JPS5823816A - Thermoplastic elastomer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to thermoplastic elastomers and methods of making the same.
The present invention relates to thermoplastic elastomers which are polymers of derovirent (ethylene-propylene) and propylene made sequentially. (B) an amorphous segment which is an elastic ethylene-propylene material; A) and (B)
are merely partially copolymerized with each other, and the weight ratio of the (A) to (B) segments is 10:90.
to 75:25 and in at least one differential thermal analysis (“D#r person”)
The product leads to a sequentially created thermoplastic elastomeric polymer characterized by lamellar chain-bent crystallinity at room temperature, as evidenced by a melting point of 50°C. The product contains two interpenetrating networks (two twisted continuous phases), one of which is of plastic nature (mainly polyzolozelene) and the other of imime-like nature (mainly ethylene-delobilene). It is believed that this is the case.

In order to introduce true immobilization properties to amorphous polymeric materials above their second-order transition temperature (glass transition temperature, rTgJ ) at room temperature, it is necessary to "fix" the polymer chains into the macromolecules. anchoritsgpoint
t) It is known that J must be introduced. When one does this by forming a chemical bond that binds all the chains together, one can call it "hardening" or "hardening" of im.
"Cross-coupling". However, chemical cross-linking of the im changes the im to the point that it can no longer be reprocessed (it is no longer a thermoplastic) and produces any waste material that must be discarded. By using physical "cross-links" instead of true chemical cross-links (such as fixed points based on Las transition temperature, crystallinity, or ionic bonding), to the point that simply chain fixation is overcome. Cross-coupling effects can be reversed and random operation can be tolerated by increasing the temperature to . Cooling refixes the chains. The resulting waste can therefore be reused. This type of im is called a thermoplastic elastomer.

One known type of thermoplastic elastomer is "TPO"
Polyolefin plastics known as (for example?
olefins) and olefins (e.g.
KPM: ethylene-derobirenim). The thermoplastic elastomeric nature of TPO is characterized by a continuous delastic (polypropylene) phase and a continuous im (KPM) phase.
It appears to arise from an interpenetrating network structure with the phase.

It can be recognized that such primers are given by the organization of "hard segments" through a continuous matrix of "cross-linked J +z r soft material".

There appears to be sufficient interaction (van der Waals forces) along the continuous interface to allow the hard segments to act as fixed points at moderate temperatures and thus provide elastic behavior. . High temperature (125
C) at rc the interaction is weakened and the stress-strain properties deteriorate rapidly. Even higher processing temperature (160℃)
At , the fixed point melts and thereby loses its rigidity, ie the material becomes thermoplastic. This allows the formulation to be shaped into the final shape.

The TPO is consistent with an interpenetrating network in electron micrographs at magnification levels from 8,000 to 20,000. “Large amount” of plastic compared to contained substances
The other end of the im region continuum is shown. Scanning electron microscopy of hexane-extracted films of TPO showed the presence of undissolved polypropylene in a continuous network throughout the film. One can see that the KPM-11" phase was also continuous by observing the pores created in the material as shown by scanning electron micrographs. The polypropylene phase
It has been shown to be a polyzologylene with a melting point in the range of 75 DEG C., and the crystallinity is of the chain-bent lamellar type.

The TPO of this type has some chemical cross-linking introduced by partial curing with peroxides or other curing agents during dynamic processing of the mixture to improve performance without destroying thermoplasticity. . The advantage of this is low compression set.

High tensile strength at high temperatures, and better tensile strength to hardness ratio. Transmission electron micrographs of these dynamically partially cross-linked TF'Os show that the two phases are better interdispersed with each other and the VCs have no flat interfaces but rather many jagged edges delineating the boundary areas. It differs in that it has an edge.

One of the objects of the present invention is to avoid the expensive and energetically demanding mixing steps required to prepare conventional compounded TPOs.Another object is to avoid any dynamic partial curing step. It is an object of the present invention to provide a thermoplastic elastomer having good properties that does not require.

April 16, 1968 and December 10, 1974 respectively! US Patent No. 3 issued by Kmmanu*l and Kontog K.
No. 378.606 and No. 3,853,969 disclose semicrystalline or crystalline Zollock copolymers. The substance of Kontos is true (substantially complete) as evidenced by the fact that it is soluble in boiling hebutane.
While block copolymers, the products of the present invention contain significant amounts (e.g. 30-70 wt elj) of hebutane-insoluble material. It is believed that the properties of Kontos' products arise not from an interpenetrating network but from field forces in the mass of im. The rigid region appears to act as an anchor point for the hs-P mucoid chain segment; the mucoid chain is apparently chemically bonded to the rigid domain.

Kontos material has low polymer yield.

Production is difficult due to high solution viscosity and relatively long reaction times. Cantos uses an "active" catalyst so that the monomer units added to the active ends of the polymer molecules present in the reaction mixture add sequentially, thus creating polymers of extremely high molecular weight and significantly Produces a viscous reaction mass. The present invention, in contrast, provides for the formation of at least some short-lived propylene species, which have no "active" end and therefore cannot continue to grow in contact with monomers added during the process. There isn't. This provides an important crystalline polypropylene phase that is characteristic of the products of this invention.

Similar rc Edmund July 20, 1976 (B+1m
on1g) Jr., U.S. Patent No. 3.970.719
No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, 2003, 1, 2, 3, 3, 3, 3, 3, 3, 4, 5, and 4 discloses sequential I-remers of polypropylene and (ethylene-propylene) made with active catalysts but without a substantially separate propylene resin phase as in the products of the present invention.

The production of thermoplastic elastomers by direct polymerization of ethylene and propylene was published in Zalf on November 26, 1981.
(Borght) et al. U.S. Patent No. 4.298.721
It will be disclosed in the issue. The product unfortunately contains only polypropylene crystallites with a DTA melting point of 10f to 130°C; molding shrinkage is high. This indication is that the product has a type of crystallinity known as tuft-like crystallinity, rather than the chain-bent lamellar type that is characteristic of the products of this invention. The products of the present invention have good properties at high temperatures, whereas the products of low melting point such as Bolly have their usefulness limited to temperatures below 80 DEG C.

Giannini on August 15, 1978
) et al., U.S. Pat. No. 4,107,414,
Isotactic polyolefins are prepared from propylene and higher alpha olefins using very useful catalysts.
- (i.e. crystalline substances containing little or no amorphous components).

The conversion rate of Mataderozeshi to polyzorogylene is low (
Also disclosed is the polymerization of pro2lene in the presence of small amounts of ethylene fed continuously or intermittently after reaching 80 mm. The elastomeric products of the present invention, in contrast, represent less than 701 of the total polymerized propylene in crystalline segments.

According to the present invention, a supported complexed titanium catalyst is used with a modified organoaluminium cocatalyst to convert zorogylene to (ethylene-propylene) or propylene to (ethylene-propylene) to zorogylene. Reactor production by step-by-step polymerization.

Thermoplastic 5#? Now that Liorefui/ has been created. Commonly used catalyst systems are catalysts based on magnesium or titanium rhodide (or its complex with an electron donor) supported on supports such as magnesium or magnesium rhodide, and alkylaronium, especially electron-based catalysts. The cocatalyst can be characterized as being an organic alkyl compound, such as a substitution or addition product of trialkylaronium with a donor. The polymer produced is 60 to 95
Total propylene content up to 7.0 - greater than 7.0 - 1 degree ratio between Pan V of 11.88 microns and Pan R of 12.18 microns in the infrared spectrum; In the Raman spectrum, 810 microns Pan V and 8
Intensity ratio greater than 1, 0 in pan r of 40 est-1 and 2880 (1! II pan r vs. 2..8
50cm pan YVC 2, 0 more than the strength ratio; less (differential thermal analysis melting point of at least 150℃;
Characterized by a flexural modulus of less than 100.00 npsi at room temperature; an elongation greater than 150 inches at room temperature.

The polymer to be produced is 1 for those with segments.
melting point from 50 to 156°C; useful deme-like properties slightly below these melting points and at least below 150°C; processability in equipment used for thermoplastics at temperatures above the upper melting point; further characterized.

Applicant has proposed that, with respect to the present invention, if the polymerization is carried out in stages such that only de-robilene is polymerized in the first phase and ethylene and propylene are polymerized in the second phase, a high melting point (150-166 as measured by a DT person) can be obtained. ℃;B, -Ke [New Methods for Determination and Determination of Polymer Properties J, 1964゜Int*racii
njs 'T'-u'b'1is)sers, 1
It has been found that the defined TL leads to materials with good tensile values for hardness values (Shore A). The new polymer of the present invention is 250°l? (120
They tend to retain their useful properties even at high temperatures (°C); in the first stage the zorogylene polymerizes and in the second stage ethylene and zorogylene, followed by the third stage tederopylene. A three-step polymerization in which the polymers are polymerized probably yields similar polymers with slightly lower Tg values and higher tensile values.

In the process of the invention, propylene is first polymerized into at least two different molecules. One species is an active polypropylene/17mer to which one unit of the other monomer can continue to add to its active terminal, while another species has a relatively short active terminal. become inactive one after another and no longer grow? Leaving Rizorogiren behind. It is therefore believed that at the end of the first stage sequential polymerization the reaction mixture contains non-active polypropylene (resin) and active polyzorogylene. When ethylene is added in the next sequential polymerization, the single polymerization can take several routes,
6c involves the addition of ethylene and zorogylene to the active polypropylene from the first stage. At the end of the second sequential polymerization the species present are pp, pp,
p-up, active BP and active p-Hp. The polymerization can be terminated at this stage or the process can proceed to a third sequential polymerization involving the addition of more zolothelene monomer;
Ru. After addition of further zolozelene the 9 polymerization can be continued with more changes. Thus, active liver and active p-'wp can add propylene and create more polyzolo, Vp-lene. The final mixture after quenching the active-limer is pp, gp, p-ip, 3P-P and P
It is possible to consider that species such as -MP -P can be omitted. Without wishing to limit the invention to any particular theory of operation, the unique nature of the products of the invention is that the catalyst used has active terminals with relatively long lifetimes, such as the prior art from Cantos. It is possible that the result is not only the production of Q-propylene, but also the production of polypropylene with short active terminals, which results in the ability to add the resinous l-riderof-rene phase to the male two-phase. It is believed that in the product of the present invention, from 10 to 70 of the total polymerized zolothelene is in the form of crystalline isotactics.

Current [p / up J and ``P /BP /P
It is not immediately clear that type J polymers would be significantly useful. Many polypropylene catalyst systems will incorporate ethylene to some extent, so some P
Preparation of /l P /P and p/wpM1dl remers is possible. The reason why it is particularly novel is that the P/EP of the present invention
and P/IP/P polyζ- has such good physical properties without undergoing intense stirring steps and without dynamic partial hardening. In almost all other cases, polymers produced with other zorogylene catalyst systems have very poor physical properties.

In these latter cases, there is clearly insufficient interfacial interaction or dispersion of the two phases (or a combination of both) to provide the required stress-strain properties. An example of such a catalyst system is the well-known alkyl halide aluminum-TtcL5AA catalyst system.

In contrast, in the case of the present invention using a supported complex titanium catalyst, a surprisingly sufficient dispersion of polypropylene is obtained to provide the required stress-strain properties.

The p/Hp/p polymerization of the present invention is a method of making products in which monomers are introduced to maximize polymerization to P/W P/P. The products are not exclusively true trisols. In practice, all of the possible combinations as mentioned above are obvious, such as polypropylene, propylene-BPf lock, HP-propylene block, ethylene-propylene copolymer, and trisol lock polymers of propylene, ethylene-propylene, and propylene. exists in Similar conditions exist with P/lP polymers. In any case, the catalyst species present 1 polymerization rate, predicate polymerization, and assembly,! i; which combine to give a mixture having the required properties of commercial interest.

The thermoplastic elastomers of the present invention exhibit microcrystals of the 60 to 95 wt. The microcrystalline value is measured by X-ray and is 1.
It ranges from 5 to 459G.

- Rideropyrene segment is 15- of fully polymerized zorogylene
70 wt. The intrinsic viscosity number (measured in tetralin at 135° C.) of the polymer is between 1.5 and 6 or even higher, and the tensile test value is not only dependent on the propylene content, but is also reflected in the intrinsic viscosity value. It also depends on the molecular weight. The flexural modulus and elongation at room temperature are less than 100,000 inches per square inch and greater than 150 inches, respectively.

The unique feature of the thermoplastic elastomer of the present invention is SU-P!
! I) The property of 7L/, which is the absorption intensity ratio of 7.0 or more at Pan r of 11.88 microns to Pan Prc of 12.18 microns in the infrared spectrum; Pan r of 810 ex-' vs. 84
Includes an intensity ratio of 1, greater than 0 in a pan PK of 0α, and an intensity ratio of 2, greater than 0 in a pan r of 2880 cm1 to a pan of 2850 i1.

The amount of propylene polymerized in the first step of the process of the present invention, in which the initial sequential polypropylene is made, is no more than 70% by weight or less of the raw propylene charged;
2nd (IP) or 3rd (IYP/P) tiers leave 3OS or more available. Typically, the amount of propylene polymerized in the first stage corresponds to no more than 50, often no more than 30, of the propylene charged in the first stage.

The thermoplastic elastomers of the present invention are disclosed in U.S. Pat. No. 4,298,721:197 to Borghi et al.
No. 4.107 of Giannini et al., Aug. 15, 1998.
．． No. 414 or European Patent Application No. 00123 of Filiddes Vetroleum Company of June 25, 1980
No. 97, the above disclosure of which is hereby incorporated by reference. As described in U.S. Pat. No. 4,298,721,
A preferred catalyst is an adduct of 2-93- or 4-valent titanium with a halogen-containing compound and an electron donating compound, the adduct comprising an activated anhydrous magnesium dihalide and in the supported state the X-ray In the powder svector, an electron donating compound (or Lewis base) and an alkali are present. and addition and/or substitution products of electronium trial'kyl.

or adducts of electron-donating compounds with aluminum-alkyl compounds containing two or more aluminum atoms bonded to each other through oxygen or nitrogen atoms (1 mole of aluminum alkyl compounds, organic or inorganic, such as Lewis bases); (by reacting an oxygen-containing acid with 0.1 to 1 mole of an ester of a di- or poly-amine or, if the titanium compound contains a di- or poly-amine as an electron donor, other Lewis bases)
The titanium compound content is t per mole of the total amount of electron donating compounds in the catalyst.
The titanium of l-0, 5, and 9 is 4 or less.

The molar ratio of halogen-containing titanium compound to aluminum alkyl compound is up to 0.001 or M.1. , as described in U.S. Pat. No. 4,107,414, the catalyst includes the following components: (-) an oxygenated organic or inorganic acid and A! -G IJ
M containing two or more M atoms bonded to each other with an alkyl compound or through an oxygen or nitrogen atom
- addition and/or substitution products of electron-donating compounds (or Lewis bases) selected from the group consisting of esters with alkyl compounds, M- The amount of alkyl compound per mole of starting M-compound! and (b) halogenated 2-. 3-
, and complexes of tetravalent T1 compounds and 70 T1 compounds on a support (the support is a normal unactivated Mg or Mn2 halide
The component ( b) X-ray powder spectrum,
indicates the expansion of the strongest diffraction line). The product that returns on contact with the electron donor, and component (1,), is further represented by the amount of T1 compound present therein, expressed as '1'1 metal, which is an electron donor compound present in bound form in the catalyst. and the catalyst has a kl/Ti no% ratio of 10
to 1.0.00.

Also suitable is the catalyst of European Patent Application No. 0.012,397 which can be described as being formed upon mixing: (A) Catalyst component (A) is mixed with: (1)
Magnesium halide or manganese halide and (2) a cocatalyst selected from the following: (-) 2M(OR)!1 (where M is aluminum.

boronate, magnesium, titanium or zirconium, n is an integer corresponding to the valence of M, and is 2-4
and R is a locarbyl group having 1-24 carbon atoms per molecule).

(b) Organic phosphites of the formula: Ri'-0 where R is an aryl, aralkyl, alkaryl or haloaryl group having from 6 to 20 carbon atoms.

(c) Aromatic phenols of the formula 2HOR1, which is an aryol group containing up to about 20 carbon atoms from R1tt6.

(d) Aromatic ketones of the following formula: R' CR5 where R is a thiophene, aryl or alkyl group, and R5 is an aryl group containing up to 6 to 2 carbon atoms; It is.

(-) Organosilanols of the formula: 6 R7810H 8 where R, R and R8 are the same or different and are a hydroxycarbyl group containing from 4 to 20 carbon atoms.

(f) Organophosphates and phosphines of the formula: 9 RlO-P-O 11 where each R is the same or different hyrrocarbyl or hyProcarbyl containing from 1 to 20 carbon atoms? It is a chrysanthemum group.

(g) Aromatic thymines of the formula: R5-NHR" where R5 is an aryl group having from 6 to 20 carbon atoms and R12 is hydrogen or having from 6 to 20 carbon atoms. It is an aryl group having

(h) Oxygenated terpenes selected from carvone, dicargane, carbenone and carbomethane.

(i) Triaryl phosphites having from 6 to 24 carbon atoms in each aryl group.

(j) Rodan-containing organophosphorus compounds having the following formula: px, &(OR'')a.

R3Px3-b and 0 0 (wherein R3 is an aryl group having from 6 to 20 carbon atoms, X is halofy, and a is 1 or 2
and b is zero or 2).

The molar ratio of (1) to (2) is from 4:1 to 100:1
Crosstalk complex Natsu (su), which is a range of heavy traffic.

(3) treating the composite obtained from (1) and (2) with titanium tetrahalide for a time sufficient to incorporate the titanium tetrahalide into at least a portion of its surface; (B) organoaluminum compound and monohalodan; a cocatalyst component comprising at least one organoaluminum compound, in which the molar ratio of component (B) to titanium compound ranges from 0.5:1 to 2000:1 and the percentage of titanium in the finished catalyst; is from about 0.1 to about 10 by weight based on dry composite.

Thermoplastic fabrication by sequential polymerization according to the present invention9! ) A preferred method of making 5KL uses a catalyst system (hereinafter referred to as the preferred catalyst system) made of titanium tetrachloride and an alkyl benzoate (methyl benzoate or more preferably a higher alkyl benzoate) on anhydrous magnesium dihalide and milled to give a particle size of less than one electron; (b) Hamm*tt
The sigma value is zero and G'! modified by alkyl di-substituted penzoates with negative (electron-IJ latch conversion) (two preferred examples are ethyl anisate and ethyl p.
-t-decylpenzoate) by reaction with a cocatalyst that is trialkylaluminum. The molar ratio of titanium tetrachloride to alkyl benzoate in (-) is 1.1:1. The weight ratio of the magnesium dihalide complexed titanium compound is 4 to 1 or higher. The molar ratio of trialkylaluminum to benzoic acid ester in (b) is between 2:1 and 1.
The ratio is up to 0:1. The molar ratio of aluminum to titanium is as low as 50:19, e.g. 50:1 to 200:1.
Or even higher.

The catalyst system used in another preferred practice of the sequential polymerization process of the present invention (hereinafter referred to as preferred catalyst system ①) is M
It can be described as TtCj carried on gCJ2 and modified by an aromatic hydroxy compound. Phenol is phenol itself, alpha-naphthol, beta-naphthol, p-chlorophenol,
p-Methylphenol (p-ri□reso) and other Fresols 9 are possible. Catalyst is Mg0%
and phenol in a vibrating ball mill or similar equipment.
Milled for 6 to 72 hours 9 and then treated the mixture with excess T ICl3 in solvent at high temperature rc.

Decanting the solvent followed by two washes with fresh solvent and drying the precipitate (all under N2) gives the desired catalyst.
Mg'CJ2 to phenocyphenol 4/1 to 100
/1. The molar ratio of MgCJ2 to 'rt(J) is from 2000/1 to 14/1.

The cocatalyst system is the same as described above for preferred catalyst system (1), with the difference that the cocatalyst and modifier must not be pre-aged. In fact, aging for 30 minutes reduces catalyst activity. The cocatalyst system includes an arun di-alkyl modified with an alkyl di-substituted penzoate. Para-substitutions are hydrogen or electron donating groups. (Hammett sigma values are zero or negative). The ratio of M to denaturant is 2/1
to infinity.

Preferred catalyst (2) is essentially the same as preferred catalyst system (2) except that preferred catalyst system (2) is the same as preferred catalyst system (2).
Note the substitution of phenol for the alkyl benzoate in the (-) of 0.
' to 80°C or higher, and ethylene-
For the chlorine stage, it is carried out at temperatures of -10° to 80°C. A preferred procedure is to heat the polymerization system to 55°C and begin polymerization while maintaining the temperature below 77°C. The second stage of copolymerization of ethylene and propylene is usually 60° and 7°.
Perform at 7℃.

The third stage, if present, is typically kept between 60° and 77°C.

The first polymerization stage is short-term from 10 to 25 minutes, and the second stage is short-term from 1513) to 45 minutes.

And the final stage, if any, only takes a short time, from 10 to 25 minutes. of course.

Longer times are also possible. The exact reaction time will depend on variables such as reaction temperature and pressure, heat transfer rate, etc.

The polymerization is preferably carried out with a hydrocarbon fraction (boiling point 9, for example 306
and 60° C.) in an organic solvent such as hexane. Other hebutane, octane.

Alternatively, solvents such as higher alkanes can also be used. Aromatic hydrocarbons can also be used, of which benzene and toluene are two sides. Since the resulting polymer is only partially soluble in the solvent.

Therefore, a slurry type polymer is provided. The solvent is "inert" in the sense that it does not adversely interfere with the catalytic or polymerization reaction. Excess zolozelene over propylene participating in the polymerization can serve as the reaction medium; isobutylene is another example of a suitable reaction medium.

The fact that the polymer is not completely soluble in the solvent system allows operation at high solids concentrations due to the low viscosity of the reaction medium for a given solids concentration, thereby keeping the exothermic polymerization under control. helps promote heat transfer. Polymerization produces a small particle slurry (easily dispersed)
Handling problems are thereby facilitated and the transfer of the reaction mixture from the reactor to the finishing equipment is easily achieved.

Finishing of the polymer includes the usual practices such as addition of polymerization terminators; addition of antioxidants, steam coagulation, or vacuum ``ram drying.'' Efficiency of polymerization (20,000-100,000
0Ii-Limer/g Titanium) eliminates the need for a cleaning step unless required to minimize aluminum residue. A washing step can be carried out if necessary. The resulting waste can be dried and granulated for use in injection molding or formed into other shapes such as flakes using conventional commercial equipment. Oil extension yields a soft polymer with an excellent tensile value to hardness ratio.

The following examples illustrate the preparation of catalysts and the practice of the invention.

At 110°C, one three-necked flask was dried in an oven, and an apparatus consisting of a mechanical stirrer, an addition funnel, a thermometer, and a reflux condenser was placed on top of the condenser to keep the apparatus under nitrogen flow. Installed the adapter. N was discharged through a bubbler containing a small amount of oil. Heptane (450 kg) and Ticja (48 g, 82,8 Il, 0.
4! 52d (54,7N
, 0.364 mol) of ethyl benzoate was added dropwise. After the addition was complete, the reaction mixture was stirred for 1 hour.

The heptane was dissipated under vacuum and the solid complex fuming in air was bottled with tape in a N2 glove box. The complex appears to remain active in the absence of air.

B) Formation of supported catalyst complexes Dry in an oven and made of a porcelain jar containing I lideropyrene and half illuminated under N2 with a mixture of 4 parts anhydrous Mg"2 per part catalyst complex. Detent. The lid was taped to further preserve the contents and the bottle was placed in a vibrating mail mill for at least 15 hours and usually 30 hours. It was stored until needed. The dried complex appears to be stable for at least 3-5 months. When dispersed in a solvent, it begins to lose its activity after about 4 days. 1g of complex is 28■
Contains titanium.

251mt3u (1,6M) is reacted with the required amount of ethyl anisate (10-40 mol) in hexane or heptane keeping the temperature below 50°C. The clear yellow liquid was aged for 4 hours before being added to the polymerization medium. The same procedure was carried out using ethyl pt-butyl benzoate in place of ethyl anisate. Use of other modifiers gave significantly poorer results. Omitting the modifier resulted in low molecular weight/IJ moms with low tensile values and high yields.

Examples 1-7 and Comparative Example 1 To a 20 gallon jacketed pressure reactor equipped with an enclosed mechanical stirrer was added 40 parts of hexane followed by 4 parts of propylene. Then 250-1.6 MEt
3At (400 mmol) was diluted with 4001 hexane and 16.79 ethyl pt-decyl penzoate (gpTnB) (equivalent to 86.4 mmol ester)
The molar ratio of Niester to Ajlt3 was 0.21.
An aged cocatalyst made up of 6 was added. The co-catalyst solution was allowed to age for one hour before being added to the reactor.

6,49 (1809Ti)1 dispersed in hexane
7) The reaction was started by adding catalyst and the pressure was maintained at 50 psig by feeding zorogylene. A regulating valve was used to regulate the pressure. As cooling progresses, the temperature becomes 13
The temperature rose from 01 to 140'lF. After 15 minutes, the supply of cyclogylene was stopped, and ethylene of cp ethylene v and aooy were rapidly supplied until the charge of ethylene was completed. At this point the pressure is 55
, 2 p-1g. To hold on to this pressure 1
Ethylene and propylene were supplied in a molar ratio of 1 to 1. B/P
Even at maximum cooling with the charge, the temperature rose to 175'ff. After 45 minutes the temperature was 148@P. The monomer feed was stopped and the reaction mixture was removed from the vessel, the reactor was rinsed with hexane, the rinse was added to the removed product, and the whole was quenched with 100 I of isopropyl alcohol. At this point add 40g of antioxidant with stirring and collect the debris? The reamer suspension was steam-coagulated. Dry and mill on! When combined, the homogeneous product gave a yield of 7730.9 (efficiency -42
, 944Ii &Rimmer/p'ri).

The relevant data for this example is in Table 1 below.

One will see a 90-day utilization of the total added ethylene and a 75-hour utilization of the total added zolothelene.

The I remer has a propylene crystallinity of 451 when determined by X-ray at a thiethylene content of 15.

The temperature of the moth is -48℃, and the polymer D'l! The melting point at 154°C indicates the presence of isotactic propylene segments.
It has a tensile value of 1736 psl at s elongation.

The 250°F property is specifically defined in U.S. Pat.
- No high temperature tensile value of the one-stage product of No. 1 and 24
This is appropriate compared to the melting point of B'FCl (20°C).

Examples 2-7, carried out under essentially equivalent conditions, are recorded in Table 1.

Example c-1, a comparative or control example outside the scope of the present invention, combines a polymer made according to the one-step process of U.S. Pat.
(included to show the difference between -).

It is clear that the tensile value of Example C-1/Lima-1 at 250° F. is zero for all practical purposes.

A 20 gallon reactor VC was charged with 40 kg of hexane and aooop of propylene as in Example 1. The solution was then heated to 132°F. 4 in pre-reacted hexane
Polymerization was initiated by addition of 00 mmol Ht 3 kl and 146 mmol (1809 titanium). At this point the pressure is 46.5 psig and pump as needed to keep the pressure at this point! − was supplied. 10
After minutes the reaction was exothermic reaching 142F and after 25 minutes the pressure was 47 paig and the temperature was 1261F. Stop the chlorine and add ethylene to increase the pressure to 55%. .

I turned it up to psig ic. The pressure was maintained at this level by feeding ethylene and the second phase was run t-
It lasted 25 minutes. The temperature was 146°FVC and the pressure was 55.3 p-1 g.

The final 25 minutes were run on propylene monomer only, during which the pressure dropped to 40°C and the temperature to 110°F'.

The polymer slurry was removed in bulk into a receiver, the 9 reactor was rinsed with hexane, and this was added into the receiver. Isozolopanol (1009) was added to stop the polymerization and the antioxidant was added with stirring. The polymer was recovered by steam coagulation, dried under vacuum and agglomerated on a mill to ensure a homogeneous mixture. -L. The yield was 4.5009 (24.7729 polymer per 11I titanium).

Physical properties are shown below Example 8 in Table 3.

It can be seen that properties such as tensile value are very good.

The high temperature tensile values are also very good.

Monomer utilization is good for ethylene and modest for propylene.

Examples 9 to 13 in Table 1 are experiments using almost the same method to provide the properties described in Table 1. Again, as expected, high temperature properties are excellent for materials of high hardness and become poorer with decreasing hardness.

, but still provides a material that maintains good tensile values. The applicant obtained a Shore hardness value of 70 or less and a tensile value of 600.
can be maintained at or above pi. This is difficult to do by TPO as a group. The oil used in this experiment was Tofflo(TM) 6056 and At1
paraffinic hydrocarbon oil from ant1a R1ahf1*ld. The oil is mixed with stabilizers on a mill or Banbury and the resultant is injection molded. Example 15-2, in which the properties of the oil-extended material of Example 15 were carried out in the same manner.
Examples 21-24 and Comparative Example 2-
4 Samples of thermoplastic elastomers within the meaning of the invention, Examples 21-24. was analyzed to determine its spectral characteristics. The results of these tests are summarized in Table 1 below.
-4, which is a description of prior art ethylene-tetrapyrene polymers.

Table ■ PAP p
/'fLp p, tp/'p thiethylene
29.4 18,0 22,0(n)13
52,29 1,73 4.85 Crystallinity (X-ray") 41.1 37.OTg('
O) -50-35-45Tm(
°C) 161162156 11.88 / 12.18 (IR ratio) 26.5
12.1 9.6810 / 840 (In ratio) 1,589 1,2168 1.4862
880/2850 (Raman ratio) 2.146
2,3510 2.351 Flexural modulus (PSI)
25,000 18.200 22.00OR,
'r, tensile strength PSI) 1.643
2,953 2.121 Elongation (ch)
650 610 390* Same polymer as Example 9 ** Same polymer as Example C-1 HP 5tsuku HP φPDM3
0.7 25,0 27,02.43 2.
87 1.2630.9 49.0 3
1,0-46 None -58 120162161 3,414,014,0 0,9251,54011,566 2,0392,2351,854 6,500112,80024,0001,2912,
913970 62097330 No l II
The data in the % table (1) show the differences between the thermoplastic elastomers of the present invention and those of the prior art. As can be seen, U.S. Pat.
As discussed in US Pat. is more than 7.0. Similarly, in the Raman spectrum, +810 cm
The intensity ratio at K and at 840α-1 is greater than 1.0 for polymers within the meaning of this invention.

While 28B 0CII Pan V vs. 2850cIL
The strength ratio of Pan r is 2.0 or more for the elastomer of the present invention. A one-step process thermoplastic elastomer representative of the prior art as disclosed by U.S. Pat. , the R ratio is less than 7.0 and the inner spectral ratio is less than 1.0.

The elastomers of the present invention are further distinguished by a differential thermal melting point of 120° C., which is slightly lower than the requirements for single-stage polymeric thermoplastic elastomers of U.S. Pat. No. 4,298,721. Characterized by a melting point of at least 150°C.

Comparative Example c-3 is illustrative of a prior art plastic copolymer. Although it is difficult to distinguish it from the polymer of the present invention based on the spectral data of this sample, it can be clearly distinguished by the lack of a glass transition temperature, which is a characteristic of crystalline plastics.

All thermoplastic elastomers have a glass transition temperature.

The crystalline plastic exemplified by Example c-3 also has a high flexural modulus, typically 100.000 T.
151 or higher, in this example 112,800 pai and low elongation, typically less than 150%, distinguished by 97 Is in this example. These properties distinguish the thermoplastic elastomers of the present invention.

This is lower than 100.000 pal and often significantly lower in flexural modulus. The thermoplastic elastomer of the present invention can also be used as a block copolymer plastic.
It is distinguished by its high elongation, which is characteristic of mu-like polymers. The thermoplastic elastom i- of the present invention has an elongation of 150% or more.

Comparative Example C-4 draws attention to a typical thermoplastic elastomer of the prior art. Often prior art thermoplastic elastomers are physical mixtures of crystalline plastics, 9 and usually blends of polyzorogyline and elastomer, such as Comparative Example 3, IEPDM. These polymers are distinguished from the thermoplastic elastomers of the present invention by their Raman spectral properties. In particular, for physically compounded thermoplastic elastomers, the ratio of strength in pan P of 2880 ml to strength in pan r of 2850 cm 1 is less than 2.0. The same ratio for thermoplastic elastomers of the present invention is greater than 2.0.

Example 26 Preparation of catalyst This example utilizes the preferred catalyst system (2).

Purified phenol (6,3, @
) and then milled for 31 hours. Materials 500-
Transfer in an inert environment to a three-necked round-bottomed flask and
1E/hedenpone and 18 III f) TlC1
4K! : Processed. Heat the mixture at 100° C. for 1 hour.

Upon cooling, the liquid was decanted and the precipitate was washed twice with fresh solvent. All the above operations were performed under dry nitrogen.

20 Gallon Reactor Experiment To a clean and dry reactor was added 40 g of hexane and 4 g of purified propylene. The solution was heated to 135"F and then treated with xt3u (80m)
, 8, F=20 da'T1) were added.

The pressure at this point was 64 palg. There was no need to feed propylene to maintain this pressure. After 15 minutes, 4001 ethylene was added rapidly.

Pressure was 86 pslg rc. The temperature is 160°I
i'eC was raised and maintained at this temperature.

After maintaining this pressure by feeding ethylene and propylene in a 4/1 molar ratio for 30 minutes, 9 reaction masses were discharged into the receiver. The reactor was washed with hexane and the hexane was added to the reaction mixture. After adding isozologyl alcohol to stop the reaction, AO449 (Trademark: Antioxidant) was added and finally the polymer was separated by steam coagulation. The polymer was dried under vacuum. The material yield was 2,070 g (100,0
00g polymer #Ti). Thiethylene is 24 and 1, V at 135°C in tetralin.

There was a 5.30-e. ML-40257°FG”!1
It was 09.

The advantage of this catalyst is high efficiency (low amount of catalyst reduces catalyst costs and eliminates the need for cleaning poly-cement)
and the omission of the ripening step in the preparation of the cocatalyst.

Example 27 In this example, only 70 or less of the propylene charged in the first stage was polymerized in that stage (as measured by total solids measurement).

This illustrates the fact that 60- or more can be left for the second stage (HP) or the third stage (EP/P).

(16A) Charge aooog propylene, 40.0009
Hexane and 600 g of the above total catalyst solution. Once polymerization begins, add additional propylene (1,105 g) to maintain pressure.
) constantly. At the end of this first stage, the total solids content is 1252 g polypropylene. The propylene used in the first stage is therefore calculated as follows: 1252 g polyzorogyline Add in the third step to make more polypropylene.

(16B) Charge 4000g propylene, 40. Cl00
g Total catalyst solution in hexane and 560I. Add an additional 1.690 i of propylene to maintain pressure during the first stage. 1295 Il of polyzolo t-rene is produced. The Zorogi wrench used in the first stage is calculated as follows: 1295N Polyzoro T-Ren 1] Commissioner of the Japan Patent Office 1, Indication of the case Patent Application No. 80834 of 1980 2, Name of the invention Thermoplastic nidistomer 3, Person making the amendment Relationship to the case Patent applicant 4, Agent 5, Date of amendment order Month, Day 6, 1939, number of inventions increased by amendment; engraving of the specification (no change in content)

Claims (9)

[Claims] (1) Contains polymers of ethylene and propylene. A thermoplastic elastomer in which said propylene is from 60 to 95% by weight of said primer, wherein the absorption intensity in the infrared spectrum of 11.88 f Kron in Pan I' versus the absorption in Pan R of 12.18 < Kron y The intensity ratio is thicker than 7.0 (; 81 in the Raman spectrum
Intensity in the band of 0CII vs. 840cst
The ratio of the intensity at the pan PVc of the Niraman spectrum at 2880 an-'f) to the intensity at the pan V of 2850 cm is greater than 2.0 (bending at room temperature) The elastic modulus is 100.
A thermoplastic elastomer characterized in that it has an elongation at room temperature of less than 1,000 lbs/in2; an elongation at room temperature of greater than 150 sq.; and a differential thermal analysis melting point of at least 10 of at least 150'O. (2) The thermoplastic elastomer according to claim 11, characterized in that it has a crystalline transformation of 15 to 45 as measured by x-rays. (3) The thermoplastic elastomer according to claim (1), which has an intrinsic viscosity of 1.5 to 6 when measured in tetralin at 135°C. (4) Inotactic A polypropylene segment having polyzologylene type crystallinity and an amorphous segment which is an elastic ethylene-propylene material, wherein said segment and said amorphous segment are only a part of each other. claim 1, characterized in that the weight ratio of the polypropylene segment to the amorphous segment is within the range of 10:90 to 75:25. Thermoplastic elastomer 1-0 described in section ) (5) The polypropylene segment is 1 based on the total weight of propylene in the thermoplastic elastomer.
Claim No. 4 (4) characterized in that the
) The thermoplastic elastomer described in item 1. (6) 3o to 7 extractable by boiling n-hexane
Thermoplastic elastomer according to claim @(1) comprising up to 0% by weight of said thermoplastic elastomer (7) Oil-extended thermal elastomer according to claim (1). (8) The thermoplastic elastomer according to claim (1), wherein the poly-i- is propylene and ethylene-propylene polymer. (9) The thermoplastic elastomer according to claim (1), wherein the 4-limer is a polymer of propylene, ethylene-zorogylene, and propylene. αQ Propylene is contacted with a polymerization catalyst under polymerization conditions in solution, which causes at least some polymer molecules to become short-lived active. ethylene and zolozelene are added to the polymerization mixture to sequentially form an ethylene-propylene corimer therein, and optionally propylene is subsequently added to the reaction mixture. Sequentially added polyzorogylene into it vc
<9° The resulting polymer has (A) polypropylene segments with crystallinity of the isotactic polyzologylene type and (B1 amorphous segments that are elastomeric ethylene-propylene materials; ) vs. (B
) of propylene and (ethylene-propylene) or of propylene and (ethylene-zorogylene) and zolozelene, characterized in that the weight ratio of Town m sex elastomeric sequential poly! - How to make. 62. The method of claim 61, wherein al) polyzorogylene segment (A) comprises 15-70% by weight of the total polymerized propylene. (13) The process according to claim .alpha., wherein less than 50% by weight of the propylene charged in the first stage is converted to polypropylene.
A process as claimed in claim 1, wherein less than 50% by weight is converted to polypropylene. Q4) The catalyst is a titanium halide or a complex of this with an electron donor supported on a halide of magnesium or manganese, and an organic aluminum compound or a substitution product or adduct of this with an electron donor. A method according to claim 1, wherein the catalyst system comprises a co-catalyst that is. al said catalyst is: (-) a catalyst which is the reaction product of titanium tetrachloride and an alkyl benzoate and is supported on anhydrous magnesium dihalide; and (b) by reaction with an electron-rich substituted penteate. A cocatalyst that is a modified trialkyl arunium dime. The method of claim 00, wherein the catalyst system comprises: al (-) is ground to a particle size of 1 electron or less. Alkyl benzoate is ethyl benzoate), 2/・Macnesium rhodanide is magnesium dichloride P? , the trialkylaluminum is triethylaluminum, the electron-rich substituted benzoate is ethyl anisate or p-t-butityl benzoate, and the catalyst (
, 1 in which the molar ratio of tetra-titanium to alkyl benzoate is 1.1:1;
In claim 4, the molar ratio of trialkylalumnium to benzoate is from 2:1 to 10:1 and the molar ratio of aluminum to titanium is from 50:1 to 200:1. Method described. aη The method of claim 00, wherein said electron-rich substituted benzoate is pt-decyl benzoate. (-) a reaction product of titanium tetrachloride and phenol supported on anhydrous magnesium dihalide; and (b) a trichloride modified by reaction with an electron-rich substituted benzoate. A cocatalyst that is an alkyl aluminum. The method according to claim 01, which is a catalyst system comprising: (1'J (-) is ground to a particle size of 1z chlorine or less. 2 Magnesium halide is magnesium dichloride r
So, is phenol itself phenol? The trialkylarudenium is triethylaldinium, the electron-rich modified benzoate is ethyl anisate or ethyl t-butylbenzoate, and the weight ratio of magnesium dichloride r to phenol is 4=1 to 100: Up to 1. A process according to claim 1, wherein the molar ratio of magnesium dichloride to titanium tetrachloride is from 2000:1 to 14:1, and wherein the molar ratio of alonium to titanium is at least 2:1. (to) the formation of / 13 ff- is sequentially propylene and (ethylene-zolozelene)yi-, and the polymerization temperature is from 20° to 80°C in the first stage and 13°C in the second stage. The method according to claim 1, wherein the temperature is from 10° to 80°C. ? 20 The polymers produced are sequential propylene, (ethylene-propylene) and propylene polymer t. 9 The polymerization temperature is in the first stage t.
to 77°C, in the second stage to 77°C, and in the third stage to 4160°C.
' to 77<0>C. (To) The polymers produced are sequential propylene and (ethylene-zorogylene) polymers, and the polymerization temperature is from 20° to 80°C in the first stage, and to 110°C in the third stage. The method according to claim 0, wherein the temperature is from °p1 to 80 °C. (c) The polymer produced is a polymer of sequential propylene, (ethylene-propylene) and zorogylene, and 9
The polymerization temperature is at the first stage t・G'! , 55° force 1 et 7
The temperature is up to 7℃, and the second stage is 606 degrees Celsius.
up to 77℃, and in the third stage t・te 1ヱ60
A method according to claim 4, wherein the temperature is from 6 to 77°C.