DE1469849A1 - Polymer mixtures - Google Patents

Description

PATENT LAWYERS ^ 1 DR.-1NG. BY KREISLER DR.-ING. SCHÖNWALD ' i C DR.-ING. TH. MEYER DR. FUES DR. EG GERT KDLNI, DEICHMANNHAUS

Cologne, November 5th, 1962 Pu / Ax

B.X. Plastice Limited, Larkshall Road, London, E.4 (England).

Polyme r close to marriage

The invention relates to mixtures that are near-chlorinated Polymers, in particular polymers and copolymers based on vinyl chloride, contain.

It is well known that objects made of polyvinyl chloride, e.g. water pipes, limited by the fact that polyvinyl chloride has a softening point which is below the temperature of boiling or almost boiling water. It has been suggested to reduce the softening point of polyvinyl chloride by certain To increase the post-chlorination process and thereby the Area of application of the objects made from this post-chlorinated material compared to those made from unmodified Expand polyvinyl chloride. However, these post-chlorinated polyvinyl chlorides can be more difficult to use process than the non-post-chlorinated polyvinyl chloride. Furthermore, the notch impact strength of these post-chlorinated ones lies Polyvinyl chlorides in the same order of magnitude as the polyvinyl chloride itself, so that with certain Applications the brittleness of post-chlorinated polyvinyl chloride manufactured rigid and hard objects is a disadvantage.

The invention is based on the plague that one Can obtain products that are easier to process

909804/1257 "

and have higher notched impact strengths than the normal post-chlorinated polyvinyl chloride and yet have its high Maintain the softening point to a considerable extent if you work with such a post-chlorinated polyvinyl chloride (the type described in more detail below) a graft copolymer mixes that of polyvinyl chloride and / or a vinyl chloride polymer and one or more ethylenically unsaturated monomers is made. Instead of the nachneben them chlorinated polyvinylchloride or β & -ϊβ £ β3? -β $ β1ϊβ can ... post-chlorinated vinyl chloride copolymers can be used.

The polymer mixture according to the invention thus contains the following components: 1) a post-chlorinated polyvinyl chloride or a post-chlorinated copolymer of vinyl chloride with a small proportion by weight of one or more copolymerizable monomers and 2) a graft copolymer obtained by grafting one or more monomers onto polyvinyl chloride or a vinyl chloride copolymer is, where as component 1) polyvinyl chloride or a yinyl chloride copolymer is used, which has preferably been post-chlorinated in suspension under UV radiation to a product which has a specific viscosity in the range from 1.40 to 1.63 at 23 ° and a chlorine content in the range 55 to 70 wt. - <fc and has only a small proportion of 1,1-dichloroethylene units, based on the total weight of the dichloroethylene units present.

The weight of the graft copolymer 2) is advantageously lower or just as high as that of the post-chlorinated polymer Component 1). Preferably the graft copolymer is in an amount from $ 5 to $ 40, especially # 15 to 40, based on the total weight of components 1) and 2), present.

The graft copolymer 2) is expediently polyvinyl chloride or a vinyl chloride copolymer on which one or more ethylenically unsaturated monomers to form a

909804/1257

Grafted product of greater mechanical flexibility have been. Mention may be made, for example, of the graft copolymers by grafting on a conjugated diolefin, e.g. butadiene and at least one copolymerizable vinyl fluoride, e.g. acrylonitrile or ethyl acrylate, to a halogen-containing Stem polymer, which in a previous process ZeB * by emulsion or suspension polymerization of vinyl chloride, The quantitative ratio of the components in the graft copolymer is not crucial, however, is the amount of polymerized during grafting Monomers preferably in the range from 20 to 70% by weight of the graft copolymer obtained as the product »As examples Such graft copolymers may be mentioned: polyvinyl chloride with grafted butadiene and aryl nitrile, polyvinyl chloride with grafted butadiene and ethyl acrylate, polyvinyl chloride with grafted chloroprene and ethyl acrylate, polyvinyl chloride with grafted butadiene and methyl methacrylate or polyvinyl chloride or vinyl chloride copolymers with butadiene grafted on and methyl methacrylate, if appropriate with a third monomer such as styrene or divinylbenzene

The graft copolymer used as component 2) can be produced by grafting the monomer or monomers onto the "parent polymer ¹ " consisting of polyvinyl chloride or a yinyl chloride copolymer with the aid of high-energy ionizing radiation or by chemical means or with the aid of UV radiation in the presence of a sensitizer .

"Ionizing rays" are rays that produce ions in the air under normal atmospheric conditions able to form, which can be determined by their charge. As rays of this kind come for example ß-rays, excited ones Electrons, thermal neutrons, excited deuterons and protons, X-rays and especially γ-rays in question. As a source of such rays, for example Atomic reactors, electron or particle accelerators, radioactive isotopes and X-ray equipment can be used.

909804/1257

As an example, a chemical method for carrying out the graft polymerization, the induction is caused by free radicals, for example using peroxide compounds, in particular water-soluble mineralischerPeroxydverbindungen or systems _for which such compounds contain, for example, a persulfate-metabisulfite system with a complexing agent for heavy metals, which prior to the graft polymerization are added, mentioned.

As vinyl chloride copolymers from which the post-chlorinated Component 1) and the graft component 2) of the invention Mixtures can be prepared, copolymers of vinyl chloride with a copolymerizable are suitable Monomers, e.g. vinylidene chloride or especially vinyl acetate. Mixed polymers are preferred in which the Vinyl chloride made up more than 80% by weight of the monomer mixture. In the case of post-chlorinated copolymers 1) makes the vinyl chloride expediently at least 95 wt .- ^ des Monomer mixture from.

In addition to the graft copolymers used as component 2), the mixtures according to the invention can contain additives usual amounts, for example plasticizers, heat and light stabilizers, antioxidants, lubricants, fillers, Contain pigments, dyes and processing aids.

Mixing can take place at elevated temperatures, e.g. at 150 to B1 200 °, for example with mixing mills, internal mixers ^, e.g. a Banbury Miecher, or extrusion, which is effective Ensure mixing of the polymers are made. The mixtures can also be obtained by mixing the post-chlorinated Polyvinyl chlorides or the vinyl chloride copolymer in the form of a suspension or emulsion with a suspension or emulsion of the graft polymer and subsequent spray-drying or coagulation and drying and finally Knead in a Banbury mixer, for example getting produced.

The mixtures according to the invention can be prepared in the customary manner

H69849

processed, for example by pressing, injection molding, calendering and extrusion. The Products can be transparent.

In the following examples, the amounts given relate to in parts by weight unless otherwise stated.

Examples 1 and 2

The following ingredients were mixed in a dough mixer in separate experiments:

Example 1 Example 2 Control

Post-chlorinated polyvinyl
chloride, parts 100 100 100 Polyvinyl chloride
Graft polymer, ⁿ 15th 30th _ Organotin
Stabilizer ^w 3 3 3 Glide wax " 0.5 0.5 0.5

A post-chlorinated polyvinyl chloride was used in each of these experiments used, which had been prepared by post-chlorination of polyvinyl chloride in suspension and had a specific gravity of 1.560 at 23 °. The polyvinyl chloride graft copolymer was made of polyvinyl chloride, Butadiene and acrylonitrile in a weight ratio of 5: 4; 1 has been manufactured. The product with the trade name "Mellite" was used for the organotin stabilizer 139 "(manufacturer Albright & Wilson, Ltd.) and the product with the trade name" Wax OP "(an ester wax, manufactured by Badisehe aniline and soda factory).

Each of the premixes was on the mixing mill with narrow Roller spacing made plastic. The surface temperatures of the orphans are given in the table below. Durcii By kneading on the rollers for about 5 minutes, a uniform mixture was obtained. After kneading, the mixtures became taken from the rollers in the form of pelts. The skin were pressed in standard molds at 180 ° for 5 minutes. After cooling in the Porm, the pellets were

909804/1257

normal tolerance to test specimens. For each sample, the Charpy notched impact strength was determined according to the ^{method described in "British Plastics 11} , April 1959, page 158, and the softening point according to British Standard 2782, Part I, 1956, Method 102c. The results obtained in these tests and the processing temperatures used are given in the following table.

Example 1 Example 2 Control

Mixing mill temperatures: front roller 185 175): 190 " rear roller 190 ° 180 ° 195

Charpy impact strength,

ft.Ib./inch notch 2.95 3.00 0.25

Softening point 110 ° 106.5 ° 118 °

It was found out that the addition of the graft copolymer to the post-chlorinated polyvinyl chloride facilitated processing on the roller mixer. The mixture produced according to Example 2 could therefore be processed more easily and at lower temperatures than the comparison sample. The processability of the product produced according to Example 1 was between the product according to Example 2 and the comparative sample. It was also found that the transparency of the compacts according to the invention was only very slightly worse than that of the comparative sample.

Example 3

Two separate tests were carried out with products of the following composition t

Example 3 control

Post-chlorinated polyvinyl chloride 100 parts 100 parts polyvinyl chloride graft copolymer 50 ■.,. '. "- _.;

Organotin Stabilizer 2 / '' ^. ·. · 2; ^ ¹ J: _c Glide wax 0.5 »0 * 5" ■ ^

In both experiments, the post-chlorinated polyvinyl chloride was a post-chlorinated product in suspension with a specific gravity of 1.560 at 23 °. The polyvinyl chloride

909804/1257,

Graft copolymers consisted of polyvinyl chloride, butadiene and methyl methacrylate in a weight ratio of 5: 1: 1 has been manufactured. Dibutyltin maleate was used as the organotin stabilizer and the product "Wax OP" was used as the glide wax.

Each of the premixes was in a high speed mixer dry mixed and made plastic on a two-roll mixer with a narrow pitch. In the same way as Described in Examples 1 and 2, test specimens were produced. The test results and the processing temperatures are given below:

Example 3 control

Temperature of the roller smelter:

front roller 180 ° 180 °

rear roller 185 ° 185 °

Notched Gharpy Impact Strength

(ft.Ib./inch notch) 1.0 0.25

Softening point 100.5 ° 117 °.

It was found that by adding the graft copolymer For post-chlorinated polyvinyl chloride, processing on the roller mixer at the temperature mentioned is considerable was relieved. The mixture according to Example 3 formed a gel immediately on contact with the rollers and yielded a smooth, cohesive fur, while the unmodified post-chlorinated polyvinyl chloride takes about

Formed a coherent product for 2 minutes.

Example 4

100 parts post-chlorinated polyvinyl chloride (as in Example 1)

3 parts of a sulfur-containing organotin compound ("Mellite 139"), 0.5 part of glide wax ("Wax OP ¹¹ ) and 50 parts of a polyvinyl chloride graft copolymer made from polyvinyl chloride, butadiene, styrene and methyl methacrylate in a weight ratio of 5 J 1: 0, 74-: 0.26 were mixed in a dough mixer, the mixture was plasticized on a two-wheel mill and kneaded on the rollers for about 5 minutes

909804/1257

180 °, that of the other roller 185 °. Wake up kneading took the mixture was removed as a skin from the rollers and allowed to cool. Parts were made in the manner described in Example 1 of the rolled head and processed into test specimens. The test results are listed below:

Öharpy notched impact strength 2.02

(ft.Ib./ inch notch)

Tensile Strength, kg / cm ² 424

Softening Point, ⁰ C 103

Examples 5 and 6

In separate experiments, the following ingredients were premixed in a dough mixer:

Example 5 Example 6

Post-chlorinated polyvinyl chloride 100 100 parts Polyvinyl chloride

Graft polymer 20 20 ^w

Sulphurous tin organics

Connection («Mellite 139"). 2 2 «..

Glide wax (»Wax OP») 0.5 0.5 ⁿ

In each of these experiments the same post-chlorinated polyvinyl chloride as in Example 1 was used. That in Example 5 was polyvinyl chloride graft polymers used made of polyvinyl chloride, butadiene, acrylonitrile and divinylbenzene in a weight ratio of 5: 4: 1: 0.1. The polyvinyl chloride graft copolymer used in Example 6 was made from polyvinyl chloride, butadiene and ethyl aorylate in a weight ratio of 5: 1: 4.

The premixes were on a two roll mixer with a narrow Nip made plastic. The surface temperature of one roller was 185 °, that of the other roller was 190 °. the Mixture was worked through for about 5 minutes. It was then removed as a pellet and allowed to cool.

Parts of the fur were pressed and the pressed pieces as in Example 1 processed into test specimens. The test results

9 0 9 8 0 4/1257

■ - 9 -

H69849

are listed below:

Example 5 Example 6

Oharpy notched impact strength

(ft.Ib./inch notch) * 0.89 0.59

Tensile strength, kg / cm ² 610 545

Elevation point, 0 112 121

It was found that "both mixes on the roller mixer gel formed faster and smooth, cohesive Pelle gave as the comparison mixture according to Example 1.

Examples 7 and 8

In separate experiments, the following ingredients were premixed in a dough mixer:

Example 7 Example 8

Post-chlorinated polyvinyl chloride 100. 100 parts

Polyvinyl chloride graft

mixed polymer 20 20 "

Organotin stabilizer 2 2 "

("Mellite 139 ^M )

Glide wax ("Wax OP") 0.5 0.5 »

In each of these attempts the post-chlorinated polyvinyl chloride was used duroh chlorination; produced in suspension, with a product having a specific gravity of 1.512 was obtained at 23 ° and a chlorine content of 62.95 ε. In Example 7, the same polyvinyl chloride graft copolymer was used as in Example 5 and in Example 8, the same polyvinyl chloride graft mono-polymer as in Example 6 used.

The premixes were among those mentioned in Examples 5 and 6 Conditions on a two-roller mixer plastic made. Pie examination of the obtained skin showed that she All pelts made from a control material without the addition of a graft isohpolymer were tougher.

9 09804/1 257 '^ ^ξ ORIGINAL INSPECTED

Claims (1)

- ίο - Patent claims 1 #) polymer mixture with improved mechanical properties, in particular an improved notch impact strength, based on post-chlorinated polyvinyl chloride or a post-chlorinated copolymer of polyvinyl chloride and a lower amount by weight of one or more copolymerizable monomers, containing, 1) post-chlorinated polyvinyl chloride or at least one » the specified post-chlorinated vinyl chloride copolymers obtained by post-chlorination in suspension under the Influence of UV radiation on products with a chlorine content in the range from 55 to 70% by weight and only a small amount of!, l-dichloroethylene unit ten - based on the total weight of the dichloroethylene units present - included, and. · 2) a Pfropfmischpolymeres, which has been obtained by graft-polymerizing one or more monomers of polyvinyl chloride or vinyl chloride copolymer _o 2, ^ polymer mixture according to claim 1, characterized in that it contains as component 1) a post-chlorinated material which at 23 ° C has a specific gravity in the range from 1.40 to 1.63. ': ■'.'-- s 3,) Polymer engemia cn naoh claims 1 and 2, characterized in that that there is component 2) compared to component 1) in a lower or at most the same amount by weight contains, with component 2) in particular in amounts of -40% by weight, preferably in amounts of .15-40% by weight,;} e-. .well is based on the total weight of 1 and 2 ORiGiNAL INSPECTED 9 09804/125 7t, er.-..- ..,: ■ 4 «) polymer mixture according to claims 1 Ms 31 thereby marked indicates that it contains a graft copolymer, that by graft polymerization of one or more ethylenic unsaturated monomer of polyvinyl chloride or a yinyl chloride copolymer to give a product of greater mechanical strength Flexibility has been preserved «, 5) polymer mixture according to claim 41 characterized that a graft copolymer is present which is produced by graft polymerization a conjugated diolefin and one or more copolymerizable vinyl monomers Polyvinyl chloride has been obtained " 6.) Polymer mixture according to Claims 1 to 5, characterized in that that a graft copolymer is present in which the weight of the grafted monomer in the range of 20-70 wt., Based on the total weight of this graft polymer is · 7) polymer mixture according to claims 1 to 6, characterized in that that at least one of the following products is present as component (2): Polyvinyl grafted with butadiene and acrylonitrile, polyvinyl chloride grafted with chloroprene and ethyl acrylate meth polyvinyl chloride grafted with butadiene and methyl ^ acrylate Grafted polyvinyl chloride or a vinyl chloride isohpolymer with butadiene and methyl methacrylate and optionally a third monomer » 8 _# ) Polymer mixture according to claim 7, characterized in that a product of polyvinyl chloride, butadiene and acrylonitrile in a weight ratio of 5: 4 i 1 is present as component (2) 909804/1257 - YtL - 9 ») Polymerengemieoh naoh claims 1 to 8, characterized in that it is a Pfropfmisohpolymeree from one Contains vinyl chloride raw polymers with more than 80 Ο · βντ ·? Ί Vinylohlorld. 10 ·) Polymer mixture according to claims 1 to 9 »daduroh ₍ that it contains a» graft copolymer obtained from the copolymerization of vinyl chloride and vinyl acetate as the parent polymer · 11 ·) polymer mixture naoh claims 1 to 10, characterized in that in the case that component (1) a is post-chlorinated vinyl chloride misohpolymer, this » sioh derived from a product that obtained from a monomer mixture with at least 95 GpV ## vinyl chloride been let 12 ·) Polymer mixture naoh claims 1 to 11, characterized in that as component (2) graft isohpolymers are present, which by plugging at least «ines monomers on the; Stammpolymer e4 * »under * the effect of high-intensity ionizing radiation, under the effect of free radicals as polymerization initiators and / or under the action of UV radiation in the presence obtained from sensitizers BlHd ·, 13 ·) Polymer mixture naoh claims 1 to 2, daduroh «ekeruvzeiohnet that e« additionally Weiohmaoher, heat or Liohtstabilisatoren, anti-oxidants ·. lubricant) contains fillers, ÄLagments and / or usual / lipid substances 14 ·) Polymertngemiaoh NaOH claims 1 to 6 and 11 to 13, ν / daduroh gekennseiohnet that it fue as Misohkomponente (2) V a product polyvinyl chloride grafted with poly m \ butadiene, acrylonitrile and Divinylbenaol or Poljrvinyl- / ohlorid 'grafted with butadiene and ithyl aylite s 909804/1257. bad original t * \ J sJ \ J m 13 « In the first place, the polyvinyl chloride, butadiene, aoryl, or divinylbenaol are present in the pre-determined ratio of 5 * 4 ι 1 ι 0.1.