Silane vulcanized thermoplastic elastomers

Detailed description of the invention

<u style="single">Background of the invention</u> Thermoplastic elastomers (TPEs) functionally exhibit the functional properties of commonly used thermosetting rubbers, but can be repeatedly melted and are therefore processed in a conventional thermoplastic manufacturing equipment. Suitable for. Most TPEs consist of two phases: a rubber material (elastomer) that is insoluble in the other phase and a fluid thermoplastic material. This rubber material exists as a dispersed phase, and the thermoplastic material is a continuous phase.

In principle, it is not necessary to bridge this rubber in the TPE, but in order to obtain better chemical resistance, mechanical properties and better control of phase separation, bridging techniques are used. Has proven to be effective. Such TPE compositions, in which bridging reactions and processing are used to achieve phase separation into multiple divided domains, are called Thermoplastic Vulcanizates (TPVs). In order to maintain their thermoplasticity, it is basically important that only the rubber phase is bridged. For a wide range of detailed explanations and reviews on TPV engineering, see, for example, S. Abdou-Sabet, RC Puydak and CP Rader.<u style="single">, Rubber Chemistry and Technology</u>, Vol.69, pp 476-493.1996 ,.

Furthermore, the mechanical practical performance of the TPV improves with the degree of bridging of this rubber phase and the reciprocal of the rubber domain particle size. In order to produce a finely dispersed, highly bridged rubber phase from a homogeneous blend of multiple polymers, dynamic bridging (mixing a blend of multiple compatible polymers well, then , Consisting of introducing a bridging system into the mixture while continuing the mixture) is used.

For thermodynamic and hydrodynamic reasons, it is desirable to increase the viscosity of the polymer during bridging, as the particles tend to agglomerate during the phase separation. Moreover, if phase reversal can occur during bridging, it favors the formation of fibrous rubber domains that impart special mechanical properties. However, the thermoplastic phase can be partially included to the extent that the thermoplasticity of the TPV is not lost, but merely to the point where better tackiness and compatibility of those polymers is achieved. It has been found that it is desirable to choose a bridging mechanism.

The selection of bridging methods and chemical reagents is based on processing requirements such as reaction rate at the processing temperature; compatibility with elastomers; side reactions with thermoplastic materials; efficiency (crosslinking produced by each molecule of the bridging agent). Number of points); No unfavorable reaction; Toxicity and danger; Coloration and odor; Depends on.

An example of such a TPV is EPDM / PP described in US Pat. No. 3,130,535. EPDM and PP are mixed well in a closed mixer, and peroxide is added to bridge the EPDM. Excess peroxides and / or unnecessarily high processing temperatures and / or unnecessarily reactive polymers will cause PP phase degradation and / or scorch. In contrast, inadequate amounts of peroxide and / or processing temperatures that are too low and / or EPDM that is less reactive will cause inadequate bridging.

One drawback of polyolefin-based TPVs is that they cannot be applied without preliminary surface treatment. U.S. Pat. No. 4,311,628 discloses that other bridging agents such as dimethylol octylphenol resin and sulfur can be used. Very good mechanical properties are achieved, but unfortunately both systems encounter too strong an odor and / or yellowing of the product and also difficulty in controlling the sulfur hardening reaction.

European Patent No. 0324434 discloses the use of silane-grafted polymers for the thermoplastic phase. After mixing, the material is shaped and left to react with atmospheric moisture. Thus, it is possible to obtain a more elastic material after moisture curing. However, the resulting moisture-cured product no longer contains thermoplastic elastomers and cannot be reused. To overcome this limitation, European Patent No. 0409542 discloses a method of mixing EPR (ethylene-propylene rubber) or EPDM with crystalline ethylene-propylene thermoplastic resin, organic functional silanes and radical generators. Has been done. The silane is grafted onto the resin by its radical generator, and the reaction of the silane with water causes bridging.

An improved method of the above method is disclosed in European Patent No. 0510559, where EPR or EPDM is first grafted, then mixed with thermoplastic PP, and then into a bridging additive consisting of water. Be mixed. The same method using very low density polyethylene (VLDPE or ultra low density polyethylene: ULDPE) is disclosed to reduce raw material costs and lower mixing temperatures. See DE No. 4402934. Also disclosed is a method in which a PP component and a PE component are simultaneously added as a dry compound together with a silane and a radical generator, and water and a catalyst for condensation are added in a subsequent step. However, adding water to the extruder at a temperature well above its boiling point is a difficult method. Moreover, the amount of water required is so small that it requires a high-performance device for its weighing, which contradicts the aim of this patent.

U.S. Pat. No. 4,146,529 [Inventor: Yamamoto et al.] Discloses that an acid-modified polypropylene is reacted with aminosilane or epoxysilane, but the purpose of this reaction is to fill the alkoxy group. Used to bond with materials and to react with non-grafted carboxylic acid anhydrides to produce less odorous, non-volatile products, bridging the alkoxy functional groups within them. Not to hang. The purpose of these compositions is to connect mineral-based fillers, not to prepare thermoplastic cured products: and in the absence of fillers, with the amino or epoxy groups of the silane. To facilitate the reaction with free volatile non-graftic acids or acid anhydrides.

German Patent DE19629429 teaches (in other publications) the use of premixes of vinylsilane, aminosilane and unsaturated carboxylic acid anhydrides, each of which is used for bridging polyolefins. Has been done.

<u style="single">Abstract of the present invention</u> The present invention teaches the production of TPVs using polymers, carboxylic acid anhydrides and aminosilanes.

<u style="single">Detailed description of the present invention</u> An object of the present invention is to produce a new TPV having a wide range of properties, a low-cost TPV, a TPV that can be applied, and to prepare a TPV in a regular mixer without the need for expensive additional equipment. To avoid the use of high levels of bridging agents (eg, metal organics or peroxides) in the preparation of TPV, and to obtain a stable TPV composition.

Composition This TPV is (a) First polymer (rubber phase), (b) Crystalline or partially crystalline thermoplastic polymer (thermoplastic resin phase), (c) Carboxylic acid anhydrides that are mixed as co-monomers in component (a) or grafted to component (a), and (d) Aminosilane; It is a bridgeable blend consisting of.

A. Polymer Suitable polyolefin rubber phase components (a) are, for example, ethylene-propylene copolymer (EPR), ethylene-propylene-diene ternary copolymer (EPDM), butyl rubber (BR), natural rubber (NR), chlorinated. Polyethylene (CPE), Silicone Rubber, Isoprene Rubber (IR), butadiene Rubber (BR), Styrene-butadiene Rubber (SBR), Ethylene-Vinyl Acetate (EVA), Ethylene-Butyl Alacrylate (EBA), Ethylene-Methyl Methacrylate (EMA) ), Ethylene-ethyl acrylate (EEA), ethylene-α-olefin copolymers [eg EXACT and NGAGE, LLDPE (linear low density polyethylene)], high density polyethylene (HDPE), and nitrile rubber (NBR). , Any polymer that can be reacted to produce a polymer containing carboxylic acid anhydride. Polypropylene is not suitable for this phase as it tends to decompose during bridging. However, if the polypropylene is a copolymer of polypropylene and an acid anhydride or a grafter, it is used. Desirably, the polymer is an ethylene polymer or copolymer having an ethylene content (in monomeric form) of at least 50% and at least 70% of those monomers being ethylene. , More desirable.

Suitable thermoplastic polymers (b) are polypropylene (PP), polyethylene, especially high density PE, polystyrene (PS), acrylolithyl-butadiene-styrene (ABS), styrene-acrylolithyl (SAN), polymethyl. Methacrylate (PMMA), thermoplastic polyesters (PET, PBT), polycarbonate (PC) and polyamide (PA).

Such polymers can be bulk phase, slurry phase, gas phase, solvent phase, interfacial polymerization [radical, ion, metal initiator (eg, metallocene, Ziegler-Natta catalyst)], polycondensation, polyaddition or theirs. Manufactured by any method known in the art, such as combination, but not limited to these methods.

It is also possible that the polymers of these two phases are the same, in which case the acid anhydride is pre-added to a portion of the polymer and the pre-reacted polymer is the rubber phase in the TPV. Will act as. Such pre-addition includes the possibility of having an acid anhydride present as a co-monomer in the polymer, or the possibility of pre-reacting the acid anhydride with the polymer. In both of these two cases, the acid anhydride is present in the polymer, so it is not always necessary to add it separately. Given this level of complexity, it is recommended that the two polymers differ from each other.

A third alternative is a method in which the rubber phase polymer and the thermoplastic phase polymer can be the same polymer, but acid anhydrides are added to the polymer as a whole. In such cases, when silane is added, some of the polymer will form a rubber phase while the other will not react (in the presence of relatively small amounts of anhydride and silane). B). During this reaction, it is important that an appropriate degree of phase separation occurs between the rubber phase and the thermoplastic phase created. This method does not always reach TPV, as it is not always possible to produce the required phase without making the process considerably more complicated, and is therefore not suitable.

In the case of two different polymers, a polymer that is more reactive with the acid anhydride will be grafted with the acid anhydride and will function as a rubber phase in its TPV. The polymer to be the rubber phase must be extrudable and capable of grafting with its acid anhydride.

The melting point of this thermoplastic phase should be lower than the decomposition temperature of aminosilane and also the decomposition temperature of the acid anhydride (unless the acid anhydride is a co-monomer in the polymer).

The molecular weight distribution peaks of these polymers are one, two or more. The melt flow value of these polymers is any value of melt flow known in the art for use in the production of thermoplastic resins and rubbers.

B. Carboxylic acid anhydride Any carboxylic acid anhydride that can be grafted by any possible mechanism can be used in the polymer to be the rubber phase. In order to achieve this graft, it is desirable that an unsaturated group is present in any of the polymers, and more preferably in the acid anhydride. The unsaturated group of the carboxylic acid anhydride may be inside or outside the ring structure (if present) as long as it is capable of reacting with this polymer. This acid anhydride also contains a halide. Mixtures of different carboxylic acid anhydrides are also used. Typical unsaturated carboxylic acid anhydrides used are isobutenyl succinic acid, (+/-)-2-octene-1-yl succinic acid, itaconic acid, 2-dodecene-1-yl succinic acid, cis-1. , 2,3,6-tetrahydrophthalic acid, cis-5-norbornene-endo-2,3-dicarboxylic acid, endo-bicyclo [2.2.2] octo5-ene-2,3-dicarboxylic acid, methyl-5- Norbornen-2,3-dicarboxylic acid, exo-3,6 -Epoxy-1,2,3,6-tetrahydrophthalic acid, maleic acid, citraconic acid, 2,3-dimethylmaleic acid, 1-cyclopentene-1,2-dicarboxylic acid, 3,4,5,6-tetrahydrophthalic acid It is an anhydride of acid, bromomalic acid and dichloromalic acid.

These acid anhydrides may be present as co-monomers in the polymer of the rubber phase or may be grafted onto the polymer that will be the rubber phase. The amount of acid anhydride used is 0.01 to 1.0% by weight based on the total amount of polymer present.

C. Aminosilane The aminosilane used in the present invention has at least one hydrolyzable group, such as an alkoxy, acetoxy or halogen group, preferably an alkoxy group. It is desirable that there are at least two such hydrolyzable groups capable of carrying out a bridging condensation reaction, so that the resulting compound is capable of carrying out such bridging. Mixtures of different aminosilanes can also be used.

Amine has a sufficient reaction rate with acid anhydride. In general, tertiary amines do not react well with acid anhydrides and should be avoided. This amino group bridges the silicon atom with a branched group to reduce yellowing of the resulting composition.

This silane has the formula: YNHBSi (OR)_a(X)_3-a, In the formula, a = 1 to 3, preferably 3; Y are hydrogen, alkyl, alkenyl, hydroxyalkyl, alkalil, alkylsilyl, alkylamine, C (= O) OR or C (= O). ) NR; R is acyl, alkyl, aryl or alkaline; X is R or halogen; B is a divalent bridging group, preferably alkylene, branched It may be (eg, neohexylene) or cyclic. B may include a heteroatom bridge, such as an ether bond. The desired B is propylene. The recommended R is methyl or ethyl. Silanes containing methoxy groups guarantee better bridging performance than ethoxy groups. Y is preferably an aminoalkyl group, a hydrogen or an alkyl group. More preferably, Y is hydrogen or a primary aminoalkyl (eg, aminoethyl) group. Desirable X is Cl and a methyl group, more preferably a methyl group. A typical silane is γ-aminopropyltrimethoxysilane [SILQUEST from Witco Corp., Greenwich, CT.USA.^R) A-1110 silane]; γ-aminopropyltriethoxysilane (Silquest A-1100 silane); γ-aminopropylmethyldiethoxysilane; 4-amino-3,3-dimethylbutyltriethoxysilane; 4-amino- 3,3-Dimethylbutylmethyldiethoxysilane; N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane (Silquest A-1120); H₂NCH₂CH₂NHCH₂CH₂NH (CH)₂)₃Si (OCH₃)₃(Silquest A-1130) and N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane (Silquest A-2120). Other suitable aminosilanes are: 3- (N-allylamino) propyltrimethoxysilane; 4-aminobutyltriethoxysilane; 4-aminobutyltrimethoxysilane; (aminoethylaminomethyl) phenetiltri Methoxysilane; aminophenyltrimethoxysilane; 3- (1-aminopropoxy) -3,3-dimethyl-1-propenyltrimethoxysilane; bis [(3-trimethoxysilyl) propyl] ethylenediamine; N-methylaminopropyltri Methoxysilane; bis- (γ-triethoxysilylpropyl) amine (Silquest A-1170) and N-phenyl-γ-aminopropyltrimethoxysilane (Silquest Y-9669).

When the aminosilane is a latent aminosilane, i.e. ureidosilane or carbamatesilane, the mixing temperature is sufficient for the individual protecting groups to be removed from the amine and the amine to react with the acid anhydride functional group: about. Must be 150-230 ° C. Examples of such latent aminosilanes are t-butyl-N- (3-trimethoxysilylpropyl) carbamate, ureidopropyltriethoxysilane and ureidopropyltrimethoxysilane. Other carbamate silanes used are disclosed in US Pat. No. 5,220,047 cited herein. Desirably, the aminosilane should not be a latent aminosilane to avoid the additional complexity of deprotection.

This aminosilane should be present at 250 to 25,000 ppm based on the weight of both polymers. It should also be present in molar equivalent ratios to acid anhydrides of about 0.1 to 10, more preferably 0.9 to 1.1, and most preferably about 1: 1.

The silane may be supported on a carrier such as a porous polymer, silica, titanium dioxide or carbon black, which facilitates addition to the polymer during the mixing step. Examples of such materials are ACCUELL polyolefin [Akzo Nobel], STAMYPOR polyolefin (DMS) and VALTEC polyolefin [Montell], SPHERILENE polyolefin (Montell), AEROSIL silica [Degussa]. (Degussa)], MICRO-CELE [Manville] and ENSACO 350G Carbon Black (MMM Carbon).

E. Additives used in some cases If the carboxylic acid anhydride is grafted to the polymer by a radical mechanism, a radical generator is required, but this acid anhydride is grafted by another mechanism or is a co-monomer of the polymer. Not needed in some cases. Suitable radical catalysts are water-soluble or oil-soluble peroxides such as hydrogen peroxide, ammonium persulfate, potassium persulfate, diisopropyl peroxide, dilauryl peroxide, di-t-butyl peroxide, di ( 2-t-butylperoxyisopropyl) benzene, 3,3,5-trimethyl-1,1-di (t-butylperoxy) cyclohexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, Various organic peroxy catalysts such as dialkyl peroxides such as 2,5-dimethyl-2,5-di (t-butylperoxy) hexin-3, dicumyl peroxide; t-butyl peroxide, t-amyl peroxide Alkyl peroxides, such as cumyl peroxides; for example, diacyl peroxides such as acetyl peroxides, lauroyl peroxides, benzoyl peroxides; peroxy esters such as ethyl peroxybenzoate; and 2-azobis (isobutyronitrile). Selected from the group of azo compounds, such as.

Radical generators exist in the range of 1/100 to 1/1 based on the molar amount of acid anhydride. Stabilizers (ultraviolet, light or aging), antioxidants, metal inactivating agents, processing aids, waxes, fillers (silica, TiO)₂, CaCO₃, Mg (OH)₂, Carbon black, etc.) and colorants may be added to the TPV. In addition, foaming agents may be added to the polymer, which produce foam when the polymer is extruded. Examples of such foaming agents are volatile hydrocarbons, hydrofluorocarbons and chlorofluorocarbons. Commonly known foaming agents such as azodicarbonamide or sodium bicarbonate (also known as sodium bicarbonate) decompose at high temperatures to produce gaseous products. These are all chemical foaming methods. A foam is also produced by blowing a liquid or gaseous foaming agent into the polymer melt. Examples are, for example, butane, CO₂, Nitrogen, water, helium, etc. The amount of such foaming agent ranges from 0.1 to 50 weight percent of the polymer.

<u style="single">Method</u> In the first reaction, the carboxylic acid anhydride is grafted (most preferably by radical mechanism) onto the rubber phase polymer. The reaction is carried out in the presence of both polymers, or the two polymers are carried out separately, but it is desirable to carry out this reaction in the presence of both polymers. Alternatively, as described above, this step is effectively performed by including the carboxylic acid anhydride as a co-monomer in the rubber phase polymer (in this case, no radical generator is required). The polymer should be grafted / copolymerized with the carboxylic acid anhydride prior to the reaction with the aminosilane, as the reaction product of the acid anhydride with aminosilane has poor graft efficiency. The prereaction between aminosilane and acid anhydride results in the formation of semiamides, which only have poor grafting properties. In this case, no bridge will occur. In contrast, the partial decomposition of the polymer and / or the plasticizing effect of this semiamide can increase the melt flow index (MFI).

In order to induce the grafting of the acid anhydride on the rubber phase polymer, it is desirable to add a radical generator with the anhydride during this grafting process. If the second thermoplastic polymer is not present at the time of grafting, the second thermoplastic polymer should be mixed with the graft rubber phase polymer before adding aminosilane, but such a method is obtained. Defects related to the mechanical properties of TPV occur.

The second step is the addition of aminosilane to the rubber phase graft polymer / thermoplastic polymer-blend. No need to add water and / or catalyst. This step is a very fast reaction between aminosilane and the grafted acid anhydride. The reaction of the grafted acid anhydride site with γ-aminopropylsilane is thought to be as follows:

<chemistry num="1"><img file="JP4732958B2_D0001.tif" /></chemistry>

The reaction between this silane and the grafted acid anhydride moiety must be rapid to obtain a crosslinkable material and must be faster than the reaction between the alkoxy group and the acid anhydride. If the reaction is slow, it may compete with the bridge of the alkoxy site and may interfere with the bridge. This reaction between the amino group and the acid anhydride is very fast, for example, with the first amino group. This reaction can be slowed down by using a second amino group. Further, this step depends on the polymer blend, for example, at a high temperature such as 50 to 200 ° C. When aminosilane is added to this polymer, it is desirable that the polymer blend be in the melting stage.

Aminosilane should be grafted onto a polymer and then bridged to form the gel phase of the bridging polymer. There is no need for another cure due to moisture to occur. Condensation catalysts are sometimes used to accelerate the bridging reaction, but semiamides should be sufficient catalysts. At temperatures as high as 60 to 200 ° C, it should be guaranteed that such a bridge will occur in 1 to 10 minutes.

It should be noted that the total amount of additives is only 0.4%, which is about 1/5 of the amount required for peroxide or vinylsilane curing. This advantage of the two-step method is a reduction in total cost and a reduction in discolorable peroxides, which is a safety issue.

All additives should be mixed in a closed mixer during and after bridging. This mixer is an extruder (uniaxial, biaxial, etc.), BUSS KO-KNEADER mixer or a simple type closed mixer. The mixing conditions depend on the polymer and the degree of bridging.

nature The product obtained is a thermoplastic cured product having extremely excellent mechanical properties. This bridged material contains a significant amount of gel, has a much lower MFI than the starting polymer, should have improved creep resistance, has higher tensile strength at rupture, and is non-bridged. Provides a material that is harder than a polymer blend. Although the final product is elastic (ie, elongation at break greater than 400%), it can be melt-processed by methods commonly known in the art for thermoplastics. The desired gel content (ie, rubber content) of this final product is between 10 and 50% by weight, most preferably 25-35% by weight. The tensile and bending modulus in the device direction (longitudinal) and lateral direction is improved, as evidenced by the dart impact strength of this material.

This TPV can be applied and has better oil resistance. This TPV is used, for example, in adhesives and sealants, cable insulators, pipes, deformed materials, molded parts, foam parts, sheets and the like.

Aminosilane rubber phase modified polymers will tend to be more compatible with this thermoplastic polymer and will provide stronger TPV.<u style="single">Example</u> Sylquest A-186: (γ- (3,4-epoxycyclohexyl) ethyltrimethoxysilane), Sylquest A-187: (γ-glycidoxypropyltrimethoxysilane) and Sylquest A-189: (γ- All silanes used, with the exception of mercaptopropyltrimethoxysilane), are shown above. Kneader: Brabender Head 50 with Banbury knives 50 cm³Is. Kneading parameters: lavender head 190 ° C / RPM 120. All percentages are weight percentages unless otherwise stated.

<u style="single">Method 1</u>: Total amount of ingredients: 55g. All components except the polypropylene homopolymer VALTEC-HL003 (+ 5% silane) were supplied to the lavender head. After 5 minutes (note the lavender torque value), VALTEC-HL003 (+ 5% silane) was added to the lavender head. Time and maximum lavender torque values were noted as bridge indicators. The compound was removed from the lavender after the value of this lavender torque had dropped, returned to its original level, and homogenization of the compound was achieved (about 10 minutes). A 1.5 mm thick test piece was molded in a pressure molding machine at 210 ° C / 20 bar.

<u style="single">Method 2</u>: The same method as method 1, but all the ingredients were supplied to the lavender head at the same time. Kneading time 15 minutes. A test piece with a thickness of 1.5 mm was molded in a pressure molding machine at 210 ° C./100 bar for 200 seconds.

Examples 1-3 have been exemplified to show that a wide range of properties can be obtained depending on the grade of the polymer. The weight percent shown for the material supported on the other material is a value based on the weight of the carrier and the material supported.

<u style="single">Example 1:</u>Composition: 75% ENGAGE8452: Ultra Low Density Polyethylene [DuPont-Dow-Elastomer, Melt Index (190 ° C / 2.16kg): 3g / 10min, Density: 0.875g / cc], 17% VALTEC-HL003: Polypropylene Homopolymer [Pollous granular SPHERIPOL from Montel^R: Melt index (230 ° C / 2.16kg): 0.7g / 10 minutes, density: 0.900g / cc], 1% VALTEC-HL003 [+ 5% impregnated INTEROX-DHBP (peroxide-hemy, Munich), 2 from , 5-Dimethyl-2,5-di (t-butylperoxy) hexane)], 2% VALTEC-HL003 (+ 5% impregnated maleic anhydride), 5% VALTEC-HL003 (+ 5% impregnated A-1100), Method 1. This maleic anhydride was absorbed into the polymer by melting it (melting point 53 ° C.), mixing it with the polymer, and cooling.

<u style="single">Example 2:</u>75% NORDEL2722: Ethylene propylene diene monomeric rubber (DuPont-Dow-Elastomer: Density: 0.88g / cm³, Mooney Viscosity at 121 ° C ML 1 + 4: 28), 17% VALTEC-HL003, 1% VALTEC-HL003 (+ 5% impregnated INTEROX-DHBP), 2% VALTEC-HL003 (+ 5% impregnated maleic anhydride) ), 5% VALTEC-HL003 (+ 5% impregnated A-1100), method 1.

<u style="single">Example 3:</u>Composition: 75% ENGAGE8842.00: Ultra Low Density Polyethylene [DuPont-Dow-Elastomer, Melt Index (190 ° C / 2.16kg) (1.0g / 10min), Density: 0.857g / cc], 17% VALTEC -HL003, 1% VALTEC-HL003 (+ 5% impregnated INTEROX-DHBP), 2% VALTEC-HL003 (+ 5% impregnated maleic anhydride), 5% VALTEC-HL003 (+ 5% impregnated A-1100), Method 1 .. Examples 4-7 illustrate the effects of methods and components.

<u style="single">Example 4 (Comparative Example):</u>Composition: 75% ENGAGE8452, 25% VALTEC-HL003, Method 2.<u style="single">Example 5 (Comparative Example):</u>Composition: 75% ENGAGE8452, 22% VALTEC-HL003, 1% VALTEC-HL003 (+ 5% impregnated INTEROX-DHBP), 2% VALTEC-HL003 (+ 5% impregnated maleic anhydride), Method 1.

<u style="single">Example 6 (Comparative Example):</u>Composition: 75% ENGAGE8452, 17% VALTEC-HL003, 1% VALTEC-HL003 (+ 5% impregnated INTEROX-DHBP), 2% VALTEC-HL003 (+ 5% impregnated maleic anhydride), 5% VALTEC-HL003 (+5) % Impregnation A-1100), method 2.

<u style="single">Example 7 (Comparative Example):</u>Composition: 75% ENGAGE8452, 17% VALTEC-HL003, 1% VALTEC-HL003 (+ 5% impregnated INTEROX-DHBP), 2% VALTEC-HL003 (+ 5% impregnated maleic anhydride), 5% VALTEC-HL003 (+5) % Impregnated hexadecylamine), method 1.

Examples 8-17 illustrate the effect of changing the type of silane. Examples 15-17 are comparative examples. All silanes were added as a 5 wt% masterbatch based on VALTEC-HL003. Preparation of the compound was carried out according to Method 1.

Physical characteristics Physical properties were measured according to the following standards: Stretch and tensile strength at break ISO 37 (50 mm / min) MFI ISO1872-1, No.18T Shore A Hardness ISO 868 Gel content ISO 6427 Torque lavender torque meter result Changes in silane Table 1 shows the properties of the materials obtained according to the method described in the experimental section.

The comparative example (Comp.Ex.) Is: Example 4) A pure blend of ENGAGE 8452 (PE) and VALTEC-HL003 (PP), Example 5) Blend of ENGAGE, VALTEC, peroxide and maleic anhydride, Example 6) A blend of ENGAGE, VALTEC, peroxide, maleic anhydride and A-1100, but all mixed at once, and Example 7) Blend of ENGAGE, VALTEC, peroxide, maleic anhydride and hexadecylamine, Consists of.

Example 4 shows the properties of a pure polymer blend, Example 5 is to evaluate the effect of silane alone, Example 6 is to show the effect of the processing method, and Example 7 is silane in this mixture. It is to prove the necessity of including.

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FIG. 1 shows the gel content obtained with different silanes and FIG. 2 shows the maximum torque observed during compound preparation. The data shown in Figures 1 and 2 show that the increase in maximum torque observed during kneading is related to the bridging reaction. All primary amines (Silquest A-1100, A-1110, A-1120, A-1130 and A-2120 silanes) can be bridged straight by grafting maleic anhydride and mixing with this polymer blend. It is clear that it induces.

In contrast, mixing all materials at the same time (Comparative Example 6) does not result in any significant bridging. The slight difference in bridging degree compared to A-1100 silane may be due to either the molar quantity difference, the number of alkoxy groups and / or the type difference, and the number of amino functional groups per molecule. Materials obtained with the second aminosilane A-1170 also show a relatively high degree of bridging, but Y-9669 (second aminosilane) does not induce significant bridging. The molecular weight of A-1170 is significantly higher than the other silanes used, and the experiments were performed with the same silane weight, so the molar amount of A-1170 is smaller than the other silanes and equal molar amounts increase gel formation. It should be noted that. The latter problem is correct for the other silanes tested, and also when hexadecylamine is used in place of the silane.

The data shown in Figure 3-5 show that in all cases where bridging was observed, significant changes in material properties were observed, contrary to the pure blend of the two polymers. .. Its meltflow index dropped to about 1/10 and to 1/30 for A-1110 silane. These materials are significantly harder, have greater tensile strength at break, and have less elongation at break. Such changes in nature are consistent with the relatively high degree of bridging in these compounds.

For the other silanes used, the properties of the resulting material cannot be blamed on the high degree of bridging. However, all silanes induce a decrease in MFI, suggesting that the molecular chain is somewhat elongated. This is clear when comparing all the comparative examples with Comparative Example 5 (including only peroxide and maleic anhydride) in which even some degree of decomposition has occurred. It should be noted that A-1110 silanes also show high MFI measurements when added at the same time as other additives.

Even if aminosilane is replaced with hexadecylamine (Comparative Example 7), a material having excellent mechanical properties and high hardness can be obtained. Since there is no possibility of bridging, this improvement in properties is probably related to the long side chains attached to the skeleton of the polymer (becoming a comb-like polymer). Therefore, TPV is not made (gel not included).

Example 18-21: Variation of Aminosilane These TPVs were prepared by the methods described above. The amount of aminosilane was kept the same (on a molar basis) in all experiments. Silane A and Silane B are:

<chemistry num="2"><img file="JP4732958B2_D0003.tif" /></chemistry>

<tables num="2"><img file="JP4732958B2_D0004.tif" /></tables>

Silanes A, B and A-1170 have slightly less yellowing than the products obtained with A-1110. A-1170 as a bridging agent provided a material with significantly improved adhesion when compared to other samples.

Application to foam-<u style="single">Examples 22-23 and Comparative Examples 24 and 25</u> Evaluate the use of TPV products for foam applications (Examples 22 and 23), and only peroxides and maleic anhydride (Examples 22 and 23).<u style="single">Comparison</u>Example 24) or just peroxide (<u style="single">Comparison</u>The formulations reacted with Example 25) were compared with each other. The material excluding the foaming agent azodicarbonamide was reacted in Brabender at 180 ° C (details of the TPV preparation method are as described above). After 10 minutes, the formulation was cooled to 160 ° C. then a foaming agent was added. In Example 23, aminosilane was added after the foaming agent was added. After mixing for another 3 minutes, a test plate was prepared at 170 ° C / 100 bar / 100 seconds. The plate was foamed in an oven at 200 ° C. for 3-5 minutes. The formulation is as shown below:

<tables num="3"><img file="JP4732958B2_D0005.tif" /></tables>

The strength of the melt is strong enough to withstand the decomposition temperature of the azodicarbonamide (200 ° C for a few minutes). Its shape remains within its original dimensions and does not stick to the support. In contrast, non-bridge samples change size during foaming, deteriorating the bubble structure and sticking to the support surface. The order of addition (whether silane is added before or after azodicarbonamide) does not significantly affect the appearance of the resulting foam or the amount of gel.

<u style="single">reference</u>Example 26-29: Although the general method using a monopolymer TPV is the same as shown above. In Examples 27-29, there is only one polymer, Example 27 is polyethylene, Example 28 is Elenac HDPE LUPOLEN 5031L: MFI (190 ° C, 2.16 kg) = 6.5, Density: 0.952. And Example 29 is polypropylene.

<tables num="4"><img file="JP4732958B2_D0006.tif" /></tables>

This graft maleic anhydride / aminosilane system can be used for pure ENGAGE resin and pure HDPE, but when used for polypropylene, no gel was formed.

<figref num="1">FIG. 1 illustrates the physical properties of the TPV prepared in the examples.</figref><figref num="2">FIG. 2 illustrates the physical properties of the TPV prepared in the examples.</figref><figref num="3">FIG. 3 illustrates the physical properties of the TPV prepared in the examples.</figref><figref num="4">FIG. 4 illustrates the physical properties of the TPV prepared in the examples.</figref><figref num="5">FIG. 5 illustrates the physical properties of the TPV prepared in the examples.</figref>