DE2735022A1 - POST-MASS POLYMERIZATION PROCESS FOR POLYVINYL HALOGENIDE AND THE COMPOSITIONS OBTAINED THEREOF - Google Patents

Description

Patent attorneys Dipl.-Ing. H. Weickmann, Dipl-Phys. Dr. K. Fincke

Dipl.-Ing. F. A. Weickmann, Dipl.-Chem. B. Huber HWEMY

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Case 3966 · ^MUNICH «> ^D ™

POST BOX (60S20

MOHLSTRASSE 22, NUMBER 9 (39 21/22

HOOKER CHEMICALS & PLASTICS CORP. Niagara Falls, New York 14302, V.St.A.

Post-bulk polymerization process for polyvinyl halides and the compositions obtained thereby

Addendum to patent (patent application P 23 23 191.6,

registered on May 8, 1973)

In the main patent specification (patent application P 23 23 191.6) is a process for the production of a polymer from a vinyl halide by a two-stage mass polymerization process described.

The present invention relates to an improvement of the method described in the main patent specification.

According to the present invention, an improved polyvinyl halide or vinyl halide copolymer which is up to 50% of a Contains comonomers by post-polymerization in a one-stage or two-stage bulk polymerization process in contact with a base polymer, using the same or a different monomer as used to produce the

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Base polymer was used, can be used. The compositions produced by the process of the invention or masses are for the production of films, coated flat structures or coated textile materials and molded objects useful. The post-polymerization process according to the invention in the liquid phase can with Base polymers in powder form produced by emulsion, suspension and bulk polymerisation processes, be performed. The base polymer can be present in a polymerization mixture in which only a portion of the Monomers has been converted to the base polymer, as in two-stage polymerization processes, or the base polymer can be used in dry, solid form. The polymers according to the invention have an improved bulk density and show less plasticizer absorption and can be used for the production of coatings for flat structures or coatings used for textile materials. Copolymers obtained by the new post-polymerization process according to the invention show improved impact resistance in addition to the improved bulk density and reduced plasticizer absorption. They are suitable for the production of molding compounds or bodies. In the inventive Bulk polymerization processes are obtained by adding the same monomer or monomers or one other monomers or other monomers after partial conversion in a two-stage bulk polymerization process of a vinyl halide monomer or monomer, or a vinyl halide monomer and comonomer, higher yields in the same reaction vessel as compared to the usual two-stage bulk polymerization process. at the two-stage bulk polymerization process according to the invention can optionally contain small amounts of hydrocarbon - rubber, dissolved or dispersed in the monomer, be added to the second reaction stage, and thereby reactor failure or fouling during the poly

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merization effectively avoided. The eventual addition of a small amount of surfactant in the second Stage contributes favorably to reducing the porosity of the polymeric product. A product with a smaller size is obtained Particle size if either an inert, finely divided additive, a surfactant, a mixture thereof or a polyolefin.

The invention relates to

(1) the preparation of homopolymers and copolymers of a vinyl halide, such as vinyl chloride, which are characterized by small particle size, high bulk density, reduced plasticizer absorption and easy processability, and

(2) the production of copolymers of a vinyl halide, such as vinyl chloride, with improved impact properties.

The viscosity of plastisols in which extender resins are used is not only determined by the plasticizer absorption properties of the polymer, but it is also influenced by the average particle size, influences the particle size distribution and the bulk density of the particles. Certain polymers of the invention are particularly suitable as an extender polymer for this application. These polymers are also used in the production of films and as a coating material for textile materials or flat materials are suitable. The high-impact polymers of the invention are used in manufacture used by compacts or pressed parts or molded bodies.

In a work entitled "Vapor Phase Polymerization of Vinyl Chloride "in Journal of Applied Polymer

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Science, Vol. 15, pp. 445-451, 1971, by Kahle et al, discloses a process for the polymerization of vinyl chloride using a liquid polymerized in the mass as a seed for the subsequent vapor phase polymerization process described. It is stated that this product exhibits reduced plasticizer absorption. In the process, general purpose polyvinyl chloride powder is ground to an appropriate size, polymer products can be produced with a small particle size. Similar processes are described in U.S. Patents 3,595,840 and 3,622,553.

FR-PS 1 588 381 describes the addition of fresh vinyl chloride and initiator to a vinyl chloride reaction mixture described, which has already been polymerized in bulk to a substantial extent in a single-stage reactor. This mixture is then subjected to bulk polymerization, so that polyvinyl chloride grains or granules with excellent plasticizer absorption in the cold and different sizes according to that. Length of their dwell time obtained at the polymerization conditions.

In US-PS 3,583,956 a process for the preparation of vinyl chloride copolymers is described, which one have a lower softening point than polyvinyl chloride, which is initially vinyl chloride up to. to a transformation polymerized by at least 40%, another vinyl monomer is added in an amount less than that of the remaining unreacted vinyl chloride, and then the polymerization at a temperature of at least 5 ° C above the first polymerization temperature, preferably 10 up to 35 ° C. In this patent it is described that the reaction after mass, solution, emulsion or suspension polymerization processes. In the examples, however, only suspension polymerisation processes are used described.

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U.S. Patent No. 3,725,367 teaches the use of a vinyl chloride latex as a seed polymer in a bulk polymerization process described in which one has vinyl chloride particles with a small particle size and a narrow size distribution in the granulate within the range from 10 to 50 / rev receives.

US Pat. No. 3,687,923 describes a process for the polymerization of vinyl chloride in the mass in which part of the monomer is polymerized with the formation of cores or nuclei and in which subsequently a A larger part of the liquid monomer is added and the polymerization is continued with gentle agitation. The amount of monomer used in the first stage of the polymerization should be at least 1/3 by weight the total amount of monomer that is converted in the reaction. An example describes a product that the 7396 particles with a size between 100 and 200 / U contains.

In US-PS 3,230,206 a process for the suspension polymerization of copolymers with heterogeneous Structure, good flow properties and impact resistance at low temperature through polymerization of acrylic acid esters and vinyl chloride. A portion of the vinyl chloride is added after 5 to 20 # of the copolymer is formed became.

In US Pat. No. 2,961,432, a method for Mass polymerization of homopolymers and copolymers described, in which mixtures of liquid monomers and polymer powders are formed and the polymerization is carried out. The monomer used corresponds to the same monomer, how it was used to make the polymer powder.

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The invention relates to a process for the production of vinyl halide polymers with a high bulk density or high bulk density and with reduced plasticizer absorption during processing as an extender resin in a polyvinyl halide plastisol and a process for the production of unusual polymers of vinyl halide by polymerization with other ethylenically unsaturated monomers, in addition to the properties , such as low plasticizer absorption and higher bulk density or higher bulk density, polymer properties such as a reduced melt viscosity, lower glass transition temperature and higher impact strength can be obtained. In the process according to the invention, particles of vinyl halide polymers or copolymers in powder form can be used as cores or seeds which are produced by known emulsion, suspension or bulk polymerization processes. These nuclei are preferably used in a post-polymerization in the liquid state under bulk polymerization conditions, with further polymerization taking place within the particles instead of on the surface of the particles which are used as cores. The post-polymerization process according to the invention can be integrated into a two-stage, liquid bulk polymerization process, in which the first stage is agitated or moved at high speed, with about 3 to about 20% by weight, preferably about 7 to about 12% by weight , of the or of the monomers are converted and at this stage a polymerization takes place in a second stage with low agitation or low stirring. In the two-stage polymerization process according to the invention, additional monomer is incorporated into the product during the second reaction stage after the partial conversion of the monomer or monomers to the polymer. The reactor productivity can be increased by about 2596 with the method according to the invention. Usually, additional initiator is used together with the additional

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chen monomers used. Alternatively, another initiator that is reactive at a higher temperature can be used at the beginning the second reaction stage are added, and the post-polymerization can be carried out at a higher reaction temperature, the is suitable for the activation of the additional initiator.

In the method according to the invention, in which a polyvinyl halide polymer or copolymer after a two-stage Bulk polymerization process is produced in the liquid phase and in which the post-polymerization during Part of the second stage can be carried out by the incorporation of additional amounts of the same Vinyl halide monomers or comonomer products with high bulk density or high bulk density and low plasticizer absorption be generated. It is not necessary to add the resins formed before or after the polymerization isolate, just polymerize the vinyl halide monomer or comonomers to powder form before the the same monomer or a different monomer is added. If the same procedure but dissimilar monomers in the Post-polymerization are used, a reduced plasticizer absorption is obtained in addition to a reduced Melt viscosity and increased impact resistance.

When vinyl halide polymers of the same particle size are produced by the bulk polymerization process are to be, the seed particles or core particles of emulsion-polymerized or suspension-polymerized Vinyl halide polymers in the post-bulk polymerization process of the present invention can be used in the liquid phase. Alternatively, the bulk polymerization process in the liquid phase described in U.S. Application Serial No. 597,617 filed July 21, 1975; for the production of seed particles with small particle size

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as a base material for the post-polymerization process according to the invention be used. Furthermore, the bulk polymerization process described in US Pat. No. 3,933,771 can alternatively be used in liquid phase or that described in U.S. Application Serial No. 674,202, filed April 5, 1976 Methods for preparing seed particles of small particle size can be used.

In a preferred method according to the invention, at least one monomer is added to the base polymer or base copolymer, which has been polymerized in the mass in the liquid phase and which acts as a seed core particle is added. Thereon This is followed by post-polymerization of the monomers with the formation of a polymer or copolymer with an increased bulk density or increased bulk density, reduced plasticizer absorption and a suitable selection of an additional monomer or additional monomers that occur during the post-polymerization reaction are added, products with increased impact resistance, reduced melt viscosity and lower glass transition temperature obtained. The additional Monomer or the additional monomers are added either all at once or continuously at one stage of the bulk polymerization process where the conversion of the bulk polymerized base polymer or Base polymers in powder form was obtained. This matches with a conversion of about 30 to 95%, preferably about 30 to 8090. If the additional monomer or monomers are added continuously, the addition rate is adjusted so that the addition is completed before the end of the polymerization cycle. The proportion of the added Monomers is generally about 1 to about 200 wt. 96, based on the resulting, converted polymer, preferably about 2 to about 150 wt. 96, based on the weight of the resulting, converted polymers.

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In a less preferred one according to the invention At least one monomer can be added to the base polymer according to a suspension or a method Emulsion polymerization process was produced. A polymer product with increased bulk density, lower glass transition temperature, reduced melt viscosity and improved impact resistance is obtained. According to the invention Polymers produced by methods have bulk weights or mass densities (for the sake of simplicity, in hereinafter referred to only as "bulk density") of about 0.3 to about 0.9 g / ml and impact strengths of about 0.276 up to 4.14 mkg (2-30 foot pounds) / 2.54 cm (1 inch) notch.

In the method according to the invention, in which the seed particles made of vinyl halide polymer, that by emulsion or suspension polymerization processes or bulk polymerization processes in liquid phase is used, the additional monomer is added to the powdered seed particles and a bulk liquid polymerization process is initiated. In a preferred method in which When an integrated bulk polymerization process is carried out, the vinyl halide monomer can either be a one-step process or polymerized by a two-step bulk polymerization process until monomer conversion between about 30 and about 9596, preferably between about 30 and around 8096, is reached. Subsequently, further monomer, which is a different monomer than the vinyl halide monomer, that was used at the beginning may be added. Alternatively, the additional monomer can be the same or different of the vinyl halide monomer used initially provided that a particle size control additive as described below is used will.

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The preferred two step bulk polymerization process used in the present invention is the process described in GB-PS 1,047,489 and US-PS 3,522,227. On both patents is expressly referred to.

The vinyl halide monomers encompassed by the present invention are, for example, vinyl fluoride, Vinyl chloride, vinyl bromide, vinyl iodide, vinylidene fluoride, vinylidene chloride, vinylidene bromide, vinylidene iodide et al, although vinyl chloride is preferred. The present invention also includes all oc-halogen-substituted, includes ethylenically unsaturated compounds which can take part in an addition polymerization reaction. The invention Polymers can be composed of the same or different cc-halogen-substituted, ethylenically unsaturated Materials are being made, and the present invention is thus intended to be homopolymers, copolymers, terpolymers and tetrapolymers formed by addition polymerization. Examples of these copolymers is a copolymer of vinyl chloride and vinylidene chloride. The term "vinyl halide polymer" as used herein Application and the claims used includes both vinyl halide homopolymers and copolymers, which under Use of vinyl halide and ethylenically unsaturated monomers copolymerizable therewith.

Although the monomer composition is only vinyl halide monomer may include or may contain, the present invention further comprises copolymers by free Free radical addition polymerization can be generated from a monomer composition comprising a predominant amount, e.g. at least 5096 vinyl halide, preferably 8096 vinyl halide, and a lesser amount, e.g., up to 50 wt. 96, of another ethylenically unsaturated monomer material, which is thus copoly-

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is merizable, contains. The other ethylenically unsaturated monomer material is preferred in amounts below 20% by weight. and more preferably in amounts below 10% by weight, based on the total monomer compounds used to prepare the Polymers are used, used. Suitable ethylenically unsaturated monomer materials that are used for the production of Base copolymers, terpolymers, interpolymers, etc. are used are, for example, the following monoolefinic Hydrocarbons, i.e. monomers containing only carbon and hydrogen, including such materials such as ethylene, propylene, butene-1, 3-methyl-butene-1, 4-methylpentene-1, pentene-1, 3,3-dimethylbutene-1, 4,4-dimethylbutene-1, Octene-1, Decene-1, Styrene and its on the core α-alkyl- or -aryl-substituted derivatives, e.g. o-, m- or p-methyl-, -ethyl-, -propyl- or -butylstyrene; α-methyl, ethyl, propyl or butyl styrene; Phenylstyrene, and halogenated styrenes such as cc-chlorostyrene; monoolefinically unsaturated Esters including vinyl esters, e.g. vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate, vinyl laurate, Vinyl benzoate, vinyl caprate, vinyl hexanoate, vinyl pchlorbenzoate, Alkyl methacrylates, e.g. methyl, ethyl, Propyl and butyl methacrylate; Octyl methacrylate, lauryl methacrylate, stearyl methacrylate, alkyl crotonates, e.g., octyl; Alkyl acrylates, e.g. methyl, ethyl, propyl, butyl, 2-ethylhexyl, stearyl, n-hexyl, n-octyl, hydroxy ether and tert-butylaminoacrylate, 2-ethoxyethyl acrylate, 2-methoxyethyl acrylate, Isopropenyl esters such as isopropenyl acetate, isopropenyl propionate, isopropenyl butyrate, and isopropenyl isobutyrate; Isopropenyl halides, e.g., isopropenyl chloride; Vinyl esters of halogenated acids, e.g. vinyl-oc-chloroacetate, Vinyl α-chloropropionate and vinyl α-bromopropionate; Allyl and methallyl esters, e.g., allyl chloride, allyl cyanide; Allyl chlorocarbonate, allyl nitrate, allyl formate and allyl acetate and the corresponding Methally! compounds; Esters of alkeny alcohols, e.g. B. ß-ethylally! Alcohol and ß-propyl-

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allyl alcohol; Halo-alkyl acrylates, for example methyl-a-chloroacrylate and ethyl-a-chloroacrylate, methyl-a-bromoacrylate, ethyl-a-bromoacrylate, methyl-a-fluoroacrylate, ethyl-a-fluoroacrylate, methyl-α-iodoacrylate and ethyl-α iodoacrylate; and alkyl-α-cyanoacrylates, for example methyl-α-cyanoacrylate and ethyl-cyanoacrylate; Itaconates such as monomethyl itaconate, Monoäthylitaconat, Diäthylitaconat, the mono- and diesters of itaconic acid with C, -C _Q alcohols; Maleates, for example monomethyl maleate, monoethyl maleate, dimethyl maleate, diethyl maleate, the mono- and diesters of maleic acid with C 1-4 alcohols; and fumarates, for example monomethyl fumarate, monoethyl fumarate, dimethyl fumarate, diethyl fumarate, the mono- and diesters of fumaric acid with C 1-4 alcohols and diethyl glutaconate; monoolefinically unsaturated organic nitriles including, for example, fumaronitrile, acrylonitrile, methacrylonitrile, ethacrylonitrile, 1,1-dicyanopropene-i, 3-octenenitrile, crotonitrile and oleonitrile; Monoolefinically unsaturated carboxylic acids including, for example, acrylic acid, methacrylic acid, crotonic acid, 3-butenic acid, cinnamic acid, maleic, fumaric and itaconic acid, maleic anhydride, and other amides of these acids, such as acrylamide, are also suitable. Vinyl alkyl ethers and vinyl ethers, for example vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl n-butyl ether, vinyl isobutyl ether, vinyl 2-ethylhexyl ether, vinyl 1-2-chloroethyl ether, vinyl cetyl ether and others; and vinyl sulfides, for example vinyl-ß-chloroethyl sulfide, vinyl-ß-ethoxyethyl sulfide, among others, are also included as well as diolefinically unsaturated hydrocarbons which contain two olefinic groups in conjugate relationship, and their halogen derivatives, for example 1,3-butadiene; 2-methylbutadiene-1,3; 2,3-dimethylbutadiene-1,3; 2-chlorobutadiene-1,3; 2,3-dichlorobutadiene-1,3; and 2-bromobutadiene-1,3, among others

Specific monomer compositions for the production of the basic copolymers are, for example, vinyl chloride and / or

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Vinylidene chloride and vinyl acetate, vinyl chloride and / or vinylidene chloride and maleic or fumaric acid esters, vinyl chloride and / or vinylidene chloride and acrylate or methacrylate esters, Vinyl chloride and / or vinylidene chloride and vinyl alkyl ethers. These mixtures are just examples of that numerous combinations of monomers possible for the formation of the copolymers. The present invention includes all such combinations or different mixtures. Although such mixtures are encompassed by the present invention it is preferred that the base polymer be composed of a vinyl halide monomer alone, and most preferred is made from vinyl chloride.

The monomer or monomers subsequently added to the partial conversion of the monomer (s) may be the same as or different from the vinyl halide polymer used to prepare the base polymer as previously described, and if different, the monomer or For example, the monomers are preferably selected from those classes of monomers which polymerize at the same or a higher rate as compared to the vinyl halide polymer. Examples of monomers useful in the post polymerization process of the present invention are those listed above. If the process product is to have high impact strength, monomers such as 1-olefins having 2 to 10 carbon atoms, for example ethylene, propylene, pentene-1, butene-1, octene-1, decene-1; Vinyl esters such as vinyl butyrate, vinyl stearate, vinyl laurate, vinyl caprate, vinyl hexanoate; Alkyl methacrylates such as octyl methacrylate; Alkyl acrylates such as ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, n-hexyl acrylate, n-octyl acrylate; Hydroxy ether acrylates, such as 2-methoxyethyl acrylate _f 2-ethoxyethyl acrylate; Maleates, fumarates and itaconates, such as monomethyl maleate, monoethyl maleate, dimethyl maleate, diethyl maleate, monomethyl itaconate, monoethyl itaconate, dimethyl

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-Vf-

itaconate, diethyl itaconate, monomethyl fumarate, monoethyl fumarate, dimethyl fumarate, diethyl fumarate, alkyl maelates, fumarates and itaconates with an alkyl group chain length of C 1 to C _Q ; Vinyl alkyl ethers and vinyl ethers, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl n-butyl ether, vinyl isobutyl ether, vinyl 2-ethylhexyl ether, vinyl cetyl ether; diolefinically unsaturated hydrocarbons containing two olefinic groups in conjugate relationship, such as 1,3-butadiene; 2-methylbutadiene-1,3; 2,3-dimethylbutadiene-1,3; 2-chlorobutadiene-1,3 was used. The impact strength values for the polymers of the invention are about 0.276 to about 4.14 mkg (2-30 foot pounds) / 2.54 cm (1 in.) Notch at ambient temperature.

When copolymers with good impact resistance at temperatures below ambient temperature as well as with good impact resistance to be prepared at room temperature by the process of the present invention is a vinyl halide monomer used alone or in a mixture with other monomers to produce the base polymer. In the post-polymerization process is a monomer or monomers, such as acrylates, are used, which alone to form rubber-like Homopolymer with a glass transition temperature of 10 ° C or lower can polymerize. Acrylic acid esters are particularly preferred monomers for the preparation of vinyl halide copolymers with good impact resistance. The acrylic acid esters that are particularly useful are those that are about 2 to about 15 carbon atoms in the alkyl group, preferred contain from about 2 to about 11 carbon atoms, and most preferably from about 4 to about 8 carbon atoms. Such monomers become either all at once or continuously in the bulk polymerization process of the present invention added when a conversion of the base vinyl halide polymer between about 30 and about 95%, preferably about 50 to about 95%, conversion to that was obtained Point in time when the base polymer is in powder form. Loading

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preferred acrylic ester comonomers for the production of polymers with impact resistance at low temperature are 2-ethylhexyl acrylate, n-hexyl acrylate and n-octyl acrylate.

The free radical mass polymerization can be carried out by the process according to the invention at temperatures between 0 and 90 ° C. The polymerization reaction is carried out in the presence of a free radical initiator. Suitable free radical initiators are organic or inorganic peroxides, persulfates, ozonides, hydroperoxides, Peracids and percarbonates, azo compounds, diazonium salts, diazotates, peroxysulfonates, trialkylborane oxygen systems and amine oxides. Azo-bis-isobutyronitrile is particularly useful in the present invention. The catalyst is used in concentrations ranging from about 0.01 to about 1.0 wt. # based on the total weight of the monomers. When used in bulk, suspension and solution polymerization are generally catalysts that are soluble in the organic phase, such as benzoyl peroxide, diacetyl peroxide, azo-bis-isobutyronitrile, diisopropyl peroxydicarbonate, Azo-bis-Ca-methyl-y-carboxybutyronitrile), caprylyl peroxide, Lauroyl peroxide, azo-bis-isobutyramidine hydrochloride, t-butyl peroxypivalate, 2,4-dichlorobenzoyl peroxide, azobis- (a, y-dimethylvaleronitrile) and Z.Z'-azo-bis-Ca ^ -dimethylvaleronitrile), used. The initiator that is used is preferably selected from a group of initiators known as "hot catalysts", or those that have a high level of free radical initiator activity own. Lower activity initiators are less preferred because they require longer polymerization times. Longer polymerization times can continue cause a preliminary product degradation, which occurs due to color disadvantages, e.g. turning pink.

The polymerization products according to the invention can be mixed with various inert additives known per se,

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such as fillers, dyes and pigments. If necessary, the polymerization products can be mixed with plasticizers, Lubricants, thermal stabilizers and ultraviolet light stabilizers are mixed.

In the post-bulk polymerization process of the present invention in the liquid phase, all other conditions and measures are those normally used for the known ones Processes for bulk polymerization of vinyl chloride in which two-stage polymerization is carried out, as described in GB-PS 1,047,489 and US-PS 3,522,227. On the content of revelation express reference is made to these literature references. In the case of the integrated post-polymerization process according to the invention, in which a two-stage bulk polymerization for vinyl halide is carried out, the reaction is carried out in carried out a reactor of the first stage, the one facility which is selected so that the monomer or monomers moves while generating high shear forces or be stirred. This device is commonly referred to as a radial turbine-type agitator. to The first stage reaction is started in the container with the monomer composition to which a catalyst is added has been loaded. Any polymerization catalyst normally used in bulk polymerization processes i.e., those described above can be used as they are for bulk polymerization processes is common. After the addition of the vinyl chloride monomer In the first stage reactor, a small amount of monomer is vented into the process to remove the air from the reactor vessel the first stage to remove. The speed of the turbine type agitator is generally between 500 and 2000 rpm or a tip speed of about 2 to 7 m / sec for the first stage reactor. One Tip speed of about 0.5 to about 2 m / sec

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■ SS * · '

used in the second stage reactor. These numbers should not be viewed as limit values. Once a conversion of at least about 3 to about 20 percent of the monomer composition In the first stage reactor has been reached, the contents of the reactor are transferred to a polymerization vessel for the second stage, the one with a low speed, low shear stirrer is equipped so that a suitable temperature control of the reaction medium is possible.

According to the method of the present invention, a polymer having a small particle size can be produced. The size of the Polymer particles is compared with the known method through the use of an additive or a surface-active Achieved by means or a mixture thereof in the first stage of the bulk polymerization process. With the or the monomers are in the polymerization reactor of the first stage 0.001 to 5 Gew.96, based on the or at the first stage vinyl chloride polymerisation existing monomers, an additive used with the polymer particle size can be controlled. The additive has an average particle size in the range of about 0.001 up to about 50 microns. A suitable additive is fumed silicon dioxide, which is available from Degussa under the trademark "Aerosil" is sold. The silica can be treated with an agent to make it hydrophobic. One such treating agent is dichlorodimethylsilane, which is used to make fumed silica and which is sold under the trademark "Aerosil R-972" by Degussa. The silica used is preferably a fumed silica with an average particle size below 10 microns.

In the present invention, both organic and inorganic solid, particulate material can

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-yg-

s that are both insoluble in the vinyl chloride monomer as are solid even at temperatures up to at least the reaction temperatures, together with the monomers described be used in the bulk polymerization process of the invention, the particle size of the polymers formed is decreased. The average particle size of the solid, inert, particulate materials is preferred in the range of 0.001 to about 50 microns. An example of an organic, solid, particulate material that useful in the process of the invention is emulsion polymerized Vinyl chloride with an average particle size of 2 microns. Examples of inorganic, solid, particulate materials other than the fumed silica used in the present invention Are useful are carbonates such as calcium, magnesium, zinc, cadmium and barium carbonates, aluminum silicates and Talk. When large amounts of solid, inert material can be added to the monomer without the cost being substantial increase or the physical properties of the polymers obtained are changed, it is possible to use organic or inorganic, solid, inert, particulate materials having an average particle size range up to 50 microns to be used. A suitable amount of useful, solid, inert, particulate materials can be formed from materials that have a particle size larger than that described above, preferred average particle size.

The surfactants used in conjunction with the vinyl chloride monomer (s) can be nonionic, cationic or anionic. In the first reaction stage, the agents are in the range from 0.01 to 5% by weight , based on the monomer or monomers, das.bzw. which is or are present in the first polymerization stage.

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The surface active agents are organic agents with structurally asymmetrical molecules that contain both hydrophilic and hydrophobic molecular parts. the Nonionic agents do not ionize, but can have a hydrophilic character due to the oxygenated Side chain, usually polyoxyethylene. The oil-soluble portion of the molecule can be aliphatic or aromatic in nature be. The cationic agents ionize so that the oil-soluble portion is positively charged. Significant examples are quaternary ammonium halides such as benzethonium chloride and cetalkonium chloride. The anionic agents form negatively charged ones Ions present in the oil-soluble part of the molecule. The ionizable group is the hydrophilic part. Examples are the sodium salts of organic acids, vie stearic acid, and sulfonates or sulfates, such as alkylarylsulfonates, e.g. sulfonates of dodecylbenzene and sulfates of straight chain primary alcohols, either fatty alcohols or Products of the oxo process, e.g. sodium lauryl sulphate. Examples of nonionic surfactants that are effective are octylphenoxy-polyethoxyethanols, which are below the trademarks "Triton X-100" and "Triton X-35" of Rohm & Haas Company of Philadelphia, Pennsylvania. Examples of anionic surfactants are: Calcium, zinc, magnesium and nickel stearates. An example of an effective cationic surfactant is a quaternized amine sold under the trademark "Quaternary O" by Ciba-Geigy Corporation.

Further examples of suitable surface-active agents and details with regard to their composition can be found in McCutcheon's Detergents and Emulsifiers, N. American Ed., 1975 Annual, pp 35-265.

Further details regarding the use of the additives described above to regulate the partial

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Chen size and surfactants can be found in the aforementioned copending patent application with the

Serial No. 597,617, filed July 21, 1975.

The use of a polyolefin additive in the first stage of the two-step vinyl halide polymerization process of the present invention enables particularly good control of the product particle size, and will continue to do so inhibits the formation of reactor deposits. Will any of the particle size regulators of the present Invention used, it is advantageous to add additional polyolefin to the reaction mixture, preferably to Beginning of the second reaction stage, to be added in order to inhibit the formation of deposits or precipitates.

It is preferred if a polyolefin is preferred in the second stage of the polymerization according to one described above Embodiment according to the invention is used, a surface-active agent of the type described above to the Second stage polyolefin added, the amount of surfactant being about 0.01 to about 0.2%, based based on the weight of vinyl halide monomer added up to that point.

The above-described presence of the surfactant in the second stage of the invention The polymerization process causes an even more complete filling of the interstices in the polymer product particles, i.e. the porosity of the polymer product particles is reduced. This causes a reduction in product particle porosity in a favorable way a reduction in the viscosity of the astisol formulations, which contain the products according to the invention incorporated as an extender resin. The addition of the surfactant Means to the second stage of the polymerization together with any of the regulating additives according to the invention

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substances for the particle size is favorable even if no olefin is added to the second stage polymerization.

The polyolefin additives of the invention are homopolymers, copolymers or terpolymers of aliphatic Hydrocarbon olefins having 2 to 8 carbon atoms. Polymers of the olefins previously described, which are also Monomer residues of aliphatic hydrocarbon polyenes, e.g. Dienes or trienes containing 4 to 18 carbon atoms can also be used. Although preferred is that the olefin polymers used in the present invention Containing only hydrogen as a substituent, halogenated olefin polymers, such as chlorinated, brominated and fluorinated polyolefins can also be used. The weight average molecular weight of the olefin polymers, Copolymers and terpolymers used as additives can range from about 50,000 to about 300,000 and more, up to 1,000,000 and higher, vary. Preferably, it has in the first stage of the process according to the invention The polyolefin additive used has a weight average molecular weight of from about 50,000 to about 1,000,000, whereas the polyolefin additive is preferred, used in the second stage has a weight average molecular weight of about 50,000 to about 300,000 owns. Furthermore, the polyolefin additive of the first stage is preferably a polyene-modified olefin polymer of the type described above, whereas the second stage polyolefin additive is preferably free from Polyene monomer residues.

In general, the amount of polyolefin used in the first stage of the polymerization according to the invention is added, about 0.05 to about 4 wt.%, Preferably about 0.1 to about 2 wt. # Based on the weight of the monomers used in the first reaction stage. The amount

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of polyolefin added to the reaction mixture at the beginning of the second stage can be as low as about 0.05 up to about 0.5 wt. 96, preferably based on the vinyl halide monomer, be; normally it is about 0.05 to about 3 wt.96, preferably about 0.1 to about 2 wt.96, based on weight of the monomer, which up to the point of addition of the polyolefin at the beginning of the second reaction stage of the polymerization was filled.

The use of olefin polymers in bulk vinyl halide polymerization processes is described in detail in US Pat. No. 674, filed April 5, 1976 described.

It is therefore an object of the present invention to provide a bulk polymerization process for production of high molecular weight, small particle size vinyl chloride polymers or copolymers, wherein the individual particle or agglomerate is characterized in that it is not porous. It is believed that the porous particles are filled with a low molecular weight polyvinyl chloride, which causes such particles made of polyvinyl chloride polymer or copolymer are more resistant to solvation at ambient temperature, compared to known polymers and copolymers.

The reaction temperature in the first and second stage reactors is generally in the range from about 25 to about 80.degree. C., preferably from about 30 to about 70.degree. The reaction pressure for the first stage reactor generally ranges from about 9.14 to about 14.8 kg / cm (130-210 psi), preferably from about 10.5 to about 13.4 kg / cm (150-190 psi), and corresponds to and results from the temperature used in the process. The reaction pressure in the second stage reactor is generally about 5.62

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to about 12.7 kg / cm (80-180 psi), preferably about 6.33 to about 7.38 kg / cm (90-105 psi), and also corresponds to and arises from that used in the method Temperature.

During the post-polymerization, the temperature of the reactor contents can be increased from about 30 ° to about 70 ⁰ C to about 60 ° C to about 80 ⁰ C, the increase in the polymerization temperature is about 10 to about 50 ⁰ C. The pressure can be increased from about 8.09 to about 15.1 kg / cm (115 to 215 psi) to about 11.2 to about 18.6 kg / cm ² (160-265 psi) to initiate the reaction, if a higher temperature initiator is added at the beginning of the second stage of a two step bulk polymerization reaction process. Further details of the two-stage bulk polymerization process in which the temperature of the reactor contents is increased during the second stage of the process can be found in U.S. Patent 3,933,771.

When the post-polymerization process is carried out at a temperature higher than that at the beginning the second stage of the polymerization process, the post-polymerization gives particles which are non-porous, are less likely to be solvated when in contact at room temperature with a primary Plasticizers for polyvinyl chloride or polyvinyl chloride copolymers come. The polymers also melt lower temperature.

In the method according to the invention, additional Monomer added during the second stage of the bulk polymerization process. In addition to those previously described Advantages of the post-polymerization, the addition of the monomer during the second stage has the advantage that the yield of polymer is increased because of the addition of monomer

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a greater yield of product is obtained from the reaction vessel used during the second stage. the Reactor productivity can thus be increased by around 25%.

The following examples illustrate the invention. In the description and the claims, unless otherwise stated, all parts and percentages are given by weight, all prints as overprints and all temperatures in ⁰ C.

Example T - comparison

Prepared in a first stage reactor of the vertical type with a capacity of 9.46 l (2 1/2 gal) made of stainless steel equipped with a stirrer of the radial turbine type, 5.2 g of fume are added Silica treated with dichlorodimethylsilane, 5.0 g Triton X-100, 2.0 g of a 29% solution Acetylcyclohexane sulfonyl peroxide in dimethyl phthalate, available under the trademark "Lupersol 228P" from the Lucidol Division of the Pennwalt Company, and 1.0g of one 40% solution of di-2-ethylhexyl peroxydicarbonate in Mineral oil sold under the trademark "Lupersol 223M" by the Lucidol Division of the Pennwalt Company. 4.99 kg (11.0 pounds) of vinyl chloride are added to the reactor at a temperature of 20 ° C and 0.45 kg (1.0 lbs) of vinyl chloride monomer is released into the atmosphere for removal purged of air from the reactor. The temperature of the mixture in the reactor is gradually increased while the mixture using the radial turbine type agitator stirred at a high speed of 2000 rpm at a temperature of 67 ° C for one hour will. It is then at this temperature for a time of 15 minutes at a reaction pressure of 11.7 kg / cm (167 psi) held.

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The mixture is then transferred to a 18.9 l (5 gal) stainless reaction vessel containing 2.2 grams of "Lupersol 223M" and 3.0 grams of lauroyl peroxide and 3.18 kg (7 lbs) of vinyl chloride. It is stirred at low speed. 0.68 kg (1.5 lbs) of vinyl chloride is vented to remove the air from the reactor. The mixture is heated at 50 ° C and the pressure is increased to 7.38 kg / cm ² (105 psi). These conditions are maintained for 4.5 hours. The mixture is then heated and a pressure of 77.1 kg / cm (170 psi) is maintained for 2.0 hours. The unreacted monomer is blown off and collected in a condensation circuit into which a filter is fitted so that any polymer particles carried over are separated. The remaining traces of residual monomer absorbed by the polymer particles are removed by placing the polymerizer under vacuum twice in succession and switching to a nitrogen atmosphere in between. All of the polymer composition is then passed through a sieve device. In this way a powdery polymer is obtained in a yield of 5.9 kg (13 lbs) of polymer. The polymer, as indicated by Coulter Counter measurements, has an average particle size of 48 microns.

Example 2

A polyvinyl chloride homopolymer polymerized in the mass is produced by the process according to the invention, using the same proportions of ingredients as in Example 1, but 4.5 kg (10 lbs) degassed Monomer after 4.5 hours of polymerization in the second Stage is added and the polymerization continues for a further 4 h. In this way, powdery polymer is obtained in a yield of 9.1 kg (20 lbs). The polymer has a average particle size of 51 microns as determined by Coulter Counter measurements.

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Using the resins prepared according to Examples 1 and 2 above, plastisols are prepared using the following recipe: 70 parts of emulsion polymerized polyvinyl chloride homopolymer sold under the trademark "Geon 121" by BFGoodrich Chemical Company, 30 parts of bulk polymerized polyvinyl chloride resin according to the above examples, and 60 parts of dioctyl phthalate. The plastisols are prepared by methods known per se by combining the ingredients, stirring uniformly at high speed and venting to remove entrained air. The viscosity of the plastisol is determined using a Brookfield viscometer Model LVT with a temperature of 25 + 0.3 ⁰ C is used. A # 3 spindle is used and the viscosity is determined after aging the plastisol for 2 hours.

Plastisol, manufactured using Brookfield viscosity using the resin of (cP)

Example 1 5350

Example 2 3700

Example 3

180 g of polyvinyl chloride polymer polymerized in the mass are placed in a 1 l glass autoclave equipped with a spiral stirring blade. The reactor is evacuated to 0.05 mm mercury pressure and then nitrogen is introduced to a pressure of 45.4 atmospheres (100 psig). This process is repeated, and then 0.5 ml of a 21 # solution of acetylcyclohexane sulfonyl peroxide in mineral spirits is added. The reactor is evacuated and cooled to 5 to 10 ° C; 345 g of vinyl chloride are added and 30 g of this are blown off. The reactor jacket is heated with water of 80 ⁰ C and the slurry is heated to a temperature of 72 ° C in the reactor. After a period of 2 hours at the

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At this temperature, the reactor is cooled to 30 ° C. and the vinyl chloride is distilled off from the reactor in the course of 2 hours. After drying for 16 hours, a yield of 31O g of polymer is obtained.

breastfeeds. It is obtained after drying at 50 ° C. during

Examination of the vinyl chloride with an optical microscope shows an average particle size of about 56 microns. The bulk polymerized starting polymer has an average particle size of 49 microns. To determine plasticizer absorption properties, a standard plastisol is prepared from 70 parts of emulsion polymerized polyvinyl chloride sold under the trademark "Geon 121" by BFGoodrich Chemical Company, 30 parts of post-polymerized polymer to be tested, and 60 parts of diisooctyl phthalate. A plastisol using the polymerized in the mass polyvinyl chloride was prepared as a starting polymer has a viscosity of 4350 cps measured with a LVT Brookfield viscometer, spindle no. 3, speed 12 rev / min at 25 ⁰ C and 2 h aging time. A similar plastisol made using the product of the post polymerization process of the present invention exhibits a viscosity of 2805 cP.

In a similar way, polyvinyl chloride powders, which are produced by suspension polymerization and alternatively, be prepared by emulsion polymerization, instead of the bulk polymerized ones used above Polymers used to make extender resins useful in making plastisols.

Example 4- comparison

A vinyl chloride polymerized in bulk in two stages is produced using a 1 liter stainless steel reactor prepared by adding a mixture of 0.10 ml

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Acetylcyclohexane sulfonyl peroxide as a 29% solution in dimethyl phthalate and 0.25 ml of di- (2-ethylhexyl) peroxydicarbonate as a 40% solution in mineral spirits are introduced into the reactor. Alternatively, the reactor is evacuated and filled with nitrogen to a pressure of 10.5 atmospheres (150 psig). 500 g of vinyl chloride monomer are added to the reactor, and the polymerization is then carried out ^{at 70 ° C. for 20 minutes.} The contents of the reactor are transferred to a tubular reactor containing 250 g of vinyl chloride, 0.20 ml of acetylcyclohexane sulfonyl peroxide as a 29% solution in dimethyl phthalate and 0.5 ml of di- (2-ethylhexyl) peroxydicarbonate as a 40% solution contains in white spirit, given. The polymerization is carried out in the reactor of the second stage at 65 ° C. for 5 hours. The polymer is then isolated by blowing off excess vinyl chloride and recovering the polymer as a dry polymer.

Examples 5 and 6

In the following table, methyl acrylate is used added to the second stage vinyl chloride bulk polymerization reaction using the same ingredients, proportions of ingredients and reaction conditions as in Example 4, except that 2 hours after the start of the polymerization the second stage a monomer is added to the polymerization mixture by pouring the monomer into a Place steel bomb and fill with nitrogen to 14.1 atmospheres (200 psig). At the time of addition there will be two Valves opened, connecting the pressurized bomb and reactor and adding can.

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Table I.

Ex. ^ Monomer No. (based on added. Vinyl chloride)

More yield molecule Rubble Glass Melt Vis- Plastisol Viscosity (2)

Monomer (%) weight weight excess viscosity (1) (Brookfield Viscom-

(continuous / ml) speed (0.2 and 2nd LVT, spindle no.3, average temp, inches / min) 12 rpm. 25 ⁰ C) weight) ( ⁰ C; after 2 h after 24 h

4 none none

5 2 methyl acrylate

6 3i6 same as above

70 83 200 0.46 73
70.2 84 800 0.53 65

71.4 95 600 0.66

8.65 x 10 ~ 7 6500 7700 1.9 χ 10 "7

8.04 χ 10 λ 5200 6200 1.89 χ 10

7.45 χ 10 ~ λ 3300 3800 1.68 χ 10

(1) The melt viscosity, determined on a polymer, the 296 dibutyltin-S, S'-bis-isooctyl mercaptoacetate which is available under the trademark "M & T-31" from M & T Chemicals, Inc., Co. using an Instron rheometer set at 200 ° C. ι

(2) The plastisol viscosity based on a standard plastisol containing 70 parts of emulsion polymer- ^ V Sated polyvinyl chloride, 60 parts of diisooctyl phthalate and 30 parts of the polymer to be tested contains. , ·

Examples 7 and 8

180 g of polyvinyl chloride polymer polymerized in the mass, prepared as in Example 4. The reactor is evacuated to 0.05 mm mercury pressure and filled with nitrogen to a pressure of 7.03 atm (100 psig) filled. The process is repeated, and then 0.5 ml of a 21% strength solution of acetylcyclohexane sulfonyl peroxide in mineral spirits is added. The reactor is evacuated and cooled to 5 to 10 ° C. 345 grams of vinyl chloride are added and 30 grams are blown off. The reactor jacket is heated with water of 80 ⁰ C and the slurry is heated to a temperature of 72 ° C in the reactor. After a period of 2 hours at this temperature the reactor at 30 ⁰ C is cooled and the unreacted vinyl chloride is distilled off from the reactor in the course of 2 h. This process is repeated to produce a second batch of polymer. The extent of the post-polymerization can be seen from the influence on the bulk density and the flow times and is shown in the table below.

Table II

Influence of post-polymerization on loose bulk density and flow time

Resin % Post-Poly Particle Loose Mass Flow Time merization size, / U density (g / ccm) (see)

Ex .4 0 9 115 - o, 52 7th , 2 N 7th 54 133 0, 58 5 , 6 •1 8th 55 129 0, 59 4th , 2 at s ρ i e 1 e until 19

The following examples are bulk polymerizations using the same proportions and ingredients and process conditions as in Example 4, except that in the first reaction step

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the reactor is charged with 450 g of vinyl chloride monomer and that the contents of the reactor of the first stage is transferred under pressure into a 2 1 glass reactor, the reactor of the second stage represents. The procedure is modified as indicated below by adding an acrylate monomer during the second Stage of the process is fed at the various times indicated below. In Examples 9 to 19, the amount of vinyl chloride in the second stage reactor is less than that of Example 4, the comparative example, and corresponds to a total of 650 g vinyl chloride monomer including the polymer in the second stage reactor, that of 450 g of vinyl chloride added to the first stage reactor and 200 g of vinyl chloride added to the reactor the second stage is added. In the following Table III are the results of the polymerization with the acrylate monomer being added during part of the second stage polymerization. The monomer is in these examples at the specified time after the polymerization reaction of the second stage is initiated was admitted all at once.

Samples of the polymer obtained according to Examples 9 to 19 are pressed under pressure and then their melting time, heat deformation and notched Izod impact strength are determined. The press molding process is as follows. 105.6 g of polymer are mixed with 2.1 g of dibutyltin, S, S'-bis (iso * octyl mercaptoacetate), 3.76 g of acrylic polymer as a processing aid, 0.52 g of low molecular weight polyethylene wax and 1.58 g of glycerol monostearate . The mixture of ingredients is processed by milling on a two roll mill which is heated to 210 ⁰ C (410 ° F). It is found that the mixture melts within 30 to 60 seconds from the start of the milling process. The preparations are milled at a temperature of 188 ° C (370 ⁰ F) in a mold, 15.2 cm 15.2 cm χ χ 0.32 cm (6 "x6" x1 / 8 ") un-

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Deformed using time intervals of 3 minutes and a pressure of 70.3 kg / cm (1000 psi). After molding, the samples are allowed to remain in the mold for an additional 2 minutes and then the pressure is increased to 225 kg / cm (3200 psi) and this pressure is held for 2 minutes. The samples are then cooled for 2 minutes and removed from the mold. These samples are then determined for heat deformation according to ASTM Test Method D-648 for heat deformation and impact strength according to ASTM Test Method D-256 for notched Izod impact strength. A special test method is used to determine the melting time, which is defined as the maximum melting torque, measured using a Brabender plastigraph. The method for determining the melting time is as follows: 55 g of polymer together with 2 parts of organic stabilizer, which is sold under the trademark "Thermolite T-31" by M&T Chemicals, are placed ^{in the Brabender dish, which is heated to 204 ° C.,} and 1 part organic stabilizer sold under the trademark "Thermolite T-187" by M&T Chemicals Corporation. The maximum melting torque is determined by determining the time from the addition of the above-described mixture of polymer and stabilizer in the Brabender plastigraph with activated rotors to the time when the maximum torque is obtained, which can be seen by a subsequent decrease in torque. The test results are shown in Table IV below.

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. Acrylate monomer Table III . Melt ASTM ϊ time (h) after the exploitation) D-648 ASTM 55 , 2 in total
velvet 27 57 , 5 at 25 ° C at -2c J ⁰ C Example, Quantity d.Addition after loading powder
start of the second
Stage takes place 53 , 9 79.4 300+ , 3 0.062 (0.45) - No. n-butyl acrylate (G) 2 - 74.9 28 56 1.24 (0.9) - 9 Il 50 2 - 75.9 45 ,8th 0.059 (0.43) - 10 Il 60 0 56 , 5 76.0 23 55 3.37 (24.4) 0, 085 (0.62) 11 Il 70 1 65 , 5 77.0 14th , 0 3.05 - (22.1) - 12th η 70 2 38 , 7 80.1 27 56 3.82 (27.7) - 13th Il 70 3 43 , 5 75.1 38 55 , 0 3.80 (27.6) 0, 16 (1.16) 14th η 70 2 52 , 5 59.9 22 57 , 5 2.58 (18.7) 0, 16 (1.14) 15th n-hexyl acrylate 90 2 53 , 4 75.0 , 5 3.39 (24.6) 0, 15th (1.12) 16 n-octyl acrylate 70 2 59 , 2 70.2 3.312 (24.0) 0, 06 (0.46) 17th 70 2 77.2 18 2-ethylhexyl acrylate 70 2 D-256 19 α-ethoxyethyl acrylate 70 Table IV time (sec) heat deformation Izod impact strength mkg / 2.54cm
must ( ⁰ C) notch (ft.Ib./inch) Example, No. 4 35 62
(Comparison) 10 12th 13th 14th 15th 16 17th 18th 19th

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Example 20

To a 1 liter glass autoclave equipped with a spiral blade is placed 300 g of polyvinyl chloride polymer polymerized in the mass, prepared according to Example 4. The reactor is evacuated to 0.05 mm mercury pressure and then nitrogen is added to a pressure of 7.03 atü (100 psig) filled. This process is repeated, and then 0.5 ml of a 21% strength solution of acetylcyclohexane sulfonyl peroxide in mineral spirits is added. The reactor is evacuated and cooled to 5 to 10 ⁰ C. 70 g of n-butyl acrylate and 100 g of vinyl chloride are added. After 2 hours of polymerization at 72 ° C., a polyvinyl chloride copolymer which is suitable for the production of molded parts is obtained with the required impact strength.

Example 21

Into a vertical, stainless steel reactor for the first stage with a capacity of 9.5 1 (2 1/2 gal), as described in Example 1 using a radial turbine type agitator having an outer diameter 3 1/4 in. (9.5 cm), add an airless mixture of approximately 4,540 grams of vinyl chloride, 0.38 ml a 50 to 53% solution of diisobutyryl peroxide initiator in odorless white spirit (Lupersol 227, Lucidol Division of the Pennwalt Company), 2.20 ml of a 40% solution of di- (2-ethylhexyl) peroxydicarbonate initiator in mineral spirits (Lupersol 223M, Lucidol Div. Of Pennwalt Co.), 0.776 grams of odorless mineral spirits, 1.081 grams of epoxidized soybean oil, and 30 grams (equivalent to 1.15% of the vinyl chloride monomer reactant) Ethylene-propylene-ethylidene norbornene terpolymer having a weight average molecular weight of about 180,000 previously dispersed in liquid vinyl chloride. In the course of 55 min, during this time with high Speed using a speed of

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2000 rpm is stirred in the stirring device, the mixture is from 20 to 70 ° C under autogenous »superatmospheric Heated pressure and then held at 70 ° C for 15 min.

The reaction mixture is then transferred to the second stage reactor as described in Example 1, which is equipped with a spiral stirrer having an outside diameter of 28.3 cm (11 1/8 ") and which is an air-free mixture of about 2270 g Vinyl chloride monomer, 3.80 ml diisobutyryl peroxide initiator, 5.5 g lauroyl peroxide initiator, 0.776 g odorless mineral spirits, 5.48 g octylphenoxy polyethoxyethanol (a liquid surfactant sold under the trademark "Triton X-100" by Rohm and Haas Co. is sold) and 91.0 g (corresponding to 1.3455 of the vinyl chloride monomer added to the polymerization reaction up to this point) ethylene-propylene copolymer with a weight average molecular weight of about 160,000. The resulting mixture is at a low speed of 63 rpm Stirred for 3 h at 49 ^° C. A further 4540 g of vinyl chloride are then added to the mixture over the course of 30 min. When the addition is complete, the reaction is stopped The mixture was stirred at 49 ° C. for 15 min. In the course of 15 minutes, the stirred reaction mixture is heated from 49 to 60 ° C. and then held at the latter temperature for 15 minutes to ensure that all of the diixobutyryl peroxide initiator has been consumed. Over the course of about 20 minutes, the stirred reaction mixture is heated from 60 to 72 ° C and then the reaction mixture is further stirred at the latter temperature until a decrease in reaction pressure indicates that the polymerization is essentially complete (or no more than about 8 ° C) h for the total duration of the reaction in the zones for the first and second reaction stages).

A solution of 1.2 g of 2,6-di-t-butyl-p-cresol antioxidant dye stabilizer in a mixture of 22.7 g ep-

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oxidized soybean oil and 2.33 g of odorless mineral spirits is added under pressure to the polymerized product in the reactor and the resulting mixture is kept at 72 ° C for 15 minutes touched. Unreacted vinyl chloride monomer is blown out of the reactor and about 9040 g of product (corresponding to a Conversion of about 79 »6% based on the total to the Vinyl chloride monomer filled into the reactor) are recovered. Determined by gel permeation chromatography, the weight average Molecular weight and number average molecular weight of the product about 72,800 and 25,600, where the ratio of weight average molecular weight to number average molecular weight is about 2.84. The product contains 12.6% deposits (i.e. particles larger than about 1.27 cm = 0.5 " 11.1% particles larger than 0.84 mm (20 mesh) but smaller than 1.27 cm, 2.0% particles larger than 0.42 mm (40 mesh), but smaller than 0.84 mm, 16.6% particles larger than 0.21 mm (70 mesh) but smaller than 0.42 mm, and 57.7% particles smaller than 0.21mm.

As determined by Coulter Counter analysis of the latter, predominant fraction of the product, 84% of the fraction has an average particle size below 44.1 microns, 50% of the fraction has an average particle size below 37.9 microns and 16% of the fraction has an average particle size below 31 tb> microns.

The bulk density of the above-described product fraction with an average particle size below 0.21 mm (70 mesh) is 0.55 g / ccm. The plastisol viscosity of this fraction amounts to 2960 cps measured with a Brookfield viscometer at 25 + 3 ⁰ C, which value is about 8% lower than a commercially available vinyl chloride homopolymer Extenderharzes (Borden 260SS, Borden Chemical Co.) was prepared as the corresponding viscosity, by suspension polymerization processes.

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Of course, the methods and conditions described above can be changed as desired by the person skilled in the art. For example, gradually increasing (i.e. increasing) the reaction temperature from 49 to 72 ° C (which is to the post-polymerization addition of additional monomer in the second reaction stage follows) carried out more quickly direct heating of the reaction mixture, as described, e.g. by heating the monomer to above 72 ° C before adding it preheated and then the hot monomer is added to the reaction mixture at 49 ° C (if necessary, the material can also be used in Share), the temperature of the resulting mixture from 49 ° to the desired final reaction temperature of 72 ° C is increased.

Example 22

A vertical stainless steel reactor equipped with a radial turbine type agitator and a sea propeller type agitator is charged with an air-free mixture of about 3506 kg vinyl chloride, 340.00 g 2.2 ^L -azo-bis- (2.4 -dimethyl-4-methoxy-valeronitrile), which contains about 3556 water, 857.14 ml of a 75% solution of di (2-ethylhexyl) peroxydicarbonate in mineral spirits, 750 ml mineral spirits, 750 ml epoxidized soybean oil and 24.33 kg (equivalent to 0.694% of the vinyl chloride monomer reactant) ethylene-propylene-ethylidene norbornene terpolymer having a weight average molecular weight of about 180,000 previously dispersed in liquid vinyl chloride. Over the course of 55 minutes, the mixture is heated from 20 to 70 ° C. under autogenous, superatmospheric pressure while stirring at high speed, and then held at 70 ° C. for 15 minutes.

The reaction mixture is placed in a horizontal reactor equipped with three paddle-type stirring blades and which is an air-free mixture of about 1724 g

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Vinyl chloride monomer, 10.2 kg of 2,2'-azo-bis (2,4-dimethyl-4-methoxyvaleronitrile) initiator, 750 ml of regular mineral spirits, and 3 »9 1 octylphenoxypolyethoxyethanol (a liquid surfactant sold by Rohm and Haas Co. under the trademark "Triton X-100). The resulting mixture is stirred at low speed for about 4.5 hours at 47 ° and then an additional 2268 kg of vinyl chloride monomer containing 2.5 kg of lauroyl peroxide initiator is added to the mixture over the course of time of 30 min. When the addition is complete, the reaction mixture is stirred for 15 min at 47 °. Over the course of 15 min, the stirred reaction mixture is heated from 47 to 60 ° and then kept at the latter temperature for 15 min to ensure that the entire Initiator, which reacts at low temperature, is consumed.In the course of 15 min, the reaction mixture is then ^{heated from 60 to 72 °} C. and the reaction mixture is stirred further at the latter temperature until a drop in pressure indicates that the polymerization is essentially complete (or no more than about 10 hours for all of the time in the zones for the first and second reaction stages).

12 l epoxidized soybean oil then become that After the reaction has ended, the reaction mixture is added as a color and heat stabilizer. After adding the epoxidized Soybean oil, the reaction mass is stirred for 15 min at 72 °.

Unreacted vinyl chloride monomer is blown out of the reactor and about 4899 kg (corresponding to one conversion of about 66.7% based on the total vinyl chloride monomer used in the reaction) are recovered. The weight average molecular weight and number average molecular weight of the product are as was determined by gel permeation chromatography, about 102,000 and about 35,300, the ratio of the weight average Molecular weight to the number average

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Union molecular weight is about 2.88. The product contains 85.3% particles less than 0.210 mm (70 mesh) in size.

As determined by Coulter Counter analysis of the latter, predominant fraction of the product, 84% of the Fraction has an average particle size below 84 microns, 50% of the fraction has an average particle size below 56.7 microns and 16% of the fraction has an average particle size below 38.7 microns.

The bulk density of the product fraction described above with an average particle size below 0.210 mm (70 mesh) is 0.65 g / cc. The plastisol viscosity of this fraction is 3438 cP, determined with a Brookfield Viscometer at 25 £ 3 ° · This value is about 3% lower than the corresponding viscosity of a commercially available one Vinyl chloride homopolymer extender resin (Borden 260SS, Borden Chemical Co.) made by suspension polymerization.

For the person skilled in the art, it goes without saying that the process conditions of the process described above correspond can be varied. For example, gradually increasing (i.e. increasing) the reaction temperature from 47 to 72 ° C (which follows the post-polymerization addition of additional monomer in the second reaction stage) faster than by directly heating the reaction mixture, as described, e.g., by preheating the monomer, prior to its addition, to about 72 ° C and then adding the hot monomer to the reaction mixture at 47 ° (if necessary, the addition can take place in partial portions), whereby the temperature of the resulting mixture is increased from 47 ° to the desired final temperature of the reaction mixture of 72 ° C.

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Claims (44)

Claims 1. Process for the production of polymers with smaller Particle size of a vinyl halide by mass polymerization according to patent (patent application P 23 23 191.6), characterized in that the following steps are carried out: (1) a monomer composition that is a vinyl halide monomer or a mixture of a vinyl halide monomer with an ethylenically unsaturated one copolymerizable therewith Contains comonomers in a first stage with high speed stirring at one temperature from about 30 to 70 ° C in the presence of an additive, who is selected from the group (a) an inorganic or organic, inert material of small particle size, which is at least up to Reaction temperature is solid and insoluble in the monomer wherein the material has an average particle size in the range of from about 0.001 to about 50 microns and that Material in an amount of 0.001 to 5 wt. 56 based on the monomer composition present in the first stage is present, (b) a surfactant in an amount of from 0.01 to 5% by weight based on the one or those in the first stage existing monomers, (c) a mixture of the inert small particle size material and the surfactant, and (d) a polyolefin in an amount of about To about 0.05 h Gew.?S, based on the monomer which is present in the first stage is polymerized, are converted to about 3 to about 20 wt.% Of the monomer into polymer, (2) The production of small particle size polymers continues by going in a second stage while the the reaction mixture at low speed 709886/0913 ORIGINAL INSPECTED agitated, polymerizes until about 30 to about 95 weight percent of the monomer composition is incorporated into the base polymer are convicted (3) adding additional monomer to the second stage, the additional monomer at least one vinyl halide monomer or at least one copolymer which is copolymerizable therewith, or contains mixtures thereof, and (4) The polymerization of the additional monomer in the second stage to form non-porous polymer particles is carried out by adjusting the polymerization temperature in the second stage after about 30 to about 80% by weight of the reaction mixture has been converted to the polymer from a range of about 30 increases to about 70 ⁰ C to a range of etv / a 60 to 80 ⁰ C, the increase in the polymerization temperature is about 10 to about 50 ⁰ C. 2. The method according to claim 1, characterized in that the additive is selected in the first stage from group (a) inert material with small particle size, (b) surfactant and (c) mixtures of the inert Small particle size material and the surfactant. 3. The method according to claim 2, characterized in that that fumed silica is used as the inert material with a small particle size. 4. The method according to claim 2, characterized in that that octylphenoxy-polyethoxyethanol is used as a surface-active agent. 5. The method according to claim 1, characterized in that the additive in the first stage is a polyolefin. 6. The method according to claim 5, characterized in that the production of polymers with a small particle size 709886/0913 through polymerization in the second stage, during which the The reaction mixture is moved or stirred at low speed until about 30 to about 95% by weight of the reaction mixture has been converted into the base polymer, in the presence Is carried out by further polyolefin, which is added in an amount of about 0.05 to about 3 wt.%, Based on the weight of the monomer composition added to the polyolefin addition up to that point. 7. The method according to claim 6, characterized in that the monomer composition which polymerizes in the first stage is vinyl chloride and that the monomer composition used in the second stage, up to about 30 to about 95% by weight of the monomer composition was converted to polymer, is polymerized, is vinyl chloride. 8. The method according to claim 7, characterized in that the polyolefin additive of the first stage is a weight average Has a molecular weight of from about 50,000 to about 1,000,000. 9. The method according to claim 8, characterized in that that the polyolefin additive for the first stage ethylene-propylene-ethylidene norbornene terpolymer is. 10. The method according to claim 8 ^ characterized in that that the polyolefin additive for the second stage is a weight average Has a molecular weight of about 50,000 to 300,000. 11. The method according to claim 10, characterized in that a surfactant is added to the polymerization of the second stage with the polyolefin additive of the second stage, the surfactant being added in an amount of about 0.01 to about 0.2% , based on 709886/0913 the weight of the monomer composition up to this Time the polyolefin was added. 12. The method according to claim 11, characterized in that the polyolefin additive for the second stage is ethylene-propylene copolymer is. 13. The method according to claim 12, characterized in that that the surfactant added in the second stage is octylphenoxy-polyethoxyethanol. 14. The method according to claim 10, characterized in that 1 to 200 wt.% Of the additional monomers, based on the weight of the resulting converted base polymer or copolymer, can be added all at once. 15 · The method according to claim 14, characterized in that the additional monomer added in the second stage is vinyl chloride. 16. The method according to claim 15, characterized in that the polymerization is continued in step (2), up to about 30 to about 80 percent by weight of the monomer composition is converted to the base polymer. 17. A method of making a polymer of a vinyl halide by bulk polymerization of a monomer composition by (1) polymerizing a vinyl halide monomer composition in a first stage with high speed stirring at a temperature of from about 30 to about 70 ^° C. until about 3 to about 20% by weight of the monomer is converted to polymer, and (2) Continuation of the production of the polymer in a second stage with stirring at low speed, 709886/0913 characterized in that the polymerization is continued in the second stage until about 30 to about 95 wt. 96 the monomer composition are converted into the polymer, and then at least one ethylenically unsaturated comonomer, which is copolymerizable with the vinyl halide monomer in the presence of the polymer, is added, this with the polymerizes at the same or a higher rate as vinyl chloride and is different from the vinyl halide monomer, and the polymerization is terminated. 18. The method according to claim 17, characterized in that the monomer composition which is polymerized in the first stage is vinyl chloride and that the monomer which is added in the second stage is an acrylate monomer selected from the group of alkyl acrylates, their homopolymers a glass transition temperature of 1O ⁰ C or lower have, or mixtures of such alkyl acrylates. 19. The method according to claim 18, characterized in that the acrylate monomer is selected from ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, n-octyl acrylate and 2-ethylhexyl acrylate. 20. The method according to claim 19, characterized in that the polymer has an impact strength of about 0.276 to about 4.14 mkg / 2.54 cm (2 to 30 ft.lbs./inch). 21. A method for producing a vinyl halide polymer by polymerizing in bulk at least one vinyl halide monomer with at least one copolymerizable therewith Comonomers in the presence of a vinyl halide base polymer, characterized in that the comonomer at least one ethylenically unsaturated compound is used, which polymerizes at the same or faster rate than vinyl chloride and which is different from the compound which 709866/0913 used to make the vinyl halide base polymer with vinyl halide monomer-comonomer polymerization being the final polymerization reaction of the process. 22. The method according to claim 21, characterized in that the vinyl halide monomer is vinyl chloride, and that the Comonoraer is an acrylate monomer selected from the group of alkyl acrylates whose homopolymers have a glass transition temperature of 1O ⁰ C or n. Mixtures of these alkyl acrylates. Have transition temperature of 10 ⁰ C or lower, or 23. The method according to claim 22, characterized in that the acrylate monomer is selected from ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, n-octyl acrylate and 2-ethylhexyl acrylate. 24. Process for the production of a vinyl halide © - polymers, characterized in that one (1) a first component which is a vinyl halide base polymer seed material, which has been produced by Hassen, suspension or polymerization processes, and at least contains a vinyl halide monomer, mixed with a second component which is at least one ethylenically unsaturated Contains comonomer which polymerizes at the same or higher rate than vinyl chloride and which differs from the compound, which was used to make the vinyl halide base polymer seed material differentiates (2) initiates the bulk liquid phase polymerization process, and (3) continue the polymerization until the conversion to the vinyl halide copolymer is completed, whereby the Bulk polymerization of the vinyl halide monomer and the second component is the final polymerization reaction of the process represents. 709886/0913 25. The method according to claim 9, characterized in that the comonomer is introduced into the second stage, if about 50 to about 95 weight 96 of the reaction mixture into the polymer were convicted. 26. The method according to claim 24, characterized in that the vinyl halide monomer is vinyl chloride and that the Comonomer is an acrylate monomer that is selected from the group of alkyl acrylates whose homopolymer has a glass transition temperature of 10 ° C or lower, or mixtures of these alkyl acrylates is selected. 27. Product, characterized in that it has been obtained by the method of claim 1. 28. Product characterized in that it has been obtained by the method of claim 5. 29. Product characterized in that it has been obtained by the method of claim 17. 30. Product, characterized in that it has been obtained by the method of claim 21. 31. Process for the preparation of a polymer with smaller Particle size from a vinyl halide by bulk polymerization, characterized in that one (1) a monomer composition comprising a vinyl halide monomer or a mixture of vinyl halide monomer an ethylenically unsaturated comonomer that is copolymerizable with it is, in a first stage with high speed stirring at a temperature of about 30 to about 70 ° C polymerized in the presence of an additive, the additive being selected from the group: 709886/0913 (a) Inorganic or organic, inert material of small particle size that is solid at least at the reaction temperature and is insoluble in the monomer, the material having an average particle size in the range of about 0.001 to about 50 microns and the material in an amount of % is present 0.001 to 5 percent, based on the monomer composition in the first stage. (b) a surfactant in an amount of from 0.01 to 5% by weight based on that of the first Level monomer present; (c) a mixture of the inert small particle size material and the surfactant; and (d) a polyolefin in an amount of from about 0.05 to about 4 percent by weight based on that in the first stage existing monomer composition, up to about 3 to about 20 % by weight of the monomer composition are converted into polymer particles, (2) the production of the small particle size polymer (s) by polymerization in a second stage continues, in which the reaction mixture is stirred at low speed until about 30 to about 95 wt.% the monomer composition are converted into the base polymer, (3) introduces further monomer into the second stage, the monomer at least one vinyl halide monomer or contains at least one comonomer copolymerizable therewith or a mixture thereof, (4) The polymerization of the additional monomer in the second stage continues to produce non-porous polymer particles by adjusting the polymerization temperature of the second stage, after about 30 to about 80 percent by weight of the reaction mixture has been converted into the polymer, from a range of about 30 to about 70 ° C increased to a range of about 60 to 80 ⁰ C, the increase in the polymerization ^{temperature is about 10 to about 50 0} C and where the 709886/0913 Second stage polymerization in the presence of a surfactant Means added to the second-stage polymerization reaction in an amount of about 0.01 to about 0.2 wt.% is added, based on the weight of the monomer composition, which is up to this point in time was added to the addition of the surfactant. 32. The method according to claim 31 »characterized in that the additive in the first stage is selected from the group comprising (a) a small particle size inert material, (b) a surfactant, and (c) a Mixture of the inert small particle size material and the surfactant. 33. The method according to claim 32, characterized in that smoke is used as the inert material with a small particle size Silica used. 34. The method according to claim 32, characterized in that the surface-active agent used in the first stage Octylphenoxy-polyethoxyethanol is used. 35. The method according to claim 31, characterized in that a polyolefin is used as the additive in the first stage used. 36. A method according to claim 35, characterized in that the polymerized at the first stage monomer composition of vinyl chloride and that the nits when zv / stage are converted to about 30 to about 95 wt.% Of the monomer composition in the polymer, of polymerized monomer is vinyl chloride . 709886/091 3 37. The method according to claim 36, characterized in that the polyolefin additive is a weight average Has a molecular weight of from about 50,000 to about 1,000,000. 38. The method according to claim 37, characterized in that the polyolefin additive is an ethylene-propylene-ethylidene norbornene terpolymer is. 39. The method according to claim 37, characterized in that 1 to 200 % by weight of the additional monomer, based on the weight of the converted base polymer or copolymer formed, is added all at once. 40. The method according to claim 39, characterized in that the additional monomer added in the second stage Vinyl chloride is. 41. The method according to claim 40, characterized in that the polymerization is continued in step (2), up to about 30 to about 80 percent by weight of the monomer composition is converted into the base polymer. 42. The method according to claim 41, characterized in that the surface-active added in the second stage Agent is octylphenoxy-polyethoxyethanol. 43. Product, characterized in that it has been obtained by the method of claim 31. 44. Product, characterized in that it has been obtained by the method of claim 42. 709886/0913