DE1946357A1 - Polymer compositions - Google Patents

Description

The present invention "deals with polymer compositions.

According to the present invention "is the method of Preparation of a polymer composition in that at least one monomer is converted into a hydrocarbon containing at least contains a tertiary carbon atom at a temperature at which the hydrocarbon and the are formed de composition are liquid, creating a. Polymer composition which is substantially homogeneous.

It is believed that during the process of the present invention, graft polymerization occurs because the homogeneous polymer compositions according to the invention the hydrocarbon and the polymer based on the added monomer, do not resemble.

If desired, a mixture of hydrocarbons can be used will. QQ9 837/20 7 6

BATH ORIGINAL

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By using the method according to the invention it is possible, for example, to produce hydrocarbon / vinyl ester polymer compositions produce that have general properties that are similar to mixtures of waxes with copolymers, which by Copolymerization of hydrocarbons such as ethylene and propylene with monomers such as vinyl acetate or other polar ones Monomers were produced without the need for expensive pressure reactors to be used, as these are "at atmospheric." Pressure can be produced.

The monomer used can be one or more of a wide variety of monomers or mixtures thereof, and particularly preferred monomers are vinyl esters of lower fatty acids, the contain up to 12 carbon atoms, for example vinyl acetate. Other monomers such as esters of acrylic, methacrylic, fumaric, maleic, or Itaconic acids can also be included in the compositions, as can compounds derived from benzene, . such as styrene and vinyl toluene monomers and monomers such as vinyl chloride and vinylidene chloride. These can be added one after the other or in mixtures, but one must note that certain. Monomers such as vinyl acetate and styrene cannot be mixed prior to reaction without serious inhibition the polymerization of any of them occurs. If desired, monomers containing addition-reactive groups can for example hydroxyl and epoxy groups, added, especially when secondary crosslinking is desired. ·

In addition, acidic monomers can be included, for example crotonic acid, acrylic acid, itaeonic acid, acid anhydrides such as maleic anhydride or half esters. The maleic anhydride "" is suitably present in an amount up to 15 percent by weight of the total monomer. It has been found that in some cases the addition of materials of this type, and particularly maleic anhydride, advantageously increases the rate of the reaction. "" ^: - "

A wide variety of hydrocarbons that make up a tertiary carbon

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containing atom atom can be suitably used.

But "particularly" preferred hydrocarbon polymers are those which have a high degree of chain branching, ie these hydrocarbons contain a large number of tertiary carbon atoms. \ Io the hydrocarbon contains only 1 tertiary carbon atom, it is preferred that the tert. The hydrocarbon or mixtures of hydrocarbons can contain other groups, "for example hydroxyl, halogen or carboxylic acid groups," although the total number of such groups should not be more than 10% by weight of the composition "It should be emphasized that none of these groups should influence the process according to the invention by inhibiting or greatly delaying the polymerization. A preferred low molecular weight of the hydrocarbon is 200, although a higher molecular weight, e.g. above 400, is preferred. These 'molecular weights are essentially average molecular weights of technical products and generally do not correspond to those of pure hydrocarbons; it could be that a pure hydrocarbon with the required properties could not be used if it were available.

Suitable hydrocarbon polymers include microcrystalline v / axis, ozokerite waxes, polypropylene, especially e. tactic polypropylene, alone or in Mischunen provided with each other or with other polymers, for example with polyethylene of low molecular weight, particularly low density polyethylene, to be substantially at! Eemperaturen below 150 ⁰ C, particularly below 120 ^c C, and most preferably below 100 ⁰ C, are liquid. In some cases a small amount of residual ITiclite saturation in the hydrocarbon can be tolerated. For example, the hydrocarbon can be a butadiene, isobutylene or butene polymer or an olefin wax alcohol. A particularly suitable mixture of hydrocarbons is a mixture of microcrystalline Vfachs and atactic polypropylene, which has a poly-

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merisat composition provides improved homogeneity having. The microcrystalline wax has an average molecular weight of about 600, and a "particularly useful atactic polypropylene is one that is medium. Molecular weight between 1,800 and 2,000 ", although other atactic polypropylenes are not excluded. The hydrocarbon polymers suitably have an average value Molecular weight up to 10,000.

The polymerization conditions suitably include an initiator, particularly initiators known to be they for the production of graft and block copolymers are more suitable than for homopolymerization, and especially preferred initiators include the peroxides of the hydroperoxide class of initiators, for example Benzoyl peroxide, tert-butyl hydroperoxide or tert-butyl perbenzoate. Alternatively, a suitable redox system can be used. The polymerization is preferably carried out at elevated temperatures executed, and when the hydrocarbon polymer is a If wax is, it can be heated until it is melted, if desired a small amount of solvent, e.g. toluene, can be added to improve the properties of the liquid to improve.

The percentage of monomer to hydrocarbon can be over vary a wide range but are suitable, although not limiting, weight ratios of hydrocarbon to Monomers are 1: 0.1 to TsIO, and a particularly preferred one Ratio is from 1: 0.3 to 1: 3.

If desired, a plasticizer can be added to the composition can be added, and any of the known plasticizers, for example dibutyl phthalate, is suitable.

The polymer composition can be prepared by stirring the molten hydrocarbon and mixing

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BATH ORIGINAL

of the catalyst and the monomer into the hydrocarbon runs. If preferred, parts of the catalyst can be added be added to the hydrocarbon itself beforehand or with parts of the monomer or monomers. It was found, that the. Satisfactory production at 70 ° C. until" 125 ° C can run even if the normal boiling point of the monomer is below the minimum temperature of this range. A higher temperature can be used if it is consistent with the properties of the initiator used. Lower temperatures are for example when Redox systems used are not excluded. If necessary the display can be carried out under an inert gas such as nitrogen.

In one process in the preparation of the polymer composition, the monomer or the monomers and, if desired, the initiators are added continuously below the surface of the hydrocarbon composition at a rate similar to that at which the polymerization takes place, "" and ^ wfrd ^ Mer Keep reflux to a minimum. It has been found that temperatures can be obtained at 10O ⁰ C in embodiments of this technique, although the outer heating devices are below this temperature. The internal temperature is maintained by the exothermic reaction.

The products which are produced by the process according to the invention combine the advantages of a polymer with those of a hydrocarbon or wax. Thus, they have melting points which rather are low, for example .6O ⁰ C to 8O ⁰ C, but they are mobile liquids that are suitable for coatings and adhesives, in many cases without the Fotwendigkeit is that one solvent has to enforce. The compositions are suitable for moistening substrates,

For example, paper if it is in a molten /) state.

* GlT 'and SXG ■■ "**

improved adhesion to many substrates,

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when they are in the dry state, especially when the monomers contain some polar groups. In addition, they show Toughness and good heat sealability or sealing properties, and their low tendency to "break," magnifies that Shielding property "against moisture of folded materials.

The invention is described in more detail by the following examples. All parts are parts by weight in grams unless otherwise specified, the melting points of the compositions were measured by differential thermal analysis using a Perkins-Elmer differential scanning calorimeter and a temperature gradient of 16 ^° C / min. applied. All preparations were carried out under nitrogen.

Example I.

A polymer composition was prepared from the following formulation:

Parts

microcrystalline wax p.100 50 Vinyl acetate 50.

Benzoyl peroxide ■ 2

. The mikrokirs tall ine wax is from Wilkins, Campbell & Company available. ......

The vinyl acetate was mixed with the benzoyl peroxide. The wax was ^{heated to 80 °} C. and then a stirrer was started. 20 wt .-? ° of the vinyl acetate benzoylperoxyds were supplied to the wax, and the remainder of the vinyl acetate-benzoyl \ peroxydmischung was added at 85 ⁰ C for a period of 11/2 to 2 hours..

The resulting composition, which is slightly yellow and in hot Condition was homogeneous, provided a clear, slightly yellow, homogeneous liquid. The products solidified on cooling «The

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Melting point obtained by differential thermal analysis was 70 ^° C. to 71 ^° C. The composition, when cold, was harder than the originally used microcrystalline wax. · ·

Example II

A polymer composition was made from the following formulation manufactured: ■

Parts

microcrystalline wax p.100 50

Vinyl acetate 150

Benzoyl peroxide 9

The vinyl acetate was mixed with the benzoyl peroxide. The wax was ^{heated to 80 0} G and then the stirrer was started. 20 $ o of the wax was added to the vinyl acetate benzoylperoxydmischung, and the rest of the vinyl acetate was added benzoylperoxydmischung at 85 ⁰ C for 3 to 4 hrs..

The resulting composition, when hot, was a clear, slightly yellow solution and had a high viscosity. The differential thermal analysis with the melting point obtained was 70 ⁰ C to 71 ° 0th The composition could be effectively plasticized and plasticized by adding dibutyl phthalate of about 10% by weight of the composition.

Example III

A polymer composition was made from the following formulation manufactured:

Parts

microcrystalline yiachs p. 100 atactic polypropylene Vinyl acetate

VeoVa 9-11

Benzoyl peroxyo.

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37, 5 12, 5 56, 2 18 b 3, O

■ ■ - 8 -.

The atactic polypropylene was manufactured by I.O.I. Ltd. obtain. VeoVa is the trade name of vinyl ester of branched-chain fatty acids, which contain 9 Ms 11 carbon atoms.

The vinyl acetate was mixed with 9-11 YeoVa then the -. * -. "J benzoyl-Perosiyd dissolved in the mixture, the polypropylene was dissolved in the microcrystalline wax by all heated together to about 100 G ⁰ 120 ⁰ Ms C . the wax polypropylene mixture was then cooled to 95 ⁰ C + 1 ° 0 and the monomer Benzoylperoxydmisehung was continuously added during 3 h.. the resulting composition was a clear, slightly applies liquid when it was hot. the one with the differential thermal Melting point obtained by analysis was 70 ^° C. to 71 ^° C.

Example IV

A polymer composition was made from the following formulation manufactured:

Parts

microcrystalline wax p.100 37.5 atactic polypropylene 12.5 Vinyl acetate 37.5 VeoVa 9-11 12.5 Benzoyl peroxide 2.0

The vinyl acetate was mixed with VeoVa and then the benzoyl peroxide was dissolved in the vinyl acetate-VeoVa mixture. The polypropylene was dissolved in the wax by heating them together to about -IOO ⁰ C TdIs 120 ⁰ C. The Wachspopylpropylenmischung was then cooled to 95 ⁰ C * 1 ⁰ C, and the vinyl-ac etat VeoVaperoxydmisehung was then added during 2 hours.. The resulting composition was a clear, slightly yellow liquid when warm, and the melting point obtained by differential thermal analysis was 70 ° 0 to 71 ° C.

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0AD ORIGINAL

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Example V

A polymer composition was made from the following formulation manufactured:

Parts

microcrystalline wax p.100 112.5 atalctisch.es polypropylene 37.5 Vinyl acetate 100 Benzoyl peroxide 2.0

Dr's benzoyl peroxide was mixed with yinylacetate with low warming. The atactic polypropylene was dissolved in the wax by being heated together to about 100 ° 0 Ms about 12O ⁰ O. The wax-propylene mixture was then to 95 ⁰ C + 1 ° a ~ bgekuh.lt, and was the Yinylacetat-benzoylperoxydmischung for a period of 3 hrs. At 92 ° C Ms ° 0 and 94 for 1 hr. At 95 ° C to 100 ⁰ G added. The resulting composition was a clear, slightly yellow liquid when warm, and the melting point obtained by differential thermal analysis was 70 ° 0 to 71 ° 0. '

AtSOiel YI

A polymer composition was made from the following formulation manufactured:

horny .

microcrystalline wax p.100 80

atactic polypropylene 20

Crotonic acid 10

Yinylacetate. 90

Benzoyl peroxide 4

The crotonic acid was dissolved in yinylacetate with low warming, and then the benzoyl peroxide was added. The polypropylene was in the wax by heating between 100 ° 0 to

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■ '-.' ■ - ίο -.

120 ⁰ G solved. The Vinylaeetät-crotonsäureperoxydmischung v / urde added to the wax-polypropylene mixture over a period of 2 1/2 to 3 hrs. At 93 ⁰ C to 95 ⁰ C. The resulting composition was a clear, slightly yellow liquid when hot and that of differential thermal analysis

melting point obtained was 70 ⁰ C to 71 ° 0th When the composition was cold, it was hard and showed no, if any, signs of dispersibility in an excess of 2% aqueous ifetrium hydroxide solution, which is in contradiction to the corresponding copolymer of vinyl acetate and crotonic acid which is in alkali would have complete dispersibility without difficulty.

At Soiel VII

A polymer composition was prepared from the following formulation:

Parts

microcrystalline V / ax p. 1.00 80 atactic polypropylene 20th l'Jal e ins aur eanhydr id '5 Vinyl acetate 95 Benzoyl peroxide 4th

The maleic anhydride was dissolved in vinyl acetate with slight warming, followed by benzoyl peroxide. The polypropylene was dissolved in the V / axle by being heated together to about 100 ⁰ G to 12O ⁰ C. The Vinylac etat-male insäur eanhydr id polypropylene wax was added to the mixture for 2 1/2 Ms 3 hrs. At 93 ⁰ C to 95 ⁰ C. The resulting composition v / ar a clear, slightly yellow liquid when it was hot, un the thermal differential with the analysis of melting point obtained was 75 ⁰ C. The cold composition was hard and exhibited in excess, warm, 2 $ aqueous hydroxide solution only signs of partial dispersibility.

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Example YIII

A polymer composition was made from the following formulation manufactured:

horny v-

microcrystalline wax p.100 146 atactic polypropylene 74 Benzoyl Peroxide ($ 75)

(in hydrocarbon phase) 4.4

Vinyl acetate 220

Benzoyl Peroxide ($ 75)

(in the monomer) 4.4

In this and the rest of the examples, the benzoyl peroxide was used moistened with 25 wt .- # water.

The preparation was ^{carried out in an 11} split "kettle fitted with a stirrer, condenser, inlet tube for monomer / initiator mixture with a tube that brought the mixture below the surface of the molten composition, as close as possible to the edge of the flask , was equipped.

The vinyl acetate was slowly added to the molten monomers in a boiling water bath, whereby the initial internal 'JJemperatur was about 95 G ^0, and 5 ml of the monomer were to admit to the top, so that the reaction could start with a certain speed. The temperature was kept slightly at about 98 ° C to '101 ⁰ C for 5 hrs., After which the product was allowed to cool, and to obtain a product that is not very different in appearance from the initial microcrystalline wax, iüas liquid product was slightly yellow, not particularly viscous, and easy to pour. It was soluble in hexane at 96.7%.

EXAMPLE XI

A polymer composition was made from the following formulation manufactured:

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Parts

microcrystalline wax p.100 102

ataktiscties polypropylene 51

Benzoyl Peroxide ($ 75) '

(in hydrocarbon) 3_, 0

Benzoyl Peroxide ($ 75)

(in the monomer) 6.1

Vinyl acetate 303

In this example, the procedure is similar to that of the example VIII, only the,, weight ratio of vinyl acetate became relative doubled to the hydrocarbon phase.

15 ml of the monomer / initiator was added to start the reaction to get going, and the rest was gradually getting below that Surface added to the composition over approximately 8 hours. In this package, a portion of benzoyl peroxide was added directly to the mixture added after 2 hours and 6 hours of the polymerization; these two ^ subsets were added to the original set used.

The final product was somewhat similar to that in Example VIII except that the molten liquid hardened more slowly, but still quite clearly. The product was a little softer and waxy and showed less adhesive properties than steel and glass. This product contained 35.9 parts of a material that Hexane was extracted.

Be is) iel X

A polymer composition was made from the following formulation manufactured:

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Ropes

microcrystalline wax 167 Polypropylene atactic 83 Benzoyl Peroxide ($ 75) (in hydrocarbons) 5 Vinyl acetate 237.5 Maleic anhydride 12.5 Benzoyl Peroxide ($ 75)

(in monomers) 10.5

The maleic anhydride was dissolved in the vinyl acetate with gentle heating, the benzoyl peroxide was dissolved therein, and a procedure similar to that described in Example VIII was followed. The total addition time was 5 hrs ,, followed by a further half hour at approximately 100 ⁰ G. The characteristic feature of this implementation was that the average temperature at 104 ° to 109 ° 0 was 0, although they at a time of reaction to 120 ° 0 rise, the outer temperature was about 95 ⁰ C. Since the nitrogen that was used before it was passed into the flask was dried, it is

unlikely that the exothermic reaction was caused by secondary reactions. The end product was when it melted was, homogeneous and quite light in color. It hardened when Cooled quickly to a waxy product, hardly odorous and wasn't particularly tough.

Example XI

A polymer composition was prepared using a technique similar to that described in Example VIII is. .

• 196 parts of atactic polypropylene were placed in a "split" flask melted, the flowability being sufficient that a stirrer could work, and 4 ml of tert-butyl perbenzoate were added after heating in a boiling water bath.

392 parts of vinyl acetate were gradually over the course of the

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Reaction added by a device that the monomer to "the The liquid provided 10.44 parts of 75/6 benzoyl peroxide were added to the vinyl acetate before beginning.

The reaction was continued for 11 hours, 75 ml of toluene was added in three stages after 3 "to 5 hours to prevent excessive viscosity from occurring. Compartment for 6 hours was added another 4 ml of tert-butyl perbonzoate The entire reaction was carried out under low reflux. An additional 50 ml of toluene was added during the last part of the reaction. The end product was gel-like and translucent, the solid content "was B3fo. The physical appearance showed no semblance of heterogeneity.

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Claims (1)

Patent claims 1. Process for the production of a polymer composition, characterized in that at least one monomer is introduced into a hydrocarbon which is at least one tertiary Contains carbon atom, at a temperature "at which the hydrocarbon and the resulting composition in are liquid state, whereby a polymer composition is provided which is substantially homogeneous. 2. The method according to claim 1, characterized in that a Monomer is a vinyl ester of a fatty acid that contains up to 12 carbon atoms. 3. The method according to claim 2, characterized in that the Vinyl ester is vinyl acetate. 4. The method according to claim 1, 2 or 3, characterized in that a monomer is an ester of an unsaturated acid. 5 «Method according to one of the preceding claims, characterized characterized in that a monomer is a compound derived from benzene. 6. The method according to claim 5, characterized in that the Compound derived from benzene, styrene or vinyl toluene is. 7. The method according to any one of the preceding claims, characterized characterized in that a monomer vinyl chloride or vinylidene chloride is. ö. The method according to any one of the preceding claims, characterized 00 98 37/207 6 characterized in that a monomer is an unsaturated acid is. . . V 9. The method according to claim 8, characterized in that the unsaturated acid is crotonic acid, acrylic acid or itaconic acid. "- 10. The method according to any one of the preceding claims, characterized characterized in that one monomer is an acid anhydride. 11 .. The method according to claim 10, characterized in that the Acid anhydride is maleic anhydride. 12. The method according to claim 11, characterized in that the maleic anhydride in an amount up to 15 $ of the total monomers is available. 13. The method according to any one of the preceding claims, characterized characterized in that the polymer composition is formed from 1 or more hydrocarbons. 14. The method according to any one of the preceding claims, characterized characterized in that the hydrocarbon is a substituted hydrocarbon. 15. The method according to any one of the preceding claims, characterized characterized in that the molecular weight of the hydrocarbon is at least 200. 16. The method according to claim 15, characterized in that the molecular weight is at least 400. .17. Method according to one of the preceding claims, characterized in that characterized in that the hydrocarbon is a microcrystalline Wax. Is. 18. The method according to any one of the preceding claims, characterized 009837/2076 BATH original characterized in that the hydrocarbon is an ozokerite wax is. 19. The method according to any one of the preceding claims ,, thereby characterized in that the hydrocarbon is an atactic polypropylene. -. 20. The method according to one of the preceding claims, characterized characterized in that the hydrocarbon still contains residual oil saturation. 21. The method according to claim 20, characterized in that the hydrocarbon is a polymer of butadiene, isobutylene or butene is. 22. The method according to claim 20, characterized in that the hydrocarbon is a wool wax alcohol. 23. The method according to any one of the preceding claims, characterized in that the hydrocarbon below »150 ⁰ C is liquid. 24. The method according to claim 23, characterized in that the hydrocarbon maintenance) 100 ⁰ C is liquid. 25. The method according to any one of the preceding claims, characterized in that the weight ratio of Kohlenvjasser- ' substance to the entire monomer of. 1: 0.1 to 1:10. 26. The method according to claim 25, characterized in that the The weight ratio of hydrocarbon to total monomer is from 1: 0.3 to 1: 3. 27. The method according to any one of the preceding claims, characterized characterized in that it is in the presence of a peroxide or Ilydroperoxide initiator is carried out. ' 009837/2076 28. The method according to claim 27, characterized in that the. Peroxide initiator Benzoyl peroxide is ... 29. The method according to claim 27, characterized in that the Peroxide is tert-butyl perbenzoate. . .- '■ 30. The method according to any one of claims * 1 to 26, characterized in that it is in the presence of a redox initiator system is carried out. 31. The method according to any one of the preceding claims, characterized characterized in that the monomer or monomers to the Hydrocarbon can be added below the surface of the hydrocarbon. 32. Method according to one of the preceding claims, characterized in that characterized in that it is run under an inert gas will. 33. The method according to claim 32, characterized in that the inert gas is nitrogen. 34 · A polymer composition prepared according to one of the The method of claims 1 to 33. ■ 00 9837/2076