Block copolymer, method of making the same, diamine precursors of the same, method of making such diamines and end products comprising the block copolymer

• US 5,461,134 A
• Filed: 12/05/1994
• Issued: 10/24/1995
• Est. Priority Date: 06/20/1986
• Status: Expired due to Term

• Current Assignee: Minnesota Mining and Manufacturing Co (3M Company)
• Original Assignee: Minnesota Mining and Manufacturing Co (3M Company)
• Inventors: Leir, Charles M., Hoffman, Jerome J.
• Primary Examiner(s): Dean, Ralph H.
• Application Number:
  US08/349,381
• Time in Patent Office: 323 Days
• Field of Search: 528/14, 528/22, 528/28, 528/37, 528/38, 524/588, 428/447, 428/423.1
• US Class Current: 528/14
• CPC Class Codes: C08G 18/61 Polysiloxanes
• CPC Class Codes: C08G 2170/40 Compositions for pressure-sensitive adhesives
• CPC Class Codes: C08G 77/26 nitrogen-containing groups
• CPC Class Codes: C08G 77/458 containing polyurethane sequences
• CPC Class Codes: Y10T 428/1457 Silicon
• CPC Class Codes: Y10T 428/31551 Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
• CPC Class Codes: Y10T 428/31598 Next to silicon-containing [silicone, cement, etc.] layer
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

Block copolymers having a repeating unit comprised of polysiloxane and urea segments are prepared by copolymerizing certain diaminopolysiloxanes with diisocyanates. The invention also provides novel diaminopolysiloxanes useful as precursors in the preparation of the block copolymers and a method of making such diaminopolysiloxanes. Pressure sensitive adhesive compositions comprising the block copolymer are also provided as are sheet materials coated with the same.

Claims

1. Organopolysiloxane diamine having a number average molecular weight of at least 5000 and containing less than 1.2% free silicone oil contamination and having the general formula:

##STR7## where;

R is at least 50% methyl with the balance of the 100% of all R radicals being selected from the group consisting of a monovalent alkyl radical having 2 to 12 carbon atoms, a substituted alkyl radical having 2 to 12 carbon atoms, a vinyl radical, a phenyl radical, and a substituted phenyl radical;

Y is an alkylene radical of 1 to 10 carbon atoms;

D is selected from the group consisting of hydrogen, an alkyl radical of 1 to 10 carbon atoms and phenyl;

n is a number of about 70 or larger.

2. Method of making an organopolysiloxane diamine having a number average molecular weight of at least 5000, comprising the steps of:

(1) combining under reaction conditions;

(a) amine functional end blocker of the general formula ##STR8## where;

Y is an alkylene radical of 1 to 10 carbon atoms; and

R is each independently selected from the group consisting of a monovalent alkyl radical having from 1 to 12 carbon atoms, a substituted alkyl radical having from 1 to 12 carbon atoms, a phenyl radical, and a substituted phenyl radical;

D is selected from the group consisting of hydrogen, an alkyl group of 1 to 10 carbon atoms and phenyl;

(b) sufficient cyclic siloxane to react with said amine functional end blocker to form a lower molecular weight intermediate organopolysiloxane diamine having a number average molecular weight less than about 2,000 and general formula ##STR9## where;

Y and D are as defined above;

R is at least 50% methyl with the balance of the 100% of all R radicals being selected from the group consisting of a monovalent alkyl radical having from 2 to 12 carbon atoms, a substituted alkyl radical having from 2 to 12 carbon atoms, a vinyl radical, a phenyl radical, and a substituted phenyl radical; and

x is a number in the range of about 4 to 40;

(c) a catalytic amount of a compound having catalytic properties, characterized by having a molecular structure represented by the formula;

##STR10## where D is selected from the group consisting of hydrogen, an alkyl radical of 1 to 10 carbon atoms, and phenyl;

Y is an alkylene radical of 1 to 10 carbon atoms;

R is each selected independently from the group consisting of a monovalent alkyl radical having from 1 to 12 carbon atoms, a substituted alkyl radical having from 1 to 12 carbon atoms, a phenyl radical, and a substituted phenyl radical; and

M⁺ is the cation K⁺, Na⁺ or N(CH₃)₄⁺ ;

(2) continuing the reaction until substantially all of said amine functional end blocker is consumed; and

(3) adding additional cyclic siloxane until said organopolysiloxane diamine having a number average molecular weight of at least about 5000 and containing less than 1.2% free silicone oil contamination is obtained.

3. The method of claim 2 wherein said catalytic amount is less than about 0.05% by weight of said organopolysiloxane diamine having a number average molecular weight of at least about 5000.

4. The method of claim 2 wherein said catalytic amount is from about 0.005 to about 0.03 weight percent of said organopolysiloxane diamine having a number average molecular weight of at least about 5000.

5. The method of claim 2 wherein said reaction conditions comprise a reaction temperature of from about 80°

C. to about 90°

C., a reaction time of about 5 to 7 hours, and dropwise addition of said additional cyclic siloxane.

6. A pressure-sensitive adhesive composition comprising an organopolysiloxane-polyurea block copolymer comprising the following repeating unit:

##STR11## where;

Z is a divalent radical selected from the group consisting of phenylene, alkylene, aralkylene and cycloalkylene;

Y is an alkylene radical of 1 to 10 carbon atoms;

R is at least 50% methyl with the balance of the 100% of all R radicals being selected from the group consisting of a monovalent alkyl radical having from 2 to 12 carbon atoms, a substituted alkyl radical having from 2 to 12 carbon atoms, a vinyl radical, a phenyl radical, and a substituted phenyl radical;

D is selected from the group consisting of hydrogen, an alkyl radical of 1 to 10 carbon atoms, and a phenyl group;

B is selected from the group consisting of alkylene, aralkylene, cycloalkylene, phenylene, polyethylene oxide, polypropylene oxide, polytetramethylene oxide, polyethylene adipate, polycaprolactone, polybutadiene, and mixtures thereof, and a radical completing a ring structure including A forming a heterocycle;

A is selected from the group consisting of ##STR12## where G is selected from the group consisting of hydrogen, an alkyl radical of 1 to 10 carbon atoms, and phenyl and a radical completing a ring structure including B to form a heterocycle;

n is a number which is 70 or larger, and

m is a number which can be zero to about 25;

and sufficient tackifier to make said composition tacky.

7. A sheet material at least partially coated with the pressure-sensitive adhesive composition of claim 6.