoms, the group (M of the ring-type phosphorus nitrogen skeleton that the band that the group of described band phosphorus nitrogen skeleton comprises at least 50wt% is made up of three phosphorus, nitrogen-atoms
1), the group (M of chain phosphorus nitrogen skeleton that is made up of two phosphorus, nitrogen-atoms at the most of the band of 30wt% at the most
2) and the group (M of the ring-type phosphorus nitrogen skeleton be made up of at least four phosphorus, nitrogen-atoms of 45wt% at the most
3).
2. flame retardant according to claim 1, is characterized in that, it has such as formula the molecular structure shown in I:
In formula I, R represents aliphatic group containing at least one carbon atom or aromatic base; A, b, c are the integer being more than or equal to 1, b and c sum is more than or equal to 2, a, b and c three sum be more than or equal to 6, n be more than or equal to zero integer.
Preferably, M
1account for more than the 80wt% of M total mass, more preferably 90 ~ 100wt%.
3. a fire-retarded epoxy resin, is characterized in that, for by epoxy resin and the resultant of flame retardant by being obtained by reacting as claimed in claim 1.
4. fire-retarded epoxy resin according to claim 3, it is characterized in that, the raw material of described reaction also comprises catalyzer, described catalyzer is can be used for epoxy resin and containing the catalyzer reacted between phenolic hydroxyl group class, and the one be preferably in imidazoles, triphenylphosphine and derivatives class thereof, tertiary amines and quaternary ammonium salts catalyzer is used alone or multiple used in combination;
Preferably, the consumption of described catalyzer is 100 ~ 20000ppm of the raw material total mass of reaction, more preferably 200 ~ 5000ppm;
Preferably, described reaction is carried out under condition that is solvent-free or that have solvent, and described solvent is one in ketones solvent, aromatic solvents, chlorinated solvents, ether solvent, ether alcohol kind solvent, alcoholic solvent and petroleum solvent oil or at least two kinds;
Preferably, the consumption of described solvent be can make fire-retarded epoxy resin solid content be 5 ~ 100% consumption, more preferably can make fire-retarded epoxy resin solid content be 20 ~ 100% consumption;
Preferably, the temperature of described reaction is 40 ~ 250 DEG C, more preferably 60 ~ 180 DEG C;
Preferably, described epoxy resin is two senses or the above epoxy resin of two senses;
Preferably, difunctional epoxy resin is one in liquid bisphenol A type epoxy resin, liquid bisphenol F type epoxy resin, solid-state bisphenol A type epoxy resin, solid-state bisphenol f type epoxy resin and bisphenol-s epoxy resin, biphenyl type epoxy resin or at least two kinds;
Preferably, the epoxy resin more than two senses is the one of phenol aldehyde type epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol-A phenolic epoxy resin and acyclic isoprenoid type epoxy resin or at least two kinds.
5. a flame-retardant composition, is characterized in that, comprises fire-retarded epoxy resin as claimed in claim 4.
6. flame-retardant composition according to claim 5, is characterized in that, also comprises the filler of resin, solidifying agent, auxiliary agent, curing catalyst and the halogen-free flame-retardance with flame retardant resistance;
Preferably, the resin described in flame retardant resistance is DOPO type epoxy resin, containing phosphorous epoxy resin, nitrogenous type epoxy resin, nitrogenous containing phosphorous epoxy resin, phosphorus containing phenolic resin, nitrogenous containing the one in phosphorous resol, silicon-contained type epoxy resin and sulfur-type epoxy resin or at least two kinds;
Preferably, described solidifying agent is one in polyphenol based compound, amino-complex, benzoxazine colophony, acid anhydrides, polyprotonic acid and boron trifluoride and complex compound thereof or at least two kinds;
Preferably, described amino-complex is aliphatic amide or the aromatic amines such as Dyhard RU 100, diethyl triamine, diaminodiphenylmethane, diaminodiphenylsulfone(DDS);
Preferably, described polyphenol based compound is one in dihydroxyphenyl propane, Bisphenol F, bisphenol S, linear phenolic resin, o-cresol urea formaldehyde, bisphenol A phenolic resin or at least two kinds;
Preferably, the consumption of described solidifying agent and the equivalence ratio 0.4 ~ 1.5 of epoxy resin;
Preferably, described curing catalyst is one in imidazoles, triphenylphosphine and derivatives class thereof, tertiary amines, quaternary ammonium salts and boron trifluoride and derivatives class thereof or at least two kinds;
Preferably, the consumption of described curing catalyst is account for epoxy resin total mass 0.001 ~ 2.5%, more preferably 0.03 ~ 1.2%;
Preferably, described filler is one in silicon-dioxide, kaolin, calcium carbonate, mica, titanium dioxide, magnesium hydroxide, aluminium hydroxide or at least two kinds;
Preferably, the consumption of described filler is below the 500phr of epoxy resin total mass;
Preferably, described auxiliary agent is one or more in defoamer, coupling agent, toughner and flow agent.
7. a preparation method for flame retardant as claimed in claim 1, is characterized in that, by the muriate of M and dihydroxyphenyl propane or its metal-salt through react, obtains the flame retardant of band dihydroxyphenyl propane base.
8. a purposes for flame retardant as claimed in claim 1, is characterized in that, it is used as the solidifying agent of epoxy resin.
9. a purposes for flame retardant as claimed in claim 5, is characterized in that, it is used as the composite metal substrate field of wiring board.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106916281A (en) * | 2015-12-28 | 2017-07-04 | 广东广山新材料股份有限公司 | Flame-retardant compound, curing agent and polyphenol base epoxy |
| US20180009980A1 (en) * | 2016-07-05 | 2018-01-11 | Guangdong Guangshan New Materials Co., Ltd. | Flame-retardant engineering plastic and preparation method thereof |
| CN107573582A (en) * | 2016-07-05 | 2018-01-12 | 广东广山新材料股份有限公司 | A kind of CABLE MATERIALS of anti-flammability and preparation method thereof |
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| CN112480373A (en) * | 2019-09-11 | 2021-03-12 | 广东广山新材料股份有限公司 | Flame-retardant epoxy resin composition and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106916281A (en) * | 2015-12-28 | 2017-07-04 | 广东广山新材料股份有限公司 | Flame-retardant compound, curing agent and polyphenol base epoxy |
| US20180009980A1 (en) * | 2016-07-05 | 2018-01-11 | Guangdong Guangshan New Materials Co., Ltd. | Flame-retardant engineering plastic and preparation method thereof |
| CN107573582A (en) * | 2016-07-05 | 2018-01-12 | 广东广山新材料股份有限公司 | A kind of CABLE MATERIALS of anti-flammability and preparation method thereof |
| CN107573665A (en) * | 2016-07-05 | 2018-01-12 | 广东广山新材料股份有限公司 | A kind of building and ornament materials of anti-flammability and preparation method thereof |
| CN107573662A (en) * | 2016-07-05 | 2018-01-12 | 广东广山新材料股份有限公司 | A kind of engineering plastics of anti-flammability and preparation method thereof |
| CN108359219A (en) * | 2018-02-28 | 2018-08-03 | 广州佳诺仕装饰工程有限公司 | A kind of Thief zone Solvent-free Modification epoxy resin and preparation method |
| CN112480373A (en) * | 2019-09-11 | 2021-03-12 | 广东广山新材料股份有限公司 | Flame-retardant epoxy resin composition and preparation method and application thereof |
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Address after: 523000 Dongguan Port Road, Guangdong (Sha Tianduan) Humen port service center, Humen port service building on the third floor Applicant after: Guangdong Guang Shan new materials Limited by Share Ltd Address before: 523990 Dongguan Port Road, Guangdong (Sha Tianduan) Humen port service center, Humen port service building 3F Applicant before: GUANG SHAN NEW MATERIALS CO., LTD. |
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Application publication date: 20150513 |