Thermoplastic vulcanizate composition and process for preparing the same

Thermoplastic sulfide composition and preparation method thereof

Figures 1-5 illustrate the physical properties of the TPV produced in the example.

Background of the invention

Thermoplastic elastomers (TPE) present the functional properties of traditional thermosetting rubbers, but they can be melted repeatedly, so they are suitable for processing in traditional thermoplastic manufacturing equipment. Most TPE consists of two phases, one is composed of rubber material (elastomer), which is insoluble in the other phase, and a flowable thermoplastic material. The rubber material exists as a dispersed phase, and the thermoplastic is a continuous phase.

Although in principle it is not necessary to cross-link the rubber in TPE, it has been proven that the use of cross-linking technology to obtain better chemical resistance, mechanical properties and better phase separation control is effective. Such TPE compositions, in which the cross-linking reaction and processing are used to achieve phase separation into individual regions, are called thermoplastic vulcanizates (TPV).

In order to maintain its thermoplastic characteristics, basically only the rubber phase is cross-linked. For an extensive and detailed description and review of TPV technology, refer to the Rubber Chemistry and Technology of S Abdou-Sabet, RC Puydak and CP Rader. Technology), Vol.69, pp 476-493, 1996.

In addition, it has been proved that the mechanical properties of TPV improve with the degree of cross-linking of the rubber phase and are inversely proportional to the particle size of the rubber area. Dynamic crosslinking (comprising of finely mixing a blend of compatible polymers, and then introducing a crosslinking system into the mixture when the mixing process continues) is used to produce a finely dispersed, highly crosslinked polymer from a homogeneous blend of polymers. The rubber phase of the union.

For thermal and hydrodynamic reasons, it is preferable to increase the viscosity of the polymer when crosslinking occurs, because the particles tend to agglomerate during phase separation. In addition, if the phase reversal method can occur when cross-linked, it is advantageous to form fibrous rubber regions that can provide specific mechanical properties. However, it has been found that it is better to choose a cross-linking mechanism, which can more or less include a thermoplastic phase, which does not achieve the purpose of removing the thermoplastic characteristics of the TPV, but only achieves better polymer viscosity and compatibility.

The choice of cross-linking method and chemicals is determined by the necessary processing conditions, for example, the reaction rate at the processing temperature; compatibility with elastomers; side reactions with thermoplastics; efficiency (produced by each cross-linking agent The number of crosslinks); no undesirable reactions; toxicity and danger; color and smell.

One example of this type of TPV described in U.S. Patent No. 3,130,535 is EPDM/PP. EPDM and PP are finely mixed in an internal mixer, and peroxide is added to crosslink EPDM. Excessive peroxide and/or too high processing temperature and/or too reactive polymer will cause PP phase degradation and/or coking. Conversely, EPDM with insufficient peroxide and/or too low processing temperature and/or poor reactivity will result in insufficient crosslinking.

The disadvantage of a polyolefin substrate TPV is that it cannot be painted without prior surface treatment. It is disclosed in U.S. Patent No. 4,311,628, and other crosslinking agents can be used, for example, dimethylol octylphenol resin and sulfur. Excellent mechanical properties can be achieved, but unfortunately both systems suffer from excessive odor and/or yellowing of the produced material, and difficulty in controlling the sulfur curing reaction.

European Patent No. 0324434 discloses the use of silane grafted polymers in the thermoplastic phase. After mixing, the material is shaped and left to react with atmospheric humidity.

Therefore, a more elastic substance can be obtained after the moisture is matured. However, the obtained moisture-cured product no longer contains the thermoplastic elastomer and cannot be recycled. In order to overcome this limitation, European Patent No. 0409542 discloses mixing an EPR (ethylene-propylene rubber) or EPDM with a crystalline ethylene-propylene thermal plastic, an organofunctional silane, and a free radical generator. The silane is grafted to the resin with a free radical generator, and cross-linked through the reaction of silane with water.

The reinforcement of the above method is disclosed in European Patent No. 0510559, in which EPR or EPDM is grafted first, and then mixed with thermoplastic PP and water-containing crosslinking additives. Reveal the same method, which uses very low or ultra-low density polyethylene (VLDPE or ULDPE) to reduce the cost of coarse materials and lower the mixing temperature. See German Patent No. DE4402943. It is also recommended to add both the PP component and the PE component, as well as the silane and free radical generators as dry compounds, and add water and condensation catalysts in the subsequent stages. However, adding water to the extrudate at a temperature considerably higher than the boiling point of water is a difficult process. In addition, the amount of water required is very low, so its measurement requires complicated instruments, which is contrary to the purpose of the present invention.

U.S. Patent No. 4,146,529 of Yamamoto et al. discloses the reaction of an acid-adjusted polypropylene with amine groups or epoxy silanes, but the purpose of this reaction is to use alkoxy groups to bond the filler The agent reacts with ungrafted carboxylic anhydride to form a low-odor, non-volatile product, instead of cross-linking the alkoxy function between itself. The purpose of these compositions is to couple mineral fillers without forming thermoplastic sulfides; or, in the absence of fillers, facilitate the dry reaction or dry reaction of the amine groups or epoxy groups of silane with free volatile ungrafted acids.

German Patent No. DE19629429 teaches (among other documents) the use of a pre-blend of vinylsilane, aminosilane and unsaturated carboxylic anhydride, which is used to crosslink polyolefins respectively.

Schematic description

Figures 1-5 illustrate the physical properties of the TPV produced in the example.

Summary of Invention

The present invention teaches the use of polymers, carboxylic anhydrides and aminosilanes to make TPV.

Detailed description of the invention

The purpose of the present invention is to prepare novel TPVs with a wide range of properties, low-cost TPVs, and paintable TPVs, allowing the preparation of TPVs in traditional mixers without the need for expensive additional equipment, and avoiding the use of large amounts of crosslinking agents when preparing TPVs (such as Organic matter or peroxide), and a stable TPV composition.

combination

TPV is a blend of (a) a first polymer (rubber phase); (b) a crystalline or partially crystalline thermoplastic polymer (thermoplastic phase); (c) a carboxylic anhydride, such as component ( The comonomer of a) is incorporated or grafted onto component (a); and (d) an aminosilane; allow it to crosslink.

A. Polymer The appropriate polyolefin rubber phase component (a) is any polymer that can be reacted, such as a carboxylic anhydride containing polymer, such as ethylene propylene copolymer (EPR); ethylene propylene diene three Polymer (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 acrylate (EBA), ethylene methacrylate (EMA), ethylene ethylene acrylate (EEA), ethylene-α- Olefin copolymers (such as EXACT and ENGAGE, LLDPE (linear low-density polyethylene)), high-density polyethylene (HDPE) and acrylic rubber (NBR). Polypropylene is not suitable for this phase because it is easily degraded during crosslinking; however, it can be used if it is a copolymer or graft of polypropylene and anhydride. Preferably, the polymer is an ethylene polymer or a copolymer with at least 50% ethylene content (in monomer), more preferably at least 70% of the monomer is ethylene.

Suitable thermoplastic polymer (b) is polypropylene (PP); polyethylene, especially high density (PE); polystyrene (PS); acrylonitrile butadiene styrene (ABS); styrene acrylonitrile (SAN) ); Packed with methyl methacrylate (PMMA); thermoplastic polyesters (PET, PBT); polycarbonate (PC); and polyamide (PA).

Such polymers can be produced by any method known in the art, including, but not limited to, dispersive phase, mud phase, gas phase, solvent phase, interface, polymerization reaction (reactive group, ionicity, metal initiation (such as metal complex ion) , Qi-Na (Ziegler-Natta)), polycondensation reaction, polyaddition or a combination of these methods. The two phases of the polymer can be made the same, and the acid anhydride is pre-added to a part of the polymer. The treated polymer will serve as the rubber phase in the TPV. This pre-addition includes enabling the anhydride to exist as a comonomer in the polymer, or pre-reacting the anhydride with the polymer. In either of these two examples However, the addition of individual anhydrides will not be necessary because it is present in the polymer. Given this level of complexity, it is preferable that the two polymers are different from each other.

The third option is that the rubber phase and the thermoplastic phase can be the same polymer, but the acid anhydride is all added to the polymer. In this example, when silane is added, part of the polymer will form a rubber phase, while the other part will not react (a small amount of anhydride and silane is assumed to be present). It is important that the rubber and thermoplastic phases produced during the process are properly separated. This method will not necessarily produce TPV, because it does not necessarily achieve the required phase without significantly increasing the complexity of the method, so it is not good.

In terms of two different polymers, the more reactive polymer with acid anhydride will be grafted with acid anhydride and will serve as the rubber phase in the TPV.

The polymer that will become the rubber phase must be extrudable and should be able to be grafted with the anhydride.

The melting point of the thermoplastic phase should be lower than the decomposition point of aminosilane and the decomposition point of the anhydride (unless the anhydride is a comonomer in the polymer).

The polymer can have a monomorph, bimorph or polymorphic molecular weight distribution. The melt flow of the polymer can be any known in the art for forming thermoplastics and rubber.

B. The carboxylic anhydride can be any carboxylic anhydride that can be grafted to the rubber phase by any possible mechanism. Preferably, there is unsaturation in the polymer or more preferably in the acid anhydride to achieve grafting. The unsaturation of the carboxylic anhydride, if present, can be inside or outside the ring structure, as long as it is allowed to react with the polymer. The acid anhydride may include a halide. Mixtures of various acid anhydrides can be used. Examples of unsaturated acid anhydrides used are isobutenyl succinic anhydride, (+/-)-2-oct-1-yl succinic anhydride, decomposed aconitic anhydride, 2-dodec-1-enyl succinic anhydride, cis- 1,2,3,6-Tetrahydropyranic anhydride, cis-5-descanene-endo-2,3-dicarboxylic acid anhydride, endo-bicyclo[2,2,2]oct-5-enyl-2 ,3-Dicarboxylic acid anhydride, methyl-5-descanene-2,3-carboxylic acid anhydride, oxy-3,6-epoxy-1,2,3,6, tetrahydropyranic anhydride, maleic anhydride Diacid anhydride, citraconic acid anhydride, 2,3-dimethylmaleic anhydride, 1-cyclopentene-1,2-dicarboxylic acid anhydride, 3,4,5,6-tetrahydropyranic anhydride, bromocis Butenedioic anhydride and dichloromaleic anhydride.

These anhydrides can be present in the rubber phase polymer as a comonomer, or grafted onto the polymer which will become the rubber phase.

The amount of acid anhydride is 0.01 to 1.0% by weight, based on the total amount of polymer present.

C. Aminosilane The aminosilane used here has at least one hydrolyzable group, such as an alkoxy group, an acetoxy group or a halogen group, and an alkoxy group is preferred. Preferably, there are at least two such hydrolyzable groups capable of undergoing cross-linking condensation reaction, so that the resulting compound can undergo this cross-linking. Mixtures of different aminosilanes can be used.

The amine must have an effective rate of reaction with the acid anhydride. Generally, tertiary amines do not react properly with acid anhydrides and should be avoided. Amine groups can be bridged to silicon atoms with branch groups to reduce the yellowing of the resulting composition.

The silane can be represented by the chemical formula YNHBSi(OR) _a (X) _3-a Indicates, where a=1 to 3, 3 is preferred, Y is hydrogen, alkyl, alkenyl, hydroxyalkyl, aralkyl, alkylsilyl, alkylamine, C(=O)OR or C( =O) NR, R is an acyl group, an alkyl group, an aryl group or an alkaryl group, and X can be R or a halo group. B is a divalent bridging group, which is preferably an alkylene group, which may be a branch (for example, a neohexyl group) or a ring system. B may contain heteroatom bridges, such as ether groups. Preferably B is propylene. Preferably R is methyl or ethyl. Silanes containing methoxy groups can ensure better cross-linking performance than ethoxy groups. Preferably Y is aminoalkyl, hydrogen, or allyl. More preferably, Y is hydrogen or a primary aminoalkyl group (for example, an aminoethyl group). Preferably X is C1 and methyl, more preferably methyl. Examples of silanes are γ-aminopropyltrimethoxysilane (SILQUEST ^R A-1110 Silane, from Witco Corp. of Greenwich, USA; γ-aminopropyl triethoxysilane (SILQUEST A-1100); γ-aminopropyl methyl -Diethoxysilane; 4-amino-3,3-dimethylbutyltriethoxysilane, 4-amino-3,3-dimethylbutylmethyldioxysilane, N-β- (Aminoethyl)-γ-aminopropyl trimethoxysilane (SILQUEST A-1120), H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ NH(CH ₂ ) ₃ Si(OCH ₃ ) ₃ (SILQUEST A-1130) and N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane (SILQUEST A-2120). Other suitable aminosilanes are as follows: 3-(N-allylamino)propyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutyltrimethoxysilane, ( Aminoethylaminomethyl)phenethyltrimethoxysilane, aminophenyltrimethoxysilane, 3-(1-aminopropoxy)-3,3-dimethyl-1-propenyl Trimethoxysilane, bis[(3-trimethoxysilyl)propyl]ethylenediamine, N-methylaminopropyltrimethoxysilane, bis-(r-triethoxysilylpropyl)amine (SILQUEST A-1170), and N-phenyl-γ-aminopropyltrimethoxysilane (SILQUEST Y-9669).

If the aminosilane is a latent aminosilane, that is, a ureidosilane or carbamate methionylsilane, the blending temperature must be sufficient to allow the individual barrier groups from the amine to leave and allow the amine to react with the acid anhydride functionality. It is about 150 to 230°C. Such latent aminosilanes are tertiary butyl-N-(3-trimethoxysilylpropyl) carbamate, ureidopropyltriethoxysilane, and ureidopropyltrimethoxysilane . Other urethane silanes that can be used are disclosed in U.S. Patent No. 5,220,047, which is incorporated herein by reference. It is preferable to avoid the additional complexity of barriers, and the aminosilane is not the latent aminosilane.

The aminosilane should be present at 250 to 25,000 ppm, based on the weight of the dipolymer. It should also be present in a molar equivalent ratio to the acid anhydride of about 0.1 to 10, preferably 0.9 to 1.1, and the best ratio of about 1:1. Silane can be driven on a carrier, such as a porous polymer, silica, titanium dioxide or carbon black, so it is easy to add to the polymer during the mixing process. Examples of such materials are ACCUREL polyene (AkzoNobel), STAMYPOR polyene (DSM) and VALTEC polyene (Montell), SPHERILENE polyene (Montell), AEROSIL silica ( Degussa), MICRO-CELE (Manville) and ENSACO 350G carbon black (MMM Carbon).

E. Additives to be selected as needed. If the carboxylic anhydride is grafted onto the polymer by a free radical mechanism, a free radical generator will be required, but if the anhydride is grafted through another mechanism or is a comonomer of the polymer, No need. Appropriate free radical catalysts can be selected from water-soluble or oil-soluble peroxides, such as hydrogen peroxide, ammonium persulfide, potassium persulfide, various organic peroxy catalysts, such as dialkyl peroxides, such as peroxides. Diisopropyl oxide, dilauryl peroxide, di-tertiary butyl peroxide, bis(2-tertiary butylperoxyisopropyl)benzene; 3,3,5-trimethyl-1, 1-Di(tertiary butylperoxy)cyclohexane; 2,5-Dimethyl-2,5-bis(tertiary butylperoxy)hexane, 2,5-dimethyl-2 ,5-Bis(tertiary butylperoxy)hexyne-3; dicumyl peroxide, alkyl hydroperoxide, such as tertiary butyl hydroperoxide, tertiary pentyl hydroperoxide, iso Propyl phenyl hydrogen peroxide, diacyl peroxides, such as acetyl peroxide, lauryl peroxide, benzyl peroxide, peroxy esters such as ethyl peroxybenzoate, and azo compounds , Such as 2-azobis (isobutyronitrile).

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

Standard additives such as stabilizers (UV, light or aging), antioxidants, metal deactivators, processing aids, waxes, fillers (silica, TiO ₂ ,CaCO ₃ ,Mg(OH) ₂ , Carbon black, etc.), and dyes are added to TPV. In addition, foaming agents can be added to the polymers, so they will form foam when they are extruded. Examples of such blowing agents are volatile hydrocarbons, hydrofluorocarbons, and chlorofluorocarbons. Generally known foaming agents such as azodicarbonate or sodium bicarbonate (basic sodium bicarbonate) decompose at high temperature to produce gaseous products. These are all chemical foaming methods. Foam can also be produced by injecting a liquid or gas blowing agent into a polymer melt. Examples are for example butane, CO ₂ , Nitrogen, water, helium and so on. Such foaming agents should be present in 0.1 to 50 weight percent of the polymer.

method

In the first reaction, the carboxylic anhydride is grafted (preferably by a free radical mechanism) onto the rubber phase polymer. The reaction can be accomplished by the presence of both polymers, or the separation of the two polymers, although it is preferable to achieve both by the presence of both polymers. As previously mentioned, this step can be effectively achieved by including carboxylic anhydride as a comonomer in the rubber phase polymer (in this example, no free radical generator is required). The polymer should be grafted/copolymerized with carboxylic acid anhydride before reacting with aminosilane, because the reaction product between acid anhydride and aminosilane only has a poor grafting effect. The previous reaction of aminosilane and acid anhydride will result in the formation of hemiamide, which will have poor grafting properties. In this case, no crosslinking occurs. Conversely, partial degradation of the polymer and/or the plasticizing effect of the semi-amide may lead to an increase in the melt flow index (MFI).

It is preferable to add a free radical generator and acid anhydride during the grafting step to induce the grafting of the acid anhydride on the rubber phase polymer.

If the second thermoplastic polymer is not present during grafting, it should be blended with the grafted rubber phase polymer before adding aminosilane; however, this method suffers from ineffectiveness from the viewpoint of the mechanical properties of the TPV produced.

The second step is to add aminosilane to the rubber phase graft polymer/thermoplastic polymer blend. This is a very rapid reaction between the aminosilane and the grafted anhydride. The reaction of grafted anhydride with γ-aminopropyl silane can be judged as:

<chemistry general="n"><img file="TW548313B_D0001.tif" /></chemistry>

The reaction between the silane and the grafted anhydride part must be rapid to obtain the cross-linked substance, and is faster than the reaction between the alkoxy group and the acid anhydride. The delayed reaction may occur together with the cross-linking of the alkoxy moiety, which can avoid cross-linking. The reaction between the amine group and the acid anhydride is very rapid, when, for example, a primary amine group is used. The reaction can be slowed by the use of secondary amine groups. In addition, this step should be a step at high temperature, for example 50 to 200°C, depending on the polymer blend. Preferably, the polymer blend is a melting stage when aminosilane is added to the polymer.

In order to form the gel phase of the crosslinked polymer, the aminosilane should be allowed to crosslink after grafting a polymer. There is no need for individual humidity maturation. A condensation catalyst can be used to facilitate the cross-linking process, although hemiamide should be a sufficient catalyst. A high temperature of 60 to 200°C for 1 to 10 minutes should ensure that this crosslinking occurs.

It must be noted that the total amount of additives added is only 0.4% of the total composition, which is about five times less than the amount required for peroxide or vinyl silane aging. This is beneficial to two aspects, the total cost is reduced and the temporary peroxide is reduced, which can show safety results.

During or after crosslinking, all ingredients should be blended in an internal mixer. The mixer can be an extruder (single screw, double screw, etc.), a BUSS KO-KNEADER mixer or a simple internal shape mixer. The mixing conditions depend on the degree of polymer and crosslinking.

nature

The resulting product is a thermoplastic sulfide with excellent mechanical properties. The crosslinked material has a significant gel content and MFI is much lower than the starting polymer. It should improve creep resistance, provide higher breaking point tension, and provide a material that is harder than the non-crosslinked polymer blend . The final product has elastic properties (that is, the breaking point extension is greater than 400%), but it can be melt-processed by methods generally known in the art. The preferred gel content (ie rubber content) of the final product is between 10 and 50% by weight, with 25-35% by weight being the best. The tensile force and modulus of elasticity in the mechanical and reverse directions are improved, just like the violent impact strength of the material.

The TPV is paintable and has better oil resistance. The TPV can be used for, for example, adhesives and sealants, cable insulation, conduits, profile images, molded parts, foamed parts, sheets, etc.

The phase-adjusted polymer of the aminosilane rubber tends to be more compatible with the thermoplastic polymer, providing a stronger TPV.

Instance

All silanes used are listed above, except SILQUEST A-186) γ-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, SILQUEST A-187 (γ-glycidoxypropyl trimethoxy) Base silane) and SILQUEST A-l89 (γ-based propoxy trimethoxysilane). Compound parameters: Brabender Head is 190°C/RPM 120. All percentages are percentages by weight unless otherwise specified.

Method I: The total amount of formula ingredients: 55 grams. All ingredients are fed into the Brabender head, except for the homopolymer polypropylene VALTEC HL003 (+5% silane). After 5 minutes (note the value of Brabender indenter torque), add VALTECHL003 (+5% silane) to the Brabender indenter. Note the time and value of the maximum Brabender torque as a cross-linking indicator. After the Brabender torque fell back to the original level and homogenization of the compound was reached (approximately 10 minutes), the compound was recovered from Brabender. A sample with a thickness of 1.5 mm was molded in a press at 210°C/20 bar.

Method II: The same steps as Method I, but all the ingredients are fed into the Brabender indenter at the same time. Combination time is 15 minutes. A sample with a thickness of 1.5 mm was molded in a press at 210°C/100 bar for 200 seconds.

Examples 1-3 are used to show that a wide range of properties can be obtained, depending on the grade of the polymer. The weight percentage of the material driven on the other material is based on the weight of the carrier and the driven material.

Example 1: Composition: 75% ENGAGE 8452 ultra-low density polyethylene (from Dupont Dow E1astomers, melting index 190°C/2.16 kg): 3 g/10 minutes; density: 0.875 g/cc), 17% VALTEc HL003 polypropylene homopolymer (from spHERIPOL of Monzaer ^ Porous particles: Melting index (230°C/2.16 kg): 0.7 g/10 minutes; density: 0.900 g/cc), 1% VALTEc HL003 (+5% immersed INTEROX DHBP (from Munchen) Chemicals (Peroxid-Chemie) 2,5-Dimethyl-2,5-bis(tertiary butylperoxy)hexane), 2% VALTEC HL003 (+5% immersed maleic anhydride) , 5% VALTEC HL003 (+5% immersion A-1100), method I. The maleic anhydride is absorbed into the polymer by melting the anhydride (melting point 53°C), blending it with the polymer and then cool down.

Example 2: Composition: 75% NORDEL 2722 ethylene propylene diene monomer rubber (DuPont Dauer elastomer: density: 0.88 g/cm ^ 3, Mooney viscosity (Mooney Viscosit y) ML 1+4:28 at 121°C ), 17% VALTECHL003, 1% VALTEC HL003 (+5% immersion INTEROX DHBP), 2% VALTEC HL003 (+5% immersion maleic anhydride), 5% VALTEC HL003 (+5% immersion A-1100), Method I.

Example 3: Composition: 75% ENGAGED 8842.00 ultra-low density polyethylene (from DuPont Dal Elastomer: Melting Index (190°C/2.16 kg) (1.0 g/10 minutes): Density: 0.857 g/cc), 17% VALTEC HL003, 1% VALTEC HL003 (+5% immersion INTEROX DHBP), 2% VALTEC HL003 (+5% immersion maleic anhydride), 5% VALTECHL003 (+5% immersion A-1100), method I.

Examples 4-7 illustrate the influence of methods and ingredients.

Example 4 (comparison): Composition: 75% ENGAGE8452, 25% VALTECHL003, method II.

Example 5 (comparative): Composition: 75% ENGAGE8452, 22% VALTECHL003, 1% VALTEC HL003 (+5% immersed INTEROX DHBP), 2% VALTEC HL003 (+5% immersed maleic anhydride), method I.

Example 6 (comparison): Composition: 75% ENGAGE8452, 17% VALTECHL003, 1% VALTEC HL003 (+5% immersed INTEROX DHBP), 2% VALTEC HL003 (+5% immersed maleic anhydride), 5% VALTEC HL003 (+5% soaked A-1100), method II.

Example 7 (comparison): Composition: 75% ENGAGE8452, 17% VALTEC HL003, 1% VALTEC HL003 (+5% immersed INTEROXDHBP), 2% VALTEC HL003 (+5% immersed maleic anhydride), 5% VALTEC HL003 (+5% soaked hexadecylamine), method I.

Examples 8-17 illustrate the effect of silane morphology changes. Examples 15-17 are controls. All added silanes are added at 5% by weight, based on VALTEC HL003. The preparation of the compound is according to Method I.

Physical properties

The physical properties are measured according to the following standards: Extension and tension at the breaking point ISO 37 (50 mm/min) MFI ISO 1872-l, No. 18T Shore A (Shore A) ISO 868 Gel content ISO 6427 Torque in Brabender Torque meter

result

Table I of the changes in silane shows the properties of the substances obtained according to the steps mentioned in the experimental part. The comparative example (Comp. Ex.) includes: Ex. 4) a pure blend of EMGAGE 8452 (PE) and VALTEC HL003 (PP); EX. 5) ENGAGE, VALTEC, peroxide and maleic anhydride Blend; EX.6) ENGAGE, VALTEC, peroxide, a blend of maleic anhydride and A-1100, but all the ingredients are mixed at once, and EX.7) ENGAGE, VALTEC, peroxide, A blend of maleic anhydride and hexadecylamine; EX.4 is a pure polymer blend to obtain properties, EX.5 evaluates the effect of silane alone, EX.6 represents the effect of treatment, and comparative example 7 is Prove the necessity of silane in the mixture.

<tables><img file="TW548313B_D0002.tif" /></tables>

Figure 1 shows the gel content obtained with different silanes, and Figure 2 shows the extreme torque observed during compound preparation. The data shown in Figure 1 and Figure 2 indicate that the maximum torque observed during compounding is related to the cross-linking reaction. Obviously all primary amines (SILQUEST A-1100, A-1110, A-1120, A-l130 and A-2120 silanes) induce direct cross-linking and are mixed in the polymer blend after the maleic anhydride grafting Mid-time.

Conversely, mixing all materials at the same time (Comparative Example 6) did not produce any significant crosslinking. Compared with A-1100 Silane, the slight difference in the degree of cross-linking can be due to the different molar content, the different number and/or the type of alkoxy group and the amine function per molecule. The material obtained by using the secondary aminosilane A-1170 also showed a higher degree of crosslinking, while Y-9669 (secondary aminosilane) did not cause significant crosslinking. Note that because the molecular weight of A-1170 is quite higher than other silanes used, and the experiment was performed with the same weight of silane, the molar amount of A-1170 is lower than other silanes, and the same molar amount produces improved gel formation . The latter is also true for other tested silanes and where hexadecylamine is used instead of silane.

The data presented in Figures 3-5 show that in all cases where cross-linking is observed, the material properties are significantly changed compared to the pure blend of the two polymers. The melting index fell to about 1/10, and even reached 1/30 in the case of A-1110 silane. The material is also significantly harder, with a higher breaking point and lower breaking point extension. The change in properties is consistent with the higher degree of cross-linking in these compounds.

Regarding the other silanes used, the nature of the resulting material cannot be attributed to the high degree of crosslinking. However, all silanes resulted in a decrease in MFI, indicating that some chain extension occurred. Compared to all the control examples, and especially compared to the control example 5 (only peroxide and maleic anhydride), this is obvious, in which a certain degree of degradation may even occur. Note that high MFI was also measured when A-1100 Silane was mixed at the same time as other components.

Changing the aminosilane with hexadecylamine (Comparative Example 7) also produced a substance with excellent mechanical properties and higher hardness. The improvement in properties may be related to the long-chain branches attached to the polymer backbone ("comb poly mers"), because cross-linking is impossible. Therefore, no TPV (no gel content) is manufactured.

Example 18-21 Variation of Amino Silane TPV was prepared according to the above procedure. The aminosilane for all operations remains the same (mole basis). Silane A and B are as follows:

<chemistry general="n"><img file="TW548313B_D0003.tif" /></chemistry>

<tables><img file="TW548313B_D0004.tif" /></tables>

Silanes A, B and A-1170 yield products, which are slightly yellower than those obtained using A-1100 and A-1170 as crosslinking agents, resulting in substances with very improved adhesion properties when compared to other samples.

Foaming applications-Examples 22-25 evaluate the use of TPV products in foam applications (Examples 22 and 23), and with only peroxide and only with maleic anhydride (Example 24) or peroxide (Example 25), respectively Comparison of reaction formulas. The substances other than the foaming agent azodicarbonate were reacted in Brabender at 180°C (the details of the preparation of TPV are as above). After 10 minutes, the formulation was cooled to 160°C and foaming agent was added. In Example 23, the aminosilane was added after the foaming agent was added. After mixing for another 3 minutes, a test sample was prepared at 170°C/100 bar/100 seconds. The sample is foamed in an oven at 200°C for 3 to 5 minutes. The formula is as follows:

<tables><img file="TW548313B_D0005.tif" /></tables>

The melting strength is high enough to support the decomposition temperature of azodicarbonate (a few minutes at 200°C). Keep the shape in the original size and do not stick to the support. Conversely, the uncrosslinked samples changed their size during the blistering period, which resulted in a poorer peak and pocket structure and adhered to the surface of the support. The order of addition (addition of silane before and after azodicarbonate) does not seem to significantly affect the appearance of the foam or the amount of gel produced.

The general procedure for single polymer TPV in Examples 26-29 is the same as above, however, in Examples 27-29, only one polymer is used, in Example 27, polyethylene is used, and in Example 28, HDPE LUPOLEN 5031L is used by EIenac: MFI (190°C, 2.16 kg) = 6.5; density: 0.952 and in Example 29, polypropylene.

<tables><img file="TW548313B_D0006.tif" /></tables>

The maleic anhydride/aminosilane grafted by the system can be used to crosslink pure ENGAGE resin and pure HDPE, but it does not produce any gel when used in polypropylene.

Schematic description

Figure 1 shows the gel content of the compound,

Figure 2 shows the extremely large torque observed in the compound,

Figure 3 shows the melting index of the compound at 190°C/5 kg,

Figure 4 shows the ductility and tension of the rupture point, and

Figure 5 shows the Shore A value of the compound.