DE1104180B - Process for the production of graft copolymers - Google Patents

Description

GERMAN

There has already been a process for the production of mixtures or compounds of rubber and polymers Proposed substances according to which a natural or synthetic rubber under im essential oxygen-free working conditions in the presence of a proportion of a polymerizable olefin compound is subjected to cold mastication, the mixture of rubber and olefin compound in the The temperature of the mastication in turn is similar to rubber. ίο

If you have such a mixture of a natural or synthetic rubber and a polymerizable Olefin compounds are subjected to cold mastication under essentially oxygen-free conditions some of the rubber molecules tore up, and the free radicals attached to the torn off ends of the molecules arise, initiate the polymerization of the polymerizable olefin compound.

The term "synthetic rubber" as used in the above-mentioned invention refers to synthetic, polymeric substances which have properties similar to natural rubber at room temperatures, in that they show considerable deformation under tension and when they are pulled Stop the tension and pull together again elastically. The 25 term "rubbery" refers to polymeric substances that have the above properties at 40 ⁰ C. In particular, the property to buy 9

to be chuk-like, defined by being a

Substance that is in vulcanized, d. H. cross-linked, 3 ° subdivided material between two horizontal non-plasticized masses contain an expansion kneading tools under load, the lower part of which revolves, suffered by at least 100% and after the

Method of manufacture
of graft copolymers

Applicant:

The Natural Rubber Producers'
Research Association, London

Representative: Dr.-Ing. F. Mayer, patent attorney,
Berlin-Dahlem, Hüttenweg 15

Claimed priority;
Great Britain 9 November 1955 and 7 May 1956

Derek John Angier, William Ferguson Watson

and Raimond John Ceresa,

Melwyn Garden City, Hertfordshire (UK) have been named as the inventor

Stress, after acting for 1 hour, is at least 80% of the stretch within 15 seconds contracts.

It has now been shown that at suitable temperatures, molecules of polymeric substances, which in themselves at room temperature, So at 25 ° C, are not rubber-like, can be broken by mastication, for example

wise in the usual rubber mills or strand 40 the following:

while the upper one is fixed. The values in Table I relate to materials that are processed at a speed of 76 revolutions per minute of the lower tool can be achieved. The breaking devices or kneaders, as used to achieve the results according to Table I and all other results cited below are shown in the drawing. This drawing illustrates in natural size

pressing or mixing, if you first mix the polymer with a material that the polymer in the transferred to a rubber-like state. This is evident from the information in Table I below, in which the changes in the viscosity of various polymers in benzene (measured in an Ubbelohde viscometer in units of 100 ml of solvent per gram of polymer) after mastication at 17 ° C in a laboratory masticator in the presence of oxygen Figure 1 is the underside of the upper tool;

Figure 2 illustrates a section through Figure 1;

Fig. 3 shows the top of the lower kneader and

4 again shows a section in this regard.

As can be seen from FIGS. 1 and 2, the upper tool has a semicircular groove 1, furthermore a sunk one Part 2 and finally a tooth 3, which is surrounded by a flat surface 4. The lower kneader according to Figures 3 and 4 have a series of concentric grooves.

and 5 percent by weight thiophenol (an effective 50 The web 5 between the two innermost grooves is opposed to

Deactivator) are listed. The laboratory masticator used was of the type described in the Journal of Scientific Instruments ", Vol. 31, March 54, pp. 98 and 99. In this machine that is the mastication continued above the level of the remaining webs by about 0.8 mm. In addition, it is through four notches 6 interrupted, which run tangential to the innermost groove and connect this with the next one.

109 539/588

Table I.

Polymer (A)

Plasticizer (B)

relationship B. Tempe A: 1 rature 3: 1 15 ° C ο: 1 35 ° C 2: 1 15 ° C 4: 1 15 ° C 3: 1 15 ⁰ C 3: 1 15 ⁰ C 3: 1 15 ° C 3: 1 15 ° C 4: 1 15 ° C 3: 1 35 ° C 3: 1 15 ° C 4: 1 15 ° C 3: 1 35 ° C 3: 1 15 ⁰ C 3: 15 ° C

Initial viscosity

To
15 minutes

To
30 minutes

Polystyrene

Polystyrene

Polystyrene

Polystyrene

Polyvinyl chloride

Ethyl cellulose

Cellulose acetate

Polyvinyl acetate

Polyvinyl acetate

Polyvinyl acetate

Polymethyl methacrylate
Polymethyl methacrylate
Polymethyl methacrylate

Polyvinyl alcohol

Poly-X-vinyl pyrrolidone

benzene
benzene
benzene
benzene

Tetrahydrofuran ethyl acetate
Methyl acetate toluene
toluene
toluene
acetone
acetone
acetone
water
water

0.96

0.96

0.96

0.96

1.30

1.08

1.12

0.38

0.38

0.38

5.30

5.30

5.30

0.265

0.150

0.85

0.94

0.95

0.68

1.13

1.05

1.06

0.37

0.33

0.37

3.88

4.91

4.99

0.263

0.140

0.76

0.92

0.94

0.55

0.96

1.03

1.00

0.35

0.30

0.36

1.48

4.02

4.61

0.256

0.131

The increased effect in terms of the viscosity of the polymer, such as when lowering the masticating temperature is observed, indicates that this process is exerted on the rupture of the polymeric molecules by the Shear based.

The invention now relates to a method by which the free radicals that are at the torn ends of the Molecules of a non-rubbery polymer form, are made to polymerize a or introduce several polymerizable olefin compounds, hereinafter referred to as monomers, the Polymers are mixed. The polymer itself is derived from a polymerizable olefin compound and the blended monomer is the same as the polymerizable olefin compound from which the polymer is derived is, the resulting product is homopolymer. If, on the other hand, the monomer is of a different nature, then that exists Product made from a mixture of homopolymers and a copolymer of an unusual type, by dividing the different types of monomeric molecules in their polymerized form into separate segments of the Molecule to be disassembled. Copolymers that are obtained in this way can accordingly be called "polymeric compounds" can be considered in which different homopolymeric sections are chemically linked to one another are.

It has been found that, for the purpose of producing polymeric materials by mastication of mixtures of non-rubbery polymers and monomers, the mixture must not be present in the form of a liquid solution of the polymer in the monomer, because otherwise an adequate shear force to initiate the polymerization by breaking apart polymeric molecules cannot be used is. Rather, the constituents of the mixture of polymers and monomers and their relative proportions should be chosen so that the mixture is rubber-like at the mastication temperature, i.e. shows the characteristics of deformation under load and an at least partial contraction after the load has been lifted. In particular, the term is rubber-like defined by the fact that such mixtures have the property of sustaining under load within one second at 25 ° C is at least a 5 ° / _o strength at break, wherein after the lifting of the load, a least 50 ° / ₀ sodium contraction of the strain takes less than 10 seconds.

Oxygen has a deactivating effect on the free radicals caused by the breaking of the polymer Molecules are created. At the same time, it has a retarding effect on the polymerization of many polymerizable substances Olefin compounds. Furthermore, it can cause discoloration of the products. It is therefore in the generally desirable, and in some cases even essential, the admission of oxygen to the mixture to prevent during mastication, for example in such a way that the mastication is carried out in a device that completely is filled with the mixture so that no free gas space remains. Mastication can also be used Carry out with the addition of an inert gas. The exclusion of oxygen does not need to be sustainable be, d. i.e., it is not necessary to process the polymer or monomer in a vacuum, and if that Monomers has a noticeable volatility at the mastication temperature, its evaporation from the A mixture of polymers and monomers is already sufficient to air during mastication to expel from the masticator. In some cases, such as when the free radicals caused by the polymer arise, are particularly active, and the monomers react to a high degree, the polymerization proceeds rapidly also possible without excluding oxygen. Otherwise, the need and the desirability of oxygen exclusion is influenced by other factors, such as the absence or presence of the polymerization inhibiting substances in the polymer and monomers, for example by the fact that the presence of an inhibitor an additional delay effect due to the oxygen in appearance occurs. Another factor is the solubility of the oxygen in the mixture of polymers and monomers. In some cases, a low concentration of oxygen even proves to be helpful because it increases the level of Polymerization increased.

The various influences of oxygen on the course of the polymerization are illustrated by the following Reflects results obtained under the same mastication conditions as those obtained Table I are based.

5 6

(a) Select a mixture of polymethyl methacrylate and vinyl nation of polymer and monomer, acetate was masticated for 20 minutes under nitrogen. It turns out, for example, that when the PoIy-Am At the end of this period, more than 85% of the mere was easily dissolved in a particular monomer that Vinyl acetate polymerized. Has a corresponding polymer been converted into a solution when the proportion of Mixture during the same period in which the counter-5 monomers are too high. So here comes the expected Masticated by air, less than 5% were not a rubber-like condition, and were not desired the vinyl acetate polymerizes, d. that is, the polymers were accordingly used for the purposes of the present invention sation was caused by the presence of air. Mixtures containing these particular monomers hinders. Not be suitable. On the other hand, the same monomers

(b) A mixture of polymethyl methacrylate and ethyl io, for example in combination with other polymers, quite acrylate, which is 27 percent by weight of the latter sub-advantageous. Furthermore, it is found that one contained for 10 minutes under nitrogen invention suitable mixtures were not obtained by mastication, and 99% of the ethyl acrylate was obtained by polymerizing a polymer with a monomer. Under the same working conditions, but combined, which is highly incompatible with it, it in the presence of air, only 75% of the 15 reached, unless a plasticizing solvent ethyl acrylate is used for the polymerization; after 15 minutes for the polymer in such a proportion that the mixture was 89%. Here, too, the rubber-like became accordingly. Certain, very insoluble polymeric polymerization due to the presence of oxygen substances, such as e.g. B. the C stage of phenol formaldehyde material is delayed. condensation products, can resist all attempts-A similar hindrance to the polymerization left 20 to versieh in a rubber-like state with a mixture of polystyrene and 25 ° / ₀ , so that in this case mixtures of polymer methyl methacrylate or such made of poly - and monomer, which are suitable for the invention vinyl acetate and 25 ° / ₀ Watch methyl methacrylate. are not achievable. However, after 10 minutes there were 99% methyl methacrylate in number of polymers with regard to the selection of more suitable the mixture of polystyrene and methyl methacrylate 25 combinations with monomers and / or plasticizing polymerized, if the mastication under nitrogen solvents no particular difficulties. Subsequent, while in the presence of air, numerous examples of suitable combi-10 minute mastication are described below, only 51% of the methyl methanate ion. For example, polymethyl methacrylate could have been polymerized. After 20 minutes acrylate without the help of a plasticizer and polyvinyl, the proportion was 60% ■ 98% of the methyl methacrylate in the 30 chloride in the presence of tetrahydrofuran combined with a mixture of polyvinyl acetate and methyl methacrylate with a wide range of monomers polymerized in 10 minutes if the mastication are used . Another aspect of the implementation under nitrogen closure took place, whereas in the inventive method is that the presence of air after 10 minutes only 28% combination of polymers and monomers or and were / ₀ was polymerized after 20 minutes only 40 °. 35 polymers, a monomer and a plasticizer in

(c) A mixture of polymethyl is masticated in a wide range of suitable proportions methacrylate and methyl methacrylate (24 weight can be varied. Too small a proportion of monomer percent of the latter) 10 minutes under nitrogen, or of monomer and plasticizer does not give a 99% of the methyl methacrylate is polymerized. A rubber-like mixture or at least an unhomo result the reaction in the presence of air, so 40 genes mixture in which the monomers are in mastis after 10 minutes, 98% of the methylation is only partially polymerized. Contains other methacrylates polymerized, d. That is, the oxygen has too high proportions of monomers or of the mixture in this case no visible effect in terms of monomer and solvent, so it will be for the the degree of polymerization. Mastication too soft to allow adequate tearing. Corresponding results are shown when one achieves 45 polymeric molecules. Then none occurs a mixture of polymethyl methacrylate and 26% noticeable polymerization. The mixture can die Styrene used. The nitrogen shield results in the form of separate particles when chewed After 20 minutes of mastication, a chuk-like polymer can be obtained at mastication temperature of 97% of styrene, while becoming rubbery in the presence of.

Air is 95% polymerized. 50 The influence on the degree of polymerization resulting from

(d) If you masticate a mixture of polystyrene and vinyl - the quantitative proportion of polymer and monoacetate (23%) for 20 minutes, after more than one in the mixture results, 23% of the results are illustrated by the following 20 minutes mastication under nitrogen polymerized by mastication of the mixtures vinyl acetate, while in mastication were achieved in the above-mentioned laboratory masticator, decoration of the mixture with admission of air in the same ₅₅ in which the mixing period shown in FIGS. 1 to 4, 40% of the vinyl acetate are polymerized. or tear device with 76 revolutions per minute

The method according to the invention for the production of poly- ran, with cooling water of 15 ° C being used,

Merer substances accordingly consists in the fact that the amount of the mixture used in each case was sufficient

Mixture of one at room temperature not chewed, not enough to fill the masticator completely; the outdoors

Chuk-like polymers, a polymerizable olefin- 60 remaining space of the masticator present air

compound and, if necessary, a plasticizing agent was displaced by nitrogen.

Solvent for the polymer of mastication under- (a) A mixture of 40 parts by weight of ethyl cellulose

is thrown, the selection of the blend component and 60 parts of methyl methacrylate was soft and sticky;

and their proportion is determined so that it was the methyl methacrylate after mastication for 20 minutes

Mixture not yet polymerized at the mastication temperature rubber-65.

is similar, and during the mastication of (b) mixtures of 60 to 45 parts by weight of ethyl access at least partially excluded from oxygen cellulose and 40 to 55 parts by weight of methyl methacrylate will .. were like rubber. Over 70% of the methyl meth-

When carrying out the acrylate according to the invention, after 20 minutes of mastication, polymeric

When driving, it is first necessary to find a suitable combination.

(c) A mixture of 70 parts of ethyl cellulose and 30 parts of methyl methacrylate was powdery; less than 10% of the methyl methacrylate was polymerized after 20 minutes of mastication. Similarly, a mixture of 80 parts of polyvinyl acetate and 20 parts of styrene, after 20 minutes was / ₀ polymerized mastication only to 20 °, while a corresponding mixture of 40 and 60 parts not polymerized, while a mixture of 70 parts of polyvinyl acetate and 30 parts of styrene showed 95% polymerization of the styrene after 20 minutes. This 70:30 mixture was initially rubber-like, the 80:20 mixture was initially powdery, and the 40:60 mixture formed a soft, viscous mass.

Further factors which influence the formation of mixtures suitable for the purposes of the invention Polymers! and monomer are temperature and molecular weight of the polymer. So there is sometimes a certain softening of the polymer by increasing the temperature for the Conversion of the same into a rubber-like state useful. On the other hand, the higher the molecular weight becomes of the polymer, the wider the range of proportions of monomers and plasticizers, which leads to the formation of a rubber-like mixture.

The mixture of polymers! and monomers can be prepared by introducing the monomer into the polymer prior to mastication, this method being applicable to both gaseous and liquid monomers. The plasticizing solvents can be introduced in the same way. If the monomer is a solid, e.g. B. acrylamide, it is necessary either to use a plasticizing solvent to give the polymer the required degree of rubber-like nature, or to masticate the mixture at temperatures at which the mixture is rubber-like. It is also often convenient to mix the polymer and monomer together when the monomer has melted. The mixture of polymers! and monomer or from polymers !, monomer and plasticizer is expediently converted into the form of a homogeneous, swollen mass before the polymerization takes place by mastication, so that a uniform polymerization can easily be achieved. For this purpose, the mass can be stirred or kneaded, for example in an open mixer, e.g. B. a Gardner mixer, and or increase the temperature. This increase in temperature is particularly useful in the case of mixtures which become gel-like at elevated temperatures. For example, the polyvinyl chloride and butyl acrylate gel quickly at 70 ⁰ C and then give on cooling to the mastication temperature of z. B. 15 ° C a rubber-like mixture. It has also been shown that one can add monomer or monomer and plasticizer to a rubber-like mixture of polymer and monomer or of polymer and plasticizer or of polymer, monomer and plasticizer during mastication; this addition could also be made to a polymer which is masticated at elevated temperature so that it is rubber-like, always provided that this addition does not deprive the material subjected to the mastication of its rubber-like character. It is thus possible to add all or part of the monomer and / or the plasticizing solvent during the mastication, either in portions or continuously. If the monomer is a solid substance at room temperature, it can be added either in solid or molten form to the rubber-like material being masticated.

The degree of rubber-like nature for the blend of polymer and monomer in the frame of the method according to the invention is required is influenced by the design of the masticator. The bigger the shear effect of the device and the more effective the cooling of the treated mixture, the higher it can be the proportion of monomer and plasticizing solvent that is permissible before the mixture is too soft for the mastication and thus for a sufficient disruption of the polymer molecules. Effective cooling units are often desirable to prevent the temperature of the mixture from increasing during the process in uncontrollably increases and thereby the degree of polymerization because of the softening that occurs Mixture impaired.

In general, any polymer that is not itself rubbery can be used to make the described Mixtures can be used in the context of the process according to the invention, provided that it is only able to turn into one to transfer rubber-like mixture with a monomer and / or plasticizer. As already mentioned, certain, highly insoluble polymers are eliminated. In general, it must be mean molecular weight of the polymer are over 1000. It can be both synthetic and natural occurring polymers can be used, including chemically modified forms of natural polymers Fabrics.

Examples of synthetic polymers that can be used include the following:

(a) Non-rubber-like addition polymers of compounds which _{contain one or more CH 2} = C <groups, for example polymethyl acrylate, polymethyl methacrylate, polyethyl methacrylate, polyethylene, polystyrene, polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, polyvinyl formaldehyde, polyvinyl butyraldehyde, polyvinyl acrylonitride, poly-N-vinyl pyrrolidone , as well as copolymers of 1,3-butadiene with high proportions of styrene or methyl methacrylate and finally trans-polyisoprene.

(b) epoxy polymers, e.g. B. from melting point 145 to 155 ⁰ C.

(c) polyethylene glycols.

(d) Linear super polyesters and super polyanides, e.g. B. Polyethylene terephthalate, polyhexamethylene adipamide, polyhexamethylene sebacamide and poly-e-caprolactam.

(e) The A and B stages of phenol condensation products with aldehydes and ketones, e.g. B. A and B-phenol and cresol formaldehyde condensation products.

Examples of naturally occurring polymeric substances that could be used would be

(a) Casein.

(b) copal resins.

(c) shellac.

(d) animal glue.

Examples of chemically modified, natural polymeric substances can be mentioned:

(a) cellulose esters, acetals and ethers, e.g. B. cellulose acetate, cellulose butyrate, cellulose formaldehyde, methyl cellulose and ethyl cellulose.

(b) Cyclized natural or synthetic rubber.

(c) rubber hydrochloride and chlorinated rubber.

1 1Ü4 Löü
9 10

Plasticizing solvents, which are created for the on-radicals when the molecules are torn apart. A turn in the manufacture of rubber-like products. A slight conversion of vinyl acetate into a mixture of polymers! and monomers! Suitable, include polymer is shown, for example, when this monomer is all liquids that swell on the polymer in connection with polystyrene is used. However, if they do not have the course or grade 5, this difficulty does not arise if one undesirably influences a mixture of the polymerization. Examples of polyvinyl acetate and monomeric! Styrene is used for such solvents in adaptation to different This implies a general principle in that, polymers are water (e.g. for polyvinyl alcohol, if one takes the roles of monomers! And polymers! Casein, glue, polymethacrylic acid and poly-N- vinyl interchanged, the degree of polymerization and the nature of the pyrrolidone), benzene (e.g. for polystyrene), tetrahydro- ίο obtained products do not remain the same,
furan (e.g. for polyvinyl chloride), ethyl acetate (e.g. for the ethyl cellulose and epoxy polymers to be used for the process according to the invention), methyl acetate (e.g. mixtures can, if desired, two or more for cellulose acetate), acetone (e.g. for polymethyl meth - polymeric substances and / or two or more monomers acrylate), dichlorethylene (e.g. for polyvinylformaldehyde), provided that the resulting mixtures are rubber-like at the methanol (e.g. for polyvinyl butyral) and dimethyl mastication temperature. On this formamide (e.g. for polyacrylonitrile). Liquids, like manner, copolymers can be prepared that contain tricresyl phosphate and dibutyl phthalate, which usually contain three or more components. In addition, used as plasticizers for synthetic polymers, the polymers can first be used with one, can be masticated to obtain valuable plasticized monomers and then also used with one product. One of the valuable 20 others. If, for example, a monomer possesses one of the possibilities of the invention, there is, however, a high softening effect compared to the polymer and the creation of stages with properties which, as a result, undesirably reduce the need for the poly to use the usual plasticizers. Degree of merization in mastication, or arises from If one uses in the production of such materials the mixture of the same with the polymer, not easily plasticizing solvents, then a rubber-like state is preferably used, so the polymer can have those that result from the end product, for example thereby allowing it to be easily removed again in one for the union with the monomer evaporation. In the meantime, a more suitable product can be transferred by allowing plasticized compositions according to the first to produce the polymer with another monomer invention by initially masticating or masticating which does not have the same disadvantages,
During or after the treatment according to the invention, the mixtures to be used according to the invention should, treatment adds a customary plasticizer. as far as possible, be free of materials which are free

The radicals to be used for the purposes according to the invention to deactivate, for example from antioxidants or from monomers, can be a monoolefin compound or substances which contain a retarding effect on the poly also more than one olefin double bond. Exercise merization, although this, as indicated in the above compounds containing one or more CH ₂ = C C groups 35 Example 1, (b), in some mixed systems, are preferred. Examples of monoolefin is not necessary. The presence of retarding compounds that can be used are acrylic acid groups in the polymeric substance is also gradually and their esters with saturated alcohols, e.g. B. methyl part. The presence of common polymerization catalyst, ethyl acrylate and n-butyl acrylate; substituted catalysts is not required and can delay the acrylic acid and esters with saturated alcohols, eg. B. 4 ° caused by the mastication polymerization methacrylic acid, methyl methacrylate, ethyl methacrylate act. However, this makes it possible to use poly-butyl methacrylate, 2-ethoxy-ethyl methacrylate and merization catalysts when the masti-2-chloroethyl methacrylate; also nitriles and amides of cation is carried out at temperatures at which they are acrylic acid and substituted acrylic acids, e.g. B. Acrylic are effective, not excluded as this is a way of nitrile, methacrylonitrile, acrylamide and n-butyl acrylamide; 45 to the ratio between the copolymer and homofern vinylidene compounds, z. B. vinylidene chloride, polymeric and modify the molecular weight of the end product methyl isopropenyl ketone and the isobutylene dimer. If necessary, similar variations can also be achieved in the end product by

(C- (CH _S ) ₃ -CH ₂ -C- (CH ₃ ) = CH ₂ ); that the process is carried out in the presence of a chain

50 transmission medium carries out. The possibility of one

then vinyl compounds such as styrene, vinyl acetate, molecular weight control by such methods Methyl vinyl ketone, N-vinylpyrrolidone, 2-vinylpyridine and is both homopolymerized and mixed poly-vinylcarbazole; as well as compounds in which oil merization is useful. Unsaturated compounds attached to fmical double bonds form part of a ring structure cannot be polymerized, but are capable of forming a mixture, z. Tie. 55 to experience polymerization can be in the mixture of

Among the examples of compounds containing more than one polymers and monomers also included

contain olefinic double bonds and are invented for; for example, maleic anhydride accelerates

Suitable purposes include the degree of polymerization when styrene is used as the monomer

bonds using conjugated olefinic double bonds.

included, e.g. B. Chlorpren and divinylbenzene, as well as 60 The mastication of the mixture can in facilities bonds in which the olefinic double bonds of the type are carried out, as they are not in rubber are conjugated, such as esters of acrylic acid and industry and are common in the plastics industry, i.e. H. of substituted acrylic acid with unsaturated alcohols, for example in an inner or with two rotors Glycols, e.g. B. allyl acrylate, allyl methacrylate mixer, provided that adequate provision is made for and ethylene dimethacrylate. 63 the cooling of the mixture during mastication

When carrying out the invention can be met, for example by a circulating coolant,

certain difficulties in polymerizing mono- and that, if necessary, oxygen by circulating a

mers with lower reactivity result, ins- inert gas, such as nitrogen or carbon dioxide,

especially when it is excluded in connection with polymers. The mastication could also be on

Substances are used that are not run through highly active free grinding rollers; however here is

11 12

the maintenance of an inert atmosphere and the products, which are useful as emulsifiers, can Avoidance of a loss of volatile monomers according to the invention from mixtures of an affinity for quite difficult in practice due to evaporation. The aqueous phase containing polymer with monomers furthermore, the mastication could be obtained in an extrusion press, which allows the formation of polymers

carry out which, of any desired type, 5 have an affinity for the oil phase or vice versa,

is held so long that it is able to rely on it. Furthermore, according to the invention, adhesive and working mixture has a sufficiently high shear effect Binder made from mixtures of polymers and mono-

to tear apart the polymeric molecules. win mers in which the polymer has adhesiveness The use of such an extruder has the opposite of one of the materials to be joined

great advantage that under normal working conditions and on the other hand the polymer according to the

the oxygen present does not make it necessary to have corresponding properties compared to the monomers

would make special arrangements for its disposal to other material.

meet; Also, the method that consists of the extrusion press is another field of application of the invention

served, particularly suitable for continuous work, in the production of chemical compounds

especially if the press before the mastication section 15 contains two or more polymers which in their homopoly-

has a preliminary stage in which homogenization is not satisfactory or not easy in meren form

of the mixture can be effected. homogeneous physical mixtures are converted

The temperature of the mixture during the mastication can, for example, compounds of polyethylene

should normally not reach a value above 150 ^° C. and acrylate and polymethyl methacrylate.

are expediently kept below 100 ⁰ C, around a 2 ° Then the invention can be used to the

ensure quick response. Molecular weight of addition polymers due to masti-

When the polymeric substance is largely modified by amorphous decoration with the monomers that make up

Structure, the degree of polymerization takes more normal- they are derived. The molecular weight

assign when the temperature of mastication lowered either increased or decreased, depending on the factors

This is of course insofar as the mixture is used for the mastication, such as temperature or concentration

Mastication in the available device of the monomer in the mixture. Appropriate setting

doesn't get too hard. On the other hand, if the mixture contains one of the conditions, the molecular weight can also be used

crystalline polymer, ζ. B. polyethylene, polyvinylidene are kept at a fairly constant level,

chloride, polyhexamethylene adipamide or polyethylene. The process of the invention is accordingly very good

terephthalate, the mastication should be suitable for the production of homopolymers at a temperature, since

temperature above the melting point of the polymer a part of the product with a further proportion of

be carried out so that the mixture of rubber monomers can be polymerized and this

is similar. Repeat the process at will.

The properties of the according to the invention It follows accordingly that the invention for

Process manufactured products differ 35 Manufacture of a large number of new, interesting substances

noticeably different from those of the polymer corresponding to the leads, which have largely varied properties

monomeric component of the mixture, but can be, and accordingly also for a large amount

not necessarily suitable between those of the two poly-turnaround areas. The method by which all

merisate. Typical properties, which are produced by the invention, these substances have in this respect one

Can be influenced, hardness, impact resistance, 40 significant advantage are that they are not the application of

Flexibility, elasticity, solubility, melting point, polymerization catalysts or the addition of foreign ones

Mouldability, injection molding, crystallization properties make materials, such as emulsifiers, necessary as they are

and fiber-forming ability. often required in conventional polymerization processes

For example, mixtures of polyvinyl are produced. The products obtained are therefore unusual chloride with butyl acrylate and ethyl acrylate products 45 dimensions free of disturbing impurities. Other pre-boosters Flexibility and elasticity as a function of parts of the method according to the invention are that of proportions of monomeric substance. It can be dispensed with using unusual equipment This way products are obtained, the properties and that the whole manufacturing method is best for like those of the customarily elaborated poly- a broad industrial production is suitable, especially then, vinyl chloride compositions, but the 50 when used in facilities such. B. an extruder, Disadvantages are eliminated, which is usually carried out with those who work continuously Use of plasticizers are connected, allow.

so especially the wandering and bleeding of the soft Another advantage of the invention is that

machers, as well as losses due to evaporation processes lead to high degrees of polymerization or polymerization

at higher temperatures. 55 speeds under safe working conditions

On the other hand, according to the invention, films can be obtained without the need for complicated arrangements for

achieve higher toughness from shellac if the latter had to be used to control the reaction; the

initially in the manner according to the invention with styrene reaction mechanism essentially creates itself

is masticated. Similarly, the formability becomes a, with a sudden increase in temperature of

of epoxy resins if one mastication 60 a correspondingly sudden decrease in the reaction

with styrene or methyl acrylate. speed is accompanied.

As an example of influencing the solubility can

are given that an example prepared according to the invention
Product made from polymethyl methacrylate and styrene at

Dissolving in benzene does not precipitate when 65 The following Tables II, III and IV give examples

for example, significantly larger proportions of methanol from polymerization products, which are caused by masti-

admits, as would be required to styrene homopolymer cation of mixtures of polymers and monomers

to fail. Also, for example, the solubility of have been achieved in the above-mentioned laboratory masticator,

animal glue in water by masticating with The air in the masticator was initially by a

Methacrylic acid decreased. 70 slow nitrogen flow, and the masti-

cation was carried out under low nitrogen pressure. In the case of Table II and III cooling water of 17 ⁰ C was taken to the circulation during the mastication. The kneading tools correspond to the version shown in the drawing, with the lower tool rotating at 76 revolutions per minute.

The polymers according to Table II were obtained from mixtures which did not contain any plasticizer, whereas in the case of Table III the mixtures contained plasticizing solvents. The examples Table IV relate to the preparation of polymers from mixtures of polymers with solid Monomers. When preparing the samples for the reaction, the dry polymer was powdered with solid monomers mixed, and this mixture was

then transferred into a gel, either by adding benzene or by warming up on the Reaction temperature.

With the exception of the mixture according to Example 38, the mixtures were prepared by mixing the polymer soaked with the monomer or plasticizer at room temperature until the mixture became rubber-like became. The mixture according to Example 38 was prepared by adding polymer

ίο and monomer heated to 70 ° C until mastication occurred, and then the masticated mixture cooled to room temperature.

The figures in the tables relating to the proportion of polymerized monomers are with a fluctuation accurate to a few percent.

Table II

Polymer Monomer ° / ₀ mono Mctsti- Poly-
meri- example more in
Starting cation ized
Mono mixture. meres Polymethyl methacrylate Methyl methacrylate Minutes ° / o 1 Polymethyl methacrylate Methyl methacrylate 40.4 7.5 88 la Polymethyl methacrylate Methyl methacrylate (containing 25th 20th 98 Ib 0.01% hydroquinone) Polymethyl methacrylate Styrene 25th 20th 96 2 Polymethyl methacrylate Acrylonitrile 33.2 20th 95 3 Polymethyl methacrylate Methacrylic acid 34.8 10 95 4th Polymethyl methacrylate Ethyl acrylate 34.0 5 86 5 Polymethyl methacrylate Divinylbenzene 36.8 10 97 6th Polymethyl methacrylate Vinyl acetate 37.5 2.5 85 7th Polymethyl methacrylate Allyl methacrylate 37.5 30th 97 8th Polymethyl methacrylate / 9-ethoxyethyl methacrylate 40.2 15th 96 9 Polymethyl methacrylate 2-chloroethyl methacrylate 31.4 5 93 10 Polymethyl methacrylate Ethyl methacrylate 40.1 10 97 11 Polymethyl methacrylate Ethylene dimethacrylate 37.0 5 97 12th Polymethyl methacrylate Allyl acrylate 40.9 10 96 13th Polymethyl methacrylate Butyl acrylate 38.3 5 92 14th Polymethyl methacrylate Methyl acrylate 37.7 5 97 15th Polymethyl methacrylate Methacrylonitrile 34.8 5 98 16 Polymethyl methacrylate Methyl isopropenyl ketone 30.2 5 87 17th Polymethyl methacrylate N-vinyl pyrrolidone 35.5 15th 97 18th Polymethyl methacrylate 2-vinyl pyridine 41.0 10 95 19th Polymethyl methacrylate 2-vinylpiridine 39.6 10 57 19b Polymethyl methacrylate Vinylidene chloride 40.0 20th 87 20th Polystyrene Methyl methacrylate 35.0 10 97 21 Polystyrene Styrene 26.3 10.0 99 22nd Polystyrene Methacrylic acid 23.4 15th 98 23 Polystyrene Diisobutylene 34.2 5 98 24 Polystyrene Diisobutylene 17.0 20th 76 24b Polyvinyl acetate Vinyl acetate 17.0 30th 89 25th Polyvinyl acetate Methyl methacrylate 12.0 20th 96 26th Polyvinyl acetate Styrene 25.0 10 98 27 Polyvinyl acetate Methacrylic acid 26.3 15th 96 28 Polyvinyl formaldehyde Methacrylic acid 26.1 2 96 29 Polyvinyl formaldehyde Methyl methacrylate 39.5 5 93 30th Polyvinyl formaldehyde Methyl methacrylate 21.0 20th 75 30b Polyvinyl formaldehyde Styrene 21.0 30th 93 31 Polyvinyl formaldehyde Styrene 25.2 15th 49 31b Polyvinyl formaldehyde Vinyl acetate 25.0 45 86 32 Polyvinyl formaldehyde Vinyl acetate 25.7 25th 41 32b Polyvinyl butyral Vinyl acetate 26.0 60 89 33 Polyvinyl butyral Vinyl acetate 23.1 20th 71 33b Polyvinyl butyral Styrene 23.0 30th 91 34 Polyvinyl butyral Methyl methacrylate 25.0 15th 97 35 24.3 10 97

Table II (continued)

Polymer Monomer ° / ₀ mono Mastic Poly- more in
Starting cation meri- example mixture ized
Mono Polyvinyl butyral Methacrylic acid Minutes meres Polyvinyl butyral Diisobutylene 29.0 1 ° / o 36 Polyvinyl chloride Butyl acrylate 20.1 15th 98 37 shellac Diisobutylene 20.0 15th 89 38 shellac Diisobutylene 28.0 10 94 39 shellac Methyl methacrylate 28.0 25th 60 40 shellac Styrene 23.2 15th 86 41 shellac Styrene 24.1 20th 85 42 shellac Vinyl acetate 24.0 45 65 42b shellac Vinyl acetate 18.9 30th 92 43 Run Congo Chopal Methyl methacrylate 19.0 60 30th 43b Run Congo Chopal Methyl methacrylate 23.3 25th 55 44 Run Congo Chopal Methacrylic acid 23.0 45 60 44b pale Congo chopal Methyl methacrylate 25.0 15th 88 45 pale Congo chopal Methyl methacrylate 15.1 25th 97 46 pale Congo chopal Methacrylic acid 15.0 45 50 46b Manila opal Methyl methacrylate 18.3 10 84 47 Manila opal Methyl methacrylate 17.4 25th 97 48 Manila opal Methacrylic acid 17.0 45 50 48b Ethyl cellulose Methacrylic acid 18.1 10 91 49 Ethyl cellulose Methyl methacrylate 46.1 10 85 50 Ethyl cellulose Methyl methacrylate 38.5 20th 93 51 Ethyl cellulose Styrene 39.0 30th 67 51b Ethyl cellulose Styrene 29.9 25th 92 52 Epoxy resin Styrene 30.0 50 54 52b Epoxy resin Styrene 12.1 15th 85 53 Epoxy resin Methyl methacrylate 12.0 25th 74 53b Epoxy resin Methacrylic acid 14.8 10 89 54 Phenol formaldehyde resin Methacrylic acid 17.1 10 96 55 Cresol formaldehyde resin (B-grade) Methyl methacrylate 16.1 20th 99 56 Cresol formaldehyde resin (B-grade) Methyl methacrylate 23.1 15th 98 57 85:15 styrene-butadiene mixed poly 23.0 30th 68 57b merisat Methyl methacrylate 91 58 Polymethyl acrylate Methyl methacrylate 24.0 10 Polyethylene methacrylate Methyl methacrylate 10.1 20th 99 59 22.2 15th 87 60 90

Polymer Tabel III ° / o des Monomer ° / o des Mastic total total cationic weight weight duration Plasticizing solvent of the Ge of the Ge (Minutes) mix mix to poly 20.1 23.9 merization example Polyvinyl chloride 19.1 Type 22.5 from min Polyvinyl chloride 19.4 21.0 at least Polyvinyl chloride 20.1 19.8 S5 ⁰ I ₀ des Poly-N-vinyl pyrrolidone Type 23.1 Methyl methacrylate 20.1 Mono Polyvinyl alcohol 16.3 Ethyl methacrylate 16.2 meren Polyacrylonitrile 14.8 Ethyl acrylate 14.5 20th 61 Casein Tetrahydrofuran 10.1 Methacrylic acid 13.2 25th 62 Animal glue Tetrahydrofuran 16.5 Methacrylic acid 14.9 20th 63 Animal glue Tetrahydrofuran 20.0 Methyl methacrylate 23.1 5 64 Polyvinylidene chloride water 14.1 Methacrylic acid 15.0 15th 65 Polyacrylamide water Acrylonitrile 20th 66 Dimethylformamide Methacrylic acid 5 67 water Methyl methacrylate 20th 68 water Methacrylic acid 0.5 69 water 25th 70 Tetrahydrofuran 15th 71 water

Table IV

Polymer Plasticizing
solvent ° / o des Monomer ° / o des Mastic Mastic Poly-
meri- total
weight Weight
tes from cationic
duration cationic
tempe- ized
Mono example by PoIy-
merem Poly-
merem rature meres Type and Type and Soft mono- Polymethyl methacrylate doer merem Minutes 7o Polymethyl methacrylate 23 26th 20th 17th 56 72 Polymethyl methacrylate benzene 23 N-vinyl carbazole 25th 20th 17th 62 73 benzene 23 Acrylamide 25th 20th 17th 41 74 Polymethyl methacrylate benzene Phenylmelamine Polymethyl methacrylate 23 acid 25th 20th 17th 48 75 benzene 23 Calcium acrylate 25th 20th 17th 70 76 Polymethyl methacrylate benzene N-tertiary butyl Polymethyl methacrylate 23 acrylamide 24 20th 17th 72 77 Polymethyl methacrylate benzene 23 Acenaphthalene 25th 20th 17th 70 78 Polymethyl methacrylate benzene 23 Methacrylamide 25th 20th 17th 59 79 Polyethylene benzene 23 Potassium methacrylate 30th 20th 17th 32 80 Polyethylene benzene none Triallyl cyanurate 23 60 100 40 81 Polyethylene none none Acenaphthalene 23 30th 95 19th 82 none none Acenaphthalene 9 30th 105 33 83 none Acenaphthalene

Example 84

Polyethylene molecular showed tearing in mastication (80 ⁰ C) in said Labormastikator, wherein the lower tool with 146 revolutions per minute circulated; by adding 0.6 ml of orthoxylene per 1 g of polyethylene, the rubber-like state occurred. 0.01 gl, l'-diphenyl-2-picrylhydrazyl was added as a deactivator. The viscosity, measured with the Ubbelohde viscometer, at 141 ° C. and with menthone as solvent, decreased from an initial value of 0.74 after 30 minutes of mastication to 0.63 and after 60 minutes of mastication to 0.59. In a similar example with polyethylene 38 percent by weight of divinylbenzene were charged at 85 ° C, to obtain a rubber-like at 8O ⁰ C mixture. This latter was masticated with nitrogen and terminating at a rotation number of 146 of the lower tool 60 minutes at 8O ⁰ C. 78% of the monomer was polymerized within this time, while non-masticated mixtures showed no measurable polymerization. After mastication, 44% of the product in toluene at 100 ⁰ C were insoluble, while nichtmastizierte mixtures were completely soluble.

Example 85

55

Polyhexamethylene revealed with 0.25 ml of methacrylic acid per gram of polymer at 7O ⁰ C a rubber-like mixture. During mastication of the same under nitrogen in said Labormastikator, the lower tool running at 86 revolutions per minute, C 81% of the monomers in the polymeric form were in 15 minutes at 70 ⁰ converted to give a harder product revealed during unmastizierte mixtures no polymerization showed and retained the original consistency.

The product of mastication was largely insoluble in 90% aqueous formic acid, whereas the Starting polymer easily dissolved.

Example 86

Styrene was incorporated into polymethyl methacrylate chips having a viscosity (in benzene) of 5.0 (100 ml / g) to give a rubber-like mixture containing 40 weight percent styrene. This mixture was passed through a Shaw press with a diameter of 2.54 cm, the drum of ^{which was heated to 40 °} C. and the head piece to 100 ^° C. and the screw of which was running at 10 revolutions per minute. This made it possible to polymerize more than 95% of the styrene.

Claims (1)

Claim: Process for the production of graft copolymers from a mixture of an inherently non-rubbery polymer, a polymerizable olefin compound and, if necessary, a solvent plasticizing the non-rubbery polymer by means of mechanical treatment of the mixture in an at least partially oxygen-free atmosphere, characterized in that the Components of the mixture and their proportions are dimensioned so that the mixture is rubber-like at the mastication temperature and this mixture is subjected to a mastication. Considered publications:
German patent specification No. 842 407. 1 sheet of drawings © 1 »539/588 3.61