Silane vulcanized thermoplastic elastomers and process of their preparation

The invention relates to silane-vulcanized thermoplastic elastomers and to a process for their preparation.

Prior art

Thermoplastic elastomers (TPE) have the functional properties of conventional rubber thermosets, but can be remelted and are therefore suitable for processing on conventional thermoplastic production equipment. Most TPE consists of two phases, one of which is a rubber material (elastomer), which is insoluble in the second phase, and the other is a meltable thermoplastic material. The rubber material is present as a dispersed phase and the thermoplastic is a continuous phase.

Although in principle it is not necessary to crosslink the rubber in TPE, the use of crosslinking technology of this material has proved to be suitable for obtaining better chemical resistance, better mechanical properties and better control of phase separation. Such TPE compositions, where a crosslinking reaction and a process for achieving phase separation into divided domains are used, are called thermoplastic vulcanizates (TPV). In order to maintain their thermoplastic character, it is essential that only the rubber phase crosslink. A comprehensive and detailed description and overview of the TPV technique can be found, for example, in the following publications: 5. Abdou-Sabet, RC Puydak and CP Rader, Rubber Chemistry and Technology, vol. 69, p.

• · · · • · • · ·· ·· ř · · · · · • · · · · • * ···· * · • · · · · • · · · • · · · · • «· · ·

476-493, 1996.

In addition, it has been shown that the mechanical properties of TPV can be improved with the degree of crosslinking of the rubber phase and with the indirect particle size ratio of the rubber domain. Dynamic crosslinking is used to form a finely dispersed, highly crosslinked rubber phase from a homogeneous polymer mixture (which consists of thoroughly mixing the compatible polymer mixture and then introducing a crosslinking system as the mixing process continues).

For thermodynamic and hydrodynamic reasons, it is advantageous to increase the viscosity of the polymer during crosslinking, as the particles tend to agglomerate during phase separation as the phases separate. In addition, if a phase inversion process can take place during the crosslinking process, this process is advantageous for the formation of fibrous rubber domains that can provide specific mechanical properties. However, it has proven advantageous to select a crosslinking mechanism which may partially affect the thermoplastic phase, but not to the point where the thermoplastic character of the TPV is lost, but only to achieve better adhesion and compatibility of the polymers.

The choice of crosslinking process and chemicals is made with respect to processing requirements, for example, reaction rate at processing temperature, elastomer compatibility, thermoplastic side reactions, efficiency (number of crosslinks formed by each crosslinker molecule), absence of undesirable toxicity and safety of the performed process, color and odor.

• 9 9 9 9 9 · · * 9 ♦

9 9 9 99 * · ·· · • 9 999 99 9 9 · 9 99 9

9 9 9 9 Ο 999 «

One example of such a TPV is EDPM / PP, described in U.S. Patent No. 3,130,535. The EDPM and PP are thoroughly mixed in a kneader and peroxide is added to crosslink the EDPM. Excess peroxide and / or excessive processing temperature and / or excessively reactive polymers will cause PP phase degradation and / or vulcanization. In contrast, insufficient peroxide and / or too low processing temperature and / or poorly reacting EDPM will cause insufficient crosslinking.

One of the disadvantages of olefin-based TPV is that they cannot be painted without pre-treatment of the surfaces. U.S. Patent No. 4,311,628 discloses that other crosslinking agents, such as dimethyloctylphenol polymer and sulfur, may be used. In this way, excellent mechanical properties can be achieved, unfortunately both systems suffer from excessive odor and / or yellowing of the resulting materials, as well as the difficulty of controlling vulcanization reactions with sulfur.

European patent 0 324 434 proposed the use of thick graft polymers in the thermoplastic phase. After mixing, the material is shaped and allowed to react with atmospheric moisture. In this way, it was possible to obtain a more elastomeric material after curing with water. However, the water-cured articles obtained no longer contain thermoplastic elastomer and cannot be recycled. To overcome this shortcoming, European Patent 0 409 542 proposes mixing EPR (ethylene propylene rubber) or EDPM with crystalline ethylene propylene thermoplastic, an organofunctional strong and a free radical source. The silane is grafted onto the polymer by a source of free radicals and crosslinking occurs by reaction of the silane with water.

« · · · • · · « • · · « • · · · <

• · «

<img file="CZ20000640A3_D0001.tif" />

· E «· · · • · · ·« · · · 9 • 9 9 9 9

An improvement of the above processes is contained in European Patent 0 510 559, according to which the EPR or EDPM is first grafted, then mixed with a thermoplastic PP and then with a crosslinking agent containing water. This patent describes the same process using very low or ultra-low density polyethylene (VLDPE or ULDPE) in order to reduce raw material costs and to achieve a lower mixing temperature, see also DE 44 02 943. It is also proposed to add the PP component and the PE component together with the strong and radical generator in the form of a dry compound, whereby the addition of water and the condensation catalyst is carried out in a subsequent step. However, adding water to the extruder at temperatures well above the boiling point is a difficult process. In addition, the amount of water required is so small that its metering requires sophisticated instruments, which is contrary to the aim of this patent.

U.S. Patent No. 4,146,529 to Yamamoto et al. Discloses the reaction of acid modified polypropylene with aminosilane or epoxysilane, but the purpose of such reactions is to use alkoxy groups to bind fillers and react with ungrafted carboxylic acid anhydride to form low odorless non-volatile products. , not to crosslink alkoxy - groups together. The intent of these compositions is to combine mineral fillers and not to form thermoplastic vulcanizates; or in the absence of a filler, promote the reaction of the amino or epoxy groups of the silane with a free, volatile, non-grafted acid or anhydride.

German patent DE 196 29 429 discloses (among other things) the use of a premix of vinylsilanes, aminosilane and unsaturated carboxylic acid anhydrides for the possible crosslinking of polyolefins.

Description of attached pictures

The attached Figures 1 to 5 show the physical properties of the TPV produced in the examples.

The essence of the invention

The present invention relates to the production of TPV using polymers, carboxylic acid anhydride and aminosilane.

It is an object of the present invention to prepare new TPVs with a wide range of properties, inexpensive TPVs, paintable TPVs, to enable the preparation of TPVs in conventional mixers without costly additional equipment, to avoid the use of large amounts of crosslinking agents (e.g. organometallic compounds or peroxides) in TPV production. permanent TPV compositions.

Ingredients :

TPV are a mixture of:

(a) a first polymer (rubber phase);

(b) a crystalline or partially crystalline thermoplastic polymer (thermoplastic phase);

(c) a carboxylic acid anhydride incorporated into the comonomer in component (a) or grafted onto component (a); and (d) aminosilane. which is allowed to crosslink.

<img file="CZ20000640A3_D0002.tif" />

A. Polymers.

Suitable components of the polyolefin rubber phase (a) are any polymers that can react to provide a carboxylic acid anhydride-containing polymer, such as an ethylene-propylene copolymer (EPR); ethylene, propylene and diene terpolymer (EPDM); butyl rubber (BR); natural rubber (NR); chlorinated polyethylenes (CPE); silicone rubber; isoprene rubber (IR); butadiene rubber (BR); styrene butadiene rubber (SBR);

ethylene vinyl acetate (EVA); ethylene butyl acrylate (EBA);

ethylene methacrylate (EMA); ethylene ethyl acrylate (EEA);

copolymers of ethylene with α-olefins (e.g. EXACT and ENGAGE, LLDPE (linear low density polyethylene)), high density polyethylene (HDPE) and nitrile rubber (NBR). Polypropylene is not suitable at this stage because it tends to decompose during crosslinking; however, if the polypropylene is a copolymer or graftomer of polypropylene with an acid anhydride, then it may be used. Said polymer is preferably an ethylene polymer or a copolymer with an ethylene content of at least 50% (per monomer), more preferably at least 70% of the monomer is ethylene.

Preferred thermoplastic polymers (b) are polypropylene (PP); polyethylene, especially high density polyethylene (PE); polystyrene (PS);

acrylonitrile butadiene styrene (ABS); styrene acrylonitrile (SAN); polymethyl methacrylate (PMMA); thermoplastic polyesters (PET, PBT); polycarbonate (PC) and polyamide (PA).

Such polymers can be made by any method well known in the art, including block polymerization, suspension phase polymerization, gas phase polymerization, solvent phase polymerization, interfacial polymerization, radical polymerization, ionic polymerization. 9 9 · • 999 9 9 • 9 9 9 9 9 9 · • 9 9 9 9 9 polymerization, metal-initiated polymerization (e.g. metallocene, Ziegler-Natta), polycondensation, polyaddition or a combination of these methods, however, the scope of the present invention is not limited by these methods.

In carrying out the process according to the invention, it is possible for the polymers for the two phases to be the same, the acid anhydride being pre-added to one portion of the polymer and the pre-reacted polymer acting as a rubber phase in the TPV. Such pre-addition means that the presence of an acid anhydride present as a comonomer in the polymer may be present in the polymer, or a pre-reaction of the acid anhydride with the polymer may occur. In both cases, a separate addition of anhydride will not be required as it will already be present in the polymer. Due to this level of complexity, it is preferred that the two polymers differ from each other.

A third alternative is that the polymer of the rubber phase and the thermoplastic phase may be the same polymer, but the acid anhydride is added to the entire polymer. If a silane is added in such a case, then a rubber phase will form from part of the polymer, while the other part will not react (provided that a relatively small amount of anhydride and silane is present). In this context, it is important to establish the correct phase separation ratio between the rubber phase and the thermoplastic phase during the process. This procedure will not necessarily lead to TPV, because it is not necessarily possible to achieve the required phases without increasing the complexity of the process and is therefore not advantageous.

In the case of two different polymers, a polymer that is more reactive with the acid anhydride will be grafted, acting as a rubber phase in the TPV.

• · · · • · · · * · * * · · · · · • · 9 9 9 9 9 9 9

9 9 9 9 9 9 9 9

9 9 9 9 9 9

The polymer from which it is to become a rubber phase must be extrudable and must be capable of being grafted onto the acid anhydride.

The melting point of the thermoplastic phase should be lower than the decomposition temperature of the aminosilane as well as the decomposition temperature of the acid anhydrides (unless the acid anhydride is a comonomer in the polymer).

The polymers may have a unimodal, bimodal or multimodal molecular weight distribution. The polymer melt flow can have values ​​commonly known and used in the art in the molding of thermoplastics and rubbers.

B. Carboxylic acid anhydrides.

In this case, any carboxylic acid anhydrides can be used, which can be grafted in any way onto the polymer that is part of the rubber phase. To carry out this grafting, it is advantageous if there is an unsaturated bond in the polymer, or more preferably if this unsaturated bond is in the acid anhydrides. This unsaturated bond of the carboxylic acid anhydrides may be internal or external to the ring structure, if present, as long as it allows reaction with the polymer. The acid anhydride may include halides. Mixtures of different carboxylic acid anhydrides can be used. Examples of unsaturated carboxylic acid anhydrides for use in the present invention include isobutenylsuccinic anhydrides, (+/-) - 2-octen-1-yl-succinic acid, itaconic acid, 2-dodecen-1-yl-succinic acid, cis-1,2,3,6-tetrahydrophthalic acid • ·

I ·

I «· · · cis-5-norbornene-endo-2,3-dicarboxylic acids, endo-bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic acids, methyl-5-norbornene-2 , 3-carboxylic acids, exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic acids, maleic acids, citraconic acids, 2,3-dimethylmaleic acids, 1-cyclopentene-1,2-dicarboxylic acids, acids

3,4,5,6-tetrahydrophthalic acid, bromomaleic acid and dichloromaleic acid.

These acid anhydrides may be present as a comonomer in the rubber phase polymer, or they may be grafted onto the polymer to become the rubber phase.

The amount of acid anhydrides used ranges from 0.01 to 1.0% by weight of the total amount of polymer present.

C. Aminosilanes.

The aminosilanes used in the present invention contain at least one hydrolyzable group, for example an alkoxy group, an acetoxy group, or a halogen group, preferably contain an alkoxy group. Preferably, at least two such hydrolyzable groups are present, capable of undergoing a condensation crosslinking reaction such that the resulting composition is capable of undergoing such crosslinking. It is also possible to use a mixture of different aminosilanes.

The amine must have a sufficient rate of reaction with the acid anhydride. Tertiary amines generally do not react appropriately with acid anhydride and should be avoided. The amino group can be bridged to the silicon atom via a branched group to reduce yellowing. • · • · · • * • · · ·

9 999 9 9

9 9 9 resulting compositions.

The silane can be represented by the general formula

YNHBSi (OR)_and(X)₃__and in which :

a = 1 to 3, preferably 3,

Y is hydrogen, alkyl, alkenyl, hydroxyalkyl, alkaryl, alkylsilyl, alkylamino, C (= O) OR or C (= O) NR,

R is an acyl group, an alkyl group, an aryl group or an alkaryl group,

X can be R or halogen,

B is a divalent bridging group, preferably representing an alkylene group which may be branched (for example a neohexylene group).

B may contain heteroatom bridges, for example an ether bond. The preferred residue B is a propylene group. The preferred residue R is methyl or ethyl. Methoxy-containing silanes can provide better crosslinking efficiency with ethoxy-containing silanes. The residue Y is preferably an aminoalkyl group, hydrogen or an alkyl group. In an even more preferred embodiment, the residue Y is hydrogen or a primary aminoalkyl group (for example an aminoethyl group). The residue X is preferably Cl and a methyl group, more preferably a methyl group. Examples of silanes are gamma-aminopropyltrimethoxysilane (SILQUEST® silane)

A-1110 from Vitco Corp., Greenwich CT, USA);

gamma-aminopropyltriethoxysilane (SILQUEST A-1100);

gamma-aminopropylmethyldiethoxysilane;

4-amino-3,3-dimethylbutyltriethoxysilane;

4-amino-3,3-dimethylbutylmethyldiethoxysilane;

9 9 9 9 9 9 9 · 9 9

9 9 9 9 9 9 9 9 9 9 _ · · ··· ·· · ··· · 0 · · · «00·«····

Ν-β- (aminoethyl) -gamma-aminopropyltrimethoxysilane (SILQUEST A-1120), H₂NCH₂CH₂NHCH₂CH₂NH (CH₂)₃Si (OCH₃)₃ (SILQUEST A-1130) and Ν-β- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane (SILQUEST A-2120). Other suitable aminosilanes are: 3- (N-allylamino) propyltrimethoxysilane,

4-aminobutyltriethoxysilane, 4-aminobutyltrimethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, aminophenyltrimethoxysilane,

3- (1-aminopropoxy) -3,3-dimethyl-1-propenyltrimethoxysilane, bis [(3-trimethoxysilyl) propyl] ethylenediamine,

N-methylaminopropyltrimethoxysilane, bis- (gamma-triethoxysilylpropyl) amine (SILQUEST A-1170) and N-phenyl-gamma-aminopropyltrimethoxysilane (SILQUEST Y-9669).

If the aminosilane is a latent aminosilane, i.e. ureidosilane or carbamatosilane, then the temperature must be sufficient with stirring to allow any blocking groups to cleave from the amine and allow the amine to react with the acid anhydride function, i.e. at a temperature of about 150 ° C to 230 ° C. ° C. Examples of such latent aminosilanes are tert-butyl N- (3-trimethoxysilylpropyl) carbamate, ureidopropyltriethoxysilane, and ureidopropyltrimethoxysilane. Other carbamatosilanes that may also be used are described in U.S. Patent No. 5,220,167, which is incorporated herein by reference. To avoid the additional complexity of unblocking, this latent aminosilane is not used as the aminosilane.

The aminosilane should be present in an amount of 250 to 25,000 ppm based on the weight of both polymers. It should also be present in a molar equivalent to acid anhydride ratio • ·

49 « · · « 9 9

9 In the range of about 0.1 to about 10, preferably in the range of about 0.9 to about 1.1, most preferably in a ratio of about 1: 1.

The silane can be supported on a support such as a porous polymer, silica, titanium dioxide or carbon black so that it can be easily added to the polymer during the mixing process. Examples of such materials are ACCUREL polyolefin (Akzo Nobel), STAMYPOR polyolefin (DSM) and VALTEC polyolefin (Montell), SPHERILENE polyolefin (Montell), AEROSIL silica (Degussa), MICRO-CEL E (Manville) and ENSACO 350G carbon black (MMM Carbon ).

E. Optional Additives.

A free radical generator is needed in cases where the carboxylic acid anhydride has been grafted onto the polymer by a free radical mechanism, but is not required in cases where the acid anhydride has been grafted either by another mechanism or is a comonomer of the polymer. A suitable free radical catalyst may be selected from the group consisting of water-soluble or oil-soluble peroxides such as hydrogen peroxide, ammonium persulphate, potassium persulphate, various organic peroxide catalysts such as dialkyl peroxides, e.g. diisopropyl peroxide, dilauryl peroxide, di-t -butyl peroxide, di- (2-t-butylperoxyisopropyl) benzene;

3,3,5-trimethyl-1,1-di- (tert-butylperoxy) cyclohexane;

2,5-dimethyl-2,5-di- (t-butylperoxy) hexane;

2,5-dimethyl-2,5-di- (t-butylperoxyhexin-3; dicumyl peroxide, alkyl hydrogen peroxides, such as t-butyl hydrogen peroxide, t-amyl hydrogen peroxide, cumyl hydrogen peroxide, diacyl peroxides, for example · * · · 4 ·

4 4 4 4 4 · 4 4 4 4 • 444 ·· · · · · · • 4 444 44 4 444 44 ·

4 4 4 4 4 4444 acetyl peroxide, lauroyl peroxide, benzoyl peroxide, peroxyesters such as ethyl peroxybenzoate and azo compounds such as 2-azobis (isobutylnitrile).

The free radical generator may be present in an amount of 1/100 to 1/1 molar of the acid anhydride.

Conventional additives such as stabilizers (UV stabilizers, light stabilizers, aging stabilizers), antioxidants, metal deactivators, processing aids, waxes, fillers (silica, TiCl 2, CaCO 2, Mg (OH) carbon black) can be added to the TPV. etc.) and dyes. In addition, blowing agents can be added to the polymers so that the polymer forms a foam during extrusion. Examples of such blowing agents are volatile hydrocarbons, fluorocarbons and chlorofluorocarbons. Commonly known blowing agents, such as azocarbamide or sodium bicarbonate, decompose at elevated temperatures to give flue gases. These are all chemical foaming processes. Foams can also be made by injecting a liquid or gaseous blowing agent into the polymer melt. Examples of such blowing agents include butane, CO 2, nitrogen, water, helium, etc. The amount of such blowing agent should be about 0.1 to 50% by weight of the polymer.

Method:

In the first reaction, the carboxylic acid anhydride is grafted onto the rubber phase polymer (most preferably by a free radical mechanism). Said reaction may be performed with both polymers present or with separate polymers, although it is preferred to perform it in the presence of both polymers.

4 4 · · 4

4 · · 0·

0 000 00 0

4 4 4 4

4 4

4 4

4 0

4 0 polymers. As mentioned above, this step can be efficiently performed by incorporating a carboxylic acid anhydride as a comonomer into the rubber phase polymer (in which case a free radical generator is not necessary). The polymer should be grafted / copolymerized with the carboxylic anhydride prior to reaction with the aminosilane because the reaction product of the acid anhydride with the aminosilane has little grafting activity. The initial reaction between aminosilane and acid anhydride would lead to the formation of semiamide, which could have poorer grafting properties. In this case, no crosslinking would occur. In contrast, partial degradation of the polymer and / or the plasticizing effect of the semiamide could lead to an increase in the melt flow index (MFI).

In carrying out this process, it is advantageous to add a free radical generator with an anhydride during the grafting step in order to cause the grafting of the acid anhydride to the rubber phase polymer.

If the second thermoplastic polymer is not present during grafting, then it must be mixed with the grafted rubber phase before the aminosilane is added. However, such a procedure has a shortcoming in the mechanical properties of the resulting TPV.

The second step is to add the aminosilane to the mixture of grafted rubber phase polymer and thermoplastic polymer. In this case, water and / or catalyst need not be added. The reaction between aminosilane and grafted acid anhydride is very fast. The reaction between the grafted portion of the acid anhydride with gamma-aminopropylsilane can be illustrated as follows:

9* 99 • » · · • 9 9 · • 9 999 »9 9999 ··

9 9 9 9

9 9 9 «

9 9 9 9 9

99 99 99 99 99

<img file="CZ20000640A3_D0003.tif" />

The reaction between the thick and grafted portions of the acid anhydride must be rapid to obtain a crosslinkable material and should be faster than the reaction between the alkoxy groups and the acid anhydride. Simultaneously with the crosslinking of the alkoxy groups, a retarded reaction could occur, which could prevent crosslinking. The reaction between the amino group and the anhydride is very rapid in cases where, for example, primary amino groups are used. The reaction can be slowed down by using secondary amino groups. In addition, this step is to be carried out at elevated temperatures, for example at a temperature in the range from 50 ° C to 200 ° C, depending on the polymer mixture used. When the aminosilane is added, the polymer mixture is preferably in the melt state.

After grafting the aminosilane onto the polymer, the reaction mixture should be allowed to crosslink to form a gel phase from the crosslinked polymer. Moisture curing does not have to take place separately. A condensation catalyst can be used to accelerate the crosslinking process, although semiamide should be a sufficient catalyst. One minute to ten minutes at an elevated temperature of 60 ° C to 200 ° C must ensure that such crosslinking occurs.

In this context, it should be noted that the total amount of ingredients is only 0.4% of the total composition, which is about five times less than the amount needed for curing.

9999 _ tg - 9 9 999 99 9 999 99 9 ^W 9 9 999999999

99 Peroxide or vinylsilane. This has two advantages, namely a reduction in overall costs and a reduction in the amount of volatile peroxides, which can be a negative factor in terms of safety.

During and after crosslinking, all components must be mixed in an internal mixer. The mixer can be an extruder (single screw, twin screw, etc.), a BUSS KO-KNEADER mixer, or a simple kneader. The mixing conditions depend on the polymers and the degree of crosslinking.

Properties:

The resulting product is a thermoplastic vulcanizate with excellent mechanical properties. The crosslinked material has a significant gel content and a significantly lower MFI value than the starting polymers, which improves creep resistance, provides higher tensile strength at break, and provides materials that are harder than non-crosslinked polymer blends. The final product has elastic properties (i.e. elongation at break of more than 400%), but can also be processed as a melt by methods commonly known in the thermoplastic art. The preferred gel content in the final product (i.e. the rubber content) is between 10 and 50% by weight, more preferably 25 to 35% by weight. The solution according to the invention achieves an improvement in the tensile and elastic modulus in the longitudinal direction and in the transverse direction, as well as the impact strength of the material.

TPV materials are paintable and have better oil resistance. These TPV materials can be used, for example, in adhesives and sealants, such as cable insulation, such as pipes, profiles, moldings, foamed parts, foils, etc.

• · · · 0 • · 0 0

0 0 t 0 0

0 0 0 0

The aminosilane-modified rubber phase polymer tends to be more compatible with the thermoplastic polymer, giving stronger TPV materials.

Examples of embodiments of the invention

The present invention will be explained in more detail with the aid of specific exemplary embodiments, which, however, are illustrative only and do not limit the scope of the invention in any way.

All silanes used are listed above except for SILQUEST A-186 (which is gamma- (3,4-epoxycyclohexyl) ethyltrimethoxysilane), SILQUEST A-187 (gamma-glycidoxypropyltrimethoxysilane) and SILQUEST A-189 (gamma-mercaptopropyltrimethoxysilane). Mixing equipment: Brabender Head 50 cm mixer with Banbury knives. Mixing parameters: Brabender Head mixer 190 ° C / 120 rpm. All percentages are by weight unless otherwise indicated.

Procedure I:

Total amount of ingredients in the mixture: 55 grams. All components were placed in a Brabender Head mixer except for VALTEC HL003 polypropylene homopolymer (+ 5% silane). After 5 minutes (Brabender torque was recorded) VALTEC HL003 (+ 5% silane) was added to the Brabender mixer. The time and the maximum value of the Brabender torque were recorded as an indicator of the attenuation. After the Brabender torque dropped back to the original level and the composition was homogenized (about 10 minutes), the composition was removed from the Brabender mixer. A 1.5 mm thick sample was extruded in a press at 210 ° C / 2000 kPa (20 bar).

• * • · • · · · a> ♦ ««

Procedure II:

Same procedure as in case I, but all components were inserted into the Brabender mixer at the same time. The mixing time was 15 minutes. A 1.5 mm thick sample was pressed in a press at 210 ° C / 10,000 kPa (100 bar) for 200 seconds.

Examples 1 to 3 are given in order to show the possibility of achieving a wide range of properties depending on the types of polymers used. The weight percentages given for the material applied to another material are based on the weight of the applied material and the carrier.

Example 1

Composition: 75% ultra low density polyethylene ENGAGE 6452 (from Dupont Elastomers:

melt flow index (190 ° C / 2.16 kg): 3 grams / 10 minutes;

O density: 0.875 g / cm),% of polypropylene homopolymer VALTEC HL003 (SHERIPOL® porous granules from Montell: melt flow index (230 ° C / 2.16 kg): 0.7 grams / 10 minutes;

density: 0.900 g / cm 3),% VALTEC HL003 (+ 5% absorbed INTEROX DHBP (2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane from Peroxid-Chemie, Munich)),% VALTEC HL003 (+ 5% absorbed maleic anhydride),% VALTEC HL003 (+ 5% absorbed A-1100), Procedure I. Maleic anhydride was absorbed into the polymer by melting the anhydrides (melting point 53 ° C), followed by mixing with the polymer and subsequent cooling.

Φ Φ · · · · · · · ·· φ · • · · · ♦ · φ φφφφ

Φ ··· φφ φ φφφφ φ φφφφφφ φ φφφ φφ φ • φ φ φφφφ φφφφ

Φ Φ »τ>

Example 2

Composition: 75% rubber from ethylene propylene diene monomer NORDEL 2722 (Dupont Dow Elastomers: density 0.88 g / cm 3, Mooney viscosity ML 1 + 4 at 121 ° C: 28),% VALTEC HL003,% VALTEC HL003 (+ 5% absorbed INTEROX DHBP),% VALTEC HL003 (+ 5% absorbed maleic anhydride),% VALTEC HL003 (+ 5% absorbed A-1100). Procedure I.

Example

Composition: 75% ultra low density polyethylene ENGAGE D8842.00 (from Dupont Dow Elastomers: melt flow index (190 ° C / 2.16 kg): 1 gram / 10 minutes, density :: 0.857 g / cm 2), % VALTEC HL003,% VALTEC HL003 (+ 5% absorbed INTEROX DHBP),% VALTEC HL003 (+ 5% absorbed maleic anhydride),% VALTEC HL003 (+ 5% absorbed A-1100). Procedure I.

Examples 4-7 show the effect of the selected process and additives.

Example 4 (comparative)

Composition: 75% ENGAGE 8452,% VALTEC HL003. Procedure II.

• · · » * · · « * ·

9 9 9 9 9 φ · · · · β * ·

Ί 9 9 9 9

Example 5 (comparative)

Composition: 75% ENGAGE 8452,% VALTEC HL003,% VALTEC HL003 (+ 5% absorbed INTEROX DHBP),% VALTEC HL003 (+ 5% absorbed maleic anhydrides). Procedure I.

Example 6 (comparative)

Composition: 75% ENGAGE 8452,% VALTEC HL003,% VALTEC HL003 (+ 5% absorbed INTEROX DHBP),% VALTEC HL003 (+ 5% absorbed maleic anhydrides),% VALTEC HL003 (+ 5% absorbed A-1100) Procedure II .

Example 7 (comparative)

Coposition: 75% ENGAGE 8452,% VALTEC HL003,% VALTEC HL003 (+ 5% absorbed INTEROX DHBP),% VALTEC HL003 (+ 5% absorbed maleic anhydrides),% VALTEC HL003 (+ 5% absorbed hexadecylamine). Procedure I.

Examples 8 to 47 show the effect of silane type variation. Examples 15 to 17 are comparative. All silanes were added in the form of a premix with a concentration of 5% by weight • · • 9 · · 9 9 · 9 · 4 · 9 9 9 9 • · · · · O 9 »· Λ ·« 4 9 9 9 ϋ 9 · based VALTEC HL003. The compositions were prepared according to the above procedure I.

Physical properties.

Physical properties were measured according to the following standards:

Elongation and tensile strength at break: ISO 37 (50 millimeters / minute),

MFI (melt flow index): ISO 1872-1, No.18T,

SHORE A hardness: ISO 868,

Gel content: ISO 6427,

Torque: the torque gauge on the BRABENDER.

Results

Use of different silanes

Table 1 shows the properties of the materials obtained according to the procedures in the experimental section. The comparative examples (designation Com. Ex.) Consisted of the following differences:

Example 4

Pure mixture of ENGAGE 8452 (PE) and VALTES HL003 (PP).

Example 5

A mixture of ENGAGE, VALTEC, peroxide and maleic anhydrides ♦ Example 6

A mixture of ENGAGE, VALTEC, peroxide, maleic anhydride and A-1100, but all mixed at once • · 9 · • 9

Example 7

A mixture of ENGAGE, VALTEC, peroxide, maleic anhydride and hexadecylamine.

Example 4 shows the properties of a pure polymer blend. Example 5 evaluates the effect of silane itself. Example 6 shows the effect of processing and Comparative Example 7 demonstrates the need for the presence of silane in the mixture.

• · · · * 9 9 9 « ·

9 9 9 9 9

99999« 9

9 9 9 9

99 99 • 9 9 9 · ♦ · ·

9 · 9 ·

9« 99 9

9 9 9 9

9 9 « 9 9

TABLE 1 (Properties of compositions)

<td>Example</td><td>Content gel (%)</td><td>Breaking strength (MPa)</td><td>Stretching (%)</td><td>MFI (190 ° C. 5 kg) (g / 10 min)</td><td>Shore A</td><td>Twist. torque (Nm)</td>

<td> 1</td><td> 35</td><td> 23</td><td> 810</td><td> 1,80</td><td> 88,00</td><td> 13</td>

<td> 2</td><td> 36</td><td> 8</td><td> 400</td><td> 0,90</td><td> 85,00</td><td> 10</td>

<td> 3</td><td> 32</td><td> 8</td><td> 800</td><td> 0,60</td><td> 74,00</td><td> 12</td>

<td>4 (cf.)</td><td> 1</td><td> 14,53</td><td> 1005</td><td> 6,00</td><td> 83,00</td><td> 5</td>

<td>5 (cf.)</td><td> 2</td><td> 16,13</td><td> 909</td><td> 7,71</td><td> 84,50</td><td> 4</td>

<td>6 (cf.)</td><td> 1</td><td> 15</td><td> 750</td><td> 7,50</td><td> 83,00</td><td> 5</td>

<td>7 (cf.)</td><td> 0</td><td> 20,94</td><td> 922</td><td> 6,75</td><td> 87,10</td><td> 4</td>

<td> 8</td><td> 30</td><td> 18,13</td><td> 739</td><td> 0,46</td><td> 88,00</td><td> 12</td>

<td>(A1100)</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td> 9</td><td> 32</td><td> 20,00</td><td> 762</td><td> 0,20</td><td> 87,30</td><td> 14</td>

<td>(A1110)</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>10 (A1120)</td><td> 31</td><td> 16,51</td><td> 756</td><td> 0,65</td><td> 88,00</td><td> 13</td>

<td>11 (A1130)</td><td> 30</td><td> 19,30</td><td> 840</td><td> 0,70</td><td> 87,40</td><td> 13</td>

<td>12 (A1170)</td><td> 20</td><td> 19,04</td><td> 932</td><td> 0,62</td><td> 87,10</td><td> 7</td>

<td>13 (A2120)</td><td> 27</td><td> 17,88</td><td> 810</td><td> 0,65</td><td> 86,30</td><td> 13</td>

<td>14 (Y9669)</td><td> 1</td><td> 25,53</td><td> 861</td><td> 1,91</td><td> 82,50</td><td> 5</td>

<td> 15</td><td> 3</td><td> 23,03</td><td> 895</td><td> 4,68</td><td> 84,30</td><td> 4</td>

<td>(A186) 16 (A187)</td><td> 1</td><td> 17,63</td><td> 877</td><td> 4,28</td><td> 85,00</td><td> 5</td>

<td>17 (A189)</td><td> 2</td><td> 20,17</td><td> 934</td><td> 4,40</td><td> 84,50</td><td> 5</td>

• · · · • 4 4 * 4

4 4 4 9 * 44494

4 4 4

4 4 » · 4 9 · • « 4 4 4

9 4 4 4 4

4 4 4 4

4 4 · 9 9

Figure 1 shows the gel contents obtained with different silanes.

Figure 2 shows the maximum torque observed during the preparation of the compositions. The values ​​shown in Figure 1 and Figure 2 show that the increase in maximum torque observed during the manufacture of the composition is related to the crosslinking reaction.

From the above results, it can be seen that all primary amines (silanes SILQUEST A-1100, A-1110, A-1120, A-1130 and A-2120) induce direct crosslinking when mixed into the polymer mixture after grafting of maleic anhydride.

In contrast, simultaneous mixing of all materials (Comparative Example 6) did not lead to any significant crosslinking. Small differences in the degree of crosslinking compared to strong A-1100 can be caused by either different molar amounts, different numbers and / or types of alkoxy groups, and the number of amine functional groups in the molecule. The material obtained using the secondary aminosilane A-1170 also shows a relatively high degree of crosslinking, while Y-9669 (secondary aminosilane) did not induce any significant crosslinking. It has been found that because the molecular weight of A-1170 is considerably higher than that of the other silanes used, the experiments being performed with the same silane weights, the molar amount of A-1170 is lower than that of the other silanes and that at equivalent molar amounts this silane causes increased gel formation. . This also applies both to the other silanes tested and to the case where hexadecylamine was used instead of the silane.

The values ​​shown in Figures 3 to 5 show in all | In cases where crosslinking was observed, significant changes in material properties versus pure blends of both polymers.

The melt flow index drops to about 1/10, in the case of A-1110 silane also to 1/30. The materials are also significantly harder.

0 « · · · • * • » · « 9 0 · • · · · · · • « ····»« · • · 9 9 0

0 β 9 9 · have higher tensile strength at break and lower elongation at break. Changes in properties are consistent with a relatively higher degree of crosslinking in these compositions.

As for the other silanes used, the properties of the resulting materials cannot be attributed to a high degree of crosslinking. However, all silanes cause a decrease in MFI, indicating that some chain elongation has occurred. This is evident in comparison with all comparative examples, and in particular with comparative example 5 (maleic acid peroxide and anhydride only), where a certain degree of degradation has also taken place. In this context, it should be noted that when silane A-1100 was mixed together with other additives, a high MFI value was also measured.

Replacement of the aminosilane with hexadecylamine (Comparative Example 7) also resulted in a material with excellent mechanical properties and higher hardness. The improvement in properties is probably associated with the attachment of long side chains to the polymer backbone (comb polymers), as crosslinking is not possible. Thus, no TPV was formed (no gel content).

Examples 18 to 21

Use of various aminosilanes

According to these examples, TPV materials were prepared as described above. The same amount of aminosilanes (molar contents) was maintained in all experiments. The silanes A and B used were as follows:

I • · 0 · • · ♦ · ♦ • · 0 0 · • 0 0 9 · ·

0 0 0 0

0 0 0 0

0 0 0 0 0 0

Target,

S / \ ^ Si (OCH 3) 3 H₂N f

CH.,

CH,

H, N ', Si (CH 2) (OCH 3) t

CH, (A) (B)

<td rowspan="2"></td><td colspan="4">Try</td>

<td>18 (A1100)</td><td>19 (silane A)</td><td>20 (silane B)</td><td>21 (A1170)</td>

<td>Ingredients</td><td>parts</td><td>parts</td><td>parts</td><td>parts</td>

<td>ENGAGE 8452</td><td> 75</td><td> 75</td><td> 75</td><td> 75</td>

<td>VALTEC HL003</td><td> 17</td><td> 17</td><td> 17</td><td> 17</td>

<td>VALTEC HL003 + 5% DHBP</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td>

<td>VALTEC HL003 + 5% anhyd. maleic acid</td><td> 2</td><td> 2</td><td> 2</td><td> 2</td>

<td>VALTEC HL003 + 5% silane</td><td> 5</td><td> 5</td><td> 4,64</td><td> 7,72</td>

<td>Gel content (%)</td><td> 26</td><td> 25</td><td> 8</td><td> 23</td>

<td>Optical appearance (Gardner scale)</td><td> 3</td><td> 2</td><td> 1</td><td> 1-2</td>

<td>Relative adhesion (hot application)</td><td>Good</td><td>Good</td><td>Good</td><td>excellent.</td>

• ·

Using silanes A, B and A-1170, products were prepared that are slightly less yellow than the product obtained with A-1100. A-1170 as a reinforcing agent leads to materials that have a very significant improvement in adhesion properties compared to other examples.

Examples 22 to 25

Foam application

According to these examples, the use of TPV products for foam applications was evaluated (Examples 22 and 23) and compared with compositions which reacted only with maleic acid peroxide and anhydride (Example 24) or optionally with peroxide (Example 25). Materials other than the azodicarbonamide blowing agent were reacted at 180 ° C in a Brabender (details on the preparation of TPV materials are the same as above). After 10 minutes, the composition was cooled to 160 ° C and a blowing agent was added.

In Example 23, aminosilane was added after the addition of the blowing agent. After further stirring for 3 minutes, test plates were prepared at 170 ° C / 1000 kPa / 100 s. The plates were foamed in an oven at 200 ° C for 3 to 5 minutes. The compositions are listed below:

• 9 · 9 «9 · ·· · 99 99 • 99« 99 9 · · 9 ·

9 9 9 99 · 999·

999999 9 9·· 99 9

9« 9 9 9 9 · ····

<td></td><td colspan="4">Example</td>

<td>Composition of parts</td><td> 22</td><td> 23</td><td> 24</td><td> 25</td>

<td>1) ENGAGE 8452 75</td><td>X</td><td>X</td><td>X</td><td>X</td>

<td>2) VALTEC HL003 17</td><td>X</td><td>X</td><td>X</td><td>X</td>

<td>3) VALTEC HL003 + 5% DHBP 1</td><td>X</td><td>X</td><td>X</td><td>X</td>

<td>4) VALTEC HL003 + 5% MAH 2</td><td>X</td><td>X</td><td>X</td><td></td>

<td>5) VALTEC HL003 + 5% A1100 5</td><td>X</td><td>X</td><td></td><td></td>

<td>6) Blowing agent GCS2 AC 15</td><td>X</td><td>X</td><td>X</td><td>X</td>

<td>Melt stability during foaming</td><td>Good</td><td>Good</td><td>stř.</td><td>šp.</td>

<td>Gel content (%) (-after foaming)</td><td>²⁶7</td><td> 33</td><td> 1</td><td></td>

<td></td><td> (33²)</td><td> (31²)</td><td>(l²)</td><td>(l²</td>

The appearance of the foam structure

The melt strength was high enough to withstand the decomposition temperature of azodicarbonamide (200 ° C for several minutes). The shape remained in its original dimensions and did not stick to the substrate. In contrast, the non-crosslinked samples changed their dimensions during foaming, which led to a poorer cell structure and adhesion to the substrate surface. The order of addition (silane before or after azodicarbonamide) did not appear to significantly affect the appearance of the resulting foam, or the amount of gel.

Examples 26 to 29

TPV with a single polymer

The general procedure was the same as above, but in Examples 27 to 29 only one polymer was used, in Example 27 polyethylene, in Example 28 HDPE LUPOLEN 503IL · 9 9 · · 9 9 9 · ♦ · · · • · · · · · · · · ···· ·· · ···· • · ··· · · · · * ♦ · · · • 9 9 · · · · 9 9 9 · by Elenac: MFI (190 ° C, 2.16 kg) = 6.5; density: 0.952 and in Example 29 polypropylene.

<td rowspan="2">Try</td><td> 26</td><td> 27</td><td> 28</td><td> 29</td>

<td>parts</td><td>parts</td><td>parts</td><td>parts</td>

<td>Engage 8452</td><td> 37,5</td><td> 46</td><td> 0</td><td> 0</td>

<td>LUPOLEN HDPE</td><td> 0</td><td> 0</td><td> 46</td><td> 0</td>

<td>VALTEC HL003</td><td> 8,5</td><td> 0</td><td> 0</td><td> 46</td>

<td>5% DHBP on VALTEC HL003</td><td> 0,5</td><td> 0,5</td><td> 0,5</td><td> 0,5</td>

<td>5% (MAH dissolved in MeOH) and VALTEC HL003</td><td> 1,5</td><td> 1,5</td><td> 1,5</td><td> 1,5</td>

<td>5% A-1100 on VALTEC HL003</td><td> 2,5</td><td> 2,5</td><td> 2,5</td><td> 2,5</td>

<td>Gel content (%)</td><td> 24</td><td> 19</td><td> 20</td><td> 0</td>

The grafted maleic anhydride and aminosilane system can be used to crosslink pure ENGAGE polymer as well as pure HDPE, but does not result in any gel when used with polypropylene.