Olefin resin and method for producing same

Patent metadata

Field	Value
Publication number	US-9714306-B2
Application number	US-201515128336-A
Country	US
Kind code	B2
Filing date	Mar 26, 2015
Priority date	Mar 28, 2014
Publication date	Jul 25, 2017
Grant date	Jul 25, 2017

Abstract

The present invention provides an olefin resin with an improved heat resistance, reduced stickiness, excellent optical and low temperature properties, as well as the balance between these physical properties. The olefin resin according to the present invention satisfies the following requirements: (I) a melting peak (Tm) is observed within the range of from 60° C. to 130° C., and the heat of fusion ΔH at the melting peak is within the range of from 5 to 150 J/g; (II) the percentage E (wt %) of a portion soluble in o-dichlorobenzene at 20° C. or lower, and the heat of fusion ΔH satisfy certain relationships; (III) the glass transition temperature (Tg) is from −80 to −30° C.; (IV) the spin-spin relaxation time (T2) of a component having the highest mobility, as obtained in a four-component approximation with a Lorentzian function performed for a free induction decay curve, is within the range of from 150 to 500 ms, and the abundance ratio of the component is within the range of from 15 to 50%; and (V) the intrinsic viscosity [η] as measured in decalin at 135° C. is within the range of from 0.1 to 12 dl/g.

First claim

The invention claimed is:

1. An olefin resin satisfying the following requirements (I) to (V):
(I) a melting peak (Tm) as measured by differential scanning calorimetry (DSC) is observed within the range of from 60° C. to 130° C., and the heat of fusion ΔH at the melting peak is within the range of from 5 to 150 J/g;
(II) the percentage E (wt %) of a portion soluble in o-dichlorobenzene at 20° C. or lower as measured by cross-fractionation chromatography (CFC), and the heat of fusion ΔH as described in (I) above, satisfy the following relationships:
when the ΔH is 5 J/g or more and less than 15 J/g, the value E is 45 wt % or less,
when the ΔH is 15 J/g or more and less than 30 J/g, the value E is 40 wt % or less, and
when the ΔH is 30 J/g or more, the value E is 30 wt % or less;

(III) the glass transition temperature (Tg) as measured by differential scanning calorimetry (DSC) is within the range of −80 to −30° C.;
(IV) the spin-spin relaxation time (T2) of a component having the highest mobility, as obtained in a four-component approximation by a Lorentzian function performed for a free induction decay curve obtained by Carr Purcell Meiboom Gill method in a pulsed nuclear magnetic resonance measurement (pulsed NMR) at 200° C., is within the range of from 150 to 500 ms, and the abundance ratio of the component is within the range of from 15 to 50%; and
(V) the intrinsic viscosity [η] as measured in decalin at 135° C. is within the range of from 0.1 to 12 dl/g.

2. The olefin resin according to claim 1 , wherein the olefin resin has a tensile elastic modulus in accordance with ASTM D638 within the range of from 2 to 120 MPa.

3. A method for producing the olefin resin according to claim 1 , the method comprising the step of copolymerizing ethylene and at least one α-olefin selected from α-olefins having from 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst comprising each of the following components (A) to (C):
(A) a transition metal compound of a transition metal of Group 4 in the periodic table, the compound comprising a ligand having a cyclopentadienyl skeleton;
(B) at least one transition metal compound selected from compounds represented by the following general formulae [B0], [B1], or [B2]; and
(C) at least one compound selected from an organometallic compound (C-1), an organoaluminum oxy compound (C-2), or a compound (C-3) which reacts with the transition metal compound (A) or the transition metal compound (B) to form an ion pair;

wherein in the general formula [B0],
M represents a transition metal atom of Group 4 or 5 in the periodic table,
m represents an integer of from 1 to 4;
R 1 represents an acyclic hydrocarbon group (C n′ H 2n′+1 , n′=1 to 20) having from 1 to 20 carbon atoms or a hydrogen atom;
R 2 to R 6 , which may be the same or different from each other, each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these are optionally bound together to form a ring;
in cases where m is two or more, two of the groups represented by R 2 to R 6 are optionally bound to each other;
n is a number satisfying the valence of M;
X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group; and
in cases where n is two or more, Xs may be the same or different from each other, and a plurality of groups represented by X are may be bonded to each other to form a ring

wherein in the general formula [B1],
M represents a transition metal of the Group 4 or 5 in the periodic table;
m represents an integer of from 1 to 4;
R 1 represents an alicyclic hydrocarbon group of a 3- to 10-membered ring, optionally including one or more substituents;
R 2 to R 6 , which may be the same or different from each other, each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these are optionally bound together to form a ring;
in cases where m is two or more, two of the groups represented by R 2 to R 6 are optionally bound to each other;
n is a number satisfying the valence of M;
X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group; and
in cases where n is two or more, Xs may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring

wherein in the general formula [B2],
M represents a transition metal of the Group 4 or 5 in the periodic table;
m represents an integer of from 1 to 4;
R 1 represents a bicyclic aliphatic hydrocarbon group having from 4 to 20 carbon atoms, optionally containing one or more substituents, wherein the two rings of the bicyclic aliphatic hydrocarbon group share at least one or more carbon atoms;
R 2 to R 6 , which may be the same or different from each other, each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these are optionally bound together to form a ring;
in cases where m is two or more, two of the groups represented by R 2 to R 6 are optionally bound to each other;
n is a number satisfying the valence of M;
X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group; and
in cases where n is two or more, Xs may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring.

4. The method for producing the olefin resin, according to claim 3 , wherein the transition metal compound (A) is a bridged metallocene compound represented by the following general formula (I):

wherein in the formula (I),
R 1 , R 2 , R 3 , R 4 , R 5 , R 8 , R 9 and R 12 each independently represents a hydrogen atom, a hydrocarbon group, a silicon-containing group, or a hetero atom-containing gro

Assignees

• Mitsui Chemicals Inc

Inventors

• Yanagimoto Yasushi
• Matsugi Tomoaki
• Iwashita Akihiko
• Nakamura Tatsuya
• Saito Junji

Classifications

• C08F210/16 Primary

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C08L23/0815

  with aliphatic 1-olefins containing one carbon-to-carbon double bond · CPC title

• C08F290/042

  Polymers of hydrocarbons as defined in group C08F10/00 · CPC title

• C08F210/06

  Propene · CPC title

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title