CS263262B1 - Kompozitypolyalkenů 8 mineral fillers - Google Patents

Abstract

Composite materials based on polyalkenes filled with mineral fillers, in which the compatibilizing component is copolymers of polyalkenes with polyethers and polyacetals, of the general formula I where R and R' are hydrogen or methyl, x is a linking group formed by dications, m is 50 to 500, n is 0 to 500, .o is 0 to 50, p,r 10 to 500, s,t is 1 to 5, y 0 to 100. The composite materials have good mechanical and processing properties.

Description

(54) Composites of polyalkenes 8 with mineral fillers

Composite materials based on polyalkenes filled with mineral fillers, in which the compatibilizing component is copolymers of polyalkenes with polyethers and polyacetals, of the general formula I where R and R' are hydrogen or methyl, x is a linking group formed by dications, m is 50 to 500, n is 0 to 500, .o is 0 to 50, p,r 10 to 500, s,t is 1 to 5, y 0 to 100. The composite materials have good mechanical and processing properties.

Γ *Ί R I Γ R ^- , 1 R I r B Ί 1 1 H- | -ch ₂ —c- 1 -CH _? — ΟΙ 1 -CH,— C ² I -ch ₂ - 1 -C· I -ch ₂ —c=»c-ch ₂ - 1 L n J 1 meter * 1 L R'J n X -4- about

jS , T*· „

H H

The invention also relates to composite materials made of polyalkenes and mineral fillers. Among structural materials, mixtures of natural and synthetic polymers with mineral fillers, such as glass, talc, kaolin, calcium carbonate, magnesium hydroxide, partially dehydrated aluminum hydroxide, titanium dioxide, are becoming increasingly important. Composites with organic fillers, such as carbon black and fibers from various materials, including carbon fibers, are also of considerable importance. Thermooxidative and photooxidative stabilizers are an integral part of all composites containing polymers. Composites may also contain other additives that improve processing or application properties. For example, dyes, plasticizers. However, most polymer - polymer or polymer - filler systems are incompatible. Van der Haals forces between molecules of individual polymers and fillers are much stronger than the attractive forces between molecules of different polymers or polymers and fillers. Composites of these incompatible materials must therefore contain additives having an affinity for both components of the composite and ensuring compatibility of the system.

Additives ensuring the compatibility of composites do not have a uniform character. This is understandable, each polymer and each filler has an affinity for other compounds. In composites of polyalkenes with mineral fillers, the compatibility problem is solved by modifying the filler. Many methods of modifying the filler are known. They consist in creating a shell, if possible, for each filler particle, which has an affinity for the filler and polyalkenes and which creates the interphase of the polymer - filler system. The modification allows the application of attractive intermolecular forces polymer - filler modification and filler - filler modification. It is highly desirable that the modification is also able to amortize (dampen) mechanical forces between the polymer and the filler, leading to the formation of microcracks, defects and, as a result, the loss of mechanical strength of the composite. One class of materials from which the filler is technically modified into composites with polyalkenes are silanes of various nature, another class is stearic acid and its derivatives, usually salts. More promising than filler modification is the addition of a polymer compatibilizing additive to the composite, for example copolymers of poly(alkene-CO-maleic anhydride) or poly(alkene-CO-acrylic acid).

The subject of the invention are composites of polyalkenes with mineral fillers, containing a polymer compatibilizing component, which contain 30 to 90% by weight of polyalkenes, 1 to 70% by weight of mineral filler and 1 to 15% by weight of copolymers of the general formula

Γ R Ί R I r R η 1 R I Γ R R' *1 1 l | •-ch ₂ —c- 1 -CH»— ΟΙ -CH»— C ² I 1 •CH»—C ² I ch ₂ -c«c-ch ₂ - 1 L rJ 1 m x R·. 1 n x » « 0

I-1_-Ip I—L_—i _r where R and R* is hydrogen or methyl x is a linking group - Si(CH ₃ ) ₂ -[0Si(CH ₃ ) ₂ ]i ^{0_si <ch} 2 ⁾ 2 1 is 3 to 6 or -(CH ₂ ) ₂ O-CH(CHj)g-CH-0(CHj) ₂ , or

-CH ₂ @ ch ₂ or (CH ₂ ) ₄ -[o-(CH ₂ ) ₄ ] _k -0-(CH ₂ ) ₄ -Okwhere k is 1 to 20, m “ 50 to 500, n « 0 to 500, O to 50, p, r » 10 to 500, s, t » 1 to 5, y = 0 to 100

Linking groups x are formed during the modification of polyalkenes with dications, for example the dication

B® ®Si(CH ₃ ) j^O-SiťCHj) ₂ Βθ where B is a paired ion, CIO®, Asf^, SbF®, Pf® is 4 to 10 or the dication of octamethylene-bis-dioxolenylium Βθ-obé (for B® to sets perchlorate hexafluoroarsenate hexafluoro hexafluoro phosphate

CH,—O. /P— ^C , ^H 2 «ζ ' or (B ) p xvlen-alpha,alpha -diylium ^®CH ClJ®B® or dication C :® | \®^(ch ₂ ) ₄ oJ (ch ₂ | ₄ | c® in which

C® Pf® or %SO ₂ CF ₃ or ®OSO ₂ F, k = 0 to 20

The interpretation of the effect of the described polymer compatibilizing additives in composites according to this invention is based on the following knowledge and ideas. The compound having the maximum affinity for the polymer component of the composite will probably be the polymer itself. The compatibilizing additive should therefore contain chains from the polymer from which the composite is prepared. In the case of a polyalkene composite - a mineral filler, i.e. from polyalkenes. Affinity to the polar surface of the filler can be ensured only by compounds with polar groups or heteroatoms (practically only O, N, halogens, etc.). Polymer analogues of this type are polyethers and polyacetals. It is known from the chemistry of low-molecular substances that using crown ethers, solvating salt cations, an electrolyte that is otherwise completely insoluble (without crown ethers) in non-polar solvents can be brought into solution. Polymer analogues of crown ethers can be chains of poly(ethers) and poly(acetals), which can coat a filler particle as a crown ether cation. They therefore have a high affinity for the filler. Block or graft copolymers of polyalkenes with poly(ethers) or poly(acetals) are therefore sought-after polymer compatibilizing additives. These copolymers have another, very welcome, function in composites from the processing point of view. Blocks or grafts of poly(ethers) melt at a lower temperature than Polyalkenes and their melt act as a lubricant during processing. The mixture flows better into the molds. In this case, the blocks with heteroatoms are bound to the polyalkene chain by covalent bonds, so they cannot be displaced.

The idea of using copolymers of the above types as compatibilizing additives could not be realized until recently, because the method of preparing these copolymers was not known. Only after finding a method of their synthesis (see AO 190 127, AO 220 722, AO 238 488, AO 238 940,

AO 240 627, AO 248 854) it is possible to practically prove the excellent compatibilizing effects of these compounds.

The invention will be further illustrated by several examples. Parts and % in the examples are by weight unless otherwise stated, PP is polypropylene.

Example 1 comparative

In a laboratory Plasticorder BRABENDER kneader, the following composite components (total 70 g) were mixed at 403 K for 10 minutes: MOSTEN 55 212 polypropylene stabilized with thermo- and photo-oxidative stabilizers (60%) + 40% Durcal 2 calcium carbonate modified (0.3% stearic acid and 0.5% calcium stearate).

Example 2

The procedure was as in Example 1, but the following components of the composite were kneaded. Polypropylene Mosten 55 212 (45%), 40% Durcal 2 untreated, 15% polypropylene copolymers with polyethoxyethylene (PEOX) blocks and grafts (95 » PP, 5% PEOX; number molar mass of the PP backbone approx. 20,000, molar mass of the PEOX blocks 3 to 6.10 ). The linking groups x form the residue of the siloxane dication SI(CH ₃ )o£si (CH ₃ ) ₂ ~θ] ₃ ~si (CH ₃ ) ₂ Example 3

Proceeded as in example 1, the components were mixed: polypropylene Mosten 55 212 (55%) + 40% Durcal 2 untreated + 5% copolymers as in example 2.

Example 4

Proceeded as in example 1, composite composition: polypropylene Mosten 55 212 (58%) + + 40% Durcal 2 untreated + 2% copolymers as in example 2.

Example 5

Proceeded as in example 1, but the following components of the composite were kneaded: polypropylene Mosten 55 212 (45%). + 40% Durcal 2 untreated + 15% copolymers of polypropylene with poly(oxyethylene) (PEOX) blocks and grafts (5 í PP, 95% PEOX), in which x were -CH ₂ /Q\ch ₂ of bis B®p xylene alpha,alpha'-diylium dication

Example 6

Proceeded as in example 1, the components were mixed: polypropylene Mosten 55 212 (55%) + 40 » Durcal 2 untreated + 5% copolymers as in example 5.

Example 7

Proceeded as in example 1, composition of the composite: polypropylene Mosten 55 212 (58 t) + + 40% Durcal 2 untreated + 2% copolymers as in example 5.

Examples

The procedure was as in Example 1, but the following composite components were kneaded: polypropylene Mosten 55 212 (45%) + 40% Durcal 2 untreated + 15% terpolymer of polypropylene with polyoxyethylene (PTHF) blocks. The ratio of polyethers was 1:1 (calculated per monomer unit) mol, the molar mass of polyethers was 3 to 6.10 (PEOX), 10 to 17.10 (PTHF), the ratio of polypropylene to polyethers was 5:95, in which the x groups were formed by the polymerization of tetrahydrofuran using 4-chlorophenyldiazonium hexafluorophosphate or (CF ₃ S0 ₃ > ₂ 0 and had the structure:

~(ch ₂ ) ₄ o[(ch ₂ ) ₄ o] (ch ₂ ) ₄ oExample 9

Proceeded as in example 1, the components were mixed: polypropylene Mosten 55 212 (55%) + + 40% Durcal 2 untreated + 5% copolymers as in example 8.

Example 10

Proceeded as in example 1, composite composition: polypropylene Mosten 55 212 (58%) and 40% Duroal 2 untreated + 2% copolymers as in example 8.

Test specimens were pressed from the composites described in Examples 1 to 10 and the yield strength σ k (MPa), elongation e (%) and tensile impact strength — 2 —2 were measured using standard tests.

RHT (kJm notch toughness VH (kJm) and in most cases also melt flow index ITT (g/10 min) and thermal resistance according to VICATA VIC <°C).

The measurement results are presented in the following table.

Table

Example if RHT VH ^ITT 21N ^ITT 49N VIC 1 22.1 440 234 5.8 0.66 2.97 103 2 19.5 510 339 6.3 3 21.5 450 271 6.1 0.81 3.35 4 21.6 280 228 6.3 0.43 1.93 109 5 rubbery, sticky 6 15.4 570 367 8.2 6.24 23.30 7 18.6 488 245 7.6 1.13 5.9 100 8 rubbery, sticky 9 17.0 510 234 8.5 10 38.5 IO 18.8 320 187 7.4 1.2 5.1 102

Example 11

The procedure was as in Example 3, but instead of PP-PEOX copolymers, a polypropylene - b, g - poly(oxymethylene) copolymer was used, in which X were octamethylene-bis-dioxolen-ylium B® esters:

- (CHj)jjOCH (CH ₂ ) JLo (CH ₂ ) ₂ Example 12

The procedure was as in Example 4, but instead of PP-PEOX copolymers, a polypropylene-b,g-poly(oxypropylene) copolymer was used.

Example 13

The procedure was as in Example 3, but the compatibilizing additive was an atactic polypropylene copolymer of identical total composition.

Example 14

The procedure was as in Example 3, but the compatibilizing additive was a copolymer of polypropylene oil with polyethers of the same total composition as in the above example.

Example ,15

Polyethylene FB-29 (55%) + 40% Duroal 2 untreated + 5% copolymers polyethylene with blocks and grafts of poly(oxyethylene) (96% Pe, 4% PEOX - molar mass of blocks (grafts) approx. 2,500) mixed at 400 K (10 min.) in a laboratory kneader Plasticorder BRABENDER, test specimens were pressed from the composite and its mechanical properties were tested. Compared to the standard (60% PE, 40% Durcal treated), samples with the copolymer showed higher toughness.

Example 16

The procedure was as in Example 15, but instead of polyethylene FB 29, the propylene-ethylene copolymer TATREN KD 703 was used. The notch toughness increased by 55% relative to the standard (60% copolymer TATREN KD 703, 40% modified Durcal).

Example 17

The procedure was as in Example 15, but instead of polyethylene FB 29, the terpolymer polypropylene-Co-ethylene-Co-1,4-hexadiene) NORDEL 1040 was used. The notch toughness increased by 50% relative to the standard with a simultaneous increase in the melt flow index.

Example 18

Composite components used as in example 6, but in different proportions:

18/1:95 t PP, 4 « _CaCO3 , 1% copolymer 18/2:70 % PP. 25 % CaCO, 5% copolymer 18/3:20 % PP, 70 % _CaCO3 , 10 í copolymer

In all cases, the presence of the copolymer replaced the standard filler treatment; in cases 18/2 and 18/3, the melt flow index increased by approximately 800% relative.

Example 19

Proceeded as in example 6, but instead of calcium carbonate, various mineral fillers were used:

19/1 Soapstone

19/2 Glass fibers (fiber diameter approx. 8.10 ^-5 m, length 10 mm) —4

19/3 Glass ballot box (ball diameter 10 m)

19/4 Magnesium hydroxide 19/5 Finely ground kaolin

19/6 Partially dehydrated aluminum hydroxide AIO(OH)

19/7 Titanium dioxide (micro-ground rutile)

Example 20

The procedure was as in Example 19, but instead of polypropylene another polyalkene was used, namely

20/1 Polyethylene

20/2 Poly(propylene-co-polyethylene) copolymer

20/3 Copolymer poly(propylene-Co-polyethylene-Co-poly-1,4hexadiene).

Example 21

The procedure was as in Example 19, but the content of the polymer matrix and mineral component was varied as in Example 18, i.e.:

21/1 95% PP, 4% mineral filler according to example 19, 1% copolymer 21/2 70% PP, 25% mineral filler according to example 19, 5% copolymer 21/3 20% PP, 70% mineral filler according to example 19, 10% copolymer

In all examples 19 to 21, the presence of the copolymer ensured compatibility of the organic

Claims (8)

1 to 5% of the copolymers completely replace the filler treatment, even in the cases represented by Examples 2 to 4 in which the copolymer contained only a small amount of polyether. 2 High polyethor copolymers are very effective and their amount of about 15% (Examples 5 and 8) is almost undesirable. 3 polyol (oxybutylene) (PTHF) as a less polar component than the poles (oxyethylene) (PEOX) forms the transition between the PP matrix and the polar poles (oxyethylene). Ptoro copolymers of PP to which blocks such as PTHF'ak are bound. PEOX needs to be fed more than the copolymer with PEOX blocks into the composite (cf. Examples 7 and 9). The presence of copolymers in composites has in all cases led to an increase in toughness. 5 The copolymers of Examples 6, 7 and 9, 10 shift the properties of the composites towards the elastomers, while significantly increasing the ITT and VH of the composites. Although copolymers impart some elastomeric properties to composites, the thermal resistance of the VICs changes only slightly in their presence. 7 The presence of copolymers means improved filler dispersion in the matrix. This is evidenced by lower values of standard deviations of measured values. 8 The presence of copolymers in composites not only replaces the filler treatment, but also shifts the overall properties of the composite to highly desirable areas, in other ways difficult to achieve. In doing so, the amount of copolymer can be sensitively varied in the ITT and VH of the composites, thereby adapting the properties of the composite to the requirements of the designers. I will invent the object Polyalkene-mineral filler composites comprising a polymeric compatibilizing component characterized in that they contain from 30 to 90% by weight of an alkene, from 1 to 70% by weight of a mineral filler and from 1 to 15% by weight of a copolymer of the general formula Γ 1.-CH2-C- f -ch ₂ -c- Γ R11 1 ΓΙCHj — C- Γ RR 'Ί 1 1 -CHj-C — C-CH ₂ - • CHj-C- R. I mx R' - 1 nx 0