CN103189399B - Method for producing chlorinated propylene-containing polymer - Google Patents
Method for producing chlorinated propylene-containing polymer Download PDFInfo
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- CN103189399B CN103189399B CN201280003487.8A CN201280003487A CN103189399B CN 103189399 B CN103189399 B CN 103189399B CN 201280003487 A CN201280003487 A CN 201280003487A CN 103189399 B CN103189399 B CN 103189399B
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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 containing propene polymer of chlorination.As chlorination containing propene polymer, taking Chlorinated Polypropylene III and propylene dichloride-alpha-olefin copolymer as representative, these polymkeric substance are as the bonding of polypropylene base being given to composition (binder constituents), widespread use in the purposes such as coating, ink, binding agent.
Background technology
In the past, as for example, chlorination method containing propene polymer (polypropylene), known has: the method, 2 of 1) polypropylene being carried out to chlorination in solid phase) method, 3 of polypropylene suspension being carried out in water to chlorination) polypropylene is only dissolved in to the method that chlorine series solvent (for example chloroform) carries out chlorination, and 4) polypropylene is disperseed, is dissolved in the method for for example, carrying out chlorination in the mixed solution of chlorine series solvent (chloroform) and water.
But there are the following problems for the chlorination method of above-mentioned prior art.
Above-mentioned 1), 2) in the chlorination method that suspends in the solid phase enumerated or water due to only polypropylene top layer chlorination, therefore can not more guarantee cl content.In addition, chlorination position easily produces bias, if the high part of crystallinity remains in polypropylene surface, even after chlorination, it is insufficient that the solvability in solvent also easily becomes.
Above-mentioned 3) although in the chlorination method that only uses chlorine series solvent enumerated can easily more guarantee cl content, but during due to chlorination, need to use free radical generating agent (for example ultraviolet ray, organo-peroxide, azo based compound etc.), therefore device, temperature treatment, stress management etc. are just absolutely necessary accordingly.Particularly, uviolizing needs specific equipment.In addition, while using organo-peroxide and azo based compound etc., need to consider the temperature treatment of half life temperature, need add chlorine continuously or off and on until there is thermolysis.In addition, from the byproduct hydrogen chloride gas of generation being released to this point system, need to carry out stress management, and be released to this point system from chlorine as hydrogen chloride gas, chlorine utilization ratio is not able to be lowered.
Above-mentioned 4) although in the mixed solution of the use chlorine series solvent enumerated and water carry out chlorination and can easily more guarantee cl content, but there are the following problems: when after chlorination reaction, hydrochloric acid phase is separated mutually with chlorine series solvent, resin polarity in chlorine series solvent is high, is separated and needs the more time.The example that uses the mixed solution of this chlorine series solvent and water to carry out chlorination is for example documented in patent documentation 1 and 2.
Above-mentioned 1)～4) chlorination method in, be difficult for occurring bias and can easily more guarantee cl content this point from chlorination position, preferably above-mentioned 4) chlorination method.Therefore, above-mentioned 4) chlorination method in, at short notice hydrochloric acid phase is separated mutually with chlorine series solvent after wishing to develop a kind of chlorination reaction, thereby manufactures more efficiently the method containing propene polymer of chlorination.
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 object of the invention is to, a kind of manufacture method containing propene polymer of chlorination is provided, the method comprises the operation of carrying out chlorination containing propene polymer in the mixed solution of chlorine series solvent and water, compared with the conventional method, the manufacture method that the method is a kind of improvement that can obtain more efficiently target compound.
Solve the means of problem
The present inventor conducts in-depth research in order to achieve the above object, found that, just can achieve the above object, thereby completed the present invention in the time that employing comprises the manufacture method of certain working procedure.
, the present invention relates to a kind of manufacture method containing propene polymer of following chlorination.
1. the manufacture method containing propene polymer of chlorination, is characterized in that, comprises the steps:
(1) be scattered in containing propene polymer the operation 1 that obtains dispersion liquid in the mixed solution containing chloroform and water by least a kind in polypropylene and propylene-alpha-olefin copolymers;
(2) under airtight, with 130 DEG C of following temperature, above-mentioned dispersion liquid is heated on one side, in above-mentioned dispersion liquid, import chlorine on one side, thus to above-mentioned operation 2 of carrying out chlorination containing propene polymer;
(3) in the reaction solution obtaining in operation 2, add water-insoluble containing epoxy compounds and leave standstill after, isolate the operation 3 containing chloroform phase; And
(4) distill mutually and remove chloroform containing chloroform from described, obtain thus the operation 4 containing propene polymer of chlorination.
2. the manufacture method as described in above-mentioned 1, wherein, in operation 1, the described of use is isotactic polymer containing propene polymer.
3. the manufacture method as described in above-mentioned 1 or 2, wherein, the described propene polymer that contains using in operation 1 is to use metallocene series catalysts synthetic.
4. the manufacture method as described in any one in above-mentioned item 1～3, wherein, the chlorine containing ratio containing propene polymer of described chlorination is 20～40 % by weight.
5. the manufacture method as described in any one in above-mentioned item 1～4, wherein, the chlorination in operation 2 is to carry out under the condition that does not use free radical generating agent.
6. the manufacture method as described in any one in above-mentioned item 1～5, wherein, the described weight ratio containing propene polymer, chloroform and water in described dispersion liquid is 1:8～20:0.8～2.
7. the manufacture method as described in any one in above-mentioned item 1～6, wherein, in operation 2, importing before chlorine, imports oxygen.
Below, manufacture method of the present invention is elaborated.
The manufacture method containing propene polymer of chlorination of the present invention is characterised in that, comprises the steps:
(1) be scattered in containing propene polymer the operation 1 that obtains dispersion liquid in the mixed solution containing chloroform and water by least a kind in polypropylene and propylene-alpha-olefin copolymers;
(2) under airtight, with 130 DEG C of following temperature, above-mentioned dispersion liquid is heated on one side, in above-mentioned dispersion liquid, import chlorine on one side, thus to above-mentioned operation 2 of carrying out chlorination containing propene polymer;
(3) in the reaction solution obtaining in operation 2, add water-insoluble containing epoxy compounds and leave standstill after, isolate the operation 3 containing chloroform phase; And
(4) distill mutually and remove chloroform containing chloroform from described, obtain thus the operation 4 containing propene polymer of chlorination.
There is the manufacture method of the present invention of above-mentioned feature particularly in operation 3, water-insoluble containing epoxy compounds by adding in the reaction solution obtaining in operation 2, can at short notice reaction solution be separated into hydrochloric phase with containing chloroform phase, its result, just 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: at least a kind in polypropylene and propylene-alpha-olefin copolymers is scattered in the mixed solution containing chloroform and water and obtains dispersion liquid containing propene polymer.
In the present invention, containing propene polymer, use at least a kind in polypropylene and propylene-alpha-olefin copolymers as raw material.
Propylene-alpha-olefin copolymers be taking propylene as main body and on propylene copolymerization the material of alpha-olefin.As alpha-olefin, for example, can use in ethene, 1-butylene, 1-heptene, 1-octene, 4-methyl-1-pentene etc. a kind or several.In these alpha-olefins, optimal ethylene, 1-butylene.Propylene composition to propylene-alpha-olefin copolymers and the ratio of alpha-olefin composition do not limit, but preferably propylene composition is more than 50 % by mole, more preferably more than 90 % by mole.
Polypropylene and propylene-alpha-olefin copolymers be preferred isotactic polymer all.Isotactic polymer demonstrates higher degree of crystallinity, can crystallization control by chlorination.For example, while giving the solvability in various organic solvents to containing propene polymer, can carry out low crystallization by improving cl content.On the other hand, to containing propene polymer film while giving cohesive force, although poorly soluble in organic solvent, by setting chlorine containing ratio compared with lowland, can keep high crystalline.In addition, use the synthetic polypropylene of metallocene series catalysts and propylene-alpha-olefin copolymers to have the crystallinity of homogeneous, the solvability in solvent is also very excellent, thereby preferably.In addition, polypropylene and propylene-alpha-olefin copolymers also can use commercially available product.
In the present invention, be scattered in the mixed solution containing chloroform and water and obtain dispersion liquid containing propene polymer above-mentioned.The main purpose that makes water is to absorb the byproduct hydrogen chloride producing when operation 2 chlorinations and the manufacturing process of simplifying target compound, the consumption of water can be set according to the amount of byproduct hydrogen chloride producing, and is 10～30% but be preferably set to the concentration of hydrochloric acid that makes to have reacted rear hydrochloric acid phase.Although the weight ratio containing propene polymer, chloroform and water in dispersion liquid is not limited, consider these factors, preferably 1:8～20:0.8～2, more preferably 1:9～15:0.9～1.8.
" operation 2 "
Operation 2: under airtight, with 130 DEG C of following temperature, above-mentioned dispersion liquid is heated on one side, import chlorine on one side in above-mentioned dispersion liquid, carry out chlorination to above-mentioned containing propene polymer thus.
When chlorination, with 130 DEG C of following temperature, dispersion liquid is heated under airtight.Temperature is as long as just not limiting in above-mentioned scope, but from guaranteeing to contain the temperature this point that propene polymer can dissolve, preferably the Da Wendu that is up in chlorination is 110～130 DEG C, more preferably 115～125 DEG C.
In the present invention, owing to containing water in dispersion liquid, by importing chlorine, in reaction system, generated continuously oxyradical (O) by following reaction, therefore can stablize and carry out chlorination to containing propene polymer efficiently.Particularly, first react with chlorine and generate hypochlorous acid by water or hydroxide ion, next decompose and generate oxyradical by hypochlorous acid.
H
2O+Cl
2→HClO+HCl
OH
-+Cl
2→HClO+Cl
-
HClO→HCl+O·
Therefore, owing to generating continuously oxyradical in reaction system of the present invention, therefore for example, without using known free radical generating agent (ultraviolet ray, organo-peroxide, azo based compound etc.), thereby in the time of manufacturing objective thing, can avoid due to the problem in the past (special purpose device, temperature treatment, stress management etc.) brought of use free radical generating agent.
Import chlorine in reaction system time, as long as be blown into chlorine in guaranteeing air-tight state.Import volume to chlorine does not limit, as long as can ensure that the chlorine containing ratio containing propene polymer of chlorination preferably becomes the amount of 20～40 % by weight.Cl content is not limited to above-mentioned scope, but preferably 20～40 % by weight, more preferably 25～35 % by weight in the present invention.Produce byproduct hydrogen chloride although import chlorine, be present in water because hydrogenchloride substantially all dissolves, therefore in manufacture method of the present invention, do not need to carry out excessive stress management etc.In addition, owing to carrying out chlorination under airtight, with carried out chlorination in non-water system compared with, can more guarantee chlorine utilization ratio in the past, thereby preferably.
To not limiting containing the weight-average molecular weight of propene polymer of the chlorination obtaining by manufacture method of the present invention, but preferably 5000～200000.Lower than 5000 o'clock, cohesive force died down and is poor to the close property of polypropylene base sometimes.On the other hand, if exceed 200000, the dissolved state variation in solvent sometimes.Preferred weight-average molecular weight is 30000～180000.In the present invention, in order to make the weight-average molecular weight containing propene polymer of chlorination less, can before importing chlorine, import oxygen.By importing oxygen, generate oxyradical and cause the cut-out containing propene polymer molecule, weight-average molecular weight can be adjusted to thus less.
" operation 3 "
Operation 3: in the reaction solution obtaining in operation 2, add water-insoluble containing epoxy compounds and leave standstill after, isolate containing chloroform phase.In addition, water-insoluble refers to solvability less than 1 % by weight in 20 DEG C of water.
In the present invention, water-insoluble containing epoxy compounds standing by adding in the reaction solution obtaining in operation 2, can at short notice reaction solution be separated into hydrochloric phase with containing chloroform phase.Water-insoluble preferably have the compound of fine water particle effect (as the effect of emulsion splitter) in aggregation liquid containing epoxy compounds, 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 carry out bisphenol type epoxy compound that polycondensation obtains, Bisphenol F and epoxy chloropropane with various ratios and carry out Bisphenol F type epoxy compounds that polycondensation obtains, make the vegetables oil with unsaturated group react with peroxy acids such as Peracetic Acid the epoxidised soybean oil, the epoxidised linseed oil etc. that obtain with various ratios.In addition, also can enumerate: Hydrogenated Bisphenol A diglycidylether, o-phthalic acid diglycidyl ester, 1, the multi-functional epoxy compounds such as 6-hexanediol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether.Wherein, particularly preferably to tert-butyl-phenyl glycidyl ether, bisphenol type epoxy compound etc.The water-insoluble addition containing epoxy compounds is not limited, but with respect to chlorination in reaction solution containing propene polymer 100 weight parts, preferably 0.1～5 weight part, more preferably 0.3～2 weight part.
As long as the time of repose after adding containing epoxy compounds can fully be separated and just be not particularly limited, but the present invention is preferably below 2 hours, more preferably below 1 hour.Like this, the present invention, compared with manufacture method in the past, can be separated within the obviously shorter time, thus manufacturing objective thing efficiently.
After being separated, isolate containing chloroform layer.In the present invention, comprise in mutually containing chloroform chlorination containing propene polymer, separation method can utilize known separation method.
" operation 4 "
Operation 4: distill mutually and remove chloroform containing chloroform from described, obtain thus the propene polymer that contains of chlorination.
To not limiting from the temperature condition and the pressure condition that distill mutually while removing chloroform containing chloroform, but efficiency, preferably start slowly to become decompression state from state more than chloroform boiling point (61 DEG C), preferably 15～70 DEG C of temperature, more preferably 25～65 DEG C.In addition, pressure condition preferably-0.09～0.08MPa, more preferably-0.08～0.05MPa.In addition, in the present invention, preferably remove after most of chloroform by underpressure distillation, the highly concentrated solution containing propene polymer of chlorination is supplied in forcing machine, when residual chloroform is removed in distillation, carrying out granulation and taking out containing propene polymer chlorination.Temperature condition and pressure condition when extruding also do not limit, but preferably start gently to carry out charging to low-temperature high-vacuum state preferably 50～150 DEG C of extruder temperatures, more preferably 60～140 DEG C from high temperature low vacuum state from the efficiency of manufacture method.In addition, forcing machine pressure condition is-0.099～-0.080MPa preferably, more preferably-0.099～-0.090MPa.
Being soluble in all kinds of SOLVENTS such as toluene, dimethylbenzene, solvent naphtha containing propene polymer of the chlorination obtaining through above-mentioned operation, can be used as and give composition to the bonding of polypropylene base, widespread use in the purposes such as coating, ink, binding agent.
The effect of invention
Manufacture method of the present invention is particularly in operation 3, water-insoluble containing epoxy compounds by adding in the reaction solution obtaining in operation 2, can at short notice reaction solution be separated into hydrochloric phase with containing chloroform phase, its result, just manufacturing objective thing is the propene polymer that contains of chlorination more efficiently.
Embodiment
Show that embodiment and comparative example are described more specifically the present invention below.But the present invention is not subject to the restriction of embodiment.
embodiment 1
In 5000L lass lining retort processed, (MFR of 230 DEG C is that 14g/ divides to add the synthetic isotactic polyprophlene of use Ziegler-Natta catalyst (Ziegler-Natta Catalyst), 165 DEG C of fusing points) 300kg, chloroform 3100kg and deionized water 420kg, airtight.
Liquid in stirred tank disperses it on one side, heat on one side, and the speed with 80kg/ hour imports chlorine in heating to starting in retort.The heating but continue to import chlorine of stopped reaction tank when temperature arrives 115 DEG C in tank, the interior temperature of tank remains on 95～120 DEG C by reaction heat.Pressure maximum in retort reaches 0.6MPa.From starting to import chlorine to the stage that has imported 276kg chlorine through 30 timesharing in 3 hours, stop importing chlorine.Continue stirred liq after 10 minutes, add 1.8kg water-insoluble containing epoxy compounds bisphenol type epoxy compound (epoxy equivalent (weight) 189g/eq).
Stop stirring, in tank, temperature remains on 80～95 DEG C and leaves standstill 1 hour, and be now clearly separated out upper strata hydrochloric acid phase and lower floor are containing chloroform phase.Lower floor is delivered in 3000L lass lining retort processed containing chloroform phase shift, and in tank, under the condition of 35～75 DEG C of temperature, tank internal pressure-0.08～0.08MPa, chloroform 2000kg is removed in part distillation.
Next, distillation has been removed to the chlorinated polypropylene solution that chloroform becomes high density and at 30～50 DEG C, be supplied to biaxial extruder, chloroform, granulation are removed in distillation under the condition of 60～140 DEG C of Heating temperatures, vacuum tightness-0.099～-0.093MPa.
The chlorine containing ratio of the Chlorinated Polypropylene III obtaining is 30.2%, and weight-average molecular weight is 180000.
embodiment 2
Except importing 0.2kg oxygen, carry out same operation with embodiment 1 before importing chlorine.The chlorine containing ratio of the Chlorinated Polypropylene III obtaining is 30.1%, and weight-average molecular weight is 140000.
embodiment 3
Except using isotactic propylene ethylene copolymer by the polymerization of metallocene series catalysts (propylene: ethene=97:3 mol ratio, MFR2g/ divides, 125 DEG C of fusing points) and importing beyond 3kg oxygen importing before chlorine, carry out same operation with embodiment 1.The chlorine containing ratio of the Chlorinated Polypropylene III obtaining is 30.0%, and weight-average molecular weight is 95000.
embodiment 4
Import 440kg chlorine except the consumption of deionized water being made as to 540kg and spending 5 hours 30 points, carry out same operation with embodiment 3.The chlorine containing ratio of the Chlorinated Polypropylene III obtaining is 39.7%, and weight-average molecular weight is 106000.
embodiment 5
Import 157kg chlorine except the consumption of deionized water being made as to 270kg and spending 2 hours, carry out same operation with embodiment 3.The chlorine containing ratio of the Chlorinated Polypropylene III obtaining is 20.4%, and weight-average molecular weight is 92000.
embodiment 6
Except importing 3kg oxygen, carry out same operation with embodiment 1 before importing chlorine.The chlorine containing ratio of the Chlorinated Polypropylene III obtaining is 30.3%, and weight-average molecular weight is 70000.
embodiment 7
Add 1.8kg to tert-butyl-phenyl glycidyl ether (epoxy equivalent (weight) 225g/eq) except interpolation 1.8kg bisphenol type epoxy compound (epoxy equivalent (weight) 189g/eq) is replaced by, carry out same operation with embodiment 1.Leave standstill after 1 hour, similarly to Example 1, be clearly separated out upper strata hydrochloric acid phase and lower floor are containing chloroform phase.The chlorine containing ratio of the Chlorinated Polypropylene III obtaining is 30.1%, and weight-average molecular weight is 176000.
embodiment 8
Add 1.8kg trihydroxymethylpropanyltri diglycidyl ether (epoxy equivalent (weight) 150g/eq) except interpolation 1.8kg bisphenol type epoxy compound (epoxy equivalent (weight) 189g/eq) is replaced by, carry out same operation with embodiment 1.Leave standstill after 1 hour, similarly to Example 1, be clearly separated out upper strata hydrochloric acid phase and lower floor are containing chloroform phase.The chlorine containing ratio of the Chlorinated Polypropylene III obtaining is 30.3%, and weight-average molecular weight is 178000.
comparative example 1
Import chlorine in embodiment 1 after, do not add bisphenol type epoxy compound (epoxy equivalent (weight) 189g/eq).Its result, tries to leave standstill similarly to Example 1 and carries out separating of hydrochloric acid layer and chloroform layer, is still emulsified state but spent 5 hours.
Claims (7)
1. the manufacture method containing propene polymer of chlorination, is characterized in that, comprises following operation:
(1) at least a kind in polypropylene and propylene-alpha-olefin copolymers is scattered in the mixed solution containing chloroform and water containing propene polymer, obtains the operation 1 of dispersion liquid;
(2) under airtight, with 130 DEG C of following temperature, described dispersion liquid is heated on one side, in described dispersion liquid, import chlorine on one side, thus to described operation 2 of carrying out chlorination containing propene polymer;
(3) in the reaction solution obtaining in operation 2, interpolation is the water-insoluble containing epoxy compounds and after leaving standstill of less than 1 % by weight to the solvability of the water of 20 DEG C, isolates the operation 3 containing chloroform phase; And
(4) distill mutually and remove chloroform containing chloroform from described, obtain thus the operation 4 containing propene polymer of chlorination.
2. manufacture method as claimed in claim 1, wherein, in operation 1, the described of use is isotactic polymer containing propene polymer.
3. manufacture method as claimed in claim 1 or 2, wherein, the described propene polymer that contains using in operation 1 is to use metallocene series catalysts synthetic.
4. manufacture method as claimed in claim 1 or 2, wherein, the chlorine containing ratio containing propene polymer of described chlorination is 20～40 % by weight.
5. manufacture method as claimed in claim 1 or 2, wherein, the chlorination in operation 2 is to carry out in the situation that not using free radical generating agent.
6. manufacture method as claimed in claim 1 or 2, wherein, the described weight ratio containing propene polymer, chloroform and water in described dispersion liquid is 1:8～20:0.8～2.
7. manufacture method as claimed in claim 1 or 2, wherein, in operation 2, importing before chlorine, imports oxygen.
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| 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 CN103189399A (en) | 2013-07-03 |
| CN103189399B true CN103189399B (en) | 2014-08-27 |
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| JP (1) | JP5229369B2 (en) |
| KR (1) | KR101380019B1 (en) |
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| JPWO2013121871A1 (en) * | 2012-02-17 | 2015-05-11 | 東洋紡株式会社 | Oxidation-modified chlorinated propylene-containing polymer composition and method for producing the same |
| WO2015190411A1 (en) * | 2014-06-11 | 2015-12-17 | 東洋紡株式会社 | Polyolefin-based adhesive composition |
| 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 |
| CN115651102B (en) * | 2022-11-09 | 2024-02-06 | 安徽省化工研究院 | Method for co-production preparation of chlorinated polypropylene |
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| JPH05230128A (en) * | 1992-02-18 | 1993-09-07 | Toyo Kasei Kogyo Kk | Production of chlorinated polyolefin |
| JP3266321B2 (en) * | 1992-06-26 | 2002-03-18 | 東洋化成工業株式会社 | Method for producing chlorinated polyolefins |
| 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 |
| US7635520B2 (en) * | 2004-05-31 | 2009-12-22 | Nippon Paper Chemicals Co., Ltd. | Chlorinated propylene random copolymer and compositions containing the same |
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| KR101380019B1 (en) | 2014-04-02 |
| TWI542607B (en) | 2016-07-21 |
| CN103189399A (en) | 2013-07-03 |
| WO2013046846A1 (en) | 2013-04-04 |
| JP5229369B2 (en) | 2013-07-03 |
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