Elastoplastic composition and its preparation

 

(57) Abstract:

Elastoplasticity a composition comprising a continuous crystalline phase polyolefin and at least two discrete phase dispersed in the phase polyolefin, one of which is dynamically vulcanized ternary ethylene-propylene rubber, and the other is amorphous and thermoplastic styrene polymer, in which at least 90% of the dispersed particles have a maximum size less than 5 microns. These compositions are obtained by mixing the components in the conditions of dynamic vulcanization of rubber. 2 C. and 8 C. p. F.-ly, 8 PL.

The object of the present invention are elastoplasticity a composition comprising a continuous crystalline phase polyolefin and at least two polymer phase dispersed in a polyolefin matrix, of which one phase is dynamically vulcanized ternary ethylene-propylene rubber, and the other phase is amorphous and thermoplastic polymer of styrene.

Elastoplasticity composition based on crystalline polymers of olefins and dynamically vulcanized ternary ethylene-propylene rubbers are well known in the literature.

Compositions produced in accordance with the method of dynamic vulcanization, have a disadvantage which is common to all of the compositions on the basis of elastomeric resins and net elastomers and is expressed in the deterioration of MERCHANTABILITY, fitness for chemical processing while increasing the percentage content of reticulated elastomeric component.

For example, compositions containing triple net ethylene-propylene rubber in excess of 70-75 weight percent relative to the polyolefin, it is not amenable to recycling.

The most interesting vulcanizing system, used in vulcanization of rubber, characterized by a further disadvantage of a significant increase in corrosion of equipment during mixing of the components.

Thus, increasing the need for elastomeric compositions which can be easily recycled and do not require curing systems, leading to the above-mentioned phenomenon of corrosion.

It was suggested in the case of compositions containing crystalline olefin polymer and vulcanized ethylene-propylene rubbers (published patent application Japan N 17187/83).

The composition described in patent application Japan, obtained by mixing in a hot condition of the polyolefin and rubber in the presence of styrene and peroxide.

In these compositions, the rubber is unvulcanized, in connection with which there are no problems associated with suitability for chemical processing characteristic of the compositions in which the rubber is present in the vulcanized state.

It is now established that you can get elastoplasticity compositions containing crystalline olefin polymer and vulcanized ternary ethylene-propylene rubber, which have improved characteristics suitable for chemical processing, even in the presence of a large number of vulcanized rubber and which do not require curing systems, causing the phenomenon of corrosion in those cases, when the phase of the polyolefin, along with vulcanized rubber, also contains a thermoplastic and amorphous polymer of styrene in the form of dispersed particles, of which at least 80% have a maximum size less than 5 microns.

Thus, the compositions of this invention contain a continuous crystalline phase polyolefin and at least sovanny ternary ethylene-propylene rubber, and one amorphous thermoplastic polymer of styrene, where ternary ethylene-propylene rubber is a copolymer of propylene with ethylene and/or alpha-olefin of the formula CH2-CHR, in which R represents an alkyl radical containing 2-10 carbon atoms, and with copolymerization of the diene, and the weight ratio between the polyolefin resin and ternary ethylene-propylene rubber is from 10/90 to 75/25, and the weight ratio between the polymer of styrene and polyolefin ranges from 10/90 to 60/40. In the compositions according to the present invention mainly 90% of the particles dispersed ternary ethylene-propylene rubber has a maximum size less than 5 microns.

Preferably the particle sizes of both dispersed phases are such that 80% of the particles have a maximum size less than 5 μm, in particular less than 2 μm.

Determination of particle size is performed using electron microscopy.

Acceptable polymers of styrene are all amorphous polymers and copolymers having thermoplastic nature.

Examples of such polymers are the "crystal" polystyrene (PS), high impact polystyrene (HIPS), thermoplastic copolymers of styrene with Acrylonitrile and Etechno hydrogenated block copolymers of styrene and butadiene can be copolymers, described in U.S. patent N 4107130.

The preferred materials are polystyrene (PS and HIPS), copolymers of styrene with Acrylonitrile containing up to 30 weight percent of Acrylonitrile block copolymers of styrene, ethylene and butylene (manufactured by the firm "was oil and known under the trade name "Kraton G 1652").

The compositions of the present invention receive in accordance with the method in which the olefin polymer and a polymer of styrene, uniformly mixed with each other, connect with triple ethylene-propylene rubber, and then to the resulting homogeneous mixture vulcanizing system, and continue stirring the mixture at a temperature of from 150oup to 280oWith over a period of time during which occurs the vulcanization of rubber.

In order to obtain a dispersion in which the particle sizes are above values, during a stage of homogenization of the polymer of styrene and polyolefin resins it is necessary to use the appropriate compatibility agents, such as graft copolymers of styrene on polyolefins, grafted copolymers of ternary ethylene-propylene rubber, polystyrene or copolymers of styrene and acrimony is a number from 5 to 50 weight percent, on the basis of a mixture of polyolefin and polystyrene.

Block copolymers of styrene containing blocks of monomer units that are compatible with polyolefins, such as block copolymers of styrene, ethylene and butylene, are also suitable to obtain a dispersion having the desired dimensional characteristics.

Order to obtain a homogeneous dispersion phase polystyrene must obtain a mixture with a polyolefin; this mixture is then used to create elastoplasticity compositions according to this invention.

To obtain these mixtures are suitable all methods used for thorough mixing and homogenization of the components. For example, this operation can be performed in a closed rubber mixer or extruder, or in a system consisting of a mixer and granulator.

For example, the mixture can be obtained by mixing in the dry state in turbomachine polyolefin and variant high impact polystyrene in the presence of peroxide and styrene, is added in an amount necessary to achieve the desired percentage of homopolymer polystyrene and graft copolymer of styrene on the polyolefin. This operation is carried out at temperatures which can't happen PLA polymer of styrene, present in these mixtures, it was found that it is possible to obtain a final composition having satisfactory properties even if the dispersed phase, or at least 80% of this phase has a maximum size equal to 40 microns.

Useful crystalline polyolefin resin include polyethylene (high, medium or low density) and polymers of alpha-olefins of the formula CH2= CHR, in which R represents an alkyl radical with 1-8 carbon atoms, obtained by using catalysts for stereoregular polymerization Ziegler-Natta.

The preferred polymer is polypropylene with a high rate of stereoregularity. Other useful alpha-polyolefins are polybutene, poly-4-methyl-1-penten, polyhexes.

In the compositions according to this invention, the olefin polymer can be present in a modified form compared to the original polymer. As a result of interaction with vulcanizing system, a polymer of styrene and ternary ethylene-propylene rubber may occur an appreciable decrease of the melting temperature of the crystalline structure (determined by differential scanning calorimetry).

Triple ethylene is Lu CH2=CHR, in which R is an alkyl radical with 2 to 10 carbon atoms and a diene monomer, which is preferably present in an amount of from 1 to 10 weight percent, calculated on the basis of the total weight of the copolymer. The diene is preferably refers to a non-conjugate type.

Acceptable diene monomers are, for example, 1,4-hexadiene; 2-methyl-1,4-pentadien; 1,4,9-decatriene, 1, 5cyclooctadiene; 1-methyl-1, 5cyclooctadiene; 1,4-cyclopentadiene; Dicyclopentadiene; ethyldiethanolamine; 4-methyl-1,4-hexadiene; 5-methyl-1,4-hexadiene; and substituted derivatives of such monomers.

Examples of olefin monomers of the formula CH2=CHR are propylene, 1-butene, 1-penten, 1-hexene, 4-methyl-1-penten, 8-methyl-1-penten, 3,3-dimethyl-1-butene, 3-methyl-1-hexene, 2,4,4-trimethyl-1-penten.

The preferred ternary copolymers of ethylene-propylene-diene, containing from 25 to 50 weight percent copolymerizable links propylene.

In these compositions the ratio of polymer of olefin and ternary ethylene-propylene rubber is in the range from 10/90 to 75/25, for example from 10/90 to 60/40, preferably from 15/85 to 50/50; and the ratio of polymer of styrene and polyolefin is typically in the range of from 10/90 DOI triple weight ethylene-propylene rubber is usually to 20/80 to 70/30, and preferably from 25/75 to 60/40.

In the compositions of this invention may be mineral fillers, carbon black, colored pigments, plasticizers, stabilizers, oil filling and basically all the usual ingredients of elastomeric compositions containing ternary ethylene-propylene rubbers.

These compositions are obtained by homogeneous mixtures of the components in the conditions of dynamic vulcanization ternary ethylene-propylene rubber.

You can apply the techniques of dynamic vulcanization as described in U.S. patents NN 4130535 and 4311628 using vulcanizing systems described in these patents.

However, it was found that an additional distinguishing feature of this invention that upon receipt of the compositions of this invention do not have to use vulcanizing system having a corrosive nature, such as those that contain phenol-aldehyde resin and activator.

A completely unexpected result is that it is enough to use dehalogenating phenol-aldehyde resin without activators, such as hydrated salts of tin and organic acids such as oxalic acid, salicylic acid, malonic and succinic keys is 2">

Useful not halogenated resins are also sold on the market; for example, such resins can be purchased from the company "Schenectady chemicals, Inc. under the trade name FR A-148.

The temperature conditions under which mixing (in the range of from 150oup to 280oC), as well as the applied shear rate (300-400 sec-1) significantly lower than those used so far.

In accordance with the preferred method of implementation of this invention, a homogeneous mixture of a polymer of olefin and polymer of styrene ternary ethylene-propylene rubber and variant with fillers get at a temperature sufficient to melt the polymer of the olefin, and during the period of time necessary to achieve a homogeneous mixture. Then add the phenol-aldehyde resin and stirring is continued at a temperature, which contributes to the vulcanization of rubber.

Ternary ethylene-propylene rubber is previously fully cured. Full vulcanization of the rubber means such vulcanization, in which the rubber is extracted at less than 2% using cyclohexane at room temperature, or in quantities less than 4% using boiling xerotica to U.S. patent N 4806558).

The process of mixing and/or mixing can be done in a closed rubber mixer, extruder or in a system that includes an indoor rubber mixer and granulator.

This process can also be done on multiple devices arranged in series, and the first apparatus is a thorough mixing and homogenization of the composition, and in subsequent units are cured.

The temperature of mixing, which are cured, usually in the range of 150oup to 280opreferably from 180o220oC.

Example 1. Table 1 shows the composition of the reaction mixture used to obtain mixtures of polypropylene and polystyrene, suitable for elastoplasticity compositions according to this invention.

These compounds were obtained in dry conditions, using Turbomeca acting in a nitrogen atmosphere.

To the polypropylene in the form of flakes and high impact polystyrene in the form of granules, if it was used, was added to the peroxide, and then styrene, producing adding small doses when heated.

Once produced the complete addition of styrene within one hour, their temperature above 130oWith and avoid plasticization subsequent hardening of the polymer.

These products are gradually cooled, and then stabilized with 0.2% make up 1010 and 0.1% synthetic hydrotalcite, which was then extrudible at a temperature of 210oC.

Selective extraction using methyl ethyl ketone and chloroform and subsequent analysis by infrared spectroscopy method undertaken in relation to the different fractions showed the presence of both products for about 10% of the grafted copolymer polystyrene-9-polypropylene. The maximum particle size of dispersed phase polymer of styrene, at least 80% of the particles were less than 2 microns.

Table 2 shows the composition and main characteristics of the elastomeric compositions obtained from polymer mixtures are presented in table 1.

The above composition, is similar to all other compositions shown in the following examples were obtained by introducing the polymer components in an indoor rubber mixer of Brabender and adding after a short mixing vulcanizing system, and then zinc oxide and oil filling.

After this mix was made for 3 minutes at tempera who was tormented by the following definitions:

suitability for chemical processing was determined by measuring the pressure in the cylinder and sprinklers during the trial extruded in the extruder. In these trials used an extruder type TR 15 (odnochastny extruder, diameter 15 mm), which operated at a temperature of 230oWith an inner diameter of the extruder crosshead 2.5 mm, ratio of length to diameter 20 and receive rate, 9.5 CC/min.

the permanent elongation at 200% measured at a temperature of 23oIn accordance with method D-412 American society for testing and materials;

residual compression after 22 hours at a temperature of 100oC, measured in accordance with method D-395 American society for testing and materials.

The advantages achieved by the use of mixtures containing amorphous phase styrene, are also evident for the more solid elastomer compositions characterized by a higher ratio of the crystalline olefinic resin and elastomer thermopolymer (see table 3).

Detrol TER 537 E2 is a ternary ethylene-propylene rubber produced by the firm "Dutra s. p. A."; Kaplan ABOUT ZOR sold by the company "Himont Italy's.p.A."

In elastoplastic the stranded maximum size less than 2 microns.

Example 2. Table 4 shows the composition of various mixtures used to obtain elastoplasticity compositions.

Table 5 shows the composition and main characteristics of the compositions obtained from the above mixtures. In a mixture of 1, the maximum size of more than 80% of the particles of the dispersed phase is present in a mixture of 1, was equal to 40 microns.

Example 3. Table 6 shows the compositions of some of the mixtures used to obtain elastoplasticity compositions.

Table 7 shows the composition and characteristics of the compositions obtained with the use of such mixtures.

In mixtures 1-4 more than 90% of the particles of the dispersed phase (polystyrene) have a maximum size of less than 1-2 microns.

These songs were also very interesting, as they have excellent elastic properties at high temperatures and good suitability for chemical processing.

Example 4. Example 4 addresses the composition, in which the vulcanizing agent is used only degalogenirovaniya phenol-aldehyde resin.

Table 8 presents the compositions and characteristics of such compositions.

1. Elastoplastic composition, on animowany phenolaldehyde resin and zinc oxide, characterized in that the composition comprises a continuous crystalline phase polyolefin and two dispersed polymer phase of a copolymer of ethylene, propylene and ethylidenenorbornene and polymer based on styrene, and the mass ratio of the polyolefin to triple copolymer of 0.17 to 0.38, and the ratio of polymer based on styrene to the polyolefin is 0.45 to 1.38.

2. The composition according to p. 1, characterized in that not more than 80% of the two particles dispersed polymer phase has a maximum size of 5 MIM.

3. The composition according to p. 1, characterized in that the ternary copolymer of ethylene is fully vulcanized.

4. The composition according to p. 1, characterized in that the polyolefin is a stereoregular polypropylene and polymer based on styrene is polystyrene, high impact polystyrene and a copolymer of styrene with Acrylonitrile content of Acrylonitrile and 30 wt.

5. The composition according to PP.1 and 2, characterized in that the polymer based on styrene is a block copolymers of styrene-ethylene-butene-styrene.

6. The composition according to PP.1-3, characterized in that the compatibility of the polymer based on styrene-polyolefin contains grafted copolymer of Calimera based on styrene-polyolefin contains grafted copolymer ternary ethylene-propylene-diene rubber on polystyrene or copolymer of styrene with Acrylonitrile.

8. The composition according to PP.1-7, characterized in that it includes oil and mineral filler.

9. The method of obtaining elastoplastic composition by mixing a copolymer of olefin with targeted supplements and dynamic vulcanization, characterized in that as a copolymer of olefin using ternary copolymer of ethylene, propylene and ethylidenenorbornene and mixing is carried out in the presence of a polyolefin and a polymer based on styrene in a mass ratio of the polyolefin and the specified ternary copolymer of 0.17-0.38 and when the mass ratio of the polymer based on styrene, polyolefin 0,45-1,38, and dynamic vulcanization is carried out dehalogenating phenolaldehyde resin and zinc oxide at 150-280°C.

10. The method according to p. 9, characterized in that use 1-10 wt.h dehalogenating phenolaldehyde resin per 100 wt.h. ternary copolymer.

 

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