CN104031209A - Method for manufacturing copolymer latex and copolymer latex - Google Patents
Method for manufacturing copolymer latex and copolymer latex Download PDFInfo
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- CN104031209A CN104031209A CN201410075023.9A CN201410075023A CN104031209A CN 104031209 A CN104031209 A CN 104031209A CN 201410075023 A CN201410075023 A CN 201410075023A CN 104031209 A CN104031209 A CN 104031209A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/14—Treatment of polymer emulsions
- C08F6/16—Purification
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
- C08L9/04—Latex
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Abstract
A method for manufacturing copolymer latex which can enable a monomer composition containing 1,3-bivinyl, acrylonitrile, and other monomer capable of copolymerizing with 1,3-bivinyl and acrylonitrile to realize emulsion polymerization in the presence of unsaturated hydrocarbon having one unsaturated bond. For an oil mixture containing the unsaturated hydrocarbon obtained by distilling polymerized copolymer latex in previous manufacture of copolymer latex, the oil mixture is blended in the emulsion polymerization system according to the condition that the proportion of 4-cyan cyclohexene relative to the total amount of a monomer composition and unused unsaturated hydrocarbon and oil mixture is below 120ppm.
Description
Technical field
The present invention relates to the manufacture method of copolymer emulsion, and the copolymer emulsion obtaining by this manufacture method.
Background technology
Butadiene type copolymer emulsion (copolymer emulsion that the 1,3-butadiene of usining is principal constituent) is widely used as tackiness agent in the electrode of paper coating field, the back side applying glue of carpet, wooden class tackiness agent, battery, tire cord field etc.
In the manufacture of butadiene type copolymer emulsion, beyond demonomerization, emulsifying agent, polymerization starter, molecular weight adjusting agent etc., also use hydrocarbon.
Manufacture method as this copolymer emulsion, for example, in No. 5-112604, Japanese patent laid-open, disclose when making aliphatics conjugated diene monomer and can carry out letex polymerization with other monomers of its copolymerization, added the method for carrying out polymerization without the branched paraffin of the carbon number 5～10 of copolyreaction.
In addition, the method for carrying out letex polymerization under the existence of unsaturated hydrocarbons of the ring-type in the ring that is selected from cyclopentenes, tetrahydrobenzene, suberene, 4-tetrahydrotoluene, 1-tetrahydrotoluene with unsaturated link(age) is disclosed in No. 2961207th, Japanese Patent Laid.
In addition, in No. 2879121st, Japanese Patent Laid, disclose under the existence of unsaturated hydrocarbons of chain with 1 unsaturated link(age), made aliphatics conjugated diene monomer, vinyl unsaturated carboxylic acid monomer and can carry out with other monomers of their copolymerization the method for letex polymerization.
Summary of the invention
When the letex polymerization of use hydrocarbon as above is carried out to industrialization, need investigation to reduce the method for manufacturing cost.
So, the object of this invention is to provide the manufacture method of the copolymer emulsion that can lower manufacturing cost.
The manufacture method of copolymer emulsion of the present invention is under the existence of unsaturated hydrocarbons with a unsaturated link(age), make to comprise 1, 3-divinyl, vinyl cyanide and can be with 1, the monomer composition of other monomers of 3-divinyl and acrylonitrile compolymer carries out the manufacture method of the copolymer emulsion of letex polymerization, it is characterized in that, for distilling by the copolymer emulsion to after polymerization the oily mixture that comprises above-mentioned unsaturated hydrocarbons obtaining in the manufacture of former copolymer emulsion, according to the 4-cyanocyclohexanoic alkene that derives from above-mentioned oily mixture, with respect to the ratio of the total amount of above-mentioned monomer composition and untapped above-mentioned unsaturated hydrocarbons and above-mentioned oily mixture, be that condition below 120ppm is admixed to above-mentioned oily mixture in this emulsion polymerization systems.
In addition, the manufacture method of copolymer emulsion of the present invention is under the existence of unsaturated hydrocarbons with a unsaturated link(age), make to comprise 1, 3-divinyl, vinyl cyanide and can be with 1, the monomer composition of other monomers of 3-divinyl and acrylonitrile compolymer carries out the manufacture method of the copolymer emulsion of letex polymerization, it is characterized in that, for distilling by the copolymer emulsion to after polymerization the oily mixture that comprises above-mentioned unsaturated hydrocarbons obtaining in the manufacture of former copolymer emulsion, according to 4-cyanocyclohexanoic alkene, with respect to the ratio of the total amount of above-mentioned monomer composition and untapped above-mentioned unsaturated hydrocarbons and above-mentioned oily mixture, be that condition below 120ppm is admixed to above-mentioned oily mixture in this emulsion polymerization systems.
In addition in the manufacture method of copolymer emulsion of the present invention, be better further to distill by oily mixture being heated to the temperature of unsaturated hydrocarbons evaporation.
In addition,, in the manufacture method of copolymer emulsion of the present invention, unsaturated hydrocarbons is better tetrahydrobenzene.
In addition, the feature of copolymer emulsion of the present invention is to be manufactured by the manufacture method of above-mentioned copolymer emulsion.
According to the manufacture method of copolymer emulsion of the present invention, the situation of the unsaturated hydrocarbons new with whole uses is compared, and the recycling by unsaturated hydrocarbons can lower manufacturing cost.
And, according to the manufacture method of copolymer emulsion of the present invention, can manufacture the copolymer emulsion that agglutinator is few.In addition, can significantly reduce the discarded amount of unsaturated hydrocarbons, reduce carrying capacity of environment.
Embodiment
In the manufacture method of copolymer emulsion of the present invention, under the existence of unsaturated hydrocarbons with a unsaturated link(age), make to comprise 1,3-butadiene, vinyl cyanide and can carry out letex polymerization with the monomer composition of other monomers of 1,3-butadiene copolymerization and acrylonitrile compolymer.
1,3-butadiene in monomer composition with for example more than 10 quality %, preferably more than 15 quality %, for example 90 quality % are following, preferably the ratio below 85 quality % is carried out fusion.
In addition, 1,3-butadiene also can comprise the unreacted 1,3-butadiene reclaiming by distillation described later.
Vinyl cyanide in monomer composition with for example more than 0.1 quality %, preferably more than 1 quality %, for example 40 quality % are following, preferably the ratio below 35 quality % is carried out fusion.
In addition, vinyl cyanide also can comprise the unreacted vinyl cyanide reclaiming by distillation described later.
As can be with 1, other monomers of 3-divinyl and acrylonitrile compolymer are (following, be denoted as other monomers), can exemplify such as the vinyl cyanide monomer beyond alkenyl aromatic monomer, vinyl cyanide, unsaturated carboxylic acid monomer, unsaturated carboxylic acid alkyl ester monomer, the unsaturated monomer that contains hydroxyalkyl, unsaturated carboxylic acid amide monomer etc.
Other monomers in monomer composition with for example more than 9 quality %, preferably more than 14 quality %, for example 89.9 quality % are following, preferably the ratio below 84.9 quality % is carried out fusion.
As alkenyl aromatic monomer, can exemplify such as vinylbenzene, alpha-methyl styrene, methyl alpha-methyl styrene, Vinyl toluene and Vinylstyrene etc.
In these alkenyl aromatic monomers, preference is as vinylbenzene.
As vinyl cyanide base monomer, can exemplify such as methacrylonitrile, α-chloroacrylonitrile, α-ethyl acrylonitrile etc.
As unsaturated carboxylic acid monomer, can exemplify monoprotic acid such as vinylformic acid, methacrylic acid, butenoic acid, diprotic acid such as toxilic acid, fumaric acid, methylene-succinic acid (or its acid anhydrides) etc.
As unsaturated carboxylic acid alkyl ester monomer, can exemplify such as methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, ethyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, glycidyl methacrylate, dimethyl fumarate, DEF, dimethyl maleate, ethyl maleate, dimethyl itaconate, monomethyl fumarate, monomethyl ester etc.
In these unsaturated carboxylic acid alkyl ester monomers, preference is as ethyl acrylate, methyl methacrylate.
As the unsaturated monomer that contains hydroxyalkyl, can exemplify such as senecioate-hydroxy methacrylate, methacrylic acid-beta-hydroxy ethyl ester, vinylformic acid hydroxy propyl ester, methacrylic acid hydroxyl propyl ester, vinylformic acid hydroxyl butyl ester, methacrylic acid hydroxyl butyl ester, methacrylic acid 3-chlorine-2-hydroxyl propyl ester, toxilic acid two (ethylene glycol) ester, methylene-succinic acid two (ethylene glycol) ester, toxilic acid-2-hydroxy methacrylate, toxilic acid two (2-hydroxy methacrylate), 2-hydroxyethyl methylfumaric acid ester etc.
In these unsaturated monomers that contain hydroxyalkyl, preference is as senecioate-hydroxy methacrylate.
As unsaturated carboxylic acid amide monomer, can exemplify such as acrylamide, Methacrylamide, N hydroxymethyl acrylamide, N-methylol methacrylamide, N,N-DMAA etc.
In these unsaturated carboxylic acid amide monomers, preference is as acrylamide, Methacrylamide.
Also have, as other monomers, the monomer that also can use such as ethene, propylene, vinyl-acetic ester, propionate, vinylchlorid, vinylidene chloride etc. to use in common letex polymerization.
These other monomers are (only a kind) use separately, and also two or more kinds may be used.In addition, in these other monomers, preference is as unsaturated carboxylic acid monomer and unsaturated carboxylic acid alkyl ester monomer.
As the unsaturated hydrocarbons with a unsaturated link(age), can exemplify for example cyclopentenes, tetrahydrobenzene, suberene, 4-tetrahydrotoluene, 1-tetrahydrotoluene, 1-amylene, 2-Methyl-1-pentene, 1-hexene, 1-heptene, 2,4,4-trimethylammonium-1-amylene, 1-octene etc.
In these unsaturated hydrocarbons, preference is as tetrahydrobenzene.
These unsaturated hydrocarbons separately (only a kind) are used, and also two or more kinds may be used.
In addition,, in the manufacture of copolymer emulsion, after polymerization finishes, these unsaturated hydrocarbons can be reclaimed from copolymer emulsion, and recycle in the manufacture after next time.
For the polymerization at copolymer emulsion is reclaimed unsaturated hydrocarbons after finishing, can unsaturated hydrocarbons be reclaimed together with residual unreacted monomer etc. from copolymer emulsion by methods such as distillations.
Distillating method for copolymer emulsion is not particularly limited, and can use known method.Be preferable over 50 ℃～100 ℃ and carry out wet distillation.
Here, the oily mixture of removing from copolymer emulsion by distillation is (following, be called oily mixture) in except containing unsaturated hydrocarbons and volatile monomer etc., the 4-cyanocyclohexanoic alkene generating as by product while also containing letex polymerization (following, referred to as 4CC).
Make 1, when 3-divinyl, vinyl cyanide and other monomers carry out letex polymerization during this oily mixture of fusion, according to the 4CC from oily mixture, with respect to monomer composition, untapped unsaturated hydrocarbons (, the unsaturated hydrocarbons of fusion in this letex polymerization (new unsaturated hydrocarbons), and remove the unsaturated hydrocarbons in oily mixture) and the total amount of oily mixture, following with for example 120ppm, preferably 100ppm is following, further preferably the ratio below 80ppm is carried out fusion.
If the 4CC that surpasses above-mentioned higher limit is brought in emulsion polymerization systems, on the situation that agglutinator generation increases and polymerization reactor inwall, the amount of dirt settling all can increase, and the yield of copolymer emulsion reduces.In addition, the particle diameter that can be observed the multipolymer of gained has the tendency that becomes large, the circulation ratio variation of polymerization.
In the polymerization of recycling oily mixture, as control, bring the method for the 4CC amount in emulsion polymerization systems into, can measure by the 4CC measuring in oily mixture, calculate the 4CC amount of bringing in emulsion polymerization systems, thereby judge whether directly to recycle.
Now, to what use in polymerization, pass through unreacted 1 of Distillation recovery, the 4CC amount containing in 3-divinyl and the unreacted vinyl cyanide by Distillation recovery is also measured, calculate the 4CC amount of bringing in emulsion polymerization systems, with the 4CC amount addition calculation of bringing into from oily mixture in emulsion polymerization system.
In addition, as reduction, bring the method for the 4CC in emulsion polymerization systems into, for example can exemplify by being heated to the temperature of unsaturated hydrocarbons evaporation oily mixture is further distilled, using the method for using as the distillment containing unsaturated hydrocarbons (below, being denoted as distillment); For example also use the method for oily mixture and distillment; Such as by the method for at least a kind in new unsaturated hydrocarbons and oily mixture and distillment and use etc.For distillment, similarly measure the 4CC amount in distillment with above-mentioned oily mixture, according to its usage quantity, calculate the 4CC amount of bringing in polymerization system, thereby judge whether to recycle.
By recycling at least a kind in oily mixture and distillment, can significantly reduce the discarded amount containing the oily mixture of unsaturated hydrocarbons.
As emulsion polymerisation process of the present invention, can use known method.In other words, the addition means for monomer and other compositions is not particularly limited.In addition,, for the addition means of monomer, can adopt any in known method.In addition,, in letex polymerization, can use known emulsifying agent, polymerization starter, chain-transfer agent, ionogen, sequestrant etc.
As emulsifying agent, can exemplify sulfuric acid, alkylbenzene sulfonate, alkyl diphenyl ether disulfonate, aliphatic sulfonate, aliphatic carboxylate, Dehydroabietate, the formaldehyde condensation products of naphthene sulfonic acid, the aniorfic surfactant such as sulfuric acid of nonionic surface active agent such as higher alcohols; Such as nonionic surface active agent such as the alkyl ester type of polyoxyethylene glycol, alkyl phenyl ether type, alkyl ether types.
These emulsifying agents separately (only a kind) are used, and also two or more kinds may be used.
As polymerization starter, can suitably use water-soluble polymerization initiators such as persulfuric acid lithium, Potassium Persulphate, Sodium Persulfate, ammonium persulphate; Oil-soluble polymerization initiators such as cumene hydroperoxide, benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, di-isopropylbenzene hydroperoxide, 1，1，3，3-tetramethylbutylhydro-peroxide; Redox Type of Collective initiator for example.
In these polymerization starters, preference is as Potassium Persulphate, Sodium Persulfate, cumene hydroperoxide, t-butyl hydroperoxide.
As chain-transfer agent, can exemplify for example alkyl sulfhydryl; Xanthation compounds such as curing dimethyl yellow ortho ester, dithiodiisopropyl xanthate; Thiuram compounds such as tetramethyl-thiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram monosulfide; Phenol compounds such as 2,6 di tert butyl 4 methyl phenol, styrenated phenol; Such as allylic cpds such as vinyl carbinols; Halogenated hydrocarbon compounds such as methylene dichloride, methylene bromide, carbon tetrabromide; Vinyl ether such as α-benzyloxy vinylbenzene, α-benzyloxy vinyl cyanide, α-benzyloxy acrylamide; Such as triphenylethane, pentaphenylethane, propenal, Methylacrylaldehyde, Thiovanic acid, mercaptosuccinic acid, thioglycollic acid-2-ethyl hexyl ester, terpinolene, alpha-methyl styrene dimer etc.
These chain-transfer agents separately (only a kind) are used, and also two or more kinds may be used.
To the particle diameter of the copolymer emulsion of the manufacture method gained of copolymer emulsion of the present invention, there is no particular limitation, and the median size based on photon correlation method for example, for more than above, the preferred 70nm of for example 50nm, below following, the preferred 270nm of 300nm.If above-mentioned lower value that the median size of copolymer emulsion is not enough, the viscosity of copolymer emulsion is high, has sometimes reluctant situation, thereby not preferred.If the median size of copolymer emulsion is greater than above-mentioned higher limit, the surface-area of copolymer emulsion diminishes, and sometimes has the situation that bonding force declines, thereby not preferred.The usage ratio of the various emulsifying agents that the particle diameter of copolymer emulsion can be used by appropriate change in the polymerization of copolymer emulsion, the kind of polymerization starter and usage quantity thereof or addition means, polywater etc. is adjusted.
Gel content to copolymer emulsion of the present invention is not particularly limited, for example 30 quality % above, preferably more than 40 quality %, for example 99 quality % following, preferably below 95 quality %.If above-mentioned lower value that gel content is not enough, the tendency that has bonding force to reduce, thereby not preferred.Gel content for example can be measured by the method for recording in embodiment described later.
In the polymerization of copolymer emulsion of the present invention, also can use as required the known additives such as oxygen supplement (Japanese: Suan Su Fill foot drug), sequestrant, dispersion agent, defoamer, antiaging agent, sanitas, antiseptic-germicide, fire retardant, UV light absorber.Kind, usage quantity for these additives are all not particularly limited, and can suitably use in right amount.
Embodiment
Exemplify embodiment below the present invention is described in more detail, but the present invention is not limited to these embodiment.In addition, in embodiment, represent that part and the % of mix proportions is based on quality criteria.And, the numerical value such as the mix proportions in embodiment, in above-mentioned example, the higher limit of available recorded corresponding position or lower value replace.
And the 1,3-butadiene using in the present embodiment, vinyl cyanide all do not contain the not enough 1ppm of 4CC().
< embodiment and comparative example >
Embodiment 1
As primary polymerization, in the polymerization reactor of resistance to pressure that possesses stirrer, add monomer, tertiary lauryl mercaptan, the tetrahydrobenzene shown in first stage of 150 parts of polywaters, 1.5 parts of Sodium dodecylbenzene sulfonatees, 1 part of Potassium Persulphate, table 1, be warming up to 70 ℃.Then, with the monomer shown in the subordinate phase of 7 hours continuous adding tables 1, tertiary lauryl mercaptan, tetrahydrobenzene.Proceed polymerization, at polymerisation conversion, surpassing moment of 98% finishes polymerization again.
Then, to the polymkeric substance of gained, use potassium hydroxide that pH is adjusted to 7, with 80 ℃, carry out wet distillation.By this, the oily mixture containing tetrahydrobenzene is separated from the polymkeric substance of gained, obtain copolymer emulsion.With 95 ℃ of parts to isolated oily mixture, distill afterwards, obtain the distillment containing tetrahydrobenzene.
By the 4CC concentration in following measuring method mensuration oily mixture and the 4CC concentration in distillment.In addition, median size and the gel content of copolymer emulsion with following measuring method, have been measured.The results are shown in table 1.
Then, as the polymerization (recycling 1) of recycling, except the monomer shown in input table 1, tertiary lauryl mercaptan, tetrahydrobenzene, oily mixture and distillment, carry out the operation same with primary polymerization, obtain copolymer emulsion.
Median size and the gel content of the copolymer emulsion of gained with following measuring method, have been measured.The results are shown in table 1.
And, as the polymerization (recycling 2) of recycling, except the monomer shown in input table 1, tertiary lauryl mercaptan, tetrahydrobenzene, oily mixture and distillment, carry out the operation same with primary polymerization in addition, obtain copolymer emulsion.
Median size and the gel content of the copolymer emulsion of gained with following measuring method, have been measured.The results are shown in table 1.
Embodiment 2～5 and comparative example 1～3
As primary polymerization, except the blended amount of monomer, tertiary lauryl mercaptan, tetrahydrobenzene being changed into the blended amount shown in table 1, carry out operation similarly to Example 1, by the polymkeric substance to gained, use potassium hydroxide that pH is adjusted to 7, with 80 ℃, carry out wet distillation, from polymkeric substance, isolate the oily mixture containing tetrahydrobenzene, obtain copolymer emulsion.In addition, with 95 ℃ of parts to isolated oily mixture, distill, obtain the distillment containing tetrahydrobenzene.
By the 4CC concentration in following measuring method mensuration oily mixture and the 4CC concentration in distillment.In addition, median size and the gel content of copolymer emulsion with following measuring method, have been measured.The results are shown in table 1 and table 2.
Then, as the polymerization of recycling, except the monomer shown in input table 1, tertiary lauryl mercaptan, tetrahydrobenzene, oily mixture and distillment, carry out the operation same with primary polymerization, obtain copolymer emulsion.
Median size and the gel content of copolymer emulsion with following measuring method, have been measured.The results are shown in table 1 and table 2.
The evaluation method > of the various physical property of <
1. the 4CC of oily mixture or distillment is containing proportional measuring method
As gas chromatograph, use the (Island Jin System of Shimadzu Seisakusho Ltd. to do institute) the GC-2014 type of system.
(1) making of sample
The oily mixture of each embodiment and each comparative example or distillment is direct as measuring sample.
(2) gas chromatography determination condition
Sample size: 1 μ L
Detector: FID
Injection temperature: 170 ℃
Detector temperature: 250 ℃
Post: length/inside diameter/thickness (liquid layer)=30m/0.25mm/0.5 μ m(DB-WAX)
Carrier gas: He1mL/ minute
Splitting ratio: 1/40
Column temperature: keep after 5 minutes in 70 ℃, be warmed up to 170 ℃ with 10 ℃/min, then be warmed up to 230 ℃ with 20 ℃/min, keep 10 minutes in 230 ℃.
(3) quantivative approach
Use is confirmed retention time (Japanese: リ テ Application シ ョ Application タ イ system) with the sample of dimethyl formamide dilution 4CC gained.Measure above-mentioned sample, according to the peak area quantification 4CC occurring in the retention time of 4CC.
And, at the 4CC that measures the unreacted acrylonitrile by Distillation recovery, when proportional, using equally the vinyl cyanide that reclaims directly as mensuration sample, with above-mentioned condition determination and quantivative approach, carry out quantitatively.
The 4CC of the unreacted divinyl by Distillation recovery, containing proportional measuring method, is with under following gas chromatography determination condition, usings the divinyl that reclaims directly as mensuration sample, to carry out quantitatively with above-mentioned same quantivative approach.
The gas chromatography determination condition > of < " 1,3-butadiene "
Sample size: 0.5 μ L
Detector: FID
Injection temperature: 250 ℃
Detector temperature: 250 ℃
Post: length/inside diameter/thickness=50m/0.53mm/50 μ m(GS-ALUMINA115-3552)
Carrier gas: He6mL/ minute
Splitting ratio: 1/50
Column temperature: keep after 3 minutes in 45 ℃, be warmed up to 195 ℃ with 6 ℃/min, keep 15 minutes in 195 ℃.
2. the measuring method of the median size in copolymer emulsion
By dynamic light scattering method, the median size of copolymer emulsion is recorded as the median size based on photon correlation method.In addition, when measuring, use the (great of FPAR-1000(Otsuka Electronics Co., Ltd. mound Electricity) system).
3. the measuring method of the gel content in copolymer emulsion
At 80 ℃, copolymer emulsion is dry to make latex film.Then the latex film that takes about 1g, is designated as Xg.Dropped in the toluene of 400ml 48 hours so that it expands dissolves.Then, with the stainless steel wire netting of 300 object after weighing, filtered, then toluene evaporates is dried, deduct the weight of net from this dried weight, the dried weight that weighs sample is also designated as Yg.According to following formula, calculate gel content.
Gel content (%)=Y/X * 100
4. the measuring method of the agglutinator amount in copolymer emulsion
After polymerization finishes, before carrying out wet distillation, take 1kg copolymer emulsion as sample, with 300 order wire nettings of stainless steel, filter.By remain in agglutinator on wire netting dry after, gravimetry, obtains the ratio with respect to sample (solids component conversion), as agglutinator incidence.With 4 following levels, evaluate its incidence.
◎: agglutinator incidence is not enough, and 0.01%(is considerably less).
Zero: agglutinator incidence is more than 0.01%, and not enough 0.02%(is few).
△: agglutinator incidence is more than 0.02%, and not enough 0.05%(is slightly many).
*: agglutinator incidence is more than 0.05% (many).
5. the evaluation method that on convergence reaction device inwall, coagulum adheres to
In the resistance to pressure polymerization reactor of 100L, make copolymer emulsion polymerization, after the copolymer emulsion obtaining is adjusted to pH6, from polymerization reactor bottom, copolymer emulsion is all discharged.
Then polymerization reactor is filled to ion exchanged water, stir after 10 minutes, from polymerization reactor bottom, ion exchanged water is all discharged.
Discharge after ion exchanged water, the coagulum of Visual Confirmation polymerization reactor inwall adheres to ratio, with respect to the ratio of the area (S) of the part that has coagulum to adhere in polymerization reactor inner wall area (S0), polymerization reactor inwall, the metewand based on following is evaluated.
(metewand)
Zero: S/S0 less than 0.1.
△: S/S0 is more than 0.1 below 0.3.
*: S/S0 is greater than 0.3.
[table 1]
[table 2]
In addition, above-mentioned explanation provides the embodiment representing for example as the present invention, but this is simple representing for example, is not determinate explanation.Concerning the practitioner of this technical field, apparent variation of the present invention is comprised within the scope of claims.
Claims (8)
1. the manufacture method of a copolymer emulsion, this manufacture method is under the existence of unsaturated hydrocarbons with a unsaturated link(age), make to comprise 1,3-divinyl, vinyl cyanide and can be with 1, the monomer composition of other monomers of 3-divinyl and acrylonitrile compolymer carries out the manufacture method of the copolymer emulsion of letex polymerization
It is characterized in that, for distilling by the copolymer emulsion to after polymerization the oily mixture that comprises described unsaturated hydrocarbons obtaining in the manufacture of former copolymer emulsion, according to the 4-cyanocyclohexanoic alkene that derives from described oily mixture, with respect to the ratio of the total amount of described monomer composition and untapped described unsaturated hydrocarbons and described oily mixture, be the condition below 120ppm, described oily mixture be admixed in this emulsion polymerization systems.
2. the manufacture method of copolymer emulsion as claimed in claim 1, is characterized in that, by described oily mixture being heated to the temperature of described unsaturated hydrocarbons evaporation, further distills.
3. the manufacture method of copolymer emulsion as claimed in claim 1, is characterized in that, described unsaturated hydrocarbons is tetrahydrobenzene.
4. a copolymer emulsion, is characterized in that, by the manufacture method of the copolymer emulsion described in any one in claim 1～3, is made.
5. the manufacture method of a copolymer emulsion, this manufacture method is under the existence of unsaturated hydrocarbons with a unsaturated link(age), make to comprise 1,3-divinyl, vinyl cyanide and can be with 1, the monomer composition of other monomers of 3-divinyl and acrylonitrile compolymer carries out the manufacture method of the copolymer emulsion of letex polymerization
It is characterized in that, for distilling by the copolymer emulsion to after polymerization the oily mixture that comprises described unsaturated hydrocarbons obtaining in the manufacture of former copolymer emulsion, according to 4-cyanocyclohexanoic alkene, with respect to the ratio of the total amount of described monomer composition and untapped described unsaturated hydrocarbons and described oily mixture, be the condition below 120ppm, described oily mixture be admixed in this emulsion polymerization systems.
6. the manufacture method of copolymer emulsion as claimed in claim 5, is characterized in that, by described oily mixture being heated to the temperature of described unsaturated hydrocarbons evaporation, further distills.
7. the manufacture method of copolymer emulsion as claimed in claim 5, is characterized in that, described unsaturated hydrocarbons is tetrahydrobenzene.
8. a copolymer emulsion, is characterized in that, by the manufacture method of the copolymer emulsion described in any one in claim 5～7, is made.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-042258 | 2013-03-04 | ||
| JP2013042258A JP5797681B2 (en) | 2013-03-04 | 2013-03-04 | Method for producing copolymer latex and copolymer latex |
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| Publication Number | Publication Date |
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| CN104031209A true CN104031209A (en) | 2014-09-10 |
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| CN201410075023.9A Pending CN104031209A (en) | 2013-03-04 | 2014-03-03 | Method for manufacturing copolymer latex and copolymer latex |
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| JP (1) | JP5797681B2 (en) |
| KR (1) | KR20140109318A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001323013A (en) * | 2000-05-17 | 2001-11-20 | Kanegafuchi Chem Ind Co Ltd | Method for producing isobutylene-based block copolymer |
| JP2003277544A (en) * | 2002-03-27 | 2003-10-02 | Jsr Corp | Copolymer latex |
| JP2005187544A (en) * | 2003-12-24 | 2005-07-14 | Nippon A & L Kk | Copolymer latex for use in dip molding, composition for use in dip molding, and dip-molded product |
-
2013
- 2013-03-04 JP JP2013042258A patent/JP5797681B2/en active Active
-
2014
- 2014-03-03 CN CN201410075023.9A patent/CN104031209A/en active Pending
- 2014-03-03 KR KR1020140025096A patent/KR20140109318A/en not_active Application Discontinuation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001323013A (en) * | 2000-05-17 | 2001-11-20 | Kanegafuchi Chem Ind Co Ltd | Method for producing isobutylene-based block copolymer |
| JP2003277544A (en) * | 2002-03-27 | 2003-10-02 | Jsr Corp | Copolymer latex |
| JP2005187544A (en) * | 2003-12-24 | 2005-07-14 | Nippon A & L Kk | Copolymer latex for use in dip molding, composition for use in dip molding, and dip-molded product |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2014169404A (en) | 2014-09-18 |
| JP5797681B2 (en) | 2015-10-21 |
| KR20140109318A (en) | 2014-09-15 |
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