CS270317B1 - Composite materials - Google Patents

Abstract

Mixtures of polyalkenes with mineral fillers have very good fluidity when they contain 1 to 15% by weight of modified polyalkenes of formula I R 1 R | R j -Cil - <--- Cil -C- Cl. -C. 1> 'J rn 1 X 1 r; Y where m + n is 5o to 1ooo, R.R 'Is 11, Cl13, C2II5, C18, H18 - C11 -, X Je fH3 / fH3 -Si -O -l Si-o CH3 'γ ^ Η3 CH \ 13 to In Si éH3 or [CH2 <O] CH2 ' to k is 0 or 1 Y Je [° (CH 2> a] p - H • N E 2 7 o 3 1 7 B l wherein a is 1 to 4, p is 5 to 50 or - O <HH3 Si _ O CH. Jb - H where b is 3 to 4 o.

Description

CS 27o317 B1 1

BACKGROUND OF THE INVENTION The present invention relates to the use of amylic copolymers to facilitate the processing of a polyalkene-mineral composition.

Mixtures of large-scale polymers with mineral fillers (talc, kaolin, calcium carbonate, magnesium hydroxide, partially dehydrated aluminum hydroxide, titanium dioxide, glass) are becoming increasingly important among structural materials.

Composites with organic fillers, such as carbon black, natural and artificial fibers (including carbon) and the like are also of great importance. In addition to the filler, composites also include thermooxidizing and (otooxidation stabilizers, dyes and additives to improve processing and application properties (plasticizers). polyalkenes with mineral fillers use copolymers formed by hydrotobic and hydrophilic polymeric chains which can ensure compatibility of individual, mostly incompatible components as described in the author's certificate No. 263262. The mutual intolerance of the polymer and filler is due to the fact that Van The Walsian forces between the polymers of individual polymers (polymer-polymer) and fillers (filler-filler) are much more attractive forces between polymer and filler molecules (polymer-filler), the problem of tolerability is solved in polyalkene-mineral fillers composites Mostly, the filler treatment (stearic acid and its salts, silanes) is made by forming a wrapper around the filler particles which affinity to the polymer filler. More promising than the addition is the addition of copolymers (eg polyalken-block (graffiti) polyacrylates, polyalkene-block (graft) poles ether, polyalkene-block (graft) polyacrylic acid etc.). Copolymer treatment also dampens the mechanical tension between the polymer and the filler resulting in microtubes, defects, and consequently the loss of mechanical strength of the composite, and results in improved dispersion of the filler in the matrix.

Particularly elastic character of the copolymer blocks or grafts. it will ensure more effective amortization of the me-phase applied voltage. As a result, the mechanical properties of the composites are improved. The addition of an amphillic copolymer having affinity to all the components of the composite not only ensures system compatibility and improves some mechanical properties (notably notch and impact strength), but can also greatly facilitate the processing of the composite, copolymers containing blocks, or grafts that melt at a lower temperature than the other component copolymers (crystalline polyalkene) or have an elastomeric character (polysiloxanes) can effectively reduce the melt viscosity of the processed composite.

The processing of well-flowing mixtures results in significant energy savings, which makes the entire production process considerably more efficient.

It has now been found, in particular, that polypropylene copolymers with polyethylene oxide, polypropylelene oxide, polytetrahydrofuran, polyoxetane and poles (dimethyl-siloxane) formed by low molecular weight and / or grafts, i.e. segments with a polymerization degree in PP-1α to 1O00 and in modifying component 3 to S0 Not only do they have the desired camping-leaching effects, but they also significantly reduce viscosity. Thus, in order to facilitate workability (to provide higher ITT values), it is desirable that the amine copolymer contained in the composite (1-5% by weight) be formed by shorter blocks or grafts than the polymer matrix chains. SUMMARY OF THE INVENTION The present invention relates to composite materials consisting of a mixture of polyalkenes with mineral fillers and modified polyalkenes containing 1 to 15% by weight of modified polyalkene general formula... 2 CS 27o31 - 1 - - 1 R 1 R. - c. ch2 1 - C. 1, 1, 1 RXR * 1 - where m + n is 5o to 1000, R, R 'is H, CH 1, C "H =, CH" C - CH -J 2 5 4 9 2' CH, CH . H3 X is - Si - O - Si Si Si cn3 Vh3 7 K <0> Y Is £ O (CH 2) and J - H, where a is 1 to 4, p is 5 to 5o or where k 0 or 1, not f 1 O - Si - Oj VH. 1 where b is 3 to 4o

The synthesis of suitable amilithilic polyalkene copolymers is very challenging in terms of experimental design, and can only be realized in an environment that completely avoids the contamination of ionic, eventually coordinating, active centers (in high-vacuum apparatus in an inert gas atmosphere). The first syntheses have only recently been realized and are based on reactions associated with the transformation of coordination active centers to ionic or radical centers (eg, Richard, D, D. Br. Polym. J. 12, 89 (1989) or cationic polyalkene modifications (see No. 19o 127, 22o 722, No. 238 24o, No. 24o 627, No. 248 854) The melt of these copolymers acts as a lubricant in the processing of composites, and the mixture flows into the molds. The invention is further illustrated by the following examples,% and parts by weight in the Examples Example 1 In a Plastlcorder Brabender laboratory kneader, they were mixed at 4o3 / 2 with a polyvalent chain bonded to the polyalkene chain by covalent bonds. for 1 min of this component (total of 7 g): polypropylene (PP) Mosten 55 212 stabilized by thermo - and photo - oxidative stabilizers (60%) + 4% CaCO ^ Durcal 2 3% of stearic acid and 0.5% of calcium stearate, a comparative composite was prepared. Example 2

Proceeding as in Example 1, the following components were also kneaded: PP Mosten 55 212 (55%), 4% untreated CaCO 3 (Durcal 2), 5 * with polypropylene copolymers with polyethylene oxide (PEOX) blocks or grafts (copolymer composition »5) % PP with polymerization degree 5o to CS 27o317 B1 3 1 ooo, 95% PEOX with 5 to 5o basic structural units in chains - linking group X - Si (Me) 2 - O - [Si (Me) 23 5 - O - Sl ( Me) 2- Example 3

Poetup As in Example 1, the composite of PP PP Mosten 55 212 (50%) + 4% of untreated CaCO 3 Durcal 2 + 2% of the copolymer as in Example 2. Example 4

Following the procedure of Example 1, the components t 55% PP Mosten 55 212 + 4%% of teak-ground limestone Durcal 2 4 5% of terpolymer PP, PEOX and polyoxytetramethylene (PTHF) were mixed, the polyether ratio 1: 1 (M ^ PEOX - 2oo to 2 'ooo; Mn PTHF "35o to 3ooo; Mn PP -» 4oo to 8ooo). Both PP and polyethers 5 and 95, Example 5

Procedure as in Example 1, Component Component t 58% PP Mosten 552 212, 4% CaCO 3 Dur-Cal 2 - Untreated, 2% Copolymer as in Example 4. Examples

Example 1, composite composition: PP Mosten 58,412 (55%) + 4% untreated CaCO 3 + 5% terpolymer according to Example 4. Example 7

As in Example 1, the components were mixed: 58% PP Mosten 5,442,440% untreated Durcal 2 4 2% copolymer as in Example 4, Example 8

Procedure and weight proportions as in Example 4, but the polymer matrix was PP Mosten 52 815, P 1 and d 9

The procedure and the weight proportions as in Example 5, with the polymer matrix being PP Mosten 52,815.

The procedure and weight proportions are the same as in Example 4, but the polymer matrix was PP Mosten 52 511. Example 11

Procedure and weight ratio of composite composition as in Example 5, polymer used - PP Moset 52 517; From the composites described in Examples 1 to 11, melt flow indexes (ITT, g / lmin,) were measured with standard tests. The polypropylene matrices used for the comparison of ITT are shown in the table.

The component V in the copolymers has a melting point of polyethers [poles (oxyte tramhylene), poles (oxyethylene), poly (oxy-1-methylenes) J, i.e. 43 to 45 ° C or has the character of a buffing liquid poly (siloxane). When processing the composite at elevated temperatures, component Y melts and acts as a non-migrating agent.

Due to the copolymer, the viscosity of the composite melt decreases and the flowability is improved. The effect of the copolymer was examined in various polyalkene matrices, in which case the ductility increases and the ITT composite increases. The mechanical properties of mixtures with copolymers correspond to the capapositis of 4 CS 27o317 B1 tens with a certain content of EPDM rubber (higher toughness), ITT values and thermal resistance according to Vicat's and surpasses them (see 263 262). PP matrix

Composite composition (matrix / filler / copolymer weight ratio) Example

ITT ITT

49 N

Bridge: O 0.57 2.59 55 212 6o: 4o: O 1 o 66 2.97 Mosten 55 t 4o not. : 5 2 6.24 23.3o 55 212 (copolymer PP - PEOX) Mosten 58 t 4o neupr. : 2 3 1,13 5, o9 55 212 (copolymer PP - PEOX)

Mosten 55 212 55: 4o no. : 5 (PP-PEOX-PTHF terpolymer) 4,97 38,48 Mosten 58 i 4o! 2 5 1,18 5,11 55 212 (terpolymer PP-PEOX-PTHF) Mosten 55: 4o nepr. ; 5 terpol. 6 6, o3 35.21 58 212 58: 4o no. : 2 t / half 7 4.74 Mosten loo! O s O 11.34 59.2o 5 2 015 55: 4o not, 5 terpol. 8 1.35 58 t 4o non. : 2 terpol. 9 17,95 Mosten loo! O s O 5.34 16.13 52 511 55: 4o not. : 5 terpol. lo 8.61 Mosten loo! O t 0 4.82 52 517 58! 4o! 2.11 8.94 µl Example 12

Proceed As in Examples 2 and 3, but instead of polypropylene-block (graft) poles (oxye thylene), polypropylene block, graft poles (oxypr opylene) was used. (Mn PP - 4,000 to 8,000; polyoxypropylene - 275 to 3,000). PP: PPOX ratio. 5 and 95. Example 13

Procedure As in Examples 2 and 3, however, the copolymer used was polyoxyethylene modified polypropylene. Polymerization step a - PP - 1o to 10o, polymerization degree of polyethylene oxide and PTHF - 5 to 50.

Claims (1)

EXAMPLE 14 The procedure as in Example 1. and the composition of the composite was 56% polyethylene FB29 4% non-treated mlcro [not] cium (CaO2) (Durcal 2) + 4% polypropylene-co-ethylene copolymer blocks PEOX and PTHF, PPη PP - co - PE 35o - 7 oooj Μη PEOX 2oo - 2 4ooiMn PTHF - 35o - 3 5oo. Example 15 Procedure as in Examples 2 to 14, but the amount of copolymer added was: 15/1 - 1%, 15/2 - 3%, 15/3 - 7 15/4%, 15/5 - 15%. Composites with a copolymer content (15/4 and 15/5) were difficult to process (rubbery, glued, bubbled), their amount above lo% in composites is intended for special applications. As in Examples 2, 3, but a polypropylene-block, (graffiti) -polyoxetane copolymer, PPη PP - 4OO to 8 µmol of Mn polyoxetane - 3oo to 3 ooo was used, Example 17 The procedure as in the examples 2 and 3, however, the copolymer used was isotactic polypropylene-modified polydimethylsiloxane blocks and grafts, copolymer composition Mn PP " 4OO-8 ooo, Mn PD-2OO-3 Ooo, Porn PP &amp; 2, however, the bonding group X 1 -CH 2 (- (-) - CH 2 -) is used, the nature of the linking group does not substantially absorb the properties of the copolymer, the object of the invention is composed of composite materials composed of a mixture of polyalkenes and mineral fillers and modified poles-alkenes, characterized by that they contain 1 to 15% by weight general modified polyalkenes of the general formula: V &quot; R &quot; R &quot;CIK-C-2; C11-12-C11 imi R 'where m + n is 50-100, R, R * is H, CH3, Cg1g, C13h3, C-CH-, CHl3 / CH3; X Is -Si - OJ Si - 3] - Si 1 CH 3 ii CH 3 λ. H 3 k or [CH 2 O) Cl 12 kk is 0 or 1 Y Is IO (CH 2) a] - L JP H, where a is 1 to 4, p is 5 to 5o or CH, 13 - O - Si _ O - H 1 CH 3 b where b is 3-4o.