HU197337B - Process for production of thermoplastic elastomer based on polidefin in dinamic vulcanization - Google Patents

Abstract

Prepn. of dynamically cured polyolefin thermoplastic elastomers (all pts.wt.): 20-80 crystalline olefin polymer, 80-20 butadiene and/or isoprene contg. elastomer, in this case with other polymers, grafting monomers, fillers structuring agents additives or mixtures thereof and 2-20 phenolic resin and a metal cpd., in this case a halogen donor. - The elastomer is thermoplastic, inexpensive, is easily compatible with elastomers used in the shoe-industry, is suitable to improve the impact resistance polystyrene homo and copolymers and the compatibility of constituents in polyolefin, polystyrene and polyolefin, polystyrene, PVC mixes. It facilitates the reuse of these. The process is suitable for the prod. of ensured quality secondary raw materials from wastes.

Description

FIELD OF THE INVENTION The present invention relates to a process for the preparation of a snow-softening elastomer comprising a crystalline polyolefin as a plastic breaker and a butadiene and / or isoprene rubber as an elastomer by dynamic vulcanization.

It is well known in the literature to prepare snow-softening polyolefin elastomers by dynamic vulcanization. The plastomeric component of dynamic vulcanization with sulfur and / or organic peroxides is usually crystalline polyolefin (primarily polypropylene) and its elastomer is ethylene / propylene co-(EPM) and / or ethylene / propylene / diene terpolymer (EPDM) rubber (3,037,954, 3,578). 643,

Nos. 806,558 and 3,862,106. U.S. Patents).

There is also an example in the literature of vulcanizing crystalline polypropylene and EPDM resin under dynamic conditions. That's 2,408,632. French patent e.g. for this purpose either halogenated phenolic resin or halogen-free phenolic resin is used together with a halogen donor and a metal oxide activator. An improved flowability resin vulcanized polypropylene and EPDM-containing thermoplastic dynamic vulcanizate is disclosed in U.S. Patent No. 195,843. Hungarian Patent No. 2415/81, which achieved improved processability by a combination of halogen-free phenolic resin and metal oxide.

In all cases, the elastomer of the thermoplastic dynamic vulcanizates prepared according to the above methods is EPDM, which is well known for crystalline polyolefins. They are used almost exclusively as isotactic polypropylene as a plastomer, since, unlike polyethylene, it is not cross-linked by peroxides. There are basically two barriers to the use of their types: on the one hand, goods are relatively high due to EPDM, which is considered to be a special elastomer; their limited shelf-life against styrene / diene block copolymers, which are very widespread.

Nos. 4,340,684, 4,333,918 and 4,350,795. U.S. Pat. No. 5,123,195 discloses the production of thermoplastic elastomers by dynamic vulcanization, the elastomer component of which is an even cheaper statistical styrene / butadiene copolymer rubber (SBR). In order to ensure proper properties, the formulation uses di- and triblock copolymers consisting of hydrogenated polydiene and polymers of vinyl-substituted aromatic compounds in addition to the above constituent and the obligatory crystalline olefin polymers. The vulcanization is carried out according to the procedure described by the sulfur and / or peroxide method. The snow-elastomer so prepared is already superior in shoe-based Bstyrene / diene block copolymers, but its flow properties are not affected by the vulcanization used, but are also inaccessible and expensive due to the extremely difficult production of the saturated elastomer component.

In many cases, one or both of the starting components are chemically modified to improve the compatibility of the blend components. For example, U.S. Patent No. 4,226,952. US patent recommends partial hydrogenation of the rubber component prior to blending the olefin copolymer and polybutadiene.

A known solution for improving the peelability is a third component of a special composition, the so-called. addition of a block copolymer improving the accessibility (U.S. Patent No. 4,299,931).

Highly dynamic vulcanization of crystalline polyolefins with unsaturated diene rubbers (e.g., SBR) could be solved without the presence of a third constituent using sulfur and / or m-phenylene bis / maleimide (U.S. Pat. No. 4,104,210). . However, this method, in particular due to the use of the quaternary maleimide derivative, provides a product with a high tensile strength and a low tensile elongation, preferably of a plastomeric nature.

There is an unmet need for a low-cost thermoplastic elastomer that is capable of improving compatibility between polyolefin and polystyrene blends and mixed wastes. It is well known that the so-called. polyolefins and polystyrene make up the vast majority of consumer plastic waste. Their rendering recyclable and their conversion into a guaranteed quality regranulate is made impossible by the absence of a suitable polymeric additive to improve their pelletability.

Our aim was to produce a snow-cured dynamic vulcanizate which, thanks to its mass produced plastics and elastomers, is inexpensive, easy to produce, easy to process, highly compatible with styrene / diene styrene and styrene copolymers, suitable for the conversion of polyolefin / polystyrene blends and wastes or possibly polyolefin / polystyrene / PVC wastes into guaranteed quality secondary raw materials.

It has now been found that a thermoplastic elastomer suitable for the above purposes can be prepared by dynamic vulcanization by using a phenolic resin crosslinking method to crystallize the crystalline olefin polymer and butadiene and / or isoprene-containing elastomers.

It will be surprising to those skilled in the art that the above-mentioned elastomers, which have extremely poor compatibility with crystalline polyolefins, can be used to provide favorable physico-mechanical and theologically compatible snow-softening elastomers.

It is also surprising that the snow-elastomer produced by the process is suitable for increasing the impact resistance of styrene polymers. This assumes that the elastomer is present in an optimal particle size distribution for the controlled course of the micro-cracking process. However, dynamic vulcanization, which is known to target the partial or total vulcanization of the elastomeric constituent and its distribution in the plastomeric matrix, is not suitable.

Likewise, it is surprising that the process snow-softening elastomer is capable of increasing compatibility between polyolefins and polyestyrenes. To date, only graft or block copolymers, one segment of which is compatible with polyolefin and the other with polystyrene, are suitable for this purpose. However, such a structure is not expected to occur in dynamic vulcanization.

Finally, it is extremely surprising that this resin vulcanization is capable of producing guaranteeable quality polyolefin / polystyrene / / PVC blends and thus recycling non-recyclable household waste plastic.

Accordingly, the present invention provides a process for the preparation of a snow-softening polyolefin-based elastomer composition by dynamic vulcanization, characterized in that, based on the weight of the composition,

20-80, preferably 30-70 parts by weight of crystalline olefin polymer,

80 to 20, preferably 70 to 30 parts by weight of butadiene and / or isoprene based elastomers, up to 100 parts by weight of other polymers known per se, grafting monomers, fillers, reinforcing agents, excipients and combinations thereof;

2 to 20, preferably 3 to 15, preferably 4 to 10 parts by weight of phenolic resin and metal oxide and / or halide, optionally in the presence of a halogen donor, are plasticized at a temperature above the softening point of the crystalline polyolefin.

The crystalline olefin polymer according to the invention is preferably low and high density polyethylene, polypropylene, polybutylene, ethylene / vinyl acetate copolymer, ethylene / acrylate copolymer, ionomer, polyolefin grafted with polar monomers, and mixtures thereof.

As butadiene and / or isoprene-containing elastomers, styrene / butadiene statistical (SBR) and block copolymers, polybutadiene (BR), polyisoprene (IR), natural rubber (NR), nitrile rubber (NBR) and butyl rubber (IIR) , as well as a combination of these, is most relevant.

Vulcanization with phenolic resin is described in more detail in U.S. Patent Nos. 3,287,440 and 3,709,840. U.S. Patents. The vulcanization of the alkylphenols preferably having various substituents and the condensation of the formaldehyde, sometimes with a halogenated phenolic resin, can be carried out essentially by the following methods:

- a halogen-containing phenolic resin, either alone or in combination with a metal oxide activator

- a halogen-free phenolic resin with an organic halogen donor and a metal oxide activator

- halogen-free phenolic resin with metal halides (Lewis acids) and possibly metal oxides.

Suitable metal oxide activators for use in the present invention include zinc oxide, magnesium oxide, titanium dioxide, silica, zeolite, and combinations thereof; Suitable Lewis acids include tin chloride, zinc chloride, bromide, ferric chloride, aluminum trichloride, boron trifluoride, titanium trichloride, tetrachloride and mixtures thereof.

Organic halogen donors according to the invention include PVC, chlorinated polyethylene (CPE), chlorinated rubber, sulfochlorinated polyethylene (CSM), chloro-paraffins, polychloroprene (CR).

Other polymers used in the invention are the following plastomers: polystyrene, styrene copolymers, polyphenylene oxide, polycarbonate, PVC and mixtures thereof, and the following elastomers: EPM, EPDM, CPE and mixtures thereof.

Fillers, chalk, dolomite, SiO2, wood flour, rubber flour, factorial, talc, synthetic fiber, glass fiber, beads, bubbles, bentonite, barite, barium ferrite, kaolin, zeolite and their mixtures are used as fillers and strengtheners according to the invention. .

Preferably, the excipient is an antioxidant, a plasticizer, a mating agent, a light absorber, a flame retardant, pigments, or mixtures thereof.

The dynamic vulcanization is conveniently carried out at 130-250 ° C or up to this temperature range in a closed mixer or extruder.

The main advantages of the process according to the invention are as follows:

- easy to carry out of cheap, mass-produced raw materials;

- the snow-elastomer it produces is easy to process and expands its range of elastomers;

- the dynamic vulcanizates produced by the process are well compatible with snow-softening elastomers for use in the shoe industry and can be used as additives thereto;

the snow-softening elastomer prepared in the process is capable of increasing the impact resistance of styrene homo- and copolymers and of modifying polyphenylene oxide;

the process-based snow-elastomer may serve as a compatibility additive in blends of polyolefin / polystyrene composition, thus allowing the waste material to be made into a guaranteed secondary raw material despite the mixed composition;

- the process for converting pliolefin / polystyrene / PVC blends into a recyclable material of guaranteed quality; the elastomer prepared by the process can be used as a compatibility additive for such compositions.

The following examples illustrate the practice of the present invention without limiting it.

Example 1

On a Brabender Plasti-Corder, the following mixture was dynamically vulcanized at 150 ° C. Low density polyethylene (KSPE, Tipolen FA 2210, product of the Tisza Chemical Plant) and high density poly5 ethylene (NSPE, Hostalen GC 7260, product of Höchst) were used as the plastomer. Elastomer SBR (S2KSZ-30 ARKP / N, Soviet type), BR (SKKD, Soviet type), NR (Smoked I, product of Malayanian Rubber), IIR (Polysar Butyl 100,

Polysar product) or. a mixture of these roles.

Table 1 shows the composition of dynamic vulcanizates and their properties.

Table 1

Composition, tensile strength (<$) and elongation at break of dynamic vulcanizates (£)

creative THE Composition, parts by weight F G B C D E plastomer KSPE 20 - - 60 70 60 NSPE - 30 40 50 - 20 Elastomer SBR 20 70 60 50 20 - 10 BR 20 - - 30 10 NR 30 - - 20 - - IIR 10 - - - - - Vukanizálószer Brominated phenolic resin (SP 1056, Schenectady company product) - - - - 1 1.8 Halogen-free phenol resin (Rousselot 7500, Neville Company Ter- meke) 10 10 10 10 6 6 - ZnO 5 3 3 3 2 - - MgO - 0.5 0.5 0.5 2 - Natural zeolite 1 0.5 0.5 0.5 0.5 - 0.2 PVC 4 1 1 1 - - polychloroprene (Baypren 230, Bayer products) - 1.5 1.5 1.5 - - SnCkx2H2O - - - - 2 - alcB - - - - 0.5 - ZnBrz - - - - 0.5 - Features. i, MPa 5.1 13.9 16.5 17.8 7.2 8.1 9.6 ε, X 200 240 300 350 280 340 310 55 Heat according to formula A thermoplastic (Application No. 3301/82) custom made elastomer in 5 massX kristálypolisztirol- position with similar composition At -20 ° C ba (PSZT, Soviet type) stirred őmledék- 4.6 kJ / m ² . in. It was made like this mix notched A, B, C and D recipes Based on the Charpy specimen (DIN 53453 standard) No. 60 4 104 210 US patent export measurable impact resistance -40, , -20 and At 23 ° C are also reproduced . In the above order 4.8 as follows, 5.2 and 6.9 ^- kJ / m ^2, this in the case of tensile strength respectively whereas the starting polystyrene is 2.9, 3.3 and the following values were obtained; 14.3, 17.0 and 4.1 kJ / m ² . The technical progress is fine example 18.7 MPa and values of elongation at break: that 186,139 no. Hungarian patent 65,190, 230 and 270X. According to our process, B, C

The thermoplastic elastomers of compositions A and D have slightly lower tensile strengths but significantly higher tensile elongations due to the enhanced elastomeric nature.

Mixture E can be used to improve the compatibility of polyolefin / polystyrene systems. The tensile strength of the 1: 1: 1 mixture of high density polyethylene / polypropylene polystyrene could be increased by 25-30% and the elongation at break by 150-200% after the incorporation of the dynamic volcanizate E at 8-10% by weight.

The Formula F dynamic vulcanizate was incorporated into a standard SBR-based shoe soles in an amount of 20-25% by weight without compromising the physical-mechanical properties of the finished product. This is particularly surprising because more than 10% by weight of the polyolefin derivative may not be included in such formulations to ensure adhesion.

Example 2

In the apparatus mentioned in Example 1, the mixtures of Table 2 were dynamically vulcanized at 190 ° C. Polypropylene homopolymer (PP-H, Tipplen H 523, product of the Tisza Chemical Plant), PP copolymer (PP-K, Tipplen K 523, product of the Tisza Chemical Company), poly (5-methyl-1-hexone) density polyethylene (LKSPE) and ethylene / vinyl acetate (E / VAC, Evatane 2805, product of ICI) were used. Elastomer is IR (SZKI-3, Soviet type), NBR (Perbunan N 1807, Bayer product), Liquid BR (Plastikator 32, NDK product), Liquid NBR (Hycar ATBN 1300X16, Goodrich product), and styrene / butadiene block copolymer ( SBS, Cariflex TR 1102, product of Shell).

-510

Table 2

Composition and Properties of Dynamically Vulcanized Thermoplastic Elastomers Composition, parts by weight

Plastomer A

PP-H 20

PP-K 10

LKSPE 10

KSPE (Example 1)

E / VAC

Elastomer

BR (Example 1) 10

IR 10

NBR

SBR (Example 1) 20

Liquid BR 20

Liquid NBR

SBS

Other polymers

PVC waste

Polystyrene waste

Graftable monomer

styrene

Vulcanization system

Brominated Phenolic Resin (Example 1) Halogen-Free Phenolic Resin (Example 1) 8

ZnO 2

NaX molecular sieve 1 (Ca, Mg) Y molecular sieve

PVC 2

orthocarbonate

CPE (Borsodi Chemical

Combinator product)

Filling, strengthening and auxiliary materials

Nail

Crete 10

Dolomites 10

talc

Cellulose fiber 5

SiO2 3

Natural zeolite

Stearic acid 0.8

Calcium stearate

Antioxidant (Flectol

H, product of Monsanto) 1

· Features.

6, MPa 12.1 e,% 140

Dynamic vulcanization of Formula A composition with dicumyl peroxide yields a tensile strength of 12.5 MPa and an elongation at break of 80%, and in the case of sulfur vulcanization, 12.0 MPa and 110% respectively.

The composition according to Formula B is the same as that described in No. 2,408,632. with the exception that the elastomeric constituent in this case is not EPDM. The technical progress is well illustrated by the fact that the

B C D E 64 50 - - - - 5 15 - - 10 15 - - - 30 - - 20 - 6 - 10 5 - - - - - - 40 10 24 50 - 20 6 - - - - - 10 5 * 5 15 15 - - - 2 3:24 5 - - - - 8 6 1.8 - - - - 1 0.5 - - - 2 5 - - - - - - 0.5 - - - 3 - 28.8 10 - - - - - - - - - - 5 - - - - - - - - - 10 0:36 0.5 - - - - - 1 0.72 0.5 - 1.5 19.2 20.0 11.9 14.1 380 300 250 90 Gyula dynamic volcanizate tenacity 55 ^8ά ^ ^& PP / EPDM based than (17.6 MPa) Na-

it has a higher elongation at break (390 X).

Formula C is disclosed in U.S. Pat. It simulates an example of a US patent, θθ, which has been dynamically vulcanized with a maleimide derivative. The patents cited for this composition show a tensile strength of 20.9 MPa and an elongation at break of 230%. The dynamic gg vulcanizate (C) according to our process has a tensile strength close to that of meg-612, but exceeds it in tensile elongation.

It is suitable as a compatibility enhancer additive for Formulation D thermoplastic elastomeric polyolefin / polystyrene / PVC compositions. Adding 5 parts by weight of dynamic vulcanizate D to 100 parts by weight of the 50:25:25 mixture and melting this mixture uniformly gives a tensile strength of about 20% to 10%.

can be increased and the elongation at break will be increased 5-fold.

Formula E, based on the plastomer and other polymer components, simulates the plastic fraction of household rubbish, 15% of which is made up of polyolefins and the remaining 1/3 is composed of polystyrene and PVC. The phenolic resin according to the process can be made by dynamic vulcanization into a thermoplastic elastomer which, due to its favorable physical-mechanical properties, can be considered as a very valuable secondary material.

Claims (2)

PATENT CLAIMS A process for the preparation of a thermoplastic polyolefin-based elastomeric composition by dynamic vulcanization, characterized in that, based on the total weight of the composition 20-80, preferably 30-70 parts by weight of crystalline olefin polymer, 80-20, preferably 70-30 parts by weight of butadiene and / or isoprene based elastomers, up to 100 parts by weight of other known polymers, graftable monomers, fillers, reinforcing agents, excipients and their combinations, and 2 to 20, preferably 3 to 15 parts by weight of phenolic resin, metal oxide and / or metal halide, optionally in the presence of a halogen donor, are plasticized at a temperature above the softening point of the crystalline polyolefin. Process according to claim 1, characterized in that the butadiene and / or isoprene20 based elastomer is a styrene / butadiene statistical and block copolymer, polybutadiene, polyisoprene, natural rubber, nitrile rubber, butyl rubber and mixtures thereof. Process according to claim 1 or 2, characterized in that the filler used in the phenolic resin vulcanization is natural and / or artificial zeolite.