Method for manufacturing thermoplastic poly(vinyl alcohol) derivative in a melt state reaction and products thereof

Patent metadata

Field	Value
Publication number	US-11897974-B2
Application number	US-201917434870-A
Country	US
Kind code	B2
Filing date	Mar 18, 2019
Priority date	Mar 18, 2019
Publication date	Feb 13, 2024
Grant date	Feb 13, 2024

Abstract

The invention relates to a method for manufacturing thermoplastic poly(vinyl alcohol) derivative in a melt state reaction and a product thereof, wherein the method thermoplastic poly(vinyl alcohol) that has been dried is heated and admixed with an organic acid anhydride that has a catenated carbon structure which ends into a vinyl group, such that a mixture is obtained which is above the melting point of the mixture, thereby causing an ester bond forming condensation reaction in a melt state, wherein at least some of the organic acid anhydride reacts with hydroxyl groups of the thermoplastic poly(vinyl alcohol), such that reaction product is formed which contains carboxylic acid residue and thermoplastic poly(vinyl alcohol) derivative which contains ester bonded pendant chains of which at least some end into vinyl groups. The invention further relates to a method for manufacturing a paper substrate and a product thereof, which contains a primer layer that contains the reaction product.

First claim

The invention claimed is:

1. A method for manufacturing thermoplastic poly(vinyl alcohol) derivative (CMP 1 ; CMP 2 ; CMP 3 ) which contains pendant chains which end into vinyl groups, the method comprising:
heating (HT 1 ) thermoplastic poly(vinyl alcohol) (PVA 1 ) having hydroxyl groups, wherein the thermoplastic poly(vinyl alcohol) (PVA 1 ) has been dried and has a degree of hydrolysis in the range of 65 to 90 mol-%, and
admixing (AD 1 ) reagent (RGT 1 ) with the thermoplastic poly(vinyl alcohol) (PVA 1 ), wherein said reagent (RGT 1 ) is an organic acid anhydride (AH 1 ; AH 2 ; AH 3 ; AH 4 ; AH 5 ) having at least a chain which has a catenated carbon structure of at least 4 carbon atoms and which ends into a vinyl group,

such that a mixture (MXT 1 ) is obtained which contains molten thermoplastic poly(vinyl alcohol) (PVA 1 ) having hydroxyl groups and organic acid anhydride (AH 1 ; AH 2 ; AH 3 ; AH 4 ; AH 5 ) which contains chains which end into vinyl groups, and
mixing (MR 1 ) the mixture (MXT 1 ) at a temperature which is above the melting point of the mixture (MXT 1 ), thereby causing a reaction in a melt state, wherein at least some of the organic acid anhydride (AH 1 ; AH 2 ; AH 3 ; AH 4 ; AH 5 ) reacts with the hydroxyl groups of the thermoplastic poly(vinyl alcohol) (PVA 1 ) in an ester bond forming condensation reaction,

such that reaction product (PROD 1 ) is formed which contains
carboxylic acid residue (RD 1 ; RD 2 ; RD 3 ) of the ester bond forming condensation reaction, wherein at least some of said carboxylic acid residue contains chains which end into vinyl groups, and
thermoplastic poly(vinyl alcohol) derivative (CMP 1 ; CMP 2 ; CMP 3 ) which contains ester bonded pendant chains of which at least some end into vinyl groups.

2. The method according to claim 1 , wherein the temperature which is above the melting point of the mixture (MXT 1 ) is in a range of 170 to 210° C.

3. The method according to claim 1 , wherein the duration of the reaction in a melt state is less than 5 minutes.

4. The method according to claim 1 , further comprising
adding inhibitor (IHB 1 ) suitable for inhibiting spontaneous radical polymerization of vinyl groups, and/or
adding catalyst (CAT 1 ) suitable for catalysing the ester bond forming condensation reaction,
wherein the inhibitor (IHB 1 ) and/or the catalyst (CAT 1 ) is added before mixing (MR 1 ) the mixture (MXT 1 ) or when mixing (MR 1 ) the mixture (MXT 1 ).

5. The method according to claim 1 , wherein the amount of the reagent (RGT 1 ) is in the range of 1 to 10 wt.-%, when determined of the total weight of the mixture (MXT 1 ).

6. The method according to claim 1 , wherein the organic acid anhydride (AH 1 ; AH 2 ; AH 3 ; AH 4 ; AH 5 ) is aliphatic and either a symmetrical anhydride (AH 2 ; AH 4 ) or an asymmetrical anhydride (AH 1 ; AH 3 ; AH 5 ).

7. The method according to claim 1 , wherein the organic acid anhydride (AH 1 ; AH 2 ; AH 3 ; AH 4 ; AH 5 ) is a fatty acid-based anhydride.

8. The method according to claim 7 , wherein the fatty acid-based anhydride contains one acyl group or two acyl groups derived from 3-butenoic acid, 2,2′-dimethyl-4-pentenoic acid, 4-pentenoic acid, 7-ocenoic acid, 8-nonenoic acid, 10-undecenoic acid, or 12-tridecenoic acid.

9. The method according to claim 1 , wherein the organic acid anhydride (AH 1 ; AH 2 ; AH 3 ; AH 4 ; AH 5 ) is undecenoyl anhydride, which is a symmetrical anhydride comprising two identical acyl groups derivable from 10-undecenoic acid, each acyl group having a vinyl group at the end.

10. The method according to claim 1 , wherein the mixing (MR 1 ) is carried out in a reactor, and/or wherein the heating (HT 1 ) of the thermoplastic poly(vinyl alcohol) (PVA 1 ) which has been dried is carried out before the admixing (AD 1 ).

11. The method according to claim 1 , further comprising
extruding (EX 1 ), and
cooling the reaction product (PROD 1 ), such that the temperature of the reaction product decreases and a solid reaction product (OBJ 1 ) is obtained, and
shaping the solid reaction product (OBJ 1 ) into compact form which is suitable for transportation.

12. The method according to claim 1 , further comprising
removing at least part of the carboxylic acid residue (RD 1 ; RD 2 ; RD 3 ) from the reaction product (PROD 1 ) during and/or after the condensation reaction, thereby obtaining recyclable carboxylic acid residue (RRD 1 ).

13. The method according to claim 12 further comprising
arranging at least some of the recyclable carboxylic acid residue (RRD 1 ) to participate into a reaction wherein organic acid anhydride (AH 1 ; AH 2 ; AH 3 ; AH 4 ; AH 5 ) having at least a chain which has a catenated carbon structure of at least 4 carbon atoms and which ends into a vinyl group is formed, thereby forming reagent (RGT 1 ) of the recyclable carboxylic acid residue (RRD 1 ).

14. The method according to claim 1 , further comprising
neutralizing at least some of the carboxylic acid residue (RD 1 ; RD 2 ; RD 3 ) of the reaction product with an alkaline reagent (BASE 1 ), thereby forming a salt of the carboxylic acid residue.

15. The method according to claim 1 , wherein the thermoplastic poly(vinyl alcohol) derivative (CMP 1 ; CMP 2 ; CMP 3 )
has a degree of hydrolysis in the range of 65 to 90 mol-%, and/or
contains a vinyl group molality (bvin) which is equal to or higher than 0.01, millimoles per gram of the thermoplastic poly(vinyl alcohol) derivative, when determined from a known amount of solid reaction product (OBJ 1 ) by first separating the carboxylic acid residue (RD 1 ; RD 2 ; RD 3 ) and the thermoplastic poly(vinyl alcohol) derivative (CMP 1 ; CMP 2 ; CMP 3 ) into two separate phases by means of heptane extraction, thereby forming two separate samples and then determining the amount of vinyl groups from the phase containing the thermoplastic poly(vinyl alcohol) derivative by iodometric titration method following the standard ISO 3961:2009(E), and/or
has a melt flow index in a range of 0.5-300 g/10 min, when measured with standard ISO 1 133 (210° C., 2.16 kg).

16. The method or the solid reaction product (OBJ 1 ) that contains thermoplastic poly(vinyl alcohol) derivative (CMP 1 ; CMP 2 ; CMP 3 ) according to claim 1 , wherein the catenated carbon structure contains 5 or more.

17. The method or the solid reaction product (OBJ 1 ) that contains thermoplastic poly(vinyl alcohol) derivative (CMP 1 ; CMP 2 ; CMP 3 ) according to claim 1 , wherein the thermoplastic poly(vinyl alcohol) derivative (CMP 1 ; CMP 2 ; CMP 3 ) is water soluble such that a solution, wherein the thermoplastic poly(vinyl alcohol) derivative (CMP 1 ; CMP 2 ; CMP 3 ) has been dissolved, is obtainable within 24 hours after mixing the solid reaction product (OBJ 1 ) with deionized water in at least 1:10 ratio (weight/weight) while continuously stirring at a temperature in the range of 40 to 80° C.

Assignees

• Upm Kymmene Corp

Inventors

• Littunen Kuisma
• Kosonen Harri
• Antila Janne
• Rautalahti Jaakko
• Rissanen Mikko

Classifications

• C08F16/06 Primary

  Polyvinyl alcohol {; Vinyl alcohol} · CPC title

• C08F8/14 Primary

  Esterification · CPC title

• C09J7/21

  Paper; Textile fabrics · CPC title

• C09J7/401

  characterised by the release coating composition · CPC title

• D21H19/20

  comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds · CPC title