Liquid injection molding inhibitors for curable compositions

• US 5,506,289 A
• Filed: 07/23/1993
• Issued: 04/09/1996
• Est. Priority Date: 07/23/1993
• Status: Expired due to Term

• Current Assignee: General Electric Company
• Original Assignee: General Electric Company
• Inventors: O'Brien, Michael J., Jeram, Edward M., McDermott, Philip J.
• Primary Examiner(s): SANDERS, KRIELLION ANTIONETTE
• Application Number:
  US08/096,314
• Time in Patent Office: 991 Days
• Field of Search: 524/306, 524/307, 524/285, 524/287, 524/288, 524/290, 524/308
• US Class Current: 524/306
• CPC Class Codes: B29K 2083/005 LSR, i.e. liquid silicone rubbers, or derivatives thereof
• CPC Class Codes: C07C 69/007 Esters of unsaturated alcohols having the esterified hydroxy group bound to an acyclic carbon atom
• CPC Class Codes: C07C 69/60 Maleic acid esters; Fumaric acid esters
• CPC Class Codes: C08G 77/12 containing silicon bound to hydrogen C08G77/045 takes precedence
• CPC Class Codes: C08G 77/20 containing silicon bound to unsaturated aliphatic groups C08G77/045 takes precedence
• CPC Class Codes: C08G 77/70 Siloxanes defined by use of the MDTQ nomenclature
• CPC Class Codes: C08G 77/80 Siloxanes having aromatic substituents, e.g. phenyl side groups
• CPC Class Codes: C08J 2383/04 Polysiloxanes
• CPC Class Codes: C08J 3/24 Crosslinking, e.g. vulcanising, of macromolecules mechanical aspects B29C35/00; crosslinking agents C08K
• CPC Class Codes: C08K 5/0025 Crosslinking or vulcanising agents; including accelerators
• CPC Class Codes: C08K 5/11 of acyclic polycarboxylic acids
• CPC Class Codes: C08L 2666/34 Oxygen-containing compounds, including ammonium and metal salts
• CPC Class Codes: C08L 83/00 Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 83/04 Polysiloxanes

Abstract

Acetylenic maleates, fumarates and related derivative compounds are new compositions of matter having the formula:

R.sub.1 O.sub.2 C--CH═CH--CO.sub.2 R.sub.2

wherein R₁ may be an organic moiety containing at least two carbon atoms triply bonded one to the other as:

--C.tbd.C--

and R₂ may be hydrogen, an organic moiety, or R₁ ; suitable for use as liquid injection molding inhibitors either singly or in combination with themselves or other liquid injection molding inhibitors when used for the process of liquid injection molding curable compositions enabling an increase in the size of articles manufactured therefrom, which new compositions of matter cure into the polymerizable or curable resins thereby creating new compositions of matter as cured resins from which said articles of manufacture are produced.

Claims

1. A liquid composition for injection into a liquid injection molding apparatus comprising a polymerizable or curable silicone resin and an effective amount of a liquid injection molding inhibitor compound having the formula:

space="preserve" listing-type="equation">R.sub.1 O.sub.2 C--CH═

CH--CO.sub.2 R.sub.2

wherein R₁ is a hydrocarbon radical having from 3 to about 22 carbon atoms containing at least two carbon atoms triply bonded one to the other as;

space="preserve" listing-type="equation">--C.tbd.C--

and R₂ is hydrogen, R₁ or a hydrocarbon radical having from 3 to about 22 carbon atoms.

9. The liquid injection molding composition of claim 1 wherein the R₂ group of the liquid injection molding inhibitor compound is hydrogen.

2. A liquid composition for injection into a liquid injection molding apparatus comprising a polymerizable or curable silicone resin and an effective amount of a liquid injection molding inhibitor compound having the formula:

space="preserve" listing-type="equation">R.sub.1 O.sub.2 C--CH═

CH--CO.sub.2 R.sub.2

wherein R₁ has the formula;

space="preserve" listing-type="equation">---R.sub.3 --C.tbd.C--R.sub.4

wherein R₃ is selected from the group of divalent hydrocarbon radicals consisting of linear or branched alkyl radicals, linear or branched alkenyl radicals, linear or branched alkynyl radicals, cycloalkyl radicals, cycloalkenyl radicals, cycloalkynyl radicals, halogenated linear or branched alkyl radicals, halogenated linear or branched alkenyl radicals, halogenated linear or branched alkynyl radicals, hydrocarbonoxy radicals containing at least two carbon atoms, halogenated hydrocarbonoxy radicals containing at least two carbon atoms, aryl radicals, linear or branched alkyl aryl radicals, halogenated aryl radicals, halogenated linear or branched alkyl-, alkenyl-, or alkynyl aryl radicals; and

wherein R4 is selected from the group of monovalent radicals consisting of hydrogen, linear or branched alkyl radicals, linear or branched alkenyl radicals, linear or branched alkynyl radicals, cycloalkyl radical, cycloalkenyl radicals, cycloalkynyl radicals, halogenated linear or branched alkyl radicals, halogenated linear or branched alkenyl radicals, halogenated linear or branched alkynyl radicals, hydrocarbonoxy radicals containing at least two carbon atoms, halogenated hydrocarbonoxy radicals containing at least two carbon atoms, aryl radicals, linear or branched alkyl aryl radicals, halogenated aryl radicals, halogenated linear or branched alkyl-, alkenyl-, or alkynyl aryl radicals; and

triorganosilyl radicals and wherein R₂ is R₁ or is selected from the group consisting of hydrogen, triorganosilyl radicals, and siloxanes.

10. The liquid injection molding composition of claim 2 wherein the R₂ group of the liquid injection molding inhibitor compound is hydrogen.

3. A liquid composition for injection into a liquid injection molding apparatus comprising a polymerizable or curable resin and an effective amount of a liquid injection molding inhibitor compound having the formula:

space="preserve" listing-type="equation">R.sub.1 C.sub.2 C--CH═

CH--CO.sub.2 R.sub.2

wherein R₁ has the formula;

space="preserve" listing-type="equation">--R.sub.3 --C.tbd.C--R.sub.4

wherein R₃ is selected from the group of divalent hydrocarbon radicals consisting of linear or branched alkyl radicals having from I to about 10 carbon atoms, linear or branched alkenyl radicals having from 1 to about 10 carbon atoms, linear or branched alkynyl radicals having from 1 to about 10 carbon atoms, cycloalkyl radicals having from 3 to about 12 carbon atoms, cycloalkenyl radicals having from about 3 to 12 carbon atoms, cycloalkynyl radicals having from about 8 to about 16 carbon atoms, fluorinated linear or branched alkyl radicals having from 1 to about 10 carbon atoms, chlorinated linear or branched alkyl radicals having from 1 to about 10 carbon atoms, brominated linear or branched alkyl radicals having from 1 to about 10 carbon atoms, fluorinated linear or branched alkenyl radicals having from 2 to about 10 carbon atoms, chlorinated linear or branched alkenyl radicals having from 2 to about 10 carbon atoms, brominated linear or branched alkenyl radicals having from 2 to about 10 carbon atoms, fluorinated linear or branched alkynyl radicals having from 2 to about 10 carbon atoms, chlorinated linear or branched alkynyl radicals having from 2 to about 10 carbon atoms, brominated linear or branched alkynyl radicals having from 2 to about 10 carbon atoms, hydrocarbonoxy radicals containing at least two carbon atoms, fluorinated hydrocarbonoxy radicals containing at least two carbon atoms, chlorinated hydrocarbonoxy radicals containing at least two carbon atoms, brominated hydrocarbonoxy radicals containing at least two carbon atoms, aryl radicals, linear or branched alkyl aryl radicals, fluorinated aryl radicals, chlorinated aryl radicals, brominated aryl radicals;

fluorinated linear or branched alkyl-, alkenyl-, or alkynyl aryl radicals;

chlorinated linear or branched alkyl-, alkenyl-, or alkynyl aryl radicals; and

brominated linear or branched alkyl-, alkenyl-, or alkynyl aryl radicals; and

wherein R4 is selected from the group of monovalent radicals consisting of hydrogen, linear or branched alkyl radicals having from 1 to about 10 carbon atoms, linear or branched alkenyl radicals having from 2 to about 10 carbon atoms, linear or branched alkynyl radicals having from 2 to about 10 carbon atoms, cycloalkyl radicals having from 3 to about 12 carbon atoms, cycloalkenyl radicals having from about 3 to 12 carbon atoms, cycloalkynyl radicals having from about 8 to about 16 carbon atoms, fluorinated linear or branched alkyl radicals having from 1 to about 10 carbon atoms, chlorinated linear or branched alkyl radicals having from 1 to about 10 carbon atoms, brominated linear or branched alkyl radicals having from 1 to about 10 carbon atoms, fluorinated linear or branched alkenyl radicals having from 2 to about 10 carbon atoms, chlorinated linear or branched alkenyl radicals having from 2 to about 10 carbon atoms, brominated linear or branched alkenyl radicals having from 2 to about 10 carbon atoms, fluorinated linear or branched alkynyl radicals having from 2 to about 10 carbon atoms, chlorinated linear or branched alkynyl radicals having from 2 to about 10 carbon atoms, brominated linear or branched alkynyl radicals having from 2 to about 10 carbon atoms, hydrocarbonoxy radicals containing at least two carbon atoms, fluorinated hydrocarbonoxy radicals containing at least two carbon atoms, chlorinated hydrocarbonoxy radicals containing at least two carbon atoms, brominated hydrocarbonoxy radicals containing at least two carbon atoms aryl radicals, linear or branched alkyl aryl radicals, fluorinated aryl radicals, chlorinated aryl radicals, brominated aryl radicals;

fluorinated linear or branched alkyl-, alkenyl-, or alkynyl aryl radicals;

chlorinated linear or branched alkyl-, alkenyl-, or alkynyl aryl radicals;

brominated linear or branched alkyl-, alkenyl-, or alkynyl aryl radicals; and

triorganosilyl radicals and wherein R₂ is R₁ or is selected from the group consisting of hydrogen, triorganosilyl radicals, and siloxanes.

4. The liquid composition of claim 3 wherein the liquid injection molding inhibitor compound comprises di(3-butynyl)maleate.

5. The liquid composition of claim 3 wherein the liquid injection molding inhibitor compound comprises di-propargyl maleate.

6. The liquid composition of claim 3 wherein the liquid injection molding inhibitor compound comprises mono-(3-butynyl)maleate.

7. The liquid composition of claim 3 wherein the liquid injection molding inhibitor compound comprises allyl-3-butynyl maleate.

8. The liquid composition of claim 3 wherein the liquid injection molding inhibitor compound comprises di-propargyl fumarate.

11. The liquid injection molding composition of claim 3 wherein the R₂ group of the liquid injection molding inhibitor compound is hydrogen.