Vinyl ether resins for structural applications

• US 20040072964A1
• Filed: 11/18/2003
• Published: 04/15/2004
• Est. Priority Date: 12/22/2000
• Status: Abandoned Application

• Current Assignee: DSM IP Assets BV (DSM-Firmenich AG)
• Original Assignee: DSM IP Assets BV (DSM-Firmenich AG)
• Inventors: Udding, Jan H., Wolters, Agnes E.
• Application Number:
  US10/450,789
• Publication Number:
  US 20040072964A1
• Time in Patent Office: Days
• US Class Current: 525/453
• CPC Class Codes: C08G 18/6715 Unsaturated monofunctional alcohols or amines
• CPC Class Codes: C08G 18/68 Unsaturated polyesters

Abstract

The invention relates to radically curable resin compositions comprising at least a resinous component with one or more vinyl ether group(s), and one or more reactive monomers, wherein said resinous component is obtained by reaction of a mixture of appropriate amounts of a) a compound containing at least one hydroxyl group and at least one vinyl ether group; b) a diisocyanate (or higher isocyanate) compound, reacting with formation of one or more urethane group(s); and c) a compound chosen from the groups of C_2-6 glycols, C_5-20 polyols having 2-5 hydroxyl groups and (un)saturated hydroxyl terminated polyester compounds, with 1-5 free hydroxyl groups and from 2-50 monomeric ester units, the content of vinyl ether groups in the resin composition being from 0.5 to 50 wt. %, calculated as the weight percentage of the HVE-compound relative to the total weight of the resin composition (excluding the weight of additives, fillers and the like), the total acid number of the radically curable resin composition being less than 10 mg of KOH per g, and wherein the curing is effected with the aid of a radical-forming system that is unstable in the temperature range from −20° C. to +110° C.

The invention also relates to a process for the preparation of such resin compositions and uses thereof.

Claims

1. Cured parts or cured structural elements with a thickness of at least 1 mm obtainable by curing radically curable resin compositions, with the aid of a radicalforming system that is unstable in the temperature range from -20C to +110C, the radically curable resin compositions comprising at least (i) a resinous component with one or more vinyl ether group(s), and (ii) one or more reactive monomers as a solvent, characterized in that

the resinous component with one or more vinyl ether group(s) in the curable resin composition Is a resin obtained by reaction of appropriate amounts of;

a) a first compound (the HVE-compound) containing at least one hydroxyl group and at least one vinyl ether group, and

b) a second compound (the D/HIC—

compound), being a dilsocyanate (or higher isocyanate), reacting with formation of one or more urethane group(s), and

c) a third compound (the G/P/HP-compound) chosen from the groups of (1) C₂₄ glycols, (2) C_5-20 polyols having 2-5 hydroxyl groups and (3) saturated or (ethylenically) unsaturated hydroxyl terminated polyester compounds, not being alkyd resins, having 1-5 free hydroxyl groups and from 2-50 monomeric ester units (the G/P/HP-compound), or mixtures thereof,

the content of vinyl ether groups in the resin composition being from 0.5 to 50 wt. %, calculated as the weight percentage of the HVE-compound relative to the total weight of the resin composition (excluding the weight of additives, fillers and the like), and

the total acid number of the radically curable resin composition with the reactive monomer(s) being less than 10 mg of KOH per 9.

2. Cured parts or cured structural elements according to claim 1, characterized in that the content of vinyl ether groups in the resin composition being from 10 to 35 wt.%/.

3. Cured parts or cured structural elements according to any of claims 1 or 2, characterized in that the IVE-compound is a vinyl ether monomer having a general structure according to formula (1), or a mixture of such vinyl ether monomers,

(A-CH═

CH—

O)_n-R (I)

wherein

A represents hydrogen or an alkyl group with 1-3 C atoms, and where, if there is more than one A, the individual A groups may be the same or different

R either represents an aliphatic group, optionally branched, with 2-20 C atoms, which may also contain a cyclohexyl or a 1.,4imethylenecyclohexyl group and in the carbon chain optionally also one or more 0 andlor S atoms, which group is substituted with at least one hydroxyl group at a position or positions being at least 2 C-atoms removed from the vinyl ether group. and which further may be substituted with one or more amino groups, which optionally are substituted with one or two alkyl groups with 1-3 C atoms, or represents a polyethylene glycol or a polypropylene glycol with an average chain length of between 2 and 120 glycol units, and

n is 1,2,3 or4.

4. Cured parts or cured structural elements according to claim 3, characterized in that the HVE-compound is a mono- and/or divinyl ether monomer having at least one free hydroxyl group.

5. Cured parts or cured structural elements according to claim 4, characterized in that the HVE-compound is hydroxybutyl vinyl ether.

6. Cured parts or cured structural elements according to any one of claims 1-5, characterized in that the resinous component with one or more vinyl group(s) is obtained from a reaction mixture wherein the first component is formed by a mixture of an HVE-compound and a hydroxylated (meth)acrylate (HA) compound.

7. Cured parts or cured structural elements according to any one of claims 1-6, characterized in that the resin composition apart from the amount of HVE-compound in the resinous component with one or more vinyl ether group(s) also contains an amount of vinyl ether monomer as reactive monomer, and that the total content of vinyl ether compounds (HVE-compound plus reactive monomer) is from 560 wt. %, relative to the weight of the total resin composition.

8. Cured parts or cured structural elements according to any one of claims 1-7, characterized in that the resin composition is further blended with an unsaturated polyester resin or vinyl ester resin or vinyl ester urethane resin, or mixture thereof.

9. Process for the preparation of a radically curable resin composition for being cured to cured parts or cured structural elements with a thickness of at least 1 mm with the aid of a radical-forming system that is unstable in the temperature range from −

20°

C. to +110°

C., which composition comprises at least (i) a resinous component with one or more vinyl ether group(s), and (ii) one or more other reactive monomers, characterized in that

A. first there are reacted, in a mixture of appropriate amounts of

(a) a first compound (the HVE-compound) containing at least one hydroxyl group and at least one vinyl ether group, and

(b) a second compound (the D/HIC-compound), being a diisocyanate (or higher isocyanate), reacting with formation of one or more urethane group(s), and

(c) a third compound (the G/P/HP-compound) chosen from the groups of (1) C_2-6 glycols, (2) C_5-20 polyols having 2-5 hydroxyl groups and (3) saturated or (ethylenically) unsaturated hydroxyl terminated polyester compounds, not being alkyd resins, having 1-5 free hydroxyl groups and from 2-50 monomeric ester units (the G/PlHP-compound), or mixtures thereof, thereby obtaining a resinous component with one or more vinyl ether group(s) and at least two urethane groups,

wherein the content of vinyl ether groups in the resin composition is from 0.5 to 50 wt. %, calculated as the weight percentage of the HVE-compound relative to the total weight of the resin composition (excluding the weight of additives, fillers and the like), and

B. dissolving said resin in one or more reactive monomers,

C. and adding any fillers and/or additives that may be required, with the proviso that the total acid number of the, optionally unsaturated, prepolymer so obtained is less than 10 mg of KOH per g (as determined according to ISO-2114).

10. Process for the preparation of curable resin compositions according to claim 9, characterized in that the content of vinyl ether groups in the resin composition being from 10 to 35 wt. %

11. Use of curable resin compositions prepared according to claim 9 or 10 for the production of moulded parts or structural materials.

12. Use of curable resin compositions prepared according to claim 9 or 10 in flooring, roofing, rock bolts or chemical anchoring.