CN100560624C - A kind of method for synthesizing halogen substituent maleimide heat-proof flame-proof resin emulsion - Google Patents
A kind of method for synthesizing halogen substituent maleimide heat-proof flame-proof resin emulsion Download PDFInfo
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- CN100560624C CN100560624C CNB200610112839XA CN200610112839A CN100560624C CN 100560624 C CN100560624 C CN 100560624C CN B200610112839X A CNB200610112839X A CN B200610112839XA CN 200610112839 A CN200610112839 A CN 200610112839A CN 100560624 C CN100560624 C CN 100560624C
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Abstract
A kind of synthetic method of halogen substituent maleimide heat-proof resin emulsion: add emulsifying agent in reactor, part aryl ethylene class monomer, itrile group vinyl monomer, oil soluble thermal decomposition initiating etc. are carried out emulsification, form elementary emulsion (a); Rest part halogen substituent maleimide monomer, aryl ethylene class monomer, itrile group vinyl monomer, oil soluble thermal decomposition initiating etc. are added tempering tank, form homogeneous phase monomer mixed solution (b); Emulsifying agent is joined in the emulsor, stir and will (b) join and carry out emulsification formation monomer emulsion (c) in the emulsor; Monomer emulsion (c) joined in the reactor to mix with (a) carry out polyreaction and form latex of heatresistant resin (d).It is good that the heat-proof flame-proof resin emulsion that obtains has outward appearance, form and structure homogeneous thermal stability height, the advantage that the polymerization process yield is high can be widely used in the heat resistance modified aspect to materials such as ABS, PC, PBT, also can be used for preparing automobile, the component of the high-temp resistant fire-retarding of household electrical appliances.
Description
Technical field
The present invention relates to a kind of synthetic method of heat-proof flame-proof resin emulsion, particularly a kind of method for synthesizing halogen substituent maleimide heat-proof flame-proof resin emulsion.
Background technology
The monomeric free-radical polymerized thing of halogen substituent maleimide, because of containing the plane five-membered ring structure on its molecular chain, can effectively suppress the rotation of chain, thereby have very high structure rigidity and thermostability, and, owing to contain halogen group on the molecular chain, have good flame retardancy, thereby be subjected to extensive concern.
The preparation of heat-proof combustion-resistant ABS resin comprises two kinds of alloyage and modification by copolymerization methods, and wherein the modification by copolymerization method is a kind of reasonable technological line.The modification by copolymerization method mainly is made up of two portions technology, what a part was a halogen substituent maleimide (XIMID) with the monomeric terpolymer XSMIA of halogen substituent maleimide of aryl ethylene class monomer (AEM) itrile group vinyl monomer (NEM) is synthetic, and another part is the synthetic of ABS graft copolymer.The synthetic of the monomeric terpolymer of halogen substituent maleimide is the assurance of heat-proof combustion-resistant ABS resin thermotolerance and flame retardant resistance, and the ABS graft copolymer is determining the balance of its over-all properties.
The synthetic of XSMIA then can be adopted various polymerization processs such as body, suspension, emulsion and solution polymerization.Halogen substituent maleimide monomer and AEM and or NEM and three's copolyreaction have and the general different characteristics of copolyreaction, polymerization rate is very fast, reaction is difficult to control.Though high temperature suspension polymerization also may address this problem, its to the requirement of equipment than higher.The molecular weight of the monomeric terpolymer of emulsion polymerisation process synthetic halogen substituent maleimide is with respect to various polymerization processs such as body, suspension and solution polymerizations, the molecular weight of polymerisate is bigger, helps improving the physical strength and the resistance toheat (especially heat-drawn wire performance) of product.
GB1026912 has described the multipolymer for preparing maleimide and MMA with the method for mass polymerization, and the initiator of employing is an organo-peroxide.GB1062872 has described the multipolymer for preparing vinylchlorid and maleimide with method of emulsion polymerization, adopts redox initiation system.CA2078337 etc. have reported the method for its solution polymerization, and its solvent generally uses organic solvents such as benzene, and initiator adopts oil soluble thermal decomposition initiating (initiator at 100 ℃ half life of decomposition less than 4 hours), as azo-initiator.What GB1086673 and GB1213061 introduced is that what it adopted is water soluble starter with the method for the multipolymer of emulsion polymerization prepared maleimide and vinylbenzene etc.In " polymer material science and engineering " 2001 (17) .1, reported in " second-order transition temperature of St-AN-PMI emulsion copolymers and the rheological " that people such as Liu Guodong deliver and described its general emulsion polymerisation process, promptly adopt emulsifying agent, and be the polymerization process of initiator with the persulphate.
US4757109 has described a kind of technology with emulsion polymerisation process synthesizing styrene, vinyl cyanide, maleimide terpolymer, employing has the anionic emulsifier of well emulsify ability in pH value is 3～9 scopes, initiator adopts redox system or Diisopropyl azodicarboxylate initiator, when this patent is pointed out with the Diisopropyl azodicarboxylate initiator, speed of response is slower, its polymerization technique is fairly simple, does not discuss in view of polymerization process.KR9510550 has also introduced a kind of technology that adopts method of emulsion polymerization synthesizing styrene, vinyl cyanide, maleimide terpolymer, what adopt is used water soluble starter of typical letex polymerization or redox initiation system, does not also discuss in view of polymerization process.
The contriver attempts to seek a kind of under the situation of comparatively convenient, easy handling, synthesizes to obtain forming the relatively emulsion polymerisation process of the XSMIA multipolymer of homogeneous that distributes in the monomer ratio scope of broad.
Summary of the invention
At the problems referred to above, the object of the present invention is to provide the synthetic method of heat-proof flame-proof resin emulsion, is a kind of halogen substituent maleimide monomer and aryl ethylene class monomer and or synthetic method of the heat-proof flame-proof resin emulsion of itrile group vinyl monomer of preparing specifically.
The synthetic method of halogen substituent maleimide heat-proof flame-proof resin emulsion of the present invention is divided into four parts.Usually the composition and the operational condition of these four parts are as follows: (being 100 mass parts in the polymerization single polymerization monomer total amount, as follows)
(A) preparation of elementary emulsion
In being housed, the reactor of stirring adds 5～100 parts of de-salted waters under 25～35 ℃, 0.05～1.0 parts of emulsifying agents, 0～1.5 part of aryl ethylene class monomer, 0.5～2.5 part of itrile group vinyl monomer, 0～0.15 part of molecular weight regulator, 0.05～0.4 part of oil soluble thermal decomposition initiating, open to stir and carry out emulsification, after the emulsification 10～75 minutes, make in 20～75 minutes that the water temperature rises to 65～90 ℃ in the reactor, keep constant temperature, kept 5～30 minutes, promptly form elementary emulsion (a);
Optimum condition is: 25～35 ℃ add 10～50 parts of de-salted waters in the reactor of whipping appts is housed, 0.2～0.8 part of emulsifying agent, 0～1.5 part of aryl ethylene class monomer, 0.5～1.0 parts of itrile group vinyl monomers, 0.02～0.1 part of molecular weight regulator, 0.1～0.3 part of oil soluble thermal decomposition initiating, open to stir and carry out emulsification, after the emulsification 20～45 minutes, make in 30～45 minutes that the water temperature rises to 70～80 ℃ in the reactor, keep constant temperature, when using redox initiation system, the reduction phase that also adds 0.5～0.75 part of redox initiation system was again kept 10～20 minutes, promptly formed elementary emulsion (a).
(B) preparation of monomer mixed solution
25～35 ℃ with 10～45 parts of halogen substituent maleimide monomers, 30～65 parts of aryl ethylene class monomers, 0.5～30 parts of itrile group vinyl monomers, 0.1～0.6 part of oil soluble thermal decomposition initiating, 0.01～0.65 part of molecular weight regulator adds tempering tank, open to stir and mix, form homogeneous phase monomer mixed solution (b).
Optimum condition is: 25～35 ℃ with 15～40 parts of halogen substituent maleimide monomers, 35～60 parts of aryl ethylene class monomers, 0.2～0.5 part of oil soluble thermal decomposition initiating, 0.5～25 parts of itrile group vinyl monomers, 0.05～0.45 part of molecular weight regulator adds tempering tank, open to stir and mix, form homogeneous phase monomer mixed solution (b).
(C) preparation of monomer emulsion
25～35 ℃ with 80～150 parts of de-salted waters, and 2.0～3.5 parts of emulsifying agents join in the emulsor, stir, and (b) joined carry out emulsification in the emulsor.Emulsification 20～75 minutes monomer emulsion (c).
Optimum condition is: 25～35 ℃ with 100～130 parts of de-salted waters, and 2.5～2.7 parts of emulsifying agents join in the emulsor, stir, and (b) joined carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (c).
(D) preparation of heat-proof flame-proof resin emulsion
Elementary emulsion (a) form good after, monomer emulsion (c) joined within 3～8 hours in the reactor in batches or continuously mixes also the temperature of maintenance system with (a) and under 50～100 ℃, carry out polyreaction.(c) add after, polyreaction was carried out 0.5～2.0 hour again, the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (d) after qualified.The solids that emulsion filtered out after reaction finished and the ratio of total monomer charging capacity are lower than 0.5%.Also can add common agent such as softening agent and thermo-stabilizer etc. after polymerization finishes, they can be mixed with the emulsion of auxiliary agent with emulsifying agent and de-salted water in emulsifying tank, and the mode with emulsion after copolyreaction finishes adds.
Optimum condition is: (a) form good after, immediately (c) joined within 4～6 hours continuously in the reactor and to mix also the temperature of maintenance system with (a) and under 70～85 ℃, carry out polyreaction.(c) add after, polyreaction was carried out 0.5～1.5 hour again, the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (d) after qualified.The solids that emulsion filtered out after reaction finished and the ratio of total monomer charging capacity are lower than 0.5%.Can also finish the emulsion that the back adds auxiliary agent in the polymerization of (d), finish all processes of preparation (d).
During preparation (a) in the present invention, must add a spot of itrile group vinyl monomer or and aryl ethylene class monomer and emulsifying agent, do not add emulsifying agent or add the halogen substituent maleimide monomer and can have influence on stability of emulsion, even have relatively large polymer formation gel and from emulsion system, separate out.Heat-up rate, thermostat temperature, constant temperature are held time also extremely importantly in the condition, also will directly have influence on stability of emulsion, exceed the related scope of this patent, also have relatively large polymer formation gel and separate out from emulsion system.
In (D) step, monomer emulsion (c) can be added in 3～8 hours in the reactor in batches and mix with (a) in the present invention, as adding 2%～7% (c) every 5～20 minutes.
Because the solubleness of XNPMI in the ST/AN mixed solution is limited, after the XNPMI formula ratio reaches certain umber, temperature is lower than 25 ℃, XNPMI will separate out with solid-state from solution, so the starting temperature of emulsion polymerization should be more than 25 ℃, and temperature is higher than 35 ℃, the part initiator will begin to decompose, thereby the configuration temperature condition of emulsion polymerization chemical generally fixes within 25～35 ℃ the scope.Normal temperature can carry out the preparation of homogeneous monomer mixed solution, the preparation of monomer emulsion, the preparation of elementary emulsion respectively down among the present invention, can shorten the production cycle like this, remedies the low shortcoming of plant factor.
Initiator adds at twice in the present invention, if do not add the part initiator in preparation when (a), then can have influence on stability of emulsion, even has relatively large polymer formation gel and separate out from emulsion system.Used initiator in the synthetic method of halogen substituent maleimide heat-proof flame-proof resin emulsion of the present invention, it is the used oil soluble thermal decomposition initiating of general radical polymerization, usually oil dissolubility thermal decomposition initiating is meant at 100 ℃ the half life of decomposition initiator less than 4 hours, comprises azo class, organo-peroxide class.The object lesson of initiator has: Diisopropyl azodicarboxylate, and 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide etc., owing to be general general type, just no longer for example many.Wherein preferred Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
The halogen substituent maleimide monomer that synthetic method adopted of halogen substituent maleimide heat-proof flame-proof resin emulsion of the present invention has following structural formula:
(Rn contains the halogen-substituted alkyl of 1-15 carbon in the formula, cycloalkyl, and substituted alkyl, aryl, substituted aryl, wherein halogens mainly is bromine, chlorine element.)
Concrete example has: N-halogenated methyl maleimide, N-halogenated ethyl maleimide, N-halo tertiary butyl maleimide, N-halo isobutyl-maleimide, N-halo cyclohexyl maleimide, N-halogenophenyl maleimide, N-halogenated methyl phenyl maleimide, N-halogenated methoxy phenyl maleimide, N-halo carboxyl phenyl maleimide, N-halogenated nitrobenzene base maleimide, N-halo naphthyl maleimide etc., these maleimide monomers can be used alone or in combination.Wherein preferred N-tribromo cyclohexyl maleimide and N-tribromo phenyl maleimide.
Aryl ethylene class monomer is the compound that contains aryl hydrocarbon or substituted arene in the vinyl monomer.
Aryl ethylene class monomer mainly contains: vinylbenzene, right/adjacent/-vinyl toluene (being also referred to as Vinyl toluene), 1.3-dimethyl styrene, 2.4-dimethyl styrene, ethyl styrene is to tert-butylbenzene ethene, alpha-methyl styrene, α-ethyl styrene, Alpha-Methyl p-methylstyrene, halogenated styrenes, haloalkyl vinylbenzene, vinyl naphthalene or the like.The combination of one or more in these monomers all can be used.Optimization styrene wherein, Vinyl toluene.
The itrile group vinyl monomer is the compound of nitrile group-containing in the vinyl monomer.
The itrile group vinyl monomer mainly contains: vinyl cyanide, methacrylonitrile etc., the combination of one or more in these monomers all can be used.
The emulsifying agent that the present invention uses, mainly contain anion surfactant, nonionogenic tenside or their compound system, for example: sodium lauryl sulphate, dodecyl sulphate potassium, Sodium dodecylbenzene sulfonate, Potassium dodecylbenzenesulfonate, potassium stearate, synthetic fatty acid potassium, anion surfactants such as sodium oleate, OP, peregal, Tween, polyoxyethylene nonionogenic tensides such as Span, wherein preferably sodium dodecyl sulfate, Sodium dodecylbenzene sulfonate or synthetic fatty acid potassium/sodium lauryl sulphate compound system.
The molecular weight regulator that the present invention uses is not particularly limited, as being general tert-dodecyl mercaptan, dodecyl mercaptan carbon etc.
The emulsion of the auxiliary agent described in the present invention, be meant the emulsion that softening agent, thermo-stabilizer, emulsifying agent and de-salted water is mixed with auxiliary agent in emulsifying tank, mode that can emulsion after copolyreaction finishes adds, and makes their degrees of scatter in polymkeric substance more even, thus better effects if.Used auxiliary agent can be a softening agent in emulsion, thermo-stabilizer etc., be employed softening agent such as DOP in the general plastic working process, DCP, Magnesium Stearate etc., thermo-stabilizer is as 1076,1010,2246, emulsifying agent such as potassium stearate, potassium oleate, synthetic fatty acid potassium etc., proportioning also is to adopt general proportioning in the prior art, as softening agent: thermo-stabilizer: the weight ratio of emulsifying agent is (1～15): (1～15): (3～10), emulsifying agent, initiator, water, softening agent, the consumption of thermo-stabilizer is identical with general letex polymerization, be conventional amount used, no longer describe in detail.Certainly the present invention also can not add the emulsion of auxiliary agent, and use directly is provided after the polymerization.
In the synthetic method of halogen substituent maleimide resin of the present invention, the amount ranges of each component is as follows:
Monomer ratio: the mass ratio of halogen substituent maleimide monomer and aryl ethylene class monomer and itrile group vinyl monomer is adjusted in 10～45/30～66.5/1～32.5, and preferable range is 15～40/35～61.5/1～26.
The characteristics of the synthetic method of halogen substituent maleimide resin of the present invention are as follows:
1. temperature of reaction can be determined according to the decomposition temperature of the initiator of selecting for use, and temperature of reaction is between 50～100 ℃, between preferred 60～90 ℃ usually.
2. whipped form and rotating speed: for letex polymerization of the present invention, because polymerization system viscosity is not high, just requiring to the shearing action that stirs is not very high, and because method that can be by regulating feed rate reaction speed easily, so this method is less demanding to reactor mixing speed and radiating capacity of equipment, as long as can guarantee to mix.Common whipped form all can, preferably the slurry formula stirs.
3. feed way: the synthetic method of halogen substituent maleimide resin of the present invention, monomer emulsion can add reactor in batches also can add reactor continuously, also can add a part earlier, adds remainder behind the reaction certain hour continuously.Batch charging or add a part of reaction certain hour earlier after during continuous charging, the influence that form multipolymer the pitch time between batch is bigger.Feed way with continuous charging for well.
The synthetic method of halogen substituent maleimide heat-proof flame-proof resin emulsion of the present invention, problems such as the instability, pH that has thoroughly solved emulsion reduces and emulsion variable color, precipitate be more.Polyreaction is very easily controlled, and reaction process is highly stable, and polymerization finishes not have substantially precipitate and produces.The polymerization reaction monomer transformation efficiency is more than 95%, resin emulsion stability with reaction finish ratio (the being lower than 0.5%) size of solids that the back emulsion filters out and total monomer charging capacity and emulsion placement more than 12 hours nondiscoloration weigh.The second-order transition temperature test result of product only shows a second-order transition temperature value, illustrates that its structural homogeneity is good.After polymerization finished, heat-proof flame-proof resin emulsion can obtain the halogen substituent maleimide heat-proof flame-proof resin product through cohesion, washing drying.
Synthetic method with halogen substituent maleimide heat-proof flame-proof resin emulsion of the present invention, the multipolymer of the halogen substituent maleimide monomer that makes, aryl ethylene class monomer and itrile group vinyl monomer, it is good to have outward appearance, form and the structure homogeneous, the thermal stability height, the advantage that the polymerization process yield is high is that the good heat-proof combustion-resistant of a kind of performance is material modified, can be widely used in the heat-proof combustion-resistant modification aspect to materials such as ABS, PC, PBT.As a kind of heat-proof combustion-resistant performance excellent material, its independent use also can be used for preparing automobile, the component of the high-temp resistant fire-retarding of household electrical appliances.
Embodiment
Following examples are to specify of the present invention, and wherein reactor reacts in water-bath for three mouthfuls of glass flask of band stirring, condenser, thermometer; The end opening glass flask that tempering tank, emulsor stir for band.Hereinafter " % ", " part " all refers to mass percent or mass fraction.
Second-order transition temperature Tg:DSC-differential thermal differential method
Vicat softening temperature: GB/T 1633-2000
Flame retardant properties test: UL-94
Resin emulsion stability with reaction finish the ratio magnitude (≤0.5%) of solids that the back emulsion filters out and total monomer charging capacity and emulsion placement more than 12 hours nondiscoloration weigh.
The preparation of the emulsion of auxiliary agent:
Under 75 ℃, 5.0% oleic acid potash soap, 10% antioxidant 1076,5% plasticizer phthalic acid dibutylester and 80% de-salted water are mixed with the emulsion of auxiliary agent in emulsifying tank.
Embodiment 1:
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 0.7 part of vinylbenzene, 0.3 part of vinyl cyanide, 0.1 part of Diisopropyl azodicarboxylate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 30 parts of N-tribromo phenyl maleimides, 44 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, and 2.7 parts of sodium lauryl sulphate join in the emulsor, open and stir, and (b) joined carry out emulsification in the emulsor.Emulsification 42 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of heat-proof flame-proof resin emulsion
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 4.8 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (d) after qualified.(d) after polymerization finished, measuring its pH was about 9.
Under 75 ℃, 5.0% oleic acid potash soap, 10% antioxidant 1076,5% plasticizer phthalic acid dibutylester and 80% de-salted water are mixed with the emulsion of auxiliary agent in emulsifying tank.
In (d), add 0.7 part of the emulsion of auxiliary agent at last, be all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate heat-proof flame-proof resin emulsion.The solids that filters out is weighed after the drying, as the criterion (≤0.5% is qualified) of emulsion reaction system stability through washing.Under this condition, this emulsion is placed nondiscoloration in 72 hours.The ratio of solids that filters out and monomeric charge amount is 0.45%.
Calculated yield 95.4% after the product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=131 ℃ with the differential calorimeter.Record its vicat softening temperature: 129 ℃, flame retardant properties reaches the V-0 level.
Embodiment 2:
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of Sodium dodecylbenzene sulfonate, and 0.7 part of vinylbenzene, 0.3 part of vinyl cyanide, 0.1 part of Diisopropyl azodicarboxylate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 30 parts of N-tribromo phenyl maleimides, 44 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open and stir, and (b) joined carry out emulsification in the emulsor.Emulsification 30 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of heat-proof flame-proof resin emulsion
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 4.5 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (d) after qualified.(d) after polymerization finished, measuring its pH was about 9, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate heat-proof flame-proof resin emulsion.The solids that filters out is weighed after the drying, as the criterion (≤0.5% is qualified) of emulsion reaction system stability through washing.Under this condition, this emulsion is placed nondiscoloration in 72 hours.The ratio of solids that filters out and monomeric charge amount is 0.42%.This emulsion is placed nondiscoloration more than 72 hours
Calculated yield 96.3% after the product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=130 ℃ with the differential calorimeter.Record its vicat softening temperature: 129 ℃, flame retardant properties reaches the V-0 level.
Embodiment 3:
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 0.7 part of vinylbenzene, 0.3 part of vinyl cyanide, 0.1 part of Diisopropyl azodicarboxylate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 30 parts of N-tribromo cyclohexyl maleimides, 44 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open and stir, and (b) joined carry out emulsification in the emulsor.Emulsification 45 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of heat-proof flame-proof resin emulsion
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 4.5 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (d) after qualified.(d) after polymerization finished, measuring its pH was about 9, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate heat-proof flame-proof resin emulsion.The solids that filters out is weighed after the drying, as the criterion (≤0.5% is qualified) of emulsion reaction system stability through washing.Under this condition, this emulsion is placed nondiscoloration in 72 hours.The ratio of solids that filters out and monomeric charge amount is 0.43%.
Calculated yield 95.1% after the product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=129 ℃ with the differential calorimeter.Record its vicat softening temperature: 129 ℃, flame retardant properties reaches the V-0 level.
Embodiment 4:
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 1.2 parts of vinyl toluenes, 0.3 part of vinyl cyanide, 0.1 part of Diisopropyl azodicarboxylate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 30 parts of N-tribromo phenyl maleimides, 43.5 parts of vinyl toluenes, and 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open and stir, and (b) joined carry out emulsification in the emulsor.Emulsification 45 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of heat-proof flame-proof resin emulsion
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 4.5 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (d) after qualified.(d) after polymerization finished, measuring its pH was about 9, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate heat-proof flame-proof resin emulsion.The solids that filters out is weighed after the drying, as the criterion (≤0.5% is qualified) of emulsion reaction system stability through washing.Under this condition, this emulsion is placed nondiscoloration in 72 hours.The ratio of solids that filters out and monomeric charge amount is 0.33%.
Calculated yield 96.1% after the product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=132 ℃ with the differential calorimeter.Record its vicat softening temperature: 133 ℃, flame retardant properties reaches the V-0 level.
Embodiment 5:
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 1.5 parts of vinylbenzene, 0.3 part of methacrylonitrile, 0.1 part of Diisopropyl azodicarboxylate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 30 parts of N-tribromo phenyl maleimides, 43.2 parts of vinylbenzene, and 25 parts of methacrylonitriles, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open and stir, and (b) joined carry out emulsification in the emulsor.Emulsification 39 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of heat-proof flame-proof resin emulsion
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 4.6 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (d) after qualified.(d) after polymerization finished, measuring its pH was about 9, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate heat-proof flame-proof resin emulsion.The solids that filters out is weighed after the drying, as the criterion (≤0.5% is qualified) of emulsion reaction system stability through washing., under this condition, this emulsion is placed nondiscoloration in 72 hours.The ratio of solids that filters out and monomeric charge amount is 0.27%.
Calculated yield 96.5% after the product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=133 ℃ with the differential calorimeter.Record its vicat softening temperature: 131 ℃, flame retardant properties reaches the V-0 level.
Embodiment 6:
A. the preparation of elementary emulsion
35 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 1.0 parts of vinylbenzene, 0.5 part of vinyl cyanide, 0.1 part of Diisopropyl azodicarboxylate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 45 parts of N-tribromo phenyl maleimides, 53.5 parts of vinylbenzene, and 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
C. the preparation of monomer emulsion
35 ℃ with 130 parts of de-salted waters, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open and stir, and (b) joined carry out emulsification in the emulsor.Emulsification 30 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of heat-proof flame-proof resin emulsion
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 5.0 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (d) after qualified.(d) after polymerization finished, measuring its pH was about 9, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate heat-proof flame-proof resin emulsion.The solids that filters out is weighed after the drying, as the criterion (≤0.5% is qualified) of emulsion reaction system stability through washing.Under this condition, this emulsion is placed nondiscoloration in 72 hours.The ratio of solids that filters out and monomeric charge amount is 0.22%.
Calculated yield 95.1% after the product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=156 ℃ with the differential calorimeter.Record its vicat softening temperature: 149 ℃, flame retardant properties reaches the V-0 level.
Embodiment 7:
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 0.8 part of vinyl cyanide, 0.1 part of Diisopropyl azodicarboxylate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, the temperature of heat transferring medium rises to 80 ℃, makes in 30 minutes that the water temperature rises to 78 ℃ in the reactor, keeps constant temperature, keeps 10 minutes, promptly forms elementary emulsion (a).
B. the preparation of monomer mixed solution
25 ℃ with 25 parts of N-tribromo phenyl maleimides, 49 parts of vinylbenzene, and 25.2 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
C. the preparation of monomer emulsion
35 ℃ with 130 parts of de-salted waters, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open and stir, and (b) joined carry out emulsification in the emulsor.Emulsification 30 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of heat-proof flame-proof resin emulsion
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 4.5 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (d) after qualified.(d) after polymerization finished, measuring its pH was about 9, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate heat-proof flame-proof resin emulsion.The solids that filters out is weighed after the drying, as the criterion (≤0.5% is qualified) of emulsion reaction system stability through washing.Under this condition, this emulsion is placed nondiscoloration in 72 hours.The ratio of solids that filters out and monomeric charge amount is 0.35%.
Calculated yield 96.5% after the product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=127 ℃ with the differential calorimeter.Record its vicat softening temperature: 127 ℃, flame retardant properties reaches the V-1 level.
Embodiment 8:
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 0.5 part of vinyl cyanide, 0.1 part of Diisopropyl azodicarboxylate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
32 ℃ with 10 parts of N-tribromo phenyl maleimides, 64 parts of vinylbenzene, and 25.5 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
C. the preparation of monomer emulsion
35 ℃ with 130 parts of de-salted waters, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open and stir, and (b) joined carry out emulsification in the emulsor.Emulsification 45 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of heat-proof flame-proof resin emulsion
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 5.0 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (d) after qualified.(d) after polymerization finished, measuring its pH was about 9, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate heat-proof flame-proof resin emulsion.The solids that filters out is weighed after the drying, as the criterion (≤0.5% is qualified) of emulsion reaction system stability through washing.Under this condition, this emulsion is placed nondiscoloration in 72 hours.The ratio of solids that filters out and monomeric charge amount is 0.14%.
Calculated yield 96.5% after the product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=107 ℃ with the differential calorimeter.Record its vicat softening temperature: 108 ℃, flame retardant properties reaches the HB level.
Embodiment 9:
A. the preparation of elementary emulsion
26 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 2.5 parts of vinyl cyanide, 0.1 part of Diisopropyl azodicarboxylate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
26 ℃ with 35 parts of N-tribromo phenyl maleimides, 40 parts of vinylbenzene, and 22.5 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
C. the preparation of monomer emulsion
35 ℃ with 130 parts of de-salted waters, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open and stir, and (b) joined carry out emulsification in the emulsor.Emulsification 44 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of heat-proof flame-proof resin emulsion
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 4.8 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (d) after qualified.(d) after polymerization finished, measuring its pH was about 9, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate heat-proof flame-proof resin emulsion.The solids that filters out is weighed after the drying, as the criterion (≤0.5% is qualified) of emulsion reaction system stability through washing.Under this condition, this emulsion is placed nondiscoloration in 72 hours.The ratio of solids that filters out and monomeric charge amount is 0.26%.
Calculated yield 96.7% after the product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=143 ℃ with the differential calorimeter.Record its vicat softening temperature: 137 ℃, flame retardant properties reaches the V-0 level.
Embodiment 10:
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 1.0 parts of vinyl cyanide, 0.1 part of Diisopropyl azodicarboxylate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 30 parts of N-tribromo phenyl maleimides, 44 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open and stir, and (b) joined carry out emulsification in the emulsor.Emulsification 37 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of heat-proof flame-proof resin emulsion
(a) form good after, immediately (c) joined in the reactor in batches and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added 2% of total amount every 5 minutes, and it was added within 4.3 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (d) after qualified.(d) after polymerization finished, measuring its pH was about 9, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate heat-proof flame-proof resin emulsion.The solids that filters out is weighed after the drying, as the criterion (≤0.5% is qualified) of emulsion reaction system stability through washing.Under this condition, this emulsion is placed nondiscoloration in 72 hours.The ratio of solids that filters out and monomeric charge amount is 0.34%.
Calculated yield 96.0% after the product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=130 ℃ with the differential calorimeter.Record its vicat softening temperature: 131 ℃, flame retardant properties reaches the V-0 level.
Embodiment 11:
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of whipping appts is housed, 0.3 part of sodium lauryl sulphate, and 1.0 parts of vinyl cyanide, 0.1 part of Diisopropyl azodicarboxylate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 58 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 30 parts of N-tribromo phenyl maleimides, 44 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open and stir, and (b) joined carry out emulsification in the emulsor.Emulsification 40 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of heat-proof flame-proof resin emulsion
(a) form good after, immediately (c) joined in the reactor in batches and to mix also the temperature of maintenance system with (a) and under 65 ℃, carry out polyreaction.The feed rate of control (c) added 4% of total amount every 10 minutes, and it was added within 7.5 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (d) after qualified.(d) after polymerization finished, measuring its pH was about 9, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate heat-proof flame-proof resin emulsion.The solids that filters out is weighed after the drying, as the criterion (≤0.5% is qualified) of emulsion reaction system stability through washing.Under this condition, this emulsion is placed nondiscoloration in 72 hours.The ratio of solids that filters out and monomeric charge amount is 0.33%.
Calculated yield 96.6% after the product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=130 ℃ with the differential calorimeter.Record its vicat softening temperature: 131 ℃, flame retardant properties reaches the V-0 level.
Embodiment 12:
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 1.0 parts of vinyl cyanide, 0.1 part of 2,2'-Azobis(2,4-dimethylvaleronitrile) is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 68 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 30 parts of N-tribromo phenyl maleimides, 44 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of 2,2'-Azobis(2,4-dimethylvaleronitrile), 0.1 part of mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open and stir, and (b) joined carry out emulsification in the emulsor.Emulsification 41 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of heat-proof flame-proof resin emulsion
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 75 ℃, carry out polyreaction.The feed rate of control (c) added it within 5.5 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (d) after qualified.(d) after polymerization finished, measuring its pH was about 9, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate heat-proof flame-proof resin emulsion.The solids that filters out is weighed after the drying, as the criterion (≤0.5% is qualified) of emulsion reaction system stability through washing.Under this condition, this emulsion is placed nondiscoloration in 72 hours.The ratio of solids that filters out and monomeric charge amount is 0.30%.
Calculated yield 96.1% after the product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=128 ℃ with the differential calorimeter.Record its vicat softening temperature: 130 ℃, flame retardant properties reaches the V-0 level.
Embodiment 13:
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of Sodium dodecylbenzene sulfonate, and 1.0 parts of vinyl cyanide, 0.1 part of Diisopropyl azodicarboxylate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 70 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 30 parts of N-tribromo phenyl maleimides, 44 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, and 1.7 parts of Sodium dodecylbenzene sulfonatees and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open and stir, and (b) joined carry out emulsification in the emulsor.Emulsification 44 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of heat-proof flame-proof resin emulsion
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 95 ℃, carry out polyreaction.The feed rate of control (c) added it within 5.5 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (d) after qualified.(d) after polymerization finished, measuring its pH was about 9, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate heat-proof flame-proof resin emulsion.The solids that filters out is weighed after the drying, as the criterion (≤0.5% is qualified) of emulsion reaction system stability through washing.Under this condition, this emulsion is placed nondiscoloration in 72 hours.The ratio of solids that filters out and monomeric charge amount is 0.18%.
Calculated yield 96.5% after the product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=131 ℃ with the differential calorimeter.Record its vicat softening temperature: 130 ℃, flame retardant properties reaches the V-0 level.
Embodiment 14:
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 1.0 parts of vinyl cyanide, 0.1 part of benzoyl peroxide is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 60 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 25 parts of N-tribromo phenyl maleimides, 49 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of benzoyl peroxide, 0.1 part of mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open and stir, and (b) joined carry out emulsification in the emulsor.Emulsification 45 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of heat-proof flame-proof resin emulsion
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 60 ℃, carry out polyreaction.The feed rate of control (c) added it within 8.0 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (d) after qualified.(d) after polymerization finished, measuring its pH was about 9, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate heat-proof flame-proof resin emulsion.The solids that filters out is weighed after the drying, as the criterion (≤0.5% is qualified) of emulsion reaction system stability through washing.Under this condition, this emulsion is placed nondiscoloration in 72 hours.The ratio of solids that filters out and monomeric charge amount is 0.45%.
Calculated yield 95.5% after the product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=121 ℃ with the differential calorimeter.Record its vicat softening temperature: 120 ℃, flame retardant properties reaches the V-0 level.
Embodiment 15:
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 1.0 parts of vinyl cyanide, 0.1 part of Diisopropyl azodicarboxylate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 10 parts of N-tribromo phenyl maleimides, 64 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, and 2.5 parts of sodium lauryl sulphate and 5.0 parts of OP join in the emulsor, open and stir, and (b) joined carry out emulsification in the emulsor.Emulsification 30 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of heat-proof flame-proof resin emulsion
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 6.0 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (d) after qualified.(d) after polymerization finished, measuring its pH was about 9, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate heat-proof flame-proof resin emulsion.The solids that filters out is weighed after the drying, as the criterion (≤0.5% is qualified) of emulsion reaction system stability through washing.Under this condition, this emulsion is placed nondiscoloration in 72 hours.The ratio of solids that filters out and monomeric charge amount is 0.35%.
Calculated yield 96.7% after the product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=110 ℃ with the differential calorimeter.Record its vicat softening temperature: 111 ℃, flame retardant properties reaches the HB level.
Embodiment 16:
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 0.7 part of vinylbenzene, 0.3 part of vinyl cyanide, 0.1 part of Diisopropyl azodicarboxylate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 30 parts of N-xylylene bromide base maleimides, 44 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of dodecyl mercaptan carbon adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, and 2.7 parts of sodium lauryl sulphate join in the emulsor, open and stir, and (b) joined carry out emulsification in the emulsor.Emulsification 45 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 5.0 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) after polymerization finished, measuring its pH was about 9.
Under 75 ℃, 5.0% oleic acid potash soap, 10% antioxidant 1076,5% plasticizer phthalic acid dibutylester and 80% de-salted water are mixed with the emulsion of auxiliary agent in emulsifying tank.
In (d), add 0.7 part of the emulsion of auxiliary agent at last, be all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin.The solids that filters out is weighed after the drying, as the criterion (≤0.5% is qualified) of emulsion reaction system stability through washing.Under this condition, this emulsion is placed nondiscoloration in 72 hours.The ratio of solids that filters out and monomeric charge amount is 0.25%.
Calculated yield 95.5% after the product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=138 ℃ with the differential calorimeter.Record its vicat softening temperature: 135 ℃, flame retardant properties reaches the HB level.
Comparative example 1:
A. the preparation of monomer mixed solution
30 ℃ with 30 parts of N-tribromo phenyl maleimides, 45 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
B. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, and 3.0 parts of sodium lauryl sulphate join in the emulsor, open and stir, and (b) joined carry out emulsification in the emulsor.Emulsification 45 minutes monomer emulsion (c).Measuring its pH is 9～10.
C. the preparation of latex of heatresistant resin
Add 30 parts of water in the reactor, treat that its temperature rises to after 79 ℃, immediately (c) joined continuously equably in the reactor also the temperature of maintenance system and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 5.0 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) after polymerization finished, measuring its pH was about 9, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin.The solids that filters out is weighed after the drying, as the criterion (≤0.5% is qualified) of emulsion reaction system stability through washing.Under this condition, the ratio of solids that filters out and monomeric charge amount is 1.8%, and is defective.
Calculated yield 91.8% after the white product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=126 ℃ with the differential calorimeter.Record its vicat softening temperature: 127 ℃, flame retardant properties reaches the V-1 level.
Comparative example 2:
A. the preparation of monomer mixed solution
30 ℃ with 30 parts of N-tribromo phenyl maleimides, 45 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
B. the preparation of latex of heatresistant resin
30 ℃ with 160 parts of de-salted waters, 0.35 part of Diisopropyl azodicarboxylate, and 3.0 parts of sodium lauryl sulphate join in the reactor, open to stir (b) joined and carry out emulsification in the emulsor.Emulsification 30 minutes monomer emulsion.Measuring its pH is 9～10.The temperature of maintenance system is carried out polyreaction under 65 ℃, after reacting 8.0 hours, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) after polymerization finished, measuring its pH was about 9, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate white latex of heatresistant resin product.The solids that filters out is weighed after the drying, as the criterion (≤0.5% is qualified) of emulsion reaction system stability through washing.Under this condition, the ratio of solids that filters out and monomeric charge amount is 2.5%.
Calculated yield 91.1% after the white product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=132 ℃ with the differential calorimeter.Record its vicat softening temperature: 129 ℃, flame retardant properties reaches the V-1 level.
Comparative example 3:
In reactor, add 160 parts of de-salted waters, 3.5 the Sodium dodecylbenzene sulfonate of part, 45 parts of vinylbenzene, 30 parts of N-tribromo phenyl maleimides, 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part molecular weight regulator, stirred 30 minutes, and be warming up to 65 ℃, isothermal reaction is warming up to 90 ℃ of reactions to 0.5 hour after 3 hours.After filtration white latex of heatresistant resin, recording its pH is about 9.The solids that the white latex of heatresistant resin that obtains filters out and the ratio of monomeric charge amount are 4.8%, calculated yield 90.2% after the product that emulsion makes after cohesion, filtration, drying is weighed, Tg=131 ℃, 130 ℃ of vicat softening temperatures, flame retardant properties reaches the V-1 level.
The elementary emulsion quick heating of comparative example 4:()
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 1.0 parts of vinyl cyanide, 0.1 part of Diisopropyl azodicarboxylate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, the temperature of heat transferring medium rises to 90 ℃, makes in 10 minutes that the water temperature rises to 78 ℃ in the reactor, keeps constant temperature, keeps 10 minutes, promptly forms elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 25 parts of N-tribromo phenyl maleimides, 49 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open and stir, and (b) joined carry out emulsification in the emulsor.Emulsification 45 minutes monomer emulsion (c).
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 5.0 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) polymerization finishes the emulsion that the back adds auxiliary agent, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin.The solids that filters out is weighed after the drying through washing, and as a tree name of declaring of emulsion reaction system stability, under this condition, the solids that filters out and the ratio of charging capacity are 3.5%.
Emulsion is calculated yield 91.5% after the product that makes after the cohesion is weighed.Record second-order transition temperature Tg=130 ℃ with the differential calorimeter.Record its vicat softening temperature: 127 ℃, flame retardant properties reaches the V-1 level.
The elementary emulsion of comparative example 5:(heats up slow)
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 1.0 parts of vinyl cyanide, 0.1 part of Diisopropyl azodicarboxylate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 85 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 25 parts of N-tribromo phenyl maleimides, 49 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open and stir, and (b) joined carry out emulsification in the emulsor.Emulsification 45 minutes monomer emulsion (c).
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 4.5 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) polymerization finishes the emulsion that the back adds auxiliary agent, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin.The solids that filters out is weighed after the drying through washing, and as a tree name of declaring of emulsion reaction system stability, under this condition, the solids that filters out and the ratio of charging capacity are 2.5%.
Emulsion is calculated yield 92.5% after the product that makes after the cohesion is weighed.Record second-order transition temperature Tg=133 ℃ with the differential calorimeter.Record its vicat softening temperature: 130 ℃, flame retardant properties reaches the V-1 level.
The elementary emulsion constant temperature time of comparative example 6:(is long)
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 1.0 parts of vinyl cyanide, 0.1 part of Diisopropyl azodicarboxylate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 45 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 25 parts of N-tribromo phenyl maleimides, 49 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open and stir, and (b) joined carry out emulsification in the emulsor.Emulsification 30 minutes monomer emulsion (c).
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 4.5 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) polymerization finishes the emulsion that the back adds auxiliary agent, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin.The solids that filters out is weighed after the drying through washing, and as the criterion of emulsion reaction system stability, under this condition, the solids that filters out and the ratio of charging capacity are 4.3%.
Emulsion is calculated yield 91.8% after the product that makes after the cohesion is weighed.Record second-order transition temperature Tg=132 ℃ with the differential calorimeter.Record its vicat softening temperature: 129 ℃, flame retardant properties reaches the V-1 level.
The elementary emulsion constant temperature time of comparative example 7:(is short)
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 1.0 parts of vinyl cyanide, 0.1 part of Diisopropyl azodicarboxylate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 3 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 25 parts of N-tribromo phenyl maleimides, 49 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open and stir, and (b) joined carry out emulsification in the emulsor.Emulsification 34 minutes monomer emulsion (c).
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 5.5 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) polymerization finishes the emulsion that the back adds auxiliary agent, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin.The solids that filters out is weighed after the drying through washing, and as a tree name of declaring of emulsion reaction system stability, under this condition, the solids that filters out and the ratio of charging capacity are 6.3%.
Emulsion is calculated yield 88.5% after the product that makes after the cohesion is weighed.Record second-order transition temperature Tg=126 ℃ with the differential calorimeter.Record its vicat softening temperature: 127 ℃, flame retardant properties reaches the V-1 level.
Comparative example 8:
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 1.0 parts of vinyl cyanide, 0.1 part of Diisopropyl azodicarboxylate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 25 parts of N-phenylmaleimides, 49 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open and stir, and (b) joined carry out emulsification in the emulsor.Emulsification 33 minutes monomer emulsion (c).
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 2.5 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) polymerization finishes the emulsion that the back adds auxiliary agent, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin.The solids that filters out is weighed after the drying through washing, and as a tree name of declaring of emulsion reaction system stability, under this condition, the solids that filters out and the ratio of charging capacity are 3.5%.
Emulsion is calculated yield 90.5% after the product that makes after the cohesion is weighed.Record second-order transition temperature Tg=127 ℃ with the differential calorimeter.Record its vicat softening temperature: 125 ℃, flame retardant properties reaches the V-1 level.
The elementary emulsion thermostat temperature of comparative example 9:(height)
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 1.0 parts of vinyl cyanide, 0.1 part of Diisopropyl azodicarboxylate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 95 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 25 parts of N-tribromo phenyl maleimides, 49 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open and stir, and (b) joined carry out emulsification in the emulsor.Emulsification 32 minutes monomer emulsion (c).
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 4.8 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) polymerization finishes the emulsion that the back adds auxiliary agent, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin.The solids that filters out is weighed after the drying through washing, and as a tree name of declaring of emulsion reaction system stability, under this condition, the solids that filters out and the ratio of charging capacity are 3.7%.
Emulsion is calculated yield 90.5% after the product that makes after the cohesion is weighed.Record second-order transition temperature Tg=128 ℃ with the differential calorimeter.Record its vicat softening temperature: 126 ℃, flame retardant properties reaches the V-1 level.
Comparative example 10:
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 1.0 parts of vinyl cyanide, 0.1 part of Diisopropyl azodicarboxylate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 60 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 25 parts of N-tribromo phenyl maleimides, 49 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open and stir, and (b) joined carry out emulsification in the emulsor.Emulsification 35 minutes monomer emulsion (c).
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 5.0 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) polymerization finishes the emulsion that the back adds auxiliary agent, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin.The solids that filters out is weighed after the drying through washing, and as a tree name of declaring of emulsion reaction system stability, under this condition, the solids that filters out and the ratio of charging capacity are 4.7%.
Emulsion is calculated yield 91.5% after the product that makes after the cohesion is weighed.Record second-order transition temperature Tg=129 ℃ with the differential calorimeter.Record its vicat softening temperature: 128 ℃, flame retardant properties reaches the V-1 level.
The elementary emulsion of comparative example 11:(primary emulsion 2+ does not have vinylbenzene)
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of Sodium dodecylbenzene sulfonate, and 1.0 parts of vinyl cyanide, 0.1 part of Potassium Persulphate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 30 parts of N-tribromo phenyl maleimides, 44 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, 0.35 part of Potassium Persulphate, and 1.7 parts of Sodium dodecylbenzene sulfonatees and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open and stir, and (b) joined carry out emulsification in the emulsor then.Emulsification 45 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 5.0 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) after polymerization finished, measuring its pH was about 8, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin, this emulsion is placed agent in 10 hours and is become pink.The solids that filters out is weighed after the drying, as the criterion (≤0.5% is qualified) of emulsion reaction system stability through washing.Under this condition, the ratio of solids that filters out and monomeric charge amount is 0.53%.
Calculated yield 92.5% after the product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=131 ℃ with the differential calorimeter.Record its vicat softening temperature: 130 ℃, flame retardant properties reaches the V-1 level.
Comparative example 12:
A. the preparation of elementary emulsion
30 ℃ add 20 parts of de-salted waters, 0.3 part of sodium lauryl sulphate, 1.0 parts of vinyl cyanide, 0.05 part of isopropyl benzene hydroperoxide in the reactor of stirring is housed.Open to stir and carry out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 65 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 35 parts of N-tribromo phenyl maleimides, 40 parts of vinylbenzene, and 24 parts of vinyl cyanide, 0.35 part of isopropyl benzene hydroperoxide, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open and stir, and (b) joined carry out emulsification in the emulsor.Emulsification 35 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 75 ℃, carry out polyreaction.The feed rate of control (c) added it within 4.5 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content is 3.5%, the reaction do not carry out substantially.
Claims (14)
1. a halogen substituent maleimide heat-proof resin emulsion synthetic method is divided into four parts, is 100 mass parts in the polymerization single polymerization monomer total amount, and composition and operational condition are:
(A) preparation of elementary emulsion
In being housed, the reactor of stirring adds 5～100 parts of de-salted waters under 25～35 ℃, 0.05～1.0 parts of emulsifying agents, 0～1.5 part of aryl ethylene class monomer, 0.5～2.5 part of itrile group vinyl monomer, 0～0.15 part of molecular weight regulator, 0.05～0.4 part of oil soluble thermal decomposition initiating, open to stir and carry out emulsification, after the emulsification 10～75 minutes, make in 20～75 minutes that the water temperature rises to 65～90 ℃ in the reactor, keep constant temperature, kept 5～30 minutes, promptly form elementary emulsion (a); The halogen substituent maleimide monomer has following structural formula:
R in the formula
nThe halogen-substituted alkyl that contains 1～15 carbon, cycloalkyl, substituted alkyl, aryl, substituted aryl, wherein, halogens is bromine, chlorine;
(B) preparation of monomer mixed solution
25～35 ℃ with 10～45 parts of halogen substituent maleimide monomers, 30～65 parts of aryl ethylene class monomers, 0.5～30 parts of itrile group vinyl monomers, 0.1～0.6 part of oil soluble thermal decomposition initiating, 0.01～0.65 part of molecular weight regulator adds tempering tank, open to stir and mix, form homogeneous phase monomer mixed solution (b);
(C) preparation of monomer emulsion
25～35 ℃ with 80～150 parts of de-salted waters, and 2.0～3.5 parts of emulsifying agents join in the emulsor, stir, (b) joined carries out emulsification in the emulsor, emulsification 20～75 minutes monomer emulsion (c);
(D) preparation of latex of heatresistant resin
Monomer emulsion (c) joined within 3～8 hours in the reactor that whipping appts is housed in batches or continuously mix with (a) and the temperature of maintenance system is carried out polyreaction under 50～100 ℃, (c) add after, polyreaction carries out promptly forming in 0.5～2.0 hour latex of heatresistant resin (d) again.
2. synthetic method according to claim 1, the condition that it is characterized in that (A) step is: 25～35 ℃ add 10～50 parts of de-salted waters in the reactor of whipping appts is housed, 0.2～0.8 part of emulsifying agent, 0～1.5 part of aryl ethylene class monomer, 0.5～1.0 parts of itrile group vinyl monomers, 0.02～0.1 part of molecular weight regulator, 0.1～0.3 part of oil soluble thermal decomposition initiating, open to stir and carry out emulsification, after the emulsification 20～45 minutes, make in 30～45 minutes that the water temperature rises to 70～80 ℃ in the reactor, keep constant temperature, kept 10～20 minutes, and promptly formed elementary emulsion (a).
3. synthetic method according to claim 1, the condition that it is characterized in that (B) step is: 25～35 ℃ with 15～40 parts of halogen substituent maleimide monomers, 35～60 parts of aryl ethylene class monomers, 0.2～0.5 part of oil soluble thermal decomposition initiating, 0.5～25 parts of itrile group vinyl monomers, 0.05～0.45 part of molecular weight regulator adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
4. synthetic method according to claim 1, the condition that it is characterized in that (C) step is: 25～35 ℃ with 100～130 parts of de-salted waters, 2.5～2.7 parts of emulsifying agents join in the emulsor, stir, (b) joined carry out emulsification in the emulsor, emulsification 30～45 minutes monomer emulsion (c).
5. synthetic method according to claim 1, the condition that it is characterized in that (D) step is: (c) joined within 4～6 hours in the reactor that whipping appts is housed continuously mix with (a) and the temperature of maintenance system is carried out polyreaction under 70～85 ℃, (c) add after, polyreaction carries out promptly forming in 0.5～1.5 hour latex of heatresistant resin (d) again.
6. synthetic method according to claim 1 is characterized in that in (D) step in 3～8 hours under 60～90 ℃ of temperature in batches every 5～20 minutes 2%～7% monomer emulsion (c) being added in the reactor and mixes with (a).
7. synthetic method according to claim 1 is characterized in that the oil soluble thermal decomposition initiating, is azo-initiator or organic peroxide initiator.
8. synthetic method according to claim 7 is characterized in that azo-initiator is Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
9. synthetic method according to claim 1 is characterized in that emulsifying agent is anion surfactant, nonionogenic tenside or their compound system.
10. synthetic method according to claim 9 is characterized in that emulsifying agent is sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, synthetic fatty acid potassium or their compound system.
11. synthetic method according to claim 1 is characterized in that aryl ethylene class monomer is that vinylbenzene is or/and Vinyl toluene.
12. synthetic method according to claim 1 is characterized in that the itrile group vinyl monomer is that vinyl cyanide is or/and methacrylonitrile.
13. synthetic method according to claim 1 is characterized in that monomer ratio: the mass ratio of halogen substituent maleimide monomer and aryl ethylene class monomer and itrile group vinyl monomer is 10～45: 30～66.5: 1～32.5.
14. synthetic method according to claim 1 is characterized in that monomer ratio: the mass ratio of halogen substituent maleimide monomer and aryl ethylene class monomer and itrile group vinyl monomer is 15～40: 35～61.5: 1～26.
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