Functionalized accelerating resins derived from renewable materials

Patent metadata

Field	Value
Publication number	US-2018282467-A1
Application number	US-201816002488-A
Country	US
Kind code	A1
Filing date	Jun 7, 2018
Priority date	Dec 8, 2015
Publication date	Oct 4, 2018
Grant date	—

Abstract

The present invention relates to curable polyurethane polymers made from renewable materials and having polymerization accelerator groups built into the polymer. In particular hydroxylated oleaginous materials derived from plant oils, such as soybean oil, are used. These renewable materials may be formed into curable polyurethane polymers having different chemical functionalities and cure mechanisms.

First claim

1 . A polymerizable polymer corresponding to the structure:
MA-U-A-U-MA
wherein A comprises an oleaginous backbone derived from hydroxylated plant oil, U comprises a hydrocarbyl linker off of which is a group comprising a urethane linkage and a polymerization accelerator group and further optionally comprising a free isocyanate group or hydroxyl group and MA comprises a member selected from the group consisting of a (meth)acrylate-containing group, an alkoxy-containing group and combinations thereof.

2 . The polymerizable polymer of claim 1 , wherein the oleaginous backbone is derived from hydroxylated soybean oil almond oil, canola oil, coconut oil, cod liver oil, corn oil, cottonseed oil, flaxseed oil, linseed oil, olive oil, palm oil, peanut oil, safflower oil, sesame oil, sunflower oil, walnut, castor oil and combinations thereof.

3 . The polymerizable polymer of claim 1 , wherein the hydroxylated plant oil has a hydroxyl functionality from about 1.0 to about 7.0.

4 . The polymerizable polymer of claim 1 , wherein the (meth)acrylate-containing group comprises a reactant residue selected from the group consisting of 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 2-hydroxybutyl acrylate, 3-(acryloyloxy)-2-hydroxypropyl methacrylate, 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, poly(propylene glycol) (meth)acrylate, 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 4-isocyanatobutyl (meth)acrylate, 3-isocyanatobutyl (meth)acrylate, and 2-isocyanatobutyl (meth)acrylate.

5 . The polymerizable polymer of claim 1 , wherein U further comprises a diisocyanate reactant residue selected from the group consisting of isophorone diisocyanate (IPDI), IPDI isocyanurate, polymeric IPDI, naphthalene 1,5-diisocyanate (NDI), methylene bis-cyclohexylisocyanate, methylene diphenyl diisocyanate (MDI), polymeric MDI, toluene diisocyanate (TDI), isocyanurate of TDI, TDI-trimethylolpropane adduct, polymeric TDI, hexamethylene diisocyanate (HDI), HDI isocyanurate, HDI biurate, polymeric HDI, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl xylylene diisocyanate, p-phenylene diisocyanate, 3,3′-dimethyldiphenyl-4,4′-diisocyanate (DDDI), 2,2,4-trimethylhexamethylene diisocyanate (TMDI), norbornane diisocyanate (NDI) and 4,4′-dibenzyl diisocyanate (DBDI).

6 . The polymerizable polymer of claim 1 , wherein the alkoxy-containing group comprises a reactant residue selected from the group consisting of 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 3-isocyanatopropyldimethylethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropyldimethylmethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxysilane, 4-aminobutyldimethylethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutylmethyldimethoxysilane, 4-aminobutyldimethylmethoxysilane, 4-amino-3,3-dimethylbutylmethyldimethoxysilane, dimethylbutyltrimethoxysilane, 1-amino-2-(dimethylethoxysilyl)propane, 3-(m-aminophenoxy)propyltrimethoxysilane, m-aminophenyltrimethoxysilane, m-aminophenyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethyethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyldimethymethoxysilane, 3-aminopropylmethylbis(trimethylsiloxy)silane, 3-aminopropylpentamethyldisiloxane, 11-aminoundecyltriethoxysilane, and 11-aminoundecyltrimethoxysilane.

7 . The polymerizable polymer of claim 1 , wherein the polymerization accelerator group comprises an aliphatic or aromatic diol compound having an active nitrogen, which diol compound may be optionally substituted.

8 . The polymerizable polymer of claim 1 , wherein the polymerization accelerator group has the structure:

wherein R 2 is a hydrocarbyl group C 1-20 which may be optionally substituted and may contain heteroatoms S or N; and n and m are each 1-13.

9 . The polymerizable polymer of claim 7 , wherein the polymerization accelerator group is a residue of the structure:

10 . The polymerizable polymer of claim 7 , wherein the polymerization accelerator group is a residue of one of the structures:

11 . A curable resin composition comprising the reaction product of claim 1 and a cure system, said cure system selected from the group consisting of a free radical initiator system, a moisture cure system and combinations thereof.

12 . A polyurethane prepared from the reaction of:
a) an NCO-terminated polymer formed from the reaction of an hydroxylated oleaginous component derived from plant oil, a diisocyanate compound and a polymerization accelerator compound comprising an aliphatic or aromatic diol compound having an active nitrogen, which diol compound may be optionally substituted; and b) a component selected from the group consisting of an hydroxylated (meth)acrylate monomer, an alkoxy-functionalized monomer, an amine-functionalized compound and combinations thereof.

13 . The polyurethane of claim 12 wherein the hydroxylated oleaginous component derived from plant oil comprises hydroxylated soybean oil.

14 . The polyurethane of claim 12 , wherein the diisocyanate is selected from the group consisting of isophorone diisocyanate (IPDI), IPDI isocyanurate, polymeric IPDI, naphthalene 1,5-diisocyanate (NDI), methylene bis-cyclohexylisocyanate, methylene diphenyl diisocyanate (MDI), polymeric MDI, toluene diisocyanate (TDI), isocyanurate of TDI, TDI-trimethylolpropane adduct, polymeric TDI, hexamethylene diisocyanate (HDI), HDI isocyanurate, HDI biurate, polymeric HDI, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl xylylene diisocyanate, p-phenylene diisocyanate, 3,3′-dimethyldiphenyl-4,4′-diisocyanate (DDDI), 2,2,4-trimethylhexamethylene diisocyanate (TMDI), norbornane diisocyanate (NDI), and 4,4′-dibenzyl diisocyanate (DBDI).

15 . A method of forming a polyurethane polymer from a renewable source, said polyurethane polymer being (meth)acrylate functionalized and/or alkoxy functionalized, said method comprising:
a) forming a polyurethane polymer by reacting an hydroxylated oleaginous component derived from plant oil with a diisocyanate compound and a polymerization accelerator compound comprising an aliphatic or aromatic diol compound having an active nitrogen, which diol compound may be optionally substituted; and b) reacting said polyurethane polymer with (i) a (meth)acrylate monomer containing hydroxyl functionality to yield said curable (meth)acrylate-functionalized polyurethane polymer; or (ii) reacting said polyurethane with an alkoxy monomer containing amine and/or isocyanate functionality to yield said curable alkoxy-functionalized monomer.

16 . The method of claim 15 , wherein the hydroxylated oleaginous component derived from plant oil comprises soybean oil.

17 . The method of claim 15 , wherein the ratios of OH/NCO equivalents are form 0.99 to 0.10.

18 . The method of claim 17 , wherein the reaction is carried out until substantially all NCO groups are reacted with OH groups.

Assignees

• Henkel IP & Holding GmbH

Inventors

• Messana Andrew D
• Dworak David P
• Jacobine Anthony F
• Gustafson Darel

Classifications

• C08G18/36

  Hydroxylated esters of higher fatty acids · CPC title

• C08G18/8051

  with compounds of C08G18/36 · CPC title

• C08F222/1065

  of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates · CPC title

• C08G18/246

  containing also tin-carbon bonds · CPC title

• C08G18/3844

  containing one nitrogen atom in the ring · CPC title