Curable petroleum resin and method for preparing same

Patent metadata

Field	Value
Publication number	US-10280266-B2
Application number	US-201515500580-A
Country	US
Kind code	B2
Filing date	Aug 3, 2015
Priority date	Aug 1, 2014
Publication date	May 7, 2019
Grant date	May 7, 2019

Abstract

This invention provides a method of manufacturing a curable petroleum resin and a curable petroleum resin obtained therefrom. The method includes (a) a process of thermally polymerizing a composition for polymerization which includes silanes and monomers, including cyclic olefins having at least one ethylenically unsaturated group selected from among C5 fractions, C9 fractions, and dicyclopentadiene of naphtha cracking, thereby enabling petroleum resins, which are thermoplastic resins, to be applied as reactive adhesives, and ultimately being capable of providing eco-friendly reactive adhesives.

First claim

The invention claimed is:

1. A method of manufacturing a curable petroleum resin, the method comprising:
a process of thermally polymerizing, in the absence of an initiator and in the absence of a Friedel-Craft catalyst or Lewis acid catalyst, a composition for polymerization which includes (a) monomers, including cyclic olefins having at least one ethylenically unsaturated group selected from among C5 fractions, C9 fractions, and dicyclopentadiene of naphtha cracking, and (b) one or more silanes of the following Chemical Formula 1:
CH 2 ═CR—(COO) x (C n H 2n ) y SiR′ 3   Chemical Formula 1

where R is a hydrogen atom or a methyl group; x and y are 0 or 1, provided that y is 1 when x is 1; n is an integer of 1 to 12; and R's are each independently an alkoxy group having 1 to 12 carbon atoms, an aryloxy group, an araloxy group, an aliphatic acyloxy group having 1 to 12 carbon atoms, an amino or substituted amino group, or a lower alkyl group having 1 to 6 carbon atoms, provided that two or less of the three R′ groups are alkyl groups.

2. The method of claim 1 , wherein the silanes are selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, and 3-(trimethoxysilyl)propyl methacrylate.

3. The method of claim 1 , wherein the thermally polymerizing the composition is performed at a reaction temperature of 150 to 300° C. for 1 to 3 hours under a predetermined pressure.

4. The method of claim 1 , wherein the monomers include dicyclopentadiene.

5. The method of claim 1 , wherein the composition for polymerization includes a non-polymerizable solvent having no ethylenically unsaturated double bond.

6. The method of claim 1 , wherein the composition for polymerization includes 5 to 50 wt % of the silanes based on a total weight of the silanes and the monomers.

7. The method of claim 5 , wherein the composition for polymerization includes the non-polymerizable solvent in an amount set so that a total concentration of monomers and silanes is 30 to 70 wt %.

8. The method of claim 1 , wherein the method includes degassing and concentration processes after the thermally polymerizing the composition.

9. A curable petroleum resin comprising:
a repeating unit derived from monomers including cyclic olefins having at least one ethylenically unsaturated group selected from among C5 fractions, C9 fractions, and dicyclopentadiene of naphtha cracking,
wherein silanes are copolymerized and a proton content of the silanes, determined using 1 H-NMR, is at least 1.7%.

10. The curable petroleum resin of claim 9 , wherein the proton content of the silanes is at least 7%.

11. The curable petroleum resin of claim 9 , wherein an Si weight ratio, which is a weight ratio of a silicon (Si) element to all elements, analyzed using an X-ray fluorescence spectrometer, is at least 0.3 wt %.

12. The curable petroleum resin of claim 11 , wherein the Si weight ratio is at least 2 wt %.

13. The curable petroleum resin of claim 9 , wherein the silanes are at least one selected from among materials represented by the following Chemical Formula 1:
CH 2 ═CR—(COO) x (C n H 2n ) y SiR′ 3   Chemical Formula 1

where R is a hydrogen atom or a methyl group; x and y are 0 or 1, provided that y is 1 when x is 1; n is an integer of 1 to 12; and R's are each independently an alkoxy group having 1 to 12 carbon atoms, an aryloxy group, an araloxy group, an aliphatic acyloxy group having 1 to 12 carbon atoms, an amino or substituted amino group, or a lower alkyl group having 1 to 6 carbon atoms, provided that two or less of the three R′ groups are an alkyl group.

14. The curable petroleum resin of claim 13 , wherein the silanes are selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, and 3-(trimethoxysilyl)propyl methacrylate.

15. The curable petroleum resin of claim 9 , wherein the monomers include dicyclopentadiene.

16. The curable petroleum resin of claim 15 , wherein a weight average molecular weight (Mw) is 500 to 2000.

17. The curable petroleum resin of claim 15 , wherein a softening point is 70 to 150° C.

Assignees

• Kolon Inc

Inventors

• Son Jung Soon
• Kim Myung Jong
• Gong Won Seok
• Park Jun Hyo

Classifications

• C08F4/34

  Per-compounds with one peroxy-radical · CPC title

• C08F240/00

  Copolymers of hydrocarbons and mineral oils, e.g. petroleum resins · CPC title

• C09J145/00

  Adhesives based on homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic system; Adhesives based on derivatives of such polymers (based on polymers of cyclic esters of polyfunctional acids C09J131/00; based on polymers of cyclic anhydrides or imides C09J135/00) · CPC title

• C08F2/06

  Organic solvent · CPC title

• C08F220/04

  Acids; Metal salts or ammonium salts thereof · CPC title