DE2130108A1 - Thermoplastic polymeric compositions based on vinyl chloride polymers - Google Patents

Description

PATENT LAWYERS

dr. W. Schalk dipl.-ing. P. Wirth dipl.-ing. G. Dan ν en berg DR.V. SCHMIED-KOWARZIK DR. P. WEINHOLD DR. D. GUDEL

6 FRANKFURT AM MAIN

GR. ESCHENHEIMER STRASSE 39 -SK / GK

PM 1375

Montecatini Edison SpA Forü Bonaparte 31
Milan / Italy

Thermoplastic polymer compositions based on vinyl chloride polymers

The present invention relates to thermoplastic polymeric compositions based on vinyl chloride polymers with a high degree of crystallinity, which are characterized by good workmanship »properties. she relates in particular to thermoplastic polymeric compositions based on it of vinyl chloride polymers with a high degree of crystallinity, which in the same devices as are used for processing thermoplastic polymer masses on the basis of a normal Viriylchloridpolymerisates, into shaped objects with high heat resistance and preferably also with good lock fastness.

As a general rule, polyvinyl chloride with a high degree of crystallinity is becoming common by polymerizing the monomer at temperatures below 0 C. using special catalytic systems, usually those "the free radicals ranurn, manufactured.

109885/1659

By working in this way, a polymer having a substantially higher crystallinity than that of the normal polymer that usually produced at temperatures around 50 C. and in the following for simplicity half as "normal polyvinyl chloride" or "normal PVC" as opposed to crystalline polymer is called, which is thus referred to as "crystalline PVC" will.

This increase in crystallinity gives the polymer a substantial one Improvement of the heat resistance properties, such as the Vicat-Durch- ' urgent temperature, the deformation temperature under constant load and boiling water shrinkage and solvent resistance; these results are even at high temperatures compared to those of normal PVC significantly improved.

Simultaneously with these improvements, the increased crystallinity of the Polymerizates lead to a deterioration in other properties, i.e. mainly processability and impact resistance, which are inferior to those of normal PVC.

"The aim of the present invention is to create polymeric compositions on the Based on vinyl chloride polymers with a high degree of crystallinity, which have 'good heat resistance and preferably also good' impact resistance own.

Another object of the present invention is to provide thermoplastic polymer compositions based on vinyl chloride polymers with a high degree of crystallinityj which have such processing properties,

109885/1659

_ 3 -

that they are easy in the device commonly used for normal PVC can be processed into molded articles with high heat resistance and preferably also with good impact resistance.

These and other objects are achieved by the polymeric compositions according to the invention achieved that essentially from

i) at least one polymer and / or copolymer of vinyl chloride with a high degree of crystallinity;

II) a methyl methacrylate polymer with a relatively low molecular weight, which is preferably between 100,000 and 1,000,000, and

III) preferably, but not necessarily, of one or more polymers Materials with high elasticity, e.g. from the group of

a) Graft copolymers of styrene monomers of the general formula:

in which FL and R_, which can be the same or different from each other, are hydrogen, a lower alkyl radical or a halogen atom, and R “denotes hydrogen or a lower alkyl radical such as methyl

with unsaturated nitriles of the general formula:

■? «■

(2) CH ₂ = C-CN

in which R ^ is hydrogen, a lower alkyl radical or halogen; and / or with acrylic monomers of the general formula: -. »

? 5

(3) CH ^ = C - COOH ₆

in which R ^ are halogen, hydrogen or a lower alkyl radical can and Rg stands for an alkyl radical with up to B carbon atoms;

109885/1659

BATH ORIGINAL

on natural or synthetic elastomers, preferably polybutadiene include, or copolymers of butadiene with ßinorn or more the monomers or terpolymers referred to above under (1), (2) and (3) or tetrapolymers containing butadiene with an odcjr several of the above with (1), (2) and (3) designated monomers and one or more <^ olefins;

b) natural elastomers

c) synthetic elastomers made from polybutadiene or copolymers of butadiene with one or more of the monomers identified above with (1), (2) and (3) plus ¹ X olefins;

d) halogenated and sulfohalogenized polyolefins, "such as chlorinated and sulfochlorinated polyethylene;

e) acrylic elastomers

f) synthetic elastomers from polymerization or copolymerization of ethylene, propylene and isobutene, if possible with diene hydrocarbons;

g) ethylene-vinyl acetate copolymers; ·, h) elastomeric polyurethanes; and

i) Graft copolymers !! of vinyl chloride on the elastomers described under b) to h)
exist.

Particularly favorable results are achieved with polymeric materials made of two or three components, which according to the invention essentially consist of:

i) Polyvinyl chloride with a high degree of crystallinity with a r.; yndiotactic index above 1, B, but preferably between 1, Π and ?., '\, dir.

further by a fjtrukturviskuHiUH.Bzcilil between U ₁ Tj- ^ lil / tj, a ;; Glass transition temperature above BO C. and rinn Vicut-DurchdrincjunnstompeniUu '

ο
about W5 C. gekennzei ohnel i.ind;

BATH ORIGINAL 109885/1659

II) polymethyl methacrylate with an average molecular weight of 200 DOO to 800,000; and preferably, but not necessarily

III) Graft copolymers of monomers with (1) and / with (?.) And / or

^em - (3) defined type in an / elastomer »that of polybutadiene or a

Copolymer of butadiene with another monomer with at least 50 L5 wt .- $ i of chemically combined butadiene, exist.

The proportions of the various components of the thermoplastic according to the invention polymeric masses can with respect to the final properties that are desired for the mass to be produced, vary within wide limits .

In the case of the tertiary masses described above, they are particularly advantageous Results obtained by using:

crystalline PVC in amounts between 50-95 parts by weight per 100 parts by weight of the thermoplastic polymer mass,

Polymethyl methacrylate in amounts between 5-45 parts by weight per 100 parts by weight the thermoplastic polymer mass and

a high resilience material of the type described above in quantities between 5-45 parts by weight per 100 parts by weight of the thermoplastic according to the invention polymeric mass.

The various components of the thermoplastic polyrnorun according to the invention Masses are used in a mixture with other, non-polymeric additives, like z.FJ. Light and heat stabilizers, antioxidants, plasticizers, Mineral fillers, lubricants, mold release agents and other known additives.

109885/1659

■ _fc ■ 21301Q8

The thermoplastic polymeric compositions of the invention can be produced be done by mixing all components in a conventional ribbon blender or preferably mechanically mixes together in a high-speed mixer of the Henschel type, to ensure the thorough mutual dispersion of the components as much as possible to facilitate.

It is also possible to pre-disperse the various non-polymeric additives such as stabilizers, lubricants and mold release agents, antioxidants

^ etc., which for an expedient. Processing are necessary to produce; this W "...»

Pre-dispersion then becomes the thermoplastic polymer phase. Materials [crystalline PVC, polymethyl methacrylate and highly elastic Material) is added, and the whole thing is done according to one of the above Procedures further mixed.

The mixture (dry mixture) obtained as described above becomes "process a homogeneous, molten mass then at a high temperature, for example between 180-22Q ^Q C in a roll mill or a Banbury mixer. The molten mass may then be rolled to foils be that can be granulated after cooling, for example, W for the preparation of test samples or small cubes.

Furthermore, the direct extrusion of the powdery phase (dry- Mixing) or the homogeneous molten mass through an extrusion head, which is equipped with a nozzle with many, very small holes and a cutting blade is provided. In this case, too, an intermediate product is obtained in granular form that is easier to handle. The cut up or Lenticular materials are then used on the usual devices in accordance with the individual, suitable for the respective object to be produced Process subjected to the various conversion processes.

BATH 109885/1659

The following examples illustrate the present invention without it to restrict.

B c; is ρ j. G 1 1

Thermoplastic masses were produced, in which the type and amount represent non-polymer additives remained the same, but different amounts of polymer Materials used in admixture with crystalline PVC.

The composition of the mixture thus obtained is shown in Table 1 below called:

Table 1

Composition of the masses
in parts by weight A. B. C. D. E. crystalline PVC (1) 100 90 65 80 55 Polyethylene methacrylate (2) - 10 5 10 45 ABS (3) - - 10 10 : non-polymeric additives Heat stabilizer (4) 2.9 2.9 2.9 2.9 2.9 Lubricant (4) 1 1 1 1 1 Mineral filler (4) 5.3 5.3 5.3 5.3 .5.3 (1) Crystalline PVC

A polyvinyl chloride having the following properties was used syniJi π tactical index 2.3

Structural viscosity number hai 25 C.
recovery temperature

0.95 dl / g.

100 ° C.

The syndiotactic index was determined based on measurements of light absorption in the IR spectrum according to Jaurn.Polym.Gcience, Vol. 41, (1959), pages 73-2, certainly.

BATH

109885/1659

213Q1Q8

The intrinsic molar viscosity, an indication of the average mole

kulargewicht of the polymer, was determined in a dilute Cyclohuxanonlösunc at '.?. ^P 5 C. corresponding to "e l'Industria lachimica", Vol 36, page 803 (1954).

The glass transition temperature was correspondingly ^l? La Chinica e l'Industria ", vol. 46, p. 116 (1964).

2) Polymethyl methacrylate

A methyl methacrylate polymerizate with the following properties was produced. ^ applies: '

average molecular weight 500,000 ■ Vicat penetration temperature 91.5

actual spec. Weight at 25 C. 1.18 g / cc

The molecular weight was determined based on measurements of the fundamental molar viscosity number at 25 ° C. in chloroform as solvent (concentration from 0.2 to 1 g / l).

The Vicat penetration temperature was determined according to ASTM procedure D 1525-58 T using a load of 5 kg in accordance with VuE ο 302-111 Rules determined.

3) ABS

A copolymer was used, produced by graft polymerization of a mixture of styrene and acrylonitrile in an aqueous emulsion onto a latex of a synthetic elastomer. The latter was prepared by aqueous emulsion polymerization and containing about 8UE GeW ₁ - ¹ Jo butadiene and about 12 parts by weight p / o acrylonitrile.

• ORIGINAL BATHROOM 109885/1659

The graft copolymer obtained had the following composition: Styrene. 29 parts by weight

Acrylonitrile 17 parts by weight

Butadiene 54 parts by weight

4) Additives for crystalline PVC

The usual, for the production of polymeric compositions based on υαη additives known to normal PVC are used. In this particular case it was a barium-cadmium stabilizer mixed with lead stearate as a heat stabilizer and epoxy octyl stearate are used.

The lubricant consisted of a mixture of calcium stearate and petroleum jelly. And the mineral filler consisted of titanium dioxide mixed with calcium carbonate.

The production of the thermoplastic polymeric compositions according to the invention was carried out carried out as follows:

The components of the above mixtures were about 15 minutes in ' mixed in a high speed mixer; i.e. they were mixed for the duration necessary was so that the mass reached a temperature of 100-110 C.

Therein the mixes were made at low speed for about 15 minutes to 30-4 ° C. cooled down.

The fo Trockon mixtures obtained were processed in a roll mill dNNN total of 10 minutes bed a temperature between 10 & -2Q0 C. ^D.

The raw calendered films thus obtained were used for making samples of different shapes and sizes depending on the physical properties to be measured.

BAD ORlGINAL. 109885/1659

a) Determination of the Vicat penetration temperature The samples were prepared as follows:

80 g of raw film was placed in a frame of 127 × 127 × 6.2 mm. then this frame was 5 minutes in a vertical platen press of 250 χ

ο 250 ram that worked at a temperature of 180-190 C., a pressure of 150 atm. subject.

The small test plate thus obtained had a thickness of 6 mm. From this Samples were then obtained with a size of 35 35 χ S mm, which were used for the * actual determination were ready.

The test was performed according to that described in modified ASTM method D-1525-58 Method, i.e. using a load of 5 kg in accordance with VDE 0302 III rules.

b) Determination of elasticity (rebound elasticity)

According to the method described under a), a small plate was a Thickness of 6 mm made, from which one can roll samples of 63.5 χ mm with a special V-shaped notch. The test was performed according to ASTM method D-256-56T.

c) Determination of the workability on the basis of measurements of the viscosity of the mass in the molten phase by means of a capillary rheometer |

To determine the viscosity of the mass in the molten state, a MCR extrusion type capillary rheometer manufactured by Instron combined with an Instron electronic dynamometer of the type TT-CM (cf. "Materia Piastiche", Aug. 1962, page 1042, and Hai 1963, page 504) are used.

The granulated materials were tested in the rheometer described above. looking for the one with a cylindrical opening 1.52 mm in diameter and one

109885/1659 ORIGINAL BATHROOM

Length to diameter ratio L / D - 33 was provided.

The materials were extruded at a temperature of 100 C. the Measurement methods were as follows;

1) the rheometer was loaded with 20-3D g of the thermoplastic to be tested Loaded mass in the form of a granulated material. .

2) The material was then subjected to a pressure of 1QQ-2UQ kg / cm "for 5 minutes Achieving thermal equilibrium compressed.

3) Then the material was at constant speeds between 0.1-50

~ 1

cm / min according to a flow gradient between 3.5-1760 seconds. ,.

4) the force required for extrusion was automatically recorded.

5) It was the approximate frictional drag in a vacuum chamber measured at all test speeds. ·

6) Then curves of the viscosities were plotted against the flow gradients

-1 and the viscosity value interpolated at a gradient value V ' = 100 see. (Data presented in accordance with ASTM method D-1703).

In table la, the values determined after the above procedure are "the physical properties for the masses given in table 1 listed qualitatively and quantitatively.

109885/1659

see - 12 -
Table 1a D. C. D. E. Mass (composition at . Tab. 1) 'Λ 96 94
6th 95
6.5 • 100
2.Ü Vicat temperature; ° C.
Izod impact strength 97
23 ° C., ₂ '

Viscosity in the molten state; poises
χ 10 ° at j * = 1U0 see "

at 180 ° C, 1.06 0.82 0.76 0.71 0.52

at 200 ⁰ G. 0.72 0.49 0, G0 0.52 0.45

Examination of the data from Table 1a clearly shows that the compositions according to the invention (B to E) surprisingly have good processing properties (cf. the viscosity value in the molten state, which is significantly lower than that of crystalline PVC per se) and good heat resistance (cf. the value of the Vicat penetration temperature, which is ^{similar to that of crystalline F 5} VC per se).

The simultaneous presence of these two properties, that is, good workability and good heat resistance, enables these compositions to be used in the manufacture of molded articles for purposes requiring high heat resistance; this heat resistance is known to be normal with thermoplastic polymer masses on the Bcr-ria vm in order to achieve F ¹ VC only B.

GchlieDlich the erfiindungsgnmnßnn masses have also din are hnhu battl ^ vrru · than those of crystalline CVC per se and which come close norniu'Jum of PVC, which is why for the production of gofoniitr.n Gun can be used appropriately sin ei iständen that füx ' intended for typical purposes for normal PVC.

"bad original

1 09885/1659.

So £ -! Iv LaIi: one has the, Ooppßlffektunj π in he simultaneous improvement of the processability and GohlagFestinkriLt of crystalline PVC without changing it Worm resistance.

For example, ρ i el 2

Rei5ipic: l 1 v. Was repeated, but instead of Λ [ίΠ Bin PfropfmischpoyJri τι since, nus styrene and Methyli.iühhanryLab (in a ratio of 75: 2Li) (UM ¹ .

(Güw.) On uirifin ayntht; tischnn [-.luatunurnn from einoin 7o: 2. ^f /-f.1x£ichi)olymuris-al; from ButacJian and iJtyrol was used. The Konifionentein and phycilcaliochen Fligensohciftfjii of the two masses F and G produced are listed in Table 2.

Table 2

Polymer components of the Mauaen AF D in Gcv. parts

crystalline F ¹ VC (1) 100 05 00

Plymethyl riethacrylate (2) - 5 10

above-mentioned graft copolymer - 10 10 no; ht- po I yrnr n-u components
Warmth:., Tabl Lisa tor (3)

Mineral oil (3)

Vicat-Üui chdrii irjunf j-j temperature; C.

zfjtl-Snhlaij f rs tit jkui t; kgcin / crn

if-kcibitut im ntischiiriol ^ eriern ^ u '' «1ÜL) sue in poises χ 10 at

2.9 2.9 2.9 1.0 1.0 1.0 5.3 5.3 5.3 97 93 .94 2 3.5 4.0

. 1.0G 0.61 0.40

200 ^D C. 0.72 0.47 0.34

BATH ORIGINAL

109885/1659

(1), (2) and (3) = The products used and their properties are in

a 1 runs.

From the above data, the valuable properties of the erfi

Masses clearly visible, even if a graft was considered highly aketisiiBS material

mixed polymerizate of butadiene, styrene and methyl methacrylate is used by vairdn.

BATH ORIGINAL 109885/1659

Claims (5)

P nent entitlements 1. Thermoplastic polymer compositions based on vinyl chloride polymers seeds with a high degree of crystallinity, which have good processing properties, ' e: a high heat resistance and preferably also a good fit have, characterized in that they essentially consist of l) at least one vinyl chloride polymer and / or copolymer with a high degree of crystallinity and a syndiotactic index of 1.8, but preferably between 1.8 and 2.4; IT) a methyl methacrylate polymer with a relatively low molecular weight, which is preferably between 100,000 and 1,000,000, and III) preferably, but not necessarily one or more high elastic polymeric materials from the group of a) Graft copolymers of gtyrene monomers of the general formula: (1) ^ -C-CH ^R 3 in which FL and Rp _1, which can be the same or different from one another, are hydrogen, a lower alkyl radical or halogen and FU is hydrogen or a lower alkyl radical, such as methyl, with unsaturated nitriles of the general formula: (2) CH ₂ = C - CN in which R. is hydrogen, a lower alkyl radical or halogen stands; and / or with acrylic monomers of the general formula: (3) CH ^ = C - COOR ₆ BATH ORIGINAL 109 885/1659 - in which R _{5 represents} halogen, hydrogen or a lower alkyl radical and R _{ß represents} an alkyl radical with up to 8 carbon atoms, on synthetic or natural elastomers, which preferably consist of polybutadiene, or copolymers of butadiene with one or more of the above under (1 ), (2) and (3) defined monomers or terpolymers or tetrapolymers which contain butadiene, one or more of the monomers defined above under (1), (2) and (3) and one or more o (-olefins,
b) natural elastomers, W c) synthetic elastomers made from polybutadiene or copolymers of butadiene with one or more of the monomers defined above under (1), (2) and (3) and with one or more c {olefins, d) halogenated polyolefins and sulfohalogenated polyolefins, such as e.g. chlorinated polyethylene and sulfochlorinated polyethylene, e) acrylic elastomers, f) synthetic elastomers from polymerization or copolymerization of ethylene, propylene and isobutylene, gagebenenfMDs. with diene hydrocarbon en, '' % g) ethylene / vinyl acetate copolymers
h) 'elastomeric polyurethanes j
i) Graft copolymers of vinyl chloride on elastomers of the flat under b) to h) described Art
exist. 2 · .- polymeric compositions according to claim 1, characterized in that they ini essential from "I) Polyvinyl chloride with a high degree of crystallinity, a syndiotactic index above 1.8, preferably between 1.8 and 2.4 _f and a structural viscosity between Q1 and -2 dl / g, a glass transition temperature 109e85 / 1659 BAD ORSGfNAL - 17 -
about 80 ⁰ C., and a Vicat soak temperature above 85 ° C. and II) a methyl methacrylate polymer with a relatively low molecular weight, preferably between 100,000 and 1,000,000 and III) Graft copolymers of monomers of the above under (1) and / or [2) and / or (3) described type on one of polybutadiene or one Butadiene copolymer with another monomer consisting of elastomers which contain at least 50% by weight of chemically bound butadiene ", exist. 3, - Polymeric masses according to claim 2, characterized in that they are made of crystalline polyvinyl chloride in amounts between 50-95 parts by weight per 100 Parts by weight of thermoplastic polymer mass, a methyl methacrylate polymer in amounts between 5-45 parts by weight per 100 parts by weight thermoplastic polymeric composition and preferably, however not necessarily a highly elastic material in amounts between 5-45 parts by weight per Parts by weight of thermoplastic polymer mass exist. -. 4. Polymeric masses according to claim 1 to 3, characterized in that they additionally stabilizers and co-stabilizers against light and heat, antioxidants, lubricants, plasticizers, pigments, dyes, Contains UV absorbers and other similar additives for processing plastic materials. 5.- tubes, plates, films and shaped objects, characterized in that that they have been produced from polymeric compositions according to claims 1 to 4. The patent attorney: 109885/1659 BATH