US2019276677A1PendingUtilityA1
Polymers, processes, compositions & uses
Est. expiryMay 27, 2036(~9.9 yrs left)· nominal 20-yr term from priority
Inventors:Cornelis Eme KoningTheo VeldhuisLeendert Jan MolhoekPaulus Franciscus Anna BuijsenJan Pieter Drijfhout
C08G 63/16C09D 5/03C09D 167/03C09D 167/04C09D 11/104C08G 63/42C09D 167/02C08G 2150/20C08K 5/20
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Claims
Abstract
The invention relates to a polymer comprising certain specific units. The invention further relates to processes for making the polymer of the invention. The invention further relates to a binder and compositions comprising the polymer, preferably to compositions suitable for paints and coatings. The invention relates in particular to water-borne, solvent-borne and powder coating compositions and preferably to curable water-borne, curable solvent-borne and curable powder coating compositions. The invention further relates to cured compositions. The invention further relates to objects, in particular coatings prepared from the compositions of the invention. The invention further relates to processes for making the compositions of the invention. The invention further relates to articles having coated thereon the compositions of the invention. The invention further relates to articles having coated and cured thereon the compositions of the invention. The invention further relates to various uses of the polymer of the invention, the binder of the invention, the composition of the invention, the cured composition of the invention and various uses of articles having coated and optionally cured thereon the compositions of the invention.
Claims
exact text as granted — not AI-modified1 . A polymer having:
a) an acid value (AV) measured titrimetrically according to ISO 2114 of at least 105 and at most 180 mg KOH/g, and b) a glass transition temperature (T g ) measured via Differential Scanning calorimetry as described in the description, of at least 30 and at most 140° C.
and wherein the polymer comprises one or more units selected from the group consisting of S1, S2, S3 S4, and combinations thereof, wherein each of S1, S2, S3, and S4 is represented by the following corresponding formula:
wherein
i) k is an integer equal to or higher than 0, and
ii) m is an integer equal to or higher than 0, and
iii) n is an integer equal to or higher than 0, and
iv) p is an integer equal to or higher than 0, and
v) the sum of k, m, n and p is equal to or higher than 1, and
vi) X is selected from the group consisting of L4, L6, L7, L8, L9, L10, L11, L12, L13, L18, L19, L20, L23, L24, L25, L26, L27, L28, L29, L30, and L31 as each of L4 to L31 is defined below, and wherein the black bold dots shown in the formulae of any one of L4 to L31 represent the attachment points of each of L4 to L31 to the S1, and wherein the attachment points are carbon atoms,
vii) Y is selected from the group consisting of L4, L6, L7, L8, L9, L10, L11, L12, L13, L18, L19, L20, L23, L24, L25, L26, L27, L28, L29, L30, and L31 as each of L4 to L31 is defined below, and wherein the black bold dots shown in the formulae of any one of L4 to L31 represent the attachment points of each of L4 to L31 to the S2, and wherein the attachment points are carbon atoms,
viii) Z is selected from the group consisting of L4, L6, L7, L8, L9, L10, L11, L12, L13, L18, L19, L20, L23, L24, L25, L26, L27, L28, L29, L30, and L31 as each of L4 to L31 is defined below, and wherein the black bold dots shown in the formulae of any one of L4 to L31 represent the attachment points of each of L4 to L31 to the S3, and wherein the attachment points are carbon atoms,
ix) T is selected from the group consisting of L4, L6, L7, L8, L9, L10, L11, L12, L13, L18, L19, L20, L23, L24, L25, L26, L27, L28, L29, L30, and L31 as each of L4 to L31 is defined below, and wherein the black bold dots shown in the formulae of any one of L4 to L31 represent the attachment points of each of L4 to L31 to the S4, and wherein the attachment points are carbon atoms,
wherein
R 1 ″, R 2 ″ is independently selected from the group consisting of H and CH 3 , and
R 3 ″, is a CH 2 or C 2 -C 34 optionally-substituted-hydrocarbylene, and
R 4 ″R 5 ″R 6 ″R 7 ″ is independently selected from the group consisting of H, CH 3 , and C 2 -C 34 optionally-substituted-hydrocarbyl,
R 8 ″, R 9 ″ is independently selected from C 1 -C 34 optionally-substituted-hydrocarbyl, and
R 10 ″, R 11 ″ is independently selected from C 1 -C 12 saturated-hydrocarbyl, and
R 12 ″ is C 4 -C 34 unsaturated-acyclic-hydrocarbyl.
2 . The polymer according to claim 1 , wherein the AV is at most 170 mg KOH/g.
3 . The polymer according to claim 1 , wherein the AV is at least 110 and at most 170 mg KOH/g.
4 . The polymer according to claim 1 , wherein the AV is at least 130 and at most 170 mg KOH/g.
5 . The polymer according to claim 1 , wherein the T g is at least 40 and at most 95° C.
6 . The polymer according to claim 1 , wherein the T g is at least 40 and at most 85° C.
7 . The polymer according to claim 1 , wherein the polymer has a MRQ of at least 1 and at most 1.4, and wherein the MRQ is
M
R
Q
=
S
total
S
specific
=
S
specific
+
S
rest
S
specific
wherein
S total =S specific +S rest , and
S specific =(total moles S1)+(total moles S2)+(total moles S3)+(total moles S4), and
S rest =the total moles of all the units of a polymer wherein said units are not any one of S1, S2, S3, S4, and
wherein the MRQ is determined is determined via NMR spectroscopy, as described in the description.
8 . The polymer of claim 7 , wherein the MRQ is at most 1.3, preferably at most 1.2.
9 . The polymer according to claim 1 wherein the polymer has:
i) a number average molecular weight (M n ) of at least 8×10 2 and at most 10 4 Da, and
ii) a polydispersity (D) (D=M w /M n ) of at least 1 and at most 10, and
iii) a T g of at least 40 and at most 85° C., and
iv) an AV of at least 110 and at most 170 mg KOH/g, and
v) a hydroxyl value (OHV) of at least 0 and at most 400 mg KOH/g, and
vi) a functionality (f) of at least 3 and at most 25,
wherein
M w is the weight average weight and is measured via Gel Permeation Chromatography according to the description, and
M n is measured via Gel Permeation Chromatography according to the description, and
OHV is measured titrimetrically via ISO 4629, and
f is as defined and measured in the description.
10 . The polymer according to claim 1 , wherein the polymer is an acid-functional polyester.
11 . The polymer according to claim 1 , wherein the polymer is ionic.
12 . A process for making a polymer as defined in claim 1 , comprising the steps of
a. providing:
a-i) a mono-epoxide selected from the group consisting of E4, E6, E7, E8, E9, E10, E11, E12, E13, E18, E19, E20, E23, E24, E25, E26, E27, E28, E29, E30, E31 and mixtures thereof, as each of E4 to E31 is represented by the following corresponding formula:
wherein
R 1 ″′, R 2 ″′ is independently selected from the group consisting of H and CH 3 , and
R 3 ′″, is a CH 2 or C 2 -C 34 optionally-substituted-hydrocarbylene, and
R 4 ′″R 5 ′″R 6 ′″R 7 ′″ is independently selected from the group consisting of H, CH 3 , and C 2 -C 34 optionally-substituted-hydrocarbyl,
R 8 ″′, R 9 ″′ is independently selected from C 1 -C 34 optionally-substituted-hydrocarbyl, and
R 10 ″′, R 11 ″ is independently selected from C 1 -C 12 saturated-hydrocarbyl, and
R 12 ′″ is C 4 -C 34 unsaturated-acyclic-hydrocarbyl,
and wherein none of R 1 ′″ to R 12 ′″ comprises any anhydride group,
and
a-ii) a reagent A selected from the group consisting of trimellitic acid anhydride, trimellitic acid, citric acid anhydride, citric acid and mixtures thereof, and
a-iii) optionally a catalyst A, and
a-iv) optionally an organic solvent, and
a-v) optionally a reagent B selected from the group comprising of anhydride A, cyclic ester and mixtures thereof,
and
b. charging a-i) to a-v) provided in step a. into a reaction vessel to form a reaction mixture, and
c. polymerizing the reaction mixture,
c-i) at a temperature of at least 60 and at most 200° C., and
c-ii) for a time of at least 0.5 hours and at most 200 hours, and
c-iii) removing water by applying vacuum, if water is formed during the polymerization of the reaction mixture, and
c-iv) optionally applying pressure with the proviso that vacuum and pressure are not applied at the same time,
to afford the polymer,
and
d. discharging the polymer from the reaction vessel and collecting said polymer,
and wherein
the molar ratio L between the moles of monoepoxide as defined in a-i) and the moles of reagent A as defined in a-ii),
Molar ratio L=moles of monoepoxide/moles of reagent A
is at least 0.1 and at most 2.9, preferably at least 0.3 and at most 2.8.
13 . A heat-curable powder coating composition comprising a binder in an amount of at least 1 and at most 100 pph composition, and wherein the binder comprises:
a) a polymer as defined in claim 1 , in an amount of at least 10 and at most 99 pph binder, and b) an acid-functional copolymerizable polymer A which is an acid functional polyester B, in an amount of at least 10 and at most 99 pph, and c) a copolymerizable agent able to react with the polymer and the acid-functional copolymerizable polymer A, in an amount of at least 1 and at most 90 pph binder, and wherein
the acid-functional polyester B is different from the polymer, and
the difference between the AV of the polymer and the AV of the copolymerizable polymer A (DeltaAV) each of the AV measured titrimetrically according to ISO 2114 is at least 30 mg KOH/g, and wherein the AV of the copolymerizable polymer A is lower than the AV of the polymer.
14 . The heat-curable powder coating composition of claim 13 , wherein the DeltaAV is at least 75 mg KOH/g.
15 . The heat-curable powder coating composition of claim 13 , wherein the DeltaAV is at least 100 mg KOH/g.
16 . The heat-curable powder coating composition according to any one of claims 13 to 15 , wherein the Weight Ratio R (WR)
Weight
Ratio
R
=
Weight
of
acid
-
functional
copolymerizable
polymer
A
Weight
of
polymer
is at least 1 and most 10.
17 . The heat-curable powder coating composition of claim 16 , wherein the WR is at least 2 and at most 8.
18 . The heat-curable powder coating composition according to claim 13 , wherein the acid-functional copolymerizable polymer A has an AV measured titrimetrically according to ISO 2114 of at least 15 and at most 40 mg KOH/g, and a T g measured via Differential Scanning calorimetry as described in the description, of at least 40 and at most 80° C.
19 . The heat-curable powder coating composition according to claim 13 , wherein the copolymerizable agent is a BHA compound in an amount of at least 2 and at most 15 pph binder.
20 . A cured composition as the composition is defined in claim 13 .
21 . An article having coated a composition as the composition is defined in claim 13 .
22 . An article having coated and cured thereon a composition as the composition is defined in claim 13 .
23 . (canceled)
24 . A product which comprises the polymer according to claim 1 , wherein the product is selected from the group consisting of paints, polishes, inks, adhesives, pastes, 3D-printing materials, automotive products, marine products, aerospace products, medical products, defense products, sports/recreational products, architectural products, bottling products, household products, machinery products, can products, coil products, energy products, textiles and electrical products.Cited by (0)
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