DE1570934A1 - Process for the preparation of polyolefin-vinyl halide graft polymers - Google Patents

Description

EDUARD LORENZ BERNHARD SEIDLER ^ MAfcÖRTTSEIDLER

LAWYERS
Bavarian Supreme Court · Qberlandesgerichf- Munich · Regional Courts AAünchenji ßid / lQ 3 3 Zjt

P 15 70 93 ^ .9 '■' ■■■

8 Munich 22 ,, Widenmayerstraße 23

V .; December 21, 64 · Telephone [0811] 297194/297834

Postal check: Munich 170280 Bank account: Bayerische Hypotheken- und

Exchange bank Munich Re 8787 Your reference
Our sign, 4 391 La / He

^Taa 14 ·. October 1968 '

Monsanto Company, St. Louis, Missouri, USA '

Process for the preparation of polyolefin yinyl halide ■ "■ - ■ goiter polymers

The invention "relates to vinyl halide polymers, in particular Mixtures of polyvinyl halides and polyolefins.

Plasticizer-free yinyichloride polymers have proven themselves "at the manufacture of rigid objects with good chemical and heat resistance proven to be useful. These rigid objects however, have specialist parts with regard to certain physical properties, for example flexibility at low temperatures and impact resistance. By adding This problem could only be partially solved with plasticizers. For example, it is known to use polyvinyl chloride and polyethylene, which is a fairly tough, pliable polymer to mix mechanically with each other, yet these two substances are incompatible in the mixture and the mixture obtained is not sufficiently homogeneous. ■

The invention is based on the discovery that improved Graft polymer blends of polyvinyl halides and polymers made of monoolefins without the use of solvents can be.

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The main aim of the invention is therefore to create vinyl halide polyolefins in graft polymer compositions improved physical properties. -_,.,

Another object of the invention is to provide vinyl halide polyolef in-graft polymer compositions having improved physical properties and without use have been produced by solvents.

Another purpose is to create procedures and means for achieving the foregoing objects.

Further purposes can be found in the description below

emerged.

According to the invention, a process for the production of polyolefin-vinyl halide graft polymers is proposed, in which the polyolefin is dissolved in the heat in the monomer to be grafted, which is characterized in that a polyolefin of the general J formula CE ", in which η is a whole Number of 2 - ^z f, or an ethylene-propylene, ethylene-acrylic / t-, iithylene-vinyl acetate or ethylene-yinyl chloride mixed polyiters at a 'l temperature above 80 ° 0 and

2 at an autogenous pressure of more than 14 kg / cm in one Dissolves vinyl halide monomers and the vinyl halide monomers polymerized by conventional processes for the polymerization of vinyl halide.

Are graft polymers of polyethylene and polyvinyl chloride has already been made in such a way that the polyethylene was dissolved in various solvents before the reaction, as it is, for example, in the USA patent specification No. 2 9 ^? 719 is described. The graft mixture is mechanical produced mixture is superior, but the use of solvents is generally impractical because they reduce the graft yield and reduce the physical properties of the

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Affect the product »,

US Pat. No. 3,047,534 is also concerned with a process for the production of graft copolymers in which the base polymer is dissolved in a polymerizable, ethylene-unsaturated monomer. However, this process aims at the use of a certain combination of suspension agents with the aid of which the graft polymerisation is carried out in a two-stage suspension process. A number of diene chewing polymers are used as the base polymer. The combination proposed by the invention of vinyl halide as graft monomers η and polyolefins of the formula CH ₂ (η = 2-4) or ethylene-propylene, ethylene-acrylate, ethylene-vinyl acetate or ethylene-vinyl chloride copolymer as base polymersA can not taken from this patent specification.

A process for the production of polyolefin-vinyl chloride graft polymers is also known from German patent specification 1 65 618. S ^{1 For} this process, however, it is essential, according to the main claim, that the base polymer is a polymer of C-Mor olefins It is true that, according to the description, the use of non-peroxidized base polymers for grafting on the vinyl chloride polymer is not ruled out; however, it is pointed out that if only slightly peroxidized polyolefins with a low molecular weight are used, an essential part of the introduced polyolefin can remain unchanged and is then not bound to the polyvinyl chloride. Thus, the skilled person is advised to peroxidize the base polymer before the graft polymerization if he wants to achieve technically acceptable results

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Invention from: it proposes the usual, unchanged, non-peroxidized polyolefin in the vinyl chloride monomer to dissolve and - with additional deviation from. the Teaching of the aforementioned German patent specification - the dissolution not under room conditions, but at one temperature above 80 ° C and a pressure of more than 14 kg / cm. The method of operation according to the invention not only saves a complex and unusual peroxidation; it also facilitates the graft polymerization, for which known polymerization techniques can be used. In addition, surpass the inventive Graft polymers also die in their properties. Products that be prepared by the method of this patent specification.

According to the invention, a graft polymer is produced by before the reaction, the base polymer composed of a polyolefin of the general formula C H "(n = 2-4) or a copolymer of ethylene with propylene, acrylate, vinyl acetate or vinyl chloride at a temperature above 80 ° C and an auto-

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A pressure of more than 14 kg / cm <is dissolved in the vinyl halide monomer. In this way, a graft reaction is achieved which would otherwise not take place and which enables the use of inexpensive, readily available polymers. However, in order to avoid degradation of the reactants, the temperature should not be higher than 120.degree.

The invention further proposes to introduce the hot solution of the base polymer in the vinyl halide monomer in water; it should be added to water as soon as possible after the solution has formed. If the temperature of the solution is something drops, some of the polymer can form a very fine precipitate. It is through this formation of precipitation that the results not significantly affected unless there is significant agglomeration. If the polycer mono-

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mer solution is injected into the water, a fine dispersion of the base polymer and monomers, which leads to optimal conversion rates and yields.

In the context of the invention, the usual emulsion. or suspension processes can be used. The catalyst and the suspending agent can be added to the water before or after the introduction of the polymer-monomer solution. However, the catalyst and the suspending agent are general preferably present in the water before the hot solution is introduced. Tray introducing the solution into the water the polymerization takes place according to normal polymerization processes :, for example according to Example I.

According to a further proposal of the invention that obtained suspension mixture at temperatures between 35 and 75 ° 0 moved until the polymerization is essentially complete. The remaining monomer is then allowed to drain off and the resin by spinning and drying won. The estimated yield is generally over 90%.

In the graft mixtures prepared according to the invention, 1 to 75 percent by weight of the base polymer is graft polymerized with 25 to 99 percent by weight of a vinyl halide monomer. Preferably 5-55 weight percent of the base polymer is graft polymerized with 95-5 weight percent of a vinyl halide monomer. The term "polymer" includes both homo- as well as Go- and interpolymers. The base polymer used is either a polyolefin of the general formula C _n Ho _n / in which η is an integer from 2-4-, which therefore includes ethylene, propylene, butylene and its isomers, or a mixed polymer of ethylene with acrylate, vinyl acetate , Vinyl chloride or propylene, '', ■.

Awake another proposal of the invention together along with the vinyl halide monomer, other monomers also be used." In such a j? All ', however, that is what it is supposed to do

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Vinyl halide monomer make up at least 70 % of the total amount of monomer. These other monomers are ethylene unsaturated monomers that are polymerizable with the vinyl halide monamers. For example, vinylidene chloride, vinyl esters of organic acids, acrylonitrile, methacrylates, maleates, fumarates and other unsaturated organic compounds can also be used as monomers.

Table I shows various compositions of graft mixtures which can be obtained by changing the ratio between the base polymer or polyethylene and the vinyl chloride monomer. These results were obtained, as described below, by extracting the graft mixture by the Soxhlet process with an azeotrope obtained from! tetrahydrofuran and 4.3 % water and the subsequent extraction with octane, which is a good solvent for the polyethylene, but not for the grafted oil.

Tabel Raw materials I. grafted
! Bearing , 5
, 9
Λ Ratio of polyethylene
to vinyl chloride 18th
42
31 25:75
50:50
75:25 Composition of the graft
mixed % Polyvinyl-? APoly- %
Ethylene chloride 65.9 17.6
24.6 32.5
10.0 58.6

To achieve an optimal physical mixture or a mixture with better tolerated components should the grafted part of the graft mixture is preferably the same

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be large or larger than the proportion of the polymer .Infolgedessen is grafted material with a polymer of vinyl chloride-lfe-haltnis of ^75: was hergestelfc 25, with respect to der.Verträglichkeit its components or its impact resistance to physical or mechanical mixing with other interpolating which are normally incompatible with the polymer are less suitable than a material with a ratio of 50:50. Table I shows that the proportion of polyethylene to the grafted material in the graft mixture increases considerably when the proportion of polyethylene in the starting materials is well over 50 % . As indicated above, the polymer content in the starting materials can be between Ί and 75 % . However, it is preferably 5-55%.

The graft polymer material obtained according to the invention can also, as the invention further suggests, with others Ethylene-unsaturated monomers produced polymer materials are physically mixed. The in the examples XI-XlV specified materials as well as styrene-acrylonitrile, Methyl styrene acrylonitrile, methyl styrene styrene <Acrylonitrile, butadiene-acrylonitrile interpolymers are used, which are usually used with the polymers of the type described J are incompatible. The optimum proportion of the grafted material “in the mixture depends to a large extent on the proportion of the base polymer in the graft mixture. It means that ' if the base polymer is erroneous, the homogeneity of the mixture is maintained and therefore the impact resistance is also lowered.

By physically mixing the graft mixture with materials such as, for example, the polyvinyl chloride homopolymer, one can achieve good, rigid mixtures in which the polyolefin content in the physical mixture finally obtained is between 1 and Λ5 yes or preferably between 5 and

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15 % . To achieve a good semi-rigid mixture, the polyolefin content in the physical mixture finally obtained should be in the range of 15-25 % .

The polymerization can be carried out by heat, radiation and polymerization catalysts be accelerated. Monomer-soluble organic peroxides have proven to be useful catalysts proven, for example benzoyl peroxide, lauroyl peroxide, 2,4- Dichlorobenzoyl peroxide, acetyl peroxide, acetylbenzoyl peroxide, other asymmetrical peroxides, tert-buty-hydroperoxide, alkyl percarbonates, Perborates, azo compounds, and mixtures thereof. The amount of the catalyst is generally from that Effectiveness of the catalyst at the polymerization temperature and on the amount of monomer and diluent. The polymerization can also advantageously be carried out in the presence of chain regulator substances. To this include, for example, chlorinated hydrocarbons, alcohols, Aldehydes, etc. However, their presence reduces the grafting effect. As a suspending agent in the context of the invention hydrophilic, macromolecular, natural or synthetic colloids and nonionic or ionic synthetic substances, as well as mixtures thereof can be used. Emulsion polymerization can be carried out using water-soluble Catalysts, for example of hydrogen peroxide or ammonium persulfate and dispersants such as sodium lauryl sulfate be performed.

If necessary, the polyblend mixtures can also contain additives, such as stabilizers, fillers, coloring substances, processing aids, Lubricants, plasticizers, etc. included. Among the processing aids and plasticizers used in the Polyblend mixtures may be included, include e.g. methyl methacrylate polymers, Styrene-acrylonitrile copolymers, styrene-methyl methacrylate copolymers, Epoxy components, chlorinated

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Paraffins etc.

The following exemplary embodiments serve to explain of the invention, which does not apply to these examples 'is restricted. Unless otherwise stated, will Quantities given on a weight basis.

Example I.

3 parts of polyethylene and 27 parts of vinyl chloride ionomer are used placed in an autoclave, which is equipped with a steam jacket, provided with a stirrer and an outlet arranged at the bottom is .. The autoclave is closed and the contents on a Temperature of 80 ° C and an autogenous pressure of about

2 · ■

15.8 kg / cm. These conditions are for a period of half an hour or until the dissolution of the polyethylene -in the. Maintain monomer. Then the outlet located on the bottom is opened so that the solution of polyethylene in the monomer is injected into a reaction vessel containing 48 parts of water, 0.1O part of methyl cellulose (oxypropylmethylcellulose with a gelling temperature of at least 65 °) and 0.075 part of lauroyl peroxide contains and its contents stirred-is. / The dispersion so obtained is stirred for about 15-16 hours at about 5O ⁰ C. After this period of time, the unreacted monomer is allowed to drain off. It is found that more than 93 % of the monomer was converted into a polymer. This resin is filtered and dried. -.

Example II ■ - ".-

The procedure of Example I is repeated with the same procedure and using the same ingredients, but replacing the polyethylene used in Example I with 3 parts of polypropylene. More than 90 % of the monomer is converted into a polymer. . :. - _;

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Example III

The procedure of Example I is repeated with the same procedure and using the same ingredients, but replacing the polyethylene used in Example I with 3 parts of an ethylene-acrylate copolymer having a polymer ratio of 80:20. More than 90 % of the monomer is converted into a polymer.

Example IV

The procedure of Example I is repeated with the same procedure and using the same ingredients, but replacing the polyethylene used in Example I with 3 parts of an ethylene-vinyl acetate copolymer having a polymer ratio of 60:40, more than 9C% of the monomer are converted into a polymer.

Example V

The procedure of Example I is repeated with the same procedure and using the same ingredients, but replacing the polyethylene used in Example I with 3 parts of an ethylene-vinyl acetate copolymer having a polymer ratio of 40:60. More than 90 %. of the monomer are converted into a polymer.

Example VI

The process of Example I is repeated with the same procedure and using the same ingredients, but the polyethylene used in Example I is replaced by 3 parts of an ethylene-propylene copolymer with a., Content of 60 % ethylene. More than 90% of the monomer is converted into a polymer *

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Example VII

The procedure of Example I is repeated with the same procedure and using the same ingredients, but using 9 parts of polyethylene instead of the 3 parts used in Example I. More than 90 % of the monomer is converted into a polymer.

Example VIII

The procedure of Example I is repeated with the same procedure and using the same ingredients, however, instead of the 3 parts used in Example I. 13.3 parts of polyethylene are used. More than 90% of the Monomers are converted into a polymer.

Example IX

The procedure of Example I would follow the same procedure and repeated using the same ingredients, but instead of that used in Example I ν 3 parts 27 parts polyethylene are used. More than 90% of the monomer are converted into a polymer.

Example X. .

100 parts of the resin obtained according to Example I are with 2.5 parts of cadmium laurate and 0.5 part of dibutyltin lauryl mercaptide as stabilizers at 149 ° C on a roller mixer mixed. Parts removed from the rolled sheet at different times are formed into 3 * 2 mm thick plates, which are cut to test specimens. The test items for the tensile and heat resistance tests are now 127 long, 13 mm wide and 3 «2 mm thick. The specimens for the impact resistance tests are 64 mm long, 13 mm wide and 3.2 mm thick. to

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For comparison purposes, a physical or mechanical Produced mixture of polyvinyl chloride homopolymer and polyethylene in equivalent proportions also in the roller mixer manufactured. When testing according to ASTM, the results given in Table II are obtained:

Table II Graft mixture Izod impact strength (mkg / cm) Mixing and rolling time 5 min. 0.28. I5 min. 0.83 25 min. 0.28

Mechanically produced mixture

0.21

0.15 0.18

Heat resistance,

Limit temperature, C 67 68.5

Tensile strength, kg / cm

Y yield point, 429 351

Breaking point 421 345

Elongation, %

Yield point 4.2 4.0 Breaking point 140. 2? Tensile modulus, kg / cm ² 2.0. 10 ⁴ 1.8. 10 ^.

In the extraction of the graft mixture and the mechanically produced mixture by the Soxhlet method with an azeotrope of tetrahydrofuran and 4.3 % water, 10.5 # of ^the mixture produced by mixing rollers was found to be insoluble. The graft mixture was 16.0% insoluble. Preliminary tests show that the Pclyvinylchlorid-Homopolymer alone completely soluble and the polyethylene in this solvent

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alone is about 95.4 % insoluble. Of the prepared by mixing rolls mixture was - hence the Polyvinylchlorld homopolymer are extracted essentially ^{completeness:} during war "mixture into the pot Pf" substantial portion of the polyvinyl chloride adhered to the polyethylene, and therefore, insoluble. ¹ by the extraction of these mixtures with octane, which is a good solvent for polyethylene, but not a solvent for the polyvinyl chloride homopolymer, was "confirmed" that grafting had occurred. During this extraction, 8.6 % of the mixture produced by mixing rollers and only 3.0% of the graft mixture were dissolved in the octane. This shows that part of the polyethylene had become insoluble due to the addition of polyvinyl chloride members.

Example XI

A graft mixture is prepared using the procedure given in Example I, but 9 parts of polyethylene are used instead of 3 parts. 55 parts of the Pfropfgemisches 45 parts polyvinyl chloride resin (specific viscosity 0.380) and 1.5 parts Dibutylzlnnmaleat physically admixed as a stabilizer in I65 G ^0. After processing in the roller mixer for a period of 15. For minutes, the composition thus obtained had good physical properties.

Example XII

Following the procedure of Example I and using the same ingredients, a graft mixture is prepared. 30 parts of this mixture are graft polyvinyl chloride resin 7.0 parts (specific viscosity 0.500) and 1.7 parts of barium laurate physically admixed at ⁰ I65 G. After roller mixer processing for 15 minutes, the composition thus obtained had good physical properties. ■. - -. -

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Example XIII

Using the procedure of Example YII and using the same ingredients, a graft mixture is prepared. 40 parts of this graft mixture are physically admixed with 60 parts of polyvinylidene chloride resin (specific viscosity 0.40) and 2.0 parts of tin oleate at 170.degree. After processing in the roller mixer for a period of Λ ¹ ) minutes, the composition thus obtained had good physical properties. ■.

Example XIV

With the procedure "of Example VII and using A graft mixture is prepared from the same constituents. 40 parts of this graft mixture will be 60 Parts of a resin copolymer of 85 parts vinyl chloride and 15 parts of vinyl acetate (specific viscosity 0.30) and 2.2 parts of calcium / zinc stearate at 160 ° 0 physically mixed in. After processing in the roller mixer for a period of 15 minutes, the resultant had Composition good physical properties.

The products according to the invention are rigid or semi-rigid mixtures that are suitable for the production of rigid or semi-rigid plates, pipes and molded bodies with an optimal combination of high impact and tensile strength values let process. The products according to the invention are also distinguished by gate flow properties at relatively low processing temperatures, high heat resistance and excellent resistance to Chemicals and solvents. As a result of the properties mentioned last as well as the high resistance those according to the invention are suitable for use against ultraviolet radiation Products excellent for many

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Twists outdoors, such as wavy and flat Roof tiles, wall coverings, etc. samples of the masses that after. Rolling times of * 5, 10 and 25 minutes on a roller mixer were taken, showed in their test that even with a relatively long processing time in the roller mixer no thermal degradation or a "discoloration takes place. These substances can by calendering, injection molding, extrusion and otherwise processed into rigid panels, pipes, structural elements, wire jackets, bottles, etc. and if necessary reinforced with, for example, asbestos fibers.

It goes without saying that within the scope of the inventive concept numerous modifications to the above methods and products are possible.

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Claims (9)

Claims 1. A process for the preparation of polyolefin-vinyl halide graft polymers, the polyolefin being dissolved in the warm in the monomer to be grafted on, characterized in that a polyolefin of the general formula CH ₂ , in which η is an integer from 2-4, or an ethylene-propylene, ethylene-acrylate, ethylene-vinyl acetate or ethylene-vinyl chloride copolymer dissolves in a vinyl halide monomer at a temperature above 80 ° O and at an autogenous pressure of more than 14 kg / cm ^ and that Polymerized vinyl halide monomers by conventional methods for the polymerization of vinyl halide. 2. The method according to claim 1, characterized in that the solution of the polymer in the vinyl halide monomers Adding water and then polymerizing. 3. Process according to claims 1 - 2, characterized in that the vinyl halide monomers at a Temperature of 35 - 75 ° C with constant movement of the dispersion practically polymerized. 4. The method according to claims 1 - 3 »characterized in that that 1-75, preferably 5-55 percent by weight of the polymer in 25-99 *, preferably 45-95 percent by weight of the vinyl halide monomer dissolves. 5. Process according to claims 1-4, characterized in that the monomers to be grafted on are at least 70%, based on the total weight of the monomers Vinyl halide and the rest of other, un- 909836/1379 saturated monomers polymerizable with vinyl halide consists. . 6. The method according to claims 1-5, characterized in that that one adds polymers to the graft mixture, which are also made from other ethylene-unsaturated monomers and optionally usually with the polymer are not compatible. 7. The method according to claim 6, characterized in that vinyl chloride homopolymer is added. 8. The method according to claims 6-'7, characterized in that that the proportion of the polymer is 1-25 percent by weight, based on the total weight. 9 098 36/1 3 7 9 ^{B /} ^ ORi _GiNAL