CN1137237C - Organic Peroxide emulsions - Google Patents
Organic Peroxide emulsions Download PDFInfo
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- CN1137237C CN1137237C CNB988123495A CN98812349A CN1137237C CN 1137237 C CN1137237 C CN 1137237C CN B988123495 A CNB988123495 A CN B988123495A CN 98812349 A CN98812349 A CN 98812349A CN 1137237 C CN1137237 C CN 1137237C
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Abstract
The invention relates to emulsions of organic peroxides comprising organic peroxide, water, antifreeze, optionally nonionic surface-active agent, and optionally protective colloid which have a low viscosity and excellent stability over time, as well as to the use of such emulsions in the polymerization of ethylenically unsaturated monomers, particularly vinyl chloride.
Description
The present invention relates to comprise the emulsion of at least a organo-peroxide, this emulsion is suitable for ethylenically unsaturated monomer, the particularly suspension of vinyl chloride monomer or emulsion (being total to) polymerization.
The suspension of ethylenically unsaturated monomer or emulsion (being total to) polymeric is realized generally being to use protective colloid and/or tensio-active agent and as the free radical polymerization initiator of polymerization starter, as organic superoxide, is formed the polymkeric substance of desired size distribution.In addition, when making vinyl chloride (be total to) polymkeric substance, the sector is being sought the improvement of productivity and is being reduced pollution to environment, for example by reducing the refuse amount that the reactor dirt generates in forming and the loss of minimizing unreacted monomer.As a result, use the large-scale polymerization unit of automatization day by day and the design of equipment to make the carrying out of whole polymerization process not enter air (so-called enclosed reaction vessel technology).
Be applicable to the polymerization initiator composition of these processes increasing be the organo-peroxide of water-emulsive organo-peroxide rather than solvent cut.This development mainly is because aqueous peroxide emulsions is easy to handle and safety.The various aqueous peroxide emulsions of this purposes has been proposed recently.For example in patent application JP Hei56-139509, the polyvinyl acetate (PVA) that contains organic superoxide, tensio-active agent, protective colloid such as partial hydrolysis and the aqueous organic peroxide emulsions of water-soluble alcohol are disclosed.Similarly, in patent application JP Hei61-130315, disclose and contain organic superoxide, nonionogenic tenside, mean polymerisation degree and be no more than 600 and the polyvinyl acetate (PVA) of at least 60% mole of degree of hydrolysis and the organo-peroxide aqueous emulsion of water-soluble alcohol.In suspension (being total to) polymerization that described aqueous peroxide emulsions contains the protective colloid that has high stability in water and is used in vinylchlorid.(being total to) polymkeric substance and (being total to) polymerization noun used in this piece document relate to homopolymer, all kinds multipolymer such as segmented copolymer, terpolymer, alternating copolymer, random copolymers etc. and relate to the polymerization process of making these polymkeric substance.
Should also be noted that and disclose the polyvinyl acetate (PVA) that comprises organo-peroxide, degree of hydrolysis 5-70% and the emulsion of water-soluble alcohol among the patent application JP Hei62-086005.
Yet traditional emulsion has various shortcomings.Specifically, the emulsion that obtains in JPA-56-139509 has high viscosity.Particularly under higher peroxide concentrations, generate the high viscosity emulsion, in producing, transport and using, be difficult for handling.In addition, reduction is used as the dispersant dosage of emulsifying agent to reduce viscosity, then can reduce stability in storage widely.
Organic peroxide emulsions with JP-A-61-130315 and the described method manufacturing of JP-A-62-086005 has acceptable viscosity, but its stability in storage deficiency, the actual inconvenience of using.In addition, although promptly demonstrate acceptable low viscosity after some traditional organic peroxide emulsions compound production, viscosity can sharply increase in time in storage, when for example storing and/or storing for a long time under the low temperature of about-20 ℃ of temperature.When the emulsive organo-peroxide has highly water-soluble and low-gravity, can observe this undesirable phenomenon.
Notice that JP-A-58-134103 discloses a kind of suspension polymerization of VC method, wherein organic peroxide emulsions is used for starting polymerization.For making PVC have high-insulation, the tensio-active agent that the preparation organic peroxide emulsions is used is selected from the non-ionic surface emulsifying agent of no poly suboxygen ethyl.
In addition, US 5278262 discloses a kind of polymerization unit and has utilized microsuspension or emulsion polymerization to prepare the method for paste PVC.Organic peroxide evocating agent be with in the solvent or VCM in emulsion form add.
An object of the present invention is to develop the emulsion of one or more organo-peroxides that almost do not have all these shortcomings.Especially, the present invention relates to can low viscous aqueous organic peroxide emulsions steady in a long-term.
The invention discloses following content:
1. moisture organic peroxide emulsions, it comprises one or more protective colloids of at least a organo-peroxide of 10-70% weight, optional one or more nonionogenic tensides that are lower than the organic solvent of 35% weight, the water of 20-35% weight, at least a frostproofer of 5-25% weight, at least a clorafin of 0.5-15.0% weight, optional 0.1-1.0% weight and optional 0.1-1.0% weight.
2. the emulsion of heading 1, wherein clorafin is a liquid for 20 ℃-25 ℃ in temperature, the content of chlorine is 40-65% weight in said clorafin.
3. heading 1 or 2 emulsion, wherein organo-peroxide is selected from the peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester, peroxidation PIVALIC ACID CRUDE (25) tert-pentyl ester, peroxidation PIVALIC ACID CRUDE (25) 1,1-dimethyl-3-hydroxy butyl ester, new peroxide tert-butyl caprate, peroxidation neodecanoic acid tert-pentyl ester and peroxidation neodecanoic acid 1,1-dimethyl-3-hydroxy butyl ester.
4. heading 1 or 2 emulsion; comprise the clorafin of the peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester of water, 40-50% weight or new peroxide tert-butyl caprate, 1-7.5% weight, the further optional frostproofer that comprises the organic solvent of 10-25% weight, at least a protective colloid or nonionogenic tenside and 15-20% weight, add up to 100% weight.
5. each emulsion is used in the suspension or emulsion (being total to) the polymeric purposes of ethylenically unsaturated monomer among the heading 1-4, wherein said monomer is selected from halogen ethene, vinylidene halide type monomer, vinyl ether, vinyl ester, (methyl) vinylformic acid and (methyl) acrylate, aromatic vinyl monomer, alpha-olefin, maleic acid ester, fumarate and ethene.
6. the purposes of heading 5, wherein ethylenically unsaturated monomer is a vinylchlorid.
Through after the various tests, the inventor finds, uses clorafin as the another kind of composition in said aqueous organic peroxide emulsions, the then easier manufacturing of these emulsions, and the emulsion viscosity that obtains is low, and extended storage stability is fabulous.
Therefore, the present invention relates to comprise at least a organo-peroxide, water, at least a frostproofer, at least a clorafin, optional at least a nonionogenic tenside and/or the optional at least a or moisture organic peroxide emulsions of kinds of protect colloidal.
Emulsion of the present invention preferably includes the clorafin of the 0.5-15.0% weight that accounts for the emulsion gross weight.In addition, also preferably using at about 20 ℃ is the clorafin of liquid.In another preferred embodiment, the amount of chlorine is the 40-72% weight of clorafin in said clorafin.
The invention still further relates to and in the suspension of one or more ethylenically unsaturated monomers or emulsion (being total to) polymerization, use said aqueous peroxide emulsions.Emulsion of the present invention is preferred for vinylchlorid (being total to) polymerization.
More preferably, be used for the chlorine that clorafin of the present invention contains the 40-65% weight that accounts for clorafin weight.These clorafins are traditional products, are generally obtained by paraffin or positive chlorination of paraffin.The character of clorafin becomes with the chlorination degree.If cl content surpasses 65% weight, clorafin generally is a solid, therefore handles inconvenient.Therefore, the general preferred cl content clorafin that is 40-65% weight.
That market is buied and suitable clorafin comprises Empara
K-43, Empara K-45 and Empara K-50 (come from AJINOMOTO CO., LTD); Toyoparax
A40 and ToyoparaxASO (coming from TOSOH CORPORATION).They can use separately or mix use as two or more clorafins.
Emulsion of the present invention preferably includes the clorafin of 0.5-15.0% weight.If clorafin content is lower than 0.5% weight in moisture organic peroxide emulsions of the present invention, then the stability in storage of emulsion is not enough, if clorafin content is higher than 15.0% weight in moisture organic peroxide emulsions of the present invention, then the viscosity of emulsion is too high.More preferably, emulsion of the present invention comprises the clorafin of 0.55-10.0% weight.The aqueous peroxide emulsions that most preferably comprises the clorafin of 0.6-6.0% weight is because these emulsions have best equilibrium property.
The transformation period that is used in the organo-peroxide of emulsion preparation preferably was at least under 75 ℃ 10 hours.In another embodiment preferred, the zero pour of used superoxide is 0 ℃ or lower, should be noted that, if use the mixture of organo-peroxide, then the zero pour of one of peroxide mixture can surpass 0 ℃, and condition is that the zero pour of organo-peroxide mixture is 0 ℃ or lower.Perhaps, zero pour is higher than 0 ℃ superoxide and can explains as following with solvent cut to reduce its zero pour.
The example that can be used in organo-peroxide of the present invention comprises peroxy dicarbonate, as peroxy dicarbonate two (1-methyl butyl) ester, peroxy dicarbonate two ester in the positive last of the ten Heavenly stems, peroxide-butyl carbonate peroxy dicarbonate two (2-ethylhexyl) ester, peroxy dicarbonate two (3-methoxyl group butyl) ester, peroxy dicarbonate two (2-ethoxyethyl group) ester etc.; The peroxyester such as the peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester, the own ester of peroxidation PIVALIC ACID CRUDE (25) uncle, peroxidation PIVALIC ACID CRUDE (25) tert-pentyl ester, peroxidation PIVALIC ACID CRUDE (25) uncle monooctyl ester, peroxidation PIVALIC ACID CRUDE (25) 1,1-dimethyl-3-hydroxy butyl ester, new peroxide tert-butyl caprate, peroxidation neodecanoic acid tert-pentyl ester, the own ester of peroxidation neodecanoic acid uncle, peroxidation neodecanoic acid uncle monooctyl ester, peroxidation neodecanoic acid α-isopropyl benzene ester, new peroxide tert-butyl caprate and peroxidation neodecanoic acid 1,1-dimethyl-3-hydroxyl butyl ester etc.; Diacyl peroxide is as two isobutyryl superoxide, two (3,5,5-trimethyl acetyl base) superoxide etc.; And two or more mixture of these superoxide.Noun uncle octyl group is used to refer to 1,1,3,3-tetramethyl butyl part.
The content of the organo-peroxide in emulsion of the present invention is generally the 10-70% weight of emulsion weight.If content is lower than 10%, then transportation cost raises, and is non-remunerative economically.Because the restriction of safety, concentration generally can not be greater than 70% weight.The concentration of superoxide is preferably 15-65% weight in emulsion, most preferably is 39-62% weight.
In the present invention, can be with the organic solvent diluting organo-peroxide to improve its thermostability or to reduce its zero pour.As the preferred organic of thinner is the softening agent known such as toluene, aliphatic hydrocrbon, DOP dioctyl phthalate (DOP) etc.When using this organic solvent, the content of said organic solvent is preferably below 35% weight of emulsion weight in the final emulsion.
Emulsion of the present invention comprises at least a frostproofer (deicing fluid).Can use various traditional frostproofers, but preferred lower alcohol or the dibasic alcohol of using.The example of said preferred lower alcohol and dibasic alcohol is methyl alcohol, ethanol, Virahol, ethylene glycol and their mixture.The preferred amount ranges of these frostproofers is the 5-25% weight of emulsion, is preferably 13-20% weight, and like this, the temperature of solidification of water is-25 ℃ or lower.Because use amount like this, emulsion has acceptable low viscosity when being low to moderate-25 ℃ in temperature.The acceptable viscosity of emulsion was generally 10 ℃ of down about 50 milli handkerchief second-500 milli handkerchief seconds, was preferably-10 ℃ of following 100-500 milli handkerchief seconds.
The water that the manufacturing emulsion is used is deionized water preferably.The consumption of water is preferably the 20-35% weight of emulsion weight.
If desired, operable in the present invention nonionogenic tenside or non-ionic surfactant mixture are traditional types.Example includes but not limited to that HLB (hydrophilic-lipophilic balance) value is not higher than the polyoxyethylene sorbitan ester of the oleic acid of the Isosorbide Dinitrate of 9 higher fatty acid such as oleic acid, lauric acid, palmitinic acid, stearic acid etc. and HLB value 10-20, lauric acid, palmitinic acid, stearic acid etc.The example of these nonionogenic tensides is Rheodol
SP-L10, RheodolSP-P10, Rheodol SP-O10, Rheodol TW-L120, Rheodol TW-P120 and Rheodol TW-O120 (coming from Kao Corporation).Preferred that uses that at least a HLB value is not higher than 9 nonionogenic tenside and the mixture of another kind of at least HLB value as the nonionogenic tenside of the nonionogenic tenside of 10-20.
If use, the nonionogenic tenside in the end content in the emulsion is generally 0.1-1.0% weight.If content is lower than 0.1% weight, then stability in storage reduces, if content is higher than 1.0% weight, particularly the HLB value is the nonionogenic tenside of 10-20, then might use the electrical insulation property of the polymkeric substance that this emulsion obtains relatively poor.
If wish to use protective colloid, preferably use hydrolysis (saponification) to become the 5-85% mole, be preferably the polyvinyl acetate (PVA) of 5-70% mole.The polyvinyl alcohol of these partial hydrolysiss also is many all polyvinyl alcohol (PVA).Most preferred protective colloid is the polyvinyl acetate (PVA) of degree of hydrolysis 50-70% mole.The example of these protective colloids includes but not limited to the Unitika Resin UMR series (degree of hydrolysis 5-70% mole) of Unitika Kasei K.K.If be used in the emulsion of the present invention, the content of protection glue is the 0.1-10% weight of emulsion weight.
Can produce emulsion of the present invention with any traditional method.The method that is used for making emulsion of the present invention below is these traditional methods a kind of only:
At first, with frostproofer and optional PVA and/or nonionogenic tenside dissolving and/be dispersed in the water, generate water.In addition, prepare the mixture of one or more organo-peroxides and one or more clorafins, as oil phase.Then, oil phase is added to said aqueous phase, with the emulsifying mixture that obtains.Perhaps, water can be added in the oil phase, then with emulsifying mixture.The emulsion that obtains like this be oil in water emulsion (water is external phase) and demonstrate outstanding stability and security.
Emulsifying step can carry out with any traditional dispersing apparatus, for example uses paddle formula, propeller formula or steamer formula mechanical rotation agitator, colloidal mill, homogenizer such as ultrasonic homogenizer, high-speed shearing equipment and line style mixing tank.The preferred median size of organic peroxide emulsions (d50) is not more than 8 microns, so that obtain good preservation stability.
Emulsion of the present invention is used to cause the suspension or emulsion (being total to) polymerization of one or more ethylenically unsaturated monomers.At least a monomer is preferably selected from the halogen vinyl, as vinylchlorid; Vinylidene halide monomer such as vinylidene chloride; The ethene ethers; Vinyl acetate such as vinyl acetate; (methyl) vinylformic acid and (methyl) acrylate; Aromatic vinyl monomer such as vinylbenzene; Alpha-olefin; Maleic acid ester; Fumarate; And ethene.Preferred monomer is a vinylchlorid.As said, vinylchlorid can homopolymerization or copolymerization.The latter's situation, comonomer can be selected from other the halogen ethene of removing beyond the vinylchlorid; Vinylidene chloride; Vinyl ether; Vinyl acetate; (methyl) vinylformic acid and ester thereof; Aromatic vinyl compound such as vinylbenzene; Alpha-olefin; Maleic acid ester and fumarate.If vinylchlorid carries out copolymerization, then the consumption of comonomer preferably is lower than 30% weight of whole monomer weights.
By the used polymerization process of the inventor, estimate the providing below of emulsion of aqueous peroxide of the present invention.But aqueous peroxide emulsions can be used in any traditional vinyl chloride monomer (being total to) polymeric method.Preferred said traditional polymerization is that vinyl chloride monomer suspends or emulsion (being total to) polymerization, because in this way use emulsion of the present invention to find to cause reactor fouling few.Because reactor fouling is few, do not need often to open, this has just reduced monomer and has escaped into the amount of environment, and has reduced the workman and be exposed to this monomeric chance.Be noted that PVA is generally as protective colloid, although in emulsion (being total to) polymerization, generally use tensio-active agent to be used as dispersing auxiliary in (being total to) polymerization that suspends.
Aqueous peroxide emulsions of the present invention is that the utmost point is suitable for making and has proportion and be lower than 1 and the composition of the organo-peroxide of highly water-soluble.Highly water-soluble is meant the water-soluble greater than 100ppm weight of superoxide, preferably is higher than 500ppm, more preferably is higher than 1000ppm.The good stability of these emulsions is not even long-time the storage as more than 6 months, can be observed yet and be separated.In addition, this emulsion has low viscosity, promptly is lower than for 500 milli handkerchief seconds under-10 ℃, make, transportation and use in handle easily.And, the few benefit of aggregation container fouling is arranged.Therefore, this emulsion is specially adapted to the especially closed reactor polymerization of the automatization of vinylchlorid of ethylenically unsaturated monomer.
The following examples and comparative example illustrate the present invention.
Embodiment 1-7, Comparative Examples A-D
The emulsion for preparing the composition shown in table 1 and 2 as follows.Common homogenizer is being housed,, and is installing ionized water, frostproofer, protective colloid and/or nonionogenic tenside in 1000 milliliters of tall form beaker of thermometer as Dissolver or Ultra Turrax .Mixture homogenization is arrived the uniform liquid of formation.Then with uniform liquid cooling to temperature 0-5 ℃.Add desired organo-peroxide solution and clorafin subsequently, the mixture that obtains is stirred 10-30 minute up to obtaining emulsion.
With the emulsion that obtains by analyzing stability in storage, average droplet size and viscosity to estimate.The results are shown in table 3.
For estimating stability, place every kind of emulsion in the Glass Containers and be stored in-10 ℃.Checked being separated of emulsion in every month.Sample is even after 6 months, does not form layering, then thinks to have good stability.If layering took place after February, then stability is general, if layering, then poor stability took place in February.The average droplet size of emulsion is measured with Microtrack FRA particle analyzer (coming from NikkisoK.K.).Calculate as operational manual, median size is d50, is the mean diameter of the accumulative total of particle.
The viscosity of emulsion is measured with E-type (taper-plate) viscometer (coming from TokyoKeiki K.K.) temperature-10 ℃ and 0 ℃.The diameter of rotor is 48 millimeters, although the angle between taper and the plate be 1 ° 34 '.Rotating speed is 1 or 2.5 rev/min.
(notes) EG=ethylene glycol, GO=Gohsenol
| Table 1 | Embodiment | |||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | ||
| Deionized water | 29 | 30 | 27.5 | 28.4 | 31.7 | 27 | 28 | |
| Frostproofer | Methyl alcohol | - | 8 | 7 | 15 | - | 10 | 8 |
| EG | 20 | 9 | 8 | - | 15 | 7 | 8 | |
| Protective colloid | KP-08 | 2 | - | - | - | - | - | 1 |
| UMR-20M | - | 2 | - | - | - | 1 | - | |
| Nonionogenic tenside | TW-P120 | - | - | 0.2 | 0.3 | 0.3 | - | - |
| SP-L10 | - | - | 0.3 | 0.5 | - | - | - | |
| Organo-peroxide | KE P | 40 | 40 | 40 | - | - | - | - |
| TO 23 | - | - | - | 50 | - | - | - | |
| KD-58 | - | - | - | - | 50 | - | - | |
| KC MC | - | - | - | - | - | 25 | - | |
| TO 36 | - | - | - | - | - | - | 50 | |
| Thinner | DOP | - | - | - | - | - | 25 | - |
| IP-1620 | - | 10 | 14 | - | - | - | - | |
| Clorafin | EM K-43 | 9 | 1 | 3 | 6 | 3 | 5 | 5 |
| Table 2 | The comparative example | ||||
| A | B | C | D | ||
| Deionized water | 29 | 30 | 28.4 | 31.7 | |
| Frostproofer | Methyl alcohol | - | 8 | 15 | 10 |
| EG | 20 | 9 | - | 7 | |
| Protective colloid | KP-08 | 2 | - | - | - |
| UMR-20M | - | 2 | - | 1 | |
| Nonionogenic tenside | RO-P120 | - | - | 0.1 | - |
| RO SP-L10 | - | - | 0.5 | - | |
| Organo-peroxide | KE P | 40 | 40 | - | - |
| TO 23 | - | - | 50 | - | |
| KD-58 | - | - | - | - | |
| KC MC | - | - | - | 25 | |
| TO 36 | - | - | - | - | |
| Thinner | DOP | - | - | - | 25 |
| IP-1620 | - | 10 | - | - | |
| Clorafin | EM K-43 | - | - | - | - |
UR＝Unitika Resin，RO＝Rheodol，
KE＝Kayaester， TO＝Trigonox，
HC＝Kayacarbon，EM＝Empara
KC=Kayacarbon comes from Nippon Synthenic Chemical Industry Co., and the Gohsenol KP-08 of Ltd. is the PVA of degree of hydrolysis 71.0-75.0% mole.The Unitika Resin UMR-20M that comes from Unitika Kasei K.K. is the PVA of 65% mole of degree of hydrolysis.The Rheodol TW-P 120 that comes from Kao Corporation is that the HLB value is 15.6 nonionogenic tenside.The Rheodol SP-L 10 that comes from Kao Corporation is nonionogenic tensides of HLB value 8.6.The Kayaester P that comes from Kayaku Akzo Corporation is the peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester (uses 75% solution, point out the amount of straight product in the table).The Trigonox 23 that comes from Kayaku Akzo Corporation is new peroxide tert-butyl caprate (use straight products).The KD-58 that comes from Kayaku Akzo Corporation is the own ester of peroxidation neodecanoic acid uncle (straight product).The Kayacarbon MC that comes from Kayaku Akzo Corporation is peroxy dicarbonate two (3-methoxyl group butyl) ester (using 50% solution).The Trigonox 36 that comes from Kayaku Akzo Corporation is two (3,5, the 5-trimethyl acetyl) superoxide (straight product).DOP is common DOP dioctyl phthalate.IP-1620 Solvent comes from Idemitsu Petroleum Chemistry Co., the different paraffin series aliphatic hydrocrbon of Ltd..Empara K-43 comes from Ajinomoto Co., the clorafin of Ltd..Table 3
Above-mentioned emulsion is used to cause the suspension polymerization of vinylchlorid.For this reason, with 0.13 gram PVA (73% mole of degree of hydrolysis) with in 370 grams 0.8 in deionized waters gram sodium bicarbonate is added to one liter glass potheater, the potheater nitrogen wash.After adding the organo-peroxide (referring to table 4) of indication output, in mixture, add 185 gram vinylchlorid.With the mixture agitation as appropriate that obtains, do and carry out polymerase 17 hour under 55 ℃.Polymer filtration with obtaining washes with water, and in 50 dried overnight.Table 4
*For the commodity Kayaster P-70 that comes from Kayaku Akzo Corporation is diluted in (70% superoxide) in the IP-1620 solvent.
| Performance test | |||||
| Embodiment | d50 | The viscosity of after preparation, measuring immediately | Stability in storage | ||
| (micron) | (milli handkerchief second) | Up to the stratified time | |||
| -10℃ | 0℃ | Month | Estimate | ||
| 1 | 1.53 | 350 | 210 | ＞6 | + |
| 2 | 1.08 | 410 | 200 | ＞6 | + |
| 3 | 1.88 | 220 | 160 | ＞6 | + |
| 4 | 3.20 | 150 | 80 | ＞6 | + |
| 5 | 3.18 | 190 | 110 | ＞6 | + |
| 6 | 5.22 | 430 | 260 | ＞6 | + |
| 7 | 2.38 | 380 | 190 | ＞6 | + |
| A | 6.68 | 170 | 110 | 1 | - |
| B | 3.35 | 560 | 280 | 3 | 0 |
| C | 7.32 | 130 | 90 | 1.5 | - |
| D | 13.60 | 350 | 180 | 1.5 | - |
| Used organo-peroxide | Type | Amount | Polymer yield | |
| (gram) | (％) | |||
| Embodiment 8 | The emulsion of embodiment 1 | Emulsion | 0.32 | 83 |
| Comparative example E | Kayaester P-70 * | Solvent | 0.18 | 82 |
By these results as can be seen, emulsion of the present invention can be used to improve the suspension polymerization of vinylchlorid.And, be noted that the resistates (being also referred to as the fouling or the dirt amount of reactor) that is bonded in the potheater sidewall is very low when using emulsion of the present invention.
Claims (6)
1. moisture organic peroxide emulsions, it comprises one or more protective colloids of at least a organo-peroxide of 10-70% weight, optional one or more nonionogenic tensides that are lower than the organic solvent of 35% weight, the water of 20-35% weight, at least a frostproofer of 5-25% weight, at least a clorafin of 0.5-15.0% weight, optional 0.1-1.0% weight and optional 0.1-1.0% weight.
2. the emulsion of claim 1, wherein clorafin is a liquid for 20 ℃-25 ℃ in temperature, the content of chlorine is 40-65% weight in said clorafin.
3. claim 1 or 2 emulsion, wherein organo-peroxide is selected from the peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester, peroxidation PIVALIC ACID CRUDE (25) tert-pentyl ester, peroxidation PIVALIC ACID CRUDE (25) 1,1-dimethyl-3-hydroxy butyl ester, new peroxide tert-butyl caprate, peroxidation neodecanoic acid tert-pentyl ester and peroxidation neodecanoic acid 1,1-dimethyl-3-hydroxy butyl ester.
4. claim 1 or 2 emulsion; comprise the clorafin of the peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester of water, 40-50% weight or new peroxide tert-butyl caprate, 1-7.5% weight, the further optional frostproofer that comprises the organic solvent of 10-25% weight, at least a protective colloid or nonionogenic tenside and 15-20% weight, add up to 100% weight.
5. each emulsion is used in the suspension or emulsion (being total to) the polymeric purposes of ethylenically unsaturated monomer among the claim 1-4, wherein said monomer is selected from halogen ethene, vinylidene halide type monomer, vinyl ether, vinyl ester, (methyl) vinylformic acid and (methyl) acrylate, aromatic vinyl monomer, alpha-olefin, maleic acid ester, fumarate and ethene.
6. the purposes of claim 5, wherein ethylenically unsaturated monomer is a vinylchlorid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9363298A JPH11171914A (en) | 1997-12-16 | 1997-12-16 | Emulsion composition of organic peroxide |
| JP363298/1997 | 1997-12-16 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1282361A CN1282361A (en) | 2001-01-31 |
| CN1137237C true CN1137237C (en) | 2004-02-04 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB988123495A Expired - Fee Related CN1137237C (en) | 1997-12-16 | 1998-12-10 | Organic Peroxide emulsions |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPH11171914A (en) |
| KR (1) | KR100560896B1 (en) |
| CN (1) | CN1137237C (en) |
| AU (1) | AU1573999A (en) |
| ID (1) | ID25494A (en) |
| TW (1) | TW459038B (en) |
| WO (1) | WO1999031194A1 (en) |
| ZA (1) | ZA9811529B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE393142T1 (en) * | 2001-03-23 | 2008-05-15 | Akzo Nobel Nv | STORAGE-Stable AQUEOUS EMULSIONS MADE OF ORGANIC PEROXIDES |
| ES2249720T5 (en) * | 2002-05-08 | 2012-06-01 | Akzo Nobel N.V. | Safe, stable and highly concentrated diacyl peroxide and peroxidicarbonate emulsions with a low value of chemical oxygen demand |
| FR2851245B1 (en) * | 2003-02-14 | 2007-03-23 | UNMEATED EMULSION OF HYDROXYPEROXYESTER | |
| RU2531349C2 (en) * | 2009-08-06 | 2014-10-20 | Акцо Нобель Кемикалз Интернэшнл Б.В. | Stable in storage and safe peroxide emulsions with high content of active oxygen |
| FR2995905B1 (en) * | 2012-09-21 | 2015-10-16 | Arkema France | ORGANIC PEROXIDE COMPOSITION WITHOUT COLLOID AGENT |
| US10100243B2 (en) | 2015-07-13 | 2018-10-16 | KMP Holdings, LLC | Environmentally preferable microemulsion composition |
| US11059779B2 (en) | 2016-03-18 | 2021-07-13 | Nouryon Chemicals International B.V. | Storage stable aqueous organic peroxide emulsions |
| JP2020138174A (en) | 2019-03-01 | 2020-09-03 | 信越化学工業株式会社 | Microcapsule |
| JP7034973B2 (en) | 2019-03-01 | 2022-03-14 | 信越化学工業株式会社 | Method for producing vinyl polymer |
| DE102019110214A1 (en) * | 2019-04-17 | 2020-10-22 | Pergan Hilfsstoffe für industrielle Prozesse GmbH | Organic peroxide emulsion, process for their preparation and their use |
| FR3099161B1 (en) * | 2019-07-22 | 2022-10-07 | Arkema France | AQUEOUS ORGANIC PEROXIDE EMULSION |
| EP3966257A1 (en) | 2020-05-20 | 2022-03-16 | Arkema France | Organic peroxide emulsion with ethanol |
| EP4153641A1 (en) * | 2020-05-20 | 2023-03-29 | Arkema France | Di-sec-butyl peroxydicarbonate emulsion |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL8000260A (en) * | 1980-01-16 | 1981-08-17 | Akzo Nv | AQUEOUS PEROXIDE EMULSION AND ITS USE IN SUSPENSION (CO-) POLYMERIZATION REACTIONS. |
| JPS57167733A (en) * | 1981-04-09 | 1982-10-15 | Rushidoole Yoshitomi Kk | Aqueous emulsion composition of organic peroxide which is stable at low temperature |
| JPS58134103A (en) * | 1982-02-02 | 1983-08-10 | Nippon Oil & Fats Co Ltd | Suspension polymerization of vinyl chloride or similar unsaturated monomer |
| JPS60258212A (en) * | 1984-06-05 | 1985-12-20 | Nippon Oil & Fats Co Ltd | Suspension polymerization of vinyl chloride unsaturated monomer |
| JPH0635484B2 (en) * | 1985-10-14 | 1994-05-11 | 化薬アクゾ株式会社 | Organic peroxide emulsion formulations |
| KR100191378B1 (en) * | 1989-09-18 | 1999-06-15 | 후루타 다케시 | Process for producing vinyl chloride resin |
-
1997
- 1997-12-16 JP JP9363298A patent/JPH11171914A/en active Pending
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1998
- 1998-12-10 ID IDW20001135A patent/ID25494A/en unknown
- 1998-12-10 CN CNB988123495A patent/CN1137237C/en not_active Expired - Fee Related
- 1998-12-10 AU AU15739/99A patent/AU1573999A/en not_active Abandoned
- 1998-12-10 WO PCT/IB1998/002130 patent/WO1999031194A1/en active IP Right Grant
- 1998-12-10 KR KR1020007006400A patent/KR100560896B1/en not_active IP Right Cessation
- 1998-12-15 ZA ZA9811529A patent/ZA9811529B/en unknown
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1999
- 1999-01-28 TW TW088101304A patent/TW459038B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| WO1999031194A1 (en) | 1999-06-24 |
| ID25494A (en) | 2000-10-05 |
| KR20010033043A (en) | 2001-04-25 |
| ZA9811529B (en) | 1999-06-23 |
| JPH11171914A (en) | 1999-06-29 |
| CN1282361A (en) | 2001-01-31 |
| KR100560896B1 (en) | 2006-03-13 |
| AU1573999A (en) | 1999-07-05 |
| TW459038B (en) | 2001-10-11 |
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