CN1334829A - Method for preparing halogenated copolymers, resulting halogenated polymers and use thereof - Google Patents
Method for preparing halogenated copolymers, resulting halogenated polymers and use thereof Download PDFInfo
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- CN1334829A CN1334829A CN 99815861 CN99815861A CN1334829A CN 1334829 A CN1334829 A CN 1334829A CN 99815861 CN99815861 CN 99815861 CN 99815861 A CN99815861 A CN 99815861A CN 1334829 A CN1334829 A CN 1334829A
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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
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
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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
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/08—Vinylidene chloride
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract
The invention concerns a method for preparing halogenated copolymers by copolymerising at least two monomers, whereby copolymerisation is carried out in an aqueous dispersion, on the intervention of a primer whereof a fraction is introduced in the polymerisation charge and the introduction of the other fraction is delayed. The resulting halogenated copolymers are copolymers with a melting temperature determined by differential thermoanalysis not more than 140 DEG C and a relative viscosity, measured at a concentration of 10 g/l in tetrahydrofurane, not less than 1.30. Said copolymers can be used for making extruded articles.
Description
The present invention relates to a kind of preparation method of halogenated copolymers, relate to resulting halogenated copolymers, relate to it and be used to prepare the purposes of extrudate and the extrudate that obtains thus.
Usually, vinylidene chloride copolymer, is all introduced all initiators when polymerization begins in described method by the preparation of aqueous dispersion polymerization method.This method needs quite high polymerization temperature usually, and this will make the multipolymer of producing have low thermostability.
In addition, vinylidene chloride has dystectic relatively characteristics usually, and this will be referred to very high processing temperature.Moreover these halogenated copolymers have low relatively thermostability and limited snappiness.Describe the low relatively thermostability of its characteristic, will make the settling that forms a large amount of degradation materials on its die head that in implementation process, uses.
Therefore, one object of the present invention relates to a kind of method that is used to prepare the halogenated copolymers that does not have the shortcoming that art methods brings.
Purpose of the present invention also relates to the halogenated copolymers that does not have prior art halogenated copolymers shortcoming.
Purpose of the present invention also relates to the purposes of these halogenated copolymers.
Purpose of the present invention also relates to the goods that multipolymer according to the present invention obtains.
For this reason, the present invention at first relates to a kind of method for preparing halogenated copolymers at least by making two kinds of monomeric copolymerizations, and in the method, copolymerization utilizes initiator to carry out in water dispersion, wherein a part of initiator is introduced in the polymerization charge, and the follow-up introducing of another part.
For the present invention, wording " introduce part in polymerization charge " is used for expression: from polymerization, introduce the part of initiator total amount with the batching of introducing simultaneously usually.
For the present invention, wording " follow-up introducing part " is used for representing: begin the back certain hour in polymerization, introduce the part of initiator total amount.
The time that the time that begins follow-up introducing initiator is normally finished by the initiator initiated polymerization of introducing in the polymerization charge.Usually, beginning follow-up introducing initiator is beginning between 10 to 60 minutes after polymerization begins.
In general, follow-up introducing initiator after polymerization begins at least 10 minutes preferably at least 15 minutes, especially preferably at least 20 minutes, most preferably begins at least 25 minutes the time.Usually, follow-up introducing initiator is no more than 60 minutes after polymerization begins, preferably be no more than 50 minutes, especially preferably is no more than 45 minutes, begins when being most preferably not exceeding 40 minutes.
Usually, follow-up injection part can once be introduced or introduce in batches or introduce continuously with single part.Preferably introduce continuously.
The follow-up introducing time cycle of carrying out initiator is usually from 60-600 minute.
Usually, the time cycle of carrying out the follow-up introducing of initiator was at least 60 minutes, and preferably at least 100 minutes, especially preferably at least 150 minutes.Usually, the time cycle of carrying out the follow-up introducing of initiator is not more than 600 minutes, preferably is no more than 500 minutes, especially preferably is no more than 400 minutes.
Advantageously, promoting agent is added in the initiator.
Usually, the promoting agent of total amount is introduced in the polymerization charge.Usually the part of promoting agent total amount is introduced in the polymerization charge, and the follow-up introducing of another part.
Usually, promoting agent consumption and the ratio between the initiator amount from 1 to 10 in the introducing polymerization charge.
Usually, introduce promoting agent consumption in the polymerization charge and the ratio between the initiator amount, be preferably greater than or equal 2, and particularly preferably be more than or equal to 3 more than or equal to 1.Usually, the ratio between the initiator amount in promoting agent consumption and the introducing polymerization charge is less than or equal to 10, preferably is less than or equal to 9.5, especially preferably is less than or equal to 9.
The promoting agent consumption of common follow-up introducing and the ratio between the initiator amount are from 0-10.
Usually, the promoting agent consumption of follow-up introducing and the ratio between the initiator amount be more than or equal to 0, is preferably greater than or equals 1, is preferably greater than especially or equals 2.Usually, the promoting agent consumption of follow-up introducing and the ratio between the initiator amount are less than or equal to 10, preferably are less than or equal to 9, especially preferably are less than or equal to 8.
Usually, promoting agent and the ratio of introducing between promoting agent in introducing polymerization charge and initiator part and polymerization period between the initiator total amount from 10% to 80%.
Usually, promoting agent of introducing between the promoting agent in introducing polymerization charge and initiator part and polymerization period and the ratio between the initiator total amount are less than or equal to 80%, preferably are less than or equal to 60%, especially preferably are less than or equal to 50%.
Usually, promoting agent of introducing between the promoting agent in introducing polymerization charge and initiator part and polymerization period and the ratio between the initiator total amount be more than or equal to 10%, is preferably greater than or equals 15%, is preferably greater than especially or equals 20%.
Usually, polymerization temperature is less than or equal to 60 ℃, preferably is less than or equal to 55 ℃, especially preferably is less than or equal to 50 ℃.
Usually, polymerization time is less than or equal to 16 hours, preferably is less than or equal to 14 hours, especially preferably is less than or equal to 12 hours, most preferably is less than or equal to 10 hours.
Advantageously, when polymerization begins, all monomers that participate in copolymerization are all introduced in the polymerization charge.
When principal monomer was halogenated monomer, preparation was suitable according to the method for halogenated copolymers of the present invention, and when principal monomer was chloride monomer, this method was specially suitable, and this method is the most suitable when principal monomer is vinylidene chloride.
For the present invention, wording " principal monomer " is used for representing: the ratio that accounts in the multipolymer that forms is at least 50% weight.
For the present invention, wording " halogenated copolymers " is used for representing: by halogenated monomer and one or more multipolymers that can obtain with the monomeric water dispersion radical polymerization of its copolymerization; Described halogenated monomer is a principal monomer.
For the present invention, wording " halogenated monomer " is used for expression: comprise terminal olefine degree of unsaturation not and the monomer of any free redical polymerization of being replaced by at least one halogen atom.Preferably, these monomers are selected from: the ethene of replacement and the derivative of propylene and only comprise two or three carbon atoms respectively.As the example of described monomer indefiniteness, what can mention is: vinylchlorid, vinylidene chloride, bromine ethene, sym-dibromoethane, vinyl fluoride, vinylidene fluoride, trifluoro-ethylene, tetrafluoroethylene, chlorotrifluoroethylene and R 1216 partially.
These can with the monomer of halogenated monomer copolymerization in, the indefiniteness example that can mention is: halogenated monomer of different nature, vinyl acetate is vinyl-acetic ester for example, vinyl ether, vinylformic acid, ester and acid amides, methacrylic acid, ester and acid amides, vinylbenzene, styrene derivatives, divinyl, alkene is ethene and propylene for example, methylene-succinic acid and maleic anhydride.
Preparation is particularly useful for making chlorine-containing copolymer according to the method for halogenated copolymers of the present invention.
For the present invention, wording " chlorine-containing copolymer " is used for representing: by chloride monomer and the multipolymer that can obtain with one or more monomeric water dispersion radical polymerizations of its copolymerization, described chloride monomer is main halogenated monomer, for example vinylchlorid and vinylidene chloride.
Can with the monomer of chloride monomer copolymerization in, the indefiniteness example that can mention comprises: chloride monomer of different nature, vinyl acetate is vinyl-acetic ester for example, Vinyl Ether, vinylformic acid, ester and acid amides, methacrylic acid, ester and acid amides, vinylbenzene, styrene derivatives, divinyl, alkene is ethene and propylene for example, methylene-succinic acid and maleic anhydride.
The preparation method of halogenated copolymers of the present invention is best suited for the preparation vinylidene chloride copolymer.
For the present invention, wording " vinylidene chloride copolymer " be used for representing vinylidene chloride and can with one or more monomeric multipolymers of its copolymerization, described vinylidene chloride is a principal monomer.
Can with the monomer of vinylidene chloride copolymerization in, the indefiniteness example that can mention comprises: vinylchlorid, vinyl acetate is vinyl-acetic ester for example, Vinyl Ether, vinylformic acid, ester and acid amides, methacrylic acid, ester and acid amides, vinylbenzene, styrene derivatives, divinyl, alkene is ethene and propylene for example, methylene-succinic acid and maleic anhydride.
When monomer is a vinylidene chloride, vinylchlorid and during corresponding at least a (methyl) Acrylic Acid Monomer of following formula, the most suitable according to the preparation method of halogenated copolymers of the present invention.
CH
2=CR
1R
2R in the formula
1Be selected from hydrogen and methyl group, R
2Be selected from-the CN group and-CO-OR
3Group, R in the formula
3Be selected from hydrogen, contain the alkyl group of 1-18 carbon atom, contain altogether 1-10 carbon atom alkoxy-alkyl group and-NR
4R
5Group, R in the formula
4And R
5Be selected from hydrogen and the alkyl group that contains 1-10 carbon atom.
For the present invention, wording " at least a (methyl) Acrylic Acid Monomer " is used for representing: vinylidene chloride copolymer can comprise one or more (methyl) Acrylic Acid Monomers, represents with (methyl) Acrylic Acid Monomer hereinafter.
(methyl) Acrylic Acid Monomer is preferably selected from acrylate and the methacrylic ester that contains 1-8 carbon atom, particularly preferably is to be selected from acrylate and the methacrylic ester that contains 1-6 carbon atom.
The example of particularly preferred acrylate and methacrylic ester is: methyl acrylate, methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-BMA, isobutyl acrylate, Propenoic acid, 2-methyl, isobutyl ester, tert-butyl acrylate, methacrylic tert-butyl acrylate, vinylformic acid n-pentyl ester, the methacrylic acid n-pentyl ester, the vinylformic acid isopentyl ester, the just own ester of methacrylic isoamyl valerate, vinylformic acid, the just own ester of methacrylic acid, vinylformic acid 2-methyl pentyl ester and methacrylic acid 2-methyl pentyl ester.
Most preferably, (methyl) Acrylic Acid Monomer is selected from acrylate and the methacrylic ester that contains 1-4 carbon atom.
The example of highly preferred described acrylate and methacrylic ester is: methyl acrylate, methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-BMA, isobutyl acrylate, Propenoic acid, 2-methyl, isobutyl ester, tert-butyl acrylate and methacrylic tert-butyl acrylate.
In this case, vinylidene chloride is a principal monomer.Usually, the ratio that accounts in the multipolymer that forms of this vinylidene chloride is at least 50% weight.
Usually, the content of vinylidene chloride in vinylidene chloride copolymer from 50% to 95% weight, preferably from 60% to 95% weight, especially preferably from 70% to 95% weight.
Usually, the content of vinylchlorid in vinylidene chloride copolymer from 3% to 50% weight, preferably from 3% to 40% weight, especially preferably from 4.5% to 30% weight.
Usually, the content of (methyl) Acrylic Acid Monomer in vinylidene chloride copolymer from 0.5% to 20% weight, preferably from 1% to 10% weight, especially preferably from 1.5% to 4.5% weight.
Preferably, when polymerization began, with all vinylidene chlorides, vinylchlorid and (methyl) Acrylic Acid Monomer were introduced in the polymerization charge.
For the present invention, wording " water dispersion copolymerization " is used for expression: the radical copolymerization in the water dispersion, also represent radical copolymerization in the water miscible liquid and the copolymerization in the water fine suspension.
For the present invention, wording " aqeous suspension radical copolymerization " is used for representing: any radical copolymerization method of carrying out in water-bearing media in the presence of oil soluble radical initiator and dispersion agent.
For the present invention, wording " water miscible liquid radical copolymerization " is used for representing: any radical copolymerization method of carrying out in water-bearing media in the presence of radical initiator and emulsifying agent.
For the present invention, wording " copolymerization in the water fine suspension ", also be referred to as the copolymerization of homogenizing water dispersion, be used for representing any radical copolymerization method, wherein, use the emulsion of oil-soluble initiator and monomer droplet to make by mechanical stirring violent in the presence of emulsifying agent.
By the water miscible liquid copolymerization, the method according to this invention is particularly useful for making halogenated copolymers.Therefore, utilize emulsifying agent to carry out copolymerization, the consumption of described emulsifying agent is known to those skilled in the art.
The example of the emulsifying agent that can mention comprises: anionic emulsifier and nonionic emulsifying agent.In anionic emulsifier, the indefiniteness example that can mention is: paraffin sulfonate, and alkyl-sulphate, alkylsulfonate, alkylaryl one-or stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate and salts of alkyl sulfosuccinates salt.In nonionic emulsifying agent, the indefiniteness example that can mention is: alkyl-or the alkylaryl ethoxylated derivative.
The example of the water soluble starter that can mention comprises: water-soluble peroxide, and as ammonium persulphate or alkali metal persulphate, hydrogen peroxide, peroxyboric acid and tert-butyl hydroperoxide.
The promoting agent that can mention comprises: independent saccharosonic acid; Or itself and iron nitrate, ammonium sulphite or alkali metal sulfite or metabisulfite, hydrazine, azanol, mercaptan, the mixture of Sulfothiorine and iron or mantoquita.
Preferably, promoting agent is selected from the mixture of saccharosonic acid and saccharosonic acid and iron nitrate, and initiator is a hydrogen peroxide.
Preferably, promoting agent is selected from S-WAT or Sodium Pyrosulfite, and initiator is selected from ammonium persulphate or alkali metal persulphate.
In addition, the invention still further relates to fusing point and be less than or equal to 140 ℃, relative viscosity more than or equal to 1.30 halogenated copolymers; Described fusing point is measured by differential thermal analysis, and relative viscosity is to measure during 10g/l concentration in tetrahydrofuran (THF).
The fusing point of measuring by differential thermal analysis of multipolymer according to the present invention is usually less than or equals 140 ℃, preferably is less than or equal to 130 ℃, especially preferably is less than or equal to 125 ℃.
The relative viscosity of multipolymer according to the present invention when 10g/l concentration (in tetrahydrofuran (THF) measure) is usually more than or equal to 1.30, is preferably greater than or equals 1.35.
Advantageously, 20 ℃ temperature more than fusing point, when on kneader, measuring, the mixture of multipolymer of the present invention and 4% weight ethoxylation soybean oil also has thermostability, steady time was more than or equal to 16 minutes, be preferably greater than or equal 20 minutes, be preferably greater than especially or equal 24 minutes.
For the present invention, wording " halogenated copolymers " is used for expression: by the halogenated monomer (being referred to as main halogenated monomer) and the multipolymer that can obtain with one or more monomeric water dispersion radical polymerizations of its copolymerization.
For the present invention, wording " main halogenated monomer " is used for representing: the ratio that described halogenated monomer accounts in the halogenated copolymers that forms is at least 50% weight.
For the present invention, wording " halogenated monomer " is used for expression: comprise terminal olefine degree of unsaturation not and the monomer of any free redical polymerization of being replaced by at least one halogen atom.Preferably, these monomers are selected from: the ethene of replacement and the derivative of propylene and only comprise two or three carbon atoms respectively.As the example of described monomer indefiniteness, what can mention is: vinylchlorid, vinylidene chloride, bromine ethene, sym-dibromoethane, vinyl fluoride, vinylidene fluoride, trifluoro-ethylene, tetrafluoroethylene, chlorotrifluoroethylene and R 1216 partially.
These can with the monomer of halogenated monomer copolymerization in, the indefiniteness example that can mention is: halogenated monomer of different nature, vinyl acetate is vinyl-acetic ester for example, vinyl ether, vinylformic acid, ester and acid amides, methacrylic acid, ester and acid amides, vinylbenzene, styrene derivatives, divinyl, alkene is ethene and propylene for example, methylene-succinic acid and maleic anhydride.
Halogenated copolymers is preferably chlorine-containing copolymer, more preferably vinylidene chloride copolymer.
For the present invention, wording " chlorine-containing copolymer " is used for representing: by chloride monomer and the multipolymer that can obtain with one or more monomeric water dispersion radical polymerizations of its copolymerization, described chloride monomer is vinylchlorid and vinylidene chloride for example.In this case, chloride monomer is a principal monomer, and promptly the ratio that accounts in the multipolymer that forms of this monomer is at least 50% weight.
Can with the monomer of chloride monomer copolymerization in, the indefiniteness example that can mention comprises: chloride monomer of different nature, vinyl acetate is vinyl-acetic ester for example, Vinyl Ether, vinylformic acid, ester and acid amides, methacrylic acid, ester and acid amides, vinylbenzene, styrene derivatives, divinyl, alkene is ethene and propylene for example, methylene-succinic acid and maleic anhydride.
For the present invention, wording " vinylidene chloride copolymer " be used for representing vinylidene chloride and can with one or more monomeric multipolymers of its copolymerization.In this case, vinylidene chloride is main monomer, and promptly the ratio that accounts in the multipolymer that forms of this monomer is at least 50% weight.
Can with the monomer of vinylidene chloride copolymerization in, the indefiniteness example that can mention comprises: vinylchlorid, vinyl acetate is vinyl-acetic ester for example, Vinyl Ether, vinylformic acid, ester and acid amides, methacrylic acid, ester and acid amides, vinylbenzene, styrene derivatives, divinyl, alkene is ethene and propylene for example, methylene-succinic acid and maleic anhydride.
Particularly preferred multipolymer is vinylidene chloride and vinylchlorid and randomly at least a multipolymer corresponding to following formula (methyl) Acrylic Acid Monomer:
CH
2=CR
1R
2R in the formula
1Be selected from hydrogen and methyl group, R
2Be selected from-the CN group and-CO-OR
3Group, R in the formula
3Be selected from hydrogen, contain the alkyl group of 1-18 carbon atom, contain altogether 1-10 carbon atom alkoxy-alkyl group and-NR
4R
5Group, R in the formula
4And R
5Be selected from hydrogen and the alkyl group that contains 1-10 carbon atom.
(methyl) Acrylic Acid Monomer is preferably selected from acrylate and the methacrylic ester that contains 1-8 carbon atom, particularly preferably is to be selected from acrylate and the methacrylic ester that contains 1-6 carbon atom.
The example of particularly preferred acrylate and methacrylic ester is: methyl acrylate, methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-BMA, isobutyl acrylate, Propenoic acid, 2-methyl, isobutyl ester, tert-butyl acrylate, methacrylic tert-butyl acrylate, vinylformic acid n-pentyl ester, the methacrylic acid n-pentyl ester, the vinylformic acid isopentyl ester, the just own ester of methacrylic isoamyl valerate, vinylformic acid, the just own ester of methacrylic acid, vinylformic acid 2-methyl pentyl ester and methacrylic acid 2-methyl pentyl ester.
Most preferably, (methyl) Acrylic Acid Monomer is selected from acrylate and the methacrylic ester that contains 1-4 carbon atom.
The example of highly preferred acrylate and methacrylic ester is: methyl acrylate, methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-BMA, isobutyl acrylate, Propenoic acid, 2-methyl, isobutyl ester, tert-butyl acrylate and methacrylic tert-butyl acrylate.
In this case, vinylidene chloride is main monomer.
Usually, the content of vinylidene chloride in vinylidene chloride copolymer from 50% to 95% weight, preferably from 60% to 95% weight, especially preferably from 70% to 95% weight.
Usually, the content of vinylchlorid in vinylidene chloride copolymer from 3% to 50% weight, preferably from 3%-40% weight, especially preferred from 4.5% to 30% weight.
Usually, the content of (methyl) Acrylic Acid Monomer in vinylidene chloride copolymer from 0.5% to 20% weight, preferably from 1% to 10% weight, especially preferably from 1.5% to 4.5% weight.
The invention still further relates to the halogenated copolymers that obtains by method of the present invention.
The invention still further relates to the purposes that halogenated copolymers according to the present invention is used to produce extrudate, block film for example diaxial orientation or blowing, single or multiple lift, the single or multiple lift pipe, the single or multiple lift sheet material and by extrusion laminate to polymeric substrate (polyvinyl chloride, polyethylene terephthalate or polypropylene) or extrusion laminate to paper and the sheet material that makes.
The invention still further relates to the extrudate that utilizes halogenated copolymers preparation of the present invention.These goods are generally used for (for example medicinal blister plastic wrapping) in food product pack field and the medicine field.
With regard to the chlorine monomer distribution, multipolymer according to the present invention is better than equally distributed known multipolymer.Unexpected is that multipolymer according to the present invention is characterised in that: its fusing point is starkly lower than the fusing point of known multipolymer.Because this performance, multipolymer of the present invention can use under lower temperature, and this enables to obtain higher yield and do not need to add stablizer when implementing.In addition, multipolymer of the present invention will have following characteristics: compare the thermostability with improvement and the snappiness of improvement with the multipolymer of prior art.When using multipolymer of the present invention, on used die head, do not observe the deposition of degradation material, and obtained the product of fine quality.In addition, multipolymer of the present invention also has the advantage more compatible with additive.
The following examples are used for illustrating the present invention, yet the present invention is not limited in the scope of embodiment.
The preparation of embodiment 1-halogenated copolymers
At first, 21.7 liters of softening waters addings are equipped with in 40 liters the reactor of impeller agitator.Then, under the stirring of 120rpm, introduce 112g Sodium dodecylbenzene sulfonate, 11520g vinylidene chloride, 3840g vinylchlorid and 640g ethyl propenoate.Temperature of reactor is risen to 40 ℃.When temperature reaches 40 ℃, add 0.8g hydrogen peroxide and 5.12g saccharosonic acid.After 30 minutes, in about 300 minutes time cycle, introduce 3.864g saccharosonic acid and 0.96g hydrogen peroxide continuously.The beginning polymerization after five hours 30 minutes, make reactor return to normal atmosphere, and placed 45 ℃ of vacuum 3 hours.Then, be cooled to room temperature.Transformation efficiency is 91%.
The alum liquor adding of 41.1 liters of 0.2g/l is equipped with in 150 liters the container of impeller agitator.With about 200rpm container is stirred then and with temperature regulation to 10-14 ℃.Then, with 5 liters of solution that contain 1.3g/1 Tai-Ace S 150, in about 30 minutes time, add all water dispersions that obtain.The temperature of container is risen to 70 ℃ and kept 1 hour 30 minutes.Then container is cooled to room temperature.So obtain slurries.In two steps these slurries are carried out drying.The first step is: at Escher Wyss
Gu carry out liquid/separation in the system, to form a filter cake.Second step was: utilize about 60 ℃ air that enters, in M ü nster type fluidized-bed filter cake is carried out drying.The result has obtained volatile matter content and has been lower than 0.3% halogenated copolymers.Volatile matter content is by to after stopping in 120 ℃ draft furnace 45 minutes, and the mass loss of sample is measured and determined.
The performance of embodiment 2-halogenated copolymers
The various performances of the halogenated copolymers that measurement embodiment 1 obtains.These performances are relative viscosities, Young's modulus under the fusing point, tension force and thermostability.
Relative viscosity is to utilize Ubbelohde (Ubbelohde) viscometer of constant K about 0.003, in 20 ℃ of measurements.Employed solvent is a tetrahydrofuran (THF).The concentration of halogenated copolymers solution in tetrahydrofuran (THF) is 10g/l.
Fusing point is to utilize Perkin Elmer
Differential thermal analyzer is measured.Use 18 milligrams of resins, heating rate is 10 ℃/minute.
Young's modulus under the tension force is to extrude on the monolithic at 30 microns non-diaxial orientation to measure according to IS0 standard 527.For this reason, utilize Brabender
Extruding machine (sheath of 19mm and length-to-diameter ratio be housed be 20 screw rod, and by Duranickel
200 * 0.5mm template die head that material is made), multipolymer and the 4% weight Edenol that embodiment 1 is obtained
The mixture of D82 ethoxylation soybean oil is extruded.Then, utilize Brabender
Rolling press is made 30 microns sheet material.
The multipolymer and the 4% weight Edenol that obtain according to embodiment 1
The mixture of D82 ethoxylation soybean oil is measured thermostability.For this reason, the 960g halogenated copolymers is introduced in the planetary-type mixer that K shape blade is housed that rotates with the speed of about 60rpm.When temperature reached 35 ℃, adding was preheated to 55 ℃ Edenol
D82 ethoxylation soybean oil 40g.When temperature reaches 70 ℃, pour into mixture in the stainless cylinder of steel and be cooled to room temperature.20 ℃ temperature more than the multipolymer fusing point, the thermostability of measurement mixture in mixing tank. for this reason,, 95 gram mixtures are introduced the Brabender that has jar by funnel
Plasti Corder
In the N50 type mixing tank, described jar by Hastelloy
The C276 material is made, and volume is 60cm
3The speed of rotation of mixing tank is 50rpm.Per 3 minutes, take out pellet monitoring color.In addition, with time be the torque of function record (newton. rice).Determine thermostability by this torque slope change in time.This slope changes the color change that is equivalent to pellet usually.
For the relative viscosity that the halogenated copolymers that obtains among the embodiment 1 records, fusing point, Young's modulus and thermostability value are summarized in the Table I under the tension force.
The preparation of embodiment 3-halogenated copolymers
At first, 21.76 liters of softening waters are added in 40 liters the reactor that impeller agitator is housed.Then, under the stirring of 120rpm, introduce 112 gram Sodium dodecylbenzene sulfonatees, 11520 gram vinylidene chlorides, 3840 gram vinylchlorid and 320 gram ethyl propenoates and 320 gram n-butyl acrylates.Then, temperature of reactor is risen to 40 ℃.When temperature reaches 40 ℃, add 0.8 gram hydrogen peroxide and 5.12 gram saccharosonic acids.After 30 minutes, in about 300 minutes time, add 4.048 gram saccharosonic acids and 1.056 gram hydrogen peroxide continuously.After the beginning polymerization six hours 20 minutes, make reactor return to normal atmosphere and in vacuum, placed 3 hours at 45 ℃.Then, it is cooled to room temperature.Transformation efficiency is 89%.
The alum liquor adding of 20 liters of 0.2g/l is equipped with in 150 liters the container of impeller agitator.Then, with about 200rpm container is stirred and with temperature regulation to 10-14 ℃.Then, with 0.7 liter of softening water and 5 liters of solution that contain 2.1g Tai-Ace S 150, in about 30 minutes clock times, add all water dispersions that obtain.Then the temperature of container is risen to 70 ℃ and kept 1 hour 30 minutes.Container is cooled to room temperature.So obtain slurries.In two steps these slurries are carried out drying.The first step is: at Escher Wyss
Gu carry out liquid/separation in the system, to form a filter cake.Second step was: utilize about 60 ℃ air that enters, in M ü nster type fluidized-bed filter cake is carried out drying.The result has obtained volatile matter content and has been lower than 0.3% halogenated copolymers.Volatile matter content is by to after stopping in 120 ℃ draft furnace 45 minutes, and the mass loss of sample is measured and determined.
The performance of embodiment 4-halogenated copolymers
With the method identical with embodiment 2, to the relative viscosity of the halogenated copolymers that obtains among the embodiment 3, Young's modulus and thermostability under the fusing point, tension force are measured.
The result of all these measurements is summarized in the Table I.
Table I
| Embodiment | Relative viscosity | Fusing point | Young's modulus under the tension force | Thermostability (fusing point+20 ℃) |
| ????2 | ????1.65 | 117℃ | ????286MPa | ＞25 minutes |
| ????4 | ????1.66 | 118℃ | ????296MPa | ＞30 minutes |
Claims (21)
1. one kind prepares the method for halogenated copolymers by at least two kinds of monomeric copolymerizations, and it is characterized in that: copolymerization is carried out in utilizing the water dispersion of initiator, and wherein a part of initiator is introduced in the polymerization charge, and the follow-up introducing of another part.
2. according to the method for preparing halogenated copolymers of claim 1, it is characterized in that promoting agent is added in the initiator.
3. according to the method for preparing halogenated copolymers of claim 2, it is characterized in that introducing the ratio from 1 to 10 between the amount of the amount of the promoting agent in the polymerization charge and initiator.
4. according to each the method for preparing halogenated copolymers of claim 2-3, it is characterized in that the ratio from 0 to 10 between the amount of the amount of the promoting agent in the follow-up introducing polymerization charge and initiator.
5. according to each the method for preparing halogenated copolymers of claim 2-4, it is characterized in that introducing the ratio from 10% to 80% between the total amount of the promoting agent introduced between promoting agent in the polymerization charge and initiator part and polymerization period and initiator.
6. according to each the method for preparing halogenated copolymers of claim 1-5, it is characterized in that polymerization temperature is less than or equal to 60 ℃.
7. according to each the method for preparing halogenated copolymers of claim 1-6, it is characterized in that polymerization time is less than or equal to 16 hours.
8. according to each the method for preparing halogenated copolymers of claim 1-7, it is characterized in that, all monomers are introduced in polymerization charge.
9. the method for preparing halogenated copolymers according to Claim 8 is characterized in that principal monomer is chloride monomer.
10. each the method for preparing halogenated copolymers is characterized in that principal monomer is a vinylidene chloride according to Claim 8-9.
11. each the method for preparing halogenated copolymers is characterized in that described monomer is a vinylidene chloride according to Claim 8-10, vinylchlorid and at least a (methyl) Acrylic Acid Monomer corresponding to following formula:
CH
2=CR
1R
2R in the formula
1Be selected from hydrogen and methyl group, R
2Be selected from-the CN group and-CO-OR
3Group, R in the formula
3Be selected from hydrogen, contain the alkyl group of 1-18 carbon atom, contain altogether 1-10 carbon atom alkoxy-alkyl group and-NR
4R
5Group, R in the formula
4And R
5Be selected from hydrogen and the alkyl group that contains 1-10 carbon atom.
12. the method for preparing halogenated copolymers according to claim 11 is characterized in that, (methyl) Acrylic Acid Monomer is selected from acrylate and the methacrylic ester that contains 1-8 carbon atom.
13., it is characterized in that copolymerization carries out in water miscible liquid according to each the method for preparing halogenated copolymers of claim 1-12.
14. halogenated copolymers is characterized in that, when measuring by differential thermal analysis, its fusing point is less than or equal to 140 ℃, and relative viscosity is more than or equal to 1.30 when measuring with the concentration of 10g/l in furans.
15. the halogenated copolymers according to claim 14 is characterized in that, 20 ℃ temperature more than fusing point, and when measuring on mixing tank, the mixture of itself and 4% weight ethoxylation soybean oil has thermostability, and steady time was more than or equal to 16 minutes.
16., it is characterized in that they are chlorine-containing copolymers according to each halogenated copolymers of claim 14-15.
17., it is characterized in that they are vinylidene chloride copolymers according to each halogenated copolymers of claim 14-16.
18., it is characterized in that they are vinylidene chloride and vinylchlorid and dispensable at least a multipolymer corresponding to following formula (methyl) Acrylic Acid Monomer according to each halogenated copolymers of claim 14-17:
CH
2=CR
1R
2R in the formula
1Be selected from hydrogen and methyl group, R
2Be selected from-the CN group and-CO-OR
3Group, R in the formula
3Be selected from hydrogen, contain the alkyl group of 1-18 carbon atom, contain altogether 1-10 carbon atom alkoxy-alkyl group and-NR
4R
5Group, R in the formula
4And R
5Be selected from hydrogen and the alkyl group that contains 1-10 carbon atom.
19. the halogenated copolymers according to claim 18 is characterized in that, (methyl) Acrylic Acid Monomer is selected from acrylate and the methacrylic ester that contains 1-8 carbon atom.
20. the purposes that is used to produce extrudate according to each halogenated copolymers of claim 14-19.
21. extrudate is characterized in that, they are according to each halogenated copolymers preparation of claim 14-19.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE9800870 | 1998-12-02 | ||
| BE9800870A BE1013023A3 (en) | 1998-12-02 | 1998-12-02 | Process for the preparation of copolymers halogenated, halogenated copolymers obtained and use thereof. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1334829A true CN1334829A (en) | 2002-02-06 |
Family
ID=3891550
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99815861 Pending CN1334829A (en) | 1998-12-02 | 1999-11-30 | Method for preparing halogenated copolymers, resulting halogenated polymers and use thereof |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP1141053A1 (en) |
| JP (1) | JP2002531604A (en) |
| CN (1) | CN1334829A (en) |
| AU (1) | AU1779000A (en) |
| BE (1) | BE1013023A3 (en) |
| BR (1) | BR9915887A (en) |
| CA (1) | CA2353881A1 (en) |
| MX (1) | MXPA01005500A (en) |
| WO (1) | WO2000032660A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104619769A (en) * | 2012-10-01 | 2015-05-13 | 株式会社吴羽 | Vinylidene chloride-based copolymer resin composition and molded product thereof |
| JP6795350B2 (en) * | 2016-08-08 | 2020-12-02 | 株式会社クレハ | A vinylidene chloride-based resin film, a wrap film using the same, and a method for producing the resin film. |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1645385A1 (en) * | 1965-09-23 | 1970-09-24 | Scott Bader Co | Process for the preparation of a copolymer by emulsion polymerization of vinylidene chloride and one or more acrylic esters |
| JPS5647414A (en) * | 1979-09-28 | 1981-04-30 | Kureha Chem Ind Co Ltd | Production of polyvinylidene chloride latex |
| EP0242234B1 (en) * | 1986-04-18 | 1992-01-15 | Kureha Kagaku Kogyo Kabushiki Kaisha | Production of vinylidine chloride copolymer latex |
| JP2773215B2 (en) * | 1989-04-07 | 1998-07-09 | ダイキン工業株式会社 | Polymer dielectric material |
-
1998
- 1998-12-02 BE BE9800870A patent/BE1013023A3/en not_active IP Right Cessation
-
1999
- 1999-11-30 CA CA002353881A patent/CA2353881A1/en not_active Abandoned
- 1999-11-30 MX MXPA01005500A patent/MXPA01005500A/en unknown
- 1999-11-30 CN CN 99815861 patent/CN1334829A/en active Pending
- 1999-11-30 BR BR9915887-6A patent/BR9915887A/en not_active IP Right Cessation
- 1999-11-30 WO PCT/EP1999/009371 patent/WO2000032660A1/en not_active Ceased
- 1999-11-30 JP JP2000585300A patent/JP2002531604A/en active Pending
- 1999-11-30 AU AU17790/00A patent/AU1779000A/en not_active Abandoned
- 1999-11-30 EP EP99961038A patent/EP1141053A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| AU1779000A (en) | 2000-06-19 |
| BE1013023A3 (en) | 2001-08-07 |
| MXPA01005500A (en) | 2003-09-10 |
| JP2002531604A (en) | 2002-09-24 |
| EP1141053A1 (en) | 2001-10-10 |
| CA2353881A1 (en) | 2000-06-08 |
| WO2000032660A1 (en) | 2000-06-08 |
| BR9915887A (en) | 2001-08-21 |
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