CN103189399A - Method for producing chlorinated propylene-containing polymer - Google Patents
Method for producing chlorinated propylene-containing polymer Download PDFInfo
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- CN103189399A CN103189399A CN2012800034878A CN201280003487A CN103189399A CN 103189399 A CN103189399 A CN 103189399A CN 2012800034878 A CN2012800034878 A CN 2012800034878A CN 201280003487 A CN201280003487 A CN 201280003487A CN 103189399 A CN103189399 A CN 103189399A
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- chloroform
- chlorination
- propene polymer
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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
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
- C08F8/22—Halogenation by reaction with free halogens
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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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
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Abstract
The present invention provides a method for producing a chlorinated propylene-containing polymer, said method comprising a step wherein a propylene-containing polymer is chlorinated in a mixed liquid of a chlorine-based solvent and water. This method is an improved production method by which an object product can be obtained more efficiently than conventional methods. The present invention specifically provides a method for producing a chlorinated propylene-containing polymer, which is characterized by comprising: (1) a step 1 wherein a dispersion liquid is obtained by dispersing at least one kind of propylene-containing polymer selected from among polypropylenes and propylene-alpha-olefin copolymers in a mixed liquid that contains chloroform and water; (2) a step 2 wherein the propylene-containing polymer is chlorinated by introducing a chlorine gas into the dispersion liquid, while heating the dispersion liquid at a temperature of 130 DEG C or less in a closed system; (3) a step 3 wherein a chloroform-containing phase is separated out after adding a water-insoluble epoxy group-containing compound into the reaction liquid obtained in step 2 and leaving the resulting liquid at rest; and (4) a step 4 wherein a chlorinated propylene-containing polymer is obtained by removing chloroform from the chloroform-containing phase by distillation.
Description
Technical field
The present invention relates to a kind of manufacture method that contains propene polymer of chlorination.As the propene polymer that contains of chlorination, be representative with Chlorinated Polypropylene III and propylene dichloride-alpha-olefin copolymer, these polymkeric substance are as giving composition (binder constituents), widespread use in purposes such as coating, printing ink, binding agent to the bonding of polypropylene base.
Background technology
In the past, as the chlorination method that contains propene polymer (for example polypropylene), known has: the method, 3 of the method, 2 of 1) polypropylene being carried out chlorination in solid phase) polypropylene suspension being carried out chlorination in water) polypropylene only is dissolved in the method that chlorine series solvent (for example chloroform) carries out chlorination, and 4) polypropylene is disperseed, is dissolved in the method for carrying out chlorination in the mixed solution of chlorine series solvent (for example chloroform) and water.
Yet there are the following problems for the chlorination method of above-mentioned prior art.
Above-mentioned 1) chlorination method that suspends in the solid phase of enumerating, 2) or the water is because therefore only polypropylene top layer chlorination can not guarantee cl content morely.In addition, the chlorination position is easy to generate bias, if the high part of crystallinity remains on the polypropylene surface, even then after the chlorination, it is insufficient that the solvability in solvent also becomes easily.
Above-mentioned 3) though in the chlorination method that only uses the chlorine series solvent enumerated can guarantee cl content easily morely, but need use free radical generating agent (for example ultraviolet ray, organo-peroxide, azo based compound etc.) during owing to chlorination, therefore corresponding device, temperature treatment, stress management etc. just are absolutely necessary.Particularly, uviolizing needs specific equipment.In addition, when using organo-peroxide and azo based compound etc., need consider the temperature treatment of half life temperature, need add continuously or off and on chlorine until thermolysis takes place.In addition, from the byproduct hydrogen chloride gas that generates being released to this point outside the system, need carry out stress management, and be released to this point outside the system from chlorine as hydrogen chloride gas, the chlorine utilization ratio is not lowered with not being able to.
Above-mentioned 4) though in the mixed solution of the use chlorine series solvent enumerated and water carry out chlorination and can guarantee cl content easily morely, but there are the following problems: when hydrochloric acid is separated mutually with the chlorine series solvent mutually after the chlorination reaction, resin polarity height in the chlorine series solvent, being separated needs the more time.The example that uses the mixed solution of this chlorine series solvent and water to carry out chlorination for example is documented in patent documentation 1 and 2.
Above-mentioned 1) in the chlorination method～4), bias be difficult for to take place from the chlorination position and can guarantee the cl content this point easily morely, preferably above-mentioned 4) chlorination method.Therefore, above-mentioned 4) chlorination method in, at short notice hydrochloric acid is separated mutually with the chlorine series solvent mutually after wishing to develop a kind of chlorination reaction, thereby makes the method that contains propene polymer of chlorination more efficiently.
The prior art document
Patent documentation
Patent documentation 1: Japanese Patent Publication 37-15934 communique
Patent documentation 2: Japanese kokai publication hei 6-9718 communique (particularly [0015] section)
Summary of the invention
Invent problem to be solved
The objective of the invention is to, a kind of manufacture method that contains propene polymer of chlorination is provided, this method comprises and will contain propene polymer carries out chlorination in the mixed solution of chlorine series solvent and water operation, compare the manufacture method that this method is a kind of improvement that can obtain target compound more efficiently with existing method.
Solve the means of problem
The present inventor furthers investigate in order to achieve the above object, found that, just can achieve the above object when employing comprises the manufacture method of certain working procedure, thereby finish the present invention.
That is, the present invention relates to a kind of manufacture method that contains propene polymer of following chlorination.
1. the manufacture method that contains propene polymer of a chlorination is characterized in that, comprises the steps:
(1) contains propene polymer with at least a kind in polypropylene and the propylene-alpha-olefin copolymers and be scattered in the operation 1 that obtains dispersion liquid in the mixed solution that contains chloroform and water;
(2) airtight down, on one side with the temperature below 130 ℃ above-mentioned dispersion liquid is heated, in above-mentioned dispersion liquid, import chlorine on one side, contain the operation 2 that propene polymer carries out chlorination to above-mentioned thus;
(3) add in the reaction solution that in operation 2, obtains water-insoluble contain epoxy compounds and leave standstill after, isolate the operation 3 that contains the chloroform phase; And
(4) distill mutually and remove chloroform from the described chloroform that contains, obtain the operation that contains propene polymer 4 of chlorination thus.
2. as above-mentioned 1 described manufacture method, wherein, the described propene polymer that contains that uses in the operation 1 is isotactic polymer.
3. as above-mentioned 1 or 2 described manufacture method, wherein, the described propene polymer that contains that uses in the operation 1 is to use the metallocene series catalysts to synthesize.
4. as any described manufacture method in the above-mentioned item 1～3, wherein, the chlorine containing ratio that contains propene polymer of described chlorination is 20～40 weight %.
5. as any described manufacture method in the above-mentioned item 1～4, wherein, the chlorination in the operation 2 is to carry out under the condition of not using free radical generating agent.
6. as any described manufacture method in the above-mentioned item 1～5, wherein, the described weight ratio that contains propene polymer, chloroform and water in the described dispersion liquid is 1:8～20:0.8～2.
7. as any described manufacture method in the above-mentioned item 1～6, wherein, in the operation 2, before importing chlorine, import oxygen.
Below, manufacture method of the present invention is elaborated.
The manufacture method that contains propene polymer of chlorination of the present invention is characterised in that, comprises the steps:
(1) contains propene polymer with at least a kind in polypropylene and the propylene-alpha-olefin copolymers and be scattered in the operation 1 that obtains dispersion liquid in the mixed solution that contains chloroform and water;
(2) airtight down, on one side with the temperature below 130 ℃ above-mentioned dispersion liquid is heated, in above-mentioned dispersion liquid, import chlorine on one side, contain the operation 2 that propene polymer carries out chlorination to above-mentioned thus;
(3) add in the reaction solution that in operation 2, obtains water-insoluble contain epoxy compounds and leave standstill after, isolate the operation 3 that contains the chloroform phase; And
(4) distill mutually and remove chloroform from the described chloroform that contains, obtain the operation that contains propene polymer 4 of chlorination thus.
Has the manufacture method of the present invention of above-mentioned feature particularly in operation 3, by adding the water-insoluble epoxy compounds that contains in the reaction solution that in operation 2, obtains, can at short notice reaction solution be separated for hydrochloric phase with contain chloroform mutually, its result, just the manufacturing objective thing is the propene polymer that contains of chlorination more efficiently.
Below, manufacture method of the present invention is described respectively by each operation.
" operation 1 "
Operation 1: contain propene polymer with at least a kind in polypropylene and the propylene-alpha-olefin copolymers and be scattered in the mixed solution that contains chloroform and water and obtain dispersion liquid.
Among the present invention, contain propene polymer as raw material, use at least a kind in polypropylene and the propylene-alpha-olefin copolymers.
Propylene-alpha-olefin copolymers be based on propylene and on propylene copolymerization the material of alpha-olefin.As alpha-olefin, for example can use in ethene, 1-butylene, 1-heptene, 1-octene, the 4-methyl-1-pentene etc. a kind or several.In these alpha-olefins, optimal ethylene, 1-butylene.Ratio to the propylene composition of propylene-alpha-olefin copolymers and alpha-olefin composition is unqualified, but preferred propylene composition is 50 moles more than the %, more preferably 90 moles more than the %.
Polypropylene and propylene-alpha-olefin copolymers be preferred isotactic polymer all.Isotactic polymer demonstrates than higher degree of crystallinity, can crystallization control by chlorination.For example, when giving solvability in various organic solvents to containing propene polymer, can hang down crystallization by improving cl content.On the other hand, film when giving cohesive force to containing propene polymer, though poorly soluble in organic solvent by setting the chlorine containing ratio than the lowland, can keep high crystalline.In addition, the crystallinity of using the synthetic polypropylene of metallocene series catalysts and propylene-alpha-olefin copolymers to have homogeneous, the solvability in solvent is also very excellent, thereby preferred.In addition, polypropylene and propylene-alpha-olefin copolymers also can use commercially available product.
Among the present invention, the above-mentioned propene polymer that contains is scattered in the mixed solution that contains chloroform and water and obtains dispersion liquid.The main purpose that makes water is to absorb the byproduct hydrogen chloride that produces when operation 2 chlorinations and the manufacturing process of simplifying target compound, the consumption of water can be set according to the amount of the byproduct hydrogen chloride that produces, but be preferably set to reaction is finished after the concentration of hydrochloric acid of hydrochloric acid phase be 10～30%.Though unqualified to the weight ratio that contains propene polymer, chloroform and water in the dispersion liquid, consider these factors, preferred 1:8～20:0.8～2, more preferably 1:9～15:0.9～1.8.
" operation 2 "
Operation 2: under airtight, with temperature 130 ℃ below above-mentioned dispersion liquid heated on one side, in above-mentioned dispersion liquid, import chlorine on one side, thus the above-mentioned propene polymer that contains is carried out chlorination.
During chlorination, airtightly with the temperature below 130 ℃ dispersion liquid is heated down.Temperature is so long as just unqualified in above-mentioned scope, but from guaranteeing to contain the temperature this point that propene polymer can dissolve, the Da Wendu that is up in the preferred chlorination is 110～130 ℃, more preferably 115～125 ℃.
Among the present invention, owing to contain water in the dispersion liquid, by importing chlorine, generate oxyradical (O) in the reaction system continuously by following being reflected at, therefore can stablize and carry out chlorination to containing propene polymer efficiently.Particularly, at first by water or hydroxide ion and chlorine reaction generation hypochlorous acid, next decompose the generation oxyradical by hypochlorous acid.
H
2O+Cl
2→HClO+HCl
OH
-+Cl
2→HClO+Cl
-
HClO→HCl+O·
Therefore, owing to generate oxyradical in the reaction system of the present invention continuously, therefore need not to use known free radical generating agent (for example ultraviolet ray, organo-peroxide, azo based compound etc.), thereby when the manufacturing objective thing, can avoid owing to the problem in the past (isolated plant, temperature treatment, stress management etc.) of using free radical generating agent to bring.
When in reaction system, importing chlorine, as long as when guaranteeing air-tight state, be blown into chlorine.To the import volume of chlorine without limits, preferably become the amount of 20～40 weight % as long as can guarantee the chlorine containing ratio that contains propene polymer of chlorination.Cl content is not limited to above-mentioned scope, but preferred 20～40 weight %, more preferably 25～35 weight % among the present invention.Produce byproduct hydrogen chloride though import chlorine, because hydrogenchloride substantially all dissolves and is present in the water, therefore do not need to carry out excessive stress management etc. in the manufacture method of the present invention.In addition, owing under airtight, carry out chlorination, compared with in non-water system, carry out chlorination in the past, can guarantee the chlorine utilization ratio morely, thus preferred.
The weight-average molecular weight that contains propene polymer to the chlorination that obtains with manufacture method of the present invention is unqualified, but preferred 5000～200000.Be lower than at 5000 o'clock, cohesive force dies down and is poor to the close property of polypropylene base sometimes.On the other hand, if surpass 200000, the dissolved state variation in solvent sometimes.Preferred weight-average molecular weight is 30000～180000.Among the present invention, for the weight-average molecular weight that contains propene polymer that makes chlorination is littler, can before importing chlorine, import oxygen.By importing oxygen, generate oxyradical and cause the cut-out that contains the propene polymer molecule, weight-average molecular weight can be adjusted to littler thus.
" operation 3 "
Operation 3: add in the reaction solution that in operation 2, obtains water-insoluble contain epoxy compounds and leave standstill after, isolate and contain the chloroform phase.In addition, water-insoluble refers to the solvability less than 1 weight % in 20 ℃ of water.
Among the present invention, water-insolublely contain epoxy compounds and leave standstill by adding in the reaction solution that in operation 2, obtains, can at short notice reaction solution be separated for hydrochloric phase with contain chloroform mutually.Water-insolublely contain the compound that epoxy compounds preferably has fine water particle effect (as the effect of emulsion splitter) in the aggregation liquid, for example can enumerate: phenyl glycidyl ether, 2-aminomethyl phenyl glycidyl ether, to monocycle oxycompounds such as tert-butyl-phenyl glycidyl ether, 4-chloro-phenyl-glycidyl ether, 4-methoxyphenyl glycidyl ether, 2-xenyl glycidyl ether, 1-naphthyl glycidyl ether, 2-ethylhexyl glycidyl ether, glycidyl allyl ethers.In addition, also can enumerate: dihydroxyphenyl propane and epoxy chloropropane with various ratios carry out bisphenol type epoxy compound, Bisphenol F and epoxy chloropropane that polycondensation obtains with various ratios carry out Bisphenol F type epoxy compounds that polycondensation obtains, make epoxidised soybean oil that peroxy acid reactions such as vegetables oil with unsaturated group and Peracetic Acid obtain, epoxidised linseed oil etc.In addition, also can enumerate: Hydrogenated Bisphenol A diglycidylether, o-phthalic acid diglycidyl ester, 1, multi-functional epoxy compounds such as 6-hexanediol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether.Wherein, especially preferably to tert-butyl-phenyl glycidyl ether, bisphenol type epoxy compound etc.Unqualified to the water-insoluble addition that contains epoxy compounds, but contain propene polymer 100 weight parts, preferred 0.1～5 weight part, more preferably 0.3～2 weight part with respect to chlorination in the reaction solution.
As long as the time of repose after containing epoxy compounds and adding can fully be separated just be not particularly limited, but the present invention is preferred below 2 hours, more preferably below 1 hour.Like this, the present invention compares with manufacture method in the past, can in the obviously shorter time, be separated, thus manufacturing objective thing efficiently.
After being separated, isolating and contain chloroform layer.Among the present invention, contain the propene polymer that contains that chloroform comprises chlorination in mutually, separation method can utilize known separation method.
" operation 4 "
Operation 4: distill mutually and remove chloroform from the described chloroform that contains, obtain the propene polymer that contains of chlorination thus.
To unqualified from containing temperature condition and pressure condition that chloroform distills when removing chloroform mutually, but from preferably beginning slowly to become decompression state from the state more than the chloroform boiling point (61 ℃) in view of the efficient, preferred 15～70 ℃ of temperature, more preferably 25～65 ℃.In addition, pressure condition is preferred-0.09～0.08MPa, more preferably-0.08～0.05MPa.In addition, among the present invention, preferably remove most of chloroform by underpressure distillation after, the highly concentrated solution that contains propene polymer of chlorination is supplied in the forcing machine, when residual chloroform is removed in distillation, the propene polymer that contains of chlorination is carried out granulation and takes out.Temperature condition and pressure condition when extruding are also unqualified, but preferably begin gently to carry out charging to the low temperature high vacuum state preferred 50～150 ℃ of extruder temperature, more preferably 60～140 ℃ from the high temperature low vacuum state from the efficient of manufacture method.In addition, the forcing machine pressure condition is preferred-0.099～-0.080MPa, more preferably-0.099～-0.090MPa.
The propene polymer that contains of the chlorination that the above-mentioned operation of process obtains is soluble in all kinds of SOLVENTS such as toluene, dimethylbenzene, solvent naphtha, can be used as and gives composition to the bonding of polypropylene base, widespread use in purposes such as coating, printing ink, binding agent.
The effect of invention
Manufacture method of the present invention is particularly in operation 3, by adding the water-insoluble epoxy compounds that contains in the reaction solution that in operation 2, obtains, can at short notice reaction solution be separated for hydrochloric phase with contain chloroform mutually, its result, just the manufacturing objective thing is the propene polymer that contains of chlorination more efficiently.
Embodiment
Show that below embodiment and comparative example are described more specifically the present invention.But the present invention is not subjected to the restriction of embodiment.
Embodiment 1
In 5000L lass lining retort processed, the synthetic isotactic polyprophlene of Ziegler-Natta catalyst (Ziegler-Natta Catalyst) is used in adding, and (230 ℃ MFR is the 14g/ branch, 165 ℃ of fusing points) 300kg, chloroform 3100kg and deionized water 420kg are airtight.
Liquid in the stirred tank makes its dispersion on one side, to retort in begin heats on one side, and the speed with 80kg/ hour imports chlorine when heating.The heating but continues to import chlorine of stopped reaction jar when temperature arrives 115 ℃ in jar, a jar interior temperature remains on 95～120 ℃ by reaction heat.Pressure maximum in the retort reaches 0.6MPa.From beginning to import chlorine to the stage that has imported 276kg chlorine through 30 timesharing in 3 hours, stop to import chlorine.Continue stirred liq after 10 minutes, add the water-insoluble epoxy compounds bisphenol type epoxy compound (epoxy equivalent (weight) 189g/eq) that contains of 1.8kg.
Stop to stir, a jar interior temperature remains on 80～95 ℃ and left standstill 1 hour, and the upper strata hydrochloric acid that clearly is separated out this moment contains chloroform mutually with lower floor mutually.Lower floor is contained the chloroform phase shift deliver in the 3000L lass lining retort processed, under the condition of temperature 35～75 ℃, jar internal pressure-0.08～0.08MPa, chloroform 2000kg is removed in the part distillation in jar.
Next, the chlorinated polypropylene solution that chloroform becomes high density has been removed in distillation under 30～50 ℃, has been supplied to biaxial extruder, 60～140 ℃ of Heating temperatures, vacuum tightness-0.099～-condition of 0.093MPa under distillation remove chloroform, granulation.
The chlorine containing ratio of the Chlorinated Polypropylene III that obtains is 30.2%, and weight-average molecular weight is 180000.
Embodiment 2
Except before importing chlorine, importing 0.2kg oxygen, carry out same operation with embodiment 1.The chlorine containing ratio of the Chlorinated Polypropylene III that obtains is 30.1%, and weight-average molecular weight is 140000.
Embodiment 3
, operate equally with embodiment 1 beyond the importing 3kg oxygen except using by the isotactic propylene ethylene copolymer (propylene: ethene=97:3 mol ratio, MFR2g/ branch, 125 ℃ of fusing points) of metallocene series catalysts polymerization and before importing chlorine.The chlorine containing ratio of the Chlorinated Polypropylene III that obtains is 30.0%, and weight-average molecular weight is 95000.
Embodiment 4
Import the 440kg chlorine except the consumption with deionized water is made as 540kg and spends 5 hours 30 minutes, operate equally with embodiment 3.The chlorine containing ratio of the Chlorinated Polypropylene III that obtains is 39.7%, and weight-average molecular weight is 106000.
Embodiment 5
Import the 157kg chlorine except the consumption with deionized water is made as 270kg and spends 2 hours, operate equally with embodiment 3.The chlorine containing ratio of the Chlorinated Polypropylene III that obtains is 20.4%, and weight-average molecular weight is 92000.
Embodiment 6
Except before importing chlorine, importing 3kg oxygen, operate equally with embodiment 1.The chlorine containing ratio of the Chlorinated Polypropylene III that obtains is 30.3%, and weight-average molecular weight is 70000.
Embodiment 7
Except interpolation 1.8kg bisphenol type epoxy compound (epoxy equivalent (weight) 189g/eq) being replaced by the interpolation tert-butyl-phenyl glycidyl ether of 1.8kg (epoxy equivalent (weight) 225g/eq), operate equally with embodiment 1.After leaving standstill 1 hour, similarly to Example 1, the upper strata hydrochloric acid that clearly is separated out contains chloroform mutually with lower floor mutually.The chlorine containing ratio of the Chlorinated Polypropylene III that obtains is 30.1%, and weight-average molecular weight is 176000.
Embodiment 8
Except interpolation 1.8kg bisphenol type epoxy compound (epoxy equivalent (weight) 189g/eq) being replaced by interpolation 1.8kg trihydroxymethylpropanyltri diglycidyl ether (epoxy equivalent (weight) 150g/eq), operate equally with embodiment 1.After leaving standstill 1 hour, similarly to Example 1, the upper strata hydrochloric acid that clearly is separated out contains chloroform mutually with lower floor mutually.The chlorine containing ratio of the Chlorinated Polypropylene III that obtains is 30.3%, and weight-average molecular weight is 178000.
Comparative example 1
Do not add bisphenol type epoxy compound (epoxy equivalent (weight) 189g/eq) after in embodiment 1, importing chlorine.Its result tries to leave standstill similarly to Example 1 and carries out separating of hydrochloric acid layer and chloroform layer, still is emulsified state but spent 5 hours.
Claims (7)
1. the manufacture method that contains propene polymer of a chlorination is characterized in that, comprises following operation:
(1) contains propene polymer with at least a kind in polypropylene and the propylene-alpha-olefin copolymers and be scattered in the mixed solution that contains chloroform and water, obtain the operation 1 of dispersion liquid;
(2) airtight down, on one side with the temperature below 130 ℃ described dispersion liquid is heated, in described dispersion liquid, import chlorine on one side, contain the operation 2 that propene polymer carries out chlorination to described thus;
(3) add in the reaction solution that in operation 2, obtains water-insoluble contain epoxy compounds and leave standstill after, isolate the operation 3 that contains the chloroform phase; And
(4) distill mutually and remove chloroform from the described chloroform that contains, obtain the operation that contains propene polymer 4 of chlorination thus.
2. manufacture method as claimed in claim 1, wherein, the described propene polymer that contains that uses in the operation 1 is isotactic polymer.
3. manufacture method as claimed in claim 1 or 2, wherein, the described propene polymer that contains that uses in the operation 1 is to use the metallocene series catalysts synthetic.
4. as any described manufacture method in the claim 1～3, wherein, the chlorine containing ratio that contains propene polymer of described chlorination is 20～40 weight %.
5. as any described manufacture method in the claim 1～4, wherein, the chlorination in the operation 2 is to carry out under the situation of not using free radical generating agent.
6. as any described manufacture method in the claim 1～5, wherein, the described weight ratio that contains propene polymer, chloroform and water in the described dispersion liquid is 1:8～20:0.8～2.
7. as any described manufacture method in the claim 1～6, wherein, in the operation 2, before importing chlorine, import oxygen.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-217415 | 2011-09-30 | ||
| JP2011217415A JP5229369B2 (en) | 2011-09-30 | 2011-09-30 | Method for producing chlorinated propylene-containing polymer |
| PCT/JP2012/067169 WO2013046846A1 (en) | 2011-09-30 | 2012-07-05 | Method for producing chlorinated propylene-containing polymer |
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|---|---|
| CN103189399A true CN103189399A (en) | 2013-07-03 |
| CN103189399B CN103189399B (en) | 2014-08-27 |
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| JP (1) | JP5229369B2 (en) |
| KR (1) | KR101380019B1 (en) |
| CN (1) | CN103189399B (en) |
| TW (1) | TWI542607B (en) |
| WO (1) | WO2013046846A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106459703A (en) * | 2014-06-11 | 2017-02-22 | 东洋纺株式会社 | Polyolefin-based adhesive composition |
| CN115651102A (en) * | 2022-11-09 | 2023-01-31 | 安徽省化工研究院 | Method for coproducing chlorinated polypropylene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104024282A (en) * | 2012-02-17 | 2014-09-03 | 东洋纺株式会社 | Polymer composition containing oxidation-modifiable chlorinated propylene and method for producing same |
| CN112279946B (en) * | 2020-10-16 | 2023-09-08 | 云南正邦科技有限公司 | Method for preparing chlorinated polypropylene by micro-channel reaction and product |
| CN115232237B (en) * | 2022-06-24 | 2023-11-03 | 瑞易德新材料股份有限公司 | Preparation method of high-chlorine low-viscosity chlorinated polypropylene |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05230128A (en) * | 1992-02-18 | 1993-09-07 | Toyo Kasei Kogyo Kk | Production of chlorinated polyolefin |
| JPH069718A (en) * | 1992-06-26 | 1994-01-18 | Toyo Kasei Kogyo Co Ltd | Production of chlorinated polyolefin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2001114843A (en) * | 1999-10-13 | 2001-04-24 | Nippon Paper Industries Co Ltd | Acid modified chlorinated polyolefin having good solvent resistance |
| JP2003171597A (en) * | 2001-12-03 | 2003-06-20 | Nippon Paper Industries Co Ltd | Primer for thermoplastic saturated norbornene resin and gluing method or coating method using the same |
| JP3898636B2 (en) * | 2001-12-28 | 2007-03-28 | 日本製紙株式会社 | Binder resin composition, production method and use thereof |
| JP4987473B2 (en) * | 2004-05-31 | 2012-07-25 | 日本製紙ケミカル株式会社 | Chlorinated propylene-based random copolymer and composition containing the same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05230128A (en) * | 1992-02-18 | 1993-09-07 | Toyo Kasei Kogyo Kk | Production of chlorinated polyolefin |
| JPH069718A (en) * | 1992-06-26 | 1994-01-18 | Toyo Kasei Kogyo Co Ltd | Production of chlorinated polyolefin |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106459703A (en) * | 2014-06-11 | 2017-02-22 | 东洋纺株式会社 | Polyolefin-based adhesive composition |
| CN106459703B (en) * | 2014-06-11 | 2018-09-25 | 东洋纺株式会社 | Polyolefins adhesive composition |
| CN115651102A (en) * | 2022-11-09 | 2023-01-31 | 安徽省化工研究院 | Method for coproducing chlorinated polypropylene |
| CN115651102B (en) * | 2022-11-09 | 2024-02-06 | 安徽省化工研究院 | Method for co-production preparation of chlorinated polypropylene |
Also Published As
| Publication number | Publication date |
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| JP2013076014A (en) | 2013-04-25 |
| CN103189399B (en) | 2014-08-27 |
| TW201319105A (en) | 2013-05-16 |
| WO2013046846A1 (en) | 2013-04-04 |
| JP5229369B2 (en) | 2013-07-03 |
| TWI542607B (en) | 2016-07-21 |
| KR20130072249A (en) | 2013-07-01 |
| KR101380019B1 (en) | 2014-04-02 |
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