US4584346A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Craze-resistant transparent resinous polymodal block copolymers
Assignee: Phillips Petroleum Co
•
Filing: 1984-02-29
•
Granted: 1986-04-22
•
Expires: 2004-02-29
Abstract
Abstract Resinous polymodal block copolymers of such as butadiene and styrene which are craze-resistant, transparent, and substantially color-free, and methods of producing the block copolymers. The copolymers are prepared by sequential charge copolymerization modes comprising the solution polymerization of at least two charges each of a conjugated diene, a monovinylarene, and a monoalkali metal initiator, at least one charge of conjugated diene monomer precedes the last charge of monoalkali metal initiator, at least one charge each of monovinylarene and of conjugated diene follows the last charge of monoalkali metal initiator, and the final charge of monomer is a charge of conjugated diene monomer, such that the number of charges of each of said components is not more than three, and the total of the charges of the three components is 8 or 9.
Inventors
- 👤 Alonzo G. Kitchen
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-04 21:48
CPC Classifications
C; C08; C08F; C08F297/00; C08F297/02; C08F297/04; C08F297/044
Claims Analysis
Total Claims: 69
Claim 1
Independent Claim
228 words
A sequential mode of block copolymerization comprising: polymerizing under solution polymerization conditions at least one monovinylarene monomer and at least one conjugated diene monomer in a ratio of about 55 to 95 weight percent monovinylarene and 45 to 5 weight percent conjugated diene, by a sequential charge polymerization process wherein at least two separate charges consisting of said conjugated diene, at least two separate charges consisting of said monovinylarene, and at least two charges of a monoalkali metal initiator are employed; at least one separate charge of each of said monovinylarene and of said conjugated diene follows the last charge of said monoalkali metal initiator; at least one separate charge of conjugated diene precedes the last charge of monoalkali metal initiator; each separate monomer charge homopolymerizes to substantial completion prior to addition of any subsequent charge; the total of the number of separate charges of each of said conjugated diene, of said monovinylarene, and of said monoalkali metal initiator, is not in excess of 3, and thereafter coupling with a polyfunctional coupling agent; wherein said sequential charge polymerization process employs a charge order: ______________________________________
Charge
Order
______________________________________
1/2 L/S
3 B
4/5 L/S
6 B
7/8 L/S
9 B
10 C
______________________________________ where L=hydrocarbyl monoalkali metal initiator addition, S=monovinylarene monomer addition, B=conjugated diene addition, and C=coupling agent addition; thereby producing a polymodal, craze-resistant, low color, resinous coupled copolymer.
Claim 2
Dependent Claim
228 words
A sequential mode of block copolymerization comprising: polymerizing under solution polymerization conditions at least one monovinylarene monomer and at least one conjugated diene monomer in a ratio of about 55 to 95 weight percent monovinylarene and 45 to 5 weight percent conjugated diene, by a sequential charge polymerization process wherein at least two separate charges consisting of said conjugated diene, at least two separate charges consisting of said monovinylarene, and at least two charges of a monoalkali metal initiator are employed; at least one separate charge of each of said monovinylarene and of said conjugated diene follows the last charge of said monoalkali metal initiator; at least one separate charge of conjugated diene precedes the last charge of monoalkali metal initiator; each separate monomer charge homopolymerizes to substantial completion prior to addition of any subsequent charge; the total of the number of separate charges of each of said conjugated diene, of said monovinylarene, and of said monoalkali metal initiator, is not in excess of 3, and thereafter coupling with a polyfunctional coupling agent; wherein said sequential charge polymerization process employs a charge order: ______________________________________
Charge
Order
______________________________________
1/2 L/S
3 B
4/5 L/S
6 B
7/8 L/S
9 B
10 C
______________________________________ where L=hydrocarbyl monoalkali metal initiator addition, S=monovinylarene monomer addition, B=conjugated diene addition, and C=coupling agent addition; thereby producing a polymodal, craze-resistant, low color, resinous coupled copolymer.
Claim 3
Dependent Claim
10 words
The resulting copolymer prepared by the process of claim 1.
Claim 4
Dependent Claim
9 words
Blends of polystyrene with the copolymer of claim 2.
Claim 5
Dependent Claim
9 words
Blister packs made of the copolymer of claim 2.
Claim 6
Dependent Claim
55 words
The process of claim 1 employing ranges of monomer additions and of monoalkali metal initiator additions at each increment: ______________________________________
L-1 (mhm) 0.3-0.55
S-1 (phm) 30-45
B-1 (phm) 0.6-9
L-2 (mhm) 0.3-0.55
S-2 (phm) 10-20
B-2 (phm) 0.6-9
L-3 (mhm) 1.1-2.8
S-3 (phm) 15-30
B-3 (phm) 3.8-2.7
Totals S(phm) 55-95
B(phm) 45-5
L(mhm) 1.7-3.9.
______________________________________
Claim 7
Dependent Claim
91 words
The process of claim 5 wherein the resultant copolymer contains relative block sizes before coupling calculated from ranges of additions: __________________________________________________________________________
S.sub.1 --B.sub.1 --S.sub.2 --B.sub.2 --S.sub.3 --B.sub.3 :
S.sub.1 (phm)
30-45
B.sub.1 (phm)
0.6-9
S.sub.2 (phm)
5-10
B.sub.2 (phm)
0.3-4.5
S.sub.3 (phm)
2.6-4.2
B.sub.3 (phm)
0.7-3.8
,
S.sub.2 --B.sub.2 --S.sub.3 --B.sub.3 :
S.sub.2 (phm)
5-10
B.sub.2 (phm)
0.3-4.5
S.sub.3 (phm)
2.6-4.2
B.sub.3 (phm)
0.7-3.8
, and
S.sub.3 --B.sub.3 :
S.sub.3 (phm)
9.7-21.6
B.sub.3 (phm)
2.4-19.4
; and molecular weights
after coupling:
M.sub.n × 10.sup.-3
80-300
and
M.sub.n × 10.sup.-3
50-200.
__________________________________________________________________________
Claim 8
Dependent Claim
54 words
The process of claim 1 employing ranges of monomer additions and of monoalkali metal additions at each increment: ______________________________________
L-1 (mhm) 0.34-0.47
S-1 (phm) 35-41
B-1 (phm) 2-4
L-2 (mhm) 0.34-0.47
S-2 (phm) 12-18
B-2 (phm) 2-4
L-3 (mhm) 1.56-2.34
S-3 (phm) 18-26
B-3 (phm) 16-23
Totals S(phm) 70-80
B(phm) 30-20
L(mhm) 2.2-3.3.
______________________________________
Claim 9
Dependent Claim
91 words
The process of claim 7 wherein the resultant copolymer contains relative block sizes before coupling calculated from narrow ranges of additions: __________________________________________________________________________
S.sub.1 --B.sub.1 --S.sub.2 --B.sub.2 --S.sub.3 --B.sub.3 :
S.sub.1 (phm)
35-41
B.sub.1 (phm)
2-4
S.sub.2 (phm)
6-9
B.sub.2 (phm)
1-2
S.sub.3 (phm)
2.7-3.7
B.sub.3 (phm)
2.4-3.3
,
S.sub.2 --B.sub.2 --S.sub.3 --B.sub.3 :
S.sub.2 (phm)
6-9
B.sub.2 (phm)
1-2
S.sub.3 (phm)
2.7-3.7
B.sub.3 (phm)
2.4-3.3
and
S.sub.3 --B.sub.3 :
S.sub.3 (phm)
12.5-18.5
B.sub.3 (phm)
11.1-16.4
; and molecular weights
after coupling:
M.sub.w × 10.sup.-3
150-200
and
M.sub.n × 10.sup.-3
90-120.
__________________________________________________________________________
Claim 10
Dependent Claim
40 words
The process of claim 8 wherein said conjugated diene monomer contains 4 to 6 carbon atoms per molecule; said monovinylarene monomer contains 8 to 10 carbon atoms per monomer; and employing a hydrocarbyl monolithium initiator as said monoalkali metal initiator.
Claim 11
Dependent Claim
18 words
The process of claim 9 employing butadiene or isoprene as said conjugated diene, and styrene as said monovinylarene.
Claim 12
Dependent Claim
23 words
The process of claim 10 employing butadiene as said conjugated diene, butyllithium as said initiator, and an epoxidized compound as said coupling agent.
Claim 13
Dependent Claim
6 words
The resulting copolymer of claim 11.
Claim 14
Dependent Claim
9 words
Blends of polystyrene and the copolymer of claim 12.
Claim 15
Dependent Claim
8 words
Blister packs comprising the copolymer of claim 12.
Claim 16
Dependent Claim
220 words
A sequential mode of block copolymerization comprising: polymerizing under solution polymerization conditions at least one monovinylarene monomer and at least one conjugated diene monomer in a ratio of about 55 to 95 weight percent monovinylarene and 45 to 5 weight percent conjugated diene, by a sequential charge polymerization process wherein at least two separate charges consisting of said conjugated diene, two separate charges consisting of said monovinylarene, and at least two charges of a monoalkali metal initiator are employed; at least one separate charge of each of said monovinylarene and of said conjugated diene follows the last charge of said monoalkali metal initiator; at least one separate charge of conjugated diene precedes the last charge of monoalkali metal initiator; each separate monomer charge homopolymerizes to substantial completion prior to addition of any subsequent charge; the total number of separate charges of each of said conjugated diene, said monovinylarene, and charges of said monoalkali metal initiators, is not in excess of 3, and thereafter coupling with a polyfunctional coupling agent; wherein said sequential charge polymerization process employs a charge order: ______________________________________
Charge
Order
______________________________________
1/2 L/S
3 B
4 S
5 B
6/7 L/S
8 B
9 C
______________________________________ where L=monoalkali metal initiator, S=monovinylarene monomer, B=conjugated diene monomer, and C=coupling agent; thereby producing a polymodal, craze-resistant, low color, resinous coupled copolymer.
Claim 17
Dependent Claim
220 words
A sequential mode of block copolymerization comprising: polymerizing under solution polymerization conditions at least one monovinylarene monomer and at least one conjugated diene monomer in a ratio of about 55 to 95 weight percent monovinylarene and 45 to 5 weight percent conjugated diene, by a sequential charge polymerization process wherein at least two separate charges consisting of said conjugated diene, two separate charges consisting of said monovinylarene, and at least two charges of a monoalkali metal initiator are employed; at least one separate charge of each of said monovinylarene and of said conjugated diene follows the last charge of said monoalkali metal initiator; at least one separate charge of conjugated diene precedes the last charge of monoalkali metal initiator; each separate monomer charge homopolymerizes to substantial completion prior to addition of any subsequent charge; the total number of separate charges of each of said conjugated diene, said monovinylarene, and charges of said monoalkali metal initiators, is not in excess of 3, and thereafter coupling with a polyfunctional coupling agent; wherein said sequential charge polymerization process employs a charge order: ______________________________________
Charge
Order
______________________________________
1/2 L/S
3 B
4 S
5 B
6/7 L/S
8 B
9 C
______________________________________ where L=monoalkali metal initiator, S=monovinylarene monomer, B=conjugated diene monomer, and C=coupling agent; thereby producing a polymodal, craze-resistant, low color, resinous coupled copolymer.
Claim 18
Dependent Claim
51 words
The process of claim 15 employing ranges of monomer additions and of monoalkali metal added at each increment: ______________________________________
L-1 (mhm) 0.39-0.78
S-1 (phm) 30-45
B-1 (phm) 0.6-9
S-2 (phm) 10-20
B-2 (phm) 0.6-9
L-2 (mhm) 1.56-3.9
S-3 (phm) 15-30
B-3 (phm) 3.8-27
Totals S(phm) 55-95
B(phm) 45-5
L(mhm) 2-4.7.
______________________________________
Claim 19
Dependent Claim
70 words
The process of claim 16 wherein the resultant block copolymer contains calculated relative block sizes before coupling: __________________________________________________________________________
S.sub.1 --B.sub.1 --S.sub.2 --B.sub.2 --S.sub.3 --B.sub.3 :
S.sub.1 (phm)
30-45
B.sub.1 (phm)
0.6-9
S.sub.2 (phm)
10-20
B.sub.2 (phm)
0.6-9
S.sub.3 (phm)
3-5
B.sub.3 (phm)
0.8-4.5
, and
S.sub.3 --B.sub.3 :
S.sub.3 (phm)
12-25
B.sub.3 (phm)
3-22.5
; and molecular weights
after coupling:
M.sub.w × 10.sup.-3
80-300
and
M.sub.n × 10.sup.-3
50-200.
__________________________________________________________________________
Claim 20
Dependent Claim
55 words
The process of claim 15 employing ranges of monomer additions and of monoalkali metal initiator added at each increment: ______________________________________
L-1 (mhm) 0.47-0.63
S-1 (phm) 35-40
B-1 (phm) 2-4
S-1 (phm) 13-18
B-2 (phm) 2-4
L-2 (mhm) 1.88-2.66
S-3 (phm) 18-25
B-3 (phm) 15-23
Totals S (phm) 70-80
B (phm) 30-20
L (mhm) 2.3-3.4.
______________________________________
Claim 21
Dependent Claim
67 words
The process of claim 18 wherein the resultant copolymer contains calculated relative block sizes before coupling: ______________________________________
S.sub.1 --B.sub.1 --S.sub.2 --B.sub.2 --S.sub.3 --B.sub.3 :
S.sub.1 (phm)
35-40
B.sub.1 (phm)
2-4
S.sub.2 (phm)
13-18
B.sub.2 (phm)
2-4
S.sub.3 (phm)
3.6-4.8
B.sub.3 (phm)
3-4.4, and
S.sub.3 --B.sub.3 :
S.sub.3 (phm)
14.4-20.2
B.sub.3 (phm)
12-18.6; and molecular weights
after coupling:
M.sub.w × 10.sup.-3
140-220, and
M.sub.n × 10.sup.-3
90-120.
______________________________________
Claim 22
Dependent Claim
40 words
The process of claim 19 wherein said conjugated diene monomer contains 4 to 6 carbon atoms per molecule; said monovinylarene monomer contains 8 to 10 carbon atoms per monomer; and employing a hydrocarbyl monolithium initiator as said monoalkali metal initiator.
Claim 23
Dependent Claim
18 words
The process of claim 20 employing butadiene or isoprene as said conjugated diene, and styrene as said monovinylarene.
Claim 24
Dependent Claim
19 words
The process of claim 21 employing butadiene as said conjugated diene, and an epoxidized compound as said coupling agent.
Claim 25
Dependent Claim
6 words
The resulting copolymer of claim 22.
Claim 26
Dependent Claim
9 words
Blends of polystyrene with the copolymer of claim 23.
Claim 27
Dependent Claim
8 words
Blister packs comprising the copolymer of claim 23.
Claim 28
Dependent Claim
10 words
The resulting copolymer prepared by the process of claim 15.
Claim 29
Dependent Claim
9 words
Blends of polystyrene with the copolymer of claim 26.
Claim 30
Dependent Claim
9 words
Blister packs made of the copolymer of claim 26.
Claim 31
Dependent Claim
222 words
A sequential mode of block copolymerization comprising: polymerizing under solution polymerization conditions at least one monovinylarene monomer and at least one conjugated diene monomer in a ratio of about 55 to 95 weight percent monovinylarene and 45 to 5 weight percent conjugated diene, by a sequential charge polymerization process wherein at least two separate charges consisting of said conjugated diene, at least two separate charges consisting of said monovinylarene, and at least two charges of a monoalkali metal initiator are employed; at least one separate charge of each of said monovinylarene and of said conjugated diene follows the last charge of said monoalkali metal initiator; at least one separate charge of conjugated diene precedes the large charge of monoalkali metal initiator; each separate monomer charge homopolymerizes to substantial completion prior to addition of any subsequent charge; the total of the number of separate charges of each of said conjugated diene, of said monovinylarene, and of said monoalkali metal initiator, is not in excess of 3, and thereafter coupling with a polyfunctional coupling agent; wherein said sequential charge polymerization process employs a charge order; ______________________________________
Charge
Order
______________________________________
1/2 L/S
3/4 L/S
5 B
6/7 L/S
8 B
9 C
______________________________________ where L=monoalkali metal initiator, S=monovinylarene monomer, B=conjugated diene monomer, and C=coupling agent; thereby producing a polymodal, craze-resistant, low color, resinous coupled copolymer.
Claim 32
Dependent Claim
222 words
A sequential mode of block copolymerization comprising: polymerizing under solution polymerization conditions at least one monovinylarene monomer and at least one conjugated diene monomer in a ratio of about 55 to 95 weight percent monovinylarene and 45 to 5 weight percent conjugated diene, by a sequential charge polymerization process wherein at least two separate charges consisting of said conjugated diene, at least two separate charges consisting of said monovinylarene, and at least two charges of a monoalkali metal initiator are employed; at least one separate charge of each of said monovinylarene and of said conjugated diene follows the last charge of said monoalkali metal initiator; at least one separate charge of conjugated diene precedes the large charge of monoalkali metal initiator; each separate monomer charge homopolymerizes to substantial completion prior to addition of any subsequent charge; the total of the number of separate charges of each of said conjugated diene, of said monovinylarene, and of said monoalkali metal initiator, is not in excess of 3, and thereafter coupling with a polyfunctional coupling agent; wherein said sequential charge polymerization process employs a charge order; ______________________________________
Charge
Order
______________________________________
1/2 L/S
3/4 L/S
5 B
6/7 L/S
8 B
9 C
______________________________________ where L=monoalkali metal initiator, S=monovinylarene monomer, B=conjugated diene monomer, and C=coupling agent; thereby producing a polymodal, craze-resistant, low color, resinous coupled copolymer.
Claim 33
Dependent Claim
55 words
The process of claim 29 employing ranges of monomer additions and of monoalkali metal initiator added at each increment: ______________________________________
L-1 (mhm) 0.3-0.63
S-1 (phm) 30-45
L-2 (mhm) 0.3-0.63
S-2 (phm) 10-20
B-1 (phm) 1.2-18
L-3 (mhm) 0.94-2.8
S-3 (phm) 15-30
B-3 (phm) 3.8-27
Totals S (phm) 55-95
B (phm) 45-5
L (mhm) 1.5-4.
______________________________________
Claim 34
Dependent Claim
81 words
The process of claim 30 wherein the resultant block copolymer contains calculated relative block sizes before coupling: ______________________________________
S.sub.1 --S.sub.2 --B.sub.1 --S.sub.3 --B.sub.2 :
S.sub.1 (phm)
30-45
S.sub.2 (phm)
5-10
B.sub.1 (phm)
0.6-9
S.sub.3 (phm)
3-4.6
B.sub.2 (phm)
0.7-4.2,
S.sub.2 --B.sub.1 --S.sub.3 --B.sub.2 :
S.sub.2 (phm)
5-10
B.sub.1 (phm)
0.6-9
S.sub.3 (phm)
3-4.6
B.sub.2 (phm)
0.7-4.2, and
S.sub.3 --B.sub.2 :
S.sub.3 (phm)
9-20.7
B.sub.2 (phm)
2.4-18.6; and molecular weight
after coupling:
M.sub.w × 10.sup.-3
80-300 and
M.sub.n × 10.sup.-3
50-200.
______________________________________
Claim 35
Dependent Claim
55 words
The process of claim 29 employing ranges of monomer additions and of monoalkali metal initiator added at each increment: ______________________________________
L-1 (mhm) 0.38-0.55
S-1 (phm) 35-40
L-2 (mhm) 0.38-0.55
S-2 (phm) 12-18
B-1 (phm) 4-8
L-3 (mhm) 1.25-2.19
S-3 (phm) 20-25
B-3 (phm) 15-22
Totals S (phm) 70-80
B (phm) 30-20
L (mhm) 2-3.3.
______________________________________
Claim 36
Dependent Claim
80 words
The process of claim 32 wherein the resultant block copolymer contains calculated block sizes before coupling: ______________________________________
S.sub.1 --S.sub.2 --B.sub.1 --S.sub.3 --B.sub.2 :
S.sub.1 (phm)
35-40
S.sub.2 (phm)
6-9
B.sub.1 (phm)
2-4
S.sub.3 (phm)
3.8-4.2
B.sub.2 (phm)
2.8-3.7,
S.sub.2 --B.sub.1 --S.sub.3 --B.sub.3 :
S.sub.2 (phm)
6-9
B.sub.1 (phm)
2-4
S.sub.3 (phm)
3.8-4.2
B.sub.2 (phm)
2.8-3.7, and
S.sub.3 --B.sub.2 :
S.sub.3 (phm)
12.4-16.6
B.sub.2 (phm)
9.3-14.6, and molecular weights
after coupling:
M.sub.w × 10.sup.-3
150-200 and
M.sub.n × 10.sup.-3
90-120.
______________________________________
Claim 37
Dependent Claim
40 words
The process of claim 33 wherein said conjugated diene monomer contains 4 to 6 carbon atoms per molecule; said monovinylarene monomer contains 8 to 10 carbon atoms per monomer; and employing a hydrocarbyl monolithium initiator as said monoalkali metal initiator.
Claim 38
Dependent Claim
18 words
The process of claim 34 employing butadiene or isoprene as said conjugated diene, and styrene as said monovinylarene.
Claim 39
Dependent Claim
19 words
The process of claim 35 employing butadiene as said conjugated diene, and an epoxidized compound as said coupling agent.
Claim 40
Dependent Claim
6 words
The resulting copolymer of claim 36.
Claim 41
Dependent Claim
9 words
Blends of polystyrene with the copolymer of claim 37.
Claim 42
Dependent Claim
8 words
Blister packs comprising the copolymer of claim 37.
Claim 43
Dependent Claim
10 words
The resulting copolymer prepared by the process of claim 29.
Claim 44
Dependent Claim
9 words
Blends of polystyrene with the copolymer of claim 40.
Claim 45
Dependent Claim
9 words
Blister packs made of the copolymer of claim 40.
Claim 46
Dependent Claim
144 words
A resinous polymodal coupled block copolymer of at least one conjugated diene monomer of 4 to 6 carbon atoms per molecule and at least one monovinylarene monomer of 8 to 10 carbon atoms per molecule, in a weight ratio of 40 to 13 percent copolymerized conjugated diene and 60 to 87 percent copolymerized monovinylarene, wherein said copolymer contains relative block sizes before coupling: ______________________________________
S.sub.1 --B.sub.1 --S.sub.2 --B.sub.2 --S.sub.3 --B.sub.3 :
S.sub.1 (phm)
30-45
B.sub.1 (phm)
0.6-9
S.sub.2 (phm)
5-10
B.sub.2 (phm)
0.3-4.5
S.sub.3 (phm)
2.6-4.2
B.sub.3 (phm)
0.7-3.8,
S.sub.2 --B.sub.2 --S.sub.3 --B.sub.3 :
S.sub.2 (phm)
5-10
B.sub.2 (phm)
0.3-4.5
S.sub.3 (phm)
2.6-4.2
B.sub.3 (phm)
0.7-3.8, and
S.sub.3 --B.sub.3 :
S.sub.3 (phm)
9.7-21.6
B.sub.3 (phm)
2.4-19.4; and molecular weights
after coupling:
M.sub.w × 10.sup.-3
80-300 and
M.sub.n × 10.sup.-3
50-200;
______________________________________ and exhibiting low haze, low color, and high craze resistance in sheet form.
Claim 47
Dependent Claim
144 words
A resinous polymodal coupled block copolymer of at least one conjugated diene monomer of 4 to 6 carbon atoms per molecule and at least one monovinylarene monomer of 8 to 10 carbon atoms per molecule, in a weight ratio of 40 to 13 percent copolymerized conjugated diene and 60 to 87 percent copolymerized monovinylarene, wherein said copolymer contains relative block sizes before coupling: ______________________________________
S.sub.1 --B.sub.1 --S.sub.2 --B.sub.2 --S.sub.3 --B.sub.3 :
S.sub.1 (phm)
30-45
B.sub.1 (phm)
0.6-9
S.sub.2 (phm)
5-10
B.sub.2 (phm)
0.3-4.5
S.sub.3 (phm)
2.6-4.2
B.sub.3 (phm)
0.7-3.8,
S.sub.2 --B.sub.2 --S.sub.3 --B.sub.3 :
S.sub.2 (phm)
5-10
B.sub.2 (phm)
0.3-4.5
S.sub.3 (phm)
2.6-4.2
B.sub.3 (phm)
0.7-3.8, and
S.sub.3 --B.sub.3 :
S.sub.3 (phm)
9.7-21.6
B.sub.3 (phm)
2.4-19.4; and molecular weights
after coupling:
M.sub.w × 10.sup.-3
80-300 and
M.sub.n × 10.sup.-3
50-200;
______________________________________ and exhibiting low haze, low color, and high craze resistance in sheet form.
Claim 48
Dependent Claim
79 words
The copolymer of claim 43 containing relative block sizes before coupling: ______________________________________
S.sub.1 --B.sub.1 --S.sub.2 --B.sub.2 --S.sub.3 --B.sub.3 :
S.sub.1 (phm)
35-41
B.sub.1 (phm)
2-4
S.sub.2 (phm)
6-9
B.sub.2 (phm)
1-2
S.sub.3 (phm)
2.7-3.7
B.sub.3 (phm)
2.4-3.3,
S.sub.2 --B.sub.2 --S.sub.3 --B.sub.3 :
S.sub.2 (phm)
6-9
B.sub.2 (phm)
1-2
S.sub.3 (phm)
2.7-3.7
B.sub.3 (phm)
2.4-3.3 and
S.sub.3 --B.sub.3 :
S.sub.3 (phm)
12.5-18.5
B.sub.3 (phm)
11.1-16.4; and molecular weights
after coupling:
M.sub.w × 10.sup.-3
150-200 and
M.sub.n × 10.sup.-3
90-120.
______________________________________
Claim 49
Dependent Claim
30 words
The copolymer of claim 44 wherein said conjugated diene monomer contains 4 to 6 carbon atoms per molecule; and said monovinylarene monomer contains 8 to 10 carbon atoms per monomer.
Claim 50
Dependent Claim
18 words
The copolymer of claim 45 wherein butadiene or isoprene is said conjugated diene, and styrene is said monovinylarene.
Claim 51
Dependent Claim
20 words
The copolymer of claim 46 wherein butadiene is said conjugated diene, and an epoxidized compound was employed to effect coupling.
Claim 52
Dependent Claim
9 words
Blends of the copolymer of claim 47 with polystyrene.
Claim 53
Dependent Claim
8 words
Blister packs comprising the copolymer of claim 47.
Claim 54
Dependent Claim
127 words
A resinous polymodal coupled block copolymer of at least one conjugated diene monomer of 4 to 6 carbon atoms per molecule and at least one monovinylarene monomer of 8 to 10 carbon atoms per molecule, in a weight ratio of 40 to 13 percent copolymerized conjugated diene and 60 to 87 percent copolymerized monovinylarene, wherein said block copolymer contains relative block sizes before coupling: ______________________________________
S.sub.1 --B.sub.1 --S.sub.2 --B.sub.2 --S.sub.3 --B.sub.3 :
S.sub.1 (phm)
30-45
B.sub.1 (phm)
0.6-9
S.sub.2 (phm)
10-20
B.sub.2 (phm)
0.6-9
S.sub.3 (phm)
3-5
B.sub.3 (phm)
0.8-4.5, and
S.sub.3 --B.sub.3
S.sub.2 (phm)
12-25
B.sub.3 (phm)
3-22.5; and molecular weights
after coupling:
M.sub.w × 10.sup.-3
80-300 and
M.sub.n × 10.sup.-3
50-200,
______________________________________ and exhibiting low haze, low color, and high craze resistance in sheet form.
Claim 55
Dependent Claim
127 words
A resinous polymodal coupled block copolymer of at least one conjugated diene monomer of 4 to 6 carbon atoms per molecule and at least one monovinylarene monomer of 8 to 10 carbon atoms per molecule, in a weight ratio of 40 to 13 percent copolymerized conjugated diene and 60 to 87 percent copolymerized monovinylarene, wherein said block copolymer contains relative block sizes before coupling: ______________________________________
S.sub.1 --B.sub.1 --S.sub.2 --B.sub.2 --S.sub.3 --B.sub.3 :
S.sub.1 (phm)
30-45
B.sub.1 (phm)
0.6-9
S.sub.2 (phm)
10-20
B.sub.2 (phm)
0.6-9
S.sub.3 (phm)
3-5
B.sub.3 (phm)
0.8-4.5, and
S.sub.3 --B.sub.3
S.sub.2 (phm)
12-25
B.sub.3 (phm)
3-22.5; and molecular weights
after coupling:
M.sub.w × 10.sup.-3
80-300 and
M.sub.n × 10.sup.-3
50-200,
______________________________________ and exhibiting low haze, low color, and high craze resistance in sheet form.
Claim 56
Dependent Claim
65 words
The copolymer of claim 50 wherein the copolymer containing relative block sizes before coupling: ______________________________________
S.sub.1 --B.sub.1 --S.sub.2 --B.sub.2 --S.sub.3 --B.sub.3 :
S.sub.1 (phm)
35-40
B.sub.1 (phm)
2-4
S.sub.2 (phm)
13-18
B.sub.2 (phm)
2-4
S.sub.3 (phm)
3.6-4.8
B.sub.3 (phm)
3-4.4, and
S.sub.3 --B.sub.3 :
S.sub.3 (phm)
14.4-20.2
B.sub.3 (phm)
12-18.6; and molecular weights
after coupling:
M.sub.w × 10.sup.-3
140-220, and
M.sub.n × 10.sup.-3
90-120.
______________________________________
Claim 57
Dependent Claim
30 words
The copolymer of claim 51 wherein said conjugated diene monomer contains 4 to 6 carbon atoms per molecule; and said monovinylarene monomer contains 8 to 10 carbon atoms per monomer.
Claim 58
Dependent Claim
18 words
The copolymer of claim 52 wherein butadiene or isoprene is said conjugated diene, and styrene is said monovinylarene.
Claim 59
Dependent Claim
21 words
The copolymer of claim 53 wherein said butadiene is said conjugated diene, and an epoxidized compound was employed to effect coupling.
Claim 60
Dependent Claim
9 words
Blends of polystyrene with the copolymer of claim 54.
Claim 61
Dependent Claim
8 words
Blister packs comprising the copolymer of claim 54.
Claim 62
Dependent Claim
141 words
A resinous polymodal coupled block copolymer of at least one conjugated diene monomer of 4 to 6 carbon atoms per molecule and at least one monovinylarene monomer of 8 to 10 carbon atoms per molecule, in a weight ratio of 40 to 13 percent copolymerized conjugated diene and 60 to 87 percent copolymerized monovinylarene, wherein said block copolymer contains relative block sizes before coupling: ______________________________________
S.sub.1 --S.sub.2 --B.sub.1 --S.sub.3 --B.sub.2 :
S.sub.1 (phm)
30-45
S.sub.2 (phm)
5-10
B.sub.1 (phm)
0.6-9
S.sub.3 (phm)
3-4.6
B.sub.2 (phm)
0.7-4.2,
S.sub.2 --B.sub.1 --S.sub.3 --B.sub.2 :
S.sub.2 (phm)
5-10
B.sub.1 (phm)
0.6-9
S.sub.3 (phm)
3-4.6
B.sub.2 (phm)
0.7-4.2, and
S.sub.3 --B.sub.2 :
S.sub.3 (phm)
9-20.7
B.sub.2 (phm)
2.4-18.6; and molecular weights
after coupling:
M.sub.w × 10.sup.-3
80-300 and
m.sub.n × 10.sup.-3
50-200;
______________________________________ and exhibiting low haze, low color, and high craze resistance in sheet form.
Claim 63
Dependent Claim
141 words
A resinous polymodal coupled block copolymer of at least one conjugated diene monomer of 4 to 6 carbon atoms per molecule and at least one monovinylarene monomer of 8 to 10 carbon atoms per molecule, in a weight ratio of 40 to 13 percent copolymerized conjugated diene and 60 to 87 percent copolymerized monovinylarene, wherein said block copolymer contains relative block sizes before coupling: ______________________________________
S.sub.1 --S.sub.2 --B.sub.1 --S.sub.3 --B.sub.2 :
S.sub.1 (phm)
30-45
S.sub.2 (phm)
5-10
B.sub.1 (phm)
0.6-9
S.sub.3 (phm)
3-4.6
B.sub.2 (phm)
0.7-4.2,
S.sub.2 --B.sub.1 --S.sub.3 --B.sub.2 :
S.sub.2 (phm)
5-10
B.sub.1 (phm)
0.6-9
S.sub.3 (phm)
3-4.6
B.sub.2 (phm)
0.7-4.2, and
S.sub.3 --B.sub.2 :
S.sub.3 (phm)
9-20.7
B.sub.2 (phm)
2.4-18.6; and molecular weights
after coupling:
M.sub.w × 10.sup.-3
80-300 and
m.sub.n × 10.sup.-3
50-200;
______________________________________ and exhibiting low haze, low color, and high craze resistance in sheet form.
Claim 64
Dependent Claim
78 words
The copolymer of claim 57 wherein said block copolymer contains block sizes before coupling: ______________________________________
S.sub.1 --S.sub.2 --B.sub.1 --S.sub.3 --B.sub.2 :
S.sub.1 (phm)
35-40
S.sub.2 (phm)
6-9
B.sub.1 (phm)
2-4
S.sub.3 (phm)
3.8-4.2
B.sub.2 (phm)
2.8-3.7,
S.sub.2 --B.sub.1 --S.sub.3 --B.sub.3 :
S.sub.2 (phm)
6-9
B.sub.1 (phm)
2-4
S.sub.3 (phm)
3.8-4.2
B.sub.2 (phm)
2.8-3.7, and
S.sub.3 --B.sub.2 :
S.sub.3 (phm)
12.4-16.6
B.sub.2 (phm)
9.3-14.6; and molecular weights
after coupling:
M.sub.w × 10.sup.-3
150-200 and
M.sub.n × 10.sup.-3
90-120.
______________________________________
Claim 65
Dependent Claim
30 words
The copolymer of claim 58 wherein said conjugated diene monomer contains 4 to 6 carbon atoms per molecule; and said monovinylarene monomer contains 8 to 10 carbon atoms per monomer.
Claim 66
Dependent Claim
19 words
The copolymer of claim 59 wherein said butadiene or isoprene is said conjugated diene, and styrene is said monovinylarene.
Claim 67
Dependent Claim
17 words
The copolymer of claim 60 wherein butadiene is said conjugated diene, and an epoxidized compound effected coupling.
Claim 68
Dependent Claim
9 words
Blends of polystyrene with the copolymer of claim 61.
Claim 69
Dependent Claim
8 words
Blister packs comprising the copolymer of claim 61.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1989-04-21 | 1989-10-21 | 1990-04-22 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1993-04-21 | 1993-10-21 | 1994-04-22 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1997-04-21 | 1997-10-21 | 1998-04-22 | $7700.00 | Window Closed / Lapsed |