Dye, filler made therefrom, compositions including the filler, and method of determining degree of cure of such compositions

Patent metadata

Field	Value
Publication number	US-10968332-B2
Application number	US-201916356942-A
Country	US
Kind code	B2
Filing date	Mar 18, 2019
Priority date	Dec 30, 2013
Publication date	Apr 6, 2021
Grant date	Apr 6, 2021

Abstract

A compound represented by formula:

and a treated filler having the compound on at least a portion of its surface. R is hydrogen or alkyl. X is alkylene, arylalkylene, or alkylarylene, each optionally interrupted by at least one of an ether, thioether, amine, amide, ester, thioester, carbonate, thiocarbonate, carbamate, thiocarbamate, urea, or thiourea, with alkylene optionally interrupted by arylene. W is hydroxyl, a sulfonic acid group, a phosphonic acid group, carboxylic acid group, —NHR 1 , epoxy, or —Si(Y) x (Z) 3-x . Y is alkyl, aryl, arylalkylenyl, or alkylarylenyl. Z is halide, hydroxyl, alkoxy, aryloxy, acyloxy, polyalkyleneoxy, —O— covalently bonded to the surface of the filler, or —O bonded to another silicon atom, and x is 0 or 1. A composition including the treated filler, a method of making the treated filler, and a method of determining the degree of cure of a curable polymeric resin are also disclosed.

First claim

What is claimed is:

1. A treated filler comprising:
an inorganic filler having on at least a portion of its surface a compound of formula

wherein
R is hydrogen or alkyl;
X is alkylene, arylalkylene, or alkylarylene, wherein alkylene, arylalkylene, and alkylarylene are optionally interrupted by at least one of an ether, thioether, amine, amide, ester, thioester, carbonate, thiocarbonate, carbamate, thiocarbamate, urea, or thiourea, and wherein alkylene is optionally interrupted by arylene;
W is hydroxyl, a sulfonic acid group, a phosphonic acid group, a carboxylic acid group, —NHR 1 , epoxy, or —Si(Y) x (Z 1 ) 3-x ;
R 1 is hydrogen, alkyl, aryl, arylalkylenyl, or alkylarylenyl;
Y is alkyl, aryl, arylalkylenyl, or alkylarylenyl;
each Z 1 is independently halide, hydroxyl, alkoxy, aryloxy, acyloxy, polyalkyleneoxy, —O— covalently bonded to the surface of the filler, or —O— bonded to another silicon atom to form a siloxane, wherein alkoxy and acyloxy are optionally substituted by halogen, and wherein aryloxy is optionally substituted by halogen, alkyl, or haloalkyl; and
x is 0 or 1,

and wherein the compound is at least one of covalently bonded or ionically bonded to the inorganic filler.

2. The treated filler of claim 1 , wherein the inorganic filler comprises at least one of alumina, tin oxides, antimony oxides, silica, zirconia, titania, glass, ceramics, calcium carbonate, or sodium metaborate.

3. The treated filler of claim 1 , wherein the inorganic filler comprises at least one of calcium carbonate, sodium metaborate, or hollow glass elements.

4. The treated filler of claim 1 , wherein W is a carboxylic acid group or —Si(Y) x (Z 1 ) 3-x , wherein x is 0, and wherein each Z 1 is independently hydroxyl, alkoxy, —O— covalently bonded to the surface of the filler, or —O— bonded to another silicon atom to form a siloxane.

5. The treated filler of claim 1 , wherein W is a sulfonic acid group, a phosphonic acid group, or a carboxylic acid group.

6. The treated filler of claim 1 , wherein X is alkylene that is optionally interrupted by at least one ether, ester, carbonate, carbamate, or arylene.

7. The treated filler of claim 1 , wherein R is H.

8. A composition comprising a curable polymeric resin and the treated filler of claim 1 .

9. The composition of claim 8 , further comprising a free radical initiator.

10. The composition of claim 9 , wherein the free-radical initiator is an organic peroxide.

11. The composition of claim 8 , wherein the curable polymeric resin is an unsaturated polyester resin.

12. The composition or method of claim 8 , wherein the composition further comprises at least one of styrene monomer, a substituted styrene monomer, an acrylate monomer, or a methacrylate monomer.

13. A method for determining degree of cure of a curable polymeric resin, the method comprising:
providing a composition comprising a curable polymeric resin, a free-radical initiator, and the treated filler of claim 1 in an amount sufficient to provide the composition with a first absorbance at a wavelength in a range from 400 nanometers to 700 nanometers; and
allowing the composition to cure to provide a cured composition, wherein the cured composition has a second absorbance at the wavelength that is different from the first absorbance.

14. A method of making the treated filler of claim 1 , the method comprising treating the inorganic filler with the compound represented by formula:

wherein
R is hydrogen or alkyl;
X is alkylene, arylalkylene, or alkylarylene, wherein alkylene, arylalkylene, and alkylarylene are optionally interrupted by at least one of an ether, thioether, amine, amide, ester, thioester, carbonate, thiocarbonate, carbamate, thiocarbamate, urea, or thiourea, and wherein alkylene is optionally interrupted by arylene;
W is hydroxyl, a sulfonic acid group, a phosphonic acid group, a carboxylic acid group, —NHR 1 , epoxy, or —Si(Y) x (Z 1 ) 3-x ;
R i is hydrogen, alkyl, aryl, arylalkylenyl, or alkylarylenyl;
Y is alkyl, aryl, arylalkylenyl, or alkylarylenyl;
each Z 1 is independently halide, hydroxyl, alkoxy, aryloxy, acyloxy, polyalkyleneoxy, —O— covalently bonded to the surface of the filler, or —O— bonded to another silicon atom to form a siloxane, wherein alkoxy and acyloxy are optionally substituted by halogen, and wherein aryloxy is optionally substituted by halogen, alkyl, or haloalkyl; and
x is 0 or 1.

15. The method of claim 14 , wherein the inorganic filler comprises at least one of alumina, tin oxides, antimony oxides, silica, zirconia, titania, glass, ceramics, calcium carbonate, or sodium metaborate.

16. The method of claim 14 , wherein the inorganic filler comprises at least one of calcium carbonate, sodium metaborate, or hollow glass elements.

17. The method of claim 14 , wherein W is a carboxylic acid group or —Si(Y) x (Z 1 ) 3-x , wherein x is 0, and wherein each Z 1 is independently hydroxyl, alkoxy, —O— covalently bonded to the surface of the filler, or —O— bonded to another silicon atom to form a siloxane.

18. The method of claim 14 , wherein W is a sulfonic acid group, a phosphonic acid group, or a carboxylic acid group.

19. The method of claim 14 , wherein W is a carboxylic acid group or —Si(Y) x (Z 1 ) 3-x , wherein x is 0, and wherein each Z 1 is alkoxy.

Assignees

• 3M Innovative Properties Co

Inventors

• Schulz Mark F
• Wendland Michael S

Classifications

• C09C3/08 Primary

  Treatment with low-molecular-weight {non-polymer} organic compounds {(C09C3/006, C09C3/048 take precedence)} · CPC title

• C09C1/021

  Calcium carbonates · CPC title

• C09B29/0801

  containing acid groups, e.g. COOH, SO3H, PO3H2, OSO3H, OPO3H2; SO2NHSO2R or salts thereof, R being hydrocarbonyls · CPC title

• C09B29/0829

  having N(-alkenylene/-alkynylene-CN)(-alkenylene/-alkynylene-CN) · CPC title

• C08K5/47 Primary

  Thiazoles · CPC title