Polymer, process and composition

Patent metadata

Field	Value
Publication number	US-9255171-B2
Application number	US-201314376232-A
Country	US
Kind code	B2
Filing date	Feb 4, 2013
Priority date	Feb 3, 2012
Publication date	Feb 9, 2016
Grant date	Feb 9, 2016

Abstract

There are described q oligomer-polymer composition [optionally substantially free of styrene (<1.5 wt-% of copolymer)] comprising oligomer composition O having a weight average molecular weight of from 1000 to 150,000 g/mol (measured by GPC) and polymer composition P having a weight average molecular weight of at least 80,000 g/mol (measured by GPC) the oligomer composition O and the polymer composition P each independently comprising a copolymer composition comprising: (a) at least 8.5 wt-% preferably >=20 wt-% of a higher itaconate diester (preferably dibutyl itaconate—DBI); (b) less than 23 wt-% acid monomer but also sufficient to have an acid value less than 150 mg KOH/g of polymer, (c) optionally with less than 50 wt-% of other itaconate monomers, and (d) optionally less than 77 wt-% of other monomers not (a) to (c). The DBI may be biorenewable. One embodiment is an aqueous dispersion of vinyl sequential polymer of two phases: A) 40 to 90 wt-% of a vinyl polymer A with Tg from −50 to 30° C.; and B) 10 to 60 wt-% of a vinyl polymer B with Tg from 50 to 130° C.; where DBI is used to prepare A and/or B and polymer A has from 0.1 to 10 wt-% of at least one acid-functional olefinically unsaturated monomer. Another embodiment is an aqueous polymer coating composition of a vinyl oligomer C of Mw from 1,000 to 150,000 g/mol and an acid value>5 mgKOH/g; and a vinyl polymer D of Mw>=80,000 g/mol and an acid value<10 mgKOH/g where D is obtained from DBI and the amount of monomers used to form C and D fall into the respective weight ratios 5 to 70 for polymer C and 95 to 30 for polymer D. A further embodiment is an aqueous suspension polymerization process for preparing vinyl polymer beads from olefinically unsaturated monomers and a free-radical initiator, where at least 10 wt-% of the monomer is DBI.

First claim

The invention claimed is:

1. An oligomer-polymer composition comprising an oligomer composition O having a weight average molecular weight of from 1000 to 150,000 g/mol (measured by GPC), and a polymer composition P having a weight average molecular weight of at least 80,000 g/mol (measured by GPC), wherein the oligomer composition O and the polymer composition P each independently comprise a copolymer comprising:
(a) optionally at least 23% by weight of at least one monomer represented by Formula 1:

 where both R 1 and R 2 independently represent an optionally substituted hydrocarbo moiety having from 4 to 10 carbon atoms,
(b) optionally at least one hydrophilic monomer in an amount sufficient that the resultant copolymer has an acid value less than 150 mg KOH per g of polymer,
(c) optionally of one or more monomers represented by Formula 2:

 where R 3 and R 4 independently represent H or an optionally substituted hydrocarbo moiety having from 1 to 20 carbon atoms
 X 1 and X 2 independently represents O or NR 5 where R 5 denotes H or an optionally substituted hydrocarbo moiety having from 1 to 20 carbon atoms
 with the proviso that when X 1 and/or X 2 are O then the respective R 3 and/or R 4 attached to the oxy group independently represent an optionally substituted hydrocarbo having from 1 to 3 carbon atoms
(d) optionally less than 77% by weight of monomers other than components (a), (b) or (c),
where the percentages or amounts of (a), (b) (c) (d) are by weight calculated as a proportion of the total weight of (a)+(b)+(c)+(d) and thus total 100%;
where independently at least one of the components (a), (b), (c), (d) and the copolymer obtained from components (a), (b), (c) and/or (d) is biorenewable as defined by an amount of carbon-14 sufficient to produce a decay of at least about 1.5 disintegrations per minute per gram carbon (dpm/gC); and
where at least one component (a) is present in either oligomer composition O or polymer composition P, and wherein the oligomer-polymer composition comprises:
(a) component (a) in an amount from 24% to 70% by weight being one or more monomers represented by Formula 1
(b) component (b) being one or more acid functional monomer(s) in an amount from 0.5% to 15% by weight, in an amount also sufficient that the resultant copolymer has an acid value of from 3 to 100 mg KOH per g of polymer,
(c) component (c) in an amount from 0.01% to 10% by weight being one or more monomers represented by Formula 2 in which X 1 and X 2 are both O and R 3 and/or R 4 independently represent an optionally substituted hydrocarbo having from 1 to 3 carbon atoms,
(d) component (d) if present in an amount less than 75% by weight of monomer(s) other than components (a), (b) or (c) not containing styrene, butyl acrylate, 2-ethyl hexyl acrylate and/or mixtures thereof; and
with the provisos that
where the copolymer is prepared by an emulsion polymerisation a chaser monomer is not used;
the copolymer is not prepared in the presence of a seed polymer comprising a poly(itaconate ester);
the copolymer is not prepared in the presence of an initiator system comprising an organoborane amine complex.

2. An oligomer-polymer composition as claimed in claim 1 , wherein component (a) comprises dibutyl itaconate.

3. An oligomer-polymer composition as claimed in claim 1 , wherein at least one of composition O and/or P:
(a) component (a) is present in an amount of from 30 to 65 wt-% and is dibutyl itaconate;
(b) optional component (b) if present is present in an amount of up to 10 wt-% and comprises an acid functional ethylenically unsaturated monomer and/or anhydride thereof;
(c) optional component (c) if present is present in an amount of from 1 to 25 wt-% and is dimethyl itaconate and/or diethyl itaconate;
(d) optional component (d) if present is present in an amount such that (a) and (d), and (b) and (c) where present, total 100% by weight.

4. An oligomer-polymer composition as claimed in claim 1 in which at least one component (d) comprises at least one polymer precursor(s) of Formula 3

wherein,
Y denotes an electronegative group,
R 6 is H, OH or an optionally hydroxy substituted C 1-10 hydrcarbo
R 7 is H or a C 1-10 hydrocarbo;
R 8 is a C 1-10 hydrocarbo group substituted by at least one activated unsaturated moiety comprising at least one unsaturated carbon-to-carbon double bond in chemical proximity to at least one activating moiety; and either:
A represents a divalent organo moiety attached to both the —HN— and —Y— moieties so the -A-, —NR 6 —, —C(═O)— and —Y— moieties together represent a ring of 4 to 8 ring atoms, and R 7 and R 8 are attached to any suitable point on the ring; or
A is not present (and Formula 3 represents a linear and/or branched moiety that does not comprise a heterocyclic ring) in which case R 7 and R 8 are attached to R 6 ; and
m is an integer from 1 to 4.

5. An aqueous polymer dispersion comprising an oligomer-polymer composition as claimed in claim 1 , wherein the aqueous polymer dispersion exhibits a minimum film forming temperature below 50° C. and comprises a vinyl copolymer derived from olefinically unsaturated monomers, with at least two phases comprising:
A) 40 to 90 wt-% of a vinyl polymer A having a glass transition temperature in the range of from −50 to 30 C; and
B) 10 to 60 wt-% of a vinyl polymer B having a glass transition temperature the range of from 50 to 130° C.; wherein
at least one of the monomers used to prepare the vinyl polymer A and/or the vinyl polymer B is di(n-butyl)itaconate (DBI) in an amount from 20 to 80 wt-% of the total monomers, wherein
optionally 10% by weight of the total amount of monomer used to form the vinyl polymer A and the vinyl polymer B comprises an amount of carbon-14 sufficient to produce a decay of at least about 1.5 dpm/gC; and wherein
the weight percentage of monomers in the vinyl polymer A and the vinyl polymer B are calculated based on the total amount of olefinically unsaturated monomers used to prepare the vinyl polymer A and the vinyl polymer B=100%; and wherein
the vinyl polymer A comprises 0.1 to 10 wt-% of at least one acid-functional olefinically unsaturated monomer, where the weight percentage of acid functional monomer is calculated based on the total amount of olefinically unsaturated monomer used to prepare polymer A=100%.

6. A process for preparing a copolymer as claimed in claim 1 , the process comprising the step of
polymerising polymer precursors in a polymerisation method the polymer precursors comprising component (a), component (b) and optionally components (c) and/or component (d), wherein
optionally the polymerisation method is selected from aqueous emulsion polymerisation and suspension polymerisation and where the method does not comprise a chaser monomer step.

7. A coating composition comprising an oligomer-polymer composition as claimed in claim 1 .

8. A substrate and/or article having coated thereon an optionally cured coating composition of claim 7 .

9. A method for preparing a coated substrate and/or article comprising the steps of applying a coating composition of claim 7 to the substrate and/or article and optionally curing said composition in situ to form a cured coating th

Assignees

• Dsm Ip Assets Bv

Inventors

• Nabuurs Tijs
• Overbeek Gerardus Cornelis
• Stubbs Jeffrey
• Gebhard Matthew Stewart

Classifications

• C08F220/1804

  C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate · CPC title

• C08F220/06

  Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof · CPC title

• C09D135/02

  Homopolymers or copolymers of esters (C09D135/06, C09D135/08 take precedence) · CPC title

• C09D133/12

  Homopolymers or copolymers of methyl methacrylate · CPC title

• C08F293/005

  using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent · CPC title