WO2006033810A1 - Process for making vinyl pyrrolidone/vinyl acetate copolymers within a short production cycle - Google Patents

Process for making vinyl pyrrolidone/vinyl acetate copolymers within a short production cycle Download PDF

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Publication number
WO2006033810A1
WO2006033810A1 PCT/US2005/031366 US2005031366W WO2006033810A1 WO 2006033810 A1 WO2006033810 A1 WO 2006033810A1 US 2005031366 W US2005031366 W US 2005031366W WO 2006033810 A1 WO2006033810 A1 WO 2006033810A1
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WIPO (PCT)
Prior art keywords
hours
production cycle
vinyl acetate
short production
vinyl pyrrolidone
Prior art date
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Ceased
Application number
PCT/US2005/031366
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French (fr)
Inventor
Drupesh Patel
Paul Taylor
John Mc Kittrick
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ISP Investments LLC
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ISP Investments LLC
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Publication of WO2006033810A1 publication Critical patent/WO2006033810A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F226/10—N-Vinyl-pyrrolidone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
    • C08F218/04—Vinyl esters
    • C08F218/06—Vinyl formate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/006—Removal of residual monomers by chemical reaction, e.g. scavenging

Definitions

  • This invention relates to a process for making vinyl pyrrolidone (VP)/vinyl acetate (VA) copolymers, and, more particularly, to improved manufacture of such copolymers having a very low residual VP level, within an advantageously short production cycle.
  • VP vinyl pyrrolidone
  • VA vinyl acetate
  • Potthoff-Karl in U.S. Pat. 5,122,582, described a process for making VP ⁇ /A copolymers by copolymerization of the monomers in isopropanol (IPA) solvent in the presence of a radical initiator, steam distilling off the IPA, replacing it with water, (although none of the examples therein include this step) adding more initiator in IPA, post-heating the mixture at about 8O 0 C for a period of 4% hours, and again, removing IPA by steam distillation.
  • the residual VP content of the copolymer solution obtained was high, e.g. 500 ppm (Ex. 1); 900 ppm (Ex. 2) and 1000 ppm (Ex.
  • VP vinyl pyrrolidone
  • VA vinyl acetate copolymers having a very low residual VP level of ⁇ 100 ppm, preferably only 50 ppm, based upon the VP monomer used, which comprises copolymerizing VP and VA in isopropanol (IPA) solvent in the presence of a radical initiator, preferably including a high temperature initiator, at about 65-90 0 C, stripping the IPA while simultaneously adding water, to form an aqueous solution of the copolymer, and then post-heating said aqueous solution at about 120-150 0 C, preferably about 130 0 C, under pressure, for a period of about 1-4 hours, preferably about 2 hours.
  • IPA isopropanol
  • the VPA/A copolymer includes, by wt., about 50-70% VP and about 30-50% VA.
  • radical initiators for use herein are dimethyl 2,2'-azobisisobutyrate, dilauroyl peroxide, dibenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, hydrogen peroxide and, percarboxylic esters such as tert- butyl pemeodecanoate, tert-amyl perpivalate, tert-butyl perpivalate, tert-butyl peroxy-2-ethylhexanoate and tert-butyl perbenzoate.
  • Preferred initiators for use during the polymerization step are t-butyl-peroxypivalate (Lupersol ® 11), and 2,2'-azodi(2-methylbutyronitrile) (Vazo ® 67); while preferred high temperature initiators for use during the post-treatment step include 2,5-dimethyl-2,5-di(t- butylperoxy) hexane (Lupersol ® 101): and di-t-butyl peroxide.
  • Example 1 The procedure of Example 1 was followed to produce a copolymer of VP/VA having a wt. ratio of 60:40 with a similarly low VP level.
  • Example 1 The procedure of Example 1 was followed to produce a VP/VA copolymer having a wt. ratio of 50:50 with a similarly low VP level.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Vinyl pyrrolidone/vinyl acetate copolymers having a very low residual vinyl pyrrolidone monomer level, i.e. < 100 ppm, preferably only 50 ppm, are made within an advantageously short production cycle, by post-treating an aqueous solution of the copolymer at an elevated temperature of about 120-150 °C, preferably about 130 °C, under pressure, in the presence of a high temperature initiator, for a period of about 1-4 hours, preferably 2 hours.

Description

PROCESS FOR MAKING VINYL PYRROLIDONE/VINYL ACETATE COPOLYMERS WITHIN A SHORT PRODUCTION CYCLE
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a process for making vinyl pyrrolidone (VP)/vinyl acetate (VA) copolymers, and, more particularly, to improved manufacture of such copolymers having a very low residual VP level, within an advantageously short production cycle.
2. Description of the Prior Art
Potthoff-Karl, in U.S. Pat. 5,122,582, described a process for making VPΛ/A copolymers by copolymerization of the monomers in isopropanol (IPA) solvent in the presence of a radical initiator, steam distilling off the IPA, replacing it with water, (although none of the examples therein include this step) adding more initiator in IPA, post-heating the mixture at about 8O0C for a period of 4% hours, and again, removing IPA by steam distillation. However, the residual VP content of the copolymer solution obtained was high, e.g. 500 ppm (Ex. 1); 900 ppm (Ex. 2) and 1000 ppm (Ex. 3), based upon the amount of VP employed. Moreover, the duration of the post-treatment step also was excessively long. Accordingly, it is the object of this invention to provide a new and improved process for making VPA/A copolymers having a very low residual VP level, i.e. < 100 ppm, preferably only 50 ppm, in which the post-treatment step is carried out in water only and requires a heating period of only 1-4 hours, preferably only about 2 hours.
DESCRIPTION OF THE INVENTION
What is described herein is a process of making vinyl pyrrolidone (VP)/vinyl acetate (VA) copolymers having a very low residual VP level of < 100 ppm, preferably only 50 ppm, based upon the VP monomer used, which comprises copolymerizing VP and VA in isopropanol (IPA) solvent in the presence of a radical initiator, preferably including a high temperature initiator, at about 65-900C, stripping the IPA while simultaneously adding water, to form an aqueous solution of the copolymer, and then post-heating said aqueous solution at about 120-1500C, preferably about 1300C, under pressure, for a period of about 1-4 hours, preferably about 2 hours.
Suitably, the VPA/A copolymer includes, by wt., about 50-70% VP and about 30-50% VA.
Examples of suitable radical initiators for use herein are dimethyl 2,2'-azobisisobutyrate, dilauroyl peroxide, dibenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, hydrogen peroxide and, percarboxylic esters such as tert- butyl pemeodecanoate, tert-amyl perpivalate, tert-butyl perpivalate, tert-butyl peroxy-2-ethylhexanoate and tert-butyl perbenzoate. Preferred initiators for use during the polymerization step are t-butyl-peroxypivalate (Lupersol® 11), and 2,2'-azodi(2-methylbutyronitrile) (Vazo® 67); while preferred high temperature initiators for use during the post-treatment step include 2,5-dimethyl-2,5-di(t- butylperoxy) hexane (Lupersol® 101): and di-t-butyl peroxide. The invention will now be described in more detail by way of the following examples, in which:
INVENTION EXAMPLE 1 Preparation of Copolymer of VP/VA (70:30 wt.%)
1. Set up a 1 -liter pressured reactor and charged 41.21 g of VP
22.01 g of vinyl acetate and 32.61 g of isopropanol.
2. Purged the reaction system 2-3 times with nitrogen to 50 psig and releasing it.
3. Heated the reactor to 8O0C.
4. At 75°C, time = 0 min, started feeding a mixture of 0.95 g Vazo® 67, 0.93 g of Lupersol® 101 and 19.30 g of isopropanol. Completed the initiator feed within 340 minutes.
Also, at time = 0 min, added a mixture of 140.29 g of VP, 74.29 g of vinyl acetate and 99.94 g of isopropanol continuously during a period of 240 minutes.
5. At 255 minutes, fed 43.83 g of VP in 19.80 g of isopropanol continuously in 60 minutes.
6. After completion of initiator feeding in 340 minutes, held the reaction mixture at 800C for 2 hours. 7. Then stripped the IPA solvent by steam distillation, while simultaneously adding water in an amount of 567 g.
8. After the solvent exchange step the solids level was about 50-60%.
9. Heated the aqueous copolymer solution under pressure to 13O0C.
10. Held the reaction mixture at 1300C for about 2 hours. The residual VP level in the mixture was 50 ppm.
EXAMPLE 2
The procedure of Example 1 was followed to produce a copolymer of VP/VA having a wt. ratio of 60:40 with a similarly low VP level.
EXAMPLE 3
The procedure of Example 1 was followed to produce a VP/VA copolymer having a wt. ratio of 50:50 with a similarly low VP level.
COMPARATIVE EXAMPLE Preparation of Copolymer of VP/VA (70:30 wt.%)
The procedure of Example 1 was followed up to step 6.
7. Heated the reaction mixture in IPA to 1300C for post-treatment.
8. Held the reaction mixture for 2 hours. The residual VP level was 1007 ppm.

Claims

WHAT IS CLAIMED IS:
1. A process of making vinyl pyrrolidone (VP)/vinyl acetate (VA) copolymers having a very low residual VP level of < 100 ppm based upon the amount of VP used in an advantageously short production cycle which comprises copolymerizing VP and VA in isopropanol (IPA) solvent in the presence of a low temperature radical initiator, continuously stripping the IPA while simultaneously adding water to form an aqueous solution of the copolymer, and post-heating said aqueous solution at about 120-150°C under pressure in the presence of a high temperature initiator, for a period of about 1-4 hours.
2. A process according to claim 1 wherein said post-heating step is carried out at about 1300C for a period of about 2 hours.
3. A process according to claim 1 wherein both said low and high temperature radical initiators are added during the polymerization step.
4. A process according to claim 1 wherein said VP/VA copolymer comprises, by wt., about 50-70% VP and about 30-50% VA.
5. A process according to claim 1 wherein said high temperature radical initiator is 2,5-dimethyl-2,5-di(t-butylperoxy) hexane.
PCT/US2005/031366 2004-09-21 2005-09-01 Process for making vinyl pyrrolidone/vinyl acetate copolymers within a short production cycle Ceased WO2006033810A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US10/946,500 US6939927B1 (en) 2004-09-21 2004-09-21 Process for making vinyl pyrrolidone/vinyl acetate copolymers having a very low residual vinyl pyrrolidone monomer level within a short production cycle
US10/946,500 2004-09-21

Publications (1)

Publication Number Publication Date
WO2006033810A1 true WO2006033810A1 (en) 2006-03-30

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5239053A (en) * 1992-02-14 1993-08-24 Isp Investments Inc. Purification of vinyl lactam polymers
US5319041A (en) * 1993-03-26 1994-06-07 Isp Investments Inc. Process for the preparation of vinylpyrrolidone/vinyl acetate copolymers
US5387641A (en) * 1993-05-25 1995-02-07 Yeung; Dominic W. K. Aqueous polymer emulsions useful as wallcovering prepaste adhesives

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5395904A (en) * 1993-12-07 1995-03-07 Isp Investments Inc. Process for providing homogeneous copolymers of vinylpyrrolidone and vinyl acetate which form clear aqueous solutions having a high cloud point
US5534564A (en) * 1994-12-13 1996-07-09 Isp Investments Inc. Process for the color stabilization of an aqueous N-vinyl heterocyclic copolymer solution
US5502136A (en) * 1994-12-28 1996-03-26 Isp Investments Inc. Process for making substantially homogeneous copolymers of vinyl pyrrolidone and vinyl acetate which form clear aqueous solutions

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5239053A (en) * 1992-02-14 1993-08-24 Isp Investments Inc. Purification of vinyl lactam polymers
US5319041A (en) * 1993-03-26 1994-06-07 Isp Investments Inc. Process for the preparation of vinylpyrrolidone/vinyl acetate copolymers
US5387641A (en) * 1993-05-25 1995-02-07 Yeung; Dominic W. K. Aqueous polymer emulsions useful as wallcovering prepaste adhesives

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