Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
2002-11-12
2004-12-14
Seidleck, James J. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C525S098000, C525S297000, C525S332200, C525S250000, C526S079000
Reexamination Certificate
active
06831134
ABSTRACT:
BACKGROUND OF THE INVENTION
1. The Field of the Invention
The present invention relates to a method for preparing a transparent block copolymer resin, a copolymer prepared from the method, and usages of the copolymer. More particularly, the present invention relates to a method for preparing a novel multicomponent copolymer that includes polymerizing only one charge of an initiator and using a multifunctional compound, unlike the conventional methods for preparing a multicomponent copolymer mixture that include polymerizing two or more charges each of an initiator, and to a mikto block copolymer with different terminal blocks prepared from the method.
2. Related Prior Art
A general purpose polystyrene(GPPS) is desirable in the aspect of inexpensiveness, processability, transparency and rigidity but inferior in flexibility and toughness.
High impact polystyrene (HIPS) invented to improve those inferior properties of GPPS remarkably improves the brittleness of polystyrene resins because of its structural characteristic that polybutadiene rubber particles are dispersed in the polystyrene. But HIPS is also disadvantageous in transparency, which is one of the strongest points of the polystyrene, as well as flexibility.
In an attempt to solve this problem, many studies have been made on the polystyrene resins excellent in transparency, rigidity, flexibility and strength, as a consequence of which block copolymers prepared by anionic polymerization using an organic metal compound as an initiator have been suggested.
The technologies of the conventional block copolymers prepared by anionic polymerization using an organic metal compound as an initiator are, however, problematic in that such an attempt to produce multi-block and multi-component copolymers for the balance of the above-mentioned properties complicates the polymerization process and only limitedly realizes the properties.
For example, U.S. Pat. Nos. 4,584,346, 5,705,569 and 6,096,828 disclose a method for preparing various block copolymers using two or more charges of an initiator and monomers. This method, which may be advantageous to provide balanced mechanical properties, requires more carefulness in controlling the purity and the amount of monomers added in multiple steps and solvents, and the added amount of the initiator, and involves a long polymerization time, thereby causing a problems in productivity and processability.
The copolymer employing a relatively simple polymerization method is represented by S-B/S, where S is a vinyl aromatic block; and B/S is a tapered block formed by simultaneously or sequentially contacting a conjugated diene monomer and a vinyl aromatic monomer. This method, introducing a tapered block in the multicomponent copolymer to balance the mechanical properties of the one-component copolymer, simplifies the process but results in a deterioration of the properties.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to prepare a transparent block copolymer resin that solves the problems with the prior art such as complicated process and unbalanced properties, and to provide a method for preparing a transparent block copolymer resin that includes using a multifunctional compound with only one charge of an initiator to introduce a terminal mikto block having a combined linear and nonlinear (i.e., combined linear, branched and radial) structure and then coupling the mikto block with a multifunctional coupling agent, thereby simplifying the synthesis process, enhancing mechanical properties such as rigidity, flexibility or strength, while maintaining toughness, and securing enhanced processability.
It is another object of the present invention to provide a block copolymer having various structures and compositions that is prepared by anionic polymerization using an alkyl lithium initiator to introduce a terminal mikto block including combined linear and nonlinear blocks.
It is further another object of the present invention to provide a bubble pack including transparent bottles prepared from the block copolymer.
To achieve the above objects of the present invention, there is provided novel methods for preparing a transparent block copolymer resin that includes polymerizing under solution polymerization conditions at least one vinyl aromatic monomer and at least one conjugated diene monomer in a ratio of 55 to 95 weight % vinyl aromatic monomer and 45 to 5 weight % conjugated diene monomer, wherein the polymerizing is conducted using a charge sequence of the following orders.
A first method of the present invention includes sequential following order:
(a) a vinyl aromatic monomer, a polar organic compound, a polymerization solvent and an anionic initiator to prepare an anionic polymer block;
(b) a multifunctional compound and a conjugated diene monomer being added to the anionic polymer block to prepare a mikto block of polymer having a combined linear and nonlinear structure block;
(c) a conjugated diene monomer;
(d) a vinyl aromatic monomer; and
(e) a multifunctional coupling agent.
A second method of the present invention includes sequential following order:
(a) a vinyl aromatic monomer, a polar organic compound, a polymerization solvent and an anionic initiator to prepare an anionic polymer block;
(b) a multifunctional compound and a conjugated diene monomer being added to the anionic polymer block to prepare a mikto block of polymer having a combined linear and nonlinear structure;
(c) a conjugated diene monomer and a vinyl aromatic monomer being added in a simultaneous or instantaneously sequential manner; and
(d) a multifunctional coupling agent.
A third method of the present invention includes sequential following order:
(a) a vinyl aromatic monomer, a polar organic compound, a polymerization solvent and an anionic initiator to prepare an anionic polymer block;
(b) a multifunctional compound and a conjugated diene monomer being added to the anionic polymer block to prepare a mikto block of polymer having a combined linear and nonlinear structure;
(c) a conjugated diene monomer and a vinyl aromatic monomer being added in a simultaneous or instantaneously sequential manner;
(d) a conjugated diene monomer and a vinyl aromatic monomer being added in a simultaneous or instantaneously sequential manner; and
(e) a multifunctional coupling agent.
A fourth method of the present invention includes sequential following order:
(a) a vinyl aromatic monomer, a polar organic compound, a polymerization solvent and an anionic initiator to prepare an anionic polymer block;
(b) a multifunctional compound and a conjugated diene monomer being added to the anionic polymer block to prepare a mikto block of polymer having a combined linear and nonlinear structure;
(c) a conjugated diene monomer;
(d) a vinyl aromatic monomer;
(e) a conjugated diene monomer;
(f) a vinyl aromatic monomer; and
(g) a multifunctional coupling agent.
A fifth method of the present invention includes sequential following order:
(a) a vinyl aromatic monomer, a polar organic compound, a polymerization solvent and an anionic initiator to prepare an anionic polymer block;
(b) a multifunctional compound and a conjugated diene monomer being added to the anionic polymer block to prepare a mikto block of polymer having a combined linear and nonlinear structure;
(c) a conjugated diene monomer and a vinyl aromatic monomer being added in a simultaneous or instantaneously sequential manner;
(d) a vinyl aromatic monomer; and
(e) a multifunctional coupling agent.
A sixth method of the present invention includes sequential following order:
(a) a vinyl aromatic monomer, a polar organic compound, a polymerization solvent and an anionic initiator to prepare an anionic polymer block;
(b) a multifunctional compound and a conjugated diene monomer being added to the anionic polymer block to prepare a mikto block of polymer having a combined linear and nonlinear structure;
(c) a conjugated diene monomer;
(d) a vinyl aromatic monomer;
(e) a conjugated diene monomer and a vinyl aromatic monomer being added in a simultaneous or instantan
Kim Jong-Geun
Kim Sam-Min
Park Jong-Hyun
Asinovsky Olga
Cook Alex McFarron Manzo Cummings & Mehler, Ltd.
Korea Kumho Petrochemical Co. Ltd.
Seidleck James J.
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