Thermoplastic compositions of interpolymers of alpha-olefin monomers with one or more vinyl or vinylidene aromatic monomers and/or one or more hindered aliphatic or cycloaliphatic vinyl or vinylidene monomers blended with vinyl halide homopolymers and copolymers

This invention relates to thermoplastic compositions of interpolymers of alpha-olefin monomers with one or more vinyl or vinylidene aromatic monomers blended with vinyl halide homopolymers and copolymers, or with one or more hindered aliphatic or cycloaliphatic vinyl or vinylidene monomers.

TR 2000 00968 T2

INTERNATIONAL SEARCH REPORT

Intern. .al Application Id

PCT / US 98/21843

<td colspan="4">A, CLASSIFICATION OF SUBJECT MATTER, _z „ „ ,,, _n________ IPC 6 C08L23 / 02 C08L25 / 02 C08L27 / 02 C08J5 / 18 // (C08L23 / 02, 27:02), (C08L25 / 02.27: 02), (C08L27 / 02.23: 02), (C08L27 / 02.25: 02)</td>

<td colspan="3">International Patent Classification (IPC)</td><td></td>

<td colspan="4">B. FIELDS SEARCHED</td>

<td colspan="4">Minimum documentation searched (classification system followed by classification symbols) IPC 6 C08L</td>

<td colspan="4">Documentation searched other than minimum documentation</td>

<td colspan="4">Electronic data base consulted during the international search (name of data bass and. Where practical, search terms used)</td>

<td colspan="4">C. DOCUMENTS TO BE CONSIDERED TO RELEVANT</td>

<td>Category </td><td colspan="2">Citation of document, with indication, where appropriate, of the relevant passages</td><td>Relevant to claim No.</td>

<td>P, x</td><td colspan="2">WO 98 27156 A (BETHEA JAMES R; CHEUNG YUNWA W (US); DOW CHEMICAL CO. (US); GATHERS) 25 June 1998 cited in the application see page 12, 1ine 31 - 1ine 38; claims</td><td> 1-24</td>

<td>P,</td><td colspan="2">WO 98 10015 A (BROOS RENE; PARK CHUNG P (DE); DOW CHEMICAL CO. (GB); THOEN JOHAN () March 12, 1998 see claims; examples 12,13</td><td> 1-24</td>

<td>to</td><td>WO 95 27755 A (DOW CHEMICAL CO.) 19 October 1995 cited in the application see claims</td><td></td><td> 1</td>

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

<td colspan="2">| j Further documents are listed in the continuation of box C.</td><td colspan="2">| y | Patent family members are listed in annex.</td>

<td colspan="2">• Special categories of cited documents: A document defining the general stale of the art E previous document but published on or alter the international filing dale L * document which may throw doubts on a priority date (c) '0' document referring to an oral disclosure, use, exhibition or other means P document published prior to the date filed</td><td colspan="2">T * later document X * document of particular relevance: the claimed invention V 'document ot particular relevance; the claimed invention When a document is combined, it is a person who is skilled in the art. document member of the same patent family</td>

<td colspan="2">Date of actual completion of the international search</td><td colspan="2">Date oi mailing ol the international search report</td>

<td colspan="2">15 February 1999</td><td> 03/03/1999</td><td></td>

<td colspan="2">Name and mailing address of the ISA European Patent Office, PB 5Θ18 Patents 2 NL · 2280 HV Rijswijk Phone. (+ 31-70) 340-2040, Tx. 31 651 epo nl. Fax: (+ 31-70) 340-3016</td><td colspan="2">Authorized officer DE LOS ARCOS, E</td>

Form PCT / ISA / 210 (second sheet) (July 1992)

Λ ..

52494

THERMOPLASTIC Blend COMPOSITIONS

The present invention relates to thermoplastic compositions blended with one or more vinyl or vinylidene aromatic monomers of α-olefin monomers and vinyl halide homopolymers and copolymers of interpolymers with one or more hindered aliphatic or cycloaliphatic vinyl or vinylidene monomers.

Aolefin / hindered vinyl or vinylidene monomer substantially random interpolymers, including materials such as α-olefin / vinyl aromatic monomer interpolymers, and their preparation are known in the art as disclosed in EP 416 815 A2. Such materials, such as ethylene / styrene interpolymers, provide a wide variety of material structures and properties that make them useful in a variety of applications, such as asphalt modifiers or compatibilizers for polyethylene and polystyrene blends as described in US 5,460,818.

The structure, thermal transitions, and mechanical properties of substantially random ethylene and styrene interpolymers, which may contain 50 mole percent styrene, are described (YW Cheung, MJ Guest; Proc. Antec '96, p. 1634-1637). It has been found that the glass transition of these polymers is in the range of -20 ° C to + 35 ° C and does not exhibit measurable crystallinity in the addition of styrene above 25 mole percent, i.e. they are substantially amorphous.

While useful in their own way, there are ongoing attempts in the art to improve the applicability of these interpolymers. In some embodiments, it may be desirable to develop these interpolymers to perform well, for example in the field of processing properties or in the increased glass transition temperature depression or in the reduced modulus or in reduced hardness or low viscosity, or in the improved final elongation area when compared to similar properties of the unmodified interpolymer. With regard to the present invention, it is advantageous to be able to adjust the glass transition process to a certain temperature range for materials containing interpolymers, in order to optimize the absorption power of the polymer, for example in sound and vibration damping. U.S. Pat. No. 5,739,200 discloses improving the properties of interpolymers of α-olefin / vinyl or vinylidene aromatic monomers by adding plasticizers.

*1.

52494

Similarly, the family of vinyl polymers such as poly (vinyl chloride) (PVC) has found application in many markets, particularly due to their diversity and good stability. This diversity is achieved by the compatibility of the polymer with various plasticizers typically used at levels that increase flexibility and processability.

The use of polymeric materials to alter the impact properties of rigid PVC is widely known. The addition of butadiene-containing polymers such as polyacrylic resins, acrylonitrile butadiene styrene terpolymers (ABS) and methacrylate butadiene styrene terpolymers (MBS) to hard PVC, for example, and chlorinated polyethylene (CPE) resins, house partition panels, vinyl window frames, power lines and spray-molded It is known that PVC products such as PVC bottles increase the impact strength. Impact modifiers are typically used in these applications at levels of 5 to 15 parts by weight per 100 parts of PVC resin. Hard PVC resins typically used in these applications are typically classified as medium or high molecular weight.

EP 0 298 282 discloses blends of vinyl chloride homo-, co-, or terpolymers with random styrene copolymers containing polar groups. U.S. Pat. No. 5,250,616 discloses blends of polyvinyl halide polymers and copolymers of styrene, acrylonitrile and butadiene.

In the case of changing the impact properties of low molecular weight or flexible PVC resins, the molten viscosity of the impact modifying material is higher than that of the PVC resin. This may result in poor dispersion and wide particle size distribution of the impact modifier material, resulting in low PVC compounds with low impact strength. The impact strength in the compound can be increased slightly by increasing the amount of modifying material, but this often lowers economic productivity.

SUMMARY OF THE INVENTION The object of the present invention is a novel novel polymer comprising one or more vinyl halide polymers and one or more aolefin monomers having at least one substantially random interpolymer of one or more vinyl or vinylidene aromatic monomers and / or one or more hindered aliphatic or cycloaliphatic vinyl or vinylidene monomers. blend compositions. The novel blend compositions provide materials with improved processing / property properties relative to unmodified polymers containing blends. Blend compositions, increased modulus and barrier properties, improved tensile strength, durability, radiofrequency (rf) depending on selection of individual blend components and composition ratios

52 494 sealability, solvent connectivity, thermal stability and ignition resistance.

In another embodiment, the invention includes one or more vinyl or vinylidene aromatic monomers and / or one or more hindered aliphatic or cycloaliphatic vinyl or vinylidene of one or more α-olefin monomers in combination with one or more vinyl halide polymers and one or more plasticizers. monomer and at least one interpolymer substantially random. These blend compositions allow the manufacture of materials which can be controlled by the glass transition width and location by varying the blend component composition ratio and the level of plasticizer. Surprisingly, some blends containing a plasticizer show a single glass transition temperature (Tg) from the thermal analysis data. In other examples, the blend compositions show a plurality of Tg when, for example, the level of plasticizer is relatively low. These blend compositions also find use in applications such as sound management and vibration damping.

The present invention relates to blend compositions comprising:

(A) 1 to 99 weight percent of at least one substantially random interpolymer based on combined weights of components A, B and C; said interpolymer (1) comprising from 0.5 to 65 mole percent of polymer units obtained from:

(a) at least one vinyl or vinylidene aromatic monomer; or (b) at least one hindered aliphatic vinyl or vinylidene monomer; or (c) at least one vinyl or vinylidene aromatic monomer and at least one hindered aliphatic vinyl or vinylidene monomer;

(2) 35 to 99.5 mole percent of polymer units obtained from at least one aliphatic α-olefin having from 2 to 20 carbon atoms;

(3) the molecular weight (M n) is greater than 1,000;

(4) melt index (b) in the range of 0.01 to 1,000;

(5) molecular weight distribution (M_wM is from 1.5 to 20; and (B) from 99 to 1 weight percent of one or more vinyl halide homopolymers or copolymers based on the combined weights of components A, B and C; and

52 494 (C) 0 to 70 weight percent of one or more plasticizers based on combined weights of components A, B and C.

The compositions of the present invention can be used in the manufacture of a wide variety of finished products such as polished, cast and spray sheets and films and injection molded parts. The compositions of the present invention are used in flexible molded products, as layers in multi-layer film structures, in applications such as automobile instrument panel leathers, as construction materials such as partitions, in flooring systems, as coatings on substrates, including polymers, paper, leather, cloth and inorganic building materials. is used as foams for heat, sound and vibration damping.

References herein to elements or metals belonging to a particular Group are described in CRC Press, Inc. (1989) and is copyrighted. References to the Group or Groups also refer to the Group or Groups contained in this Periodic Table using the IUPAC system for numbering groups.

The numerical values ​​referred to herein include all values ​​in one unit increments from the lower value to the higher value, provided that there is at least 2 units between a lower value and a higher value. For example, when the amount of a component or a process variable value, such as temperature, pressure, time, is specified to be in the range of 1 to 90, preferably 20 to 80, more preferably 30 to 70, 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc. is expressly stated herein. For values ​​less than one, a unit is considered 0.0001, 0.001, 0.01 or 0.1, as appropriate.

These are merely examples of what is specifically intended, and it is recognized that all possible combinations of numerical values ​​between the specified minimum value and the maximum value are likewise clearly stated in this application.

The term "hydrocarbyl" as used herein refers to any aliphatic, cycloaliphatic, aromatic, aryl substituted aliphatic, aryl substituted cycloaliphatic, aliphatic substituted aromatic or aliphatic substituted cycloaliphatic group.

The term "hydrocarbyloxy" refers to a hydrocarbyl group having an oxygen bond between itself and the carbon atom to which it is attached.

The term "copolymer" as used herein refers to a polymer wherein at least two different monomers are polymerized to form the copolymer.

52 494 The term "interpolymer" as used herein refers to a polymer wherein at least two different monomers are polymerized to form the interpolymer. Such copolymers, terpolymers and the like. It enters.

The term &amp; quot; substantially random &amp; quot; as used herein in the substantially random interpolymer clause comprising an α-olefin and a vinyl or vinylidene aromatic monomer or hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer, is used by the Bernoulli statistical model or JC Randall by POLYMER SEQUENCE DETERMINATION. Carbon-13 NMR Method (Academic Press New York, 1977, p. 71-78) as described in the first or second level of the Markovian statistical model. Preferably, the substantially random interpolymer comprising an α-olefin and a vinyl or vinylidene aromatic monomer comprises up to 15 percent of the total amount of vinyl or vinylidene aromatic monomer in blocks of vinyl or vinylidene aromatic monomer comprising more than 3 units. More preferably, the interpolymer is not characterized by a high degree of isotacticity or syndiotacticity.

This means that the substantially random interpolymer is¹³ It means that the peak areas corresponding to the main chain methylene and text carbons representing meso diad sequences or racemic diad sequences in the NMR spectrum should not exceed 75 percent of the total peak area of ​​the main chain methylene and text carbons.

Ethylene / Blocked Vinylidene Interpolymers

The substantially random α-olefin / vinyl or vinylidene aromatic interpolymers of the present invention include, but are not limited to, one or more α-olefins with one or more vinyl or vinylidene aromatic monomers and / or one or more hindered aliphatic or cycloaliphatic vinyl or interpolymers prepared by polymerizing with vinylidene monomer.

Suitable α-olefins include, for example, α-olefins containing from 2 to 20, preferably from 2 to 12, more preferably from 2 to 8 carbon atoms. Particularly suitable are ethylene, propylene, butene-1,4-methyl-1-pentene, hexene-1 and octene-1. These α-olefins do not contain an aromatic moiety.

Suitable vinyl or vinylidene aromatic monomers which can be used to prepare the interpolymers include, for example, those expressed by the formula:

52494

R

I (CH₂)_n

R1-C = C (R²)₂ where R¹ R &amp; lt; 2 &amp; gt; is selected from the group of radicals consisting of hydrogen and alkyl radicals having from 1 to 4 carbon atoms, preferably hydrogen or methyl; each R² is independently selected from the group of radicals consisting of hydrogen and alkyl radicals having from 1 to 4 carbon atoms, preferably hydrogen or methyl; Ar is a phenyl group or a phenyl group substituted with 1 to 5 substituents selected from the group consisting of halo, C1-4-alkyl and C1-4 -haloalkyl; n is a value of zero to 4, preferably zero to 2, most preferably zero. Exemplary vinyl or vinylidene aromatic monomers include styrene, vinyl toluene, α-methylstyrene, t-butyl styrene, chlorostyrene, and all isomers thereof. Of these monomers, styrene and lower alkyl10 or halogen substituted derivatives are particularly preferred. Preferred monomers include styrene, α-methyl styrene, lower alkyl- (C1-C)₄or phenyl ring substituted styrene derivatives such as ortho-, meta- and para-methylstyrene, ring halogenated styrenes, para-vinyl toluene, or mixtures thereof. A more preferred aromatic vinyl monomer is styrene.

The term "blocked aliphatic or cycloaliphatic vinyl or vinylidene compounds" refers to additional polymerizable vinyl or vinylidene monomers corresponding to the formula:

a »

R - C = C (R²)₂ where A¹ a sterically bulky aliphatic or cycloaliphatic substituent of up to 20 carbons, R¹ R &amp; lt; 2 &amp; gt; is selected from the group of radicals consisting of hydrogen and alkyl radicals having from 1 to 4 carbon atoms, preferably hydrogen or methyl; each R² is independently selected from the group of radicals consisting of hydrogen and alkyl radicals having from 1 to 4 carbon atoms, preferably hydrogen or methyl; or alternatively R¹ and A¹ together form a ring system. The term &amp; quot; sterically bulky &amp; quot; means that the monomer bearing this substituent does not normally have the additional polymerization capacity with standard Ziegler-Natta polymerization catalysts at a rate comparable to ethylene polymerizations. Preferred hindered aliphatic or cycloaliphatic vinylidene compounds are monomers wherein one of the carbon atoms having ethylenic unsaturation is tertiary or quaternary substituted. Examples of such substituents include cyclic aliphatic groups such as cyclohexyl, cyclohexenyl, cyclooctenyl, or alkyl or

52 494 aryl substituted derivatives, tert-butyl, norbomyl. The most preferred hindered aliphatic or cycloaliphatic vinylidene compounds are various isomeric vinyl-ring substituted derivatives of cyclohexene and substituted cyclohexenes and 5-ethylidene-2-norbomer. 1-, 3- and 4-vinylcyclohexene are particularly suitable. Simple linear α-olefins, including ethylene, propylene, butene-1, 4-methyl-1-pentene, α-olefins containing from 3 to 20 carbon atoms such as hexene-15 or octene-1, are sterically hindered aliphatic or cycloaliphatic vinyl or they are not examples of vinylidene compounds.

Substantially random interpolymers may be modified by typical inoculation, hydrogenation, functionalization or other reactions well known to those skilled in the art. The polymers can be readily sulfonated or chlorinated to obtain derivatives functionalized according to established techniques.

A method for preparing substantially random interpolymers is disclosed in EP-A-0,416,815 by James C. Stevens et al. and U.S. Pat. No. 5,703,187, which includes polymerizing a mixture of polymerizable monomers in the presence of one or more metallocene or strong geometry catalysts in combination with various auxiliary catalysts. Preferred operating conditions for these polymerization reactions are pressures in the range from atmospheric to 3000 atmospheres and temperatures in the range of -30 ° C to 200 ° C. Polymerizations at temperatures above the autopolymerization temperature of the associated monomers and removal of unwanted monomer may result in the formation of some homopolymer polymerization products, for example, production of atactic polystyrene.

Examples of suitable catalysts and methods for preparing substantially random interpolymers are described in US Application Serial No. 4, 5,759,751, filed May 20, 1990. 702,475 (EP-A514,828), as well as US Patents 5,055,438; 5,057,475; 5,096,867; 5,064,802; 5,132,380; 5,189,192; 5,321,106; 5,347,024; 5,350,723; 5,374,696; 5,399,635, 5,470,993; 5,703,187; and 5,721,185; all of these patents and applications are incorporated herein by reference.

Substantially random α-olefin / vinylidene aromatic interpolymers can also be prepared by the methods described in JP 07/278230 using compounds represented by the following general formula;

52 494 ζ \ _ζ* ^ΧC ^ Cp2^ZXR2 where Cp^l and Cp² independently of one another are cyclopentadienyl groups, indenyl groups, fluorenyl groups or substituents; R¹ give² are independently hydrogen atoms, halogen atoms, hydrocarbon groups having carbon numbers 1-12, alkoxy groups or aryloxy groups; M is a group IV metal, preferably Zr or Hf, most preferably Zr; give³ cp¹ and Cp²is an alkylene group or silanediyl group used to crosslink.

Substantially random α-olefin / vinyl or vinylidene aromatic interpolymers are described in John G. Bradfield et al. (WR Grace &amp; Co.), WO 95/ 32095, RB Pannell (Exxon Chemical Patents, Inc.), WO 94/00500; and Plastics Technology, p. 25 (September 1992).

Substantially random interpolymers containing at least one aolefin / vinyl aromatic / vinyl aromatic / α-olefin tetrad described in Francis J. Timmers et al. In WO 98/09999 are also suitable. These interpolymers contain additional signals whose intensity is three times greater than peak to peak noise. These signals are seen in the chemical shift range of 43.70-44.25 ppm and 38.0-38.5 ppm. A proton test NMR test indicates that the signals in the chemical shift region at 43.70-44.25 ppm are text carbons and the signals in the 38.0-38.5 ppm region are methylene carbons.

These new signals may be introduced into sequences containing the addition of vinyl aromatic monomer to the two head-tail, followed by the addition of at least one α-olefin, for example an ethylene / styrene / styrene / ethylene tetrad, wherein the styrene monomer additions of said tetrads are formed in only one 1,2 (head-to-tail) form. It is believed to be connected. Those skilled in the art will have a carbon / ethylene aromatic monomer / vinyl aromatic monomer / ethylene tetrad similar carbon for these tetrads containing a vinyl aromatic monomer other than styrene and an α-olefin other than ethylene.¹³ It will be appreciated that it will lead to NMR peaks, but with little different chemical shifts.

These interpolymers are prepared by applying polymerization at temperatures in the range of -30 ° C to 250 ° C in the presence of catalysts such as those expressed by the formula:

52494

<img file="TR200000968T2_D0001.tif" />

Mar '₂ wherein: each Cp is independently a cyclopentadienyl group, in each occurrence, which is π-linked to M; E = C or Si; M is a group IV metal, preferably Zr or Hf, most preferably Zr; each R at each occurrence is independently H, hydrocarbyl, arsydrocarbyl or hydrocarbylsilyl containing up to 30, preferably 1 to 20, more preferably 1 to 10 carbon or silicon atoms; each R 'in each occurrence is independently H, halo, hydrocarbyl, hydrocarbyloxy, arms hydrocarbyl or hydrocarbylsilyl containing up to 30, preferably 1 to 20, more preferably 1 to 10 carbon or silicon atoms, or the two R' groups together are a C 1-10 hydrocarbyl substituted 1,3 Configure butadiene; m is 1 or 2; and optionally, but preferably, this polymerization is carried out in the presence of an activating cocatalyst. Particularly suitable substituted cyclopentadienyl groups include those represented by the formula:

(R)₃ wherein each R is independently at each occurrence H, hydrocarbyl, arms hydrocarbyl or hydrocarbylsilyl containing up to 30, preferably 1 to 20, more preferably 1 to 10 carbon or silicon atoms, or the two R groups together form a divalent derivative of such a group. Preferably, R is independently at each occurrence (including all suitable isomers) hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl or silyl, or (where appropriate) the two R groups are bonded together to indenyl, fluorenyl, tetrahydroindenyl, forms a fused ring system such as tetrahydrofluorenyl or octahydrofluorenyl.

Particularly preferred catalysts include, for example, racemic- (dimethylsilanediyl) -bis- (2-methyl4-phenylindenyl) zirconium dichloride, racemic- (dimethylsilanediyl) -bis- (2-methyl-4-phenylindenyl) zirconium 1,4-diphenyl-1, 3-butadiene, racemic- (dimethylsilanediyl) -bis- (2-methyl-4-phenylindenyl zirconium di-C 1-4 alkyl, racemic- (dimethylsilanediyl) -bis- (2-methyl-4-phenylindenyl) zirconium di-C 4 alkoxide or any combination thereof.

The following titanium-based strong geometry catalysts can also be used: [N- (1,1-dimethylethyl) -1,1-dimethyl-1 - [(1,2,3,4,5-η) -1,5,6, 7-tetrahydro-s-indacen-l9

52 494 yl] silanaminato (2-) - N-titanium dimethyl; (1-indenyl) (tert-butylamido) dimethyl-silane titanium dimethyl; ((3-tert-butyl) (1,2,3,4,5-yl-1-indenyl) (tert-butylamido) dimethylsilane titanium dimethyl; and ((3-isopyropyl) (1,2,3,4,5-yl) -1-indenyl) (tert-butyl amido) dimethylsilane titanium dimethyl or any combination thereof.

Other methods for preparing blend components of the present invention substantially random α-olefin / vinylidene aromatic interpolymers are disclosed in the literature. Longo and Garssi {Makromol. Chem., Vol. 191, pages 2387 to 2396 [1990] and D'Anniello et al. (Journal of Applied Polymer Science, Vol. 58, pp. 1701-1706 [1995]) discusses the use of a catalytic system based on methylalumoxane (MAO) and cyclopentadienyltitanium trichloride (CpTiCl3) to prepare an ethylene-styrene copolymer. Xu and Lin {Polymer Preprints, Am. Chem. Soc., Div. Polymer. Chem., Vol. 35, pp. 686,687 [1994]) describes copolymerization using an MgCl2 / TiClVNdCb / AlCl2B14 catalyst to obtain random copolymers of styrene and propylene. Lu et al. {Journal of Applied Polymer Science, Vol. 53, pages 1453 to 1460 [1994]) discloses copolymerization of ethylene and styrene using a TiCl4 / NdCl3 / MgCl2 / Al (Et) 3 catalyst. Manufacture of α-olefin / vinyl aromatic monomer interpolymers such as propylene / styrene and butene / styrene are disclosed in US patent no. No. 5,244,996, or to Mitsui Petrochemical Industries Ltd., U.S. Pat. And DE 197 11 339 A1 to Denki Kagaku Kogyo KK.

Isoolefin / paraalkylstyrene interpolymers, such as isobutylene and a para-alkylstyrene comonomer, which are random copolymers of C4-C7, C4 to C7 isomonoolefin, include para-methylstyrene interpolymer blend components, preferably containing at least 80 weight percent, more preferably at least 90 weight percent para isomers. It is located. These interpolymers include benzene halogenoxide, phenoxide, carboxylate, thiolate, thioether, thiocarbamate, dithiocarbamate, thiourea, xanthate, cyanide, malonate, amine, amide, carbazole, phthalimide, cyanide, and and other functional groups such as halogenated or other functional groups which are introduced by nucleophilic substitution with other groups such as mixtures thereof.

Preferred materials can be characterized as isobutylene interpolymers containing the following monomer units arranged at random intervals along the polymer chain:

52 494 The interpolymers of isomonoolefin and the method for their preparation are described in particular in US Patent 5,162,445.

The most useful of these functionalizing materials are elastomeric, random isobutylene and para-methylstyrene interpolymers containing 0.5 to 20 mole percent para-methylstyrene, of which up to 60 mole percent of the methyl substituent groups on the benzyl ring contain a bromine or chlorine atom, preferably a bromine atom. These polymers have a substantially homogeneous composition distribution such that at least 95 percent by weight of the polymer has a para-alkylstyrene content within 10 percent of the average para-alkylstyrene content of the polymer. More preferred polymers have a narrow molecular weight distribution (M) of less than 5, more preferably less than 2.5._w(Mn) is characterized by a preferred viscosity average molecular weight in the range of 200,000 to 2,000,000 and a preferred numerical average molecular weight in the range of 25,000 to 750,000 as determined by Gel Permeation Chromatography.

The interpolymers can be prepared by slurry polymerization of the monomer mixture using a Lewis Acid catalyst followed by halogenation in solution, preferably bromination, in the presence of halogen and a radical initiator such as heat and / or light and / or a chemical initiator.

Brominated interpolymers containing from 0.1 to 5 mole percent of bromomethyl groups, most of which are monobromomethyl, are also preferred, usually less than 0.05 mole percent dibromomethyl substituents in the copolymer. More preferred interpolymers contain from 0.05 to 2.5 weight percent, preferably from 0.05 to 0.75 weight percent bromine based on the weight of the interpolymer and are substantially free of ring halogen or halogen in the polymer backbone chain. Such interpolymers, methods of preparing them, vulcanization and inoculation methods and the functionalized polymers obtained therefrom are described in particular in the aforementioned US Pat. No. 5,162,445. These interpolymers are commercially available.

Exxpro ™ Specialty Elastomers from Exxon Chemical.

Vinyl Halide Homopolymers and Copolymers

Vinyl halide homopolymers and copolymers are a group of resins using the vinyl structure CH2 = CXY as building blocks; wherein XF is selected from the group consisting of Cl, Br, and 1, and YF is selected from the group consisting of Cl, Br, I, and H.

The vinyl halide polymer component of the blends of the present invention includes homopolymers and copolymers of vinyl halides with copolymerizable monomers such as α-olefins,

52 494 for example, but not limited to ethylene, propylene, vinyl esters of organic acids containing from 1 to 18 carbon atoms, such as vinyl acetate, vinyl stearate, and the like; vinyl chloride, vinylidene chloride, symmetric dichloroethylene; acrylonitrile, methacrylonitrile; alkyl acrylate esters wherein the alkyl group contains from 1 to 8 carbon atoms such as methyl acrylate and butyl acrylate; the corresponding alkyl methacrylate esters; dialkyl esters of dibasic organic acids wherein the alkyl groups contain 1-8 carbon atoms, such as dibutyl fumarate, diethyl maleate and the like.

Preferably, the vinyl halide polymers are homopolymers or copolymers of vinyl chloride or vinylidene chloride. Poly (vinyl chloride) polymers (PVC) can be divided into two main groups according to their degree of hardness. These are “rigid” PVC and “flexible” PVC. Flexible PVC differs from rigid PVC mainly by the presence and quantity of plasticizers in the resin. Flexible PVC typically has better machinability, lower tensile strength and higher elongation than rigid PVC.

Of the vinylidene chloride homopolymers and copolymers (PVDC), copolymers with vinyl chloride, acrylates or nitriles are typically used commercially and are most preferred.

The choice of comonomer significantly affects the properties of the polymer obtained. Perhaps the most prominent features of various PVDCs are their low gas and liquid permeability, their barrier properties; and chemical resistance.

Various PVC and PVCD formulations containing trace amounts of other materials to alter the properties of PVC or PVCD are also within the scope of the invention; these include, but are not limited to, polystyrene, styrenic polymers, polyolefins and other ethylene / α-olefin copolymers, including homo and copolymers containing polyethylene and / or polypropylene, polyacrylic resins, butadiene-containing polymers such as acrylonitrile butadiene styrene terpolymers (ABS) and methacrylate. butadiene styrene terpolymers (MS) and chlorinated polyethylene (CPE) resins.

The family of vinyl halide polymers for use as blend components of the present invention also include chlorinated PVC derivatives known as chlorinated PVC (CPVC), typically prepared by final chlorination of the base resin. Although CPVC is based on PVC and shares some of its characteristics, CPVC is a unique polymer with a much higher melting temperature range (410-450 ° C) and a higher glass transition temperature (11530 135 ° C) than PVC.

52494

plasticizers

Extensive information is available on the plasticization of PVC and it is generally known that many thermoplastics can be plasticized. With regard to this type of technology, see, e.g. “Plasticizers” in Modem Plastics Encyclopedia, October 1988, Vol. 11, pp. 180-184, McGraw Hill, 1989. Typical families of plasticizers, depending on the type of polymer, include phosphoric acid derivatives, phthalic acid derivatives, trimellitate esters, benzoates, adipate esters, epoxy compounds, phosphate esters, glutarates and mineral oils. On the basis of molecular weights, plasticizers are classified as “monomeric ları or“ polymeric ”. Compared to monomeric plasticizers, polymeric plasticizers generally exhibit higher persistence, lower compatibility and lower plasticization efficiency. Plasticizers can be classified as “primary er if they have high compatibility with a particular polymer or“ secondary er if they have a lower compatibility. Mixtures of two types of plasticizers can be used to achieve cost / performance balances. Suitable modifiers that can be used as the plasticizing component (C) include at least one plasticizer selected from the group consisting of phthalate esters, trimellitate esters, benzoates, adipate esters, epoxy compounds, phosphate esters (triaryl, trialkyl, mixed alkyl aryl phosphates), glutarates and oils. .

Particularly suitable phthalate esters include, for example, diethyl, dibutyl phthalate, diisobutyl phthalate, butyl2-ethylhexyl phthalate, dioctyl phthalate, diisooctyl phthalate, dinonine phthalate, diisonyl phthalate, didecyl phthalate, diisodecyl phthalate, dialkyl phthalate, diundecyl phthalate di (n-hexyl, n-octyl, n-decyl) phthalate (P610), di (n-octyl, mixed aliphatic esters such as n-decyl) phthalate (P810); and aromatic phthalate esters such as diphenyl phthalate ester; or mixed aliphatic-aromatic esters such as benzyl butyl phthalate, or any combination thereof.

Additives

Antioxidants (eg hindered phenols such as Irganox (R) 1010), phosphites (and Irgafos (R) 168 of wax) (both are registered trademarks and supplied by Ciba-Geigy Corporation, NY), UV additives such as stabilizers, adhesion additives (eg polyisobutylene), antiblock additives, colorants, pigments, fillers can also be included in the interpolymers used in the present invention and / or blends to the extent that they do not interfere with the improved properties of the present invention.

52494

The additives are used in functionally equivalent amounts known to those skilled in the art. For example, the amount of antioxidant used is the amount that prevents the polymer or polymer blend from oxidizing in the temperatures and environment used during storage and final use of the polymers. This amount of antioxidant is generally in the range of 0.01 to 10, preferably 0.05 to 5, more preferably 0.1 to 2 weight percent based on the weight of the polymer or polymer blend. Similarly, the amount of any of the additives listed is functionally equivalent, such as the amount required to antiblock the polymer or polymer blend, produce the desired amount of filler loading to achieve the desired result, colorant or amount required to obtain the desired color from the pigment. These additives are suitable for use in the range of 0.05 to 50 weight percent, preferably 0.1 to 35 weight percent, more preferably 0.2 to 20 weight percent based on the weight of the polymer or polymer blend. In the case of fillers, however, they can be used in amounts up to 90 percent by weight, based on the weight of the polymer or polymer blend. Additives such as fillers also play a role in the aesthetics of the final product by providing a glossy or matte finish.

Final Blend Combinations

The compositions of the present invention can be melt-blended or compounded in the extruder or rolling mill used to dry the individual components and then directly to make the finished product (e.g., the automotive part), or to pre-melt the melt in a separate extruder or rolling mill (eg a Banbury mixer). including any suitable method.

Thermoforming and various injection molding processes (eg, Modem Plastics Encyclopedia / 89 October 1988, Vol. 65, which may be used to form products or articles useful therefrom from the compositions herein).

Number 11, p. 264-268, "Introduction to Injection Molding" and p. 270-271, &amp; quot; Injection Molding Thermoplastic &amp; quot; and injection molding processes (e.g., Modern Plastics Encyclopedia / 89 October 1988, Vol. 65, Issue 11, p. 217-218, &amp; quot; Extrusion-Blow Molding &amp; quot;); There are many types of molding process including profile extrusion. In addition, direct blending to produce sheets and films and final part forming in a single melt processing process can be mentioned. Products manufactured include sports equipment, food containers or other household products, shoes and automotive products, such as soft instrument panel coating. This

52 494 The compositions of the invention may be selected to control part aesthetics, such as gloss or matt appearance, together with the final part formation process.

The compositions of the present invention can also be used in plastisols or waxes, wherein the polymer component is dispersed in a fluid of the plasticizer. Additional components such as viscosity modifiers, diluents or thickeners may also be used to control rheology. The final formulations may also include stabilizers and fillers such as calcium carbonate, clays, kieselguhr, barites, silica, mica and talc to control properties and aesthetics. These plastisols or pastes can be used in a variety of applications such as, but not limited to, shaped products such as toys, gaskets, films and sheets, as coatings on polymeric substrates, paper, leather, cloth, and as inorganic building materials and as foams for heat, sound and vibration damping. have. Plastisols can be applied by dipping, rotating casting, spraying systems and manual molding.

Properties of Individual Blend Components and Final Blend Compositions

a) Ethylene / Vinyl or Vinylidene Aromatic or Blocked Vinyl or Vinylidene Interpolymers

Interpolymers comprising one or more α-olefins and one or more vinyl or vinylidene aromatic monomers and / or one or more hindered aliphatic or cycloaliphatic vinyl or vinylidene monomers used in the present invention are substantially random polymers. These interpolymers are generally from 0.5 to 65 percent, preferably from 1 to 55, more preferably from 2 to 50 mole of at least one vinyl or vinylidene aromatic monomer and / or hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer, and from 35 to 99.5 percent, preferably 45 to 99, more preferably 50 to 98 moles of at least one aliphatic α-olefin having 2 to 20 carbon atoms.

The number average molecular weight (M „) of these interpolymers is generally greater than about 1,000, preferably from about 5,000 to about 1,000,000, more preferably from about 10,000 to about 500,000.

The melt index (I2) of the interpolymer (s) applicable to the present invention is from 0.01 to 1000, preferably from 0.1 to 100, more preferably from 0.5 to 30 g / 10 minutes.

The polydispersity ratio of the interpolymer (s) applicable to the present invention is M_w/ M „1.5 to 20, preferably

1.8 to 10, more preferably 2 to 5.

52494

When preparing the substantially random interpolymer, some homopolymer may be formed, for example due to homopolymerization of the vinylaromatic monomer at elevated temperatures. The presence of vinyl aromatic homopolymer is generally not detrimental to the purposes of the present invention and can be tolerated. The vinyl aromatic homopolymer may be separated from the interpolymer, if desired, by extraction techniques such as selective precipitation from the solution with a nonsolvent for the interpolymer or vinyl aromatic homopolymer. For purposes of the present invention, it is preferred that no more than 20 weight percent, preferably no more than 15 weight percent atactic vinyl aromatic homopolymer, based on the total weight of the interpolymers, is present.

b) Vinyl Halide Polymer

The blends were prepared using both flexible and rigid PVC. 55 and 80 Shore A hardness samples were prepared for blends containing flexible PVC. The molecular weight of PVC is usually expressed by a K value or viscosity number, which is in the range of 50 to 80. The higher the K value, the higher the molecular weight. Typical MWD for PVC (M_wM) 2.0 to 2.5. The table below shows the correlation between K value and Mn.

kM_n —28,000

-80,000

c) Final Blend Compositions

The blends comprise from 1 to 99 weight percent, preferably from 5 to 95 weight percent, more preferably from 10 to 90 weight percent of at least one substantially random interpolymer.

The blends further comprise 1-99 weight percent, preferably 5 to 95 weight percent, more preferably 10 to 90 weight percent of at least one vinyl chloride polymer.

The blends further comprise 0-70 weight percent, preferably 5 to 50 weight percent, more preferably 10 to 40 weight percent of at least one plasticizer.

The following examples are intended to illustrate the invention without limiting the scope of the invention in any way.

EXAMPLES

Test Methods

a) Density and Melt Flow Measurements.

52494

The density of the polymer compositions for use in the present invention was measured according to ASTM D-792. The molecular weight of the polymer compositions for use in the present invention was conveniently demonstrated by a melt index measurement determined according to ASTM D1 238, Condition 190 ° / 2.16 kg (officially known as "Condition (E)" and also known as I2).

b) ⁿC-NMR Chemical Shifts:

The interpolymers disclosed are carbon¹³ The following procedures and conditions were used to determine NMR chemical shifts. Five to ten weight percent polymer solutions were prepared in a mixture of 50 volume percent 1,1,2,2-tetrachloroethane-d2 and 50 volume percent 1,2,4-trichlorobenzene in 0.10 molar chromium tris (acetylacetonate). NMR spectra were taken at 130 ° C using a reverse-gated decoupling sequence with a pulse width of 90 ° and a pulse delay of five seconds or more. The spectra were referenced to the isolated methylene signal assigned at 30,000 ppm.

c) Part Preparation and Testing Procedures:

The P610 plasticizer was obtained from CP HalT. P610 is a mixed linear dialkyl (hexyl, octyl, decyl) phthalate ester having a molecular weight of 400.

d) Compression molding:

The samples were melted at 190 ° C for 3 minutes and molded by compression at 190 ° C under a pressure of 20,000 lb for a further 2 minutes. The molten materials were then quenched in a press equilibrated at room temperature.

e) Differential Scanning Calorimetry (DSC):

A DuPont DSC2210 was used to measure the thermal transition temperatures and transition temperature for the samples. To eliminate the previous thermal history, the samples were first heated to 160 ° C. The heating and cooling curves were recorded at 10 ° C / min. Melting (second heat t_m) and crystallization (t_c) temperatures were recorded from the peak temperatures of endotherm and exotherm, respectively.

f) Dynamic Mechanical Spectroscopy (DMS):

The dynamic mechanical properties of the compression-compressed samples were monitored using a Rheometrics 800E mechanical spectrometer. Samples were run in solid state torsional rectangular geometry and purged under nitrogen to prevent thermal degradation. In general, the samples were cooled to -100 ° C and a force of 0.05 percent.

52 494 Done. The vibration frequency was fixed at 10 rad / s and the temperature was raised in 5 ° C increments.

g) Mechanical Testing:

Tensile properties of compression molded samples were measured using an Instron 1145 tensile machine. ASTM-D638 (microdraw) samples were tested at a cross-rate of 5 in / min. The data given were the average of four tensile measurements. The standard deviation for the final properties was typically 10 percent of the reported mean value. Yield stress (ob, MPa) and tensile strength (σ, MPa) and Young's Modulus (E, MPa) at the bend point of the stress deformation curve were measured.

h) Tensile stress relaxation:

Uniaxial tensile stress relaxation was evaluated using an Instron 1145 tensile machine. Compression molded film with a tensile length of 10 mils (~ 20 mil thickness) 20 minutes'¹ deformation rate to a stress level of 50 percent. The force required to maintain 50 percent elongation was monitored for 10 minutes. The stress relaxation magnitude Sr is defined as the percentage = (fiff / fi) x 100, where f is the initial force and ff is the final force,

i) Thermal Mechanical Analysis:

The upper service temperature (TMA (1mm)) was determined from the thermal mechanical analyzer (Perkin Elmer TMA 7 series) scanned at 5 ° C / min and with a load of 1 Newton and defined as the point at which the probe enters the sample 1 mm.

Individual Blend Components ESI # 1 Preparation

ESI # 1 is a substantially random ethylene styrene interpolymer containing 74 weight percent styrene and 26 weight percent ethylene (based on the weight of substantially random ethylene styrene interpolymer) and 9 weight percent of actactic polystyrene (based on the combined weight of substantially random ethylene styrene interpolymer and atactic polystyrene) . The interpolymer was prepared in a 400 gallon (1512 L) agitated semi-continuous batch reactor. The reaction mixture consisted of a mixture of about 250 gallons (6660 L) of cyclohexane (85 weight percent) and isopentane (15 weight percent) and a solvent containing styrene. Prior to the addition, the solvent, styrene and ethylene were purified to remove water and oxygen. The inhibitor in styrene was also removed. The inert materials were removed by washing the vessel with ethylene. Then the pressure of the container

52 494 ethylene to a set point. Hydrogen was added to control the molecular weight. The temperature in the vessel was brought to the set point by changing the jacket water temperature on the vessel. Prior to polymerization, the vessel was heated to the desired operating temperature and the catalyst components titanium: (Ν-1,1-dimethylethyl) -dimethyl (1- (1,2,3,4,5-eta) -2,3,4,5-tetramethyl -2,45 cyclopentadien-1-yl) silanaminato) (2-) N) -dimethyl, (CAS # 13 5072-62-7), tris (pentafluorophenyl) boron, (CAS # 001109-15-5) and modified flow control of methylaluminoxane Type 3A (CAS # 146905-79-5) (based on a 1/3/5 mol ratio, respectively) was combined and added to the vessel. After initiation of polymerization, ethylene was added to the reactor as needed to maintain vessel pressure and allowed to proceed. In some cases, hydrogen was added to the headspace of the reactor to maintain a mole ratio relative to the ethylene concentration. At the end of the application, the catalyst flow was stopped, the ethylene was removed from the reactor, then 1000 ppm of Irganox * 1010 antioxidant was added to the solution and the polymer was isolated from the solution by steam stripping in a vessel or using an evaporative removal extruder. In the case of steam stripped material, additional treatment was required on an extruder-like equipment to reduce residual moisture and unreacted styrene.

ESI # 2 Preparation

ESI # 2 was applied to the conditions in Table 1 containing 27 weight percent styrene and 73 weight percent ethylene (based on the weight of the substantially random ethylene styrene interpolymer) and 1 weight percent of the austic polystyrene (based on the combined weight of the substantially random ethylene styrene interpolymer and the atactic polystyrene). is a substantially random ethylene styrene interpolymer prepared essentially as described for ESI # 1.

Table 1

<td rowspan="2">Single Component</td><td colspan="2">uploads solvent</td><td colspan="2">uploads styrene</td><td colspan="2">Pressure</td><td>Temp.</td><td>Added h₂</td><td>Work Time</td><td>the solution Polymer</td>

<td>lb</td><td>kg</td><td>lb</td><td>kg</td><td>psig</td><td>kPa</td><td>° C</td><td>Gram</td><td>Hour</td><td>Heavy, percent</td>

<td>ESI # 1</td><td> 252</td><td> 114</td><td> 1320</td><td> 599</td><td> 42</td><td> 290</td><td> 60</td><td> 0</td><td> 2.8</td><td> 11.5</td>

<td>ESI # 2</td><td> 1196</td><td> 542</td><td> 225</td><td> 102</td><td> 70</td><td> 483</td><td> 60</td><td> 7.5</td><td> 6.1</td><td> 7.2</td>

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Table 1 continued

<td>Single Component</td><td>Melting Index g / lom</td><td>Styrene of polymer total weight percentage</td><td>Percentage by weight as talc level</td><td>Insulation Method</td>

<td>ESI # 1</td><td> 0.18</td><td> 81.7</td><td> &lt;2.5</td><td>Steam peeling</td>

<td>ESI # 2</td><td> 0.03</td><td> 29.8</td><td> 0</td><td>extruder</td>

ESI # 3 Preparation

ESI # 3 was prepared as described below, under the conditions of Table 2, 73 weight percent styrene and 27 weight percent ethylene (based on the weight of the substantially random ethylene styrene interpolymer) and 9 weight percent of the atactic polystyrene (substantially random ethylene styrene interpolymer and atactic polystyrene). is a substantially random ethylene styrene interpolymer containing a weight based on its combined weight). Catalyst (dimethyl [N- (1,1-dimethylethyl) -1,1-dimethyl] - [(1,2,3,4,5-p) -1,6,6,7-tetrahydro-3-phenyl-s -indaken-1-yl] silanaminato (2 -) - N-titanium).

Preparation of 3,5,6,7-Tetrahydro-s-Hydrindaken-1 (2H) -one.

Indan (94.00 g, 0.7954 mol) and 3-chloropropionyl chloride (100.99 g, 0.7954 mol) were stirred in CH 2 Cl 2 (300 mL) at 0 ° C, while the AlCl 3 (130.00 g, 0.9750 mol) was slowly added under a stream of nitrogen. It was. The mixture was then allowed to stir at room temperature for 2 hours. Volatiles were then removed. The mixture was cooled to 0 ° C and concentrated H 2 SO 4 (500 mL) was added slowly. Since mixing was left early in this step, the resulting solid had to be broken frequently with a spatula. The mixture was then left under nitrogen at room temperature overnight. The mixture was heated until the temperature reached 90 ° C. These conditions were maintained for 2 hours, while a spatula was periodically used to stir the mixture. After the reaction time, crushed ice was added to the mixture and rotated.

The mixture was then taken into a beaker and washed intermittently with H 2 O and diethylether, then the fractions were filtered and combined. The mixture was washed with H 2 O (2 x 200 mL). The organic layer was separated and the volatiles were removed. The desired product was isolated as pale yellow crystals by recrystallization from hexane at 0 ° C (22.36 g, 16.3 percent yield).

1 H NMR (CDCl 3): d2.04-2.19 (m, 2H), 2.65 (t, ³Jhii = 5.7 Hz, 2H), 2.84-3.0 (m, 4H), 3.03 (t, ³Jhh = 5.5 Hz, 2H), 7.26 (s, 1H), 7.53 (s, 1H).

52494 ¹³C NMR (CDCl 3)₃); d25.71, 26.01, 32.19, 33.24, 36.93, 118.90, 122.16, 135.88, 144.06, 152.89, 154.36, 206.50.

GC-MS: Calcd for C12H12O 172.09, found 172.05.

1,2,3,5, -Tetrahydro-7-phenyl-s-indaken.

3,5,6,7-Tetrahydro-s-Hydrindaken-1 (2H) -one (12.00 g, 0.06967 mol) was stirred at 0 ° C in diethylether (200 mL), while PhMgBr (0.15 mol, 35.00 mL, (3.0 M solution in diethyl ether) was added slowly. After the reaction period, the mixture was quenched by pouring on ice. The mixture was then acidified (pH = 1) with HCl and stirred vigorously for 2 hours. The organic layer was separated, washed with H 2 O (2 x 100 mL) and dried over MgSO 4. After filtration, the volatiles were removed and the desired product was isolated as a dark oil (14.68 g, 90.3 percent yield).

1 H NMR (CDCl 3); d2.0-2.2 (m, 2H), 2.8-3.1 (m, 4H), 6.54 (s, 1H), 7.2-7.6 (m, 7H). GC-MS. Calcd for C18H16 232.13, found 232.05.

1.2.3.5. Preparation of tetrahydro-7-phenyl-s-indaken, dilithium salt.

1.2.3.5-Tetrahydro-7-phenyl-s-indaken (14.68 g, 0.06291 mol) was stirred in hexane (150 mL) while nBuLi (0.080 mol, 40.00 mL, 2.0 M solution in cyclohexane) was slowly added. The mixture was then allowed to stir overnight. At the end of the reaction time, the solid was collected by suction filtration as a yellow solid, which was washed with hexane, dried under vacuum and used without further purification or analysis (12.2075 g, 81.1 percent yield).

Chlorodimethyl (1,6,6,7-tetrahydro-3-phenyl-s-indacen-1-yl) silane preparation.

1,2,3,5-Tetrahydro-7-phenyl-s-indakene, dilithium salt (12.2075 g, 0.05102 mol) in THF (50 mL) was added dropwise at 0 [deg.] C. in a Me2SiCl2 (19.5010). g,

0.1511 mol). After the reaction period, the volatiles were removed and the residue was extracted using hexane and filtered. Removal of the hexane resulted in the isolation of the desired product as a yellow oil (15.1492 g, 91.1 percent yield).

1 H NMR (CDCl 3): δ 0.33 (s, 3H), 0.38 (s, 3H), 2.20 (p, ³JHh = 7.5 Hz, 2H), 2.9-31 (m, 4H), 3.84 (s, 1H), 6.69 (d, ³JHh = 2.8 Hz, 1H), 7.3-7.6 (m, 7H), 7.68 (d, ³J_HH = 7.4 Hz, 2H).

¹³C NMR (CDCl3): d0.24, 0.38, 26.28, 33.05, 33.18, 46.13, 116.42, 119.71, 127.51,

128.33, 128.64, 129.56, 136.51, 141.31, 141.86, 142.17, 142.41, 144.62.

52494

GC-MS: Calculated for C20H21ClS1 324.11, found 324.05.

N- (1,1-Dimethyl ethyl) -1,1-dimethyl-1- (1,5,6,7-tetrahydro-3-phenyl-s-indacen-1-yl) silanamine.

Chlorodimethyl (1,6,6,7-tetrahydro-3-phenyl-s-indaken-1-yl) silane (10.8277 g, 0.03322 mol) was stirred in hexane (150 mL) while NEt3 (3.5123 g, 0.03471 mol) and t-butylamine (2.6074 g, 0.03565 mol) was added. This mixture was allowed to stir for 24 hours. After the reaction time the mixture was filtered and the volatiles were isolated to give the desired product as a dark, red-yellow oil (10.6551 g, 88.7 percent yield).

1 H NMR (CDCl 3): d0.02 (s, 3H), 0.04 (s, 3), 1.27 (s, 9H), 2.16 (p, ³JHh = 7.2 Hz, 2H), 2.9-3.0 (m, 4H), 3.68 (s, 1H), 6.69 (s, 1H), 7.3-7.5 (m, 4H), 7.63 (d, ³JHh = 7.4 Hz, 2H). ¹³C NMR (CDCl3): d-0.32, -0.09, 26.28, 33.39, 34.11, 46.46, 47.54, 49.81, 115.80, 119.30, 126.92, 127.89, 128.46, 132.99, 137.30, 140.20, 140.81, 141.64, 142.08, 144.83.

Preparation of N- (1,1-dimethylethyl) -1,1-dimethyl-1- (1,5,6,7-tetrahydro-3-phenyl-s-indacen-1-yl) silanamine, dilithium salt.

N- (1,1-dimethylethyl) -1,1-dimethyl-1- (1,5,6,7-tetrahydro-3-phenyl-s-inden-1-yl) silanamine (10.6551 g, 0.02947 mol) ) in hexane (100 mL), while nBuLi (0.070 mol, 35.00 mL, 2.0 M solution in cyclohexane) was slowly added. This mixture was allowed to stir overnight, at which time no salt precipitated from the dark red solution. Reaction time time ended, the volatiles were removed and the residue was washed rapidly with hexane (2 x 50 mL). The dark red residue was then pumped dry and used without further purification or analysis (9.6517 g, 87.7 percent yield).

Dichloro [N- (1,1-dimethylethyl) -1,1-dimethyl-1 - [(1,2,3,4,5-η) -1,5,6,7-tetrahydro-3-phenyl-syndaquinene -1-yl] silanaminato (2 -) - N] titanium preparation.

N- (1,1-Dimethylethyl) -1,1-dimethyl-1- (1,6,6,7-tetrahydro-3-phenyl-syndacen-1-yl) silanamine, dilithium salt in THF (50 mL) 4.5355 g, 0.01214 mol) was added dropwise to a slurry of TiCl 3 (THF) 3 (4.5005 g, 0.01214 mol) in THF (100 mL). This mixture was allowed to stir for 2 hours. PbCl2 (1.7136 g, 0.006162 mol) was added and the mixture was allowed to stir for an additional hour. After the reaction time ended, the volatiles were removed and the residue was extracted using toluene and filtered. Removal of the toluene resulted in the isolation of a dark residue. This residue was slurried in hexane and cooled to 0 ° C. The desired product was then isolated by filtration as a red-brown crystalline solid (2.5280 g, 43.5 percent yield).

52 494 1 H NMR (CDCl 3): d0.71 (s, 3H), 0.97 (s, 3H), 1.37 (s, 9H), 2.0-2.2 (m, 2H), 2.9-3.2 (m, 4H), 6.62 ( s, 1H), 7.35-7.45 (m, 1H), 7.50 (t, ³JHh = 7.8 Hz, 2H), 7.57 (s, 1H), 7.70 (d, ³JHH = 7.1 Hz, 2H), 7.78 (s, 1H).

^]1 H NMR (C6D6): d 0.44 (s, 3H), 0.68 (s, 3H), 1.35 (s, 9H), 1.6-1.9 (m, 2H), 2.5-3.9 (m, 4H), 6.65 ( s, 1H), 7.1-7.2 (m, 1H), 7.24 (t, ³J_Hh = 7.1 Hz, 2H), 7.61 (s, 1H), 7.69 (s, 1H), 7.77-7.8 (m, 2H).

¹³C NMR (CDCl3): d, 29, 3.89, 26.47, 32.62, 32.84, 32.92, 63.16, 98.25, 118.70, 121.75, 125.62, 128.46, 128.55, 128.79, 129.01, 134.11, 134.53, 136.04, 146.15, 148.93.

¹³C NMR (C)₆D₆): d0.90,3.57, 26.46, 32.56, 32.78, 62.88, 98.14, 119.19, 121.97, 125.84, 127.15, 128.83, 129.03, 129.55, 134.57, 135.04, 136.41, 136.51, 147.24, 148.96.

Dimethyl [N- (1,1-dimethylethyl) -1,1-dimethyl-1 - [(1,2,3,4,5-η) -1,5,6,7-tetrahydro-3-phenyl-syndacene Preparation of 1-yl] silanaminato (2 -) - N] titanium.

Dichloro [N- (1,1-dimethylethyl) -1,1-dimethyl-1 - [(1,2,3,4,5-η) -1,5,6,7-tetrahydro-3-phenyl-syndaquinene -1-yl] silanaminato (2 -) - N] titanium (0.4970 g, 0.001039 mol) was stirred in diethylether (50 mL) while MeMgBr (0.0021 mol, 0.70 mL, 3.0 M solution in diethylether) was slowly added. The mixture was then stirred for 1 hour. After the reaction period, the volatiles were removed and the residue was extracted using hexane and filtered. Removal of the hexane resulted in the isolation of the desired product as a golden yellow solid (0.4546 g, 66.7 percent yield).

1 H NMR (C₆D₆): d0.071 (s, 3H), 0.49 (s, 3H), 0.70 (s, 3H), 0.73 (s, 3H), 1.49 (s, 9H), 1.71.8 (m, 2H), 2.5- 2.8 (m, 4H), 6.41 (s, 1H), 7.29 (t, ³J_HH = 7.4 Hz, 2H), 7.48 (s, 1H), 7.72 (d, ³Jhh = 7.4 Hz, 2H), 7.92 (s, 1H).

¹³C NMR (C)₆D₆): d2.19, 4.61, 27.12, 32.86, 33.00, 34.73, 58.68, 58.81, 118.62, 121.98, 124.26, 127.32, 128.63, 128.98, 131.23, 134.39, 136.38, 143.19, 144.85. Preparation of cocatalyst (bis (hydrogenated-tallowalkyl) methylamine) (B-FABA).

Methylcyclohexane (1200 mL) was placed in a 2 L cylindrical flask. With stirring, bis (hydrogenated-tallowalkyl) methylamine (ARMEEN® M2HT, 104 g, crushed) was added to the flask and stirred until completely dissolved. Aqueous HCl (IM,

200 mL) was added to the flask and the mixture was stirred for 30 minutes. A white precipitate formed immediately. At the end of this time, the flask had LiB (C6F5) 4-Et2O-3 LiCl Mw = 887.3; 177.4 g). The solution began to turn milky white. The flask is provided with a 23

52494

The 6 ”Vigreux column was installed and the mixture was heated (140 ° C outside wall temperature). A mixture of ether and methylcyclohexane was distilled from the flask. The biphasic solution was only slightly foggy. The mixture was allowed to cool to room temperature and the contents were placed in a 4 L separatory funnel. The aqueous layer was removed and discarded and the organic layer was washed twice with H 2 O and the aqueous layers were again discarded. The H10 saturated methylcyclohexane solutions were measured to contain 0.48 weight percent diethyl ether (Et10).

The solution (600 mL) was transferred to a 1 L flask, sparged with nitrogen well and transferred to dry box. The solution was passed through a column containing 13X molecular sieves (1 ”diameter, 6” height). This reduced the level of Et 10 from 0.48 weight percent to 0.28 weight percent. The material was then stirred on fresh 13X sieves (20 g) for four hours. It was then determined that the measured Et 10 level was 0.19 percent by weight. The mixture was then stirred overnight to reduce the Et 10 level to approximately 40 ppm. The mixture was filtered using a funnel equipped with a frit with a pore size of 10-15 (m to give a clear solution (molecular sieves were rinsed with additional dry methylcyclohexane). The concentration was measured by gravimetric analysis to obtain a value of 16.7 percent by weight.

polymerization

ESI # 3.6 gallons (22.7 L) was prepared in an oil jacketed Autoclave continuously stirred tank reactor (CSTR). Mixing was performed with a magnetically coupled stirrer with Lightning A-320 propellers. The reactor was complete liquid at 475 psig (3,275 kPa). Process flow entered from the bottom and output from the top. The heat transfer oil was circulated through the liner of the reactor to remove some of the reaction heat. At the outlet of the reactor there was a micro-motion flowmeter that measures flow and solution density. All lines on the outlet of the reactor were drawn with 50 psi (344.7 kPa) steam and isolated.

Ethylbenzene solvent was introduced into the reactor at 30 psig (207 kPa). The feed to the reactor was measured with a MicroMotion mass flow meter. A variable speed diaphragm pump controlled the feed rate. At the outlet of the solvent pump, a side stream was taken to provide flow streams for the catalyst injection line (1 lb / h (0.45 kg / h)) and the reactor stirrer (0.75 lb / h (0.34 kg / h). microflow needle valves were controlled by manual adjustment. Unblocked styrene monomer was fed to the reactor at 30 psig (207 kpa). The feed to the reactor was measured with a Micro-Motion mass flow meter. A variable speed diaphragm pump controlled the feed rate. Styrene flows remaining

52 494 solvent stream. Ethylene was introduced into the reactor at 600 psig (4,137 kPa). The ethylene stream was measured with a Micro-Motion mass flow meter immediately before a Research valve that controlled the flow. A Brooks flowmeter / controller was used to deliver hydrogen to the ethylene stream at the outlet of the ethylene control valve. The ethylene / hydrogen mixture combines with the solvent-styrene stream at ambient temperatures. When entering the reactor, the solvent / monomer temperature was reduced to ~ 5 ° C by a exchanger containing -5 ° C glycol on the jacket. This current went through the bottom of the reactor. The three-component catalyst system solvent flow also entered the reactor through the bottom, but through a gate different from the monomer stream. The catalyst components were prepared in an inert atmosphere instrument chamber.

The diluted components were placed in nitrogen-reinforced cylinders and loaded into the catalyst operating tanks at the process site. From these operating tanks, the catalyst was pressurized up with piston pumps and the flow was measured by Micro-Motion mass flowmeters. These currents combine with each other and the catalyst flushing solvent just before entering the reactor through a single injection line.

The polymerization was stopped by adding catalyst kill (water mixed with solvent) to the reactor product line after measuring the microprocessing flowmeter solution density. Other polymer additives may be added together with the catalyst killer. A static mixer in the line provided the dispersion of the catalyst kill and additives in the waste stream of the reactor. This stream then entered post-reactor heaters providing additional energy for the solvent removal stream. This stream occurred when the effluent exited the post-reactor heater and the pressure dropped from 475 psig (3,275 kPa) to an absolute pressure of ~ 250 mmn in the reactor pressure control valve. This flowing polymer entered a hot oil jacketed evaporator. Approximately 85 percent of the volatiles were removed from the polymer in the evaporator. The volatiles came out of the evaporator. The stream was condensed with a glycol jacketed heat exchanger and entered the suction section of a vacuum pump and discharged into a glycol jacketed solvent and styrene / ethylene separation vessel. Solvent and styrene came out from the bottom of the vessel and ethylene. The ethylene stream was measured with a Micro-Motion mass flow meter and analyzed for composition. To calculate the ethylene conversion, the measurement of aerated ethylene plus the calculation of the dissolved gases in the solvent / styrene stream were used. The polymer separated in the evaporator was pumped to a ZSK-30 evaporator vacuum vacuum extruder with a gear pump. The dry polymer exited the extruder as a single twist. This strand was cooled while being drawn from a water bath. Excess water was blown from the twist with air and the twist was cut into pellets with a twist slitter.

52494

ESI # 4 Preparation

ESI # 4, 72 percent by weight styrene and 28 percent by weight ethylene (based on the weight of the substantially random ethylene styrene interpolymer) and 3 percent by weight of the actic polystyrene (substantially random ethylene styrene interpolymer) as described for ESI # 3 under the conditions in Table 2. and based on the weight of the atactic polystyrene).

Preparation of ESI # 5

ESI # 5, 57 percent by weight styrene and 43 percent by weight ethylene (based on the weight of the substantially random ethylene styrene interpolymer) and 3 percent by weight of the polystyrene (substantially random ethylene styrene interpolymer) as described for ESI # 3 under the conditions in Table 2. and based on the weight of the atactic polystyrene).

Preparation of ESI # 6

ESI # 6, 20 percent by weight styrene and 80 percent by weight ethylene (based on the weight of the substantially random ethylene styrene interpolymer) and 8 percent by weight of the austolic polystyrene (substantially random ethylene styrene interpolymer) as described for ESI # 3 under the conditions in Table 2. and based on the weight of the atactic polystyrene).

ESI # 7 Preparation

ESI # 7 is essentially 20 percent by weight styrene and 80 percent by weight ethylene (based on the weight of the substantially random ethylene styrene interpolymer) and 8 percent by weight of the austolic polystyrene (substantially random ethylene styrene interpolymer) as described for ESI # 3 under the conditions in Table 2. and based on the weight of the atactic polystyrene).

ESI # 8 Preparation

ESI # 8, 57.7 weight percent styrene and 40 weight percent ethylene (based on the weight of the substantially random ethylene styrene interpolymer) and 3.1 weight percent polystyrene (substantially random ethylene styrene interpolymer) substantially as described for ESI # 3 under the conditions in Table 2. and based on the weight of the atactic polystyrene).

52494

Preparation of ESI # 9

ESI # 9 is 73.3 weight percent styrene and 26.7 weight percent ethylene (based on the weight of the substantially random ethylene styrene interpolymer) and 8.6 percent by weight of the polystyrene (substantially random ethylene styrene interpolymer) as described for ESI # 3 under the conditions in Table 2. and based on the weight of the atactic polystyrene).

PCV # 1

PVC # 1 is a flexible PVC available from the supplier BF Goodrich Company, known under the trade name Geon 80 ™. Shore of this material

Hardness of 80.

PCV # 2

PVC # 2 is a flexible PVC, also known as Geon 55 ™, a registered trademark of the supplier BF Goodrich Company. The Shore A Hardness of this material was 55.

RPCV # 1

RPVC # 1 is a rigid PVC available from the supplier BF Goodrich Company, known under the trade name M1000 ™.

The process conditions used to prepare the various catalysts, cocatalysts and individual ethylene styrene interpolymers for use in the blend compositions of the present invention are summarized in Table 2.

<img file="TR200000968T2_D0002.tif" />

Table 2

<img file="TR200000968T2_D0003.tif" />

<td>s s</td><td>Ti Ratio</td><td>she is</td><td>Γ</td><td>SHE IS rh</td><td>SOA</td><td>soar</td><td>SHE IS</td><td>SHE IS</td>

<td></td><td></td><td>»Zi</td><td>Osman</td><td>trace,</td><td>M ·</td><td>• Z</td><td>«Z</td><td>TRACE,</td>

<td>TO:</td><td>g</td><td>CN</td><td>SHE IS\</td><td>CN</td><td>CN</td><td>CN</td><td>CN</td><td>CN</td>

<td>pa</td><td>^δ</td><td>mh</td><td>CN</td><td>-H</td><td></td><td></td><td></td><td>mh</td>

<td>RM</td><td>IM •SHE IS</td><td> &lt;</td><td></td><td> &lt;:</td><td> “&lt;</td><td> &lt;:</td><td> &lt;:</td><td>° C</td>

<td> 3</td><td>. a</td><td>it</td><td></td><td>pQ</td><td>it</td><td>it</td><td>OA</td><td>it</td>

<td>I</td><td> 1</td><td>&lt; TL. one</td><td>PROVINCE,</td><td>PL</td><td>Phi</td><td>pp</td><td>Phi</td><td>plan,</td>

<td></td><td>province</td><td>it</td><td></td><td>Oasi</td><td>m</td><td>0QU</td><td>Oasi</td><td>Oasi</td>

<td rowspan="2">&gt; m soar -M I</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td> &lt;3</td><td>C3</td><td>a</td><td>x&gt;</td><td>Λ</td><td> 03</td><td> 03</td>

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

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

<td>S</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>SHE IS CA · • 3</td><td></td><td>she is\ tFr</td><td>CN soar</td><td>S0</td><td>cs cs</td><td>&lt;0s oo</td><td>S</td><td>«Zu</td>

<td>HE IS</td><td>•S</td><td rowspan="2"> 00</td><td>SHE IS\</td><td> 00</td><td> 00</td><td> 00</td><td> 00</td><td> 00</td>

<td>:SHE IS Q</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

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

<td></td><td> *2</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td> 3</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td> 03</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>he is</td><td>(a 'ob Μ- »</td><td>Cs s — ✓ ^ 0</td><td> 7(4.4)</td><td>tt «Z&gt; s.✓ SHE IS</td><td>= H rt SHE IS</td><td> 3 (4.2)</td><td> .0 (5.4</td><td>= H Osman SHE IS</td>

<td>IM '03 CZ)</td><td>03 03 JA</td><td>he is CN</td><td>&lt;p</td><td>CN M-1</td><td>OS</td><td>CSI</td><td>CN mh</td><td>© CN</td>

<td></td><td>I</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

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

<td>te ·</td><td>M s</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td> &lt;&gt;</td><td>IA</td><td>f **&gt;</td><td></td><td></td><td>* Ί Γ</td><td>cz</td><td>ζ- \</td><td>Z- \ cz</td>

<td>he is &lt;D</td><td>to</td><td>&lt;N \</td><td>she is</td><td>etc</td><td>CN</td><td>CN</td><td>&lt;Zi</td><td>cn S-✓</td>

<td rowspan="2">hydrogen</td><td>('hour</td><td>«z</td><td>she is</td><td>CN M &lt;</td><td>&lt;z</td><td>«Z</td><td>CN</td><td>«Z,</td>

<td> £</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td rowspan="2">(A ·</td><td>s·-*. «3</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td>/-s</td><td></td>

<td></td><td>AFront</td><td></td><td>I / O</td><td> 00</td><td>tt</td><td>SOA</td><td> 00</td><td></td>

<td></td><td></td><td> ©&gt;</td><td>&lt;^ S</td><td>she is</td><td>rh</td><td>MH</td><td> ©</td><td> ©</td>

<td></td><td></td><td></td><td> '«—*'</td><td></td><td></td><td></td><td> **</td><td>^S'M^Z</td>

<td>&lt;L&gt;</td><td> *5</td><td>she is</td><td>MH</td><td>r- »</td><td>she is</td><td>V \</td><td>r-</td><td>SHE IS</td>

<td> 3</td><td></td><td>MH</td><td>mh</td><td>mh</td><td>&lt;z</td><td>CZ</td><td>mh</td><td>mh</td>

<td>ω</td><td>MP</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

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

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

<td></td><td> _</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td rowspan="2">IA *</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>D (a</td><td>/-s r-</td><td> 00</td><td>Ζ "· \</td><td></td><td>S'</td><td>/-s 'φ</td><td>Z "s r »</td>

<td></td><td>ab</td><td> 00 *</td><td>mm</td><td> 00</td><td>CN</td><td>cz</td><td>bile</td><td>bile</td>

<td>C &lt;Tr&gt;</td><td></td><td>s · ✓ CN</td><td>SHE IS</td><td>s »✓ SOA</td><td>soar</td><td></td><td>soar</td><td>S-✓ CN</td>

<td>SHE IS</td><td>03 03 {Λ</td><td>Osman</td><td rowspan="2">&lt;&gt; CN</td><td>00 = H</td><td>soar CN</td><td>© CZ</td><td>bile</td><td>Osman MH</td>

<td>cz&gt;</td><td>I</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>MM</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>IM</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>:SHE IS</td><td>she is</td><td></td><td>OS</td><td>CN</td><td>Osman</td><td>Γ-</td><td>ΓΜ</td><td>CN</td>

<td>reactant</td><td>she is the czar</td><td>M SOA</td><td>SOA r-</td><td> © 00</td><td>00 SHE IS</td><td>Osman SHE IS MM</td><td>SHE IS 00</td><td>soar</td>

<td>SHE IS</td><td></td><td>CZ</td><td>rt</td><td>«Z</td><td>S0</td><td>r-</td><td> 00</td><td>Osman</td>

<td> §</td><td></td><td> =«=</td><td>= Tfa</td><td>tFC =</td><td>3te</td><td></td><td>tt =</td><td></td>

<td rowspan="2">s</td><td rowspan="2">= A =</td><td></td><td></td><td>MM</td><td>MM</td><td>MM</td><td>MM</td><td>MM</td>

<td>CZ)</td><td>CZ)</td><td>CZ)</td><td>CZ)</td><td>CZ)</td><td>CZ)</td><td>CZ)</td>

<td>z</td><td></td><td>pa</td><td>pa</td><td>pa</td><td>PJ</td><td>pa</td><td>pa</td><td>pa</td>

.3

OS

52494

Preparation of Blends

Example 1

Example 1 was a blend containing 25 weight percent ESI # 1 and 75 weight percent PVC # 1. The blend was prepared by melting the components in a molten state using the Haake mixer equipped with a Rheomix 3000 bowl operating at 170 ° C and 40 rpm. The capacity of this mixer was 310 cc. The optimum volume for effective mixing was approximately 70 percent or 220 cc. Calculations were made taking into account the density and composition of each component to prepare a dry blend of materials to achieve 70 percent volume filling. The dry blended materials were then added gradually to the preheated calibrated bowl as the rotors rotated at 43 rpm. To prevent degradation of the flexible PVC, the materials were heated to approximately 160 degrees Celsius. A small melting heel was formed in the mixer, dry blend was added in small increments and allowed to melt and merge with the heel before further blends were added. This took about three minutes until the whole blend was added. A sealing foot was then lowered into the melt bowl, and the molten blend was allowed to stir for ten more minutes with a roller knife. At the end of this time, the rotors were stopped, the mixer was removed, and the molten blend was removed and allowed to cool for testing and analysis.

Example 2

Example 2 was a blend containing 75 weight percent ESI # 1 and 25 weight percent PVC # 1.

The blend was prepared essentially as described in Example 1.

Example 3

Example 3 was a blend containing 50 weight percent ESI # 2 and 50 weight percent PVC # 1. The blend was prepared essentially as described in Example 1.

Example 4

Example 4 was a blend containing 75 weight percent ESI # 3 and 25 weight percent PVC # 2. The blend was prepared by blending in a Haake Rheomix 3000 bowl mixer. The capacity of this mixer was 310 cc. The optimum volume for effective mixing was approximately 70 percent or 220 cc. Calculations were made taking into account the density and composition of each component to prepare a dry blend of materials to achieve 70 percent volume filling. The dry blended materials were then added step by step to the preheated calibrated bowl as the rotors rotated at 30 rpm. Distortion of flexible PVC 29

52 494 To avoid this, the materials were heated to approximately 150 degrees Celsius. A small melting heel was formed in the mixer, dry blend was added in small increments and allowed to melt and merge with the heel before further blends were added. This took about two minutes until the whole blend was added. A sealing foot was then lowered into the melt bowl, and the molten blend was allowed to stir for ten more minutes with a roller knife. At the end of this time, the rotors were stopped, the mixer was removed, and the molten blend was removed and allowed to cool for testing and analysis.

Example 5

Example 2 was a blend containing 50 weight percent ESI # 3 and 50 weight percent PVC # 2.

The blend was prepared essentially as described in Example 4.

Example 6

Example 6 was a blend containing 75 weight percent ESI # 4 and 25 weight percent RPVC # 1. This blend was prepared on a Haake Microl8 Extruder. This was a twin co-rotating extruder with 18 mm propeller and ~ 31 L / D. A dry blend of blend materials was fed to the extruder feed throat by means of a KTRON drill feeder at a rate of about 1.8 kg per hour. The extruder was preheated to the following zone conditions for one hour: 1135 degrees C, 2-165 degrees C, 3-165 degrees C, 4-165 degrees C, 5-175 degrees C, and die temperature 175 degrees C. The extruder was operated at 100 rpm. The extrudate having a melting temperature of 160-178 degrees C was quenched in a water bath, dried with an air knife and cut into pellets.

Example 7

Example 7 was a blend containing 50 weight percent ESI # 4 and 50 weight percent RPVC # 1. The blend was prepared essentially as described in Example 6.

Example 8

Example 8 was a blend containing 25 weight percent ESI # 4 and 75 weight percent RPVC # 1. The blend was prepared essentially as described in Example 6.

Example 9

Example 9 was a blend containing 50 weight percent ESI # 6 and 50 weight percent RPVC # 1. The blend was prepared essentially as described in Example 6.

52494

Example 10

Example 10 was a blend containing 50 weight percent ESI # 5 and 50 weight percent RPVC # 1. The blend was prepared essentially as described in Example 6.

The analysis of the various Tg values ​​for these examples in Table 3 shows that although the blends of rigid PVC # 1 and ethylene / styrene interpolymers (Examples 6-10) have double wide Tgs due to the immiscibility of the two components, The flexible PVC and ethylene / styrene interpolymers may have a double wide Tg (as in Example 1) or a single narrow Tg (as in Examples 2-5) by simply changing the relative amounts of the flexible PVC and ethylene / styrene interpolymer. reveals an amazing result.

Furthermore, the analysis of Eb values ​​for blends of Examples 2 and 3 as compared to that of the individual components shows the synergistic effect of blending on tensile elongation at break. Thus, Example 2 individual blend components had an Eb (375 percent) higher than the Eb values ​​of ESI # 1 (282 percent) or PVC # 1 (198 percent). The synergistic effect on the Eb of the blend was also observed in Example 3, where the individual blend components ESI # 2 (397 percent) or PVC # 1 (198 percent) had an Eb (481 percent) higher than the Eb values.

Examples 1, 4 and 5 in Table 3 show that, in addition to the similar synergistic effects of blending on Eb, the percentage of stress relaxation (percent SR) observed for the blends may be higher than that observed for the individual blend components; Example Example

The SR percentage of 5 was higher than that of the 94 blend component ESI # 3 (92 percent).

Examples 6-10 of Table 3 were blends of rigid PVC with ethylene / styrene interpolymers. Hard PVC # 1 had a very low Eb value (13 percent) and showed essentially no tensile relaxation. ESI # 4's E_b value was 244 percent and the SR percentage was 93 percent. The blend of Example 6 containing as high as 25 percent by weight of RPVC # 1 could also have an Eb of 272 percent and an SR percent of 88 percent. Increasing the RPVC # 1 content to 50 percent as in Example 7 gave an Eb, which was again 32 percent.

<img file="TR200000968T2_D0004.tif" />

* .·*

<img file="TR200000968T2_D0005.tif" />

Table 3

<img file="TR200000968T2_D0006.tif" />

<td>T (Imm) ° C</td><td> 00</td><td> 00 00</td><td> 63</td><td></td><td> 57</td><td> 66</td><td> 104</td><td> 85</td><td>SHE IS</td><td></td><td> 63</td><td> 70</td><td> 82</td><td> 48</td><td> 43</td><td> 80</td><td> 92</td><td> 121</td><td> 101</td><td>r * N 00</td>

<td>SR percent</td><td>* Ί Γ SHE IS\</td><td> 30</td><td> 92</td><td> 93</td><td> 69</td><td>m</td><td>r-</td><td> 56</td><td> 1</td><td></td><td> 86</td><td> 67</td><td> 1</td><td> 84</td><td> 94</td><td> 88</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td>

<td>_to</td><td> 282</td><td> 397</td><td> 265</td><td> 244</td><td> 956</td><td> 589</td><td>00 FRONT</td><td> 160</td><td>fc</td><td></td><td> 129</td><td> 375</td><td> 481</td><td> 708</td><td> 492</td><td> 272</td><td>CN ΠΊ</td><td>tj-</td><td>FRONT</td><td>00 f * N</td>

<td>Tm / Xtlty περχεντχίγι ° C / percent</td><td></td><td> 71/15</td><td></td><td></td><td></td><td> 90/29</td><td></td><td></td><td></td><td></td><td></td><td></td><td> 71/18</td><td></td><td></td><td></td><td></td><td></td><td> 89/29</td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>UO cn rc</td><td></td><td></td><td></td><td></td><td> 06</td><td>Front</td><td> 92</td><td> * *</td><td> 92</td>

<td></td><td>SHE IS cc</td><td> 00 1</td><td>C * N</td><td> 30</td><td></td><td>Γγ</td><td> 1</td><td> -31</td><td> 89</td><td></td><td>rJ · • "H one</td><td>FRONT</td><td> -20</td><td></td><td>NO</td><td> 29</td><td> 23*</td><td>«n</td><td>FRONT</td><td>CN</td>

<td>- - X® .D Ul CU O Oh §</td><td> 20.2</td><td> 18.5</td><td> 15.0</td><td> 13.6</td><td> 00</td><td> 30.4</td><td> 7.7</td><td> 3.6</td><td> 46.5</td><td></td><td> 2.6</td><td> 13.6</td><td> 10.3</td><td>l&gt;</td><td> 100</td><td> 17.5</td><td> 12.7</td><td> 25.2</td><td> 9 6</td><td>S</td>

<td>I. 'S l £ ° 2</td><td> 15.2</td><td> 2.7</td><td> 15.1</td><td> 4.6</td><td>NO</td><td> 5.2</td><td> 4.2</td><td> 3.6</td><td> 55.3</td><td></td><td>cn</td><td>ι / Ί</td><td>rc * S</td><td></td><td> 0.7</td><td> 5.0</td><td></td><td> 25.6</td><td> 10.4</td><td> 5.9</td>

<td>TO MPa</td><td> 609.7</td><td> 6 61</td><td> 582.0</td><td> 215.3</td><td> 3.8</td><td> 26.6</td><td>* Ί Γ oo</td><td> 3.4</td><td> 1482.9</td><td></td><td> 16.7</td><td> 12.7</td><td> 26.9</td><td> 3.6</td><td>00 ΓΊ</td><td> 222.6</td><td> 397.8</td><td> 910.2</td><td> 331.3</td><td> 142.9</td>

<td>TO C4 O ^ 3)</td><td> 0.20</td><td> 0.03</td><td> 2.50</td><td>SHE IS</td><td>00Τ</td><td>00Ί</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Compound (wt.% styrene)</td><td> %74</td><td> %27</td><td>fc &gt; T⁵</td><td>CN r »</td><td> %57</td><td> %20</td><td> 1</td><td> 1</td><td></td><td></td><td> 25/75</td><td> 75/25</td><td> 50/50</td><td> 75/25</td><td> 50/50</td><td> 75/25</td><td> 50/50</td><td>»R&gt; IrDA&gt;</td><td> 50/50</td><td> 50/50</td>

<td>Mixture</td><td>Ethylene / Styrene</td><td>Etilcn / Duration of</td><td>Ethylene / Styrene</td><td>Ethylene / Styrene</td><td>Ethylene / Styrene</td><td>Ethylene / Styrene</td><td>I</td><td> 1</td><td>I</td><td></td><td>ESI # 1 / PVC # 1</td><td>ESI # 1 / PVC # 1</td><td>ESI # 2 / PVC # 1</td><td>ESI # 3 / PVC # 2</td><td>ESI # 3 / PVC # 2</td><td>ESI # 4 / RPVC # 1</td><td>SHE IS &gt; -φ = 8 = GO ω</td><td>ESI # 4 / # 1 RPVC</td><td>ESI # 6 / RPVC # 1</td><td>ESI # 5 / RPVC # 1</td>

<td>Single Component</td><td>ESI # 1</td><td>ESI # 2</td><td>ESI # 3</td><td>ESI # 4</td><td>ESI # 5</td><td>ESI # 6</td><td>PVC # 1</td><td>PVC # 2</td><td>RPVC # 1</td><td>blends</td><td>Example 1</td><td>Example 2</td><td>Example 3</td><td>Example 4</td><td>Example 5</td><td>Example 6</td><td>Example 7</td><td>Example 8</td><td>Example 9</td><td>Example 10</td>

Conflicts with Tg Tm

52494

Example 11-18

Examples 11-18 of Table 4 were blends of ethylene / styrene interpolymers with Hard PVC, all containing the same amount of P 610 plasticizer (20 weight percent). Various styrene blend containing ESI and RPVC # 1 (stabilized pellet form) with a plasticizer

Prepared in Haake Micro 18 Extruder. A dry blend of ESI and RPVC was introduced into the extruder via a drill KTRON feeder. The plasticizer was injected in Zone 3 as a liquid using a displacement pump and an injector port. The dry blend feedrate was monitored by measuring the timed feed at the drill bit. The syringe system feed rate was monitored by the timed weight loss of the plasticizer cup. The calibration curves for each of these were used to obtain the correct settings of the drill feeder and displacement pump to produce the desired ratio of plasticizers to solids at a total feed rate of about 0.9-11 kg (2-2-5 pounds) per hour. The zone temperature settings in degrees Celsius were: 1-137, 2-170, 3-180, 4-180, 5-180, kah-170. The extruder was operated at 105 rpm. The resulting extrudate having a melting temperature of 165 ° C was quenched with water, air-dried and cut into pellets.

Examples 11-13, 14-15 and 16-18 in Table 4 all show how the Tgs of the blends can be varied over a wide range by varying the relative amounts of ethylene / styrene interpolymer and Hard PVC # 1. The magnitude of this change was shown by comparing the Tgs of Examples 16-18 with the binary mixtures of P610 plasticizer and RPVC # 1 and P610 plasticizer and ESI # 9 as measured in Comparative Examples 1 and 2.

<img file="TR200000968T2_D0007.tif" />

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Table 4

<td>S o λ ° H</td><td>SHE IS</td><td>"SHE IS &lt;/ *)</td><td> 65</td><td> 140</td><td></td><td> 95</td><td> 96</td><td>SHE IS</td><td> 34</td><td> 63</td><td> 45</td><td> 74</td><td> 104</td><td>F «</td><td> 43</td>

<td>TO_b, percent</td><td> 586</td><td> 1119</td><td> 187</td><td>m</td><td></td><td> 671</td><td> 123</td><td>m</td><td> 182</td><td></td><td>SHE IS 00</td><td>r * · »</td><td>SHE IS\</td><td> 232</td><td> 470</td>

<td>Tm / Xtyl ° C / yüzdc</td><td> 91.1/28.6</td><td> 1</td><td> 1</td><td> 1</td><td></td><td> 88.9/32.5</td><td> 88.0/36.9</td><td> 87.6/42.6</td><td> 1</td><td></td><td></td><td> 1</td><td> 1</td><td> &lt;</td><td></td>

<td>CN r \ p ¥</td><td></td><td> 1</td><td> 1</td><td></td><td></td><td> 36.4</td><td> 34.6</td><td> 47.1</td><td> 69.3</td><td> 58.5</td><td></td><td> 58.6</td><td> 54.3</td><td> 48.3</td><td> -3.6</td>

<td>she is H °</td><td> 1</td><td> 3.5</td><td> 31.8</td><td>68 _I</td><td></td><td> -13.9</td><td> -12.1</td><td></td><td> -19.3</td><td> -25.4</td><td></td><td> -8.4</td><td> -15.1</td><td></td><td></td>

<td>_Λ C3 Λ «Λ Pl S (X §</td><td> 25.5</td><td>»• H</td><td> 12.6</td><td> 46.5</td><td></td><td> 13.5</td><td> 3.9</td><td> 98</td><td> 0.3</td><td> 4.4</td><td> 0.5</td><td> 4.3</td><td> 6 6</td><td> 16.2</td><td>SHE IS</td>

<td>r ⁰³&gt;&gt; «λ Ph Ü 0-. §</td><td>-4 »Ru</td><td>«n</td><td> 601</td><td> 55.4</td><td></td><td> 3.9</td><td></td><td> 6.6</td><td> 0.5</td><td> 5.3</td><td> 0.7</td><td> 4.6</td><td> 12.2</td><td> 12.3</td><td> 0.3</td>

<td>03 W o</td><td> 63.2</td><td> 3.5</td><td> 384.9</td><td> 1482.9</td><td></td><td> 39.5</td><td> 65.6</td><td> 147.4</td><td> 2.2</td><td> 170.3</td><td> 2.7</td><td> 162.2</td><td> 475.0</td><td> 181.1</td><td> 0.7</td>

<td>TO d o. HH I-M weed</td><td> 080</td><td></td><td> 2.20</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Compound (wt.% styrene)</td><td> 20.0</td><td> 57.7</td><td> 73.0</td><td> 1</td><td></td><td> 60/20/20</td><td> 40/40/20</td><td> 20/60/20</td><td> 60/20/20</td><td> 40/20/20 1</td><td> 60/20/20</td><td> 40/40/20</td><td> 20/60/20</td><td> 75/25</td><td> 75/25</td>

<td>Mixture</td><td>Ethylene / Stircea</td><td>Ethylene / Stircea</td><td>Ethylene / Styrene</td><td> 1</td><td></td><td>ESI # 7 / RPVC # l / P61</td><td>ESI # 7 / RPVC # 1 / P61</td><td>ESI # 7 / RPVC # 1 / P61</td><td>ESI # 8 / RPVC # 1 / P61</td><td>ESI # 8 / RPVC # 1 / P61</td><td>ESI # 9 / RPVC # l / P61</td><td>ESI # 9 / RPVC # l / P61</td><td>ESI # 9 / RPVC # 1 / P61</td><td>RPVC # l / P610</td><td>ESI # 9 / P610 j</td>

<td>Single Component</td><td>ESI # 7</td><td>ESI # 8</td><td>ESI # 9</td><td>RPVC # 1</td><td>blends</td><td>Example 11</td><td>Example 12</td><td>Example 13</td><td>Example 14</td><td>Example 15</td><td>Example 16</td><td>Example 17</td><td>Example 18</td><td>Comp. Ex. one</td><td>Comp. Ex. 2nd</td>

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