Suspension polymerization

• US 4,833,179 A
• Filed: 10/02/1987
• Issued: 05/23/1989
• Est. Priority Date: 07/27/1987
• Status: Expired due to Term

• Current Assignee: 3M Company
• Original Assignee: Minnesota Mining and Manufacturing Co (3M Company)
• Inventors: Young, Chung I., Enanoza, Rudyard M.
• Primary Examiner(s): Schofer, Joseph L.
• Assistant Examiner(s): SAROFIM, NABIL F
• Application Number:
  US07/104,092
• Time in Patent Office: 599 Days
• Field of Search: 526/328.5, 526/260, 526/194, 526/212, 526/264, 526/318.4, 526/240, 522/183, 525/260
• US Class Current: 522/183
• CPC Class Codes: C08F 220/10 Esters
• CPC Class Codes: C09J 7/385 Acrylic polymers

Abstract

The present invention relates to a method for suspension polymerization of a pressure-sensitive acrylate copolymer bead having a glass transition temperature of 0° C. or less. The method comprises making a monomer premix comprising an acrylic acid ester of non-tertiary alcohol, the alcohol having from 1 to 14 carbon atoms, with the average number of carbon atoms being about 4 to about 12, a polar monomer copolymerizable with the acrylic acid ester, a chain transfer agent, a free-radical initiator, and a modifier moiety selected from the group consisting of 2-polystyrylethyl methacrylate macromolecular monomers, reactive zinc salts and hydrophobic silicas. The premix is then combined with a water phase containing a sufficient amount of suspending agent to form a suspension. The suspension is concurrently agitated and polymerization of the polymer premix is permitted until polymer beads are formed. The polymer beads are then collected. The amount of the modifier moiety must be sufficient to render the copolymer bead non-agglomerating at room temperature and safely handleable and transportable.

Claims

1. A method for suspension polymerization of a pressure-sensitive acrylate copolymer bead having a glass transition temperature of 0°

C. of less, comprising the steps of;

(a) making a monomer premix comprising;

(i) acrylic acid ester of non-tertiary alcohol, said alcohol having from 1 to 14 carbon atoms, with the average number I to 14 carbon atoms, with the average number of carbon atoms being from about 4 to about 12;

(ii) a polar monomer copolymerizable with said acrylic acid ester;

(iii) a chain transfer agent;

(iv) a free-radical initiator; and

(v) a modifier moiety;

(b) combining said monomer premix with a water phase containing a suspending agent to form a suspension;

(c) concurrently agitating said suspension and permitting polymerization of said monomer premix until copolymer beads are formed, and

(d) collecting said copolymer beads,

whereby said modifier moiety is present in an amount of from about 0.05 part to about 10 parts per 100 parts monomer premix.

2. The method of claim 1 wherein the modifier moiety is selected from the group consisting of macromolecular monomers, hydrophobic silicas, and reactive zinc salts.

3. The method of claim 2 wherein the modifier moiety is a macromolecular monomer.

4. A method according to claim 1 further comprising a photocrosslinker.

5. A method according to claim 4 wherein the photocrosslinker is acryloxybenzophenone.

6. The method of claim 1 wherein the monomer premix comprises:

(a) from about 80 to about 95 parts of said acrylic acid ester of non-tertiary alcohol;

(b) from about 5 to about 10 parts of said polar

(c) from about 0.05 to about 10 parts of said modifier moiety;

(d) from about 0.01 to about 1 part of said free radical initiator; and

(e) from about 0.01 to about 0.3 part of said chain transfer agent.

7. A method according to claim 1 wherein the water phase comprises:

(a) from about 0.01 to about 5 parts of said suspension agent;

(b) from 0 to about 3 parts of a surfactant; and

(c) water to 100 parts.

8. A method according to claim 1 comprising the steps of:

(a) making a monomer premix consisting essentially of;

(i) from about 80 to about 95 parts of an acrylic acid ester selected from the group consisting of isooctyl acrylate, dodecyl acrylate, isononyl acrylate, and butyl acrylate;

(ii) from about 5 to about 20 parts of a polar copolymerizable monomer selected from the group consisting of acrylic acid, methacrylic acid, acrylamide, and N-vinyl pyrrolidone;

(iii) from about 0.01 to about 0.5 part of a chain transfer agent selected from the group consisting of mercaptans, alcohols, and carbon tetrabromide;

(iv) from 0.05 to 10 parts of a modifier moiety selected from the group consisting of 2-polystyrylethyl methacrylate macromolecular monomer, hydrophobic silica, zinc methacrylate, zinc acrylates, and zinc oxide; and

(v) from about 0.01 to about 1 part 2,2'"'"'-azobisbutryronitrile;

(b) forming a suspension by combining said monomer premix with a water phase comprising;

(i) from about 0.01 to about 5 parts of a suspending agent;

(ii) from 0 to about 5000 ppm of a surfactant; and

(iii) water;

(c) concurrently agitating said suspension and permitting polymerization of said monomer premix for at least 4 hours at from about 40°

C. to about 75°

C. to form copolymer beads; and

(d) collecting said copolymer beads.

10. A storage-stable, safely handleable and transportable pressure-sensitive copolymer bead made by the process of claim 1.

11. A storage-stable, safely handleable and transportable pressure-sensitive copolymer bead made by the process of claim 2.

12. A storage-stable, safely handleable and transportable pressure-sensitive copolymer bead made by the process of claim 6.

13. A storage-stable, safely handleable and transportable pressure-sensitive copolymer bead made by the process of claim 8.

16. A sheet material comprising a pressure-sensitive acrylate adhesive made from the copolymer beads of claim 13.

9. A method for suspension polymerization of a pressure-sensitive acrylate copolymer bead having a glass transition temperature of 0°

C. of less, comprising the steps of;

(a) making monomer premix comprising;

(i) acrylic acid ester of non-tertiary alcohol said alcohol having from 1 to 14 carbon atoms, with the average number of carbon atoms being from about 4 to about 12;

(ii) a polar monomer copolymerizable with said acrylic acid ester;

(iii) a chain transfer agent;

(iv) a free-radical initiator;

(v) form about 0.05 to about 10 parts 2-polystyrylethyl methacrylate macromolecular monomer;

(b) combining said premix with a water phase containing a suspending agent to form a suspension;

(c) concurrently agitating and polymerizing said suspension until polymer beads begin to form;

(d) adding a basic compound to adjust pH to from 9 to

(e) adding a modifier moiety selected from the group consisting of hydrophobic silica, zinc octoate, zinc acetate and mixtures thereof to said suspension and continuing agitation until polymer beads are coated; and

(f) collecting said polymer beads.

14. A storage-stable, safely handleable and transportable pressure-sensitive copolymer bead made by the process of claim 9.

15. A free-flowing copolymer bead made by drying said copolymer beads of claim 9.

17. A sheet material comprising a pressure-sensitive acrylate adhesive made from the copolymer beads of claim 14.