Reinforced thermoplastic polyolefin composition

 

(57) Abstract:

Describes reinforced thermoplastic polyolefin composition comprising a mineral filler and Melanesian. As it contains polyolefin (A) from 30 to 98 wt.% polyolefin having a density from 0.94 g/cm3and the rate of melt flow of less than 10 g/10 min, selected from the group consisting of homopolymers of ethylene and copolymers of ethylene with at least one other alpha-olefin containing from 3 to 10 carbon atoms, as filler it contains (A) from 70 to 2 wt.% at least one carbonate of a metal belonging to group IIa of the Periodic system, in the form of particles having a size of from 0.07 to 10 μm, and contains (C) from 0.01 to 10 weight. o'clock, counting to 100 hours (A)+(B), Melanesian General formula

< / BR>
where R and R1can be independently selected from hydrogen and alkyl radicals containing from 1 to 8 carbon atoms; R2is hydrolyzable by alkoxygroup containing from 1 to 6 carbon atoms, or halogen atom; R3is an alkyl radical containing from 1 to 8 carbon atoms; X is a radical of the formula or aromatic, cyclic aliphatic or heterocyclic divalent radical, where R

The present invention relates to reinforced thermoplastic polyolefin compositions. In more detail, the present invention relates to reinforced thermoplastic polyolefin compositions, suited for the production of these products having such mechanical properties as elasticity, especially at temperatures below 0oC that are superior to the corresponding properties of unreinforced polyolefin compositions.

As you know, the polyolefins are widely used in a variety of end products, including films, fibers, molded or termoformovannyh products, pipe or coatings. In some cases, such applications, especially when the produce polyolefin shaped articles by molding, it is necessary to cast the product surpassed in hardness and strength are products that can be made from the original individual polyolefin.

It is known and described in the literature many ways of modifying the properties of polyolefins; they include the cross-linking of polymers or the inclusion in the polymer matrix additives, supremeacy metals of the second and third groups of the Periodic system, and so forth. Usually polyolefin compositions reinforced with fillers tend to be more rigid than the original polymers themselves, the end products from reinforced polymers are also characterized by high dimensional stability.

However, it is known that polyolefins because of its unipolarnosti not suitable for reinforcing inorganic additives or fillers; indeed, the increase in rigidity and dimensional stability is usually accompanied by deterioration of other important properties, including strength, elasticity and so on. In order to avoid such disadvantages, the proposed or modified olefinic polymers, imparting monomers with polar groups in the hydrocarbon chain, or to use so-called "adhesion promoters", namely compounds that cause increased adhesion or bonding between the fibers and polymer matrix.

Thus, for example, Patents great Britain N 1,110,930 and 1,177,200 reveal reinforced compositions comprising a polyolefin, an inorganic filler and organosilane containing group which can be hydrolyzed and capable of reacting with hydroxyl groups present in Neorganicheskie the silane.

U.S. patent N 3,956,230 discloses polymeric compositions, such as, for example, polyolefins, reinforced filler containing hydroxyl groups. The filler and the polymer make compatible by mixing them in the presence of a coupling agent such as maleic anhydride and a free radical initiator.

The UK patent N 2,225,328 discloses reinforced composition comprising polyethylene modified by grafting of at least one unsaturated carboxylic acid, ethylene or anhydride of such a carboxylic acid, and silicate of aluminum, the surface of which is treated aminosilanes.

Published European Patent N 0 171 513 discloses reinforced compositions comprising a polyolefin, a carbonate of a metal of group IIA of the Periodic system and agent for compatibility, including at least one grafted polyolefin with carboxylic acids or anhydrides.

Description of Japanese Patent N 74-041,096, published on 07 November, 1974, discloses polyolefin compositions with fillers obtained by reaction of a polyolefin, maleic acid or anhydride and the glass fibers pre-treated coedine as, for example, N, N-hexamethylene-bis-melaminovaya acid, N, N-dodecamethyl-bis-melaminovaya acid or N,N'-isophorone-bis-melaminovaya acid as a coupling agent capable of promote adhesion between the polyolefin and glass fibers.

U.S. patent N 4,429,064 describes the use melaminovoi acid or silane derivative melaminovoi acid as an agent for promotion of adhesion of the mica to the polyolefin. In the description of the specified U.S. Patent says that the resulting compositions show improved mechanical strength; examples of the present compositions with tensile strengths at break of not more than 419 n/mm2and impact strength Izod determined at room temperature on notched bars, not more than 3.4 kgs m/cm, which corresponds to 33.4 j/m

The object of the present invention is to further improve the performance of reinforced thermoplastic polyolefin compositions, in particular at temperatures below ABOUToC, such as -40oC.

In accordance with the present invention, this and other characteristics are achieved with the use of at least one carbonate of a metal belonging to group II of the Periodic with whom and, promoting adhesion between the inorganic filler and the polyolefin.

Therefore, the object of the present invention is a reinforced thermoplastic polyolefin composition, comprising:

(A) from 30 to 98 wt.% polyolefin selected from the group consisting of homopolymers of ethylene and copolymers of ethylene with at least one other alpha-olefin having from 3 to 10 carbon atoms; and accordingly

(B) from 70 to 2 wt.% at least one carbonate of a metal belonging to group IIa of the Periodic system; and

(C) from 0.01 to 10 weight. hours (per 100 h (A)+(B) ) of a silane-derived melaminovoi acid of General formula

< / BR>
where R and R1can be independently selected from hydrogen and alkyl radical having from 1 to 8 carbon atoms; R2is CNS hydrolyzable group having from 1 to 6 carbon atoms, or a halogen atom; R6is an alkyl radical having from 1 to 8 carbon atoms; X is a radical of the formula or aromatic, cyclic aliphatic or heterocyclic divalent radical, where R4is hydrogen or an alkyl radical having from 1 to 18 carbon atoms, and n is an integer from 1 dinovia compositions of the present invention, which comprise from 50 to 80 wt.% polyolefin (A), from 50 to 20 wt.% carbonate of a metal belonging to group IIa of the Periodic system (B), and from 0.05 to 5 wt.% silane-derived melaminovoi acid, (C) of formula (1) above, considering a relatively mixture of (A)+(B).

In the compositions of the present invention particularly preferred are silanes, derivatives of maleic acid, of the formula (I), where R and R1is hydrogen; R2- linear or branched alkoxyalkyl; containing from 1 to 4 carbon atoms, such as-O-CH3-O-C2H5, -O-C3H7or-O-C4H9; R4is hydrogen, n is 2 or 3 and 3-m 0.

Silanes derived melaminovoi acid having the formula (I), above, are well known products and are available commercially. You can brush up in accordance with known methods, are widely described in the literature, for example in U.S. Patent N 4,429,064. The method of obtaining such silanes of the formula (I) is the reaction melaminovoi acid (Polyamid maleic acid) with a reactive organosilane General formula (II)

< / BR>
where X, R2, R3and m have the same meanings as defined above, and A is a functional group capable reallymy group, the vinyl group or halogen atom. The preferred method involves the reaction of gamma-aminoalkylsilane with maleic anhydride or its reactive derivative such as maleic acid or its alkyl ester or chloride, at a temperature of 70oC in an atmosphere of nitrogen at a molar ratio of 1:1.

Used in the compositions of the present invention, the polyolefin may be homopolymer ethylene and/or a copolymer of ethylene with at least one other alpha-olefin containing from 3 to 10 carbon atoms. Examples of such alpha-olefins are propylene, butene-1, hexene-1, hepten-1 and so on. When the polyolefin is homopolymer of ethylene or a copolymer with a smaller number (for example, from 2 to 25 wt.%) at least one other C3-C10alpha-olefin, the density of the polyolefin is in the range from 0.85 to 0.97 g/cm3mainly from 0,940 to 0,960 g/cm3. The rate of flow of the melt (Melt Flow Index) of the polyolefin is usually lower than 15 g/10 min, preferably from 2 to 10 g/10 min.

Although preferred in the compositions of the present invention are the polyolefins of high density, for specific applications or products, if you want, you can use the lotnosti (LLDPE), individually or in mixtures with each other. These types of polymers are commercially known, for example, under the trademark ESCORENE'LL 1201XV (LLDPE) from Soc EXXON; RIBLENEAK 1912 (LDPE) from Soc ENICHEM; ERACLENHUG 5013 (HDPE) from SOc ENICHEM. Especially preferred in the compositions of the present invention is a high density polyethylene (HDPE). To obtain the considered compositions of the present invention can use any commercially available carbonate of a metal belonging to group IIa of the Periodic system. Specific examples of such carbonates include calcium carbonate, barium carbonate, magnesium carbonate, or mixtures thereof; especially preferred individual calcium carbonate or a mixture of magnesium carbonate. As known from practice, it can be important to the size of the filler particles, it is chosen depending on the desired properties. Usually particles of small size tend to inform the products higher impact strength than larger pieces, even if reduced strength and requires a greater number of agent for compatibility. Typically, the particle size of the carbonate of a metal belonging to group IIa of the Periodic system, has a value of from 0.02 to 40 μm, preferably from 0.07 to 1>from Soc UMBRIA MINE-RA-RIA, and so forth.

Compositions of the present invention can be obtained by downloading the components of the composition in any order in apparatus for mixing, suitable to obtain thermoplastic compositions, and then bringing the temperature of the mixture to a value equal to at least the melting point of the polymer, i.e. up to 180-220oC. you Can use single-screw and twin-screw mixer, Banbury mixers, and other known mixers to obtain mixtures of thermoplastic polymers.

Instead of sapana derived melaminovoi acid of the formula (I), with a carbonate of a metal of Group IIa, and the polymer can be mixed connection prior to receiving the additives, which are then in the process of stirring under heating and under melting react with each other at least partially, giving an additive of the above formula (I).

Thus, it is possible, for example, be mixed with carbonate and polyolefin individual maleic anhydride and a reactive silane of the formula (II) or their mixture.

To obtain the final composition additive of the various components, including the aforementioned prior connection can be performed in any sequence, when uilu can be downloaded directly to the device for production of products, mainly in apparatus for casting under pressure, or apparatus for the extrusion of sheet or other polyolefins, or apparatus for molding blast. Typically, however, you first need to present the composition in the form of fragmented molded particles, such as granules, which are then loaded into the apparatus for the production of shaped products.

Reinforced polymer compositions of the present invention have a high impact strength Izod, especially at low temperatures, such as -40oC, and high turnover, which makes them particularly suitable for use in injection molding. Indeed, the rate of flow of the melt compositions of the present invention is usually higher than 1.5 g/10 min at 190oC and 2.16 kg

In addition, you can optionally included in compositions of the present invention are well known additives and/or auxiliary connections for improved performance: thermal stability, resistance to oxidation and the action of light; you can add other additives such as pigments, dyes, agents for fire, release agents, other types of thermoplastic resins or rubbers to impart high impact qualities. Those to whom it into practice here are some illustrative examples, not limiting the scope of the invention. In the examples, all proportions and percentages are by weight, unless specifically stated. To determine the characteristics of the compositions in the examples used the following methods.

The mechanical properties. Elasticity (impact strength) of the samples notched Izod measured at +23oC and -40oC, acting in accordance with the procedure of ASTM 256, test specimens 3.2 mm thick, elongation and bending modulus measured using the procedure of ASTM d 638.

Thermal properties. The heat distortion temperature under load 0,455 MPa (n/m2106determine, using the standard procedure ASTM d 648.

Rheological properties. The rate of melt flow (M. F. I.) determine, using the procedure ASTD 1238 at 190oC and 2.16 kg

Examples 1-6. In the mixer for dry mixing upload the following components: high density polyethylene (HDPE), ERACLENE HUG 5013, with the rate of melt flow of 4.5 g/10 min, in quantities specified in the table, and calcium carbonate, produced and sold by Soc. OMOI under the trade name OMUAGARD2 URM, in the amount indicated in the table. To the resulting mixture specified in the table the number of silane derived melaminovoi the thus Obtained mixture was thoroughly stirred for 15 min and then ekstragiruyut through a twin screw extruder ICMA San Giorgio MC-33 at a temperature of 230oC and 300 rpm Extrudate used for injection molding, using a Battenfeld 750 press under the following conditions: the temperature of the cylinder and the injector 200oC, mold temperature 50oC, the time of injection is 20, the total cycle time is 45 C.

In the following next table shows the thus obtained properties of the specimens tested.

1. Reinforced thermoplastic polyolefin composition comprising a mineral filler and Melanesian, characterized in that it contains polyolefin (A) from 30 to 98 wt.% polyolefin having a density from 0.94 g/cm3and the rate of melt flow of less than 10 g/10 min, selected from the group consisting of homopolymers of ethylene and copolymers of ethylene with at least one other alpha-olefin containing from 3 to 10 carbon atoms, as filler it contains (A) from 70 to 2 wt.% at least one carbonate of a metal belonging to group IIA of the Periodic system, in the form of particles having a size of from 0.07 to 10 μm, and contains (C) from 0.01 to 10 weight.h., counting to 100 hours (A) + (B), Melanesian General formula I

< / BR>
where R and R1can be independently selected from hydrogen and alkyl radicals containing from 1 to 8 carbon atoms;

R3is an alkyl radical containing from 1 to 8 carbon atoms;

X can be a radical of the formula or aromatic, cyclic aliphatic or heterocyclic divalent radical, where R4is a hydrogen atom or an alkyl radical containing from 1 to 18 carbon atoms;

n is an integer from 1 to 4;

m is an integer from 1 to 3 inclusive.

2. The composition according to p. 1, characterized in that it comprises from 50 to 80 wt.% polyolefin (A), from 50 to 20 wt.% carbonate of a metal belonging to group IIA of the Periodic system, (b) and from 0.05 to 5 wt.%, starting from a mixture of (A) + (B), Melanesian (S) of formula I are presented in paragraph 1.

3. Composition under item 1 or 2, characterized in that Melanesian (C) has the formula I presented in paragraph 1, where R and R1are hydrogens, R2is a linear or branched CNS radical containing from 1 to 4 carbon atoms; R4is hydrogen, n is 2 or 3 and 3 - m 0.

4. The composition according to p. 3, wherein R2selected from the group consisting of-O-CH2, -OC2H5, -O-C3H7and-O-C4H9.

5. The composition according to p. 1, characterized in that the polyolefin has come to yubom from the preceding paragraphs, characterized in that the particle size of the carbonate of the metal below 4 μm.

 

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